WO2002000046A1 - Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke - Google Patents

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

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Publication number
WO2002000046A1
WO2002000046A1 PCT/US2000/017452 US0017452W WO0200046A1 WO 2002000046 A1 WO2002000046 A1 WO 2002000046A1 US 0017452 W US0017452 W US 0017452W WO 0200046 A1 WO0200046 A1 WO 0200046A1
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Prior art keywords
group
tobacco
filter
toxin
combinations
Prior art date
Application number
PCT/US2000/017452
Other languages
English (en)
French (fr)
Inventor
Anthony Cerami
Carla Cerami
Peter Ulrich
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.
Priority to ES00941705T priority Critical patent/ES2286026T3/es
Priority to JP2002504839A priority patent/JP4447218B2/ja
Priority to DE60034968T priority patent/DE60034968T2/de
Priority to EP00941705A priority patent/EP1309253B1/en
Priority to DK00941705T priority patent/DK1309253T3/da
Priority to HK03104807.2A priority patent/HK1052440A1/zh
Priority to MXPA03000125A priority patent/MXPA03000125A/es
Priority to AU2000256373A priority patent/AU2000256373A1/en
Priority to CA002414377A priority patent/CA2414377A1/en
Priority to BRPI0017258-8A priority patent/BR0017258B1/pt
Priority to CNB008197873A priority patent/CN1271960C/zh
Priority to PCT/US2000/017452 priority patent/WO2002000046A1/en
Priority to AT00941705T priority patent/ATE362718T1/de
Publication of WO2002000046A1 publication Critical patent/WO2002000046A1/en

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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 lo toxin-removing filter device. Agents may also be incorporated into smolcing and smokeless ⁇ tobacco to prevent volatilization and absorption, respectively, of nucleophilic toxins.
  • Tobacco smoke is a complex mixture which includes numerous chemical compounds and
  • Tobacco smoke contains chemical toxins such as
  • U.S. Patent 5,076,294 provides a
  • U.S. lo 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.
  • U.S. Patent 5,060,672 also describes a filter for specifically removing aldehydes, such as
  • a radical scavenger of 1 aldehydes such as oxidized glutathione or urea, or a compound of high nucleophilic activity
  • Patent 5,706,833 describes a wet-disintegrable filter rod comprising certain water-soluble
  • nucleophile and nucleophilic refer to a
  • an electrophile which is capable of accepting the electron pair, such as an active carbonyl lo 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
  • Toxic products present in tobacco also is enter the body by these methods of using tobacco which do not involve combustion, and
  • nucleophilic toxins present in tobacco and tobacco smoke may be removed from tobacco and 2i tobacco smoke by agents, or filters derivatized with chemical moieties comprising 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.
  • 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 following classes: aldehydes, activated ketones, anhydrides, and active esters. The compound hematein may also be used.
  • 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 i cigarettes, cigars, pipes, as well as in the form of separate filters placed between the tobacco
  • 3 sidestream smoke are aspects of the invention.
  • Such filters may range in size from the filter of a cigarette to replaceable filters is for commercial or industrial air handling systems.
  • Suitable filter matrices bearing substituents that may trap nucleophiles may include
  • a 2i porous filter element such as a cigarette filter may be prepared which comprises an agent 22 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.
  • Activated ketones useful in the practice of the present invention may include ⁇ -dicarbonyl compounds, ⁇ - dicarbonyl compounds, ⁇ -dicarbonyl compounds, and ⁇ , ⁇ -unsaturated ketones.
  • ⁇ -dicarbonyl compounds may include camphorquinone, ninhydrin, phenylglyoxal, and alloxan; ⁇ -dicarbonyl compounds may include 5, 5 -dimethyl- 1,3- cyclohexanedione and dibenzoylmethane; ⁇ -dicarbonyl compounds may include succinylphenone and hydrindantin; and ⁇ , ⁇ -unsaturated ketones may include 1,2- dibenzoylethylene, curcumin, and dicinnamalacetone.
  • Non-limiting examples of anhydrides useful for the present invention include non-polymeric anhydrides such as 2-dodecen-l-ylsuccinic anhydride, bicyclo(2,2,2)oct-7-ene-2,3,5,6- tetracarboxylic dianhydride, diethylenetriaminepentaacetic dianhydride, ethylenediaminetetraacetic dianhydride, and (+)-diacetyl-L-tartaric anhydride.
  • non-polymeric anhydrides such as 2-dodecen-l-ylsuccinic anhydride, bicyclo(2,2,2)oct-7-ene-2,3,5,6- tetracarboxylic dianhydride, diethylenetriaminepentaacetic dianhydride, ethylenediaminetetraacetic dianhydride, and (+)-diacetyl-L-tartaric anhydride.
  • Non-limiting examples of active esters include N- ⁇ -t-butoxycarbonyl-L-alanine-N-hydroxysuccinimide ester, N- ⁇ -t-butoxycarbonyl-L-glutamic- ⁇ -benzyl ester- ⁇ -N-hydroxysuccinimide ester, ⁇ -t- butoxycarbonyl-aminocaproic acid N-hydroxysuccinimide ester, N-hydroxysuccinimidyl- modified agarose, and 6-aminohexanoic acid N-hydroxysuccinimidyl ester-modified agarose.
  • N-hydroxysuccinimidyl-modified agarose is preferred.
  • the device may comprise a porous filter 1 matrix wherein the filter matrix bears chemical substituents which trap nucleophiles, or the
  • 2 filter may comprise a porous matrix and one or more agents that chemically trap
  • aldehydes aldehydes, activated ketones, anhydrides, and active
  • 16 matrices bearing substituents or moieties that may trap nucleophiles include periodate-
  • nucleophilic toxins present in tobacco smoke may be included in a porous filter matrix.
  • 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 following classes: aldehydes, activated ketones, anhydrides, and active esters.
  • the compound hematein may also be used.
  • suitable compounds are recited above.
  • FIGURE 1 is a graph depicting a dose response of the removal of tar, measured colormietricaliy, from cigarette smoke by an agent and device of the present invention.
  • FIGURE 2 is a graph depicting a dose response of the removal of tar, measured gravimetrically, from smoke from two different types of cigarettes by an agent and device of the present invention.
  • FIGURE 3 depicts the removal of tar by a formulation of an agent of the present invention in the fo ⁇ n of granules.
  • FIGURE 4 depicts the removal of staining pigments from tobacco smoke by an agent and device of the present invention.
  • FIGURE 5 depicts a dose response of the removal of mutagens from tobacco smoke by an agent and device of the present invention.
  • FIGURE 6 depicts the removal of nitrosamines from tobacco smoke by an agent and device of the present invention.
  • 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-nitrosopyrrolidine, benzo[a]pyrene, N- nitrosodiethanolamine, and cadmium.
  • mainstream smoke i.e, that which is inhaled from the smoking device.
  • porous, fibrous smoke filters remove a portion of these toxic compounds
  • 17 compounds remain in the inhaled smoke and contribute to enormous morbidity and mortality, is mainly lung and other cancers, other lung diseases such as emphysema, and cardiovascular
  • Nucleophilic compounds present in tar and tobacco smoke include hydrazine and the i aromatic amines 4-aminobiphenyl, 2-naphthylamine, and aniline, among other compounds.
  • toxins 24 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.
  • nucleophile-trapping groups such as aldehydic groups
  • 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.
  • Agents that may be incorporated into a filter matrix capable of trapping nucleophilic compounds may be selected from aldehydes, activated ketones, anhydrides, and active esters.
  • the compound hematein may also be used.
  • Compounds are preferably of low vapor pressure in order to remain within the filter and not become volatilized on exposure to a stream of heated air and tobacco smoke.
  • An insoluble, polymeric nucleophile-trapping agent is preferred.
  • 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 unbixrned 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.
  • Activated ketones may include ⁇ -dicarbonyl compounds, ⁇ -dicarbonyl compounds, ⁇ -dicarbonyl compounds, and ⁇ , ⁇ -unsaturated ketones.
  • ⁇ -dicarbonyl compounds may include camphorquinone, ninhydrin, phenylglyoxal, and alloxan; ⁇ - dicarbonyl compounds may include 5,5-dimethyl-l,3-cyclohexanedione and dibenzoylmethane; ⁇ -dicarbonyl compounds may include hydrindantin and succinylphenone; and ⁇ , ⁇ -unsaturated ketones may include 1,2-dibenzoylethylene, curcumin, and dicinnamalacetone.
  • Non-limiting examples of anhydrides useful in the present invention include the non- polymeric anhydrides 2-dodecen-l-ylsuccinic anhydride, bicyclo(2,2,2)oct-7-ene-2,3,5,6- tetracarboxylic dianhydride, diethylenetriaminepentaacetic anhydride, ethylenediaminetetraacetic dianhydride, and (+)-diacetyl-l-tartaric anhydride.
  • Non-limiting examples of active esters include N- ⁇ -t-butoxycarbonyl-L-alanine-N-hydroxysuccinimide ester, N- ⁇ -t-butoxycarbonyl-L-glutamic- ⁇ -benzyl ester- ⁇ -N-hydroxysuccinimide ester, ⁇ -t- butoxycarbonyl-aminocaproic acid N-hydroxysuccinimide ester, N-hydroxysuccinimidyl- modified agarose, and 6-aminohexanoic acid N-hydroxysuccinimidyl ester-modified agarose.
  • N-hydroxysuccinimidyl-modified agarose is preferred.
  • 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 mayu 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. 1 Prior uses of aldehydes in tobacco smoking articles has been limited to the inclusion of
  • the preferred agent of the present invention is dialdehyde starch. Also known as oxidized
  • starch or polymeric dialdehyde it is prepared by the periodate oxidation of starch, which
  • Dialdehyde starch has been used previously for other applications, such as for increasing the i wet strength of paper, such as tissue paper; for hardening gelatin; for making water-resistant 2 adhesives; and for tanning leather. In enzyme studies, dialdehyde starch has been used to aid
  • 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- hydroxysucc rimidyl groups, such as Sigma Chemical Co. Catalog No. H8635, N- hydroxysuccimmidyl-activated SEPHAROSE(R) or Catalog No.
  • 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 fo ⁇ n 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.
  • the device may be useful to individuals who work or live in an environment in which nucleophilic toxins such as those produced from tobacco smoke may permeate the air, and such individuals wish to gauge their exposure to
  • the device may also be useful to determine the proper time to change a filter
  • the dosimeter is in the
  • nucleophilic toxins they chemically react with and adhere to the agent on the disk.
  • nucleophilic toxins from tobacco smoke are brown-pigmented, the disk will darken in color
  • the device to enhance color production as nucleophilic toxins bind to the agent, hi an another
  • a dosimeter device may comprise an air-collecting system, such as a pump or
  • Toxins present in the introduced air sample bind to the agent,
  • the graduations may be precalibrated depending on the
  • the amount of nucleophilic toxin bound to the column is not limited to the amount of nucleophilic toxin bound to the column.
  • agent within a dosimeter device may be determined by refiectometry to dete ⁇ nine pigment i color density, or by another detector means known to the skilled artisan for determining color
  • An automated device may provide an analog or digital
  • the column configuration of the agent and filter material of the present invention as i described in the dosimeter embodiment may also be used to determine the amount of filter 2 material necessary to effectively remove nucleophilic toxins from a particular smoking 3 device, in order to assist in the manufacture of smoking devices with reduced nucleophilic 4 toxins in the smoke.
  • the resulting length of pigmented 6 filter agent represents the amount of toxins present, and indicates the amount of filter material 7 that must be incorporated into a cigarette filter, for example, in order to effectively remove s toxins from the amount of tobacco present in the smoking device.
  • the agents and filter material of the present invention may also be used to measure the level i of nucleophilic toxins present in smoking or smokeless tobacco and other materials by using 2 the agents and filter materials of the present invention in a dipstick format.
  • a predetermined 3 amount of porous filter material comprising an agent of the present invention may be 4 immersed in a suspension or extract of tobacco leaves, extracted cigarette filters, or another solution suspected of containing pigmented nucleophilic toxins in need of quantitating. After removal, the color intensity of the dipstick may be compared visually to known standards or electronically, by refiectometry, to a pre-established standard curve, to display the toxin level.
  • 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 0.25 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 mis 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 0.25 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 mis 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 ELIS A 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 mis 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.
  • Dialdehyde starch was prepared in granular form using various binders, examples of which
  • dialdehyde starch (lOg) was suspended in 50 mis of distilled water. This solution was boiled for 2 hours until it became a clear yellowish paste. The paste was cooled to room temperature and divided into four 10 ml aliquots. The following amounts of dry dialdehyde starch was then blended into one of each of aliquots: 2 g, 5 g 10 g and 25 g. The materials were then dried at 37 C for 38 hours, and then crushed into granules. All of the different types of granules were sized through a #16 mesh to give a material retained on a #30 mesh. All granules were then dried at 37 C to a constant weight. All granules had moderate-good resistance to crushing.
  • EXAMPLE 4 Removal of Staining Pigments from Tobacco Smoke 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 mn. 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 MgCl 2 , 5 mM glucose-6-phosphate, 500 micromolar NADP and rat liver S9
  • microsomal nucleases in triplicate for 30 minutes at 37 C. The bacteria were then plated on minimal glucose plates. After a 48 hour incubation period at 37 C, the number of revertant mutants on each plate was counted. Each bar in the graph represents the average number of colonies on three plates ⁇ standard deviation.
  • 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 mis 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.
  • 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.
  • Ordinary 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

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  • 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)
PCT/US2000/017452 2000-06-26 2000-06-26 Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke WO2002000046A1 (en)

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ES00941705T ES2286026T3 (es) 2000-06-26 2000-06-26 Metodos y dispositivos para eliminar las toxinas nucleofilas del tabaco y del humo del tabaco.
JP2002504839A JP4447218B2 (ja) 2000-06-26 2000-06-26 タバコ及びタバコの煙からの求核性毒素の除去方法、薬剤及び装置
DE60034968T DE60034968T2 (de) 2000-06-26 2000-06-26 Verfahren und vorrichtung zum entfernen von nukleophilen toxinen aus tabak und tabakrauch
EP00941705A EP1309253B1 (en) 2000-06-26 2000-06-26 Methods and devices for removing nucleophilic toxins from tobacco and tobacco smoke
DK00941705T DK1309253T3 (da) 2000-06-26 2000-06-26 Fremgangsmåder og indretninger til fjernelse af nukleofile toksiner fra tobak og tobaksrög
HK03104807.2A HK1052440A1 (zh) 2000-06-26 2000-06-26 從煙草和煙草演中去除親核毒素的方法、媒劑和裝置
MXPA03000125A MXPA03000125A (es) 2000-06-26 2000-06-26 Metodos, agentes y dispositivos para eliminar las toxinas nucleofilas del tabaco y el humo del tabaco.
AU2000256373A AU2000256373A1 (en) 2000-06-26 2000-06-26 Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke
CA002414377A CA2414377A1 (en) 2000-06-26 2000-06-26 Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke
BRPI0017258-8A BR0017258B1 (pt) 2000-06-26 2000-06-26 método e dispositivo para redução do nìvel de toxinas nucleofìlicas presentes no ar contendo produtos da combustão de tabaco.
CNB008197873A CN1271960C (zh) 2000-06-26 2000-06-26 从烟草和烟草烟雾中除去亲核毒素的方法、试剂和装置
PCT/US2000/017452 WO2002000046A1 (en) 2000-06-26 2000-06-26 Methods, agents and devices for removing nucleophilic toxins from tobacco and tobacco smoke
AT00941705T ATE362718T1 (de) 2000-06-26 2000-06-26 Verfahren und vorrichtung zum entfernen von nukleophilen toxinen aus tabak und tabakrauch

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

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JP (1) JP4447218B2 (enrdf_load_stackoverflow)
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DE102008011671A1 (de) * 2008-02-28 2009-09-10 Krieg, Gunther, Prof. Dr.-Ing. Verfahren und Vorrichtung zur Erkennung von Zigarettenkippen und Zigarettenasche in Getränkeflaschen
ITRM20110051A1 (it) * 2011-02-04 2012-08-05 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.
US11109619B2 (en) 2013-09-06 2021-09-07 Massachusetts Institute Of Technology Filter materials including functionalized cellulose

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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
US8952038B2 (en) * 2010-03-26 2015-02-10 Philip Morris Usa Inc. Inhibition of undesired sensory effects by the compound camphor
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
US10383369B2 (en) * 2017-06-07 2019-08-20 Rai Strategic Holdings, Inc. Fibrous filtration material for electronic smoking article

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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
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GB957783A (en) * 1959-10-14 1964-05-13 British United Shoe Machinery Improvements in or relating to the preparation of collagen fibres
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
US5052415A (en) * 1988-06-13 1991-10-01 B.A.T. Cigarettenfabriken Gmbh Process for the impregnation of fibers of a tobacco smoke filter with dicarboxylic or polycarboxylic acids or anhydrides thereof
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JP2006515211A (ja) * 2003-01-15 2006-05-25 ストライカー コーポレイション ア コーポレイション オブ ザ ステート オブ ミシガン 救急用簡易ベッドの積み降ろし装置
DE102008011671A1 (de) * 2008-02-28 2009-09-10 Krieg, Gunther, Prof. Dr.-Ing. Verfahren und Vorrichtung zur Erkennung von Zigarettenkippen und Zigarettenasche in Getränkeflaschen
DE102008011671B4 (de) * 2008-02-28 2012-04-26 Gunther Krieg Verfahren zur Erkennung von Zigarettenkippen und Zigarettenasche in Hohlkörpern, insbesondere Getränkeflaschen
ITRM20110051A1 (it) * 2011-02-04 2012-08-05 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.
WO2012104887A1 (en) * 2011-02-04 2012-08-09 Hsd Holding Smart Device S.R.L. Use of a reticulated dextran polymer as a filter against the inhalation of substances injurious to the health
US11109619B2 (en) 2013-09-06 2021-09-07 Massachusetts Institute Of Technology Filter materials including functionalized cellulose

Also Published As

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EP1309253B1 (en) 2007-05-23
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
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

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