U.S. patent number 3,670,074 [Application Number 05/108,961] was granted by the patent office on 1972-06-13 for sunscreen formulation containing triethanolamine neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid.
This patent grant is currently assigned to Miles Laboratories, Inc.. Invention is credited to Abraham J. Doner, deceased.
United States Patent |
3,670,074 |
Doner, deceased |
June 13, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
SUNSCREEN FORMULATION CONTAINING TRIETHANOLAMINE NEUTRALIZED
2-HYDROXY-4-METHOXY-BENZOPHENONE-5-SULFONIC ACID
Abstract
An active sunscreen ingredient comprised of
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid, neutralized with
triethanolamine, and formulated with various compatible vehicles to
produce effective sunscreens for human use.
Inventors: |
Doner, deceased; Abraham J.
(late of North Miami Beach, FL) |
Assignee: |
Miles Laboratories, Inc.
(Elkhart, IN)
|
Family
ID: |
22325063 |
Appl.
No.: |
05/108,961 |
Filed: |
January 22, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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698679 |
Dec 18, 1967 |
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Current U.S.
Class: |
424/60; 424/59;
424/47; 514/942 |
Current CPC
Class: |
A61K
8/466 (20130101); A61Q 17/04 (20130101); Y10S
514/942 (20130101) |
Current International
Class: |
A61l 023/00 () |
Field of
Search: |
;424/59,60,331 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
sagarin Cosmetic Science and Technology 1957, pp. 767. .
Lester, Handbook of Cosmetic Materials, 1954, pp. 320..
|
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Ore; Dale R.
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part application of application Ser. No.
698,679 filed Dec. 18, 1967, now abandoned. Attention is also
directed to prior application Ser. No. 358,616 filed Apr. 8, 1964,
now abandoned.
Claims
I claim:
1. A sunscreen formulation in the form of an emulsified lotion
suitable for application to human skin comprising; an active
ingredient consisting essentially of
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in amounts ranging
from 0.1 percent to 30 percent of said formulation, said sulfonic
acid being neutralized with triethanolamine, and a compatible
vehicle comprising a mixture of, by weight, 3 percent to 5 percent
glycerol monostearate, 1 percent to 3 percent cetyl alcohol, 1
percent to 3 percent isopropyl palmitate, 1 percent to 15 percent
dimethyl silicone oil, 0 percent to 3 percent light liquid
petrolatum, 0.1 percent to 1 percent polyvinyl pyrrolidone, 3
percent to 30 percent sorbitol and up to 100 percent water.
2. A sunscreen formulation as defined in claim 11 wherein the
compatible vehicle includes a preservative amount of preservative
material selected from the group consisting of methyl paraben,
propyl paraben and mixtures thereof.
3. A sunscreen formulation in the form of an emulsified lotion
suitable for application to human skin comprising; an active
ingredient consisting essentially of
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in amounts ranging
from 0.1 percent to 30 percent by weight of said formulation, said
sulfonic acid being neutralized with triethanolamine, and a
compatible vehicle comprising a mixture of, by weight, 3 percent to
5 percent glycerol monostearate, 2 percent cetyl alcohol, 2 percent
isopropyl palmitate, 3 percent dimethyl silicone oil, 2 percent
light liquid petrolatum, 0.5 percent polyvinyl pyrrolidone, 7
percent sorbitol and up to 100 percent water.
4. A sunscreen formulation in the form of an emulsified lotion
suitable for application to human skin comprising; an active
ingredient of 2-hydroxy-4methoxy-benzophenone-5-sulfonic acid in an
amount of 10 percent by weight of said formulation, said sulfonic
acid being neutralized with triethanolamine, and a compatible
vehicle comprising a mixture of, by weight, 5 percent glycerol
monostearate, 2 percent cetyl alcohol, 2 percent isopropyl
palmitate, 3 percent dimethyl silicone oil, 2 percent light liquid
petrolatum, 0.5 percent polyvinyl pyrrolidone, 7 percent sorbitol
and up to 100 percent water.
5. A sunscreen formulation in the form of an emulsified lotion
suitable for application to human skin comprising; an active
ingredient consisting essentially of
2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in amounts ranging
from about 3 percent to 10 percent by weight of said formulation,
said sulfonic acid being neutralized with triethanol-amine, and a
compatible vehicle comprising a mixture of, by weight, 3 percent
glycerol mono- and di-stearate, 19 percent sorbitol, 1 percent
ceresin wax, 1 percent beeswax, 11 percent mineral oil and up to
100 percent water.
6. A sunscreen formulation in the form of a liquid suitable for
application to human skin comprising; an active ingredient of
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in an amount of 10
percent by weight of said formulation, said sulfonic acid being
neutralized with triethanolamine, and a compatible vehicle
comprising a mixture of, by weight, 20 percent denatured alcohol, 3
percent dimethyl silicone oil and up to 100 percent water.
7. A sunscreen formulation in the form of a liquid suitable for
application to human skin comprising; an active ingredient of
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in an amount of 10
percent by weight of said formulation, said sulfonic acid being
neutralized with triethanolamine, and a compatible vehicle
comprising a mixture of, by weight, 30 percent denatured alcohol, 3
percent dimethyl silicone oil, 0.5 percent glycerol monostearate
and up to 100 percent water.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to ultraviolet absorbers and more
particularly to sunscreen formulations for protection of human skin
from solar radiation.
2. Prior Art
Many sun tanning formulations for human skin are known, however,
these do not effectively screen solar radiation from the skin.
Chronic exposure to sunlight, even with such sun tanning
formulations, has a deleterious effect on at least certain humans.
For example, chronic exposure to sunlight appears to significantly
influence aging of human skin and/or produce skin cancer.
Additionally, sunlight appears to precipitate or at least aggravate
lupus erythematosus and concentrate skin lesions of pellagra and
porphyria to the exposed skin areas. Also, a significant number of
commonly used drugs produce photosensitivity in certain humans,
which often result in polymorphic light sensitive eruptions. Among
the more commonly used agent which produce sensitivity are the
sulfonamides, tranquilizers of the phenothiazine type, the
sulfonylurea oral antidiabetic agents and the antihypertensive
diuretic agents.
The most common observation of the deleterious effect of exposure
to sunlight is severe sunburn. However, a much less observed but
just as common an effect of a single moderately severe sunburn is
the abnormal characteristics of the blood vessels of a subject who
has been exposed and which abnormalities remain present for a
period of time ranging from 4 to 15 months. At present, no truly
effective sunscreen agents are known that are compatible with human
skin, and it will be appreciated that sun tanning agents are
entirely different since they do not effectively absorb ultraviolet
light. While certain benzophenone derivatives are utilized as
sunscreen agents in protecting natural and man-made materials, such
as textile goods, dyes and coloring agents, various resins, coating
and film materials, and miscellaneous chemical compositions against
the action of sunlight, these benzophenones are unsuitable for
human skin for a number of reasons, including that they are highly
irritating and do not lend themselves to acceptable formulations
for human use.
Accordingly, it is an object of the invention to provide an
effective sunscreen formulation for human skin that overcomes the
aforesaid and additional disadvantages of heretofore available
materials and to provide an adequate and safe protection for human
skin from the effects of sunlight.
Other objects, features and advantages of the invention will become
apparent to those skilled in the art from the teachings of the
principles of the invention in connection with the disclosure of a
preferred embodiment thereof in the specification and claims.
SUMMARY OF THE INVENTION
The invention provides a sunscreen formulation containing an active
ingredient for the protection of human skin from solar radiation
comprised of a triethanolamine neutralized 2-hydroxy-4-methoxy
benzophenone-5-sulfonic acid, in a compatible vehicle, which may
include an emulsifier, such a glycerol monostearate, a wax, such as
beeswax, water, an alcohol, such as denatured or cetyl alcohol,
thickening agents, preservative agents, perfumes, etc. The amount
of active ingredient within the formulation ranges in amounts from
about 0.1 percent to about 30 percent.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention provides a sunscreen agent that prevents and/or
substantially minimizes the photochemical degradation and other
adverse effects caused by exposure of human skin to sunlight
through the absorption of ultraviolet wave lengths. The sunscreen
agents of the invention absorb or screen radiation wave lengths
responsible for erythema on human skin, minimizes the aging effects
of solar radiation on humans and inhibits freckling or irregular
pigmentation from such radiation. The sunscreen agents of the
invention are readily incorporated into various types of vehicles
for cosmetic materials, such as make-up bases, face powders,
after-shave lotions, etc. for use by individuals who freckle, are
afflicted with chloasma, or prefer their natural color, as well as
by others. The sunscreen agents of the invention also tend to
decrease sunlight accelerated aging and sunlight induced
carcinogenesis on exposed human skin which has been coated with a
formulation of said agents.
The sunscreen agents of the invention comprise
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid neutralized with a
neutralization agent having properties of triethanolamine and are
formulated into any desired carrier, vehicle, emulsion, cream,
lotion, ointment, solution, suspension, gel, aerosol or in any
other form suitable for human usage. In its most preferred form,
the active sunscreen agent of the invention is
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid neutralized with
triethanolamine. The amount of active sunscreen agent of the
invention in a given formulation ranges from about 0.1 percent to
about 30 percent or more as desired.
The emulsions, gels, vehicles, etc. utilized in preparing
sun-screen formulations containing the active sunscreening agents
of the invention contain any one or combinations of; cetyl alcohol,
stearyl alcohol, stearic or lauric acids and all other fatty acids
and alcohols generally used in cosmetic and like materials
emulsions or other formulations intended for human use; various
waxes such as beeswax, microcrystalline wax, spermaceti, etc., and
all other waxes generally used in cosmetic and like material
emulsions or other formulations intended for human use; various
petroleum materials, such as petrolatum, liquid petrolatum, mineral
oil, silicone oil, etc. and all other oils, fats, and the like
materials generally used in cosmetic and like material emulsions or
other formulations intended for human use; fatty acid esters, such
as isopropyl myristate and similar esters of fatty acids having a
composition generally ranging from about C.sub.3 to about C.sub.20,
various silicone derivatives, polyvinyl pyrrolidone methyl or
propyl paraben, C.sub.1 to C.sub.4 glycols, various stearates, and
other materials whether similar or otherwise that are generally
used or considered suitable for use in cosmetic and like material
emulsions or other formulations intended for human use.
Additionally, the vehicle materials, emulsifiers, combination of
emulsifiers, and other like material compatible with the active
sunscreen ingredients or agents of the invention are also selected
from various anionic surfactants, including amine soaps of fatty
acids such as characterized by triethanolamine stearate; cationic
surfactants, such as characterized by monoethanol ammonium
fluoride; amphoteric surfactants such as characterized by N-fatty
.beta.-amino-propionate (RNH--CH.sub.2 --CH.sub.2 --COOH); and
nonionic surfactants such as characterized by sorbitan derivatives
of C.sub.12 to C.sub.20 fatty acids, polyoxyethylene sorbitan
derivatives of C.sub.12 to C.sub.20 fatty acids, polyoxyethylene
esters of C.sub.12 to C.sub.20 fatty acids, glyceryl stearates,
fatty acid polyisopropylene complexes; and ethylenes oxide fatty
alcohol lanolin complexes. Other compatible materials, vehicles,
carriers, gels and like materials include perfumes, clays,
preservative agents, etc. and are all utilizable with the active
sunscreen agents of the invention in formulating suitable gels,
emulsions, either of the water-in-oil type or the oil-in-water
type, aerosols, etc. or other forms suitable for application to
humans.
In order to illustrate the invention and compare it with known
sun-protective agents, comparative evaluations were made of
twenty-four agents by applying such agents to the shaved abdomens
of albino rabbits and determining the Minimal Erythema Dose
(M.E.D.). An embodiment of the invention within this comparative
group was triethanolamine neutralized
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid. The M.E.D. for an
unprotected rabbit (i.e. one without having any protective agent on
it) was found to be 25-30 seconds. Of the known protective agents,
the longest or best protection provided was 3 to 5 minutes and only
four of the preparations studied gave results that were this
satisfactory. A 5 percent concentration of PABA
(para-amino-benzoic-acid) and a 5 percent concentration of
triethanolamine neutralized
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in a compatible
vehicle, each provided protection for about 20 to 25 minutes. By
doubling the concentration of these two agents in similar
formulations and applying them to rabbits, the M.E.D. was increased
in both instances to approximately 100 minutes. However, PABA and
its esters tended to produce epidermal sensitization and to produce
cross-sensitization reaction with benzocaine, sulfonamides, and the
aniline dyes.
The active sunscreen agents of the invention generally comprise
suitably neutralized 2-hydroxy-4-methoxy-benzophenone-5-sulfonic
acid, and similar benzophenone derivatives having the formula:
##SPC1##
wherein A is selected from a neutralizing agent having properties
characterized by triethanolamine. The active sunscreen agents of
the invention are utilized in a variety of formulations and are
present therein in amounts ranging from about 0.1 percent to about
30 percent by weight.
In order to further illustrate, and not limit the sunscreen agents
of the invention in various formulations, bases, carriers,
emulsifiers and other compatible vehicles, the following examples
are set forth.
A 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid is available
from Antara Chemical, New York, New York under the registered
tradename "UVINUL MS-40" and "UVINUL-40-20 percent Aqueous
Solution." "UVINUL MS-40" is a free flowing powder at 25.degree.
C., light-cream in color and has a molecular weigh of 309 and a pH
2 for a 1 percent aqueous solution, with a solubility of about 5
g/100 mls of water at 25.degree. C. after 15 minutes of agitation.
Of course "UVINUL MS-40-20% Aqueous Solution" is the same material
in an aqueous solution at the concentration indicated. In preparing
sunscreen formulations utilizing powdered "UVINUL MS-40," the
powder is first dissolved in water and then combined with a
suitable neutralizing agent and a particular vehicle.
EXAMPLE I
A typical embodiment of an oil-in-water emulsion formulation
utilizing "UVINUL MS-40-20% Aqueous Solution, " (referred to as
Benzophenone Derivative) in its neutralized form, an the active
ingredient is as follows, with all parts being by weight unless
otherwise noted.
Active Ingredient Amounts Benzophenone Derivative 10%
Triethanolamine (U.S.P.) Q.S.* Emulsion Vehicle "ARLACEL 165"
(Glyceryl Monostearate) 5% Cetyl Alcohol 2% Isopropyl Palmitate 2%
Dimethyl Silicone Oil 3% Light Liquid Petrolatum 2% Polyvinyl
Pyrrolidone 0.5% "Sorbo 70%" 10% Distilled Water to 100%
"ARLACEL 165" is a tradename for a glyceryl monostearate containing
emulsifier available from Atlas Chemical Industries, Inc., of
Wilmington, Delaware and "Sorbo 70%" is a tradename for a sorbitol
containing emollient having 70 percent solids also available from
Atlas Chemical Industries, Inc. An alternative emulsifier usable in
place of "ARLACEL 165" is "Promulgen," a tradename for an
emulsifier available from Robinson Wagner Company, Inc., of
Mamaroneck, New York.
The above embodiment of a particular formulation can be varied by
adjusting the amount of active ingredient so as to vary between
about 0.1 percent to about 30 percent and by adjusting and/or
omitting certain ingredients of the vehicle. For example, the
amount of glycerol monostearate can vary between about 3 percent to
5 percent, the silicone oil, i.e. dimethyl silicone oil, and/or the
petrolatum can be replaced by mineral oil and the amount varied
between about 1 percent to 15 percent, the amount of sorbitol
varied between about 3 percent to 30 percent or partially replaced
by a glycol, the amounts of isopropyl palmitate, and polyvinyl
pyrrolidone may also be varied and/or replaced with other
comparable material and even omitted as exemplified in further
embodiments set forth hereinafter. Of course, minor amounts
perfumes and/or preservative agents are added as desired.
It will be understood that the invention is not limited to the
specific proprietary items set forth in the examples but includes
all emulsifiers, emollients, carriers, vehicles, preservatives,
perfumes and other materials generally found in cosmetic materials,
sun protective formulations, etc., suitable for use on human
skin.
The formulation of the above embodiment of an oil-in-water emulsion
is carried out by placing the appropriate amounts of "ARLACEL 165,"
cetyl alcohol, dimethyl silicone oil and light liquid petroletum in
a suitable steam-jacketed kettle or the like and subjecting the
mixture to slow agitation and heating conditions to about
70.degree. C. so as to form a first solution. The remaining
ingredients of the emulsion vehicle, i.e. all of the remainder
ingredients except the active ingredient, are placed in another
suitable container and slowly agitated and heated up to about
75.degree. C. to form a second solution. The two solutions are then
combined with continuous and vigorous agitation by adding the
second solution to the first solution. Thereafter the sulfonated
2-hydroxy-4-methoxy-benzophenone derivative is neutralized with a
sufficient amount of an amine having properties characterized by
triethanolamine and added to the combined solutions at about
35.degree. C. with agitation sufficient to achieve a generally
homogeneous or uniform mixture. Perfumes or preservative agents
such as methyl and/or propyl paraben or the like can readily be
included in the formulation in an appropriate amount, if
desired.
EXAMPLE II
A typical embodiment of a water-in-oil formulation utilizing
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in its neutralized
form as the active ingredient is as follows, again all parts being
by weight unless otherwise noted.
Active Ingredient Amounts Benzophenone Derivative 3% to 10%
Triethanolamine (U.S.P.) Q.S.* Emulsion Vehicle "ARLACEL 186"
(Mono- and di- Glycerides of fat forming fatty acids) 3% "SORBO"
(70% aqueous solution of d-sorbitol) 27% Ceresin Wax 1% Beeswax 1%
Mineral Oil 11% Water to 100%
"ARLACEL 186" and "SORBO" are tradenames of an emulsifier and an
emollient respectively, available from the Atlas Chemical
Industries, Inc. referred to earlier.
The formulation of the above embodiments is carried out by
preparing an intermediate gel comprised of adding a small amount of
"SORBO" and "ARLACEL 186" and subjecting the mixture of mechanical
agitation to form a relatively thick slurry. Thereafter, the
remainder of "SORBO" ingredient is added with continuous agitation
and then the benzophenone derivative, in its neutralized form, the
waxes and the mineral oil are added to the intermediate gel and
slowly agitated and heat up to about 70.degree. C. The water is
then heated to about 72.degree. C. and added to the gel mixture
with continuous agitation. The agitation is continued until the
resultant formulation cools to room temperature. In order to
provide maximum smoothness and stability, the formulation is
subjected to homogenization or milling procedures.
EXAMPLE III
A typical embodiment of a liquid solvent formulation utilizing
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in its neutralized
form as the active ingredient is as follows, with all parts being
by weight.
Active Ingredient Amounts Benzophenone Derivative 10% Neutralizing
Agent Q.S.* Solvent Vehicle Specially Denatured Alcohol (SDA-40)**
20% Alcohol Soluble Silicone Oil 3% Purified Water to 100%
** A denatured ethyl alcohol approved by the U.S. Government for
use in various cosmetics and like formulations.
The formulation of the above embodiment is carried out by combining
the active ingredient with the solvent vehicle under vigorous
agitation and gentle heat conditions for a period of time
sufficient to produce a relatively clear solution. Perfumes or the
like are also added as desired.
EXAMPLE IV
A typical embodiment of a gel (clear or opaque) formulation
utilizing 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid in its
neutralized form as the active ingredient is as follows, with all
parts being by weight.
Active Ingredient Amounts Benzophenone Derivative 10%
Triethanolamine (U.S.P.) Q.S.* Gel Vehicle Specially Denatured
Alcohol (SDA-40)** 30% Alcohol Soluble Silicone 3% "Carbopol 940"
(Synthetic Hydrophilic Colloids in white free flowing powder form)
0.5% Water to 100%
"Carbopol 940" is a tradename for an emulsifier material comprised
of a vinyl polymer with active carboxyl groups available from B. F.
Goodrich Company (The Merck Index, 8th Edision, 1968, Page 201).
The formulation of the above gel embodiment is carried out by
combining the gel vehicle with the benzophenone derivative under
agitation and heat conditions sufficient to produce a clear gel
solution. Thereafter the triethanolamine is slowly stirred into the
solution until a gel forms. The formed gel is suitable for use on
human skins.
The benzophenone derivative is carried into an appropriate vehicle
by dissolving or suspending it in water, alcohol, glycerine,
propylene glycol or any other suitable solvent or combination of
solvents generally recognized as safe or compatible to human skin.
Further suitable suspension agents, such as organic clays, pectin,
synthetic resins, etc. are also utilizable in appropriate
proportions in the formulations of the invention, additionally,
tragacanth, agar-agar or similarly characterized thickening agents
are also suitable for use in the formulations of the invention.
In order to further illustrate the sunscreen agents and
formulations of the invention and to illustrate their relative
effectiveness on humans and compared them with known sun protective
agents, a number of known sun protective agents and the sunscreen
formulation essentially identical to that of Example I having
various concentrations of active sunscreen ingredients were applied
to male and female volunteers. An ultraviolet lamp, Burdick Model
QA-450-N, producing ultraviolet radiation ranging from 2,400 to
3,300 angstroms, with the majority of the radiation being between
2,800 to 3,200 angstroms was used. (Sunburn to human skin is
generally produced by the electromagnetic spectrum located between
2,900 and 3,170 angstroms, with maximal effects at about 2,970
angstroms.) The M.E.D. (Minimal Erythema Dose) for each volunteer
was established on the abdomen and the back with the ultraviolet
lamp at a distance of thirty inches. The various formulations
studied were applied by hand and rubbed into a skin area in the
same manner as an individual does before being exposed to the sun.
No excess material was utilized and the amount varied, but was
generally only sufficient to permit the volunteers to feel
comfortable. In each instance, the applied formulations were
allowed to dry before exposure to the ultraviolet and the results
were averaged.
Average Protection Sun Protective Material In M.E.D. units
__________________________________________________________________________
5% Menthyl anthranilate less than 5 Ethoxyethyl methoxy-cinnamate
less than 5 Para-amino-benzoic acid 15% in Aquaphor 30 but less
than 40 Red Veterinary Petrolatum 40 but less than 60
2-ethoxy-ethyl-p-methoxy-cinnamate less than 5 Yellow Vasoline
(U.S.P.) 30 but less than 40 Digalloyl-trioleate less than 5 10%
neutralized benzophenone derivative of the invention in a lotion
base 150 5% neutralized benzophenone derivative of the invention in
a location base 10 but less than 20 2% neutralized benzophenone
derivative of the invention in a lotion base 5 10% neutralized
benzophenone derivative of the invention in an alcohol vehicle 40
The emulsion vehicle of Example I, without the active ingredient
less than 5 Non-neutralized benzophenone derivative results incon-
clusive.sup.3
In summation, the invention provides active sunscreen agents or
ingredients compatible with a wide variety of vehicles or carriers
in sunscreen formulations wherein the active ingredient is present
in amounts ranging from about 0.1 percent to about 30 percent. The
preferred active ingredient of the invention is
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid neutralized with
triethanolamine, although other suitably neutralized
2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid derivatives are
also utilizable.
It is to be understood that the foregoing relates only to the
preferred embodiments of the invention and changes, modifications
and variations can be effected without departing from the scope or
spirit of the novel concepts of the invention.
* * * * *