U.S. patent application number 12/844069 was filed with the patent office on 2011-02-17 for photolytic artificial lung.
This patent application is currently assigned to PHAROS, LLC. Invention is credited to Kurt Dasse, Bruce F. Monzyk.
Application Number | 20110038760 12/844069 |
Document ID | / |
Family ID | 25443643 |
Filed Date | 2011-02-17 |
United States Patent
Application |
20110038760 |
Kind Code |
A1 |
Monzyk; Bruce F. ; et
al. |
February 17, 2011 |
PHOTOLYTIC ARTIFICIAL LUNG
Abstract
The present invention is directed to a photolytic artificial
lung. The photolytic artificial lung converts water to oxygen for
blood absorption, regulates pH, the removes carbon dioxide, and
co-produces electrical power is disclosed. The photolytic
artificial lung includes a photolytic cell where all of the
chemical reactions occur. The photolytic cell disclosed herein can
also be used to direct chemical reactions in organs other than the
lung. Also disclosed herein is a gas sorption device for removing
carbon dioxide from the system by chemical sorption.
Inventors: |
Monzyk; Bruce F.; (Delaware,
OH) ; Dasse; Kurt; (Wellesley, MA) |
Correspondence
Address: |
FAY SHARPE LLP
1228 Euclid Avenue, 5th Floor, The Halle Building
Cleveland
OH
44115
US
|
Assignee: |
PHAROS, LLC
|
Family ID: |
25443643 |
Appl. No.: |
12/844069 |
Filed: |
July 27, 2010 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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10939696 |
Sep 13, 2004 |
|
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12844069 |
|
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09920385 |
Aug 1, 2001 |
6866755 |
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10939696 |
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Current U.S.
Class: |
422/119 ;
422/121; 96/136 |
Current CPC
Class: |
B01D 2255/20776
20130101; A61M 1/32 20130101; B01D 2259/4575 20130101; C25B 1/55
20210101; B01D 53/326 20130101; B01D 2255/802 20130101; C01B
13/0207 20130101; Y02P 20/151 20151101; A61M 1/3687 20130101; B01D
53/864 20130101; B01D 2255/2073 20130101; A61M 1/3683 20140204;
A61M 1/327 20140204; Y02C 20/40 20200801; A61M 1/3681 20130101;
A61M 1/3627 20130101; B01D 2257/504 20130101; A61M 2205/8206
20130101; B01D 53/885 20130101; A61M 1/3679 20130101 |
Class at
Publication: |
422/119 ; 96/136;
422/121 |
International
Class: |
A62B 7/08 20060101
A62B007/08; B01D 53/02 20060101 B01D053/02 |
Claims
1. A gas sorption device comprising: a coalescence compartment
comprising a gas head space and a gas coelescor connected to said
gas head space; and a gas sorber connected to said coalescence
compartment, wherein gas accumulating in said gas head space moves
to said gas sorber, and said gas sorber converts gas to a solution
or solid.
2. The gas sorption device of claim 1, wherein said gas sorption
device further comprises an entry point connected to said gas head
space for entry of hydrogen gas.
3. The gas sorption device of claim 1, wherein said coelesor
further comprises an outlet connected to said coelesor for the
removal of said solution.
4. A photolytic artificial lung comprising a photolytic cell and a
gas sorption device, the photolytic cell containing a light
activated catalyst having the ability to convert water to oxygen
upon light activation; and the gas sorption device comprising a
coalescence compartment comprising a gas head space and a gas
coelesor connected to the gas head space; and a gas sorber
connected to the coalescence compartment, wherein CO.sub.2 gas
accumulating in the gas head space moves to the gas sorber, and the
gas sorber converts the CO.sub.2 gas to a solution or solid.
5. The photolytic artificial lung of claim 4, wherein the gas
sorption device further comprises an entry point connected to the
gas head space for entry of hydrogen gas.
6. The photolytic artificial lung of claim 4, wherein the gas
sorption device further comprises an outlet connected to the gas
sorber for the removal of the solution or solid.
7. The photolytic artificial lung of claim 4, wherein the gas
sorption device does not comprise a gas permeable membrane.
8. The photolytic artificial lung of claim 4, wherein the
coalescence compartment is tilted to have an upper end and a lower
end, CO.sub.2 enters the coalescence compartment at the upper end,
and hydrogen gas enters the coalescence compartment at the lower
end.
9. The photolytic artificial lung of claim 4, wherein the
coalescence compartment further comprises a means for controlling
temperature.
10. The photolytic artificial lung of claim 4, wherein the gas
sorber contains a sorbent which is reactive with CO.sub.2 gas.
11. The photolytic artificial lung of claim 4, wherein the gas
sorber contains a sorbent which is reactive with CO.sub.2 gas.
12. The photolytic artificial lung of claim 11, wherein the sorbent
is a solid.
13. The photolytic artificial lung of claim 11, wherein the sorbent
is a solution.
14. The photolytic artificial lung of claim 4, wherein the gas
sorber further comprises an outlet which is connected to the
coalescence compartment for the recycling of residual hydrogen
gas.
15. The photolytic artificial lung of claim 4, wherein the gas
sorber has a plurality of 90.degree. flow path changes.
16. The photolytic artificial lung of claim 4, wherein the CO.sub.2
gas enters at one end of the gas sorber and sorbent enters at an
opposite end of the gas sorber.
17. The photolytic artificial lung of claim 4, wherein the gas
sorber further comprises a pH indicator.
Description
[0001] This application is a continuation of co-pending prior U.S.
patent application Ser. No. 10/939,696, filed on Sep. 13, 2004.
Application Ser. No. 10/939,696 is a divisional of U.S. patent
application Ser. No. 09/920,385, filed Aug. 1, 2001 which issued as
U.S. Pat. No. 6,866,755. The disclosures of all of these
applications are hereby incorporation herein by reference in their
entirety.
FIELD OF THE INVENTION
[0002] The present invention is directed to a photolytic artificial
lung that utilizes light energy to achieve physiological gas
exchange in fluids, such as in the blood stream of a patient
experiencing respiratory difficulties, and to a photolytic cell
used for the same. It finds particular applications in conjunction
in the field of artificial organs and the medical arts. However, it
is to be appreciated, that the invention will also find
applications in related fields due to the photo-electro chemical
transformations involved therein.
BACKGROUND OF THE INVENTION
[0003] The lung is the main organ in the respiratory system, in
which venous blood is relieved of carbon dioxide and oxygenated by
air drawn through the trachea and bronchi into the alveoli. There
are two lungs, a right and a left, the former consisting of three,
the latter of two, lobes. The lungs are situated in the thoracic
cavity and are enveloped by the pleura.
[0004] In humans, each lung is connected with the pharynx through
the trachea and larynx. The base rests on the diaphragm and the
apex rises slightly above the sternal end of the first rib. The
lungs include the lobes, lobules, bronchi, bronchioles,
infundibula, and alveoli or air sacs.
[0005] The lungs contain about 300 million alveoli and their
respiratory surface is about 70 square meters. Adults average about
15-20 respirations per minute. The total capacity of the lung
varies from about 3.6 to 9.4 liters in adult men and about 2.5 to
6.9 in adult women.
[0006] The left lung has an indentation, called the cardiac
depression, for the normal placement of the heart. Behind this is
the hilum, through which the blood vessels, lymphatics, and bronchi
enter and leave the lung.
[0007] Air travels from the mouth and nasal passage to the pharynx
and the trachea. Two main bronchi, one on each side, extend from
the trachea. The main bronchi divide into smaller bronchi, one for
each of five lobes. These further divide into a great number of
smaller bronchioles. Additionally, there are about 50 to 80
terminal bronchioles in each lobe. Each of these divides into two
respiratory bronchioles, which in turn divide to form 2 to 11
alveolar ducts. The alveolar sacs and alveoli arise from these
ducts. The spaces between the alveolar sacs and alveoli are called
atria.
[0008] The alveolus is the point at which the blood and inspired
air are separated only by a very thin wall or membrane that allows
oxygen and nitrogen to diffuse into the blood and carbon dioxide
and other gases to pass from the blood into the alveoli. The
alveoli contain small pores that serve to connect adjacent alveoli
to each other.
[0009] The primary purpose of the lung is to bring air and blood
into intimate contact so that oxygen can be added to the blood and
carbon dioxide can be removed. This is achieved by two pumping
systems, one moving a gas and the other a liquid. The blood and air
are brought together so closely that approximately one micrometer
(10.sup.-6 meter) of tissue separates them. The volume of the
pulmonary capillary circulation is about 150 ml, but this is spread
out over a surface area of approximately 750 sq feet. This
capillary surface area surrounds 300 million air sacs called
alveoli. There blood that is low in oxygen but high in carbon
dioxide is in contact with the air that is high in oxygen and low
in carbon dioxide for less than one second. This allows for the
blood to be replenished with oxygen and for the excess carbon
dioxide to be removed.
[0010] Hemoglobin, the iron-containing pigment of red blood cells,
then carries the oxygen from the lungs to the tissues. In the
lungs, hemoglobin combines readily with oxygen, by a process called
oxygenation, to form a loose, unstable compound called
oxyhemoglobin. In the tissues, where oxygen tension is low and
carbon dioxide tension is high, oxyhemoglobin liberates its oxygen
in exchange for carbon dioxide. The carbon dioxide then becomes
carried by the blood serum to the lungs, where the whole
oxygenation process begins again.
[0011] There have been numerous efforts in the past 40 years to
achieve artificial lung function. Unfortunately, no new innovative
respiratory assist therapy has been developed for patients with
severe, life-threatening lung disease. This is largely due to
inadequate knowledge of pulmonary pathophysiology, a lack of
emerging therapies, and insufficient mechanisms for providing
intermediate to long-term respiratory support. The lack of adequate
technology for respiratory support for the patient with
deteriorating lung function, in particular, has had profound
effects on the quality of life for this increasingly large segment
of the population.
[0012] The number of deaths annually from all lung disease is
estimated to be approximately 250,000 (150,000 related to acute,
potentially reversible respiratory failure and 100,000 related to
chronic irreversible respiratory failure) with an estimated
economic burden of disease in the range of 72 billion dollars per
year. Furthermore, the emotional toll of progressive respiratory
failure is profound, particularly as it affects children and
adolescents with progressive pulmonary disease. The impact of this
public health problem can be conceived in terms of the direct costs
for intensive, sub-acute, and long-term health care services, and
the indirect costs associated with lost wages and productivity for
the patient and the patient's family, and the increased need for
support services.
[0013] While the death rates for cardiovascular disease, cancer,
and all other major diseases have recently decreased significantly,
the rate of death related to chronic pulmonary lung disease (CPLD)
has increased by 54%. Lung disease also represents one of the
leading causes of infant mortality, accounting for 48% of all
deaths under the age of one. For these patients, respiratory
assistance during pulmonary failure has been achieved by employing
ventilator therapy, despite the enormous cost and morbidity
associated with this modality.
[0014] Furthermore, it is well accepted that closed,
positive-pressure, mechanical ventilation, applied at moderate
levels of intensity, for short periods of time, is a somewhat safe
and efficient means for improving gas exchange in patients with
acute respiratory failure. However, with prolonged duration of
intensive respiratory support, serious adverse effects may occur.
These effects, including oxygen toxicity, baromtrauma, altered
hormone and enzyme systems, and impaired nutrition, may result in
further injury to the failing lungs, or add significantly to the
morbidity and mortality for these patients. As a result,
alternative methods have been sought for augmenting blood gas
exchange, where mechanical ventilation is inadequate or cannot be
safely applied.
[0015] In view of the above and other reasons, there has been great
interest in developing an artificial means for accomplishing
physiological gas exchange directly to the circulating blood and
bypassing the diseased lungs. While previous efforts have provided
some measure of success, they have been limited in their usefulness
or hindered by excessive cost.
[0016] One approach to artificial lung function has been by gas
sparging or diffusion of gas across the membrane surface of hollow
fibers placed within the blood supply. Previous efforts have
achieved some success, and have taught much to pulmonary
physiologists, but gas sparging or diffusion has yet achieved the
degree of gas exchanges optimally desired.
[0017] Furthermore, other methods and artificial lung systems have
been developed from introducing gaseous oxygen by air sparging.
However, gas sparging is very detrimental to biological tissues
such as red blood cells. Also, gas sparging attempts to control the
differential pressure across thin gas/liquid membranes such as
those found in porous-walled hollow fibers.
[0018] Another approach to artificial lung function, extracorporeal
membrane oxygenation (ECMO), constitutes a mechanism for prolonged
pulmonary bypass, which has been developed and optimized over
several decades but has limited clinical utility today as a
state-of-the-art artificial lung. The ECMO system includes an
extra-corporeal pump and membrane system that performs a gas
transfer across membranes. Despite the numerous advances in the
implementation of ECMO over the years, its core technology is
unchanged and continues to face important limitations. The
limitations of ECMO include the requirement for a large and complex
blood pump and oxygenator system; the necessity for a surgical
procedure for cannulation; the need for systemic anticoagulation; a
high rate of complications, including bleeding and infection;
protein adsorption and platelet adhesion on the surface of
oxygenator membranes; labor intensive implementation; and
exceedingly high cost. As a result of these limitations, ECMO has
become limited in its utility to select cases of neonatal
respiratory failure, where reversibility is considered to be highly
likely.
[0019] The development of the intravenous membrane oxygenation
(IVOX) also represented a natural extension in the artificial lung
art, since it was capable of performing intracorporeal gas exchange
across an array of hollow fiber membranes situated within the
inferior vena cava but did not require any form of blood pump. The
insertion of the IVOX effectively introduced a large amount of gas
transfer surface area (up to 6000 cm.sup.2) without alteration of
systemic hemodynamics. Unfortunately, as with ECMO, the IVOX system
has numerous limitations, including only a moderate rate of
achievable gas exchange; difficulty in device deployment; a
relatively high rate of adverse events; and a significant rate of
device malfunctions, including blood-to-gas leaks due to broken
hollow fibers.
[0020] A further approach to treat lung disease, is through the use
of lung transplants. The improvement of methods to transplant
viable lungs into patients is fundamentally the most significant
recent advance in the therapy of chronic lung diseases. The most
common indications for lung transplantation are emphysema,
pulmonary fibrosis, cystic fibrosis, and pulmonary hypertension.
Selection conditions emphasize the presence of irreversible disease
localized to the respiratory system, and social and psychological
conditions supportive of the ability to go through extended
pulmonary rehabilitations. In contrast, the absence of these
conditions present relative contraindications to this approach. The
donor organ should originate in a relatively healthy, infection
free individual, under the age of 65. Following these guidelines,
success has been achieved in increasing numbers for patients
throughout the United States.
[0021] Profound limitations in the number of donor organs has made
this option unrealistic for the great majority of patients who
would benefit the most. While rationing is the standard for all
transplantable organs, the need for rationing is particularly acute
in the case of the lungs, owing to the following issues: (1) the
large discrepancy between donor and recipient numbers (3350
registration for lung transplant in 1999 and only 862 performed);
(2) the relatively low yield of usable lungs, with only 5-10% of
multiorgan donors yielding lungs acceptable for transplantation;
and (3) the absence of effective temporary methods to support blood
gas exchange during the waiting period prior to transplantation.
The complexity of this problem is increased even further, when
considering the inevitable compromise between supplying organs to
patients who are the most ill, and who have the most to gain, but
for whom outcomes are generally poor, versus relatively healthier
patients with no complications, who have less need but for whom
outcomes are predictably better. For example, a patient with
emphysema is highly likely to achieve a positive outcome from
transplantation, but generally will not exhibit improved survival.
In contrast, a patient with cystic fibrosis has considerably higher
risk of surgery due to the presence of multiorgan involvement of
the disease, but for these young patients, successful
transplantation optimizes survival.
[0022] Therefore, a serious need exists for new technology and
therapeutic approaches that have the potential to provide
intermediate to long-term respiratory support for patients
suffering from severe pulmonary failure. Also, the need for an
efficient and inexpensive technology to achieve sustained gas
exchange in the blood, thereby bypassing the diseased lungs without
resorting to chronic ventilation, remains paramount.
SUMMARY OF THE INVENTION
[0023] In one aspect, the present invention is directed to an
photolytic artificial lung. It may be utilized for lung replacement
and/or for oxygenation supplementation of the blood stream. It is
particularly useful for treating a number of lung afflictions.
[0024] The photolytic artificial lung is a device, internal or
external to the body, that utilizes light, such as a laser or lamp,
to achieve physiological and therapeutic gas exchange in the blood
stream. In such an exchange, oxygen is dissolved into the blood
stream while carbon dioxide is removed and pH is controlled. This
is due to the use of photochemistry. The photolytic artificial lung
oxygenates blood without the deleterious effect on red blood cells
associated with direct gas sparing (i.e. blood cell lysis, pH
balance difficulties, etc.), while simultaneously controlling blood
pH and carbon dioxide content.
[0025] More particularly, the photolytic artificial lung includes a
photo-electro chemical cell (or "photolytic cell") that, in part,
operates similar to the photosynthesis process that takes place in
green plants. The photolytic artificial lung utilizes the
photolytic cell to convert light energy in order to simultaneously
generate oxygen from water, useful acidity and electrical energy.
The photolytic cell also removes carbon dioxide from the blood
stream. One or more photolytic cells can be included in the
photolytic artificial lung of the present invention depending on
the quantity, quality, etc. of desired gas exchange.
[0026] The light energy utilized in the present invention is
ultraviolet ("UV") light or visible light, with the laser form
being the most preferred. However, the light energy can also be
broad-band, received by the way of a "light pipe" fiber optic cable
or by the way of an attenuated total reflectance (ATR) link.
[0027] In the artificial lung, oxygen is generated from water
present in the blood stream by means of the light dependent
chemical reactions, photolysis and disproportionation. This is
followed by the removal or clearing of carbon dioxide by the
reactions of bicarbonate ion protonation and dehydration.
[0028] Photolysis is the initiation of a chemical reaction as a
result of absorbing one or more quanta of radiation. Here, water is
converted into oxygen by a light-activated catalyst, such as a
semiconducting metal oxide. The metal oxide is utilized as a
photo-absorbent material or a photo-absorption element. It is
photolytically irradiated to form, from water present in the blood
stream, hydrogen ions, hydrogen peroxide or other forms of oxygen
gas precursor (active oxygen, "AO") and electrons by the absorption
of one or more quantra of electromagnetic radiation. The free
electrons generated are then electrically conducted away to avoid
reversal of the reaction and optionally utilized to drive
electrical devices, such as a pump.
[0029] For example, it has been found that active oxygen is readily
generated in the present invention by the use of the anatase form
of titania (TiO.sub.2(a)) as the light absorbent material. The
photo energy of light, such as ultraviolet laser light (about 350
nm), selectively excites TiO.sub.2 semiconductor transition (about
350-390 nm band, or about 3.1 eV) with minimal material radiation
or transmission. The ultraviolet energy produces charge separation
in the anatase form of TiO.sub.2, which then produces active oxygen
(OA) and free electrons. The free electrons are then subsequently
electrically conducted away due to the semi-conducting property of
the anatase. Alternatively, other suitable light absorbent
materials can also be utilized in the present invention at various
wavelengths provided that the energy is sufficient to produce
active oxygen.
[0030] Disproportionation is a chemical reaction in which a single
compound serves as both oxidizing and reducing agent and is thereby
converted into a more oxidized and a more reduced derivative. For
example, hydrogen peroxide (active oxygen) produced during
photolysis can be converted by means of manganese dioxide
(MgO.sub.2), or other catalytic agents and/or processes, into
dissolved oxygen (DO) and water. This reaction produces dissolved
oxygen (DO) from water and by-passes the harmful gaseous state.
[0031] Additionally, in the artificial lung of the present
invention, carbon dioxide is removed from the blood stream by the
means of the reactions of protonation and dehydration. In essence,
the hydrogen ions formed during photolysis react with the
bicarbonate (HCO.sub.3.sup.-) and carbonate (CO.sub.3.sup.=) ions
present in the blood stream causing conversion of these ions into
carbonic acid. In the presence of carbonic anhydrase, a blood
component, the carbonic acid then quickly dissociates into water
and carbon dioxide. The carbon dioxide gas is then subsequently
vented into the environment.
[0032] Alternatively, due to concerns with infection in human lung
assistance applications, a novel method and device is also
disclosed herein for removing carbon dioxide from the system by
molecular absorption. In this embodiment, carbon dioxide is removed
from the blood stream by means of a carbon dioxide absorber device
(i.e., a sorber), or other similar gaseous removal devices, under
sterile conditions.
[0033] Consequently, the artificial lung of the present invention
produces oxygen directly from water present in the blood stream,
omitting the gaseous state which has previously caused pressure,
shear, weight, and bulkiness problems with other blood oxygenation
technologies. At the same time, the artificial lung also utilizes
the hydrogen ions produced from the water to release the carbon
dioxide. Additionally, the reactions occurring in the artificial
lung do not involve the generation or use of high temperatures or
pressures associated with previous devices and/or processes. The
photolytic artificial lung is preferably designed to be
self-contained and self-regulated. It requires no external gas
supply.
[0034] A brief description of the pertinent reactions involved in
the embodiment of the present invention utilizing anatase as the
light absorbent material is provided below:
[0035] Photolysis:
##STR00001##
[0036] Disproportionation:
##STR00002##
[0037] Protonation (H.sup.+ ions from photolysis reaction):
H+Na.sup.++HCO.sub.3.ident.Na+H.sub.2CO.sub.3
[0038] CO.sub.2 Gas Generation:
H.sub.2CO.sub.3.ident.H.sub.2O+CO.sub.2.uparw.
[0039] Catalyzed Dehydration (optional):
##STR00003##
[0040] The primary function of the photolytic artificial lung of
the present invention is to provide respiration assistance in
patients with lung disease, both in acute as well as chronic
conditions. However, other medical applications are also feasible
which also require the photochemical reactions of the present
invention and/or the convenience of photolytic power. These
include, among others, in-body drug level maintenance and release,
and the contribution to the function of other organs such as the
kidneys and the liver.
[0041] Additionally, the mix of products generated by the
photolytic artificial lung of the invention, can be used in driving
complex chemical processes, such as fermentations, and the
regulation of drug levels. It can also be used to provide
point-of-use chemicals such as hydrogen peroxide. The ability to
produce electrical power can further be utilized in remote
locations, and in powering small pumps (for example, it is
contemplated that the electricity generated from the artificial
lung can be used to drive an intravenously located blood pump,
etc.). Parallel processes like oxidation and reduction can also be
driven simultaneously at low then high (or visa versa) pH. The
presence of fundamental oxygen and pH transformations can still
further lead to many broad applications from sensors to industrial
chemical processing, and as an energy source to remote sites.
[0042] In a more particular embodiment, the photolytic artificial
lung of the present invention comprises an inlet for receiving
blood from the blood stream of a patient. A pump extracts blood
from the patient and moves the blood into at least one flow-through
photolytic cell via the inlet. The photolytic cell contains a
light-activated catalyst that converts water into oxygen, while at
the same time removing carbon dioxide as described above. A light
supply provides light energy to the photolytic cell. An outlet
moves blood out of the photolytic artificial lung and back into a
patient.
[0043] The photolytic cell is compatible with blood and provides
high yields of oxygen to the blood stream. The resulting photolytic
artificial lung is capable of use externally or internally by a
patient, as well as in a stationary or portable form. Furthermore,
the artificial lung is scalable to allow the photo-activated gas
exchanges to be accomplished in a small and wearable
extra-corporeal device, or in an intra-corporeal device inserted
into a patient's venous blood supply.
[0044] In a further aspect, the present invention is also directed
to a photolytic cell. The photolytic cell includes a transparent
window. An anode is adjacent to the transparent window. A
light-activated catalyst abuts the anode. A cell flow through area
is adjacent to the light activated catalyst. A cation exchange
membrane borders the cell flow through area. A catholyte abuts the
cation exchange membrane. A cathode is present adjacent to the
catholyte and is connected to the anode.
[0045] In another aspect, the present invention is further directed
to a gas absorption or sorption device for collecting and
converting a gas, such as carbon dioxide, to a solution or solid.
The gas sorption device comprises a coalescence compartment
including a gas head space and a coelesor connected thereto,
wherein gas accumulates and/or is concentrated in the gas head
space. A gas sorber connected to the coalescence compartment allows
for the movement of gas from the gas head space to the gas sorber
and the gas sorber converts gas to a solution or a solid. The
sorber can be disposed or regenerated thereby avoiding the
continuous venting of carbon dioxide to the atmosphere.
[0046] In an additional aspect, the present invention is further
directed to a method for delivering oxygen to an aqueous
bicarbonate ion solution. The method comprises moving the solution
into a photolytic cell wherein light is utilized by a
light-activated catalyst to produce oxygen from water, with a small
concomitant pH change to cause a release of carbon dioxide; and
moving the oxygenated solution out of the photolytic cell.
[0047] In still another aspect, the present invention is yet
further directed to a method for oxygenating blood from a patient.
The method includes moving deoxygenated blood into a photolytic
cell; converting water to dissolved oxygen in the photolytic cell;
binding dissolved oxygen to blood hemoglobin; forming carbon
dioxide in the photolytic cell; removing carbon dioxide formed in
the photolytic cell; and moving oxygenated blood out of the
photolytic cell. This process emulates, to a certain degree,
selected portions of the natural process by which plants produce
oxygen, namely photosynthesis, and the way the lung eliminates
carbon dioxide, namely through a pH drop. This method produces
dissolved oxygen directly from water, omitting the gaseous state.
It can be utilized to achieve therapeutic gas exchange in patients
with respiratory failure.
[0048] These and other objects and features of the invention will
be apparent from the detailed description set forth below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0049] The present invention will become more fully understood from
the detailed description given below and the accompanying drawings.
The description and drawings are given by way of illustration only,
and thus do not limit the present invention.
[0050] FIG. 1 shows a perspective view of an embodiment of a
photolytic artificial lung designed for external or extra-corporeal
usage.
[0051] FIGS. 2A-2D illustrate the various embodiments of the
photolytic artificial lung set forth in FIG. 1. FIG. 2A shows a
general illustration of the photolytic artificial lung connected
externally to a patient. FIG. 2B shows an interior view of the
components of one embodiment of the photolytic artificial lung.
FIG. 2C also shows an inside view of an alternative embodiment of
the photolytic artificial lung, and FIG. 2D illustrates the
chemical reactions occurring therein.
[0052] FIG. 3 shows a schematic view of the photolytic cell which
was used to collect the laboratory data set forth herein.
[0053] FIG. 4 shows an overall schematic diagram of the preferred
embodiment of the photolytic artificial lung of the present
invention.
[0054] FIG. 5 shows a diagram of the gas sorption device.
[0055] FIG. 6 shows a schematic diagram of the coalescence
collector.
[0056] FIG. 7 shows an interior view of the gas sorber device.
[0057] FIG. 8 shows a graph illustrating the plot of observed
electrical current generated by the photolysis cell versus laser
power intensity.
[0058] FIG. 9 shows a graph illustrating the relationship of the pH
profile of the anolyte and catholyte during photolysis using the
photolysis cell.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0059] The present invention is directed to a photolytic artificial
lung having among other components, a photolytic cell. The
photolytic cell is the fundamental functional unit of the
invention. It acts as a general purpose oxygen generation, carbon
dioxide remover and a pH controller. The photolytic cell includes a
photochemically active material for use in producing various
chemical reactions that enable the exchange of oxygen and carbon
dioxide in the blood stream. By optimizing a relative balance
between light activation, photolytic cell surface area and blood
flow, it is designed to maximize efficient gas transfer. The
photolytic cell, when used as a photolytic artificial lung
application for lung replacement/supplementation, will oxygenate
blood without the deleterious effect on red blood cells associated
with direct gas sparing while simultaneously controlling blood pH
and carbon dioxide contact.
[0060] Moreover, many devices other than an artificial lung can be
derived and implemented based upon the photolytic cell. For
example, the photolytic cell can be utilized to perform numerous
operations including chemical processes, fermentation systems,
regulation of drug levels, and replacement or assistance of one or
more organ functions. Consequently, as a result of the somewhat
similar photo-electrochemical transformations involved, the
photolytic cell component of the invention can have additional
applications outside of the artificial organ field.
[0061] In the preferred embodiment, the present invention is
directed to the use of the photolytic cell in a novel respiratory
assist device and process i.e., a photolytical artificial lung. The
photolytic artificial lung includes one or more photolytic cells
having photochemically active material and associated components
for the production of oxygen, the regulation of pH, the removal of
carbon dioxide, and the co-production of electrical power. The
electrical power can be used to produce additional chemical changes
or reactions. Optionally, the invention may include a photolytic
chamber to house or hold a sufficient number of stacked or
assembled photolytic cells to perform the rate of gas exchange
desired.
[0062] The technology of the present invention is based in part, on
the photo-initiated electrochemical transformation that mimics, to
some degree, the natural process of photosynthesis. In
photosynthesis, energy derived from sunlight is used to drive key
metabolic reactions that fuel the growth of plants along with the
production of oxygen.
[0063] The present photolytic artificial lung combines aspects of
photosynthesis and the operations of the lung. In the lung, oxygen
is transferred from the air to the blood as dissolved oxygen that
is available for binding to hemoglobin (Hb) for transport to body
tissues, and carbon dioxide is released from the blood into the
air. The equilibrium shifts from the binding of dissolved oxygen to
Hb and release of carbon dioxide are driven by gas pressure
differences and carbonic anhydrous catalysis.
[0064] In the present invention, the photolytic artificial lung
uses light energy to produce oxygen from water. Additionally, a
concomitant small pH change causes a release of carbon dioxide from
whole blood or serum. In the preferred embodiment, chemical
materials formed in the chemical processes from the photolytic
artificial lung are insoluble solids thereby preventing blood
contamination.
[0065] Preferably, the photolytic artificial lung of the instant
invention comprises a blood inlet cannula, a pump, at least one
photolytic cell, a light source that irradiates the photolytic
cells, an oxygenated blood outlet cannula and a carbon dioxide vent
and/or absorption device. A power source and/or batteries can be
present to power the pump or light source. One or more in-line
sensors and processors can be present to monitor and optimize the
flow through the system, the amount of oxygen and/or carbon dioxide
generation, the presence of toxins, etc. Desaturated blood
circulating through the device will be pumped through the
photolytic cells where light activation will result in oxygen
generation and ultimate carbon dioxide removal.
[0066] More particularly, FIG. 1 shows an embodiment of a
photolytic artificial lung 10 developed as an extra-corporeal
respiratory assist system. The artificial lung 10 includes a blood
inlet 12 that cannulates blood from the patient into the artificial
lung 10. The blood inlet 12 is connected to a pump 14 that draws
blood from the patient into the artificial lung 10. The pump 14
directs desaturated blood through one or more photolytic cells 16
where light activation (for example, laser at 350-380 nm) results
in oxygen generation and ultimate carbon dioxide removal via a
carbon dioxide sorption device 24 or external ventilation. A power
supply 18 or optional battery 19 activates the light source 20. The
light source 20 emits light photos 21 which irradiate the
photolytic cells 16. In turn, the photolytic cells 16
photochemically initiate a series of chemical reactions that
produce oxygen and remove carbon dioxide from the blood. Oxygenated
blood travels from the artificial lung 10 back to the patient by
way of a blood outlet 22. Consequently, the artificial lung 10
takes blood from the venous circulation of a patient and returns it
to the arterial circulation.
[0067] The present photolytic artificial lung omits the gaseous
state that causes problems which have limited other blood
oxygenation technologies, while consuming carbon dioxide. It also
eliminates the need for an external oxygen source and minimizes the
risk of inflammation produced by hollow fiber technology.
[0068] Also, the present photolytic artificial lung does not
require the careful control of temperature or pressure. As briefly
mentioned above, all materials for use in the present photolytic
artificial lung remain as insoluble solids to prevent blood
contamination. Blood contact with the coatings is minimized.
Diffusion layers, which can decrease oxygenation rates, are
minimized using electrical conduction of electrons and cations to
and from the photolytic site, as is done in photosynthesis, by
incorporating thin films having good photolytic transparency, and
electrical and electrochemical conduction.
[0069] The wave length, beam size, pulse duration, frequency and
fluency of the light source are adjusted to produce maximum and/or
efficient gas exchange. Similarly, pump rate, flow-through
capacity, etc. of the photolytic cells are also so adjusted. This
is accomplished by sensors and regulators which also monitor
reaction chemistry, toxins, etc. The sensors and regulators have
the capacity to auto-regulate various parameters of the system in
response to the conditions monitored by the sensors.
[0070] Most preferably, the photolytic artificial lung is designed
to provide at least about 150 ml of dissolved oxygen per minute at
5 L/min of blood flow through the system for a human patient. Also,
the components utilized for the photoactivated gas exchange are
biocompatable.
[0071] The photolytic artificial lung can be designed so that it is
an extra corporeal device or an intra-corporeal device. For
example, the photolytic artificial lung can be designed as a
miniaturized, implantable unit. Such a unit is configured to be
implantable and it uses a transcutaneous energy transmission system
and/or an internal light source for energy conversion.
[0072] FIG. 2A shows a simple representation of a patient attached
to a photolytic artificial lung 10 as an extra-corporal device.
FIGS. 2B and 2C are enlargement views showing the components of
various embodiments of the photolytic artificial lung 10. FIG. 2D
shows the chemical transformations which occur in each compartment
of the various embodiments of the artificial lung.
[0073] The photolytic artificial lung 10 pumps venous blood from
the patient to the photolytic artificial lung 10 through a blood
inlet 12. The venous blood enters by means of a flow distributor 25
into one or more photolytic cell(s) 16. The photolytic cell(s) may
be optionally arranged to form a stack of photolysis cells 27. The
amount of blood entering and leaving the photolytic cell(s) 16 is
controlled by flow distributor 25. See FIG. 2B.
[0074] A light source 20 irradiates the photolytic cell(s) 16,
thereby initiating the photochemical reactions within the
photolytic cell(s) 16 that ultimately form dissolved oxygen that
binds to blood hemoglobin (Hb). Excess carbon dioxide and hydrogen
formed from the chemical reactions in the photolytic cell(s) 16
enter one or more gas sorption devices 24 for storage and/or
eventual venting through a venting outlet 28. Once the blood has
been oxygenated, and the carbon dioxide removed, the blood returns
to the artery of a patient by way of blood outlet 22. Among the
components of the photolytic artificial lung not illustrated in
this embodiment is the blood pump, power supply, control
electronics and sensory technology for monitoring reaction
chemistry, the amount of oxygen, carbon dioxide, etc. generated the
presence of potential toxins, etc.
[0075] The main component of the photolytic artificial lung is the
photolytic cell 16. See, for example, FIG. 2C. Light energy 21 from
a light source 20 enters the photolytic cell 16 through a
transparent window 30 and activates a layer of light-activated
catalyst 32. As discussed in more detail below, an example of such
a light activated catalyst is anatase (TiO.sub.2). Depending on the
catalyst 32 used, the light-activated catalyst 32 converts water
into intermediate active oxygen, hydrogen ions and excess
electrons, or directly converts water into dissolved oxygen. An
optional second catalyst 34 can be used to convert the intermediate
active oxygen to dissolved oxygen, O.sub.2. An example of such a
second catalyst is manganese dioxide (MnO.sub.2). Excess electrons
are formed during the conversion of water to dissolved oxygen and
are conducted out from the catalyst 32 to an anode conductor layer
36 such as gold or titanium metal film. In chamber 37, the
dissolved oxygen binds to hemoglobin (Hb) in the blood and the
oxygenated blood returns to the patient via an arterial blood
outlet 22.
[0076] Additionally, in chamber 37, bicarbonate ions which are also
present in the deoxygenated blood react with the hydrogen ions
generated above to form carbonic acid. The carbonic acid is then
converted to water and carbon dioxide by carbonic anhydrase. The
water formed reacts with electrons at the cathode 38 to form
hydrogen gas (H.sub.2) and hydroxyl groups. The hemoglobin also
releases carbon dioxide when the oxygen binds to the hemoglobin.
The excess carbon dioxide and hydrogen created from the reactions
occurring in the photolytic cell 16 enter one or more gas sorption
devices 24 for storage or venting.
[0077] FIG. 3 shows a flow-through embodiment of the photolytic
cell 16. In the flow-through cell embodiment, the following main
components of the photolytic cell 16 are assembled, i.e. a
conductive coating of vacuum deposited Ti metal 36, a coating of
adherent TiO.sub.2 (anatase) 32, an optional MnO.sub.2 particulate
layer 34, and then tested using a bicarbonate solution. A UV laser
light 20 was shown on the transparent glass or quartz substrate so
to initiate the reactions. As discussed below, this cell was
utilized to collect pH and data as a function of laser U.V.
irradiation demonstrating the effectiveness of the invention.
[0078] In this regard, the photolytic cell 16 of FIG. 3 includes a
transparent window 30 or wave guide for the entry of light energy
in the form of photons 21 from a light source 20 such as an
ultraviolet laser light. On one side of the glass slide is an anode
conductor layer 36, such as titanium metal film. Attached to the
anode conductor layer 36, is a layer of a light activated catalyst
32 such as anatase (TiO.sub.2). An optional catalyst layer 34, such
as manganese dioxide, is adjacent to the light activated catalyst
layer 32. The photolytic cell 16 includes one or more layers of
silicone gaskets or spacers 40 and an acrylic housing 42. A pair of
anolytes 44 (in/out) are connected to the light activated catalyst
layer 32 or optional catalyst layer 34 and extend through the
photolytic cell 16 away from the transparent window 30. The
photolytic cell 16 further includes a cation exchange member 46,
such as a NAFION.RTM. membrane. A pair of catholytes 48 (in/out)
are connected to the cation exchange member 46 and extend outwardly
through the photolytic cell 16 generally away from the transparent
window 30. The photolytic cell 16 further includes a cathode layer
38, such as Pt foil, adjacent to the cation exchange member 46. The
operation and use of this embodiment of the invention is more
particularly described in the Examples below.
[0079] FIG. 4 is a schematic drawing showing the electrical and
chemical transformations which occur in the photolytic cell 16 of
the photolytic artificial lung 10. Venous blood (low in oxygen and
high in carbon dioxide) from a patient enters the photolytic cell
16 through inlet 12 by way of a peristaltic pump 14. Light photons
(hv) 21 generated by light source 20 enter through a transparent
window 30 or waveguide and activate the light activated catalyst 32
such as 100 .mu.m TiO.sub.2 (anatase). The light activated catalyst
32 either directly converts water to dissolved oxygen or converts
water to active oxygen and hydrogen ions and an optional second
catalyst 34, such as maganase dioxide (MgO.sub.2) on a porous film,
converts active oxygen (e.g. H.sub.2O.sub.2) into dissolved oxygen
(DO). The dissolved oxygen then binds to hemoglobin present in the
blood.
[0080] The electrons released from the conversion of water to
oxygen are collected in the collector electron anode 36. An
electrical current formed from a battery 49 allows the electrons to
flow from the anode 36 to the cathode 38, such as graphite or
nickel, so that the electrons do not react with the active oxygen
to cause a back reaction and the reformation of water.
[0081] The electrical current and electron flow can be regulated by
a current regulator 50 or resistor 52. The electrons can react with
water to form hydrogen gas, H.sub.2, and a hydroxyl ion (OH.sup.-).
The hydrogen gas formed is moved to a gas sorption device, where it
is stored and/or released (i.e., expired). Sodium (Na.sup.+) ions
from the blood migrate across the cation exchange membrane 46 and
react with hydroxyl ions to form sodium hydroxide (NaOH) in the
catholyte 48. The hydrogen ions formed from the conversion of water
at the light activated catalyst reacts with bicarbonate ions to
form carbonic acid, which is converted by carbonic anhydrase enzyme
present in the blood or added to form carbon dioxide and water. The
carbon dioxide formed in the photolytic cell 16 along with the
carbon dioxide released from the blood is moved to one or more gas
sorption devices 24 or vented. The oxygenated blood exits the
photolytic cell 16 via an outlet 22 and returns to the artery of
the patient.
[0082] The various particular components and/or processes of the
present invention are described in more detail below:
[0083] 1. Transparent Window 30
[0084] The transparent window 30 can be formed from glass, quartz
slides, quartz, etc. Glass is useful in forming the transparent
window provided that the UV transparency is adequate at the
wavelength needed. Quartz slides are also useful because of its
high UV transparency. For the transparent window, light entry into
and through the transparent window can be from the back, side, or
bottom. Edge illumination through the transparent window can
optionally include a lens or wave guide.
[0085] The transparent window can further include a wave guide. A
wave guide uniformly distributes photons (hv) from the light over
the surface of the light activated catalyst. Particularly, the wave
guide causes the light photons to travel in a path so that the
photons maximally contact the entire layer of the light activated
catalyst. Light enters the wave guide in the side of the
transparent window generally parallel to the surface of the light
activated catalyst that is attached to the transparent window. The
wave guide allows for maximal light photon contact with the light
activated catalyst without directly illuminating the side of the
entire light activated catalyst attached to the transparent window.
The wave guide also allows form maximal photolytic cell staking
because light is not required to directly illuminate the light
activated catalyst but rather can be indirectly illuminated by side
or edge entry in the transparent window. The wave guide provides
additional efficiency to light used in the photolytic cell because
the light can be spread across the entire surface of the light
activated catalyst.
[0086] 2. Anode Conductor Layer 36
[0087] The anode conductor layer 36 conducts electrons formed from
the reaction of water to oxygen out of the anode. The anode
conductor layer prevents the electrons from reacting back with the
oxygen to reform water, thereby allowing maximal formation of
oxygen. The anode conductor layer is applied or attached to at
least one side of the transparent window.
[0088] The anode conductor layer can be formed at least two
different ways. The anode layer can be formed by attaching a thin
film of uniform metallic conductor to the transparent window using
vapor deposition. The film preferably has a thickness of less than
about 0.2 .mu.m. Preferably, the film is formed from gold or
titanium. Gold remains metallic at all conditions but can be very
efficient at UV light blockage or reflection. Titanium can be
oxidized to TiO.sub.2 by adding O.sub.2 to the deposition chamber
to yield a possible catalyst layer with excellent adhesion.
[0089] The anode conductor layer 36 can also be formed by using
photo-resist technology. Under photo-resist technology, grids are
prepared with masks using vapor deposition. Conductor line spacing,
width and thickness optimization may be required to prevent
excessive attenuation, and provide sufficiently close conductive
areas to sweep electrons away from the light activated catalyst
layer.
[0090] 3. Catalysts 32 and 34
[0091] A light activated catalyst 32 is coated onto the anode
conductor layer. The light activated catalyst is photochemically
activated and reacts with water to form dissolved oxygen or a free
radical oxygen intermediate that is ultimately converted to
dissolved oxygen. The term active oxygen in the present application
defines any free radical oxygen intermediate formed in the
photolytically catalyzed reaction of water that is ultimately
converted to dissolved oxygen. The active oxygen formed is in the
form of a peroxide, such as hydrogen peroxide, H.sub.2O.sub.2, or
peroxide ion salt, hydroxyl free radical, super oxide ion, etc.,
and is converted into dissolved oxygen in the presence of a
catalyst. The active oxygen formed depends on the light activated
catalyst used. Also, depending on the light activated catalyst
used, water may be photolytically converted directly into dissolved
oxygen without first forming an active oxygen.
[0092] Several different catalysts can be employed for producing
dissolved oxygen photochemically. One catalyst that can be used to
photochemically produce oxygen is zinc oxide. By using zinc oxide,
peroxide (H.sub.2O.sub.2) is produced directly from water at blood
pH. H.sub.2O.sub.2 is an excellent form of active oxygen for
providing sufficient potential diffusion distance, and also for the
disproportionate reaction to dissolved is oxygen and water via a
solid MnO.sub.2 catalyst (similar to green plant O.sub.2 generation
site) occurring photochemically at <340 nm by way of metal ion
assisted disproportionation with catalase and other
hydroperoxidases. Zinc oxide film has other positive attributes
including, known film formation technology (e.g. via the
zinc/nitrate/glycine reaction), low toxicity concerns, and low
cost.
[0093] An additional catalyst that can be used to photochemically
produce dissolved oxygen is tungstate (WO.sub.3) that is exposed to
visible light and using e.sup.-.sub.scb removal. WO.sub.3 yields
oxygen (O.sub.2) directly from water without the need to first
produce an active oxygen species. Oxygen is generated
stoichiometrically and the "back reaction" is unfavored so that
there is not significant competition to the direct formation of
dissolved oxygen. Only visible light is needed to generate
dissolved oxygen from WO.sub.3, no more than about 496 nm. WO.sub.3
films present low toxicity concerns. Preferably, the use of
WO.sub.3 further includes the removal of excess e.sup.-.sub.scb
formed during oxygen formation from water.
[0094] Another catalyst suitable for reacting with water is
TiO.sub.2 (anatase) irradiation with, followed by dissolved oxygen
production at a metal catalyst, such as a MnO.sub.2 catalyst, or
other similar catalyst. TiO.sub.2 removes the e.sup.-.sub.scb
efficiently from the production area in order to ultimately obtain
good dissolved oxygen production and minimize any back reaction to
reform reactants. The removal of e.sup.-.sub.scb is performed
through conduction via the semi-conductor property of the
TiO.sub.2(a) with enhancement via application of a small DC bias
voltage. TiO.sub.2 irradiation also presents low toxicity concerns.
TiO.sub.2 provides very high insolubility and kinetic inertness to
minimize dissolution and fouling during use and maintenance.
Preferably, UV light is chopped or pulsed during TiO.sub.2
irradiation to allow time for the chemical reactions to occur since
with continuous irradiation causes the e.sup.-.sub.scb to
accumulate and force a back reaction to form water. A pause in the
irradiation allows time for the slower, but still extremely fast
irradiation in the range of {circle around (3)} sec to msec to
occur to occur.
[0095] A further catalyst for reacting with water to ultimately
form dissolved oxygen is a semiconductor powder (SCP)-filled UV/VIS
light transparent thermoplastic film. SCP-filled thermoplastic film
is relatively inexpensive to manufacture and form into shape. SCP
film is easily moldable, extrudable, cut and machined. SCP can be
used very efficiently in surface applied only form. Also, SCP has
low toxicity concerns. Optimized commercial products (conductive
plastic filler powders) are available with good properties for
dispersion, particle-to-particle electrical conductivity (for
e.sup.-.sub.scb removal), and resistance to sloughing off that can
be used with the present photolytic artificial lung.
[0096] The following additional preferred conditions may be used
for each of the above-mentioned catalysts. First, an application of
a small (e.g. up to a few volts DC) bias voltage can be applied to
help ensure that the e.sup.-.sub.sch is quickly conducted away from
the production site. Second, a chopped illumination, instead of a
continuously applied illumination, may allow secondary chemical
reactions to occur since the secondary chemical reactions are
slower than the photochemical reactions and enhance photo yields by
allowing the excited electrons to exit the system and not be
present for regeneration of starting material, i.e., water.
[0097] Of the above-mentioned catalysts, the TiO.sub.2 (anatase)
catalyst followed by a second metal catalyst is the most preferred.
When the TiO.sub.2 catalyst is used, the light-titanic interaction
is the first step in the ultimate formation of dissolved oxygen. It
is known that surface hydrated particulate TiO.sub.2 (anatase)
solid, TiO.sub.2(a)--OH.sub.2 or Ti.sup.IVO.sub.2(a)--OH, is an
efficient UV light (hv) acceptor at wave lengths <390 nm,
resulting in active oxygen formation from sorbed water and hydroxyl
groups. The most probable reaction is believed to be:
Ti.sup.IVO.sub.2(a)--OH+hv.fwdarw.Ti.sup.III--.OH*
[0098] It is noted that other bonds to Ti have been omitted for
clarity. The reactant and product of the above reaction are solid
materials. In the above reaction, H.sub.2O is already bonded to the
surface of the TiO.sub.2(a) catalyst as H.sub.2O or as hydroxyl ion
(OH.sup.-), i.e. Ti.sup.IVO.sub.2(a)--OH.sub.2 or
Ti.sup.IVO.sub.2(a)--OH, respectfully. Hence, no atoms are required
to move during the very fast photon absorption process. The *
represents a low lying excited electronic state where the energy of
the photon is used to transition or excite an electron from a
nonbonding orbital on the oxygen to a molecular orbital centered on
the titanium ion, hence converting the titanium into a trivalent
oxidation state. The molecular orbital centered on the titanium ion
is known to be a part of the semiconduction band ("scb"), and so
the electron is readily conducted away from the site to form a
bipolar charged grain, or, if connected to a closed DC electrical
circuit, resulting in full charge separation, i.e.,
Ti.sup.III--.OH*.fwdarw.[Ti.sup.IV--.OH].sup.++e.sup.-.sub.(scb).uparw.
[0099] If the e.sup.-.sub.scb is not conducted away or otherwise
removed by reaction with an oxidant present in the solution, the
e.sup.-.sub.scb could react with the hydroxyl free radical and
reverse or back react so that the system would return to its
original state and form water. In this latter case there would be
no net reaction and the photolytic energy will appear as a small
amount of heat. Hence the charge separation process and removal of
e.sup.-.sub.scb is considered an important first step of the
photolytic cell dissolved oxygen generation process.
[0100] The hydroxyl free radical (.OH) group present is used to
represent the initial form of the active oxygen generated by the
photolytic process. It is not certain that .OH is the dominant
species present when TiO.sub.2(a) is photolyzed. The active oxygen
formed could generally be in the form of a superoxide, hydrogen
peroxide, or a hydroxyl free radical. However, the form of this
active oxygen produced has sufficient thermodynamic driving force
to form active oxygen from water. For the TiO.sub.2(a) catalyst at
neutral pH, these highly reactive hydroxyl free radicals either
back react as described above, or rapidly dimerize to form
(.mu.-peroxo) titanium (IV) and hydrogen ions, i.e.
##STR00004##
[0101] These H.sup.+ ions are valuable for blood --CO.sub.2 level
control. The rate of dissolved oxygen production is the rate at
which the active oxygen splits out to form O.sub.2(aq) and reforms
TiO.sub.2(a), i.e.
Ti.sup.IV--O--O--Ti.sup.IV.fwdarw.Ti.sup.IV--O--Ti.sup.IV+1/2O.sub.2(aq)-
(as dissolved oxygen)
[0102] In an unwanted but unharmful second side reaction, any
O.sub.2(aq) produced can react with e.sup.-.sub.scb previously
produced but not yet conducted away. These e.sup.-.sub.scb negative
charges tend to reside on the surfaces of the TiO.sub.2 particles
so that the negative charge are most separated. Therefore, these
e.sup.-.sub.scb electrons are available for reduction reactions
with O.sub.2 or the .mu.-peroxide linkage to produce species such
as O.sub.2.sup.-, O.sup.=, O.sup.-, etc., thereby decreasing
dissolved oxygen yields. In order to minimize side reaction, the
illumination is pulsed instead of continuous. The delay caused by
illumination pulsation allows the e.sup.-.sub.scb to be conducted
away in one direction and the dissolved oxygen to diffuse away in
another (E. Pelizzetti, M. Barbeni, E. Pramauro, W. Erbs, E.
Borgarello, M. A. Jamieson, and N. Serpone, Quimica Nova (Brazil),
288 (1985)). Also, illumination pulsation prevents the local
populations of O.sub.2(aq) and e.sup.-.sub.scb from becoming so
high that reaction between them becomes fast. The pulse rates
involved are extremely short in the .mu.sec-msec range so that
there is little effect on O.sub.2(aq) production rates. Enhanced
yields are also possible for photolytically established charge
separation when a bias voltage is present across the coating. (X.
Z. Li, H. L. Liu, and P. T. Yue, Envison-Sci-Technology, 2000, 34,
4401-4406.) A small bias voltage may also be used to further reduce
the amount of e.sup.-.sub.scb present and produce more dissolved
oxygen.
[0103] Another way to increase the amount of dissolved oxygen
production in the TiO.sub.2(a) system is to provide a means to
speed the rate of release of the trapped .mu.-peroxide as hydrogen
peroxide as to active oxygen.
Ti.sup.IV--O--O--Ti.sup.IV+H.sub.2O.fwdarw.Ti.sup.IV--O--Ti.sup.IV+H.sub-
.2O.sub.2(aq)
[0104] H.sub.2O.sub.2 is an excellent form for the active oxygen
species as it readily migrates and is easily catalyzed to
disproportionate into dissolved oxygen and water.
##STR00005##
[0105] Stable free radicals (SFRs) can be used to release the
trapped {circle around (3)}-peroxide as hydrogen peroxide. SFRs can
exist as free radicals for extended periods of time relative to the
hydroxyl free radical. SFRs have been found useful for promoting
electron transfer reactions. They electronically and reversibly
rearrange into reduced or oxidized species one electron at a time
as set by the reaction conditions. Biological systems are known to
use SFRs as respiratory carriers, such as quinone coenzymes
including ubiquinone, vitamin K, etc. The SFR shuttles the
reactivity from the point of generation to the point of
H.sub.2O.sub.2 production, or even directly to the metal ion
MnO.sub.2 catalyst for dissolved oxygen production. Components
found in biological systems such as vitamins E, C, K, etc. also may
function in the role of SFRs except without recycle. At least four
classes of SFRs exist from which a suitable agent can be selected:
hindered hydroxylated aromatics (quinones, substituted phenolics);
organic peroxide precursors (alcohols, etc.); peracid precursors
(acylating agents, etc.); and nitroxides, RN.fwdarw.O.
[0106] Therefore, for the TiO.sub.2(a) photocatalyst to be useful,
a means for releasing the .mu.-peroxide energy is needed, such as
soluble H.sub.2O.sub.2, since H.sub.2O.sub.2 can diffuse to the
MnO.sub.2 for dissolved oxygen production, or by conducting the
oxidizing power to another active oxygen form, such as SFRs in the
adjacent solution that can be used in dissolved oxygen production,
or using the Ti.sup.IV--O--O--Ti.sup.IV content to electronically
remove electrons from the MnO.sub.2 cluster/particle (as is done in
green plant photosynthesis by the "D" to protein). In the last
means, only an electron flows from the water through the MnO.sub.2
to the .mu.-peroxo linkage through delocalized bonds. This electron
replaces the e.sup.- lost from the TiO.sub.2(a)--OH system as
e.sup.-.sub.scb.
[0107] The formation of H.sub.2O.sub.2 as the active oxygen is
valuable since H.sub.2O.sub.2 can be rapidly converted to dissolved
oxygen in 100% yield using many different methods: thermally; metal
ion catalysis; particulate/surface catalysis; base catalysis; and
free radical reaction with reductant initiation. Preferably, metal
ion catalysis, such as, MnO.sub.2(s), provides an efficient
catalyst for H.sub.2O.sub.2 disproportionation to water and
O.sub.2, on thin film substrate constructs.
##STR00006##
[0108] Photo catalyst systems such as zinc oxide, ZnO, release
peroxide as the active oxygen more readily than does TiO.sub.2.
Less acidic metal ions under the Lewis acid/base theory definition
cannot sufficiently stabilize the highly alkaline peroxide ion
relative to water protonation (pK.sub.a1 of H.sub.2O.sub.2 is 11.38
(25.degree. C.)) to form it within the solid phase, and so hydrogen
peroxide, H.sub.2O.sub.2, is readily formed from ZnO:
##STR00007##
[0109] ZnO films and particles can be prepared in a number of ways
with varying but controlled composition, morphology and porosity.
For example, mirrors of zinc, doped zinc, and zinc alloys and can
be sputtered down onto an optically transparent support, followed
by oxidation with O.sub.2(g). This treatment produces a metal/metal
oxide (Zn/ZnO) film. Another highly effective approach to
semiconducting ZnO-based films is to utilize a process for optical
glass coatings. (L. R. Pederson, L. A. Chick, and G. J. Exarhos,
U.S. Pat. No. 4,880,772 (1989).) The optical glass coating
technique is based on applying a zinc nitrate/glycine aqueous
solution as a dip or spray, followed by drying (110.degree. C. for
15 min), then heating (450-500.degree. C. for 3 min) to initiate a
self-oxidation reaction during which the carbon and nitrogen exits
as gases leaving an adherent yet porous film bonded to the
underlying surface (e.g. glass) and is referred to as the glycine
nitrate process. (L. R. Pederson, L. A. Chick, and G. J. Exarhos,
U.S. Pat. No. 4,880,772 (1989).) The ZnO film is normally produced
doped with alumina by including aluminum nitrate in the aqueous
formulation for the initial dip. Many other metal ion blends are
also possible with this technique.
[0110] Tungstate only requires visible light to produce dissolved
oxygen, and produces dissolved oxygen directly without requiring a
second catalyst to form dissolved oxygen. The lower photon energy
requirement for WO.sub.3 is due to the smaller band gap of 2.5 eV
versus at least 3 eV for TiO.sub.2(a). As with the TiO.sub.2
anatase system, high yields are possible with the WO.sub.3 catalyst
if the e.sup.-.sub.scb is removed. The production of O.sub.2
increases very significantly if RuO.sub.2 (ruthenium oxide) is
placed on the surface of the WO.sub.3. This is consistent with the
fact that RuO.sub.2 is a known good catalyst for O.sub.2 production
and so represents a route to improving other approaches.
[0111] An advantage may exist if the dissolved oxygen producing
film could be a filled plastic. Such materials are often
inexpensive and manufactured easily. Commercial sources exist for
semi-conducting, low light absorbing, inorganic fillers for
plastics which are supplied in ready made condition for
incorporation into plastics, making the plastics electrically
conductive. For example, E.I. duPont Nemours, Inc. sells
electroconductive powders (EPC) under the trade name ZELEC.RTM. ECP
for such purposes. The conductive substance in ZELEC.RTM. ECP is
antimony-doped tin oxide (SnO.sub.2:Sb). The bulk of these
materials, onto which the conductor is coated, are familiar
inorganics such as mica flakes, TiO.sub.2, and hollow silica
shells, or ECP-M, ECP-T and ECP-S respectively. Pure
SnO.sub.2:Sb-based material is designated ECP-XC and is a much
smaller particle than the other materials. About 25-45% by weight
of the ECP products are used so that the particles are sufficiently
close to each other to provide internal electrical connections
throughout the otherwise non-conducting plastic. ECP-S and ECP-M
normally perform best for lower concentrations. Thin films of
ECP-XC can provide an attractive coating because they are very fine
grained and strongly light absorbing.
[0112] The TiO.sub.2 layer can be formed a variety of ways. The
TiO.sub.2 layer can be formed by sol gel, drying and baking. A
product under the trademark LIQUICOAT.RTM. from Merck & Co.,
Inc., which hydrolyzes Ti(OR).sub.4 type material in water to form
TiO.sub.2 and 4ROH can be used to form the TiO.sub.2 layer under a
sol gel/drying/baking process. TiO.sub.2 can also be formed from
preparing an anatase suspension from dry powder, then dipping,
drying, and baking the suspension to form the TiO.sub.2 layer.
Another way the TiO.sub.2 layer can be formed is by e-beam
evaporating titanium and subsequently exposing the titanium to
O.sub.2 within a deposition chamber. The TiO.sub.2 layer can also
be formed by adding titanium salt to water and adjusting the pH to
.about.2-7 to form a suspension, then dipping the suspension and
allowing the suspension to dry.
[0113] Active oxygen is created from TiO.sub.2 by irradiation with
UV light, but the chemical form of the active oxygen is very
reactive and can be lost by side reaction occurring in close
proximity to the TiO.sub.2 particle surface where active oxygen is
generated. There are at least three ways to minimize the loss of
active oxygen to unwanted side reaction: 1) move the active oxygen
to dissolved oxygen conversion point closer to the active oxygen
generation point, i.e. move the metal ion catalyst as close as
possible to the TiO.sub.2, which may require intimate contact
between these two materials, in the order of angstroms; 2)
electrically connect the two points, as is done in photosynthesis
by a protein capable of conducting electrons; or 3) convert the
active oxygen into a longer lived intermediate active oxygen
species that has time to migrate to more distant MnO.sub.2 centers
for conversion to dissolved oxygen.
[0114] The amount of active oxygen lost by side reactions can be
minimized by introducing an active oxygen carrier molecule into the
media, or "D," by analogy to a photosynthetic system. Agents for
use with species D can be selected from two groups, those that
readily form organic peroxides, and those that form "stable" (i.e.
long-lived) free radicals. Organic peroxides are useful because
they easily produce dissolved oxygen when contacting MnO.sub.2, and
readily form by oxygen insertion. The organic peroxide reactions
are as follows:
[TiO.sub.2]--Ti.sup.IV--OH+hv->{[TiO.sub.2]--Ti.sup.IV.OH}
where the excited electronic state corresponds to the
ligand-to-metal charge transfer (free radical pair), and is
followed by the reaction:
{[TiO.sub.2]--Ti.sup.III.OH}+H.sub.2O-->[TiO.sub.2]--Ti.sup.IV--OH+H.-
sup.++.OH
where conduction of the e- into the semiconductor conduction band
and away from the side of the particle near the .OH prevents
recombination of that e.sup.-. As shown in the reaction above, the
TiO.sub.2 anatase is regenerated. The above reaction produces a
hydrogen ion for eventual CO.sub.2 removal. Also, the active oxygen
produced in the above reaction is in close proximity to TiO.sub.2
as a free radical hydroxyl groups, .OH.
[0115] As .OH is extremely reactive, lasts only for a very short
time and does not diffuse far. One way to increase the amount of
time that .OH is present is by introducing a species that
stabilizes the .OH. Similar to photosynthesis, a species "D" is
introduced into the test system to capture the hydroxyl free
radical in a longer lived species. The species D is generally shown
the in following chemical reaction:
D+.OH->D*
where D can be RC(O)OH:
##STR00008##
or D can be R.sub.3COH:
##STR00009##
[0116] or D can be a free radical scavenger that forms a stable
free radical:
##STR00010##
or D can be 2,6-di-tertbutyl phenol:
t-Bu--Ar--OH+.OH->t-Bu--Ar--O.+H2O
[0117] The 2,6-di-tertbutyl phenol is the most desired D species,
as a strongly reducing .H radical is not formed that would consume
OH.sup.- and [TiO.sub.2]--Ti.sup.III in wasteful reactions,
regenerate the starting materials, and result in a low
photochemical yield.
[0118] The catalyst used to convert active oxygen into dissolved
oxygen includes metal ions capable of redox cycling, such as
Fe.sup.II, Fe.sup.III, Cu.sup.I, Cu.sup.II, Co.sup.II, Co.sup.III,
Mn.sup.II, Mn.sup.III, Mn.sup.IV, etc., or metal oxides formed from
metal ions capable of redox cycling, such as manganese dioxide,
MnO.sub.2. The present reaction produces dissolved oxygen directly
from water and by-passes the gaseous state. The MnO.sub.2 catalyst
is most preferred because it forms dissolved oxygen efficiently and
is not highly selective of the active oxygen form.
[0119] One way to facilitate the conversion of active oxygen to
O.sub.2 is by doping the surface of the TiO.sub.2 anatase with
manganese (Mn). Surface doping the TiO.sub.2 with Mn provides a
highly productive active oxygen to O.sub.2 conversion catalyst.
Active oxygen disproportionation is rapid when dropped on a
Mn-doped anatase. Alternatively, active oxygen can also be
converted to O.sub.2 by placing MnO.sub.2 on the surface of the
anatase in conductive form. In this form, electrons are
catalytically passed from water to the active oxygen region of the
anatase. Such an arrangement more closely mimics photosynthesis
O.sub.2 production.
[0120] Another way to convert active oxygen to O.sub.2 in the
photolytic cell is by using a MnO.sub.2 octahedral molecular sieve
(MOMS) material as the dissolved oxygen catalyst. The MOMS material
has an open gel-like structure and is closely related to zeolites
in structure. The MOMS material is easily formed from manganese
salts through precipitation and drying.
[0121] Active oxygen may also be converted to O.sub.2 in the
photolytic cell by a superoxide dismutase (SOD) catalyst. SOD
catalyst is already available in the human body and can provide the
required conversion of active oxygen, e.g. as O.sub.2.sup.-, into a
dissolved oxygen precursor, i.e. H.sub.2O.sub.2, to supplement the
photolytic cell and Mn-doped anatase.
[0122] Blood is routinely exposed to active oxygen forms and blood
already has built-in measures for self protection against low
levels of excessive active oxygen. ("Inorganic Biochemistry", G. L.
Eichhorn (Ed)., Chap. 28, p 988 (Elsevier, Scientific Publ., NY
(1975), and "Advances in Inorganic and Bioinorganic Mechanisms", A.
G. Skes (Ed), p 128 (1986) (Academy Press, NY)) Active oxygen forms
within the body in the form of species such as peroxides
(R--O--O--H) and superoxide (O.sub.2(aq).sup.-), which are
disproportionated to dissolved oxygen and H.sub.2O respectively by
hydroperoxidases, such as catalase which contains zinc ion,
peroxidase which contains iron ion, etc., and superoxide dismutase
metal ion-based enzymes, such as ferriprotophyrin IX.
Alternatively, these enzymes can utilize active oxygen forms to
oxidize a wide range of chemical reductants such as ascorbic acid
and other vitamins such as such as vitamin E and vitamin K.
Although the photolytic artificial lung does not rely on such
protection mechanisms, it is noteworthy that low levels of such
molecules are not new to body chemistry and that conventional
mechanisms for handling such exposures exists.
[0123] 4. Blood Exchange
[0124] Hemoglobin from blood follows the following steps of
reactions within the photolytic cell.
Hb(h.s. Fe.sup.II)+O.sub.2.delta.Hb(l.s. Fe.sup.I)O.sub.2
HbO.sub.2+2H.sup.+(pH 6.8-7.6) .delta.H.sub.2Hb2.sup.++O.sub.2
N-- of two alpha-chains (pKa 8.0) and His .beta.146 (pKa 6.5)
residues are bases for H.sup.+ reaction
CO.sub.2+H.sub.2O.lamda.H.sub.2CO.sub.3.lamda.H.sup.++HCO.sub.3.sup.-
Hb(R--NH.sub.2)+CO.sub.2.lamda.R--NH--COO.sup.-+H.sup.+
[0125] When water reacts with a light activated catalyst, the
hydrogen ion that is released rapidly reacts with an
HCO.sub.3.sup.- ion and forms H.sub.2CO.sub.3. The photolytic cell
has excess HCO.sub.3.sup.- ions to react with hydrogen ions.
[0126] The photolytic cell allows the blood to achieve the proper
mass balance. The mass balance of blood traveling through the
photolytic cell is as follows:
##STR00011##
[0127] Alternatively, quinone can be replaced with
Fe(CN).sub.6.sup.3-. The quinone or Fe(CN).sub.6.sup.3- Q could be
in homogeneous solution or film form.
[0128] 5. Cation Exchange Membrane 46
[0129] The cation exchange membrane 46 allows for the diffusion of
cations in the photolytic cell. Particularly, the cation exchange
membrane allows a cation, such as a sodium ion (Na.sup.+) from
blood to diffuse through the membrane and subsequently form sodium
hydroxide (NaOH) in the catholyte. The cation exchange membrane is
commercially available under the trademark NAFION and is available
from E.I. du Pont Nemoirs Inc. NAFION cation exchange membranes are
a perfluorosulfonic acid/PTFE copolymer in an acidic form. Although
NAFION cation exchange membranes are the preferred membrane, one
skilled in the art would recognize that other cation exchange
membranes are also suitable in the photolytic cell.
Anode
[0130] The anodic compartment of the photolytic cell has the
following series of reactions:
##STR00012##
The overall net anodic reaction from the above reactions is as
follows:
hv+1/4Hb+2NaHCO.sub.3.fwdarw.2CO.sub.2(g).mu.+H.sub.2O+1/2Hb.sub.0.5O.su-
b.2+2e.sup..GAMMA.+2Na.sup.+
[0131] The two electrons formed in the anodic reaction are
conducted away to the cathode via the anode conductor layer. The
two Na.sup.+ ions are moved to a catholyte via a cation exchange
membrane.
[0132] 6. Catholyte 48
[0133] Sodium hydroxide (NaOH) builds in the catholyte during the
series of reactions in the photolytic cell. It is preferred that
the NaOH is purged occasionally from the catholyte. If sodium
chloride (NaCl) is used in the catholyte instead of NaOH, NaCl(s)
may eventually form within the catholyte and would periodically be
purged.
[0134] The reactions occurring in the cathode of the photolytic
cell are as follows:
2NaHCO.sub.3.lamda.2Na.sup.++2HCO.sub.3.sup.-
2e.sup..GAMMA.+2H.sub.2O+.ident.H.sub.2(g)+2OH.sup..GAMMA.
2OH.sup..GAMMA.+2HCO.sub.3.sup.-.ident.2CO.sub.3.sup.=+2H.sub.2O
4Na.sup.++2CO.sub.3.sup.2-.lamda.2Na.sub.2CO.sub.3
The overall net cathodic reaction is as follows:
2e.sup..GAMMA.+2Na.sup.++2NaHCO.sub.3.fwdarw.H.sub.2(g).mu.+2Na.sub.2CO.-
sub.3
[0135] The Na.sub.2CO.sub.3 that is produced causes pH to rise.
Based upon the overall anodic and cathodic cell reactions, the
overall net photolytic cell reaction is:
hv+1/4Hb+4NaHCO.sub.3.fwdarw.H.sub.2(g)+2Na.sub.2CO.sub.3+2CO.sub.2(g)+H-
.sub.2O+1/2Hb.sub.0.5O
[0136] 7. Battery/Current Regulator
[0137] As shown in FIG. 4, the photolytic cell can include a
battery 49, current regulator 50, or resistor 52. An electrical
current formed from a battery 49 allows electrons to flow from the
anode 36 to the cathod 38. The intial bias voltage caused by the
current supplied from the battery initiates the removal of
electrons formed during the conversion of water to dissolved oxygen
and prevents the electrons from reacting with the active or
dissolved oxygen to reform water. The initial bias voltage also
allows more dissolved oxygen to be produced as the removal of the
electrons minimizes the reformation of water. Additional external
electrical contacts can monitor or apply a particular voltage to
the photolytic cell.
[0138] The current regulator and resistor help control the flow of
electrons from the anode to cathode, thereby controlling the amount
of dissolved oxygen formation. The resistor creates a fixed control
in the current flow, whereas the current regulator can be adjusted
to increase or decrease the resistance of the current flow.
Increasing the resistance of the current lowers the number of
electrons flowing from the anode to the cathode, thereby lowering
the overall production of dissolved oxygen. Decreasing the
resistance of the current increases the flow of electrons from the
anode to the cathode, thereby increasing the amount of dissolved
oxygen produced.
[0139] 8. Optimal Gas Sorption Device 24
[0140] Continual venting of carbon dioxide gas out of the
photolytic cell presents the problem of potential infection. A gas
sorption device minimizes and provides control over potential
infection risks by avoiding continuous venting of the CO.sub.2 to
the atmosphere. The gas sorption device captures CO.sub.2 gas
released from the oxygenated blood in a concentrated form. The
concentrate can be processed or disposed of occasionally so that
the sterility of the photolytic cell is not continuously subjected
to possible contaminants due to the continual venting of the
CO.sub.2 gas.
[0141] CO.sub.2 can be captured using a number of different ways by
a gas sorption device 24. The gas sorption device can use the
process of chemi-absorption and convert CO.sub.2 into a
concentrated solid or solution form. The concentrate formed in the
gas sorption device can then be disposed of as disposable
cartridges having liquid or solid CO.sub.2, or regenerated.
[0142] FIG. 5 shows the general schematic of the gas sorption
device 24 and path of CO.sub.2 to the gas sorption device 24 for
absorbing CO.sub.2. The photolytic cell 16 forms dissolved oxygen
that associates with the deoxygenated blood flowing through the
cell. The CO.sub.2 produced in the anode of the photolytic cell 16
from the conversion of bicarbonate ion to carbonic acid is present
as small bubbles as a result of carbonic anhydrase activity. These
bubbles are readily released within a coalescence compartment 54 so
that the use of membranes are avoided. Four moles of CO.sub.2 gas
is released per mole of O.sub.2 gas formed. When O.sub.2 is formed
at the targeted flow of 150 cc/min gas at STP, the moist CO.sub.2
flow rate is about 600 mL/min at STP. CO.sub.2 is trapped when
entering the coalescence compartment 54 by a gas coelesor 56. In or
near the bottom of the gas coalesor 56 an entry point 58 exists for
hydrogen gas (H.sub.2) coming from the cathodic compartment. The
H.sub.2 gas merely sweeps across the head space 60 above the gas
coelesor 56 in the coalescence compartment 54 and collects CO.sub.2
gas. The flow is provided by the same pump 14 that is used to
provide the photolytic cell 16 with blood since the photolytic cell
16 is either a fully liquid-filled closed system, or a cascading
overflow (but non-portable) system. The CO.sub.2/H.sub.2 gas
mixture exits the top of the gas head space 60, near the blood
entry point. When O.sub.2 is formed at the targeted flow of 150
cc/min gas at STP, the H.sub.2 flow rate is at least about twice
the O.sub.2 flow rate or 300 mL/min (STP). The gas mixture then
flows to a sorber 62.
[0143] FIG. 6 shows a coalescence compartment 54. The coalescence
compartment 54 can be a small plastic reservoir having a relatively
small volume, and can be any shape. Preferably, the coalescence
container 54 has a downward tilt. The whole blood travels through
the coalescence container 54 through the coelesor 56 and returns to
the patient at the bottom of the tilt. H.sub.2 gas enters at an
entry point 58 into the gas head space 60 and sweeps the CO.sub.2
through the gas head space 60 and into a sorber (not shown). The
coalescence container 54 can be used as a temperature control
point.
[0144] FIG. 7 shows a sorber 62. The sorber 62 converts CO.sub.2
gas into either a solution or solid depending on the sorbent 64
used within the sorber 62 without the need for mechanical mixing or
pumping. The high capacity, low pressure drop, sorber 62 for
CO.sub.2 gas operates at mild pressure with a gravity feed and
without the need for high surface area contactor. The
CO.sub.2/H.sub.2 gas mix enters the sorber 62 at an entry point 66
near the bottom of the sorber 62. Intimate mixing of gas and liquid
is accomplished by the 90.degree. flow path changes, cross-path
gas/liquid paths, and counter-current configuration. The CO.sub.2
reacts with the sorbent 64 in the sorber 62 to form a solid or
solution. The solid or solution formed can be removed through an
outlet 70. Hydrogen gas can be swept out through a sweeping outlet
68 and be reused in the coalescence compartment (not shown).
Preferably, the sorber 62 is small and has a total internal volume
of about 25 cc. The entire sorber 62 is contained within the
sterile unit. Since blood is not involved in the sorber 62,
potentially detrimental effects in the blood are avoided. Also, the
large orifices and membrane-free operation prevents potential
fouling. The sorber 62 can have a vertical orientation but can also
be designed with broad orientation accommodation. The entire sorber
62 is contained within the sterile unit.
[0145] The sorbent material 64 within the sorber 62 can be a solid
or a solution. As a solution, the sorber can also be the catholyte
for the photolytic cell. The sorbent 64 as a solution is consumed
at a rate of 2-6 mL/min for the a CO.sub.2 gas flow rate of 600
mL/min at STP. The high capacity, low pressure drop, sorber 62 for
CO.sub.2 gas operates at mild pressure with a gravity feed and
without the need for high surface area contacter. Alternatively,
the sorber 62 can use a solid sorbent 64 where the sorbent 64 is a
packed bed of sorbent granules. Since blood is not involved in the
sorber 62, potentially detrimental effects in the blood are
avoided. Also, the large orifices and membrane-free operation
prevents potential fouling. The sorber 62 can have a vertical
orientation but can also be designed with a broad orientation
accommodation. Sorbent materials are selected to react with the
CO.sub.2 gas to form bicarbonates and carbonates as solutions,
solids, or combinations of these. Individual sorbents can be
blended to obtain synergistic blends which, for example, might
react faster, be more cost effective, and/or hold more carbon
dioxide equivalents than the pure materials. Table 1 is a list of
sorbent materials along with their CO.sub.2 capacity
equivalents.
TABLE-US-00001 TABLE 1 Sorbent Solutions and Solids for CO.sub.2
Maximum molarity of CO.sub.2 Solution solution when fully loaded or
of Chemical or density % sorbent in sorbent initially CO.sub.2
sorbing Form of Sorbent Solid g/cc solution (20-25.degree. C.)
charged. capacity Sorbed CO.sub.2 Na.sub.2CO.sub.3 soln 2.53 31.3
(35.degree. C.) NaHCO.sub.3 NaOH soln 1.52 50 19.01 NaHCO.sub.3
catholyte and (w/ OH- from Na.sub.2CO.sub.3 PAL cell) NaCl soln TBD
TBD TBD TBD NaHCO.sub.3 catholyte and (w/ OH- from Na.sub.2CO.sub.3
PAL cell) KCl soln TBD TBD TBD TBD KHCO.sub.3 and catholyte
K.sub.2CO.sub.3 (w/ OH- from PAL cell) KOH soln TBD TBD TBD TBD
KHCO.sub.3 and catholyte K.sub.2CO.sub.3 (w/ OH- from PAL cell)
CaCl.sub.2 soln 40. 5.03 5.33 cc/mi CaCO.sub.3(s) catholyte 320
cc/hr pKsp = 8.32 (w/ OH- from 7.7 L/hr PAL cell) Ca(OH).sub.2
solid TBD TBD TBD TBD CaCO.sub.3(s) pKsp = 8.32 MgCl.sub.2 soln
1.28 30.00 4.021 catholyte (w/ OH- from PAL cell) Mg(OH).sub.2
solid TBD TBD TBD TBD MgCO.sub.3(s) pKsp = 9.2 soda lime solid TBD
TBD TBD TBD CaCO.sub.3(s) pKsp = 8.32 nonvolatile soln TBD TBD TBD
TBD R.sub.4N.sup.+HCO.sub.3.sup.- amines (e.g. MEA, DEA, etc.) (1)
MEA and DEA are monoethanol amine and diethanol amine respectively.
Polyol amines, polyamines, and zwitterionic materials are other
suitable organic CO.sub.2 sorbents. (2) CaCO.sub.3 is not expected
to be regeneratable. (3) Note that the halide salt systems, e.g.
NaCl, KCl, CaCl.sub.2 and MgCl.sub.2, or mixtures thereof as are
represented by brines such as Lockes-Ringer solution, saline
solution, etc., sorb CO.sub.2 by using the cathodically produced
OH.sup.-, the salt just providing charge balance at the membrane
and electrode, and in the sorber/desorber.
[0146] HCO.sub.3.sup.- loses CO.sub.2 easily and the sorbent can be
regenerated thermally, disposed of as a disposable cartridge, or
regenerated continuously through the self sterilizing and
self-cleaning caustic heating operation at mild temperatures and
pressures. Alternatively, the sorbent can be continuously
regenerated. For the carbonate sorbent system, the pH will vary
from an initial pH of 11.6 to a pH of 8.3 when exhausted and could
be monitored using a pH indicator dye or pH electrode.
[0147] Hydrogen gas produced in the cathode and used to sweep the
CO.sub.2 from the blood to the coalescence compartment will
accumulate unless vented. H.sub.2, being an extremely small
molecule, readily diffuses through most non-metallic materials,
especially plastics, ceramics, etc. The venting of H.sub.2 can be
controlled by selecting materials of construction that allow
diffusion. No particular membranes, vessels, pumps, filters, one
way valves, etc. are required to diffuse H.sub.2. The role of
H.sub.2 as a sweep gas has a very broad range of acceptable flow
rates for proper function since the CO.sub.2 will self-flow in its
absence and a negative pressure will develop in the CO.sub.2 sorber
as the chemistry is quantitative (CO.sub.2 efficiently absorbed
down to low P.sub.CO2 values).
[0148] 8. Light Supply 20
[0149] The light supply is used in the photolytic cell to provide
the photon energy necessary to activate the catalyst converting
water into oxygen. The light source can be from any known light
source including, but not limited to, sunlight, UV light, laser
light, incandescent light, etc., depending on the activation
requirement for the light activated catalyst used. Preferably, the
blood flowing through the photolytic artificial lung is not exposed
to the light in order to prevent irradiation of the blood.
[0150] The light source may provide a particular wavelength of
light depending upon the catalyst used. When tungstate (WO.sub.3)
is used as a light activated catalyst, the light source exposes
visible light in order to activate WO.sub.3. When TiO.sub.2 or ZnO
is used as a light activated catalyst, the light source used has a
wavelength in the UV range.
[0151] Preferably, the light source used in the photolytic
artificial lung is a laser light. The wavelength of laser light can
be manipulated in order to attain a higher efficiency in exciting
the light activated catalyst and forming active oxygen. Also, laser
light allows the photolytic artificial lung to dissipate less
overall heat. The laser light can be directed in a small area to
energize the light activated catalyst and avoid contact or
irradiation with other components of the photolytic artificial
lung. A particularly preferred laser light that can be used to
activate TiO.sub.2 is an argon laser at 364 nm (400
mwatts/cm.sup.2), which has a total power of about 2 watts,
although other UV sources, including an HG arc lamp at 365 nm line,
are also available.
[0152] It is preferred that the light from the light source be
evenly spread within the photolytic cell. The even spreading of the
light from the light source allows for maximal excitation of the
catalyst in order to convert more water into either active is
oxygen or dissolved oxygen. Along these lines, light from the light
source can enter the photolytic cell through the transparent window
from many positions. Light from the light source can enter directly
through the transparent window and come into contact with the
catalyst. Alternatively, light can enter the transparent window
from a side, back, bottom, or corner position and move through the
transparent window by a wave guide to provide photon energy and
excite the light activated catalyst. Side entry of light into the
transparent window of the photolytic cell occurs at about at least
a 68.degree. angle. Preferably, side entry of light into the
transparent window occurs at an angle of from about 70.degree. to
about 80.degree..
[0153] 9. Pump
[0154] A peristaltic pump or some other simple pump drives blood
through the photolytic artificial lung. The pump draws venous
deoxygenated blood from a patient and moves the blood through the
photolytic artificial lung. Preferably, the photolytic artificial
lung only requires a pump to draw blood from a patient, as the flow
produced by the pump drawing blood from the patient also moves the
blood through the photolytic cell for oxygenation and back into the
patient.
[0155] 10. Sensors Monitoring Reaction Chemistry
[0156] The photolytic artificial lung can include one or more
sensors that monitor the different chemical reactions occurring
within the photolytic cell. The sensors can be used to measure for
potential toxins and toxin levels. Various sensors and sensor
systems can be used including visual observations of color changes
of redox indicator dyes or gas bubble formation, closed electrical
current measurements and pH measurements, and dissolved oxygen
probe analysis. Gas chromatography assays can also be performed. A
dissolved oxygen probe can be used to test and monitor O.sub.2
generation, as dissolved oxygen, in real time. Also, the photolytic
artificial lung can incorporate one or more portals to insert a
dissolved oxygen probe, CO.sub.2 probe, pH monitor, etc. in
different locations if necessary. The photolytic artificial lung
can also incorporate separate sampling chambers to trap gas bubbles
for testing. These sampling chambers could also incorporate a
device, such as a septum for a hypodermic needle for instance, to
obtain a sample for further testing. One skilled in the art would
recognize numerous sensors could be used for monitoring the
reaction chemistries occurring within the photolytic cell.
[0157] The photolytic artificial lung and photolytic cell can also
include one or more process regulator devices that respond to the
readings provided by the sensors. The process regulator devices
increase or decrease the amount of dissolved oxygen or CO.sub.2
output, lower toxin levels, etc., depending on the requirements of
the patient or of the photolytic cell. It is within the purview of
one utilizing the photolytic artificial lung to determine what
process regulator devices are required.
[0158] All of the seals in the photolytic artificial lung are made
of an inert material that properly seals blood flowing through the
photolytic artificial lung from accidental contamination. The seals
of the photolytic lung should also be formed of a material that
does not interact with the blood. Preferably, the seals are formed
of a silicone-based material.
[0159] Laminar flow is minimized within the photolytic artificial
lung. Minimization of laminar flow is accomplished by using current
commercial cells, such as electrodialysis, electrodeionization,
etc. Commercially available cells accommodate electrodes,
membranes, and thin liquid chambers with flow distributors, and
provide good seals and corrosion resistance. The cells are
available in lab scale units for process development work. A
particularly preferred commercial cell is the FM01-LC device from
ICI Chemicals and Polymers, Electrochemical Technology, Cheshire,
UK.
Multiple Photolytic Cells
[0160] Preferably, the photolytic artificial lung uses a plurality
of photolytic cells in a stacked formation. The plurality of
photolytic cells receive blood flow from the venous circulation and
are exposed to photo-activation via a directed laser light source.
The stacking of a plurality of photolytic cells allows for a large
overall surface area for blood to receive maximal exposure to
dissolved oxygen. Also, stacking a plurality of photolytic cells
allows the overall photolytic artificial lung to achieve a smaller
size, thereby allowing the photolytic artificial lung to be
miniturized.
Photolytic Cell has Broader Applications
[0161] The photolytic cell as described may be used for
photochemical processes beyond the preferred embodiments described
above. The photolytic cell may be used in other organs to cause or
regulate chemical reactions occurring within the system. The
photolytic cell may be used in organs including, but not limited
to, heart, lungs, brain, kidney, liver, etc. Alternatively, the
photolytic cell may be used outside of a biological system in order
to control reactive activity. Also, one having ordinary skill in
the art would recognize that the photolytic cell could also be used
as a potential energy source due to the production of
electrons.
EXAMPLES
[0162] Having generally described the invention, the following
examples are included for purposes of illustration so that the
invention may be more readily understood and are in no way intended
to limit the scope of the invention unless otherwise specifically
indicated.
[0163] A prototype photolytic artificial lung was produced in order
to demonstrate the ability of the device and accompanying processes
to re-oxygenate synthetic blood serum (Locke's Ringer Solution),
with concomitant CO.sub.2 removal and pH control, using thin film
constructs. In this regard, a photolytic test flow cell (see FIG.
3) was constructed using exemplar materials for the elements of the
photolytic artificial lung--a conductive coating of vacuum
deposited Ti metal, a coating of adherent TiO.sub.2 (anatase), a
MnO.sub.2 particulate layer, and then a bicarbonate solution. A
U.V. laser light was introduced to the transparent glass or quartz
substrate. This cell was used to collect pH and cell electrical
current data as a function of laser U.V. irradiation. The details
of the construction of such a prototype and the results produced
thereby are discussed below.
[0164] In this regard, a photolytic test flow cell as shown in FIG.
3 of the photolytic artificial lung was prepared. Specifically,
among other components the following layers of the photolytic cell
were assembled: light source 20; transparent window 30; e.sup.-
conductor (anode) 36; TiO.sub.2 photo catalyst 32; MnO.sub.2
catalyst 34; NAFION.RTM. cation exchange membrane 46; catholyte 48;
and conductor (cathode) 38. The particular parameters of these
components and others are as follows:
Glass/Quartz Slide 30 Preparation
[0165] A glass slide was degreased by swirling in toluene or MEK.
The slide was flash dried in air for less than about 1 minute. The
slide was then soaked in warm Micro.RTM. cleaning solution for
about 2 minutes. The slide was rinsed thoroughly with 18M.OMEGA. DI
water. The slide was immediately thereafter soaked in a water bath
for about 2 minutes. The slide was rinsed thoroughly with water
from a squirt bottle and drained but not allowed to dry. With
caution, the slide was submerged in a solution of concentrated
sulfuric acid and was allowed to stand for 2 minutes. A plastic
hemostat was used to hold the slide when it is inserted/withdrawn
from the sulfuric acid. The slide was withdrawn, allowed to drain,
and rinsed thoroughly with water. The slide was then soaked in a
water bath for about 2 minutes. A water break test was then
performed on the slide. Using a plastic (Nalgene.RTM.) beaker with
cover watch glass, the slide was dipped for 2 minutes in a solution
of 0.1% HF and 1N HCl. The surface of the glass now contained
Si--OH linking groups. These slides were kept wet, and stored in 5%
HNO.sub.3.
Catalyst Layer 32 Preparation
[0166] About 1.0 g of TiO.sub.2 (anatase) was added to a plastic
(Nalgene.RTM.) beaker with a cover watch glass, and a magnetic stir
bar. In a hood, 80 mL of 0.1% HF and 1N HCl was added to the
TiO.sub.2. A stirrer stirred the beaker until the solids were well
suspended. The beaker was mixed for 60 seconds and was proceeded
immediately to the next step of dividing the slurry between two 50
mL capped centrifuge tubes. The tubes were centrifuged for at least
5-10 minutes. The supernatant was discarded. Each tube was rinsed 3
times with 40 mL portions of water. The tube was capped, vortexed
thoroughly, centrifuged, decanted, and the steps were repeated.
Each tube was rinsed 3 times with 40 mL portions of isopropanol
(iPrOH). Optionally, one or more inorganic silane and/or
titanate-coupling agents can be added to the last alcohol rinse to
facilitate agglomeration and adhesion in the final coating. The
aggressive oxidizing environment of the UV/TiO.sub.2 during use may
rapidly degrade organic-based coupling agents and so inorganic
couplings may be favored.
Application of the Catalyst to the Glass Slide
[0167] The pretreated TiO.sub.2 anatase particles were magnetically
re-suspended from one of the tubes in a jar containing isopropanol
sufficiently deep to cover the glass microscope slide. Magnetic
stirring was initiated to keep the particles suspended. The amount
of particles used is an adjustable parameter in determining the
thickness of the final coating produced.
[0168] A sufficient amount of Ti(iOPr).sub.4 (TTIP) was added to
yield a 0.2 vol % solution (e.g., by adding 160 uL TTIP per 80.0 mL
isopropanol). Using a plastic hemostat to hold the slide, the
treated glass slide was rinsed thoroughly with water and was again
tested under the water break test. The slide surface was rinsed
thoroughly with isopropanol. The slide was soaked for 2 minutes in
isopropanol and rinsed again with isopropanol. The slide was
immediately hung in the TTIP/isopropanol solution and stirred. The
vessel was covered to minimize pickup of moisture from the air, and
allowed to react for about 120 seconds. During this time, the TTIP
reacted with the Si--OH groups on the surface of the glass slide to
form O--Si--O--Ti-iOPr linkages, although the linkages may not have
formed rapidly until the heating step below. The slide was removed
very slowly (e.g. 1 cm/min) using the hemostat and was laid flat on
an inverted bottle cap in a vacuum desiccator to dry for a few
minutes. The standing time in the room air (humidity level and
contact time) was adjustable since water vapor diffuses to the
surface of the slide causing hydrolysis reactions (the "sol" in
sol-gel), i.e.,
Ti(iOPr).sub.4+2H.sub.2O.fwdarw.TiO(iOPr).sub.2+2iPrOH
TiO(iOPr).sub.2+2H.sub.2O.fwdarw.TiO.sub.2+2iPrOH
[0169] Excess water must be avoided so that the silanol groups on
the surface of the slide may react, i.e.,
glass surface
--Si--OH+Ti(iOPr).sub.4.fwdarw.Si--O--Ti(iOPr).sub.3+iPrOH
[0170] Similar reactions couple the TiO.sub.2 anatase particles to
the surface of the glass and to each other,
TiO.sub.2(anatase)-Ti--OH+Ti(iOPr).sub.4.fwdarw.TiO.sub.2(anatase)-Ti--O-
--Ti(iOPr).sub.3+iPrOH
[0171] It is noted, however, that thoroughly desiccated
(water-free) surfaces are also not useful since dehydration of
surface Si--OH and Ti--OH groups occurs, which would remove the
hydrogen needed to produce the iPrOH product at low energy. The
time spent at this room temperature condition can be adjusted since
the coating slowly reacts during this time.
[0172] While still lying flat, the slide is oven-dried at
80-90.degree. C. for 20 minutes to finish the cure. The time,
temperature and heating rate (.degree. C./min) parameters are
adjustable. Heating too fast can blow out solvent, causing massive
disruption of the film due to out gassing, while heating too high a
temperature can cause too much condensation resulting in shrinkage,
leading to pulling away of the film and cracking. Porosity is
expected to be important so that water can penetrate and active
oxygen can leave the reaction zone.
[0173] In order to obtain slides having a thicker TiO.sub.2
coating, the above steps are repeated one or more times.
[0174] The slide was heated to 250.degree. C. for two hours to
fully cure and set the coatings. This temperature was needed to
convert the amorphous TiO.sub.2 formed from the TTIP into anatase.
Ind. Eng. Chem. Res. 1999 38(9), 3381. Alternatively, a slide can
be pretreated as above except heat the coating to 350.degree. C. at
the rate of 3.degree. C./min and hold at this temperature for 2 hr.
Miller, et al. Environ. Sci. Technol. 1999, 33, 2070. Another
alternative is to prepare the sol-gel solution in place of the
anatase/TTIP slurry. Colloid C in Aguado, M. A., et al., Solar
Energy Materials. Sol. Cells, 1993, 28, 345. The slide was then
removed and allowed to cool to room temperature.
[0175] The coating adhesion of the TiO.sub.2 anatase to the glass
slide was tested by abrasion with a rubber policeman, tape test,
etc. Also, the coating adhesion was tested for other properties
including thickness, tendency to crumble/flake off, visual
appearance, etc.
[0176] The experiments were repeated as needed to improve adhesion
and other properties. An additional step of a 400.degree. C.
treatment for one hour can used to set TiO.sub.2 (anatase)
particles onto a quartz sand slide (Haarstrick, et. al. 1996).
TiO.sub.2 Coating Photochemistry Testing
[0177] Two TiO.sub.2 coating photochemistry testing procedures were
conducted, the first to determine whether electrons were generated
and the second to determine whether active oxygen was generated.
First, the TiO.sub.2 was tested by a negative charge/electron
generation test. Methyl viologen (MV.sup.2+) blue color (MV.sup.+)
was applied onto the anatase coating and was subjected to laser
light. A rapid appearance of dark blue color qualitatively,
validating electron formation. MV.sup.+ blue color was not
permanent since MV.sup.+ is a free radical/charge transfer complex,
which easily releases e.sup.- and returns to colorless ground
state. Dried coating inhibited the performance of coating (dried
minerals block surface sites), but was easily cleaned.
[0178] A second test conducted on the TiO.sub.2 coating layer was
the active oxygen generation test. Methylene blue was used on the
TiO.sub.2 coating to determine the presence of active oxygen. The
methylene blue color was rapidly destroyed at the point of the
laser light in the presence of anatase coating, validating active
oxygen formation, to since oxidized oxygen reacts with methylene
blue.
Light Source
[0179] The light source used was an argon laser at 364 nm line (400
mwatts/cm.sup.2) available (tunable to lower powers). The argon
laser used has a total power of 2 watts. Alternatively, a number of
UV sources were available for use, including Hg arc lamps using a
365 nm line.
Anode Conductor Layer 36
[0180] The anode conductor layer was formed by placing a very thin
film of uniform metallic conductor having a thickness of less than
about 0.2 {circle around (3)} m using e-beam vapor deposition onto
a transparent window. The thin film was formed of Ti metal.
Conductor line spacing, width and thickness optimization may be
required for the anode conductor layer to prevent excessive
attenuation while provide sufficiently close conductive areas to
sweep electrons away from TiO.sub.2 layer.
Dissolved Oxygen Generating Catalyst Layer 34
[0181] A dissolved oxygen generating catalyst layer was formed from
MnO.sub.2 particles onto the surface of the TiO.sub.2 (anatase)
layer. The MnO.sub.2 particles were applied (<5u) as a iPrOH
slurry with or without the anatase/Ti(iPrO)4 mixture. A significant
surface of the TiO.sub.2 (anatase) layer was coated (.about.1/3) by
the MnO.sub.2. Adding the MnO.sub.2 drop wise and allowing it to
evaporate was effective. The MnO.sub.2 was added to increase %
surface area covered by MnO.sub.2 particles and to make the
MnO.sub.2 more adherent using the Ti(iOPr).sub.4 binder.
Flow Through Cell
[0182] The flow through cell was designed with fluid inlets and
outlets on the same side. Silicone gaskets and spacers, acrylic
external housing and stainless steal tubing connectors were used in
forming the flow through cell. In the flow through cell, the anode
was the continuous Ti plate and the cathode was a platinum foil
strip.
Electrical Connection of Flow Through Cell
[0183] The electrical connection of the flow through cell was wired
as an open circuit with a current meter and current regulator
inline. The electrical connection of the flow through cell could
also be formed by applying bias voltage added with the in-line
current meter and current regulator. The electrical connection of
the flow through cell could also be formed by placing a resistor
and a current meter inline with a voltage reading across the
resistor.
Divided Cell
[0184] A divided cell was designed with both sets of fluid inlets
and outlets on the same side with the through-anode,
through-acrylic housing and silicone spacer internal flow paths and
on the side opposite the glass slide. The divided cell was further
designed to include silicone gaskets or spacers, acrylic external
housing, NAFION membrane, and stainless steel tubing
connectors.
Active Oxygen Testing
[0185] A Locke's Ringer saline test solution was prepared with 150
ppm redox dye (methyl viologen, MV.sup.2+). Also, a 10 uM solution
of methylene blue was prepared in the Locke's Ringer solution.
Matthews, R. W., J. Chem. Soc., Faraday Trans. 1, 1989 85(6), 1291.
The molar absorbtivity for methylene blue at 660 nm is
66,700.+-.350 cm.sup.-1M.sup.1. The coated test slide was assembled
with an attached UV lamp/laser. The Locke's Ringer solution was
then added to the coated test slide via a circulating pump. After
steady conditions were attained, the coating was illuminated
directly/indirectly with UV light. The saline solution was
monitored for appearance of blue color
(MV.sup.2+(colorless)+e-.fwdarw.MV.sup.+(blue)) and dissolved
oxygen. Gas samples were sampled for GC assay (CO.sub.2, O.sub.2
not due to air).
Results
[0186] The artificial lung was tested in order to determine whether
the chemical formulations occurred as predicted. The testing was
conducted using Locke's Ringer solution, which is a saline solution
that mimics blood. The qualitative results of the testing are as
follows:
[0187] 1. Highly efficient U.V. light absorption by thin films of
TiO.sub.2 (anatase) to impart energy into the anatase matrix was
visually apparent in that the UV light is substantially absorbed.
Attenuation by any metal conducting film present was measured and
corrected separately.
[0188] 2. Generation of active oxygen (AO) at the anatase surface
using the energy from the UV light was evidenced by methylene blue
dye disappearance at the surface of the anatase film opposite the
side irradiated by the UV laser.
[0189] 3. Generation of free electrons (e.sup.-) at the anatase
surface using the energy from the UV light was evidenced by methyl
viologen blue dye color appearance at the surface of the anatase on
the side opposite the side irradiated and only at the location of
irradiation.
[0190] 4. Transport of the free electrons (e.sup.-) generated above
to a conductive Ti anode surface, which were then swept away so
that the free electrons do not recombine with the active oxygen
also produced above was evidenced by electrical current in the
anatase semiconductor film, to a metallic collector, wire and amp
meter. The electrical current was found to flow only when the laser
was on and the electrical current never flowed when the laser was
off. The effect was observed through numerous off/on cycles, and
the electrical current measured was proportional to the laser
intensity up to a saturation point.
[0191] 5. The release of hydrogen ions (H.sup.+) and pH drop was
found for the anodic compartment in a continuously circulated and
irradiated cell. The opposite pH change was found for the cathodic
compartment, which was consistent with the pH effect expected when
water is separated into active oxygen and hydrogen ions at the
anatase surface. FIG. 9 shows a plot of the pH profile of the
anolyte and catholyte during photolysis using the photolytic cell.
The opposite trends in the plot are as predicted based on the
photosynthesis mimic chemistry, decrease in pH in the anolyte and a
pH increase in the catholyte. The lower initial pH in the catholyte
in Run 1/6 reflects a startup condition with a slightly lower pH.
Run 1/7 used a pre-equilibrated photolytic cell to remove any
inconsistent readings during start up conditions.
[0192] 6. The conversion of HCO.sub.3.sup.- ions from the synthetic
serum electrolyte, i.e., Locke's Ringer solution, into CO.sub.2,
was in part observed by the formation of more is H.sub.2O. H.sub.2O
is the expected product to be formed along with CO.sub.2 during the
bicarbonate ion conversion to carbonic acid and ultimate conversion
to H.sub.2O and CO.sub.2 using the H.sup.+ ions released during the
formation of active oxygen. CO.sub.2 production was measured by gas
chromatography (GC) analysis of off-gases, or calculated from pH
changes. The CO.sub.2 level found by GC analysis was significantly
greater than atmospheric level, further indicating the formation of
CO.sub.2.
[0193] 7. The generation of alkalinity at the cathode and related
pH change indicated that the free electrons produced during the
reaction of water into active oxygen were conducted away from the
anode and consumed in a non-O.sub.2 reducing manner, i.e., by
reduction of water to hydroxide ion and H.sub.2 gas.
[0194] 8. Generation of O.sub.2 as dissolved oxygen from an
MnO.sub.2 catalyst coating on the anatase from an active form of
oxygen added to the test media was found.
[0195] All of the verified steps appeared to react at good rates.
Using the electrical current generated, a rough size for the
photolytic cell unit for a 100 ml/min O.sub.2 flow rate was
calculated and found reasonable. Also, a number of coating
fabrications were tested that were designed to allow MnO.sub.2
particles, as a coating or dopant, to react with long-lived,
soluble forms of active oxygen. These MnO.sub.2 coatings were found
to generate abundant quantities of dissolved oxygen under the
testing conditions.
Calculating Size of Photolytic Cell Required
[0196] Preliminary testing was conducted on the photolytic cell to
determine the size of a cell required to generate the target oxygen
rate in an average adult human body of about 150 mL/min (STP) of
O.sub.2 for 5 L/min of blood flow, which is the average normal
adult human blood flow rate. FIG. 8 shows the measure of the cell
current versus the laser power setting in 0.60 g/L NaHCO.sub.3 and
4% MeOH electrolyte. It is noted that the laser power setting is
not the same as the actual impinging laser beam energy, but rather
the laser power setting is greater than and proportional to the
actual laser beam energy by a factor of about 2. Also, the power
setting is of the laser itself and not of the 363.8 nm beam after
it is separated from the other two lines produced by the laser. The
laser power setting was measured after the laser moved around the
optics bench and penetrated the glass slide and Ti collector
film
[0197] Although the data in FIG. 8 represents early exploratory
testing and is far from optimized, it was used to calculate the
size of a cell that would be needed to generate the target oxygen
rate, 150 mL (STP)/min. From FIG. 8, a limiting cell current
density of 70 uA/cm.sup.2 can be estimated. Using this value, a
cell surface area needed to generate 150 cc O.sub.2 gas/min (STP)
was calculated. If one flat sheet cell were used in contact with
the blood, it would need to be 7.5.times.7.5 meters in area (56
m.sup.2) to provide 150 mL O.sub.2 gas/min. Since no optimization
has been done to date which might improve rates and since stacking
of smaller plates to achieve a net large surface area is routine in
electrochemical cell technology, this level of performance is
considered encouraging as an early test result. Although the
quantum efficiency was not determined in this qualitative testing,
it appeared to be low. Many options are available to improve on the
quantum yield. An improvement of 10 times would require a blood
contact area (BCA) of 75 cm on a side, which then could be cut in
half (by area) to 53 cm square by double siding the cell, i.e., one
cathode, two anodes. Using six pairs, as is done in automotive
batteries for example, reduces these dimensions to a cube of about
20 cm on a side, well within acceptable dimensions for an emergency
use extracorpreal device without ancillary equipment. Therefore, a
sufficiently small photolytic artificial having a small stack of
photolytic cells appears possible with a 10 time improvement over
the current production rates, assuming a high correlation between
cell electrical current and dissolved oxygen production. Reasonable
target values for optimized photo current efficiencies are expected
to be in the 0.1-10% range.
[0198] FIG. 8 also shows that spreading the laser beam to about 1
cm.sup.2 resulted in about the same current production as did
leaving the beam as a 3-4 mm spot. This result suggests that the
photons were being supplied faster than they could be consumed.
Therefore, significantly enhanced utilization of the laser power
appears possible. Efficiency enhancements might be accomplished by
pulsing the beam to allow the chemical reactions to keep up and/or
further spreading it using optics.
[0199] The invention has been described with reference to the
preferred embodiments. Obviously, modifications and alterations
will occur to others upon a reading and understanding the preceding
detailed description. Particularly, it is clear to one having
ordinary skill in the art that the photolytic cell can be modified
and used in numerous other reactions and reaction systems. It is
also apparent that the present photolytic cell can be used in
organs other than the lungs, and that the cell can be used in
living systems other than humans. Furthermore, one skilled in the
art would appreciate based upon the preceding detailed description
that the photolytic cell can be used in forming chemical reactions
in solutions other than whole blood. It is intended that the
invention be construed as including all such modifications and
alterations in so far as they come within the scope of the appended
claims or the equivalents thereof.
* * * * *