EP1309253B1 - Methods and devices for removing nucleophilic toxins from tobacco and tobacco smoke - Google Patents

Methods and devices for removing nucleophilic toxins from tobacco and tobacco smoke Download PDF

Info

Publication number
EP1309253B1
EP1309253B1 EP00941705A EP00941705A EP1309253B1 EP 1309253 B1 EP1309253 B1 EP 1309253B1 EP 00941705 A EP00941705 A EP 00941705A EP 00941705 A EP00941705 A EP 00941705A EP 1309253 B1 EP1309253 B1 EP 1309253B1
Authority
EP
European Patent Office
Prior art keywords
tobacco
filter
smoke
air
agents
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00941705A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1309253A1 (en
Inventor
Anthony Cerami
Carla Cerami
Peter Ulrich
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GLYCANEX B.V.
Original Assignee
Cerami Consulting Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cerami Consulting Corp filed Critical Cerami Consulting Corp
Publication of EP1309253A1 publication Critical patent/EP1309253A1/en
Application granted granted Critical
Publication of EP1309253B1 publication Critical patent/EP1309253B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive

Definitions

  • This invention relates generally to methods, devices and agents for the removal of nucleophilic toxins present in tobacco and tobacco smoke.
  • Nucleophilic toxins are removed by the passage of tobacco smoke or air containing tobacco smoke through a nucleophilic toxin-removing filter device.
  • Agents may also be incorporated into smoking and smokeless tobacco to prevent volatilization and absorption, respectively, of nucleophilic toxins. Dosimetry of nucleophilic tobacco combustion products is used to monitor toxin exposure.
  • Tobacco smoke is a complex mixture which includes numerous chemical compounds and particulates which to a major extent are responsible for both the enjoyment of smoking and the dangers to health in so doing.
  • Use of tobacco products, especially smoking, is associated with increased incidence of lung and other types of cancer, emphysema, and cardiovascular disease. Less lethal adverse effects such as tooth discoloration and facial wrinkling also occur.
  • the purported addictive component nicotine, compounds responsible for flavor, and those either proven harmful or believed to be harmful to human health are the purported addictive component nicotine, compounds responsible for flavor, and those either proven harmful or believed to be harmful to human health.
  • Tobacco smoke contains chemical toxins such as carbon monoxide and hydrogen cyanide, and known carcinogens such as formaldehyde and hydrazine. Specific compounds in tobacco smoke may fall into more than one of these categories, such as those responsible for flavor. Methods for reducing the exposure of smokers to these toxic compounds without affecting the flavor of smoke have been sought for many decades.
  • a porous filter is provided as a first line trap for harmful components, interposed between the smoke stream and the mouth.
  • This type of filter often composed of cellulose acetate, both mechanically and by adsorption, traps a certain fraction of the tar present in smoke.
  • This type of filter is present on most cigarettes available, yet it allows a significant amount of harmful compounds to pass into the mouth.
  • Epidemiological data connects use of filtered cigarettes with adverse health effects.
  • U.S. Patent 5,076,294 provides a filter element containing an organic acid, such as citric acid, which reduces the harshness of the smoke.
  • a significant body of art focuses on removing formaldehyde, a prevalent component of tobacco smoke with an established and adverse toxicological profile.
  • U.S. Patent 4,300,577 describes a filter comprising an absorptive material plus an amine-containing component which removes aldehydes and hydrogen cyanide from tobacco smoke.
  • Patent 5,009,239 describes a filter element treated with polyethyleneimine modified with an organic acid, to remove aldehydes from tobacco smoke.
  • U.S. Patent 5,850,840 describes the stabilizing of early glycosylation products in tobacco and tobacco smoke by reaction with compounds such as acetaldehyde.
  • U.S. Patent 4,246,910 describes a filter impregnated with alkali ferrate compounds, or activated carbon or alumina impregnated with potassium permanganate, for removing hydrogen cyanide from tobacco smoke.
  • Patent 5,060,672 also describes a filter for specifically removing aldehydes, such as formaldehyde, from tobacco smoke by providing a combination of an enediol compound, such as dihydroxyfumaric acid or L-ascorbic acid, together with a radical scavenger of aldehydes, such as oxidized glutathione or urea, or a compound of high nucleophilic activity, such as lysine, cysteine, 5,5-dimethyl-1,3-cyclohexanedione, or thioglycolic acid.
  • U.S. Patent 5,706,833 describes a wet-disintegrable filter rod comprising certain water-soluble polymers which serve as disintegrable adhesives.
  • US Patent 5 850 840 describes a filter for removing advanced glycolisation end-products from tobacco smoke.
  • nucleophile and nucleophilic refer to a negative ion or neutral molecule, such as an amino group or primary or secondary amine, that brings an electron pair into a chemical reaction with another molecule or positive ion, called an electrophile, which is capable of accepting the electron pair, such as an active carbonyl group.
  • Nucleophilic compounds will chemically react with compounds bearing active carbonyl groups, such as aldehydes, anhydrides, activated ketones, and active esters.
  • Smokeless tobacco includes tobacco products which are used by methods other than smoking, for instance, as snuff and chewing tobacco. Toxic products present in tobacco also enter the body by these methods of using tobacco which do not involve combustion, and these products are also associated with numerous adverse sequelae of tobacco use.
  • nucleophilic compounds incorporated in a filter were used to trap aldehyde-type toxins in tobacco smoke
  • the nucleophilic toxins present in tobacco and tobacco smoke may be removed from tobacco and tobacco smoke by agents, or filters derivatized with chemical moieties comprising these agents, which chemically trap nucleophilic compounds.
  • Tar, mutagens, and known carcinogens present in tobacco and tobacco smoke may be effectively removed by these agents or filters comprising these agents which chemically traps nucleophilic toxins.
  • agents which trap nucleophilic toxins may be incorporated into air filters to remove tobacco-derived toxins from room air, to reduce exposure to second-hand (sidestream) smoke.
  • the invention described herein provides a method for reducing the level of nucleophilic toxins present in tobacco or in mainstream and/or sidestream tobacco smoke by incorporating agents into the tobacco or passing the tobacco smoke through a filter element comprising agents which chemically react with and trap nucleophilic compounds present in tobacco combustion products.
  • the agents may be admixed with smoking or smokeless tobacco.
  • the filter element may comprise a porous filter matrix wherein the filter matrix bears chemical substituents which trap nucleophiles, or the filter may comprise a porous matrix and one or more agents that chemically trap nucleophiles.
  • Agents with low vapor pressures and high melting points, such as insoluble, polymeric agents, are preferred for use in a smoking device filter.
  • nucleophile-trapping agents of the present invention may comprise or be incorporated into air filters for removing tobacco combustion product toxins from room air.
  • Non-limiting examples of the types of agents that may be added to tobacco, or that comprise or may be incorporated into the filter of the present invention which traps nucleophiles include compounds belonging to the classe of aldehydes.
  • the methods, agents and devices of the present invention while removing toxic nucleophilic compounds from tobacco and tobacco smoke, preferably do not detract from the flavor of the tobacco product.
  • the agents and devices of the present invention may be used with cigarettes, cigars, pipes, as well as in the form of separate filters placed between the tobacco source and the mouth. Removal of toxic nucleophilic compounds from mainstream and sidestream smoke are aspects of the invention.
  • suitable agents will trap nucleophiles present in the tobacco or formed during burning, and not release them when the agent itself burns, during, for example, the smoking of a cigarette.
  • Agents incorporated into smokeless tobacco must be of acceptable low toxicity and stability to achieve the trapping of nucleophilic toxins while present within the oral cavity or other routes of exposure.
  • Filters for use in tobacco smoking devices such as cigarettes or separate cigarette filters are contemplated, as well as filters for use in air treatment or filtration systems through which room or ambient air is actively or passively exposed, to remove nucleophilic toxins therefrom.
  • filters may range in size from the filter of a cigarette to replaceable filters for commercial or industrial air handling systems.
  • Suitable filter matrices bearing substituents that may trap nucleophiles may include periodate-oxidized (dialdehyde) derivatives of the polysaccharides cellulose, starch, agarose, and partially-acetylated cellulose; or other polymers, resins or plastics of suitable porosity for use as a tobacco smoke filter and derivatizable with aldehydic moieties.
  • a porous filter element such as a cigarette filter may be prepared which comprises an agent capable of trapping nucleophilic toxins present in tobacco smoke.
  • Non-limiting example of aldehyde compounds that may be used as the agent in the porous filter or tobacco additive of the present invention include dialdehyde starch, dialdehyde cellulose, adenosine dialdehyde, inosine dialdehyde, O-phthaldialdehyde, aldehyde agarose, and ethylenedioxybis(3-benzaldehyde). Dialdehyde starch is preferred.
  • the device may comprise a porous filter matrix wherein the filter matrix bears chemical substituents which trap nucleophiles, or the filter may comprise a porous matrix and one or more agents that chemically trap nucleophiles.
  • Agents with low vapor pressures and high melting points, such as insoluble, polymeric agents, are preferred for use in a smoking device.
  • the types of agents that is used in the filter of the present invention include compounds belonging to the classe of aldehydes. Non-limiting examples of agents capable of chemically reacting with and trapping nucleophilic compounds present in tobacco smoke are recited above. Passage of tobacco smoke through the device mechanically and adsorptively removes compounds and particulates, and the agent or moieties chemically react with and trap nucleophilic compounds present in the tobacco smoke.
  • Suitable filter matrices bearing substituents or moieties that may trap nucleophiles include periodate-oxidized (dialdehyde) derivatives of the polysaccharides cellulose, starch, agarose, and partially-acetylated cellulose; or other polymers or plastics of suitable porosity for use as a tobacco smoke filter and derivatizable with aldehydic moieties.
  • Agents with low vapor pressures and high melting points, such as insoluble, polymeric agents, are preferred.
  • Non-limiting examples of the types of agents that may be used in the filter of the present invention include compounds belonging to the classe of aldehydes. Non-limiting examples of suitable compounds are recited above.
  • Human carcinogens include benzene, 2-naphthylamine, 4-aminobiphenyl, and the radioactive element polonium-210.
  • Probable human carcinogens include such compounds as formaldehyde, hydrazine, N-nitrosodimethylamine, N-nitrosodiethylamine, N-nitrosopyzrolidine, benzo[a]pyrene, N-nitrosodiethanolamine, and cadmium.
  • Reduction in exposure of individuals to toxic compounds present in tobacco and tobacco smoke may be achieved by the agents and device of the present invention at several points along the route from the tobacco itself to the point of exposure by the individual.
  • Agents may be added to or blended into the tobacco itself, either smoking or smokeless tobacco, which bind and sequester toxins, not permitting them to be leached or absorbed from the smokeless tobacco or not permitting them to be volatilized into the smoke as the tobacco burns.
  • a second stage of intervention is in removing toxic products from the smoke stream. This may be achieved to some extent by toxin-sequestering agents added to the tobacco itself, which before burning act as a filter.
  • a filter placed between the column of combusting tobacco and the mouth, or in a separate device, through which the smoke passes before entering the body.
  • present filters remove particulates, tar, and other components from the smoke.
  • exhaled tobacco smoke or sidestream smoke produced from the burning smoking device and present in the environment may be filtered of toxins by passing ambient room air through or in contact with a material or filter which removes toxins.
  • porous, fibrous smoke filters remove a portion of these toxic compounds by mechanical trapping and adsorption to the fibrous surface. Nevertheless, toxic compounds remain in the inhaled smoke and contribute to enormous morbidity and mortality, mainly lung and other cancers, other lung diseases such as emphysema, and cardiovascular disease including heart attack and stroke. Numerous theories exist relating various pathophysiological disease processes with specific tobacco smoke components. It is apparent from this body of work that tobacco smoke contains toxins which are incompatible with health, and that reduction of the exposure to the body of these toxins is prudent.
  • a significant reduction in the level of mutagens and tar present in tobacco smoke may be achieved without reduction in enjoyment of the product by the use of a filter which in addition to providing a mechanical porous barrier, also traps nucleophilic compounds present in tobacco smoke.
  • Nucleophilic compounds present in tar and tobacco smoke include hydrazine and the aromatic amines 4-aminobiphenyl, 2-naphthylamine, and aniline, among other compounds.
  • the aforementioned smoke components are known mutagens and known or suspected carcinogens.
  • Filter materials capable of trapping nucleophilic toxins from tobacco smoke include a filter in which the filter matrix material bears nucleophile-trapping groups, such as aldehydic groups; alternately, one or more agents capable of trapping nucleophiles may be incorporated into the filter matrix.
  • These toxins may also be removed by incorporating suitable nucleophile-trapping agents directly into the tobacco, and furthermore, these toxins may be removed from smokeless tobacco products by incorporating suitable nucleophile-trapping agents in the smokeless tobacco product.
  • nucleophilic-trapping methods, agents and devices of the present invention which for example comprise aldehydic groups on a filter material, from the significant body of prior art in which electrophilic substances, such as aldehydes, were desirably removed from tobacco smoke by filters comprising nucleophiles.
  • the present invention is essentially the reverse of the prior art.
  • aldehydes in smoke were trapped by amino groups in or on filters; in the present invention, amines in the tobacco smoke are trapped by aldehydes in or on the filters.
  • Suitable filter matrices bearing substituents that may trap nucleophiles may include periodate-oxidized (dialdehyde) derivatives of the polysaccharides cellulose, starch, agarose, and partially-acetylated cellulose; or other polymers, resins or plastics of suitable porosity for use as a tobacco smoke filter and derivatizable with aldehydic moieties.
  • periodate-oxidized (dialdehyde) derivatives of the polysaccharides cellulose, starch, agarose, and partially-acetylated cellulose or other polymers, resins or plastics of suitable porosity for use as a tobacco smoke filter and derivatizable with aldehydic moieties.
  • Suitable compounds for incorporation directly into smoking and smokeless tobacco products comprise those suitable for the intended purpose.
  • suitable agents must have a toxicological profile compatible with the extent of exposure to the individual, and furthermore not interfere with the taste, flavor, or enjoyment of the product.
  • Compounds should be of low toxicity and preferably not absorbed.
  • the agents For incorporation into smoking tobacco to sequester nucleophilic toxins in the tobacco and that formed upon burning, the agents must not interfere with the flavor or enjoyment of the product, the rate of combustion of the smoking product either during or between inhalation, and not release the sequestered toxin when the agent within the tobacco is burned.
  • Nucleophile-binding agents present in the tobacco act in part like a porous filter material for smoke passing through the as-yet unburned portion of the tobacco column.
  • the presence of the toxin-removing material should not interfere with the draw, or resistance to passage of air and smoke, through the tobacco column or filter.
  • Non-limiting examples of aldehyde compounds that may be used in the present invention include dialdehyde starch, dialdehyde cellulose, adenosine dialdehyde, inosine dialdehyde, O-phthaldialdehyde, aldehyde agarose, and ethylenedioxybis(3-benzaldehyde).
  • Polymeric aldehyde compounds are preferred; of these, dialdehyde starch is preferred.
  • the foregoing agents may be prepared in various forms for incorporation into the filter element of the devices of the invention and for use in the methods of the invention. Such forms do not detract from the ability of the agents to bind nucleophilic toxins from tobacco smoke, but permit more facile manufacture of a suitable filter. Numerous methods known to one of skill in the art may be used to prepare the agent in a form suitable for incorporation into a filter, one non-limiting example being a granularized material prepared by comminution of a dried, extruded paste prepared from the agent, such as dialdehyde starch, and a binder, such as cornstarch. Alternate binding agents may include dialdehyde starch itself.
  • aldehydes Prior uses of aldehydes in tobacco smoking articles has been limited to the inclusion of aldehyde compounds as aroma or flavor modifiers.
  • the compounds n-hexenal, n-octanal, n-nonenal, n-decanal, n-tetradecanal, n-heptanal, n-undecanal, and n-dodecanal were incorporated into the tobacco or filter material in accordance with U.S. Patent 4,627,449, in order to improve the aroma and taste of the tobacco smoke and particularly the aroma of sidestream smoke, i.e., the smoke which passes from the burning tobacco directly to the environment.
  • These compounds are volatilized from the tobacco into the smoke to mask the adverse odors of burning cigarettes. Their vapor pressures make them unsuitable for use in the present invention as they would be volatilized and lost from the filter and unable to trap nucleophiles from tobacco smoke.
  • dialdehyde starch Also known as oxidized starch or polymeric dialdehyde, it is prepared by the periodate oxidation of starch, which produces free aldehyde groups that may react with nucleophiles such as alcohols, amines, hydrazines, hydrazides, and other reagents that condense with aldehydes.
  • Dialdehyde starch may be obtained from any of a number of chemical suppliers, such as Sigma Chemical Company (Catalog No. P9265) or a manufacturer, Monomer-Polymer & Dajac Laboratories, Inc.
  • Dialdehyde starch has been used previously for other applications, such as for increasing the wet strength of paper, such as tissue paper; for hardening gelatin; for making water-resistant adhesives; and for tanning leather.
  • dialdehyde starch has been used to aid in the attachment of proteins to polymer surfaces, by chemically reacting with hydroxyl groups of a polymer film. It was further used directly as a polymer surface-modifying agent in U.S. Patents 5,281,660 and 5,563,215 to enable biologically active molecules and subsequently cells to bind to the modified surface without altering the biological properties of the molecules.
  • Moderate heat treatment 50°C to 150°C was necessary in order for the dialdehyde starch to bind to the polymer surface.
  • agents suitable for the practice of the present invention may be selected from polymers such as agarose (e.g. SEPHAROSE(R)), cellulose, chitosan, dextran (e.g., SEPHADEX(R)), polyvinylpyrrolidone, and the like, which may be chemically derivatized to provide free nucleophile-trapping groups.
  • agarose may be derivatized to contain N-hydroxysuccinimidyl groups, such as Sigma Chemical Co. Catalog No. H8635, N-hydroxysuccinimidyl-activated SEPHAROSE(R) or Catalog No. A9019, 6-aminohexanoic acid N-hydroxysuccinimide ester coupled to SEPHAROSE(R).
  • Aldehyde-agarose (Sigma Chemical Co. Catalog No. A9951) may also be used; one method of preparation involves derivatization of agarose with 4-aminobutyraldehyde diethyl acetal, and subsequent mild acid hydrolysis of the acetal to generate the aldehyde (Korpela and Hinkkanen, 1976, Analytical Biochem. 71:322-323).
  • insoluble polymers recited above may also be used directly as the filter material of the present invention.
  • the device of the present invention may be prepared by any one of several methods known to the skilled artisan wherein the toxin-removing agent or agents are incorporated into an air filter or tobacco smoke filter at any of a number of stages in the manufacturing process.
  • an agent or agent so the present invention may be mixed with the raw material comprising the mechanical filter and then co-extruded or spun to form fibers comprising filter material and the toxin-removing agent, which may then be made into filters.
  • extruded or spun fibers comprising the filter material may be coated with a molten agent or agents of the present invention, or a solution of the agent or agents in a suitable solvent, prior to the manufacture of the filters.
  • the agent may be dissolved or suspended in a plasticizer and they sprayed onto the filter fibers.
  • the filter devices of the present invention may be prepared from existing mechanical filters by preparing a solution or suspension of the agent or agents in a solvent, absorbing the solvent into the porous filter material, and then removing the solvent by evaporation, drying, freeze-drying, lyophilization, critical point drying, or another suitable method.
  • the filter material would retain its mechanical properties as a barrier to particulate materials and an extensive surface to which tar may be adsorbed.
  • an agent of the invention may be prepared in a granular form for incorporation into the filter of a smoking device. Binding agents such as cornstarch or gum arabic may be used to aid in the preparation of granules.
  • dialdehyde starch is used as the nucleophilic-toxin-trapping agent
  • dialdehyde starch itself may be used as the binder to granulate dialdehyde starch in an active nucleophilic-toxin-trapping form.
  • the filter material itself for example, cellulose acetate
  • the filter material itself, for example, cellulose acetate
  • cellulose acetate may be prepared and chemically derivatized to contain aldehyde groups, following standard methods.
  • cellulose may be partially acetylated or a certain percentage of the acetate groups on cellulose acetate may be hydrolyzed by treatment at high pH. The resulting partially-acetylated cellulose then may be subjected to periodate oxidation.
  • the cellulose acetate may retain its fibrous and porous filter characteristics while also bearing aldehyde substituents capable of trapping nucleophilic toxins in tobacco smoke.
  • Other polysaccharides with filter-like properties such as cellulose, agarose, and the like may also be periodate treated to produce free aldehyde groups.
  • the filter material will retain its mechanical filtration properties, by providing a mechanical barrier and extensive surface area to which tar may be adsorbed, in addition to its nucleophile-binding activity.
  • air filters available for these systems to filter particulates and other air contaminants may be prepared which also contain an agent or agents of the present invention; alternatively the filter material itself may be derivatized or be prepared from an agent of the present invention, such that the air filter retains its mechanical filtration properties and in addition has the ability to remove nucleophilic toxins from the air.
  • Similar filters or replaceable filter cartridges may be prepared for smaller units, such as those used to filter or purify the air in a single room or shared air space, automobile, bus, train, car, aircraft passenger compartments, racetracks, gambling and off-track betting parlors, bars, saloons, and similar areas in which tobacco products, especially smoking tobacco products, are used, and in some instances in which exposure to sidestream smoke is of particular concern to nonsmokers present therein.
  • a personal air filtration system similar in construction to a gas mask or face mask, may also be prepared using a filter device of the present invention, for individuals in proximity to such areas but seeking personal protection from the harmful effects of sidestream smoke.
  • the filter agent of the present invention would not be expected to remove aldehydes from tobacco smoke, such as formaldehyde, unless the compounds also possess a group which may be trapped by an aldehyde.
  • trapping of amines by the filter agent of the present invention may produce new functional groups which may then be capable of absorbing, trapping, and chemically inactivating aldehydes and nitrosamines.
  • Cigarette smoke was filtered through 250 mg portions of each of the compounds listed in Table I. In order to achieve adequate draw with filters made from dialdehyde starch and oxidized starch, these compounds were deposited onto cellulose acetate fibers which had been spread out into swatches 0.64-7.6 cm (0.25 by 3 inches). The treated fibers were then dried overnight at 37 C. The smoke from one cigarette was drawn through the filter material and then through 3 mls of distilled water using a water-pipe smoking device which was constructed from a 25 ml glass Erlenmeyer flask attached to a vacuum source with an air flow rate of approximately 35 ml/min.
  • cellulose acetate filter fibers were spread out into a swatch 0.64 cm by 7.6 cm (0.25 inches by 3 inches) and then coated with the following amounts of dialdehyde starch suspended in distilled water: 250 mg, 125 mg, 25 mg and 0 mg. The treated fibers were dried at 37 C overnight and then made into a tobacco cigarette using a tube cigarette maker.
  • the smoke from 1 of each type of filter cigarette was then drawn through 3 mls of distilled water using a water-pipe smoking device which was constructed from a small (25 ml) glass Erlenmeyer flask attached to a vacuum source with an air flow rate of approximately 35 ml/min. Three 100 microliter aliquots were removed from each flask, placed into ELISA plated wells and read in an ELISA plate reader at 405 nm.
  • Cellulose acetate filter fibers were spread out into a swatch 0.25 inches by 3 inches and then coated with the following amounts of dialdehyde starch suspended in distilled water: 250 mg, 125 mg, 100 mg, 50 mg, 25 mg and 0 mg.
  • the treated fibers were dried in a 37 C oven overnight and then made into a tobacco cigarette using a tube cigarette maker.
  • the smoke from five of each type of filter cigarette was then drawn through 5 mls of acetone using a water-pipe smoking device which was constructed from a small (25 ml) glass Erlenmeyer flask attached to a vacuum source with an air flow rate of approximately 35 ml/min.
  • Figure 2 indicates that filters containing an agent of the present invention can remove over 90% of the tar from both "light” and “regular” tobaccos. If over 250 mg/filter is used, tar is still removed, but the "drag" may be judged too difficult by the typical smoker.
  • Dialdehyde starch was prepared in granular form using various binders, examples of which are described below.
  • Cellulose acetate filters were spread out into swatches of 0.25 inches by 3 inches and then coated with 250 mg or 0 mg of dialdehyde starch suspended in distilled water. The treated fibers were then dried in a 37°C oven overnight and then made into a tobacco cigarette. The smoke from 2 of each type of cigarette was drawn into 1 ml of Phosphate Buffered Saline and the placed immediately on ice. Each sample was then applied to ELISA plate wells coated with 5% non-fat milk (100 microliters/well). Plates were incubated for 3 days @ 37°C and then washed four times with 0.05% Tween/PBS. Pigments which remained bound to the wells were then solubilized in 100 microliters DMSO. Absorbance was then read at 405 nm. Results in Figure 4 show the average of three wells ⁇ standard deviation.
  • a bacterial mutagenicity assay was performed as described by Ames et al. (Maron DM and Ames BN. 1983. Revised methods for the Salmonella mutagenicity assay. Mutation Research 113:173-215). Briefly, Salmonella strain TA98 was cultured overnight at 37 C in Oxoid nutrient broth #2, incubated with serial dilutions of cigarette smoke condensate from the following filter cigarettes: 250 mg dialdehyde starch/filter, 125 mg dialdehyde starch/filter, and 0 mg/filter diluted in 0.1 M sodium phosphate, pH 7.4 containing 33 mM KC1, 8 mM MgC1 2 , 5 mM glucose-6-phosphate, 500 micromolar NADP and rat liver S9 microsomal nucleases, in triplicate for 30 minutes at 37 C.
  • Tester strain TA 98 detects frameshift mutations, such as those generated by aromatic primary amines. Mutagens in the sample are detected as the number of bacteria induced to revert to their wild-type phenotype.
  • Figure 5 shows that increasing amounts of dialdehyde starch present in the cigarette filter result in a decrease in the mutagenicity of the smoke extract. Using the 250 mg filter, the number of revertants was no different than the negative control.
  • Cellulose acetate filter fibers were spread out into a swatch 0.25 inches by 3 inches and then coated with 250 mg of dialdehyde starch suspended in distilled water. The treated fibers were dried at 37 C overnight and then made into a tobacco cigarette using a tube cigarette maker. The smoke from one of each type of filter cigarette was then drawn through 3 mls of distilled water using a water-pipe smoking device which was constructed from a small (25 ml) glass Erlenmeyer flask attached to a vacuum source with an air flow rate of approximately 35 ml/min.
  • Figure 6 shows that 250 mg of the agent of the present invention diminished the level of nitrosamines in the tobacco smoke extract by several fold.
  • a double-blind taste test was performed on 12 individuals in an office environment in a large city. The subjects were asked to fill out a brief questionnaire inquiring about their age, years of smoking, daily usage and preferred brand. After answering these questions, the subjects then lit two cigarettes, one with the filter of the present invention comprising dialdehyde starch, and one with a regular filter. As they smoked the cigarettes side by side, they were asked to record which cigarette was preferred and to describe any differences perceived between the two.
  • the average age of the participants was 41 years, average duration of smoking 18.4 years, and each smoked on average 25.7 cigarettes per day. Eight of the twelve participants preferred the test cigarette with the dialdehyde starch filter over the control cigarette, and four individuals did not prefer one cigarette over the other.
  • Cigarettes with cellulose acetate filters or with filters comprising an agent of the present invention were evaluated an independent laboratory for total particulate matter, nicotine, tar, water and carbon monoxide, according to the standardized FTC method.
  • the cigarettes tested were made by treating cellulose acetate filters with 250 mg dialdehyde starch (DAS) in distilled water ("DAS Filter Cigarettes”). The treated fibers were dried overnight and incorporated into cigarettes using a tube cigarette maker.
  • DAS Filter Cigarettes 250 mg dialdehyde starch
  • the treated fibers were dried overnight and incorporated into cigarettes using a tube cigarette maker.
  • two types of control cigarettes were run: the standard "Kentucky Reference” cigarettes (provided by Lab Stat, Kitchener, Ontario, Canada) and "Ordinary Cigarettes" which were constructed in the laboratory of the inventors.
  • Cigarettes were constructed the same way as the filter cigarettes of the invention and they contain the same amount of tobacco and cellulose acetate fibers, but do not contain the filter additive.
  • Results shown indicate that 58% of this group of smokers thought the DAS filtered cigarette was a regular cigarette, 33% thought it was a light cigarette and 8% thought it was an ultralight cigarette. Taken together the taste test results demonstrate that the DAS filtered cigarettes not only taste like ordinary cigarettes (unlike other "safer” cigarettes), but are also preferred by smokers.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)
  • Manufacture Of Tobacco Products (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
EP00941705A 2000-06-26 2000-06-26 Methods and devices for removing nucleophilic toxins from tobacco and tobacco smoke Expired - Lifetime EP1309253B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2000/017452 WO2002000046A1 (en) 2000-06-26 2000-06-26 Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke

Publications (2)

Publication Number Publication Date
EP1309253A1 EP1309253A1 (en) 2003-05-14
EP1309253B1 true EP1309253B1 (en) 2007-05-23

Family

ID=21741534

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00941705A Expired - Lifetime EP1309253B1 (en) 2000-06-26 2000-06-26 Methods and devices for removing nucleophilic toxins from tobacco and tobacco smoke

Country Status (13)

Country Link
EP (1) EP1309253B1 (enrdf_load_stackoverflow)
JP (1) JP4447218B2 (enrdf_load_stackoverflow)
CN (1) CN1271960C (enrdf_load_stackoverflow)
AT (1) ATE362718T1 (enrdf_load_stackoverflow)
AU (1) AU2000256373A1 (enrdf_load_stackoverflow)
BR (1) BR0017258B1 (enrdf_load_stackoverflow)
CA (1) CA2414377A1 (enrdf_load_stackoverflow)
DE (1) DE60034968T2 (enrdf_load_stackoverflow)
DK (1) DK1309253T3 (enrdf_load_stackoverflow)
ES (1) ES2286026T3 (enrdf_load_stackoverflow)
HK (1) HK1052440A1 (enrdf_load_stackoverflow)
MX (1) MXPA03000125A (enrdf_load_stackoverflow)
WO (1) WO2002000046A1 (enrdf_load_stackoverflow)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1585474B1 (en) * 2003-01-15 2010-11-10 Stryker Corporation Ambulance cot loading and unloading device
EP1856991B1 (en) * 2005-02-02 2014-12-31 Daicel Chemical Industries, Ltd. Cigarette filter material and cigarette filter
JP4739875B2 (ja) * 2005-09-13 2011-08-03 ダイセル化学工業株式会社 たばこフィルターの製造方法
DE102008011671B4 (de) * 2008-02-28 2012-04-26 Gunther Krieg Verfahren zur Erkennung von Zigarettenkippen und Zigarettenasche in Hohlkörpern, insbesondere Getränkeflaschen
US8952038B2 (en) * 2010-03-26 2015-02-10 Philip Morris Usa Inc. Inhibition of undesired sensory effects by the compound camphor
IT1404015B1 (it) * 2011-02-04 2013-11-08 Hsd Holding Smart Device S R L Uso di un polimero di destrano reticolato come filtro contro l'inalazione di sostanze nocive per la salute
JP5882775B2 (ja) * 2012-02-13 2016-03-09 株式会社Adeka セルロース系樹脂組成物及びフィルム
ES2935037T3 (es) * 2013-09-06 2023-03-01 Massachusetts Inst Technology Materiales de filtro que incluyen celulosa funcionalizada
US10383369B2 (en) * 2017-06-07 2019-08-20 Rai Strategic Holdings, Inc. Fibrous filtration material for electronic smoking article

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3063892A (en) * 1959-10-14 1962-11-13 United Shoe Machinery Corp Preparation of hide fiber
US3346519A (en) * 1964-11-12 1967-10-10 Hawley Products Co Process of adhering anionic and non-ionic substances to anionic substances
DE2230118A1 (de) * 1972-06-21 1974-01-24 Heinrich Borgwaldt Fa Verfahren zur herstellung von filtern fuer tabakwaren
DE3820089A1 (de) * 1988-06-13 1989-12-14 Bat Cigarettenfab Gmbh Verfahren zur impraegnierung von fasern eines tabakrauchfilters mit di- oder polycarbonsaeuren bzw. anhydriden derselben
US5706833A (en) * 1993-07-13 1998-01-13 Daicel Chemical Industries, Ltd. Tobacco filters and method of producing the same
DE4416101C2 (de) * 1994-04-19 1997-06-12 Reemtsma H F & Ph Tabakerzeugnisse oder Tabakerzeugnissen ähnliche Waren mit antioxidativ wirkenden Naturstoffen und Verfahren zur Herstellung derselben
US5850840A (en) * 1995-11-15 1998-12-22 Alteon Inc. Methods for measurement and treatment predicated on the presence of advanced glycosylation endproducts in tobacco and its combustion byproducts
US6119701A (en) * 1998-02-13 2000-09-19 Cerami Consulting Corp. Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke

Also Published As

Publication number Publication date
MXPA03000125A (es) 2004-12-06
JP4447218B2 (ja) 2010-04-07
EP1309253A1 (en) 2003-05-14
CN1271960C (zh) 2006-08-30
DE60034968D1 (de) 2007-07-05
BR0017258B1 (pt) 2011-03-22
HK1052440A1 (zh) 2003-09-19
CN1454063A (zh) 2003-11-05
ATE362718T1 (de) 2007-06-15
CA2414377A1 (en) 2002-01-03
DE60034968T2 (de) 2008-01-24
WO2002000046A1 (en) 2002-01-03
ES2286026T3 (es) 2007-12-01
DK1309253T3 (da) 2007-09-17
JP2004500901A (ja) 2004-01-15
BR0017258A (pt) 2004-01-06
AU2000256373A1 (en) 2002-03-28

Similar Documents

Publication Publication Date Title
US6119701A (en) Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke
US6615842B1 (en) Methods for removing nucleophilic toxins from tobacco smoke
KR100302955B1 (ko) 담배필터및그제조방법
US6615843B2 (en) Tobacco smoke filter and relative composition made of antioxidant and mineral substances
JP3966856B2 (ja) タバコ主流煙からｐ−ベンゾセミキノンを減少させる活性炭フィルタ
PT756461E (pt) Produtos do tabaco ou artigos semelhantes contendo substancias naturais com propriedades antioxidantes e processo para producao dos mesmos
JP3145702B2 (ja) 喫煙組成物
EP1309253B1 (en) Methods and devices for removing nucleophilic toxins from tobacco and tobacco smoke
Haussmann et al. Comparison of fresh and room-aged cigarette sidestream smoke in a subchronic inhalation study on rats
US20090126747A1 (en) Plant extracts and uses thereof in filter systems
US6796312B2 (en) Process and apparatus for the removal of toxic components of tobacco smoke and the standardization of the health hazards related to those components
Rosenkrantz et al. Acute and subacute inhalation toxicity of Turkish marihuana, cannabichromene, and cannabidiol in rats
US20240315323A1 (en) Reduction of amines and nitrosamines in cigarette smoke vapors through a filter functionalized with olive tree polyphenols
CN101238913B (zh) 一种有效截留重金属元素的卷烟滤嘴及其制造方法
CN1907156A (zh) 从烟草和烟草烟雾中除去亲核毒素的装置
US3602233A (en) Smoking device incorporating microporous glass particle filter
DE1517297C (de) Rauchfilter fur Tabakwaren
Stratton et al. Tobacco Smoke and Toxicology
JPH02100663A (ja) たばこ煙用フィルター
JPH03160979A (ja) たばこ煙用フィルター
Dalhamn for instance the mucus transport, the ciliary activity, and the free lung cells are
WO2010053580A2 (en) Reducing the risk of smoke-related disease
Dalhamn CHRONIC PULMONARY DISEASE-THE ETIOLOGICAL FACTORS IN SMOKE
CZ58996A3 (cs) Způsob odstraňování škodlivých oxidačních a karcinogenních těkavých nitrososloučenin z cigaretového kouře za použití biologických látek

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20030120

AK Designated contracting states

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIN1 Information on inventor provided before grant (corrected)

Inventor name: CERAMI, CARLA

Inventor name: CERAMI, ANTHONY

Inventor name: ULRICH, PETER

17Q First examination report despatched

Effective date: 20050321

RTI1 Title (correction)

Free format text: METHODS AND DEVICES FOR REMOVING NUCLEOPHILIC TOXINS FROM TOBACCO AND TOBACCO SMOKE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070523

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: GLYCANEX B.V.

REF Corresponds to:

Ref document number: 60034968

Country of ref document: DE

Date of ref document: 20070705

Kind code of ref document: P

NLT2 Nl: modifications (of names), taken from the european patent patent bulletin

Owner name: GLYCANEX B.V.

Effective date: 20070704

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: E. BLUM & CO. AG PATENT- UND MARKENANWAELTE VSP

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070523

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2286026

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070630

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20071023

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20080226

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070824

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20070523

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070626

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090625

Year of fee payment: 10

Ref country code: CH

Payment date: 20090630

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20090713

Year of fee payment: 10

Ref country code: GB

Payment date: 20090701

Year of fee payment: 10

Ref country code: DE

Payment date: 20090629

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20091228

Year of fee payment: 10

Ref country code: DK

Payment date: 20091223

Year of fee payment: 10

REG Reference to a national code

Ref country code: HK

Ref legal event code: WD

Ref document number: 1052440

Country of ref document: HK

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20091222

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20091229

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20100104

Year of fee payment: 10

BERE Be: lapsed

Owner name: GLYCANEX B.V.

Effective date: 20100630

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20110101

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Ref country code: CH

Ref legal event code: PL

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100626

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20110228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110101

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110715

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110705

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100627