CA2667903A1

CA2667903A1 - Composition for the treatment of skin conditions

Info

Publication number: CA2667903A1
Application number: CA002667903A
Authority: CA
Inventors: Farrell Munroe; Roland Leblanc
Original assignee: SCALLOP SHELL POLLUTION SOLUTION Ltd
Current assignee: SCALLOP SHELL POLLUTION SOLUTION Ltd
Priority date: 2006-10-31
Filing date: 2007-10-29
Publication date: 2008-05-08
Also published as: EP2086557A1; SE0950392L; RU2009120523A; MX2009004692A; GB2456475A; GB0909306D0; WO2008052302A1; WO2008052326A1; CN101616679A; FI20095600A; JP2010508142A; AU2007314097A1; EP2102111A1; GB0909297D0; DK200900672A; AU2007314032A1; DK200970014A; MX2009004690A; GB2456976A; BRPI0718098A2

Abstract

A composition for the treatment of various skin conditions where the composition comprises a solution which has been passed at least one time through a column containing a packing solid comprised of crushed mollusk shells of at least one size in diameter. This solution is then in admixture with a pharmaceutically acceptable carrier. This composition has effective applications as a cleaner and disinfectant and has also been found beneficial for the treatment of skin and other bodily diseases. Additionally, the shells can be pulverized and used as an active ingredient in the preparation of an ointment useful for medical treatments.

Description

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:14 FAX 819 953 9538 CIPO / PCT OFFICE Q003/024 02 September 2008 02-09-2008 COMPOSITION FOR THE TREATMENT OF SKIN CONDITIONS

F:ELD OF THE INVENTION
The present invention relates generally to a composition for topical application that comprises an extraction solution mixed with a pharmaceutically acceptable carrier, wherein the solution is produced by repeatedly filtering a liquid through a filter/extraction colunrnn housing crushed mollusk shell particles. This composition can be used for the treatment of a variety of skin conditions.

BACKGROUND OF THE INVENTION
The present invention is an improvement over Canadian Patent Application No.

2,566,562, wherein a process is disclosed for the preparation of a solution for use in the treatment o' skin diseases. Further developments have been revealed that outline the use of the w,'orementioned solution for the production of a new composition. For a ready understanding of the solution itself, and the process of manufacture therefor, the reader is directed to Canadian Patent Application No. 2,556,562.
Shells derived from mollusks are generated as industrial waste from fisheries around the world. It is common practice to dump the shell waste into the ocean. However, shells have been e:Y"iciently used as a source of calcium and for obtaining antibacterial agents, as well as for purifying water. It has been shown that the powder obtained from shells of scallops, oysters, c:ams, and other mollusks, or a solution containing the powder, has antibacterial and antiviral p.roperties, as well as a use as a water purifying agent. It has also been found that the aforesaid powder has demonstrated useful properties when applied as a deodorant for sterilization, as a preservative agent and for selected medicinal use.
Medicinal properties of mollusk shell powder and extract are well proven and tested. For example, European Patent Application No. 1676583 describes a therapeutic agent for periodontal disease that is prepared by utilizing a scallop shell material, and which has antimicrobial activity against periodontal disease-inducing bacteria. In particular, the shells are crushed and are then subjected to calcination, to convert the calcium carbonate in the original shells to calcium oxide, by firing at a high temperature. An aqueous solution is then formed with the newly formed calcium oxide powder and the original calcium carbonate powder.

I

A1ZlIDED 8E~8T

U.S. Patent Application No. 2004/0028748 describes a remedy for dermatophytosis, obtained from a product formed by grinding shells having a crystalline structure and forming an aqueous dispersion of the product. In particular, the ground shells are calcinated by heating the particles in excess of 1000 C, and the aqueous solution is obtained by the use of both the originally ground shells and calcinated shells.
Japanese Patent Application No. 2004/256785 describes a soap which has an auxiliary therapeutic effect for relieving itching associated with atopic derrnatitis and psoriasis. The primary active ingredient in the soap is a fine powder prepared by high temperature calcination of scallop shells, oyster shells, clam shells and the like.
United States Patent No. 6,627,229 describes an antiviral agent produced by applying a heat treatment of between 700 C to 1200 C to the pulverized powder of a calcium-containing substance originating from animals, such as clamshell, crustacean shell, bone, coral and pearl.
U.S. Patent Nos. 6,365,193 and 6,488,978 to Sasaki et al. disclose that burned shells can be used as antibacterial agents and water purifying agents. Sasaki et al.
disclose heating a shell in an atmosphere of inactive gas and burning the shell. In particular, the antibacterial agent is obtained by burning a powder from the shell of a surf clam in an atmosphere of inactive gas. The powder can be easily dissolved into water and used as an antibacterial solution.
The above uses of shells demonstrate the vast area of applications in which shell properties can be exploited. Further developments directed to new uses of shell material are desired and needed to manage and reduce the great quantity of shell waste produced every year.
Most of the above-identified applications require the use of crushed shells or a powder obtained from the shells of mollusks, where in all instances, heat treatment under high temperatures are employed, in order to effect calcination upon the shell particles. All of these procedures consequently require expensive equipment and complex set-up procedures to achieve these high temperatures, when in fact, calcination may not be a necessary step in order to reveal the inherent medicinal properties of the shell particles.
Furthermore, a large proportion of therapeutic agents that are prescribed and/or recommended by physicians for skin conditions contain harsh chemicals, such as lower monohydric alcohols i.e. ethanol and isopropanol. However, the abundance of these alcohols in the therapeutic agents often contributes to drying and irritation of the skin where the agent is applied. The lack of these and other additives in the present invention will minimize the adverse RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:14 FAX 819 953 9538 CIPO / PCT OFFICE C7J004/024 30 Dece ber 2008 30-12-2008 effects associated with these chemicals.

SUMMARY OF THE INVENTION
It is an object of the present invention to provide a composition, comprising an extract from mollusk shells, containing mainly calcium, that is safe for the human body and environmentally friendly. Further, this composition inherits the antibacterial, antiviral and ancillary healing properties of the shells and as indicated heretofore may effectively be utilized for the treatment of sldn diseases. Additionalty, it is desired that the composition lOes not cause any significant drying or irritation of the skin.
Moreover, the composition and process of manafaotme thereof of the present invention are simple, and as such, are economically advantageous. Therefore, the ,:,omposition of the present invention can be available to the general public at an affordable -3rice.
According to an aspect of the present invention, there is provided a composition for topical application, comprising an exttaction solution mixed with a pharmaceutically acceptable catrier, wherein the solution is produced by repeatedly filtering a liquid through a i3lter/extrac6on column housing crushed mollusk shell particles.
According to another aspect of the present invention, there is provided a composition for topical application, comprising fine cnished mollusk shell particles mixed with a pharmaceutically acceptable carrier, the crushed molIusk shell particles being boiled and/or baked at a temperatire in the range of 100 C to about 300 C prior to placement in the column.
According to a further aspect of the present invention, there is provided a composition for topical application comprising dissolving fine crushed mollusk shell particles into a solution, the crushed mollusk shell particles being boiled and/or baked at a temperature in the range of 100 C to about 300 C prior to placement in the column.

BRIEF DESCRIPTZON OF T'1-IE DRAWINGS
The above and other features of the present invention will become more apparent from the appended drawings, wherein:
Figure 1 shows a cross-sectional view of the extraction column comprising an inlet, an outlet, and a housing member, AIGUIDSD 8H&aT

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:15 FAX 819 953 9538 CIPO / PCT OFFICE 1A005/024 30 Dsce ber 2008 30-12-2008 Figure 2a is an exploded cross-sectional view of the upper half of the extraction column and illustrates the empty column set-up;
Figare 2b is an exploded cross-sectional view of the upper half of the extraction column and illustiates the column filled with the packing member;

3a Abff.tIDED SHEET

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.. - . .

02 9epte ber 2008 02-09-2006 = =

Figure 3 is an exploded cross-sectional view of the lower half of the extraction column and illustrates the empty column set-up;
Figure 4 illustrates a cross-sectional view of the apparatus comprising two extraction columns in a tandem arrangement;
Figure 5 illustrates the measured turbidity of the extraction solution with exposure time;
Figure 6 illustrates the increase of the amount of calcium det.ermined in the extraction solution with exposure time;
Figure 7 illustrates the changes that occur in pH of the extraction solution with exposure time and also compares the effect utilizing different ratios of shell particles to solvent has on pH;
Figure 8 illustrates the changes that occur in the conductivity of the extraction solution with exposure time and also compares the effect utilizing different ratios of shell particles to solvent has on conductivity;
Figure 9 illustrates the changes that occur of the amount of calcium recovered in the extraction solution with exposure time and also compares the effect utilizing different ratios of shell particles to solvent has on calcium.

DETAILED DESCRIPTION OF THE INVENTION
One component of an embodiment of the present invention is an extraction solution that is mixed with a pharmaceutically acceptable carrier. The process for production of the extraction solution is similar to that which is disclosed in the priority document of the present application, that being Canadian Patent Application No. 2,556,562, and is herein discussed with reference to the Figures.
Fig. 1 illustrates a filter/extraction column (10) comprising an inlet (11), an outlet (13), two screens (14), and a housing member (12). The housing member (12) defines a passageway (1 2a) that can be filled with crushed mollusk shells.
Fig. 2a illustrates an exploded view ofthe upper half ofthe filter/extraction column (10), comprising a top coupling (16), a screw-in stopper (15) and an outlet (13) placed in the stopper (15). A screen (14) may be placed at the top of the housing member (12) in order to contain the cnsshed mollusk shells in the filter/extraction column (10). The top coupling (16) is fitted with a coupling inside lip (17) in order to attach the screen (14) to the housing member. An interchangeable seal (18), such as silicon can be used to inhibit leaking of the column.

ANMBD SHEET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:15 FAX 819 953 9538 CIPO / PCT OFFICE Q007/024 -:- _._..__.. ......._._._._.. _ ._ -.. . . .. .. _.._ .. _ 02 8eptmober 2008 02-09-2008 Fig. 2b illustrates an exploded view ofthe lowerhalfofthe extraction column, comprising tue bottom coupling (16), stopper (15) and an inlet (11) placed in the stopper (15). The bottom coupling can also be fitted with the coupling inside lip (17) in order to attach the screen (14) to the housing member (12) so as to contain the crushed mollusk shells into the filter/extraction column. The inlet (11) is designed for connection to a plastic valve and a pump used to feed the column with a solvent. An interchangeable silicon seal (18) can be used to avoid leaking of the column.
Fig. 3 illustrates the filter/extraction column (10), comprising an inlet (11), an outlet (13), top and bottom identical screens (14), and a housing member (12). The housing member (12) contains crushed mollusk shell particles which may be of equal or different sizes. In one embodiment shown in Fig. 3 the housing member contains at the bottom portion crushed shell particles of sizes between 0.5 and 1 mm in diameter (20) and crushed shell particles of sizes between 3 and 4 mm in diameter (21) in the upper portion. However, the crushed mollusk shells can be comprised of particles of about equal size distributed evenly along the passageway according to the filter/extraction needs in one or a plurality of zones. A
zone is defined as c.ontaining crushed shell particles of approximately the same diameter. The packing of the column with crushed shell particles can follow a regular distribution according to a desired gradient or an irregular distribution.
Fig. 4 illustrates a cross-sectional view of the apparatus (1) according to the present invention and comprises at least two filter/extraction columns (2,3), in a tandem arrangement.
In the two-column apparatus (1) the,filter/extraction columns are arranged linearly so that the outlet (13) of the first column (2) is connected to the inlet (11) of the second column (3) by a connecting tube (23). The housing member (12) of the first column (2) can contain at the bottom thereof crushed shell particles of sizes between 0.5 and i mm in diameter (20), and crushed shell particles of sizes between 3 and 4 mm in diameter (21) thereafter. The housing member (12) of the second colunm (3) may contain crushed shell particles coated with iron oxide or hematite (24). It is believed that coating the crushed shell particles with iron oxide or hematite may substantially improve the purifying properties of the filter/extraction columns by reducing the metal content in the solution passed through the apparatus (1). Analysis of the water passed through the filter/extraction columns apparatus (1) showed nearly zero content of aluminum and arsenic in the extraction solution.

S
ALUlIDED 8A8ET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:15 FAX 819 953 9538 CIPO / PCT OFFICE R008/024 02 9ept ber 2008 02-09-2008 In the practice of the process of the present invention for production of an extraction solution, shells are collected directly off the fishing boat and put in tote boxes for transportation to the manufacturing plant. The sheils are then cleaned by electric drills and wire brushes and throughly washed with water under high pressure to ensure effective cleaning.
The cleaning and washing steps may be followed by a cooling step in which the shells are left on a wire rack for an amount of time necessary to cool the shells to the ambient temperature. In the next.step the saells are then subjected to a heat treatment, by any means known to one sldlled in the art, e.g.
boiling or baking, such that the shells reach a temperature in the range of about 100 C to about 300 C. It is also contemplated within an aspect of the present invention that the shells are subjected to multiple heat treatments, such as boiling and baking, as long as the shells reach the aforesaid temperature range. The main purpose of the beat treatment is to remove any remaining mollusk tissue, to coerce the opening of the intrinsic pores of the shells, and to further expose the inner layer of the shells by eradicating the protective layer. This heat treatment makes the inner layer, which contains the majority of the active ingredients, more susceptible to leaching when used in the above-described apparatus.
At this point, the whole of the shells are crushed by any means known to one skilled in the art. The resulting particles are then separated and sorted according to size by the use of sieves, filters or the like. Scallop shell particles of a size about 1 mm to about 6 mm in diameter are preferably selected, more preferably is a size of about 2 mm to 5 mm in diameter, and most preferably is a size of about 3 mm to 4 mm in diameter. Although particles of a size ranging from aoout 10 m to about 25 mm may be utilized while still remaining within the scope of the present invention. These particles are then introduced into the filter/extraction column. Alternatively, particles of about the same diameter or a mixture of particles with a range of different diameters may be used in the filter/extraction column according to the present invention.
The effectiveness of the extraction solution, and hence, the composition itself, in the tneatment of a variety of sldn conditions will be determined by several factors including the pH
o-Fthe solvent used and the particle size of the crushed shells that form the paclcing members of the extraction column. Preferably, the solvent is water. More preferably, the solvent is distilled water or reverse osmosis purified water. By passing the water through the filter/extraction column (10) one can control, inter alia, the turbidity, the pH, the calcium content, the conductivity and the suspended solids ofthe extraction solution. The number ofpassesi the water flowrate and the ratio of water to shells in the column determine the properties of the extraction solution, and hence the composition itself. The particle diameter of the crushed shells has been AMEMED SHEET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:16 FAX 819 953 9538 CIPO / PCT OFFICE 1A009/024 -c-._... .-- ----- .. . -._...-------_- . -------.. -.- ... _ .. ---...... -I T 02 eeptember 2008 02-09-2008 = . .

shown to be relatively inversely proportionate to the effectiveness of the composition. For example, it is preferred that the particle diameter of the crushed shell be between 1 mm and 6 rnm, more preferably between 2 mm and 5 mm, and most preferably between 3 mm and 4 nun, in order to produce an extraction solution that is effective as a topical composition when combined with an acceptable carrier.
Fig. 5 illustrates the Turbidity vs. Exposure time as determined in Example 1 detailed below. It will be noted that the measured turbidity of the extraction solution decreases as it is subject to exposure time to the filter/extraction column. Tbe turbidity was measured after each pass of solvent tiirough the extraction column. After an exposure time of 12 hours the measured turbidity of the extraction solution was about 2.2 NTU. The above measurements of turbidity are correlated with the measurements of the amount of suspended solids in the extraction solution &fler each pass. Accordingly, as is shown in Table I of Exanzple 1 as time passes the amount of suspended solids decreases from 6 mg/L after the first pass of solvent through the filter/extraction column to about 0 mg/L after 12 hours.
Fig. 6 illustrates the amount of calcium measured after eacb pass of water through the extraction column versus the exposure time. The final extaction solution contains approximately 121 times more calcium than the starting solvent. It is preferred that the calcium content of the extraction solution is higher than 14 mg/L, and more preferably is higher than 20 mg/L. Other factors that can impact upon the effectiveness of the extraction solution, and hence the composition, are the pH and the turbidity of the extraction solution. In order to optimize the effectiveness of the extraction solution, while still making it tolerable to topical application, the pH of the extraction solution is preferably between 6.0 and 10.0, more preferably between 6.5 and 9.0 and most preferably between 7.0 and 8Ø The turbidity should be less than 6 NTU
iJnits.
According to an embodiment of the present invention, a composition is formed when the extraction solution, wherein the extraction solution is pmduced by repeatedly filtering a liquid through a filter/extraction column housing crushed mollusk shell particles, after having attained all of its desired properties through this filtration process, is in admixture with a pharmaceutically acceptable carrier. Specific methods or processes that are used to combine the extraction solution with the pharmaceutically acceptable carrier are not limited, and any sort of mixing method utilizing any sort of known mixing apparatus is contemplated within the scope of the present invention.
A preferred process of mixing the extraction solution with an acceptable carrier comprises RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:16 FAX 819 953 9538 CIPO / PCT OFFICE Z010/024 ,.-.... .--.. --... -..- -------- -- ----- ---..---- -..--_-- _ ... .._....-..-...

02 9epte ber 2008 02-09-2008 Ltilizing a common kitchen mixing apparatus. The extraction solution, in it's entirety, is added incrementally to half of the total weight of the acceptable carrier at the beginning of the process.
After thorough mixing has occurred, the remaining carrier is added and incorporated into the composition. The benefit to this process is that the development of air bubbles within the composition is significantly reduced and it also helps to ensure constant consistency of the product.
The pharmaceutically acceptable carrier of the present invention can be, but is not limited to, a cream, a lotion, a gel, an ointment and a paste. Preferably, the carrier is petrolatum, a base emulsifying ointment or Eucerin. More preferably, the carrier is a base emulsifying ointment cr Eucerin"`''. In an alternate embodiment of the present invention, the carrier may include any combinations of the above-mentioned compounds.
According to an embodiment of the present invention, when the acceptable carrier is Eucerin~', the extraction solution is mixed with the Eucerin" at a ratio of about 1:1 to about 7:1, ty weight. Preferably, the ratio of extraction solution to Eucerin" is 7:1, by weight. The upper 1 mit of these ratios is defined by the ability of the extraction solution to be incorporated into the F?ucerin. At the upper limit of the stated ratios, that being 7:1, the Eucerin"" becomes saturated, and subsequent addition of extraction solution is no longer incorporated. Accordingly, any ratio of extraction solution to Eucerin' that allows for supersaturation of Eucerin" with tie extraction solution resides within the scope of the present invention.
These ratios produce a cream that is easy to apply onto the skin.
According to an embodiment of the present invention when the acceptable carrier is a tase emulsifying ointment, the extraction solution is mixed with the base emulsifying ointment at a ratio of about 0.5:1 to about 7:1, by weight. Preferably, the ratio of extraction solution to base emulsifying ointment is 5:1, by weight. The upper limit of these ratios is defined by the ability of the extraction solution to be incorporated into the base emulsifying ointment. At the upper limit of the stated ratios, that being 7:1, the base emulsifying ointment becomes sahuated, and subsequent addition ofextraction solution is no longer incorporated.
Accordingly, any ratio of extraction solution to base emulsifying ointment that allows for the supersaturation of base emuisifying ointment with the extraction solution resides within the scope of the present invention. These ratios produce a cream that is smooth, easy to apply onto the skin and appears tt) be absorbed with ease through the pores of the skin.

AtMIDSD SHEET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:16 FAX 819 953 9538 CIPO / PCT OFFICE Q011/024 02 September 2008 02-09-2008, According to another embodiment of the present invention, a composition is formed when fine crushed mollusk shell particles are added to a ph.arniaceutically acceptable carrier. In the present invention, "fine cnished mollusk shell particle" is defined as a crushed mollusk shell particle that is less than or equal to 250 m in diameter. More preferably, a fine crushed mollusk chell particle is less than or equal to 150 m in diameter. The pharmaceutically acceptable carrier is as defined above.
The fine crushed mollusk shell particles are prepared according to the crushed mollusk shell particles of the present invention. That is, after the shells have been adequately cleaned, the shells are then subjected to at least one heat treatfnent, by any means known to one skilled in the art, e.g. boiling and/or baking, such that the shells reach a temperature in the range of about 11.00 C to about 300 C. Preferably, the shells are baked at about 300 C for 15 minutes and/or are boiled at about 100 C for 15 minutes prior to placement in the column. The shells are then arushed by any means known to one skilled in the art. The resulting particles are then separated and sorted according to size by the use of sieves, filters or the like. It is during this sorting step that the fine crushed mollusk shell particles are identified. These fine crushed mollusk shell particles are then incorporated into a composition comprising a pharmaceutically acceptable c=.arrier. Preferably, the fine particles are incorporated into the composition at about 0.01% to 0.5%, by weight. More preferably, the fine particles are incorporated into the composition at about 0.03%, by weight. The limitation in regard to the. addition of the fine particles to the composition is that even though the particles are fine, they are still quite granular in nature.
Accordingly, if the fine particles are incorporated into the composition at a higher percentage by weight than the above-mentioned range, it has been found that the use of the composition is limited as it will become excessively abrasive and has an overwhelming tendency to severely dehydrate the sldn when applied.
According to a preferred embodiment of the present invention, a composition is formed when the extraction solution of the present invention is in admixture with a phatmaceutically acceptable carrier, and wherein fine crushed mollusk shell particles are subsequently added to this composition. Similar to the parameters listed above, when the carrier is Eucerin", the ratio of extraction solution to carrier is about 1:1 to about 7:1, by weight.
Preferably, the ratio of extraction solution to EucerinT' is 7:1, by weight. When the carrier is the base emulsifying ointment, the ratio of extraction solution to carrier is about 0.5:1 to about 7:1, by weight.
Preferably, the ratio of extraction solution to base emulsifying ointment is 5:1, by weight. The fine particles are identical to those defined above. Preferably, the fine particles are incorporated AIMIIDSD SBBET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:17 FAX 819 953 9538 CIPO / PCT OFFICE Q012/024 02 Septe¾ober 2008 02-09-2008 into the composition of the present embodiment at about 0.01% to 0.5%, by weight. More preferably, the fine particles are incorporated into the composition at about 0.03%, by weight.
The limitation in regard to the addition of the fine particles to the composition is that even though the particles are fine, they are still quite granular in nature. Accordingly, if the fine particles are incorporated into the composition at a higher percentage by weight than the above-mentioned range, it has been found that the use of the composition is limited as it will become excessively abrasive and has an overwhelming tendency to severely dehydrate the skin when applied.
A further embodiment of the present invention is the use of any of the above-described compositions for topical application. Preferably, the use of any of the compositions according to the present invention is for the treatment of at least one skin condition.
More preferably, the use of the compositions according to the present invention are for the treatment of at least one skin condition, where the at least one skin condition is selected from the group consisting of psoriasis, acne, herpes-zoster, skin diseases associated with varicella-zoster virus, insect bites, insect stings, blisters, xerodeima, burns, sunburns, rashes, athlete's foot, eczema and dermatitis, including contact dermatitis and atopic dermatitis.
According to yet another embodiment ofthe present invention, fine crushedmollusk shell particles are dissolved into an aqueous solution. Preferably, the fine particles are incorporated into the solution at about 5% to 20%, by weight. The aqueous solution may be any solution that is capable of dissolving the above-mentioned amount of fine crushed mollusk shell particles, provided that it is also safe for topical application. Preferably, the aqueous solution is water or the extraction solution. It is contemplated within an embodiment of the present invention that rhis solution that contains dissolved fine crushed mollusk shell particles can be used for the ireatment of at least one skin condition. Preferably, the at least one skin condition is selected :'rom the group consisting of hyperhidrosis and pitted keratolysis.
According to yet another embodiment of the present invention, the extraction solution is ireated with sodium hydroxide (NaOH). Preferably, the NaOH is introduced into the extraction solution of about 0.1% to 4%, by weight. Preferably, the extraction solution has a calcium concentration of about 30 mg/L to > 1000 mg/L. The addition of the NaOH, upon being =horoughly dispersed through the solution, will cause an increase in the pH of the solution, :wulting in the concomitant precipitation of some of the calcium. This extraction solution, :ncluding the precipitated calcium, may be used interchangeably, with any of the extraction ,iolutions as described according to the compositions of the present invention.

AtOIDBD 9HS&T

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:17 FAX 819 953 9538 CIPO / PCT OFFICE IA013/024 02 Septe ber 2008 02-09-2008 . .

Example 1 An extraction column (10) was constructed with a 6 inch diameter 4 feet long PVC pipe with two couplings (16) closing each end as described in Figure 1. The top coupling (16) had a 90 elbow screw-in with a 3/4 inch plastic tube connected thereto. The top coupling (16) and the plastic tube connected to it represent the outlet (13) according to the present invention.
The bottom coupling (16) as constructed had a straight adapter screwed in the coupling stopper and connected to a plastic tube representing the inlet (11) according to the present invention. A 12 V, 360 gallon/hour pump was connected to the inlet of the column (10) and was used to pump distilled water through the column (10). The top and the bottom of the column (10) were designed in the same way except that the bottom coupling (16) had a 3/4 nipple with a 3/4 plastic tube connected to a plastic valve and the 12 V pump. Two screens (14) as shown in Fig.
1 were used to keep the crushed scallop shells inside the passageway (12a).
The composition of the crushed shells was comprised of a mixture of 0.5 and 1 mm e:iameter scallop shell particles. The mass of the smaller particles was approximately 10 kg and be column (10) was filled to within two inches of the screen (14) of the upper coupling. 'ilie rest of the column (10) was filled with larger diameter particles of 3 and 4 mm.
After the first pass of distilled water, the extraction solution had a high suspended solids concentration. The suspended solids concentrations were found to diminish with exposure time.
Table I shows the suspended solids concentration in the solution as measured by the Hach Company DR- 2400 Spectrometer. This method of determining suspended solids is a simple, direct measurement which does not require the filtration or ignition/weighing steps as do gravimetric procedures. While the USEPA specifies the gravimetric method for solids determinations, this method is often used for checking in-plant processes.
Test results are measured at 810 nm. This method is documented in the Hach Water Analysis Handbook, method 8006 page 963.
The accuracy of the spectrometric method of measuring the suspended solids concentration was compared against the gravimetric method as described in the Hach Water Analysis Handbook, method 8271 page 947. The mass of the aluminum dish was measured with E. Scientech 120 analytical balance to the nearest 1 mg. A 100 ml sample from the solution was taken in situ and placed into the aluminum dish. The dish with sample was placed in a preheated crven and evaporated at 103-105 C for approximately six hours. The disb was then taken out of the oven and allowed to cool at room temperature in a desiccator. The dish with sample was then taken out of the desiccator and mass measurements were effected to the nearest 0.1 mg with the I-lGlIDBD SHEBT

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:18 FAX 819 953 9538 CIPO / PCT OFFICE 1N14/024 02 eepte ber 2008 02-09-2008 Scientech 120 analytical balance. This was the first mass measurement of the sample. The dish and sample were put into the preheated oven again for a period of one hour and mass measurements were effected until the results did not differ by more than 0.4 mg. A second lla measurement of the mass was done in the same manner as above. Table 2 below shows the suspended solids concentration in the solution as measured by the gravimetric method.

Total Solids Analysis Table 2 Initial tray lst dried d dried weight Weight diff otal Solids eight eight (g) g) 1 S` and 2na weight g/L
B (A) 0.4 m ra 1 8.1982 8.2109 8.2106 0.0003 0.124 ra 2 8.2245 8.2395 8.2393 0.0002 0.147 Tray 3 8.31 8.3253 8.3250 0.0003 0.15 Tray 4 8.2486 8.2620 8.2620 0.0000 0.144 ra 5 8.2659 8.2805 8.2806 0.0001 0.147 Total Solids Calculations Equation: mg/L Total solids= ( A - B) X 1000 Sample volume ml Where:
A = Weight (mg) of sample + tray B = Weight (mg) of dish % Error of Results % of error =(DhDl) x 100 0.15 mg - 0.124mg) x 100 = 0.5 % error # of data points 5 Where:
Dh = Highest numerical data results obtained D1= Lowest numerical data results obtained Example 2 Two extraction columns (10) were constructed as indicated above in Example 1 (see Fig.
4). The two columns (10) were arranged in tandem with the outlet of the first column (10) directly connected to the inlet of the second column (10). A 12 V, 360 gallon/hour pump was connected to the inlet of the first column (10) and was used to pump distilled water through the first and second column (10).

The packing member of the first column (10) was made of a mix of smaller 0.5 and 1 mm in diameter scallop shell particles. The mass of the smaller particles was about 10 kg while the column should be filled two inches below the screen (14) of the upper coupling (16). The rest of the column (10) was filled with larger diameter particles of 3 and 4 mm as described in Example 1.

The packing member of the second column (10) was made of crushed scallop shell RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:18 FAX 819 953 9538 CIPO / PCT OFFICE 9015/024 02 9epte ber 2008 02-09-2008 particles coated with iron oxide or hematite (Fe2O3). The coating of the crushed shell particles with iron oxide can be effected by any process Imown to a person skilled in the art. In the present invention, the coating of the scallop shells is effected by soaking the shells in iron oxide or hematite for 4 hours, then baldng the shells and solution for 4 hours at 200 C. The shells should then be washed with distilled water and dried in an oven at 200 C for three hours.
Contaminated water with a high content of aluminum and arsenic was passed through the apparatus comprising the two extraction columns arranged in tandem. It has been found in, practice that the aluminum and arsenic content of the resulting extraction solution was reduced to 0 m Example 3 An extraction column (10) was constructed with a 5.08 cm diameter, 79 cm long clear acrylic pipe with two couplings (16) closing each end as descn'bed in Figure 1. The top coupling (16) had a 90 elbow screw-in with a 3/4 inch plastic tube connected thereto.
The top coppling (16) and the plastic tube connected to it represent the outlet (13) according to the present ilvention.
The bottom coupling (16) as constructed had a straight adapter screwed in the coupling (16) stopper and connected to a plastic tube representing the inlet (11) according to the present civention. A 12 V, 360 gallon/hour pump was connected to the inlet of the column (10) and was used to pump distilled water or reverse osmosis-derived water, through the column (10). The top and the bottom of the column (10) were designed in the same way except that the bottom coupling (I6) had a 3/4 nipple with a 3/4 plastic tube connected to a plastic valve and the 12 V
pump. Two screens (14) as shown in Fig. 1 were used to keep the crushed scallop shells inside tae passageway (12a).
Scallop shells were washed and cleaned with distilled water and then dried such that the shells reached a temperature of 100 T. The shells were then crushed, and after sorting based i:pon size, the composition utilized was comprised of a mixture of 3 and 4 mm diameter scallop shell particles. The volume and type of the solvent loaded onto the column (10) was 1 L ofwater.
Two distinct scenarios were tested in regard to the amount of crushed shells in order to optintize running conditions. The amount of shells that was utilized was either A) about 0.35 lb, providing for a ratio of water to scallop shells of about 1 to 0.35 (w/w), or B) about 1 lb, providing for a ratio of water to scallop shells of about I to 1(w/w). The column was filled to within two inches of the screen (14) ofthe upper coupling (16). The water was then successively A1UtIDED SHEET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:18 FAX 819 953 9538 CIPO / PCT OFFICE Q016/024 02 9epte ber 2008 02-09-2008 rin through the column. In both scenarios, the solvent outflow was about 2.16 L/minute.
When the resulting extraction solution was analyzed, there was some variation in the measured parameters according to which ratio of scallop shells to water was utilized. As can be seen from Fig. 7, pH of the solutions are fairly close in value.
Referring now to Fig. 8, the conductivity, measured in micro siemens, is presented for both of the above-mentioned scenarios. The latter scenario (B) where a greater proportion of shells are utilized produced a higher conductivity. The maximum conductivity attained over the observed time frame for both scenarios was (A) 58.9 lr,s/cm and (B) 95.8 s/cm.
In order to understand the relationship between the two different scenarios and conductivity, calcium concentration was measured. As can be seen from Fig. 9, the latter scenario (B) contained a considerably higher calcium concentration than the former scenario (A).
After the final pass of the solution from scenario A through the column, the solution contained 2Ø83 times more calcium than the initial solution, whereas after the final pass of the solution from scenario B through the column (10), the solution contained 32.5 times more calcium than the initial solution.
Referring now to Figure 10, the turbidity, measured in NTU Units, is presented for both af the above-mentioned scenarios. There is a general overall decrease in measured turbidity over time, however, there is very little difference, if any; when a comparison is made between the solutions that were made with different ratios of shell particles to solvent.
Both scenarios were able to achieve values of less than one NTU Unit.

This series of Examples illustrates that the extraction of calcium from the crushed shell particles continues to be more efficient in accordance with an increase in the ratio of crushed shell particles to solvent. It should be noted that ratios of crushed shell particles to solvent other than those listed here are all contemplated within the scope ofthe invention, and should be based upon the desired properties of the resulting extraction solution.

The embodiments of the invention described herein are exemplary and numerous modifications, variations and rearrangements can be readily envisioned to achieve substantially equivalent results, all of which are intended to be embraced within the spirit and scope of the invention.

AIffiID8D SSBET

RECU 11/03/2009 20:21 00223388995 PT4 03/11/2009 15:18 FAX 819 953 9538 CIPO / PCT OFFICE Q017/024 02 8epte ber 2008 02-09-2008 INDUSTRIAL APPLICABILITY
The invention provides a topically applied composition for the treatment of various skin conditions, where an extraction solution is prepared by repeatedly filtering a liquid through a filter/extraction column housing crushed mollusk shell particles and is then in admixture with a pAatmaceutically acceptable carrier. The resulting composition has numerous properties. In particular, this composition can be effectively implemented as treatment for a plethora of skin-associated maladies. Further, the present invention provides an application for an industrial w-aste product, mollusk shells, that are generated in large quantities from fisheries around the world, and it is believed that it would be fiscally and environmentally sound to implement uses of this waste product that is beneficial to the public.

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AMMIDIM SHEET

Claims

1. A composition for topical application, comprising an extraction solution mixed with a pharmaceutically acceptable carrier, wherein the solution is produced by repeatedly filtering a liquid through a filter/extraction column housing crushed mollusk shell particles, the crushed mollusk shell particles being boiled and/or baked at a temperature in the range of about 100 ° C to about 300 °C prior to placement in the column.

2. The composition according claim 1, wherein the liquid is water.

3. The composition according to claim 2, wherein the water is distilled water or reverse osmosis purified water.

4. The composition according to anyone of claims 1 to 3, wherein crushed mollusk shells are boiled at a temperature of at least about 100 °C for a period of about 15 minutes prior to being crushed into particles and placed in the filter/extraction column.

5. The composition according to any one of claims I to 4, wherein crushed mollusk shells are baked at a temperature of at least about 300 °C for a period of about 15 minutes prior to being crushed into particles and placed in the filter/extraction column.

6. The composition according to anyone of claim 1 to 5, wherein the crushed mollusk shell particles are boiled at a temperature of at least about 100 °C
for a period of about 15 minutes prior to placement in the filter/extraction column.

7. The composition according to any one of claims I to 6, wherein the crushed mollusk shell particles are baked at a temperature of at least about 300 °C for a period of about 15 minutes prior to placement in the filter/extraction column.

8. The composition according to any one of claims 1 to 7, wherein the concentration of calcium in the extraction solution is greater than 14 mg/L.

9. The composition according to any one of claims 1 to 8, wherein the concentration of calcium in the extraction solution is greater than 20 mg/L.

10. The composition according to any one of claims 1 to 9, wherein the pH of the extraction solution is between 6 and 10.

11. The composition according to any one of claims 1 to 10, wherein the pH of the extraction solution is between 6.5 and 9Ø

12. The composition according to any one of claims 1 to 11, wherein the pH of the extraction solution is between 7.0 and 8Ø

13. The composition according to any one of claims 1 to 10, wherein the turbidity of the extraction solution is less than 6 NTU.

14. The composition according to any one of claims 1 to 13, wherein the composition further comprises fine crushed mollusk shell particles.

15. The composition according to claim 14, wherein the fine crushed mollusk shell particles have a particle size <= 250 µM in diameter.

16. The composition according to claim 15, wherein the particle size is <= 150 µM in diameter.

17. The composition according to any one of claims 14 to 16, wherein the fine crushed mollusk shell particles are boiled at a temperature of at least about 100 °C for a period of about 15 minutes prior to addition to the composition.

18. The composition according to any one of claims 14 to 17, wherein the fine crushed mollusk shell particles are baked at a temperature of at least about 300 °C for a period of about 15 minutes prior to addition to the composition.

19. The composition according to any one of claims 1 to 18, wherein the extraction solution is treated with sodium hydroxide in an amount of from about 0.1% to 4% by weight of the solution, prior to mixture with the carrier.

20. The composition according to any one of claims 1 to 19, wherein the carrier is a cream.

21. The composition according to any one of claims I to 19, wherein the carrier is a lotion.

22. The composition according to any one of claims 1 to 19, wherein the carrier is an ointment.

23. The composition according to any one of claims 1 to 19, wherein the carrier is a paste.

24. The composition according to any one of claims 1 to 19, wherein the carrier is a get.

25. The composition according to any one of claims 1 to 19, wherein the carrier is petrolatum.

26. The composition according to any one of claims 1 to 19, wherein the carrier is a base emulsifying ointment.

27. The composition according to claim 26, wherein the extraction solution is mixed with the base emulsifying ointment at a ratio from about 0.5:1 to about 7:1, by weight.

28. The composition according to claim 27, wherein the ratio is from about 5:1 to about 6:1.

29. The composition according to any one of claims 1 to 19, wherein the carrier is Eucerin TM

30. The composition according to claim 29, wherein the extraction solution is mixed with Eucerin at a ratio of from about 1:1 to about 7:1, by weight.

31. The composition according to claim 30, wherein the ratio is from about 6:1 to about 7:1.

32. A composition for topical application, comprising fine crushed mollusk shell particles mixed with a pharmaceutically acceptable carrier, wherein the fine crushed mollusk shell particles are baked and/or boiled at a temperature in the range of about 100°C to about 300°C prior to mixing with the carrier.

33. The composition according to claim 32, wherein the fine crushed mollusk shell particles have a particle size <= 250 µM in diameter.

34. The composition according to claim 33, wherein the particle size is <= 150 µM in diameter.

35. The composition according to any one of claim 32 to 34, wherein the fine crushed mollusk shell particles are boiled at a temperature of at least about 100 °C for a period of about 15 minutes prior to being mixed with a pharmaceutically acceptable carrier.

36. The composition according to any one of claims 32 to 35, wherein the fine crushed mollusk shell particles are baked at a temperature of at least about 300 °C for a period of about 15 minutes prior to being mixed with a pharmaceutically acceptable carrier.

37. The composition according to any one of claims 32 to 36, wherein the pharmaceutically acceptable carrier is selected from the group consisting of a cream, a lotion, a paste, a gel, eucerin, petrolatum and a base emulsifying ointment.

38. The composition according to any one of claims 32 or 37, wherein the fine crushed mollusk shell particles are mixed with the carrier at about 0.01% to about 0.5%, by weight.

39. The composition according to any one of claims 32 to 38, wherein the fine crushed mollusk shell perticles are mixed with the carrier at about 0.03%.

19a

40. Use of the composition according to any one of claims I to 39 for the treatment of at least one skin condition.

41. Use of the composition according to claim 40, wherein the at least one skin condition is selected from the group consisting of psoriasis, acne, herpes-zoster, skin diseases associated with varicella-zoster virus, insect bites, insect stings, bums, sunburns, blisters, rashes, xeroderma, athlete's foot and dermatitis.

42. A composition for topical application comprising dissolving fine crushed mollusk shell particles into a solution, wherein the fine crushed mollusk shall particles are baked and/or boiled at a temperate in the range of about 100°C to about 300°C
prior to being dissolved in the solution.

43. The composition according to claim 42, wherein the solution is water.

44. The composition according to claim 42 or 43, wherein the crushed mollusk shell particles have a particle size <= 250 µm in diameter.

45. The composition according to claim 44, wherein the particle size is <= 150 µM in diameter.

46. The composition according to anyone of claim 42 to 45, wherein the fine crushed mollusk shell particles are boiled at a temperature of at least about 100 °C for a period of about 15 minutes prior to being dissolved into solution.

47. The composition according to any one of claims 42 to 46, wherein the fine crushed mollusk shell particles are baked at a temperature of at least about 300 °C for a period of about 1:5 minutes prior to being dissolved into solution.

48. Use of the composition according to any one of claims 42 to 47 for the treatment of at least one skin condition.

49. Use of the composition according to claim 48, wherein the at least one skin condition is selected from the group consisting of hyperhidrosis and pitted keratolysis.