WO2005074729A1

WO2005074729A1 - Filter for reducing the harmful substances present in smoke

Info

Publication number: WO2005074729A1
Application number: PCT/EP2005/000635
Authority: WO
Inventors: Francisco Javier Vila Pahi; Josep Escaich Ferrer; Ramon Ruhi Roura; Purificacion Morales Garcia
Original assignee: Bioiberica, S.A.
Priority date: 2004-01-28
Filing date: 2005-01-21
Publication date: 2005-08-18
Also published as: ES2243125B1; ES2243125A1

Abstract

This invention relates to a filter to reduce the quantity of all or part of the harmful substances present in smoke, which comprises a sulfated polysaccharide or else a mixture of sulfated polysaccharides, in acid form or forming a salt, where the sulfated polysaccharide is selected from the group consisting of chondroitin sulfate, heparin, hyaluronic acid sulfate, keratan sulfate, inulin sulfate, xanthan sulfate, gellan sulfate, pullulan sulfate, curdlan sulfate, alginic acid sulfate, laminarin sulfate, pectin sulfate, dermatan sulfate, and heparan sulfate, where the sulfated polysaccharide may be totally or partially hydrolised. Preferably, the sulfated polysaccharide is chondroitin polysulfate sodium salt and the filter is a tobacco smoke filter.

Description

D E S C R I P T I O N

"Filter for reducing the harmful substances present in smoke"

Technical field of the invention This invention relates to a filter for reducing the harmful substances present in smoke. Moreover, this invention relates to a filter for tobacco smoke, to a method for preparing the filter and to its use. It also relates to a smoking item, more specifically a cigarette. Moreover, this invention relates to the use of a sulfated polysaccharide for treating smoke in the smoking of fish.

Prior State of the Art Smoke emitted by industrial installations and automobiles, as well as the smoke from forest fires, contain substances which pollute the environment and which, due to their toxicity, have a long-term noxious effect on people's health. Another type of smoke, which is equally a cause for concern, is the smoke derived from the combustion of tobacco. Primary smoke is the smoke the smoker introduces into his/her mouth when smoking, and secondary smoke is that which emanates from the lit end of the smoking item, for instance, the cigarette. Tobacco smoke is a very complex mixture. Tobacco contains thousands of different components (approximately 2,500 have been identified in tobacco).

More than 4,000 compounds are formed when tobacco is burnt at variable temperatures with variable oxygen concentrations, among them nicotine, which is the agent that creates addiction, and tar (a solid product formed by a set of substances, most of them carcinogenic). It is estimated that tobacco is responsible for five million deaths a year throughout the world. For smokers, health risks due to the use of tobacco include: lung disease (emphysema, chronic bronchitis, lung cancer), coronary disease

(angina, heart attacks), atherosclerosis and peripheral vascular disease

(aneurisms, hypertension, blood clots, strokes), mouth/dental/gingival diseases

(including oral cancer), other cancers (kidney, bladder, and pancreas) and, in pregnancy, increased foetal death, premature birth, and babies with low weight at birth. For non-smokers who are indirectly exposed to smoke, health risks include: increased risk of lung cancer, compared to those who are not exposed to smoke, and, in babies and children, increased frequency of respiratory infections; this is why it is very important to prepare filters for premises where smoking is allowed. Attempts to reduce the amount of toxic compounds that reach smokers has led to the preparation of tobacco smoke filters which are located between the tobacco that is burnt and the smoker. Conventional filters are prepared with cellulose acetate, with or without activated carbon. However, these conventional filters are only partially efficient in reducing the amount of toxic and carcinogenic compounds. Moreover, those that contain activated carbon are not well received by smokers because they reduce the smoke aroma and taste. In some patents, chemical methods are described for reducing the tar and nicotine in tobacco. These chemical compounds are usually carboxylic acids, metals, and transition metal oxides. EP 673,667 discloses a filtering sheet that comprises a matrix made of polymeric organic material (for instance, paper) with granules of calcium phosphate compounds dispersed throughout. In the description, they mention that the calcium phosphate granules may contain active substances adsorbed on their surface, in order to modify their physicochemical properties and their immunological properties. These active substances may be, for instance, polysaccharides, and, among them, they mention chondroitin sulfate. In addition to not being described in any example, in no case do they mention the use of chondroitin sulfate by itself, without being adsorbed on the calcium phosphate granules, for reducing the harmful substances present in smoke. US 4,242,226 discloses a filter that comprises a product in the form of an activated carbon matrix which has a metal dispersed therein. This product is formed by chemical reaction between a metal's cations and anionic groups that are chemically bonded to a substance that is basically made of a polyhexose derivative, followed by pyrolysis and activation of said product. In the description they mention that polyhexose may be, for instance, inulin, and the anionic groups may be sulfonic acid groups. It is clear that the product contained in the filter is not inulin sulfate; this sulfated polyhexose may be used as raw material that is processed before preparing the filter product. Some patent documents describe tobacco smoke filters that contain alginic acid or alginates. Among these documents, we will cite: JP 7039361, GB 654,994, FR 1,081,215, and JP 56091836. However, so far we have not found any filter disclosed which contains alginic acid sulfate. A sulfated polysaccharide that has been found disclosed for use in manufacturing filters to reduce the harmful substances present in smoke, and more specifically tobacco smoke filters, is cellulose sulfate. Patent US 3,661 ,160 relates to a tobacco smoke filter that comprises ethyl cellulose sulfate sodium salt. However, so far no filter has been found described which contains cellulose polysulfate. Patent US 5,947,127 mentions that carrageenan (a polysaccharide that already contains sulfate groups in its structure) may be included in the tobacco filter as an adhesive. They use this water-soluble polysaccharide in order to avoid the use of plasticizers. We have not found any filter described which contains carrageenan polysulfate. From all of the foregoing, we may conclude that there is a need for an improved filter in order to reduce the amount of harmful substances present in smoke, more specifically in tobacco smoke, which may, in the latter case, maintain a sufficient level of smoke aroma and taste. Thus, providing new filters is an issue of great interest for both human beings and for the environment.

Disclosure of the invention This invention provides a new filter to reduce the amount of all or part of the harmful substances present in smoke, which comprises a sulfated polysaccharide or else a mixture of sulfated polysaccharides, in acid form or forming a salt, where the sulfated polysaccharide is selected from the group consisting of chondroitin sulfate, heparin, hyaluronic acid sulfate, keratan sulfate, inulin sulfate, xanthan sulfate, gellan sulfate, pullulan sulfate, curdlan sulfate, alginic acid sulfate, laminarin sulfate, pectin sulfate, dermatan sulfate, and heparan sulfate, and the sulfated polysaccharide may be totally or partially hydrolised. In a preferred embodiment, the sulfated polysaccharide is selected from the group formed by: chondroitin sulfate; heparin; hyaluronic acid sulfate; keratan sulfate; inulin sulfate; xanthan sulfate; gellan sulfate; pullulan sulfate; curdlan sulfate; alginic acid sulfate; laminarin sulfate; pectin sulfate. In an equally preferred embodiment, the sulfated polysaccharide is a polysulfated polysaccharide selected from the group formed by: chondroitin polysulfate; hyaluronic acid polysulfate; keratan polysulfate; inulin polysulfate; xanthan polysulfate; gellan polysulfate; pullulan polysulfate; curdlan polysulfate; alginic acid polysulfate; laminarin polysulfate; pectin polysulfate. The most preferred polysulfated polysaccharide is chondroitin polysulfate sodium salt. Inulin polysulfate sodium salt is equally preferred. In an equally preferred embodiment, the filter is an industrial filter for the treatment of smoke. In another equally preferred embodiment, the filter is a filter for engine exhaust pipes. In another equally preferred embodiment, the filter is a filter for gas masks. In another equally preferred embodiment, the filter is a filter for premises where smoking is allowed. In another equally preferred embodiment, the filter is a filter for tobacco smoke, with the sulfated polysaccharide preferably in solid form, dispersed throughout the fibrous material, or else, with equal preference, with the sulfated polysaccharide in solid form, in a specific cylindrical section of the filter with the same diameter as the filter. Another aspect of this invention is a method for preparing a tobacco smoke filter, which includes the following stages: (a) preparation of an aqueous solution of the sulfated polysaccharide; (b) application of the aqueous solution to a fibrous material in sufficient quantity for the sulfated polysaccharide to retain the harmful substances arising from the combustion of tobacco; (c) drying of the filter in order for the sulfated polysaccharide to remain in solid form. Another aspect of this invention is an item for smoking tobacco, preferably a cigarette. Another aspect of this invention is the use of a tobacco smoke filter, designed to reduce the amount of all or part of the harmful substances that result from the combustion of tobacco, especially when the harmful substances are the components of tar, as well as toxic gases. Another aspect of this invention is the use of a tobacco smoke filter to reduce nicotine. This invention also relates to a filter to reduce the amount of all or part of the harmful substances present in smoke, which comprises a polysulfated polysaccharide or else a mixture of polysulfated polysaccharides, in acid form or forming a salt, where the polysulfated polysaccharide may be totally or partially hydrolised. The filter is preferably a tobacco smoke filter and the preferred polysulfated polysaccharide is cellulose polysulfate. Carrageenan polysulfate is equally preferred. Yet another aspect of this invention is the use of a sulfated polysaccharide in acid form or a salt thereof selected from the group consisting of chondroitin sulfate, heparin, hyaluronic acid sulfate, keratan sulfate, cellulose sulfate, inulin sulfate, carrageenan sulfate, xanthan sulfate, gellan sulfate, pullulan sulfate, curdlan sulfate, alginic acid sulfate, laminarin sulfate, pectin sulfate, dermatan sulfate, heparan sulfate, and their mixtures, for treating the smoke that is used in the smoking of fish and its derivatives. The sulfated polysaccharides used in this invention are well-known, and may be produced by partial or total sulfonation of the free hydroxyl groups present in the structure of commercial polysaccharides: chondroitin sulfate, heparin, hyaluronic acid, keratan sulfate, cellulose, inulin, carrageenan, xanthan, gellan, pullulan, curdlan, alginic acid, laminarin, pectin, dermatan sulfate, or heparan sulfate. Sulfonation of a hydroxyl group gives rise to the corresponding sulfate group. Chondroitin sulfate, heparin, keratan sulfate, dermatan sulfate, heparan sulfate, and carrageenan are polysaccharides which are already partially sulfated. When in the specifications of this invention we talk about the degree of sulfation this refers to the % of sulfate groups on anhydrous base (with respect to the molecule). When in the specifications of this invention we talk about sulfated polysaccharide, this refers to a sulfated polysaccharide with any degree of sulfation. By polysulfated polysaccharide we understand a sulfated polysaccharide with a high degree of sulfation, which includes the totally sulfated polysaccharide. Sulfated polysaccharides may be totally or partially hydrolised by chemical or enzymatic methods. This invention includes both sulfated oligosaccharides (partial hydrolysis) and disaccharide units (total hydrolysis). Sulfated polysaccharides may be produced by partial or total sulfonation of the free hydroxyls of the above-mentioned commercial polysaccharides, using methods disclosed in the literature, such as for instance by means of chlorosulfonic acid/pyridine (T. Astrup et a/., Ada Physiol. Scand., 8, 215-226 (1944)), or else by means of chlorosulfonic acid/dimethylformamide (P. Vongchan, Carbohydrate Research, 337, 1239-1242 (2002)), or else using piperidine-Λ/-sulfonic acid (N. Kinzo et a/., Carbohyd. Res., 21, 420-426 (1972)), or else using the sulphur trioxide-pyridine complex (C. Mahner et. a/., Carbohyd. Res., 331, 203-208 (2001)). In order to obtain different degrees of sulfation, the above-mentioned methods may be modified (changing the reagent concentrations, the reaction temperature, reaction times, etc.). Also, if so desired, different polysaccharide hydroxyls may be selectively sulfonated, by means of protection/deprotection of the polysaccharide hydroxyls. When, in the specifications of this invention, we say that the sulfated polysaccharide is forming a salt, this refers to a salt of an alkaline metal, such as for instance sodium or potassium, a salt of an alkaline-earth metal, such as for instance calcium or magnesium, or else an organic salt, such as for instance salt with trimethylamine, with triet ylamine, or with an amino acid, such as for instance lysine, arginine, proline, glycine, or serine. Salification of the sulfated polysaccharide may be performed by means of well-known, simple chemical methods. The sulfated polysaccharide or the mixture of sulfated polysaccharides may be added to the fibrous material of a conventional filter in solution or in solid form, or it may be used in powder form or granules as the main filter component. If it is added in solution, the sulfated polysaccharide may be dissolved in water and the resulting solution may be used to pulverise or impregnate the fibrous material of a conventional filter, subsequently drying it in order that the sulfated polysaccharide remains in solid form. In this way, the sulfated polysaccharide will be dispersed throughout the fibrous material of the conventional filter. If it is added in solid form, generally as a powder, the sulfated polysaccharide may be mixed with the fibrous material, subsequently compacting it. In this case, the sulfated polysaccharide will also be dispersed throughout the fibrous material of the conventional filter. It may also be added in solid form such that the sulfated polysaccharide remains in a specific cylindrical section of the filter with the same diameter as the filter. In order to do this, for instance, the filter of a conventional cigarette, made of fibrous material, may be separated from the part of the cigarette which contains the tobacco, without altering the paper that covers said filter, such that an empty cylindrical container remains. The separated filter may be transversely cut in two parts; one of them may be placed once again inside the empty cylindrical container that had remained. The sulfated polysaccharide, or the mixture of sulfated polysaccharides, may be applied in solid form to the part of the conventional filter that has been re-introduced into the paper cylindrical container, forming a cylindrical section with the same diameter as the filter.

Subsequently, the other part of the conventional filter that had been separated may be replaced, in contact with the sulfated polysaccharide section, such that the cylindrical section with the sulfated polysaccharide remains in the inner part of the commercial cigarette filter. The sulfated polysaccharide may also be introduced, in the form of powder or granules, into containers, for instance cigarette holders, which may later be coupled, for instance, to a cigarette, a pipe, or a cigar. In this way, the container may contain the sulfated polysaccharide by itself or it may additionally contain a fibrous support. In this invention, when we talk about tobacco smoking items, this relates, for instance, to cigarettes, pipes, or cigars. One advantage that may be obtained from the invention lies in the fact that the invention filters notably reduce a significant part of the components of tar. Another advantage lies in the fact that when smokers smoke cigarettes containing the invention filters, they do not detect that the tobacco smoke aroma and taste are altered.

Detailed description of the preferred embodiments The following examples are merely for illustration purposes and do not represent a restriction on the scope of this invention. Chemical Examples

Example 1 : Preparation of chondroitin polysulfate sodium salt 1-A: Preparation of chondroitin polysulfate sodium salt using chlorosulfonic acid/pyridine 30 L of pyridine were added to a jacket reactor. 15 L of chlorosulfonic acid were slowly added, while stirring, preventing the solution temperature from exceeding 75°C. 10 kg of chondroitin sulfate (CS oral 100 marketed by

Bioiberica S.A.) mixed with 20 L of pyridine were added to the resulting mixture.

Stirring was continued and it was heated to 90°C; these conditions were maintained for two hours. Subsequently, 250 L of methanol were added and the stirring was maintained for several more minutes, after which the stirring was stopped and it was allowed to decant. The supernatant was separated and the precipitate was dissolved with

100 L of a saline solution at room temperature. It was precipitated once again, by adding methanol, under constant stirring. The stirring was continued for several more minutes and the stirring was stopped. The supernatant was decanted and the precipitate was dissolved with de-ionised water by stirring at room temperature. Salt was added, the pH was readjusted to 5.3, it was heated to 90°C, and hydrogen peroxide was added; these conditions were maintained, while stirring, for 1 h. Once this time elapsed, it was filtered through diatomaceous earth. The resulting solution was ultrafiltered and diafiltered three times through a membrane with a molecular cut-off between 1 ,000 and 5,000 daltons. The final solution was subject to treatment with hydrogen peroxide at a

45°C temperature for 40 minutes, after which sodium chloride was added again, it was stirred until total dissolution, and precipitated with methanol under vigorous stirring. It was allowed to decant, the supernatant was separated and the solid was anhydrated. It was drained and vacuum-dried at 60°C. The dry product was crushed and homogenised. Chondroitin polysulfate sodium salt was produced with an yield greater than 90 %.

Degree of sulfation obtained (total organic sulfates): 41.5% expressed on an anhydrous base.

Free sulfates: < 0.5%

IR (KBr) cm^-1: 3467, 1634, 1235, 1055, 1024, 996, 820 1-B: Preparation of chondroitin polysulfate sodium salt using chlorosulfonic acid/dimethylformamide The preceding method (1-A) was used, but, instead of pyridine, dimethylformamide (DMF) was used. Example 2: Preparation of inulin polysulfate sodium salt With constant stirring, at a temperature < 6°C, 88 mL (1.32 mol; 1.8 eq /OH) of chlorosulfonic acid were added drop by drop to 580 mL (7.20 mol) of dry pyridine. The resulting mixture was heated to 75°C and subsequently 40 g (0.25 mol) of inulin (Fibruline Standar, marketed by Trades S.A.) were added. The stirring and the heating to 100°C were continued for 5 h. Once this time elapsed, the reaction mixture was allowed to cool down to approximately 50°C and 50 mL of de-ionised water were added in order to destroy the chlorosulfonic acid excess. During this step, the ambient temperature was slightly increased and two phases appeared. The crude reaction product was allowed to rest until it reached room temperature. The upper phase (pyridine) was separated by suction, while the oily lower phase was poured over a 10 % solution of sodium acetate in methanol. The precipitate that was formed was allowed to sediment. The supernatant was separated by decanting and discarded. Treatment with the sodium acetate methanolic solution was repeated twice and, in the last step, the solid was separated by vacuum filtering by means of a type k-100 depth filter (Pall Corporation. Seitz-k-100). The produced filter (brown solid) was dissolved in distilled water and the resulting solution was vacuum filtered by means of a k-100 depth filter in order to eliminate the insoluble matter remainders resulting from the reaction. The filtering resulting from the preceding step was a dark amber colour solution which was treated with quaternary ammonium (Quartamin). As a consequence, a very abundant solid was formed which was isolated by vacuum filtering using a Hyflo earth pre-Iayer (100 g). The filter was abundantly washed with distilled water. The inulin polysulfate-Quartamin complex was carefully separated from the filtering earths and treated with a 20 % NaCI aqueous solution, at 80°C, for two hours. Once the two hours of reaction elapsed, the heating was stopped, and when the temperature reached 60°C, isopropanol was added. Stirring was maintained for 30 min. and, subsequently, the mixture was poured into a decanting funnel in order to separate the aqueous phase from the organic one. The organic phase (isopropanol + quaternary ammonium) was discarded. The aqueous phase was vacuum filtered in order to eliminate the Hyflo earth remainders. A mixture of methanol / acetone was poured over the aqueous phase. The brown precipitate that was formed was allowed to sediment. The supernatant was separated by decanting and discarded. The sediment was washed with methanol and subsequently dissolved in de-ionised water. The pH of the resulting solution was adjusted between 10.5-11 with 10% NaOH. The solution was heated to 50°C and was treated for 15 min with H₂O₂. Finally, the heating was stopped and the pH was adjusted to 5.5 with a 2% acetic acid solution. When the decoloured solution reached ambient temperature, a 10% methanol / sodium acetate solution was poured thereon. A white or slightly yellow precipitate was immediately formed which was allowed to sediment. The supernatant was separated by decanting and the sediment was abundantly anhydrated with methanol. The inulin sulfate was separated by vacuum filtering with a No. 3 porous plate and was dried in a vacuum heater at 30°C until the methanol concentration was equal to or lower than 0.3 %. The product was obtained in the form of a fine, amorphous powder, white or slightly yellow in colour.

Determination of the degree of sulfation (organic sulfates) of the obtained inulin polysulfate sodium salt Exactly 150 mg of the product were weighed, they were dissolved in water, and the resulting solution was taken to 250 mL with the same solvent. 5 mL of this solution were pipetted, they were transferred to a 50 mL beaker, and

25 mL of water were added. It was photometrically assessed at 420 nm, with a

0.1% (0.00279 M) Λ/-cetylpyridinium chloride (CPC) solution. The sulfate content was calculated using the following equation: ° ^υ4

Where:

V: Volume of the 0.1% CPC solution consumed, in mL.

W: Weight of the sample, in mg.

PPS: Weight loss by desiccation of the product (105°C, 4 h), in %. Degree of sulfation obtained: 58.0%, expressed on anhydrous base, which corresponds to a completely sulfated inulin molecule (sulfonation of all the hydroxyls)

Free residual pyridine and pyridine in salt form: 127 ppm (the permitted limit is 200 ppm)

Free sulfates: 0.08%

IR (KBr) cm^-1: 2900 (C-O-H), 1247 (S=O), 800 (C-S-O)

Examples of Filter Efficiency

Example 1: Comparison of the efficiency of a conventional filter containing avicel and a conventional filter containing chondroitin polysulfate sodium salt This procedure may be applied to the evaluation of a conventional filter containing any sulfated polysaccharide in the invention. The filter of a commercial cigarette (Ducados or Fortuna brands) was separated from the part of the cigarette containing the tobacco, without altering the paper covering said filter, such that an empty cylindrical container was left. The separated filter was transversely cut in two parts, one of which was re- introduced into the empty cylindrical container that had remained. The solid- state chondroitin polysulfate sodium salt was applied to the part of the conventional filter that had been re-introduced into the cylindrical paper container, forming a cylindrical section with the same diameter as the filter. Subsequently, the other part of the conventional filter that had been separated was put in place again, in contact with the chondroitin polysulfate sodium salt section, such that the chondroitin polysulfate sodium salt cylindrical section remained in the inner part of the commercial cigarette filter. Following the same procedure, a filter was prepared which, instead of chondroitin polysulfate sodium salt, contained avicel (commercial name of a microcrystalline cellulose). In this way, Ducados and Fortuna cigarettes were prepared with modified filters, where, in a specific cylindrical section of the filter with the same diameter as the filter, the chondroitin polysulfate sodium salt or else the avicel were found, in variable quantities (see Table 1). The cigarettes were inserted into an RM 200 model Heinrich-Borwaldt Technik machine, a machine that is especially designed for the analysis of the components of tobacco smoke. The results are shown in Table 1. After a specific number of suctions, the quantity of matter (TPM) retained in the fiberglass filter installed in the machine, and through which all the suctioned smoke passes, i.e. the smoke resulting from the combustion of tobacco and which has passed through the cigarette filter, was determined. The quantity of nicotine and water contained in the fiberglass filter was determined, and these data were used to calculate the quantity of tar (TAR). The results were expressed in mg/cigarette, and the data correspond to the mean of four cigarettes. Table 1 shows the greater efficiency of the filter containing chondroitin polysulfate sodium salt as compared to the one containing avicel, both regarding the reduction in the quantity of nicotine and, especially, the reduction in the quantity of tar. The greater efficiency of the filter may also be observed when we increase the quantity of chondroitin polysulfate sodium salt. Table 1

CPS: Chondroitin polysulfate sodium salt RH: Relative humidity in the experiment room TPM: Total matter retained in a fiberglass filter installed in the machine TAR = tar = TPM - nicotine - water Example 2: Determination of hydrogen cyanide, phenolic compounds, and compounds containing carbonyl groups arising from tobacco smoke, by comparing a filter containing avicel and one containing chondroitin polysulfate sodium salt with a standard filter This procedure may be applied to the evaluation of a conventional filter containing any sulfated polysaccharide in the invention. The method of analysis of cigarette smoke of the Arista Laboratories (www.aristalabs.co.uk) was used. The cigarettes into whose filters avicel or chondroitin polysulfate sodium salt were incorporated were of the commercial brand Marlboro, and the filter preparation procedure is the same as the one described in detail in Example 1 of filter efficiency. The filter of the Kentucky cigarette, reference 2R4F, was taken as standard filter. The results of the determination of phenols are shown in Table 2, those of the determination of compounds containing carbonyl groups are shown in Tables 3 and 4, and the results of the determination of hydrogen cyanide are shown in Table 5. The data obtained correspond to the mean of three cigarettes. All the tables show a greater efficiency of the cigarette whose filter contains chondroitin polysulfate sodium salt, which notably reduces the quantity of all the studied compounds included in the Tables. The suctioned smoke of a cigarette whose filter contains chondroitin polysulfate sodium salt exhibits a lower quantity of the highly toxic and carcinogenic compounds that make up tar (see Tables 2, 3, 4, and 5).

Table 2

CPS: Chondroitin polysulfate sodium salt Table 3 Sample | No. suet | Formaldehyde | Acetaldehyde I Acetone | Acrolein

CPS: Chondroitin polysulfate sodium salt Table 4

CPS: Chondroitin polysulfate sodium salt Table 5

CPS: Chondroitin polysulfate sodium salt Example 3: Comparison between a conventional filter, a conventional filter containing chondroitin polysulfate sodium salt, and a conventional filter containing chondroitin sulfate sodium salt The cigarettes into whose filters chondroitin polysulfate sodium salt (produced following the procedure in Chemical Example 1) or chondroitin sulfate sodium salt (CS oral 100 marketed by Bioiberica S.A.) were incorporated were of the commercial brand Marlboro (red box, King Size Red), and the cigarette filter preparation procedure in Example 1 of the Filter Efficiency was followed. The Marlboro cigarettes with modified filters were compared to commercial Marlboro cigarettes (red box, King Size Red). In order to analyse the components of the tobacco smoke, the procedure described in Example 1 of the Filter Efficiency was followed. In this case, the quantity of carbon monoxide (CO) was also determined, in mg/cigarette, following the standard method. The results are shown in Table 6, where one can observe the greater efficiency of the filter containing chondroitin polysulfate sodium salt or the one containing chondroitin sulfate sodium salt as compared to the conventional filter (Marlboro cigarettes), with a reduction in the amount of nicotine, carbon monoxide, and tar being observed. Table 6

CS: Chondroitin sulfate sodium salt CPS: Chondroitin polysulfate sodium salt CO: Carbon monoxide TPM: Total matter retained in a fiberglass filter installed in the machine TAR = tar = TPM - nicotine - water

Claims

C L A I M S

1. A filter to reduce the amount of all or part of the harmful substances present in smoke, which comprises a sulfated polysaccharide or else a mixture of sulfated polysaccharides, in acid form or forming a salt, where the sulfated polysaccharide is selected from the group consisting of chondroitin sulfate, heparin, hyaluronic acid sulfate, keratan sulfate, inulin sulfate, xanthan sulfate, gellan sulfate, pullulan sulfate, curdlan sulfate, alginic acid sulfate, laminarin sulfate, pectin sulfate, dermatan sulfate, and heparan sulfate, and the sulfated polysaccharide may be totally or partially hydrolised.

2. The filter according to claim 1 , wherein the sulfated polysaccharide is selected from the group formed by: chondroitin sulfate; heparin; hyaluronic acid sulfate; keratan sulfate; inulin sulfate; xanthan sulfate; gellan sulfate; pullulan sulfate; curdlan sulfate; alginic acid sulfate; laminarin sulfate; pectin sulfate.

3. The filter according to claim 1 , wherein the sulfated polysaccharide is a polysulfated polysaccharide selected from the group formed by: chondroitin polysulfate; hyaluronic acid polysulfate; keratan polysulfate; inulin polysulfate; xanthan polysulfate; gellan polysulfate; pullulan polysulfate; curdlan polysulfate; alginic acid polysulfate; laminarin polysulfate; pectin polysulfate.

4. The filter according to claim 3, wherein the polysulfated polysaccharide is chondroitin polysulfate sodium salt.

5. The filter according to claim 3, wherein the polysulfated polysaccharide is inulin polysulfate sodium salt.

6. The filter according to claims 1 to 5, which is an industrial filter for the treatment of smoke.

7. The filter according to claims 1 to 5, which is a filter for engine exhaust pipes.

8. The filter according to claims 1 to 5, which is a filter for gas masks.

9. The filter according to claims 1 to 5, which is a filter for premises where smoking is allowed.

10. The filter according to claims 1 to 5, which is a filter for tobacco smoke.

11. The tobacco smoke filter according to claim 10, wherein the solid-form sulfated polysaccharide is dispersed throughout the fibrous material.

12. The tobacco smoke filter according to claim 10, wherein the solid-form sulfated polysaccharide is found in a specific cylindrical section of the filter with the same diameter as the filter.

13. A method for preparing a tobacco smoke filter, which comprises the following stages: (a) preparation of an aqueous solution of the sulfated polysaccharide in claim 1; (b) application of the aqueous solution to a fibrous material in sufficient quantity for the sulfated polysaccharide to retain the harmful substances resulting from the combustion of tobacco. (c) drying of the filter in order for the sulfated polysaccharide to remain in solid form.

14. Tobacco smoking item which incorporates a filter according to claims 1 to 12.

15. Tobacco smoking item according to claim 14, which is a cigarette.

16. Use of a tobacco smoke filter according to claim 10, in order to reduce the amount of all or part of the harmful substances resulting from the combustion of tobacco.

17. Use according to claim 16, wherein the harmful substances are the com ponents of tar.

18. Use according to claim 16, wherein the harmful substances are toxic gases.

19. Use of a tobacco smoke filter according to claim 10, in order to reduce nicotine.

20. A filter to reduce the amount of all or part of the harmful substances present in smoke, which comprises a polysulfated polysaccharide or else a mixture of polysulfated polysaccharides, in acid form or forming a salt, where the polysulfated polysaccharide may be totally or partially hydrolised.

21. The filter according to claim 20, which is a filter for tobacco smoke.

22. The filter according to claim 20 or 21 , wherein the polysulfated polysaccharide is cellulose polysulfate.

23. The filter according to claim 20 or 21 , wherein the polysulfated polysaccharide is carrageenan polysulfate.

24. Use of a sulfated polysaccharide in acid form or a salt thereof selected from the group consisting of chondroitin sulfate, heparin, hyaluronic acid sulfate, keratan sulfate, cellulose sulfate, inulin sulfate, carrageenan sulfate, xanthan sulfate, gellan sulfate, pullulan sulfate, curdlan sulfate, alginic acid sulfate, laminarin sulfate, pectin sulfate, dermatan sulfate, heparan sulfate, and their mixtures, for the treatment of the smoke used in the smoking of fish and its derivatives.