U.S. patent application number 11/660443 was filed with the patent office on 2009-05-28 for photo electrochemical procedure to break the water molecule in hydrogen and oxygen using as the main substrate the melanines, their precursors, analogues or derivates.
Invention is credited to Arturo Solis Herrera.
Application Number | 20090134007 11/660443 |
Document ID | / |
Family ID | 37498851 |
Filed Date | 2009-05-28 |
United States Patent
Application |
20090134007 |
Kind Code |
A1 |
Solis Herrera; Arturo |
May 28, 2009 |
Photo electrochemical procedure to break the water molecule in
hydrogen and oxygen using as the main substrate the melanines,
their precursors, analogues or derivates
Abstract
This invention consists essentially in the employment of the
melanines, precursors of the melanines, derivates of the melanines,
variants, analogues of the melanines, or their precursors natural
or synthetic, pure or mixed with organic or inorganic compounds,
metals ions drugs; as water electrolyzing materials, employing as
its only or main energy source light, natural or synthetic,
coherent or not, in the hydrogen producing systems from water known
as photoelectrochemical. These systems integrate a semiconductor
material and a water electrolyzing element within a monolytic
design to produce hydrogen directly from water, employing light
(from 200 to 900 nm wavelengths) as its only or main energy source
Although simple in concept, the challenge was to find a material
that could bear or sustain the whole process. At least two basic
criteria should be met: the system or compound that absorbs the
Light should generate enough energy to Start, continue, support and
finish the water photolysis or photoelectrolizing reaction, within
low price, being stable and durable in a watery environment,
requisites that the melanines, their analogues, precursors or
derivates, fulfill reasonably and efficiently, which is an
important and critical advance in solving out the main problem of
the photo electrochemical designs. The procedure may be used to
generate hydrogen and oxygen atoms and high energy electrons or in
reverse sense, synthesizing water molecules binding hydrogen and
oxygen atoms, thus producing electricity, these can be employed
together or with other new and important industrial processes to
obtain energy and to store it, since the melanines may store the
electricity and gasses; property that would have a multiplying
effect, it may be used also to the reduction of carbon dioxide,
nitrates, sulphates, and other molecules.
Inventors: |
Solis Herrera; Arturo;
(Aguascalientes, MX) |
Correspondence
Address: |
Arturo Solis Herrera
Lopez Velarde 108 Centro
Aguascalientes
20000
M
|
Family ID: |
37498851 |
Appl. No.: |
11/660443 |
Filed: |
October 13, 2005 |
PCT Filed: |
October 13, 2005 |
PCT NO: |
PCT/MX2005/000092 |
371 Date: |
February 16, 2007 |
Current U.S.
Class: |
204/157.5 ;
544/200 |
Current CPC
Class: |
Y02E 60/50 20130101;
H01M 14/005 20130101; C25B 1/55 20210101; H01M 8/0656 20130101;
Y02P 20/133 20151101; Y02E 60/36 20130101 |
Class at
Publication: |
204/157.5 ;
544/200 |
International
Class: |
B01D 57/00 20060101
B01D057/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 9, 2005 |
MX |
GT/A/2005000006 |
Claims
1. I start my claimings about the employment of the melanines as an
electrolyzing material or MEDIO, of the water molecule, in presence
of light, since it generates energy when tweaking the water
molecule, obtaining hydrogen and oxygen atoms, as well as high
energy electrons, or the opposite reaction, binding back hydrogen
and oxygen atoms, obtaining water molecules and electric current.
This are processes that are intensively pursued in the lab and in
the industry because of the advantages that it provides to generate
and control an event of this nature, having as its only energy
source to start, drive and finish the whole process the visible
luminous energy that is consider as a removable resource, and the
end products are highly ecologic. Until now this process has never
been done in the lab or in the industry because they lack of a
subtract or a material that could bear these events completely,
from the induction or beginning of the process, followed by the
energizing of the process and the ending of it with the obtention
of the desired products, commonly, hydrogen, oxygen atoms, high
energy electrons, electric current, all depending on the direction
of the reaction, going through the different chemical reactions
that comprise these steps. This substrate should be tong tasting,
efficient, trustable, easy to reproduce, not pollutant when made,
when used or when recycled, and advantageous when compared with
other known ways to produce hydrogen and/or electric energy, not
applicable in high scale for different technic, ecologic, politic
or economic reasons, and that are based in removable energy
resources, unlike the actual processes that general and massively
are applied to generate energy from not removable energy resources
that are alarming getting to its depletion, not considering the
energy generation from atoms, whose employment has generated
catastrophes, and nature pollution worst than a nightmare Exposing
in this patent the advantages of the employment of removable
resources, based in ecologic processes whose economic, politic and
technic feasibility is high, makes our claims characterized by the
use of a substrate that fills the needed requisites to generate
energy from removable resources such as the sunlight and water,
whose production, employment and recycling are remarkably ecologic.
The improvement we propose and claim comprises the employment of
the melanines, their precursors, melanin's derivates, variants,
analogues, natural or synthetic, pure or mixed (with organic or
inorganic compounds, metals, ions or drugs) as the main element to
any photo electro chemical process that allow us to break water
molecules in hydrogen and oxygen atoms and/or its derivates in an
incomplete reduction that use as its main source of energy light
from any emission (natural, synthetic, coherent or not) with
wavelengths among 200 and 900 nm, even though some other
wavelengths and forms of energy may be useful (sound, mechanic
agitation, magnetic fields, etc) depending on the physic-chemical
configuration of the system, which will also led as a result high
energy electrons generations or the opposite reaction, the binding
back of the hydrogen and oxygen atoms making water molecules, and
generating electricity or electric current There may be generation
of incomplete oxygen atom reduction such as superoxide atoms, anion
superoxide molecules, hydrogen peroxide and oxyhydrides. All these
taking place in a room temperature and is susceptible of
modification according to the variables and parameters surrounding
this kind of design, for example the nature of the employed
melanin, the addition of some metals, as well as inorganic or
organic compounds, pharmacs, pressure, temperature, pH, gasses, the
shape of the container, rheologic characteristics of the contents.
The energizing of the process is made through natural or artificial
light, visible, invisible, focused, coherent, etc. The
possibilities to modify the characteristics of the process are huge
and so is the resultant efficiency on the generation of the desired
end products such as the quantity of the generated hydrogen or
oxygen atoms or high energy electrons, or in the reverse reaction
water molecules, electricity or electric current, oxyhidriles,
peroxide hydrogen. There is the possibility to optimize any photo
electro chemical design with melanines, their analogues,
precursors, or derivates, pure or mixed, natural or synthetic, but
always having them as the central compound and this possibility
permits the widespread or massive employment of alternate sources
of energy (hydrogen oxygen, high energy electrons, water and
electricity) from removable resources such as the water and
sunlight. The processes above mentioned may be used isolated or
adjoined with other known methods or to be known processes to
produce energy through hydrogen or electric current.
2. Due to the improvement that suppose or comprises my proposal, I
claim, like in number 1; the employment of the melanines, their
precursors, derivates of the melanines, variants, analogues of the
melanines, natural or synthetic, pure or mixed (organic or
inorganic compounds, metals, ions, drugs) for photo electro
chemical process as claimed in number 1 where such substances may
be polyhydroxilindol, eumelanine, pheomelanine, allomelanine,
neuromelanine, humic acid, fullerenes, graphite, polyindoquinone,
acetylene-black, pyrrole-black, indole-black, benzene black,
thiophene-black, aniline-black, hydrated polyquinones,
sepiamelanines, dopa-black, dopamine-black, adrenaline-black,
adrenaline-black, catechol-black, 4 amine catechol-black, (single
linear chain, aliphatic, aromatic) and/or their precursors, such as
phenols, aminophenols, diphenols, indol-polyphenols, cyclodope, DHI
and DHICA, quinones, semiquinones or hydroquinones, L-tyrosine,
L-dopamine, morpholine-ortho-benzoquinone,
dimorpholine-orto-benzoquinone, morpholincathecol,
orthobenzoquinone, porphyrin-black, pterin-black, ommochrome-black,
free nitrogen precursors any of the above mentioned, in any size of
the particle (from 1 angstrom to 2-3 cm). Any of the compounds
mentioned above, electro active, in suspension, solution or gel,
that absorb ultrasound in 1 MHz interval, natural or synthetic of
vegetal, animal or mineral origin, pure or mixed with organic or
inorganic compounds, ions, metal, drugs or others as the main or
accessory materials. In the process the concentrations mainly of
the melanin, that may fluctuate from 0.1% to 100% or more,
depending on the melanin's Physic-chemical characteristics and
rheologic of the design. Given the melanin's characteristics, we
claim its employment to the reduction of the carbon dioxide
reduction, sulphate and nitrates. And overall, we claim its
employment in any industrial, medical, laboratory process, isolated
or as a part of series of processes based completely or partially
on the melanin's characteristics, its analogues, precursors or
derivates, to generate oxygen atoms, hydrogen and high energy
electrons, or the opposite reaction: binding hydrogen and oxygen
atoms to form water molecules and electricity or electric current.
The forementioned in an environment that has water molecules in any
form or variant analogues precursors or derivates, employing as the
only or main source of energy natural or synthetic light, coherent
or not, concentrated or disperse, as well as other different
wavelengths comprised among 200 and 900 nm of the electromagnetic
spectrum. It is also possible to energize the process through
sound, mechanic agitation and magnetic field and others.
3. We also claim as in number 1, the employment of the melanines,
precursors of the melanines, derivates of the melanines, variants,
analogues of the melanines, natural or synthetic, pure or mixed
(with organic or inorganic compounds, metals, ions, drugs) in
designs with the objective to produce energy either producing
electric current when binding hydrogen and oxygen atoms, to form
water molecules, or generating hydrogen and oxygen atoms when
breaking photo-electro-chemically the water molecule, or profiting
the melanines's properties to generate hydrogen peroxide,
superoxide anion, oxyhydrides, and monoatomic or molecular oxygen,
or high energy electrons. All these starts breaking the water
molecule, employing as the main energy source electromagnetic
radiations, in wavelengths among 200 and 900 nm, although some
other wavelengths and other kinds of energy (sound, mechanic
agitation, magnetic fields) may be useful. We also claim the
melanines's property to store energy, it may function as a battery
or accumulator, this means that they do not only generate energy,
but also they are able to store it for a period of time within
certain limits.
4. We claim according to number t, that in the apparatus or design
that allows the employment of the melanines, derivates of the
melanines, their variants analogues of the melanines, natural or
synthetic, pure or mixed (with organic or inorganic compounds,
metals, ions drugs), for photo-electro-chemic processes, or energy
producing as claimed in 1 to 3, through the employment of magnetic
fields in a low to significant intensity.
5. We claim as in number 1 the employment of melanines, precursors,
derivates, variants, analogues of melanines, natural or synthetic,
pure or mixed (with organic or inorganic compounds, metal, ions or
drugs) for the photo electrochemical process that permits the
breaking down of the water molecule in hydrogen and oxygen atoms
and/or their derivates from incomplete reductions, using Light from
any source (natural or synthetic, coherent or not) mainly in
wavelengths among 200-900 nm,
6. We claim. Like in 1 and 2; the employment of the melanines,
precursors of the melanines, derivates of the melanines, variants,
analogues of the melanines, natural or synthetic, pure or mixed
(With organic or inorganic compounds metals, ions or drugs) for
photoelectrochemic processes, as claimed in number 1, where such
substances substances may be polyhydroxiindol, eumelanine,
pheomelanine, allomelanine, neuromelanine, humic acid, fullerenes,
graphite, polyindoquinone, acetylene-black, pyrrole-black,
indole-black, benzene-black, thiophene-black, aniline-black,
hydrated polyquinones, sepiamelamines, dopa-black, dopamine-black,
adrenaline-black, adrenaline-black, catechol-black, 4 amine
catechol-black, (single linear chain, aliphatic, aromatic) and/or
their precursors, such as phenols, aminophenols, diphenols,
indol-polyphenols, cyclodope, DHI and DHICA, quinones, semiquinones
or hydroquinones, L-tyrosine, L-dopamine,
morpholine-ortho-benzoquinone, dimoroholene-orto-benzoquinone,
morpholincatheeol, orthobenzoquinone, porphyrin-black,
pterin-black, ommochrome-black, free nitrogen precursors any of the
above mentioned, in any size of the particle (from 1 angstrom to
2-3 cm). Any of the compounds mentioned above, electro active, in
suspension, solution or gel, that absorb ultrasound in 1 MHz
interval, natural or synthetic of vegetal, animal or mineral
origin, pure or mixed (with organic or inorganic compounds, ions,
metal, drugs or pharmacs) as the main, central principal or
essential materials. In the process the concentration of the
melanines should be taken in to account and may fluctuate from 0.1%
to 100% or more.
7. We claimed, like in 1 and 2, the employment of the melanines,
precursors of the melanines, derivates of the melanines, variants,
analogues, natural or synthetic, pure or mixed (with organic or
inorganic compounds, metals, ions or drugs) in designs that have
the objective to produce energy either producing electric current
when binding hydrogen and oxygen atoms, or generating hydrogen
directly from breaking photoelectrochemically the water, or
profittin the melanines's property to generate hydrogen peroxide,
superoxide anion, oxyhydrides and monoatomic or molecular oxygen as
in number 1.
8. We claim, like in number 1; the system that allows the
employment of the melanines, precursors of the melanines, derivates
of the melanines, derivates of the melanines, variants, analogues
of the melanines, natural or synthetic, pure or mixed (with
inorganic or organic compounds, metals, ions or drugs) to the
photoelectrochemic process or energy production as claimed in
number 1 to 3, that comprises the application of magnetic fields in
a low or significant energy, and with events that may occur under
physic or chemic stimuli, internal or external. To expose such
substances they must be in a container. Such apparatus permits the
control of the partial pressure of the gases and these may vary
from 0.1 mmHg to 3 or 4 pressure atmospheres, may fluctuate from
0.1 mm of Hg until some atmospheres of pression.
9. We claim, like in 1; the apparatus that allows the employment of
the melanines, precursors of the melanines, derivates of the
melanines, variants, analogues of the melanines, natural or
synthetic, pure or mixed (with organic or inorganic compounds,
metals, ions, drugs, or pharmacs) to the photoelectrochemic process
or energy producing as claimed in number 4, whose container allow
the exposure of such substances in a wider area through a flat
shape or any other like the described before in this patent.
Description
PURPOSE OF THE INVENTION
[0001] The technological field in which this invention may be
applied is in the alternative procedures to obtain energy;
different from petroleum, charcoal, hydroelectric, chemical and
nuclear. It is particularly focused on the photoelectrochemical
procedures, that break down the water molecule, generating Hydrogen
and Oxygen atoms and high energy electrons, being energized by
light. This has also applications as a new method for the redox of
the carbon dioxide, nitrate and sulphate. Since the reactions with
the substrate that we propose occur in both senses, our invention
is also applicable for electricity generation, because this
substance permits to bind hydrogen and oxygen atoms forming water
molecules and generating electrical current too.
BACKGROUND
[0002] Referring to the actual techniques, the procedures known by
now to break the water molecule into hydrogen and oxygen are among
others:
[0003] a.) The use of high intensity electrical current
(Electrolysis).
[0004] b.) Water heating up to two thousand .degree. C.
[0005] c.) Breaking the water molecule through the
solar/electrochemical (photoelectrochemical) method, which is
integrated by a semiconductor and a water electrolyzing material in
a monolytic design, to obtain hydrogen directly from water
employing light as its only energy source. Conceptually simple, the
challenge was to find an adequate substrate or material that could
support or sustain the whole process, and until now the ideal or
adequate material was not found yet, since some are very expensive,
pollutant, inefficient, scarce, mostly are quickly degradated or
inactivated, water unstable or require very difficult and extreme
working conditions, frequently only possible in the laboratory.
Because of these, no one is cost-benefit, until now, economically,
ecologically, politically to be used in high scale, reducing its
utility to some specific and tiny processes.
[0006] d.--) Another method was to break down the water through
solar energy (with mirrors for instance) to raise the water
temperature to two thousand grades centigrades, temperature
required in the laboratory to break down the water molecule.
[0007] e.--) Another method is the employment of photosynthetic
organisms (autographs) such as green algae and cyanobacteriae, that
produce hydrogen from water as part of their metabolic activities,
using luminous energy as its mainly source. This photobyiological
technology promising, but since oxygen is produced together with
hydrogen, this technology must resolve the limitations because most
of these enzymatic systems are oxygen-labile. Besides, the amounts
of hydrogen obtained are very low to be economically viable.
[0008] f.--) Another procedure is water electrolysis using
electricity to break the water molecule in its components (hydrogen
and oxygen). Two kinds of electrolyzes are used for the commercial
hydrogen production: alkaline and proton interchange membranes, but
these cannot compete economically with the natural gas
hydrogen-produced. (Source: US Department of Energy. Energy
Efficiency and Renewable Energy, Hydrogen, Fuel Cells and
Infrastructure Technologies Program, Hydrogen, Production &
Delivery).
[0009] Another natural material that breaks the water molecule and
that has been studied is the chlorophyll, but since its light
affinity is among is 400 nm and 700 nm wavelength, the rest of the
luminous energy is lost, it is estimated that 80% of the employed
energy is wasted, besides, its production is complex and very
expensive, for example, it requires at least -8.degree. C. to
preserve, and it is only active in vivo, in vitro, it is rapidly
degradated (approx. 20 sec).
[0010] These were the reasons why we decided to employ the
melanines as water electrolyzing elements, because its light
affinity is among 200 to 900 nm, besides, some of the physiologic
characteristics of the tissues that normally contain them; it
called up our attention specially the oxygen concentrations, so we
decided to contrast the hypothesis that when the melanin or the
melanines are enlightened, photolysis of the water molecule occurs
generating hydrogen and oxygen atoms, as well as other products
such as OH, hydrogen peroxide, super oxide anion and high energy
electrons, also sustaining and catalyzing the inverse reaction;
binding hydrogen and oxygen atoms forming water molecules and
generating electricity.
DETAILED DESCRIPTION OF THE INVENTION
[0011] This invention consists mainly in relating that at room
temperature, with natural or artificial light as the only energy
source, is possible to achieve photolysis or to break down the
water molecule in hydrogen and oxygen atoms, as well as high energy
electrons, but also it is possible to bind the hydrogen and oxygen
atoms, process through which we obtain water and electricity. All
this reactions are supported as the main or principal electrolyzing
material the melanines, their analogues, precursors or derivates
(polihidroxiindol, eumelanine, pheomelanine, allomelanine,
neuromelanite, humic acid, humic acid, fullerenes, graphite,
polyindolquinones, acetylene-black, pyrrole-black, indole-black,
benzene black, thiophene-black, aniline-black, hydrated
polyquinones; sepiomelanines, dopa-black, dopamine-black,
adrenaline-black, catechol-black, 4 amine catechol-black, in single
linear chain, aliphatic or aromatic, or their precursor like
phenols, amine phenols, bi phenols, indol poly phenols, semi
quinones or hydroquinone, L-tyrosine, L-dopamine, morfoline or to
benzo quinona, di morphoilno orto benzoquinone, morfolincatecol,
orto benzoquinona, porphyrin-black, pterin-black, ommochrome-black,
and others), precursors nitrogen free, All of the compounds above
mentioned, electro active, in suspension, solution or gel that
absorb ultrasound in 1 Mhz interval, natural or synthetic, from
mineral, animal or vegetal origin, pure or mixed with organic or
inorganic compounds, ions, metals (gadolinium, iron, niquel,
cupper, erbium, europium, praseodymium, dysprosium, holmium,
chromium, or manganese; the Gadolinium is a very effective
material. The metal is incorporated inside the melanines as ions or
particles, as well as drugs or pharmaceutical energizing the photo
electro chemic design with light (natural or synthetic, coherent or
not, monochromatic or polychromatic) with wave lengths among 200
and 900 nm, even though other wave lengths and some other kinds of
energy such as kinetic, are also variably effective, depending on
the rest of the conditions (pH, temperature, pressure, etc Magnetic
fields may be applied on these kind of designs, of low or
significant intensities. The events on this design may happen
either under physical or chemical stimuli, internal or external. We
propose the employment of the melanines (listed above) as water
molecule electrolyzing materials, using as its principal or only
source of energy tight, particularly wavelengths among 200 and 900
nm, in the hydrogen production systems known as photo electro
chemical methods. These methods integrate a semiconductor and a
water electrolytic material in a monolithic design to produce
hydrogen and oxygen atoms directly from water, employing light as
its only source of energy, with the challenge of finding a
substrate that could bear the whole process. At least two basic
criteria should be met: that the light absorbing system or compound
should generate enough energy to start, sustain and support the
whole or at least a significant part of the process and the
photolysis reaction (definition below). All this shouldn't be too
expensive but stable and long lasting especially in an aqueous
environment. Criteria that melanines, their analogues, precursors
and or derivates meet reasonably and efficiently, fact that
represents an advance when solving out the main problem of the
photo electro chemical designs. The shape of the container may be
very varied; cubic, cylindric, spheric, polyedric, rectangular,
etc. One of the main requisites for the material is to be
translucent in order to allow the light to enter and depending on
the wavelength of the light to be used, the walls could be made for
example of quartz, so that the recipient's wall do not absorb the
UV radiations, or when employing certain wavelengths, the material
made for the recipient could be specially tailored in a color that
allows the maximum transparency or absorption of the desired
wavelengths from the electromagnetic spectrum. It can be glass, or
any polymer whose characteristics of transmission of the
electromagnetic radiations tits to the final needs of the
photoelectrochemical design. The wavelengths that can be used to
energize the design are among 200 nm to 900 nm.
[0012] Inside the cell, the main material, the indispensable solute
to have our photo electrochemical design working is the melanines,
their analogues, precursors and or derivates. Properly dissolved in
water and irradiated, the photolytic activity of the melanines is
immediate, starting in 3 picoseconds (3.times.10.sup.-12 seconds)
and this remarkable ability of the melanin to captivate photons
among wavelengths from 200 and 900 nm (and some other wavelengths)
probably accomplished by the peripheral portions of the molecule,
followed by the generation of high energy electrons from low energy
electrons.
[0013] This high energy electrons go to the free radical core of
the compound, where they might probable be captivated by elements
such as iron, copper, gadolinium, europium etc., and transferred to
a primary electron acceptor, of unknown nature until now, binding
that is complex and implies ionic interactions pH dependent. This
electron transference releases energy which is used to establish a
proton gradient within the system.
[0014] The combination of the water and melamine molecules is what
can be named a photo system, which is capable of absorbing luminous
energy to use it for at least 2 interrelated activities: removing
electrons from water (water oxidation) and creating a proton
gradient. Melanin's compounds are closely related fact that
enhances the quickly energy transference. As soon as 3 picoseconds
after lightning, the melanin's reaction cores respond transferring
a photo excited proton, to the primary electron acceptor, leading
to a positively charged donor and a negatively charged acceptor.
The relevance of these opposite charged species, is evident when we
consider their oxy-reduction ability, since one is missing an
electron, and can accept electrons, fact that makes it an oxidant
agent. On the other side, the other compound has an extra electron
that can easily lose becoming a reduction agent. This event: the
creation of an oxidant a and a reductor agent from light takes less
than a billions part of a second and is the first essential step of
the photolysis. Due to their opposite charges, these compounds
exhibit an evident attraction among them, and their separation is
estabilized (probably) through its own movement to opposite sides
of the molecule, being the negatively charged compound the one that
first lets go its electron to a quinone (Q1) and then the electron
is transferred to a second kind of quinone (q2), and this produces
a semi reduced kind of quinone molecule that can be strongly
related or located to the melanin's reaction core. With every
transference, the electron is closer to the reaction core of the
molecule of melanin.
[0015] The positively charged portion of the melanin is reduced,
and this prepares its reaction core for the absorption of another
photon. The second photon sends a second electron into the same
route (a negatively charged molecule towards the first and second
molecule of quinone (Q1 and Q2), absorbs two electrons and mixes
with two protons. The protons used in this reaction may derive from
this same melanine molecule or from the water that surrounds it,
leading to a diminishing hydrogen ions concentration in this
photosystem, and this contributes to the formation of a proton
gradient. Theoretically, the quinone reduced molecule is
dissociated in the reaction core of the melanin, being replaced by
a new quinone molecule. This reactions take place at room
temperature, but when modifying it, this reactions may be somehow
enhanced, depending on the rest of the variables, such as pH,
magnetic fields, solutes and solvents concentrations, partial
gasses pressure, electrodes composition and shape, distribution,
shape and cells interconnections, and also, we must take into
account the product we need from the process, hydrogen and oxygen
or water and electricity. In the presence of metals or Bore, the
hydrogen works with -1.
[0016] The breaking down of the water molecule in hydrogen and
oxygen atoms its a highly endergonic reaction, since it is a very
stable binding.(.DELTA.H=+286 kJ)
[0017] In the laboratory, breaking the water molecule (in hydrogen
and oxygen atoms) requires a high intensity electrical current or a
high temperature up to almost 2000.degree. C. All this (water
electrolysis or photolysis) is made by the melanin in an
environmental temperature employing only the energy take out of the
light, mainly among 200 and 900 nm wavelengths (other wavelengths
should not be excluded), either from a natural or an artificial
source of light, coherent or not, collimated or disperse, mono or
polychromatic.
[0018] It is estimated that the redox potential of the oxidized
form of the quinone is approximately +1.1V, which is strong enough
to attract the strongly bind low energy electrons from the water
molecule (redox potential of +0.82), and break it into hydrogen and
oxygen atoms. The breaking of the water molecule by photo pigments
is called photolysis. It is estimated that the oxygen molecule
formation during photolysis requires the simultaneous toss of four
electrons from two water molecules according to the reaction:
2H.sub.2O.fwdarw.4H.sup.++O.sub.2+4e.sup.-
[0019] A reaction core can only generate a positive charge or its
oxidant equivalent at a time. This problem can hypothetically be
solved by the presence of 4 nitrogen atoms in the reaction core of
the melanin, and each one transfers an electron. This nitrogen
concentration, may gather tour positive charges when transferring
the electrons, one at a time to the closest molecule of a quinine.
This electron transference of the quinone's atoms present in the
reaction core of the melanin is done through a positively charged
tyrosine residue. After each electron is transferred to the quinine
it is regenerated, the pigment is re oxidized (again to quinine)
after the absorption of another photon to the photosystem. So the
storage of the four positive charges (oxidative equivalent) by the
nitrogen atoms in the reaction core, is modified by the successive
absorption of four photons by the melanin photosystem.
[0020] Once this charges are gathered, the oxygen releaser quinone
complex, is capable of catalyzing the 4e.sup.- of 2H.sub.2O
removal, forming one O.sub.2 molecule, and totally regenerating the
reduced nitrogen stored in the reaction core The photosystem must
be irradiated several times before releasing O.sub.2 and Hydrogen
enough to be measured, which indicates that the effect of the
individual photoreactions must accumulate before O.sub.2 and
Hydrogen are released. The protons produced by photolysis are
released in the medium, where they favor the proton's gradient.
[0021] The quinones are considered as mobile electron transporters.
Don not forget that all electron transference are exergonic and
take place as the electrons are successively taken by transporters,
with an increasing electron affinity (more positive redox
potential). The need for electrons mobile transporters is obvious.
The electrons generated by the photolysis may pass on several
inorganic acceptors that reduce them. These electron pathways may
get to (according to the composition of the compound) to the
eventual nitrate (NO.sub.3.sup.-) molecule reduction into
(NH.sub.3) ammonia molecules or the sulphates in to sulfhydryl
(SH.sup.-); reactions that turn the inorganic waste into compounds
needed for life. So the solar light energy may be used not only to
reduce the most oxidized form of carbon atoms (CO.sub.2), but also
to reduce the most oxidized forms of Nitrogen and Sulphur.
[0022] The O.sub.2 molecule production requires the removal of two
water molecules and the absorption of four photons, one by each
electron.
[0023] The cell design is an important parameter to optimize the
obtention of the reaction product we particularly want, placing
electrodes, their nature, the employment of magnetic fields, adding
varied compounds (organic or inorganic, ions, metals, drugs or
pharmacs) to the photosystem that initially it is only water and
melanin, plus electrolytes, plus pharmacs, as weft as manipulating
temperature, gasses's partial pressures, the management of the
generated electric current, the magnetic field application, pH
level, the material used to tailor the cells and the shape and
distribution of the interior compartment, etcetera, as well as
other variables that are susceptible of manipulation, in order to
have the final design Retrieving electrons or protons or oxygen,
and end compounds according to the media composition in which we
solve the melanin. The melanines, their precursors, variants or
analogues of the melanines (their analogues, synthetic or natural
precursors, pure or mixed with organic or inorganic compounds,
metals) allow a remarkable flexible design according to the
objective we pursue.
[0024] The optimization of the photoelectrochemical design, is a
matter of the objective we want to give it for example, to have a
larger proton and oxygen generation, or electricity the biggest the
area exposed of the liquid compound to the light, through an
extended continent, as well as other procedures such as the
addition of electron carrier compounds, the melanines dopaje, or
positive microlens to focus the light, etc. The continent design is
practically illimited, it may be spheric, cubic, rhomboid,
polyedric, concave-flat, convex-flat, biconvex, biconcave, with
microlens aside (in the side exposed to light to focus it) and flat
in the other side, cylindric, cylindric rounded, empty cylindric,
rounded cone (straight), rectangular pyramidic, truncated spheric
segment, spheric with cylindric perforation, sphere with conical
perforations. Since the liquid fits in any shape, it only needs a
translucent continent, to allow the light to enter the most, and
depending on the kind of melanine used (doped or not) it will be de
convenience of choosing a specific wavelength to enlighten the
soluble melanine, but unto now, one of the greatest gifts of the
synthetic soluble melanine is that it absorbs most wavelengths of
the electromagnetic spectrum. Even though, it seems that the best
absorption is of wavelengths among 200 and 900 nm.
[0025] The control of the gasses partial pressures on the inner
cell is an important variable and depending on the shape of the
cell and the use given, these pressures may go from 0.2 mm Hg up to
3 to 4 pressure atmospheres. Another variable that should be taken
in to account is the concentration of the different substances
solved in the liquid, being critical the melanines's which can go
from 0.1% up to 100%, another variable susceptible of modification
is the proportion between the different compounds of the formulae
(according to what we want to use it for), because we can add
potassium 0.1 up to 10%, sodium 0.1 up to 10%, chlorum 0.1 up to
10%, calcium 0.1 up to 10%, iron 0.1 up to 10%, cupper 0.1 up to
10%, arsenic 0.1 up to 10%, gold 0.1 up to 10%, PLATA 0.1 up to
10%, NIQHEL 0.1 up to 10%, gadolinium 0.1 up to 10%, europium,
erbium, etc. The final volume may go from 1 microliter up to 10-20
titers depending on the size of the recipient and the available
space for it, about the temperature, this can oscile from 2 to
45.degree.G, the exchange time of the solution may be every 14
minutes, several months or up to 2 or 3 years. The compartments
within the cell may be used in different shapes such as small
spheres, (micro spheres, several tens), or bigger spheres whose
size may fit only 3 or 4 times inside the entire design. About the
shape of the inside cell it can have cubic interior, rhomboid,
polyedric, concave flat, convexes flat, biconvexus, biconcave, with
microlenses biconvexes, or flat-convexes, cylindrical, rounded
cylindrical; empty cylindrical; rounded cone (straight), truncated
cone, rectangled prism (straight) oblique prism; rectangled
pyramidic (straight); truncated pyramid, truncated spherical
segment, spherical segment, spherical section; spherical with
cylindric perforation, spherical with conical perforations; torus
(ring with circular section); cylindrical with sloped cut,
cylindrical wedge, barrel, prism-like, and combinations between
them. The microlens optic power may be from 0.1 up to 100
dioptries, the redox properties of the material employed in the
manufacture of the compartment (iron, silver, niquel, gold,
platinum, gallium arseniure, silicated, gadolinium, europium,
erbium, praseodymium, dysprosium, holmium, chrome, manganese; plumb
selenium; and alloys within them or others)) according to the best
characteristics in order to get electrons or hydrogen, but we must
not forget that in the presence of metals or bore, the hydrogen
works with -1; another variable, is the solution initial pH, in may
go from 2 or 3, up to 8 or 9 pH unities, being the most commonly
used around 7, the forementioned are variables that may be modified
in order to control the photo electro lysis process and adapt it to
the needs of the protect in which we use the photoelectrochemic
design. Even though the heart of any effective photo electro
chemical design is the melanines
[0026] The melanines, the melanines's precursors, the melanines's
derivates, variants and melanines's analogues, water solubles,
where they catalyze the photolysis process without any significant
change, except when some materials are present such as manganese,
iron cupper, plumb, and other, whose resultant products together
with the oxygen partial reduction (superoxide anion, hydroxide
radical, hydrogen peroxide, quinones and orthoquinones) may quickly
or slowly damage the melanines efficiency, both when for example,
pure melanine is employed in a 10% concentration, the lifetime of
the compound is long enough to be economically convenient (years),
and also, the melanin synthesis is really efficient, that's why
economically and ecologically is a viable process, since the
melanin is totally biodegraded The cell only requires a periodic
distillated water supply, as well as a soluble melanin exchange, or
in the given case a renewal of the substance that were added to the
design to optimize or trigger the processes obtained after the
tight exposure of the photoelectrochemic design. The ecologic
advantage of having as end products only water molecules, oxygen
atoms or molecules, hydrogen, high energy electrons and electrical
current is easily noticeable. There is a scarce (if any) generation
of CO2 molecules, responsible of green house effect.
[0027] The electrons transference frees energy which is used to
establish a proton gradient. The proton movement during the
electron transportation in the reaction may be compensated by other
ion displacement, so using a membrane and a solvent with the right
solutes we can build a membrane potential with the proton
captivated by the melanin.
[0028] The photo electrolyzing properties of the melanin explain
coherent and congruously the peak seen in the electro retinogram
generated by the Light irradiation. When the melanin is radiated,
the intracellular pH drops, and this activates the chlorine
channels pH-sensitive in the basolateral cellular membrane (the
light peak is an increase in the potential that follows the FOT
phase (Fast Oscillation through) and constitute the slowest and
longest compound of the direct current electro retinogram. (Kris
1958, Kolder 1959, Kikadawa 1968, Steinberg 1982.)
[0029] The melanines, their analogues, precursors or derivates
oxidize the water molecule into O, O.sub.2 and H.sub.2, spending
the energy they get from the Light (photons) and also reduce oxygen
atoms with hydrogen atoms producing H.sub.2O molecules and
releasing electricity. The cell design may be tailored, to what we
want to obtain. It produces H2 and O2 atoms with the light but this
production may be increased through the DOPAGE of the melanines
(melanin, its precursors, variants, derivates or analogues natural
or synthetic), with metals, or conditioning organic or inorganic
molecules as well as modifying the electrolytes concentrations,
adding pharmacs or controlling the light characteristics over the
liquid containing water and melanines melanin, its precursors,
variants, derivates or analogues natural or synthetic), for example
with a design based on microlens to condens or select certain
wavelength, employing coherent or disperse light, monochromatic,
polychromatic, continuous, discontinuous, natural, artificial, etc
The photoelectrochemical reactions occur in both senses, the water
molecule is broken, but also built, so we can obtain electric
current from the design and also it may be optimized through the
melanin dopage, with different substances (pharmaceuticals, metals,
electrolytes, inorganic or organic molecules and others) or
focusing the light through lens among others. The box that contains
the liquid may have different shapes adapted to the different needs
in the roof of the houses, of the cars, buildings, industrial
processes, plants, etc. cells interconnected, but the principal
compound of the design still is the melanin (melanines, their
precursors, derivates, variants, analogues, water soluble that lead
to and effectuate the water photolysis in the presence of tight
(invisible or not).
[0030] The melanines, their precursors, derivates, variants and
analogues, remove electrons from the water and establish a proton
gradient. The tight dependent reactions may also produce energy to
reduce CO.sub.2 a CH.sub.2O, nitrates to ammoniac and sulphates to
sulphydriles. A compound described in the literature known to
induce and carry out these processes is the chlorophyll, out it
absorbs light mainly in the extreme regions of the visible
electromagnetic spectrum, it is estimated that 80% of the
irradiated energy is lost, opposite to our proposal of employing
the melanin, because it absorbs electromagnetic radiations, soft
and hard, all the visible spectrum and the infrared wavelengths
close and far (Spicer & Goldberg 1996). It is not (unlikely
that in may absorb some other kinds of energy such as kinetic or
other wavelengths from the electromagnetic spectrum.
EXAMPLES
[0031] We have done several low scale experiments once we Inferred
this interesting properties of the melanines, and according to the
relation structure-activity of the molecule after placing synthetic
soluble melanine in water, we got a 1% solution, that we stored in
5 polyethylene translucent high density bottles of 20 ml in room
temperature, measuring pH before and after illuminating it for 30
minutes with visible natural light (sun) not concentrated at 8 am.
We got an average drop of 2 tenths of pH unit (from 7.3 to 7.1) in
an open design.
[0032] We consider it significant because the melanines have a
buffer capability per se, and indubitable the variation should be
bigger but it is masked by this intrinsic property of the melanines
(buffer), reason why we only detected a part of these important pH
changes, which magnitude depends on the biological system, if it
was bigger it would probably destroy or harm importantly the cell,
but a small variation such as the one we detected is enough to
induce the biological responses in which this extraordinary
compound is involved, in order to dimension the biological
importance of a decrement of 0.2 pH units, we will quote that this
decrement induces an increment of more than 10% of the calcium, in
serum. Besides, the pH of the whole blood is between 7.38 to 7.44,
in arterial blood is between 7.36 to 7.41 and the venous blood
oscillates between 7.37 to 7.45, the variations are in a very
narrow interval, therefore, the two tenths of pH unit variation in
a biological system is really significant.
[0033] In a closed design, we estimated the hydrogen productions
according to the electric current generation, and obtained average
values of 50 uA (500 mV) and 150 uA (1100 mV) in between peaks,
which means at least one or two pH unities, this is equivalent to a
Hydrogen production of 1.times.10.sup.-7 mol/litter for each pH
unit. The molecular weight of the hydrogen, indicates that a mot is
equivalent to a gram of hydrogen. On the other side, the
melanocyte, is the cell with the highest affinity for calcium in
the body, thousand times more than the bone, because even though it
has more quantity, only mineral calcium is deposited in the bone.
It is worth saying that such variation from 0.2 to 1.0 pH unit; and
the reverse reaction that occurred once the containers were placed
in a dark place, was anticipated by our theoric background, when we
performed the experiments, we known already what was going to
happen, as the matter of fact, we didn't do many experiments, we
only made two or three times, obtaining the results we expected.
The melanin solutions employed in the experiments, had at least 3
years of prepared and were not doped, and as the theoric background
states, it is a long lasting compound, very water stable, doesn't
requires preservers, does not need refrigeration despite of time,
it doesn't get contaminated with microorganisms, because we only
kept the solutions in fresh and dry environment; reason why we are
quite sure that the reaction was going to happen, even though the
magnitude couldn't be anticipated because the buffer capacity of
the melanines is not known, or is impossible to measure precisely
because the melanine chemical formula is not completely known This
experiment also proved that the melanin does not requires
preservers, and their electrolyzing properties are kept despite of
time (3 years of prepared). Now, we are working in protocols that
lead us to answer some of the many questions generated from this
experiments, but since the extraordinary possibilities of
industrial medical energetic and laboratory applications of this
electrolyzing property of the melanin, we decided to protect right
away its employment in the energy production photoelectrochemical
processes. Another example that sustains our patent is the fact
that the blood that enters the eye (arterial blood) through the
choroid vessels, all surrounded by melanocytes; presents an oxygen
saturation of 97%, and when it exists the eye, in the vorticoses,
the oxygen saturation is of 94%, while the CO2 is of 40%. Notice
only a 3% drop of the oxygen saturation is intriguing. This unusual
characteristic is not explained by the quick ocular blood flow,
that amazingly goes from 10 to 20 mL/min/g, 10 to 20 times more
than the brain's (0.5 mL 7 min/g), besides, if true, then the
oxygen saturation of the retinal vessels would be similar (97% in
the artery and 94% in the central retinal vein, with a CO2 of 40%),
but it is not. In the retinal vessels it is like in the rest of the
body, 97% oxygen at the entrance, and 60% oxygen saturation in the
veins at the exit, and a CO2 of 40%. This intriguing difference is
not explained in the literature until now, but is solved if we take
in to account the electrolyzing property of the melanin, which is
never mentioned in the literature, and we are the first to infer
and describe. Another biologic success that sustains our patent, is
that when enlightening the pigmented epithelium cells of the
retina, normally, a drop of the intracel pH is measured, fact that
in all the searched literature until now, is not explained, they
only say mat an unidentified substance might be responsible for it,
but if we take in to account this electrolyzing property of the
melanin whose employment we are patenting, that in presence of
light, the melanin breaks the water molecule and generates hydrogen
and oxygen atoms, then both previously described events are
explained. The mysterious oxygen saturation of 94% of the venous
choroid blood (normally the choroid is very pigmented), and the
drop of the citoplasmatic pH of the pigmented epithelium cells of
the retina when enlightened.
[0034] There must be a reason why the nature provided so much
pigment in the eye, 40% more than in the skin. Another example that
supports our patent is a peak generated by light observed in the
electroretinogram; the recording of the electric activity of the
retina, pigmented epithelium and choroids. When enlightening, the
melanin and with the generation of atoms of hydrogen, the
intracellular pH drops, and it activates the chlorum pH dependant
channels in the basolateral cell membrane. The tight peak is a
increase in the potential that follows the FOT phase (fast
oscillation through) and constitutes the slowest and longest
compound of the direct current electroretinogram, fact whose
molecular substrate was not dilapidated yet, but the electrolyzing
properties of the melanin explain it quite.
* * * * *