EP1213977A1 - Filtering method and filter consisting of nitrogen-containing cycles or heterocyles such as dna or rna designed in particular for filtering tobacco smoke and cigarette containing such a filter - Google Patents

Filtering method and filter consisting of nitrogen-containing cycles or heterocyles such as dna or rna designed in particular for filtering tobacco smoke and cigarette containing such a filter

Info

Publication number
EP1213977A1
EP1213977A1 EP00962594A EP00962594A EP1213977A1 EP 1213977 A1 EP1213977 A1 EP 1213977A1 EP 00962594 A EP00962594 A EP 00962594A EP 00962594 A EP00962594 A EP 00962594A EP 1213977 A1 EP1213977 A1 EP 1213977A1
Authority
EP
European Patent Office
Prior art keywords
filter
molecules
nitrogen
active principle
dna
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.)
Granted
Application number
EP00962594A
Other languages
German (de)
French (fr)
Other versions
EP1213977B1 (en
Inventor
Frédéric MAILLARD
Guy Hadad
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of EP1213977A1 publication Critical patent/EP1213977A1/en
Application granted granted Critical
Publication of EP1213977B1 publication Critical patent/EP1213977B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive

Definitions

  • the present invention relates to a filtration method and a filter for general use, especially applicable to tobacco products, and in particular for the mouthpiece of a cigarette filter.
  • the object of the invention is more particularly to protect the molecules of the human genome against the toxic carcinogens of inhaled smoke.
  • Cigarette filters known to date generally contain polysaccharide derivatives, of natural or thermoplastic origin, polyesters, such as polyethylene and polypropylene terephthalate.
  • Patent EP 434332 and EP 434339 of RJ Reynolds Tobacco Cie describe such filters, they can also contain dried tobacco grains. In these various patents, mention is made of the use of salts, acids, bases, surfactants, in a medium with basic PH.
  • patent WO 96/00019 describes a cigarette filter enriched with Fe ++, Cu ++ or Mg ++ ions.
  • the objective is the retention of free radicals and particularly the protection of metalloproteins.
  • WO 96/10929 describes a free radical inhibitor, such as an O-alkylated derivative of 2,4-monofurfurylidene sorbitol, associated with an antioxidant, the action of which is to filter Polycyclic Aromatic Hydrocarbons (HPA), mainly 3,4-Benzo-a-pyrene (BaP), with known carcinogenic power.
  • HPA Polycyclic Aromatic Hydrocarbons
  • BaP 3,4-Benzo-a-pyrene
  • fluoride has anti-tumor effects. It is involved in particular in the composition of dexamethasone and 5-fluorouracil.
  • the filtration process according to the invention has a selective, direct chemical, anti-carcinogenic action. It is intended to filter toxic products, in particular polycyclic aromatic hydrocarbons (HPA) such as benzo (a) pyrene (BaP) and nitrosamines, contained in the tobacco smoke of a cigarette.
  • HPA polycyclic aromatic hydrocarbons
  • BaP benzo
  • nitrosamines contained in the tobacco smoke of a cigarette.
  • the filtration process includes the step of controlling the rate of toxic products relative to that of nicotine so that the reduction in the rate at the outlet of the filter is greater than a predetermined threshold.
  • One of its main properties is the selective mode of action of the process according to the invention, with respect to toxic carcinogenic products in relation to nicotine. Its second main characteristic is its direct chemical action. That is to say, its action with respect to toxic carcinogenic products at the level of the very reactive site of DNA.
  • the process according to the invention comprises the following steps:
  • the step of capturing all or part of the toxic products by means of an active principle acting on said toxic products according to molecular processes comparable to those according to which the DNA and / or RNA of the human cell reacts with respect said toxic products the step of controlling the operating conditions of the filter by operating in a substantially non-aqueous medium and of basic pH, preferably greater than or equal to 8,
  • the step of adjusting the mass of the active principle so that it is greater than or equal to 0.1% of the mass of the cigarette filter and preferably greater than or equal to 1% of the mass of the filter.
  • the inventors have noted that it is with the minimum quantities of active principle and under the operating conditions mentioned above that it is possible to control the rate of toxic products, in particular the rate of polycyclic aromatic hydrocarbons (HPA) and of nitrosamines, compared to that of nicotine.
  • HPA polycyclic aromatic hydrocarbons
  • nitrosamines compared to that of nicotine.
  • said active principle is composed of molecules consisting of one or more nitrogen rings or nitrogen heterocycles, preferably nitrogen heteroaromatics, in particular pentacycles or hexacycles or a combination of the two.
  • said active principle must be in the form:
  • the molecule of the active principle is DNA and / or RNA and / or a derivative of DNA or RNA, such as for example adenosine triphosphate (ATP), adenosine monophosphate cyclic (AMP), adenyl cyclase.
  • the invention also relates to a cigarette filter implementing the method described above.
  • the cigarette filter according to the invention has a selective, direct chemical, anti-carcinogenic action. It is intended to filter particularly polycyclic aromatic hydrocarbons (HPA) and in particular benzo (a) pyrene (BaP) as well as nitrosamines, in retaining the nicotine level and flavor aromas for the satisfaction and pleasure of the smoker.
  • the filter comprises an active principle composed of molecules consisting of one or more nitrogen cycles or nitrogen heterocycles, and in particular nitrogen heteroaromatics, in particular pentacycles or hexacycles or a combination of the two.
  • said active principle must be in the form of a chain of said molecules and / or of said molecules linked to a fiber, in particular a cellulose acetate fiber, in a common chemical arrangement.
  • the mass of said nitrogenous cycles or heterocycles and particularly of nitrogenous heteroaromatics is at least equal to or greater than 0.1% of the total mass of the filter.
  • the medium in which said nitrogenous heterocycles or heterocycles and particularly nitrogenous heteroaromatics operate is a substantially non-aqueous medium having a basic pH. Under these operating conditions, it has been found that it is possible to substantially reduce, at the outlet of the filter, the level of polycyclic aromatic hydrocarbons relative to nicotine.
  • the rate can be reduced by more than 90% by retaining the nicotine level and flavor aromas for the satisfaction and pleasure of the smoker.
  • other fibers of natural or artificial origin are also used, mainly aromatics of ethylene (for example, polyethylene terephthalate), propylene (for example, polypropylene terephthalate), fluorinated salt medium.
  • the molecules are made of polymer in the broad sense.
  • the active principle consists exclusively of molecules and / or said polymers.
  • the mass of said nitrogenous cycles or heterocycles and particularly of nitrogenous heteroaromatics is at least equal or greater than 1% of the total mass of the filter.
  • the humidity level of the filter is between 5 and 10%.
  • the pH of the filter is greater than 8.
  • the molecule of the active principle is DNA and / or RNA and / or a derivative of DNA or RNA, such as for example adenosine triphosphate (ATP), adenosine monophosphate cyclic or adenyl cyclase.
  • ATP adenosine triphosphate
  • adenosine monophosphate cyclic or adenyl cyclase adenosine monophosphate cyclic or adenyl cyclase.
  • toxic carcinogenic products contained in tobacco smoke, directly affecting the DNA and / or RNA molecules of the human cell, are selectively captured by the filter according to molecular processes comparable to those according to which said toxic products act on the DNA and / or RNA of the human cell.
  • the molecule of the active principle is added, on at least one of the nitrogen rings or nitrogen heterocycles and particularly of the nitrogen heteroaromatics, to at least one function chosen from a group comprising the functions:
  • At least one molecule of the active principle is added with one or more sugars such as ribose or deoxyribose.
  • at least one molecule of the active principle is added with one or more acid functions, in particular phosphoric acid (H3PO4) pentavalent and / or another molecule comprising a trivalent phosphorus.
  • H3PO4 phosphoric acid
  • the polymerization is carried out in the broad sense at the level of the nitrogen cycles, that is to say nitrogen heterocycles and particularly nitrogen heteroaromatics and / or added functions and / or acids and / or sugars.
  • the molecule of the active principle comprises one or more atoms and / or one or more molecules and / or one or more radicals and / or one or more ions of a halogen, such as in particular fluorine.
  • the molecule of the active principle is located in a medium containing halogenated salts, in particular sodium fluoride salts
  • said fiber is partially halogenated, such as in particular by fluorine.
  • said fiber, partially halogenated or not is in a medium comprising atoms, molecules, radicals or ions of a halogen, such as in particular fluorine.
  • the invention also relates to a method of manufacturing a filter comprising an active principle composed of chains of molecules having the characteristics defined above. Said method comprises the step of extruding and / or rolling together said chains of molecules. In the case where said molecules are linked in a chemical arrangement common to fibers, in particular cellulose acetate fibers, said manufacturing process comprises the step of extruding and / or rolling together said fibers.
  • the invention also relates to a filtration device of general application comprising an active principle composed of molecules and / or fibers having the characteristics and operating under the conditions defined above.
  • the filtration device according to the invention is such that said molecules and / or said fibers are incorporated into separate compartments, or in the form of grains and / or filaments.
  • the filtration device according to the invention is such that said molecules and / or said fibers are present in a gelatinous, liquid or gaseous physical state.
  • the filtration device can be applied to the selective filtration of toxic products.
  • the filtration device according to the invention can be applied to the selective purification of tobacco smoke, in order to maintain the usual levels of nicotine, for the satisfaction of the smoker, and of tar containing the flavors of tobacco, for the preservation of the taste. .
  • the invention also relates to a cigarette comprising a filtration device such as that described above.
  • the cigarette according to the invention comprises a tobacco rod 2. At one end of the rod 2 is mounted a filtration device 1 such as that described above.
  • the invention protects molecules in the human genome against the toxic carcinogens of tobacco smoke.
  • this filter has the particularity of preserving in their entirety the usual levels of nicotine and the tars of the aromas.
  • This low-cost filter the maximum efficiency of which allows practical and industrial production for the best satisfaction of the smoker and his pleasure thanks to the preservation of the taste, while considerably reducing the risks involved, particularly in the field of bronchopulmonary and cardiovascular pathology.
  • the invention in question here is intended to protect the human genome from attack by carcinogens, the main process involved in the mechanism of initiation and promotion of the cancer phenomenon.
  • the invention is less concerned with indirect attack processes cells produced at the level of molecules such as metalloproteins or globulins involved in the immune response system.
  • the carcinogenic etiogeny is due to molecules which are not always originally found in the tobacco itself, but which are intermediate pyrolysis derivatives formed along the stem of the cigarette through a cooling corridor to the filter during inhalation-aspiration.
  • These derivatives, free radicals or carbocations, are electrophilic. Free radicals and carbocations are now better known as genotoxicity agents modifying the rules of duplication of DNA and / or constituting adducts with it. They can also be responsible for disorders in the DNA coding of proteins essential for cell life.
  • the invention implements molecules of which several nucleophilic nuclei prevent the electrophilic attack of these agents.
  • the molecules according to the invention filter, thanks to their quantity present in the filter, the toxins whose destiny would be to have a carcinogenic action in the body of the smoker either in situ, or after a process of metabolization in the faith of the smoker.
  • the compounds and radicals to be filtered constitute powerful adducts with DNA by penetration into cell nuclei or after passage, for precancerogens, by bioactivating systems of the body, and cause mutagenic and carcinogenic processes. It is known that the carcinogenic process most often involves electrophilic atoms in molecules whose transmembrane passage to the cell nucleus is favored by a medium of positive electrical density.
  • nucleophilic dipoles of voltage, ⁇ electronic clouds which form nucleophilic poles of attraction for electrophilic compounds and radicals.
  • the components of the filter molecules according to the invention and in particular the nucleotides of DNA and RNA, obstruct the compounds and radicals to be filtered even before they reach the human genetic heritage.
  • FIG. 1 represents the diagram of an example of a molecule according to the invention.
  • the radicals RI, R2, R3 and R4 are amino functions, ketones, aldehydes, methyls, alkenes, alkyls, aryls, etc. These functions, added to the molecule, can be used to filter alkyl or aryl epoxides , sulphate esters, nitrosamines with direct carcinogenic power.
  • radicals RI, R2, R3 and R4 can also be one or more atoms or a radical of a halogen such as fluorine.
  • the molecules of the purine or pyrimidine type can be produced in the form of filaments, single-stranded strands obtained by denaturation of DNA, or strands of RNA most often simple. It is known that DNA or RNA can be obtained by culturing microorganisms, by bursting nuclei and by a gel electrophoresis method.
  • the filter can use one or more halogens, but preferably fluorine, in the form of an atom, a molecule, a radical or an ion.
  • fluorine can be previously added to a phenyl nucleus possible precursor of synthesis of the molecule according to the invention via a mineral acid, a Bronsted acid, or a Lewis acid .
  • halogenation the syndrome of "polymer fever" or "Influenza Like” will be avoided by carrying out a partial halogenation of the fibers.
  • the halogen salts used are preferably soluble salts of alkali and alkaline earth metals, for example sodium fluoride.
  • the molecules according to the invention and / or the other fibers of the filter can be extruded or rolled together with halogen salts, as for example in the manufacturing process described in patent WO / 24078 of
  • Certain toxic substances are to be excluded, such as the carboxylic acids of fluorine or their precursors, particularly fluoroacetic acid as well as certain dangerous organophosphates.
  • the level of halogen used will not exceed the threshold imposed by the measures to restrict biodegradation and the level of consumable fluorine.
  • the filter may also have, for the fibers of the molecules according to the invention and / or for the other fibers of the filter, a distribution with a high fluorine content and then with a lower fluorine content, from the center to the periphery of the filter or vice versa, or in separate compartments arranged according to the length of the filter.
  • the filter as described here, has the function of filtering more effectively electrophilic compounds and radicals such as Polycyclic Aromatic Hydrocarbons (HPA) - and especially BaP - and Nitrosamines.
  • HPA Polycyclic Aromatic Hydrocarbons
  • the filter also comprises, in certain variant embodiments, surfactant solvents or other materials (acids of mineral or carboxylic type, bases or salts in particular for the conservation of a certain basic PH.
  • surfactant solvents or other materials ascids of mineral or carboxylic type, bases or salts in particular for the conservation of a certain basic PH.
  • the molecules of the filter according to the invention operate in a basic pH of greater than or equal to 8, thereby facilitating conservation of nicotine as described above.
  • the acid, base and salt functions can either be added to the molecules according to the invention and / or to the other fibers of the filter substrate, or located at their contact. They can also be used for the halogenation of the molecule of the active principle and / or of the other fibers of the filter substrate.
  • the greater cleanliness of the inhaled flow, combined with an action of decluttering of the tissues, allows a very favorable prognosis as regards the limitation of bronchopulmonary, cardiovascular pathology and mutagenic or carcinogenic processes.
  • the filter is used for general filtration of pollutants and toxic products.
  • the filter thus described is not necessarily in contact with tobacco; it can for example be housed in a cigarette holder.
  • the mass of nitrogen rings and nitrogen heterocycles and particularly of nitrogen heteroaromatics present in the filter represents at least 0.1% and, preferably, more than 1% of the total mass of the filter. Tests performed.
  • Standard-size cigarette filter injected with single-stranded salmon DNA filaments composed of about a thousand nucleotides, the mass of DNA being 10 mg per cigarette filter, the filter being dried before smoking and dosage.
  • Humidity level 7 ⁇ 2%, PH: about 8
  • the filter is injected with single-stranded strands of salmon DNA, length of approximately 2000 base pairs and for an amount equal to 10 mg for a conventional cigarette filter.
  • Humidity level 7 ⁇ 2% PH: about 8
  • the filter consists on its axis of a mixed compartment of filaments of salmon DNA and polypropylene terephthalate fibers, and of a compartment consisting only of these latter fibers.
  • the mass of DNA filaments representing 10 mg for a conventional cigarette filter.
  • the cigarette filter is made up of a mixture of linear filaments of salmon DNA tangled with polypropylene terephthalate fibers.
  • the mass of DNA filaments representing 10 mg for a conventional cigarette filter.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)

Abstract

The methods concerns a method for general use and more particularly used for tobacco products. The method uses in particular nitrogen-containing heterocycles such as DNA and RNA bases and complementarily polymer fibers. Said molecules and said fibers can partly halogenated, or in halogenated salt media. The halogen is preferably fluorine. Fluorine may be added to may bei n the form of a medium of fluorinated salts such as NaF, KF, Na2PO3F. The filtering acts against the formation of human intracellular DNA or RNA adducts, while preserving the nicotine and the tobacco aromas.

Description

PROCEDE DE FILTRATION ET FILTRE COMPOSE DE CYCLES OU D' HETEROCYCLES AZOTES TELS QUE L'ADN OU L'ARN DESTINE NOTAMMENT A LA FILTRATION DE FUMEE DE TABAC ET CIGARETTE COMPORTANT UN TEL FILTREFILTRATION PROCESS AND FILTER COMPRISING CYCLES OR HETEROCYC L E S AZ OTE S SUCH AS DNA OR RNA, ESPECIALLY FOR FILTERING FU M E E D AND ABAC E T CIGARETTE COMPRISING SUCH A FILTER
La présente invention concerne un procédé de filtration et un filtre d'usage général, applicable en particulier aux produits tabagiques, et notamment pour l 'embout filtre d'une cigarette. L'invention a plus particulièrement pour objet de protéger les molécules du génome humain contre les toxiques cancérigènes de la fumée inhalée. Les filtres de cigarette connus à ce jour contiennent en général des dérivés polysaccharidiques, d'origine naturelle ou thermoplastique, des polyesters, tels que les polyethylène et polypropylène térephtalate. Les brevets EP 434332 et EP 434339 de RJ Reynolds Tobacco Cie décrivent de tels filtres, ils peuvent contenir également des grains de tabac séchés. Dans ces différents brevets, il est fait mention de l'utilisation de sels, d'acides, de bases, de tensioactifs, dans un milieu à PH basique.The present invention relates to a filtration method and a filter for general use, especially applicable to tobacco products, and in particular for the mouthpiece of a cigarette filter. The object of the invention is more particularly to protect the molecules of the human genome against the toxic carcinogens of inhaled smoke. Cigarette filters known to date generally contain polysaccharide derivatives, of natural or thermoplastic origin, polyesters, such as polyethylene and polypropylene terephthalate. Patent EP 434332 and EP 434339 of RJ Reynolds Tobacco Cie describe such filters, they can also contain dried tobacco grains. In these various patents, mention is made of the use of salts, acids, bases, surfactants, in a medium with basic PH.
Plus particulièrement contre les substances cancérigènes, le brevet WO 96/00019 décrit un filtre de cigarette enrichi d'ions Fe++, Cu++ ou Mg++. L'objectif est la rétention de radicaux libres et particulièrement la protection des métalloprotéines. Le brevet WO 96/ 10929 décrit un inhibiteur de radicaux libres, tel qu'un dérivé O-alkylé du 2,4-monofurfurylidène sorbitol, associé à un antioxydant, dont l'action est de filtrer les Hydrocarbures Polycycliques Aromatiques (HPA), principalement le 3,4-Benzo-a-pyrène (BaP), au pouvoir cancérigène connu. Par ailleurs, il est connu que le fluor a des effets antitumoraux. Il intervient notamment dans la composition de la dexaméthasone et du 5-fluorouracile. De plus, l 'utilisation du papier filtre de laboratoire au polytetrafluoroéthylène (PTFE) est connue. Le procédé de filtration selon l'invention a une action sélective, chimique directe, anti-cancérigène. Il est destiné à filtrer les produits toxiques, en particulier les hydrocarbures polycycliques aromatiques (HPA) tel que le benzo(a)pyrène (BaP) et les nitrosamines, contenus dans la fumée de tabac d'une cigarette.More particularly against carcinogenic substances, patent WO 96/00019 describes a cigarette filter enriched with Fe ++, Cu ++ or Mg ++ ions. The objective is the retention of free radicals and particularly the protection of metalloproteins. WO 96/10929 describes a free radical inhibitor, such as an O-alkylated derivative of 2,4-monofurfurylidene sorbitol, associated with an antioxidant, the action of which is to filter Polycyclic Aromatic Hydrocarbons (HPA), mainly 3,4-Benzo-a-pyrene (BaP), with known carcinogenic power. Furthermore, it is known that fluoride has anti-tumor effects. It is involved in particular in the composition of dexamethasone and 5-fluorouracil. In addition, the use of laboratory filter paper with polytetrafluoroethylene (PTFE) is known. The filtration process according to the invention has a selective, direct chemical, anti-carcinogenic action. It is intended to filter toxic products, in particular polycyclic aromatic hydrocarbons (HPA) such as benzo (a) pyrene (BaP) and nitrosamines, contained in the tobacco smoke of a cigarette.
Le procédé de filtration comprend l'étape de maîtriser le taux des produits toxiques par rapport à celui de la nicotine de manière à ce que la réduction du taux à la sortie du filtre soit supérieure à un seuil prédéterminé. Ainsi, la nicotine et les arômes du goût pour la satisfaction et le plaisir des fumeurs sont conservés.The filtration process includes the step of controlling the rate of toxic products relative to that of nicotine so that the reduction in the rate at the outlet of the filter is greater than a predetermined threshold. Thus, nicotine and flavor aromas for the satisfaction and pleasure of smokers are preserved.
Le mode d'action sélectif du procédé selon l'invention, vis à vis des produits toxiques cancérigènes par rapport à la nicotine, est une de ses principales propriétés. Sa seconde caractéristique principale est son action chimique directe. C'est-à-dire son action vis à vis des produits toxiques cancérigènes au niveau du site réactif même de l'ADN.One of its main properties is the selective mode of action of the process according to the invention, with respect to toxic carcinogenic products in relation to nicotine. Its second main characteristic is its direct chemical action. That is to say, its action with respect to toxic carcinogenic products at the level of the very reactive site of DNA.
De préférence, pour maîtriser le taux des produits toxiques, notamment le taux des hydrocarbures polycycliques aromatiques (HPA) et des nitrosamines, par rapport à celui de la nicotine, le procédé selon l 'invention comprend les étapes suivantes :Preferably, in order to control the level of toxic products, in particular the level of polycyclic aromatic hydrocarbons (HPA) and of nitrosamines, relative to that of nicotine, the process according to the invention comprises the following steps:
- l'étape de capter tout ou partie des produits toxiques au moyen d'un principe actif agissant sur lesdits produits toxiques selon des processus moléculaires comparables à ceux selon lesquels réagit l'ADN et/ou l'ARN de la cellule humaine vis à vis desdits produits toxiques, - l'étape de contrôler les conditions opératoires du filtre en opérant en milieu sensiblement non aqueux et de pH basique, de préférence supérieur ou égal à 8,the step of capturing all or part of the toxic products by means of an active principle acting on said toxic products according to molecular processes comparable to those according to which the DNA and / or RNA of the human cell reacts with respect said toxic products, the step of controlling the operating conditions of the filter by operating in a substantially non-aqueous medium and of basic pH, preferably greater than or equal to 8,
- l'étape d'ajuster la masse du principe actif de telle sorte qu'elle soit supérieure ou égale à 0,1 % de la masse du filtre de la cigarette et de préférence supérieure ou égale à 1 % de la masse du filtre.the step of adjusting the mass of the active principle so that it is greater than or equal to 0.1% of the mass of the cigarette filter and preferably greater than or equal to 1% of the mass of the filter.
Ce sont les attaques contre les molécules d'ADN et/ou d'ARN de la cellule humaine qui sont principalement à l'origine des tumeurs cancéreuses. Par conséquent, en filtrant la fumée de tabac par des mécanismes moléculaires de même nature que ceux qui dégradent l'ADN et/ou l'ARN, on capte de manière sélective et directe les produits toxiques cancérigènes, contenus dans la fumée de tabac.It is attacks against DNA and / or RNA molecules in the human cell that are the main cause of cancerous tumors. Consequently, by filtering tobacco smoke by molecular mechanisms of the same nature as those which degrade DNA and / or RNA, the toxic carcinogenic products contained in tobacco smoke are selectively and directly captured.
Les inventeurs ont constatés que ce sont avec les quantités minimales de principe actif et dans les conditions opératoires ci-dessus mentionnées qu'il est possible de maîtriser le taux des produits toxiques, notamment le taux des hydrocarbures polycycliques aromatiques (HPA) et des nitrosamines, par rapport à celui de la nicotine.The inventors have noted that it is with the minimum quantities of active principle and under the operating conditions mentioned above that it is possible to control the rate of toxic products, in particular the rate of polycyclic aromatic hydrocarbons (HPA) and of nitrosamines, compared to that of nicotine.
De préférence, ledit principe actif est composé de molécules constituées d'un ou plusieurs cycles azotés ou heterocycles azotés, de préférence des hétéroaromatiques azotés, notamment de pentacycles ou d'hexacycles ou d'une association des deux. Avantageusement, selon l'invention, ledit principe actif doit se présenter sous la forme :Preferably, said active principle is composed of molecules consisting of one or more nitrogen rings or nitrogen heterocycles, preferably nitrogen heteroaromatics, in particular pentacycles or hexacycles or a combination of the two. Advantageously, according to the invention, said active principle must be in the form:
- d'une chaîne desdites molécules et/ou- a chain of said molecules and / or
- desdites molécules liées, dans un arrangement chimique commun, à une fibre tel qu'une fibre composée d'acétate de cellulose.- Said molecules linked, in a common chemical arrangement, to a fiber such as a fiber composed of cellulose acetate.
De préférence, la molécule du principe actif est de l'ADN et/ou de l'ARN et/ou un dérivé de l'ADN ou de l'ARN, comme par exemple l'adénosine triphosphate (ATP), l'adénosine monophosphate cyclique (AMP), l'adényl- cyclase. L'invention concerne également un filtre de cigarette mettant en œuvre le procédé ci-dessus décrit. Le filtre de cigarette selon l'invention a une action sélective, chimique directe, anti-cancérigène. Il est destiné à filtrer particulièrement les hydrocarbures polycycliques aromatiques (HPA) et notamment le benzo(a)pyrène (BaP) ainsi que les nitrosamines, en conservant le taux de nicotine et les arômes du goût pour la satisfaction et le plaisir du fumeur. Le filtre comporte un principe actif composé de molécules constituées d'un ou plusieurs cycles azotés ou heterocycles azotés, et particulièrement des hétéroaromatiques azotés, notamment de pentacycles ou d'hexacycles ou d'une association des deux.Preferably, the molecule of the active principle is DNA and / or RNA and / or a derivative of DNA or RNA, such as for example adenosine triphosphate (ATP), adenosine monophosphate cyclic (AMP), adenyl cyclase. The invention also relates to a cigarette filter implementing the method described above. The cigarette filter according to the invention has a selective, direct chemical, anti-carcinogenic action. It is intended to filter particularly polycyclic aromatic hydrocarbons (HPA) and in particular benzo (a) pyrene (BaP) as well as nitrosamines, in retaining the nicotine level and flavor aromas for the satisfaction and pleasure of the smoker. The filter comprises an active principle composed of molecules consisting of one or more nitrogen cycles or nitrogen heterocycles, and in particular nitrogen heteroaromatics, in particular pentacycles or hexacycles or a combination of the two.
Avantageusement, ledit principe actif doit se présenter sous la forme d'une chaîne desdites molécules et/ou desdites molécules liées à une fibre, notamment une fibre d'acétate de cellulose, dans un arrangement chimique commun. La masse desdits cycles ou heterocycles azotés et particulièrement des hétéroaromatiques azotés est au moins égale ou supérieure à 0,1 % de la masse totale du filtre. Le milieu dans lequel lesdits cycles ou heterocycles azotés et particulièrement des hétéroaromatiques azotés opèrent est un milieu sensiblement non-aqueux ayant un pH basique. Dans ces conditions opératoires, il a été constaté qu'il est possible de réduire de manière substantielle, à la sortie du filtre, le taux des hydrocarbures polycycliques aromatiques par rapport à la nicotine. Le taux peut être réduit de plus de 90 % en conservant le taux de nicotine et les arômes du goût pour la satisfaction et le plaisir du fumeur . Selon une variante de réalisation du filtre, on utilise également d'autres fibres d'origine naturelle ou artificielle, principalement des aromatiques de l'éthylène (par exemple, le polyethylène térephtalate), du propylène (par exemple, le polypropylène térephtalate), en milieu de sels fluorés. Avantageusement, dans une variante de réalisation de l'invention, les molécules sont constituées en polymère au sens large. Avantageusement également, dans une autre variante de réalisation de l'invention, le principe actif est exclusivement constitué de molécules et/ou desdits polymères.Advantageously, said active principle must be in the form of a chain of said molecules and / or of said molecules linked to a fiber, in particular a cellulose acetate fiber, in a common chemical arrangement. The mass of said nitrogenous cycles or heterocycles and particularly of nitrogenous heteroaromatics is at least equal to or greater than 0.1% of the total mass of the filter. The medium in which said nitrogenous heterocycles or heterocycles and particularly nitrogenous heteroaromatics operate is a substantially non-aqueous medium having a basic pH. Under these operating conditions, it has been found that it is possible to substantially reduce, at the outlet of the filter, the level of polycyclic aromatic hydrocarbons relative to nicotine. The rate can be reduced by more than 90% by retaining the nicotine level and flavor aromas for the satisfaction and pleasure of the smoker. According to an alternative embodiment of the filter, other fibers of natural or artificial origin are also used, mainly aromatics of ethylene (for example, polyethylene terephthalate), propylene (for example, polypropylene terephthalate), fluorinated salt medium. Advantageously, in an alternative embodiment of the invention, the molecules are made of polymer in the broad sense. Advantageously also, in another alternative embodiment of the invention, the active principle consists exclusively of molecules and / or said polymers.
De préférence, la masse desdits cycles ou heterocycles azotés et particulièrement des hétéroaromatiques azotés est au moins égale ou supérieure à 1 % de la masse totale du filtre.Preferably, the mass of said nitrogenous cycles or heterocycles and particularly of nitrogenous heteroaromatics is at least equal or greater than 1% of the total mass of the filter.
Avantageusement, le taux d'humidité du filtre est compris entre 5 et 10%.Advantageously, the humidity level of the filter is between 5 and 10%.
Avantageusement, le pH du filtre est supérieur à 8.Advantageously, the pH of the filter is greater than 8.
De préférence, la molécule du principe actif est de l'ADN et/ou de l'ARN et/ou un dérivé de l'ADN ou de l'ARN, comme par exemple l 'adénosine triphosphate (ATP), l'adénosine monophosphate cyclique ou l'adényl- cyclase.Preferably, the molecule of the active principle is DNA and / or RNA and / or a derivative of DNA or RNA, such as for example adenosine triphosphate (ATP), adenosine monophosphate cyclic or adenyl cyclase.
Ainsi, les produits toxiques cancérigènes, contenus dans la fumée de tabac, affectant directement les molécules d'ADN et/ou d'ARN de la cellule humaine, sont captés sélectivement par le filtre selon des processus moléculaires comparables à ceux selon lesquels lesdits produits toxiques agissent sur l'ADN et/ou l'ARN de la cellule humaine.Thus, toxic carcinogenic products, contained in tobacco smoke, directly affecting the DNA and / or RNA molecules of the human cell, are selectively captured by the filter according to molecular processes comparable to those according to which said toxic products act on the DNA and / or RNA of the human cell.
Avantageusement, la molécule du principe actif est additionnée, sur l'un au moins des cycles azotés ou heterocycles azotés et particulièrement des hétéroaromatiques azotés, d'au moins une fonction choisie dans un groupe comprenant les fonctions :Advantageously, the molecule of the active principle is added, on at least one of the nitrogen rings or nitrogen heterocycles and particularly of the nitrogen heteroaromatics, to at least one function chosen from a group comprising the functions:
- aminé NH2,- NH2 amino,
- cétone, aldéhyde,- ketone, aldehyde,
- méthyle - alcène, alcyle ou aryle,- methyl - alkene, alkyl or aryl,
Avantageusement, au moins une molécule du principe actif est additionnée d'un ou plusieurs sucres tels que le ribose ou le désoxyribose. Avantageusement, au moins une molécule du principe actif est additionnée d'une ou plusieurs fonctions acides, notamment de l'acide phosphorique (H3P04) pentavalent et/ou d'une autre molécule comportant un phosphore trivalent.Advantageously, at least one molecule of the active principle is added with one or more sugars such as ribose or deoxyribose. Advantageously, at least one molecule of the active principle is added with one or more acid functions, in particular phosphoric acid (H3PO4) pentavalent and / or another molecule comprising a trivalent phosphorus.
Avantageusement, dans le cas d'une chaîne de molécules constituée en polymère, la polymérisation est effectuée au sens large au niveau des cycles azotés, soit des heterocycles azotés et particulièrement des hétéroaromatiques azotés et/ou des fonctions additionnées et/ou des acides et/ou des sucres.Advantageously, in the case of a chain of molecules made up of a polymer, the polymerization is carried out in the broad sense at the level of the nitrogen cycles, that is to say nitrogen heterocycles and particularly nitrogen heteroaromatics and / or added functions and / or acids and / or sugars.
Avantageusement, la molécule du principe actif comporte un ou plusieurs atomes et/ou une ou plusieurs molécules et/ou un ou plusieurs radicaux et/ou un ou plusieurs ions d'un halogène, tel que notamment le fluor.Advantageously, the molecule of the active principle comprises one or more atoms and / or one or more molecules and / or one or more radicals and / or one or more ions of a halogen, such as in particular fluorine.
Avantageusement, la molécule du principe actif est située dans un milieu contenant des sels halogènes, notamment des sels de fluorure de sodiumAdvantageously, the molecule of the active principle is located in a medium containing halogenated salts, in particular sodium fluoride salts
NaF.NaF.
Avantageusement, dans le cas où ledit principe actif se présente sous la forme d'une chaîne desdites molécules et/ou desdites molécules liées à une fibre, ladite fibre est partiellement halogénée, tel que notamment par le fluor. Avantageusement également dans ce cas, ladite fibre, partiellement halogénée ou non, est dans un milieu comportant des atomes, des molécules, des radicaux ou des ions d'un halogène, tel que notamment le fluor.Advantageously, in the case where said active principle is in the form of a chain of said molecules and / or of said molecules linked to a fiber, said fiber is partially halogenated, such as in particular by fluorine. Advantageously also in this case, said fiber, partially halogenated or not, is in a medium comprising atoms, molecules, radicals or ions of a halogen, such as in particular fluorine.
L'invention concerne également un procédé de fabrication d'un filtre comportant un principe actif composé de chaînes de molécules ayant les caractéristiques ci-dessus définies. Ledit procédé comprend l 'étape d'extruder et/ou de rouler ensemble lesdites chaînes de molécules. Dans le cas où lesdites molécules sont liées dans un arrangement chimique commun à des fibres, notamment des fibres d'acétate de cellulose, ledit procédé de fabrication comprend l'étape d'extruder et/ou de rouler ensemble lesdites fibres. L'invention concerne également un dispositif de filtration d'application générale comportant un principe actif composé des molécules et/ou des fibres ayant les caractéristiques et opérant dans les conditions ci-dessus définies.The invention also relates to a method of manufacturing a filter comprising an active principle composed of chains of molecules having the characteristics defined above. Said method comprises the step of extruding and / or rolling together said chains of molecules. In the case where said molecules are linked in a chemical arrangement common to fibers, in particular cellulose acetate fibers, said manufacturing process comprises the step of extruding and / or rolling together said fibers. The invention also relates to a filtration device of general application comprising an active principle composed of molecules and / or fibers having the characteristics and operating under the conditions defined above.
Avantageusement, le dispositif de filtration selon l'invention est tel que lesdites molécules et/ou lesdites fibres sont incorporées dans des compartiments séparés, ou se présentant sous la forme de grains et/ou de filaments.Advantageously, the filtration device according to the invention is such that said molecules and / or said fibers are incorporated into separate compartments, or in the form of grains and / or filaments.
Avantageusement, le dispositif de filtration selon l'invention est tel que lesdites molécules et/ou lesdites fibres se présentent selon un état physique gélatineux, liquide ou gazeux.Advantageously, the filtration device according to the invention is such that said molecules and / or said fibers are present in a gelatinous, liquid or gaseous physical state.
Le dispositif de filtration peut être appliqué à la filtration sélective de produits toxiques. Le dispositif de filtration selon l'invention peut être appliqué à la purification sélective de la fumée du tabac, afin de conserver les taux usuels de nicotine, pour la satisfaction du fumeur, et de goudron contenant les arômes du tabac, pour la conservation du goût.The filtration device can be applied to the selective filtration of toxic products. The filtration device according to the invention can be applied to the selective purification of tobacco smoke, in order to maintain the usual levels of nicotine, for the satisfaction of the smoker, and of tar containing the flavors of tobacco, for the preservation of the taste. .
L'invention concerne également une cigarette comportant un dispositif de filtration tel que celui ci-dessus décrit. Ainsi que cela est représenté sur la figure 2, la cigarette selon l'invention comporte une tige de tabac 2. A l 'une des extrémités de la tige 2 est monté un dispositif de filtration 1 tel que celui ci-dessus décrit.The invention also relates to a cigarette comprising a filtration device such as that described above. As shown in Figure 2, the cigarette according to the invention comprises a tobacco rod 2. At one end of the rod 2 is mounted a filtration device 1 such as that described above.
L'invention protège les molécules du génome humain contre les toxiques cancérigènes de la fumée de tabac. De plus, dans le cas d'un article à fumer, ce filtre a la particularité de préserver dans leur totalité les taux usuels de nicotine et les goudrons des arômes. Ce filtre à faible coût et dont l'efficience est maximale permet une réalisation pratique et industrielle pour le meilleur de la satisfaction du fumeur et de son plaisir grâce à la conservation du goût, tout en allégeant considérablement les risques encourus, particulièrement dans le domaine de la pathologie bronchopulmonaire et cardiovasculaire. L'invention dont il est question ici est destinée à protéger le génome humain contre les attaques des produits cancérigènes, principal processus investi dans le mécanisme de l'initiation et de la promotion du phénomène cancéreux. L'invention s'attache moins aux processus indirects d'attaques cellulaires réalisés au niveau de molécules telles que les métalloprotéines ou les globulines engagées dans le système de réponse immunitaire. Dans le cas d'un filtre d'article à fumer, l'étiogénie cancérigène relève de molécules qui ne se situent pas toujours originellement dans le tabac lui- même, mais qui sont des dérivés intermédiaires de pyrolyse constitués le long de la tige de la cigarette à travers un couloir de refroidissement jusqu'au filtre lors de l'inhalation-aspiration. Ces dérivés, radicaux libres ou carbocations, sont électrophiles. Les radicaux libres et les carbocations sont désormais mieux connus comme agents de génotoxicité modifiant les règles de duplication de l'ADN et/ou constituant avec lui des adduits. Ils peuvent être aussi responsables de troubles dans le codage par l'ADN des protéines indispensables à la vie cellulaire. L'invention met en œuvre des molécules dont plusieurs noyaux nucléophiles préviennent l'attaque électrophile de ces agents. Les molécules selon l'invention filtrent, grâce à leur quantité présente dans le filtre, les toxiques dont la destinée seraient d'avoir une action cancérigène dans le corps du fumeur soit in situ, soit après un processus de métabolisation dans le foi du fumeur. Dans le corps humain, les composés et radicaux à filtrer constituent des adduits puissants avec l'ADN par pénétration dans les noyaux cellulaires ou après passage, pour les précancérigènes, par des systèmes bioactivants du corps, et entraînent des processus mutagènes et cancérigènes. Il est connu que le processus cancérigène met en cause le plus souvent des atomes électrophiles dans des molécules dont le passage transmembranaire vers le noyau cellulaire est favorisé par un milieu de densité électrique positive.The invention protects molecules in the human genome against the toxic carcinogens of tobacco smoke. In addition, in the case of a smoking article, this filter has the particularity of preserving in their entirety the usual levels of nicotine and the tars of the aromas. This low-cost filter, the maximum efficiency of which allows practical and industrial production for the best satisfaction of the smoker and his pleasure thanks to the preservation of the taste, while considerably reducing the risks involved, particularly in the field of bronchopulmonary and cardiovascular pathology. The invention in question here is intended to protect the human genome from attack by carcinogens, the main process involved in the mechanism of initiation and promotion of the cancer phenomenon. The invention is less concerned with indirect attack processes cells produced at the level of molecules such as metalloproteins or globulins involved in the immune response system. In the case of a smoking article filter, the carcinogenic etiogeny is due to molecules which are not always originally found in the tobacco itself, but which are intermediate pyrolysis derivatives formed along the stem of the cigarette through a cooling corridor to the filter during inhalation-aspiration. These derivatives, free radicals or carbocations, are electrophilic. Free radicals and carbocations are now better known as genotoxicity agents modifying the rules of duplication of DNA and / or constituting adducts with it. They can also be responsible for disorders in the DNA coding of proteins essential for cell life. The invention implements molecules of which several nucleophilic nuclei prevent the electrophilic attack of these agents. The molecules according to the invention filter, thanks to their quantity present in the filter, the toxins whose destiny would be to have a carcinogenic action in the body of the smoker either in situ, or after a process of metabolization in the faith of the smoker. In the human body, the compounds and radicals to be filtered constitute powerful adducts with DNA by penetration into cell nuclei or after passage, for precancerogens, by bioactivating systems of the body, and cause mutagenic and carcinogenic processes. It is known that the carcinogenic process most often involves electrophilic atoms in molecules whose transmembrane passage to the cell nucleus is favored by a medium of positive electrical density.
Selon l'invention, pour filtrer ces molécules précurseurs de génotoxicité, on utilise des molécules constituées de dipôles nucléophiles, de forces de tension, de nuages électroniques π qui réalisent des pôles nucléophiles d'attraction pour les composés et radicaux électrophiles. Au cours des essais, il a été constaté que les composants des molécules du filtre selon l'invention, et notamment les nucléotides de l'ADN et de l'ARN, font obstacle aux composés et radicaux à filtrer avant même qu'ils n'atteignent le patrimoine génétique humain.According to the invention, to filter these precursor molecules of genotoxicity, molecules made up of nucleophilic dipoles, of voltage, π electronic clouds which form nucleophilic poles of attraction for electrophilic compounds and radicals. During the tests, it was found that the components of the filter molecules according to the invention, and in particular the nucleotides of DNA and RNA, obstruct the compounds and radicals to be filtered even before they reach the human genetic heritage.
On va maintenant décrire la figure 1 qui représente le schéma d'un exemple de molécule selon l'invention. Les radicaux RI, R2, R3 et R4 sont des fonctions aminés, cétones, aldéhydes, méthyles, alcènes, alcyles, aryles, etc.. Ces fonctions, additionnées à la molécule, peuvent servir à filtrer des époxydes d'alkyle ou d'aryle, des esters sulfates, des nitrosamines au pouvoir cancérigène direct.We will now describe FIG. 1 which represents the diagram of an example of a molecule according to the invention. The radicals RI, R2, R3 and R4 are amino functions, ketones, aldehydes, methyls, alkenes, alkyls, aryls, etc. These functions, added to the molecule, can be used to filter alkyl or aryl epoxides , sulphate esters, nitrosamines with direct carcinogenic power.
Ces radicaux RI, R2, R3 et R4 peuvent aussi être un ou plusieurs atomes ou un radical d'un halogène tel que le fluor. A titre d'exemple, les molécules de type purine ou pyrimidine peuvent être réalisées sous la forme de filaments, brins monocaténaires obtenus par dénaturation d'ADN, ou brins d'ARN le plus souvent simples. Il est connu que l'ADN ou l'ARN peuvent être obtenus par culture de micro-organismes, par éclatement des noyaux et un procédé d'électrophorèse en gel.These radicals RI, R2, R3 and R4 can also be one or more atoms or a radical of a halogen such as fluorine. By way of example, the molecules of the purine or pyrimidine type can be produced in the form of filaments, single-stranded strands obtained by denaturation of DNA, or strands of RNA most often simple. It is known that DNA or RNA can be obtained by culturing microorganisms, by bursting nuclei and by a gel electrophoresis method.
Le filtre peut utiliser un ou plusieurs halogènes, mais de préférence le fluor, sous forme d'atome, de molécule, de radical ou d'ion. Quand il est utilisé, le fluor peut être préalablement additionné sur un noyau phényl précurseur possible de synthèse de la molécule selon l'invention par l'intermédiaire d'un acide minéral, d'un acide de Bronsted, ou d'un acide de Lewis.The filter can use one or more halogens, but preferably fluorine, in the form of an atom, a molecule, a radical or an ion. When it is used, fluorine can be previously added to a phenyl nucleus possible precursor of synthesis of the molecule according to the invention via a mineral acid, a Bronsted acid, or a Lewis acid .
Dans le cas d'une halogenation, le syndrome de la "fièvre des polymères" ou "Influenza Like" sera évité en procédant à une halogenation partielle des fibres. Les sels halogènes utilisés sont de préférence des sels solubles de métaux alcalins et alcalino-terreux, par exemple le fluorure de sodium. Les molécules selon l'invention et/ou les autres fibres du filtre peuvent être extrudées ou roulées ensemble avec des sels halogènes, comme par exemple dans le procédé de fabrication décrit dans le brevet WO/24078 deIn the case of halogenation, the syndrome of "polymer fever" or "Influenza Like" will be avoided by carrying out a partial halogenation of the fibers. The halogen salts used are preferably soluble salts of alkali and alkaline earth metals, for example sodium fluoride. The molecules according to the invention and / or the other fibers of the filter can be extruded or rolled together with halogen salts, as for example in the manufacturing process described in patent WO / 24078 of
Caredent Ltd.Caredent Ltd.
Certains toxiques sont à exclure, comme les acides carboxyliques du fluor ou leurs précurseurs, particulièrement l'acide fluoroacétique ainsi que certains organophosphorés dangereux. Le taux de l'halogène utilisé ne dépassera pas le seuil imposé par les mesures de restriction de la biodégradation et du taux de fluor consommable.Certain toxic substances are to be excluded, such as the carboxylic acids of fluorine or their precursors, particularly fluoroacetic acid as well as certain dangerous organophosphates. The level of halogen used will not exceed the threshold imposed by the measures to restrict biodegradation and the level of consumable fluorine.
Dans le cas d'une halogenation, le filtre peut également présenter pour les fibres des molécules selon l'invention et/ou pour les autres fibres du filtre une distribution à haute teneur en fluor puis à moindre teneur en fluor, du centre vers la périphérie du filtre ou l'inverse, ou en compartiments distincts disposés selon la longueur du filtre.In the case of halogenation, the filter may also have, for the fibers of the molecules according to the invention and / or for the other fibers of the filter, a distribution with a high fluorine content and then with a lower fluorine content, from the center to the periphery of the filter or vice versa, or in separate compartments arranged according to the length of the filter.
Le filtre, tel que décrit ici, a la fonction de filtrer de façon plus efficace les composés et radicaux électrophiles tels que les Hydrocarbures Polycycliques Aromatiques (HPA) - et surtout le BaP - et les Nitrosamines.The filter, as described here, has the function of filtering more effectively electrophilic compounds and radicals such as Polycyclic Aromatic Hydrocarbons (HPA) - and especially BaP - and Nitrosamines.
Le filtre comporte aussi, dans certaines variantes de réalisation, des solvants tensio-actifs ou d'autres matériaux (des acides de type minéral ou carboxylique, des bases ou des sels en particulier pour la conservation d'un certain PH basique. Les molécules du filtre selon l'invention fonctionnent en pH basique de préférence supérieur ou égal à 8, ce qui facilite la conservation du taux de nicotine comme indiqué plus haut.The filter also comprises, in certain variant embodiments, surfactant solvents or other materials (acids of mineral or carboxylic type, bases or salts in particular for the conservation of a certain basic PH. The molecules of the filter according to the invention operate in a basic pH of greater than or equal to 8, thereby facilitating conservation of nicotine as described above.
Les fonctions acides, bases et sels peuvent être soit additionnées aux molécules selon l'invention et/ou aux autres fibres du substrat du filtre, soit situées à leur contact. Elles peuvent servir aussi à I'halogénation de la molécule du principe actif et/ou des autres fibres du substrat du filtre. La plus grande propreté du flux inhalé, conjuguée à une action de désencombrement des tissus, permet un pronostic très favorable quant à la limitation de la pathologie broncho-pulmonaire, cardiovasculaire et des processus mutagènes ou cancérigènes.The acid, base and salt functions can either be added to the molecules according to the invention and / or to the other fibers of the filter substrate, or located at their contact. They can also be used for the halogenation of the molecule of the active principle and / or of the other fibers of the filter substrate. The greater cleanliness of the inhaled flow, combined with an action of decluttering of the tissues, allows a very favorable prognosis as regards the limitation of bronchopulmonary, cardiovascular pathology and mutagenic or carcinogenic processes.
Le filtre a un usage général de filtration des polluants et des produits toxiques. Dans le cas de la filtration d'article à fumer, le filtre ainsi décrit n'est pas nécessairement au contact du tabac; il peut par exemple être logé dans un fume-cigarette.The filter is used for general filtration of pollutants and toxic products. In the case of filtration of a smoking article, the filter thus described is not necessarily in contact with tobacco; it can for example be housed in a cigarette holder.
Au cours des essais dans le cas d'un article à fumer, il a été constaté que quelques milligrammes du principe actif ajoutés à la masse du filtre en milieu d'humidité correspondant à celle d'un filtre conventionnel de cigarette, soit de l'ordre de 7 ± 2 %, suffisent à filtrer la quasi totalité des produits cancérigènes incriminés dans le tabac.During the tests in the case of a smoking article, it was found that a few milligrams of the active ingredient added to the mass of the filter in a humidity medium corresponding to that of a conventional cigarette filter, namely around 7 ± 2%, is sufficient to filter almost all of the carcinogens incriminated in tobacco.
De façon générale, la masse des cycles azotés et des heterocycles azotés et particulièrement des hétéroaromatiques azotés présents dans le filtre représente au moins 0,1 % et, préférentiellement, plus de 1 % de la masse totale du filtre. Tests réalisés.Generally, the mass of nitrogen rings and nitrogen heterocycles and particularly of nitrogen heteroaromatics present in the filter represents at least 0.1% and, preferably, more than 1% of the total mass of the filter. Tests performed.
Les tests ont été réalisés dans les conditions suivantes. Filtre de cigarette de dimensions standards injecté de filaments monocaténaires d'ADN de saumon composés d'un millier de nucléotides environ, la masse de l'ADN étant de 10 mg par filtre de cigarette, le filtre étant séché avant les tests de fumage et de dosage.The tests were carried out under the following conditions. Standard-size cigarette filter injected with single-stranded salmon DNA filaments composed of about a thousand nucleotides, the mass of DNA being 10 mg per cigarette filter, the filter being dried before smoking and dosage.
Taux d'humidité : 7 ± 2 %, PH : environ 8Humidity level: 7 ± 2%, PH: about 8
Cigarettes témoins utilisées: Peter Stuyvesant ™ normales et « extra light ». Cigarettes utilisées dont le filtre est modifié: Peter Stuyvesant ™ normales. 1) Comparatif Peter Stuyvesant normales et Peter Stuyvesant normales modifiées.Control cigarettes used: Peter Stuyvesant ™ normal and "extra light". Cigarettes used whose filter is modified: Peter Stuyvesant ™ normal. 1) Comparison of normal Peter Stuyvesant and modified normal Peter Stuyvesant.
2) Comparatif Peter Stuyvesant Extra Light et Peter Stuyvesant normales2) Comparison of Peter Stuyvesant Extra Light and Peter Stuyvesant normal
Teneurs moyennes exprimées par cigarette.Average contents expressed by cigarette.
Mesures de nicotine et goudrons selon les normes ISONicotine and tar measurements according to ISO standards
3402/4387/3308/10315/103623402/4387/3308/10315/10362
Mesures de benzo(a)pyrene selon l'article "Mariner D.C; Tuck D.J.; FrostBenzo (a) pyrene measurements according to the article "Mariner D.C; Tuck D.J .; Frost
B.E.; benzo(a)pyrene analysis in main stream cigarette smoke, CORESTA meeting Hamburg 1999, abstr. ST3". Les teneurs en benzo(a)pyrene ont été arrondies à 0.5 ng/cigarette.b, e .; benzo (a) pyrene analysis in main stream cigarette smoke, CORESTA meeting Hamburg 1999, abstr. ST3 ". The benzo (a) pyrene contents have been rounded to 0.5 ng / cigarette.
Exemple de filtres selon l'inventionExample of filters according to the invention
Exemple 1Example 1
Filtre de cigarette conventionnel en acétate de cellulose d'environ 200mg.Conventional cigarette filter in cellulose acetate of around 200mg.
Le filtre est injecté de brins monocaténaires d'ADN de saumon, d'une longueur de 2000 paires de bases environ et pour une quantité égale à 10 mg pour un filtre de cigarette usuel.The filter is injected with single-stranded strands of salmon DNA, length of approximately 2000 base pairs and for an amount equal to 10 mg for a conventional cigarette filter.
En milieu de sels à 0,1 % de NaF.In the middle of 0.1% NaF salts.
Taux d'humidité : 7 ± 2% PH : environ 8Humidity level: 7 ± 2% PH: about 8
Exemple 2Example 2
Filtre de cigarette conventionnel en acétate de cellulose d'environ 200mg.Conventional cigarette filter in cellulose acetate of around 200mg.
Le filtre est constitué sur son axe d'un compartiment mixte de filaments d'ADN de saumon et de fibres de polypropylène térephtalate, et d'un compartiment constitué uniquement de ces dernières fibres. La masse des filaments d'ADN représentant 10 mg pour un filtre de cigarette usuel.The filter consists on its axis of a mixed compartment of filaments of salmon DNA and polypropylene terephthalate fibers, and of a compartment consisting only of these latter fibers. The mass of DNA filaments representing 10 mg for a conventional cigarette filter.
En milieu de sels à 0,1 % de NaF.In the middle of 0.1% NaF salts.
Taux d'humidité : 7 ± 2%Humidity level: 7 ± 2%
PH : environ 8 Exemple 3PH: about 8 Example 3
Filtre de cigarette conventionnel en acétate de cellulose d'environ 200mg.Conventional cigarette filter in cellulose acetate of around 200mg.
Le filtre de cigarette est composé d'une mixture de filaments linéaires d'ADN de saumon emmêlés à des fibres de polypropylène térephtalate. La masse des filaments d'ADN représentant 10 mg pour un filtre de cigarette usuel.The cigarette filter is made up of a mixture of linear filaments of salmon DNA tangled with polypropylene terephthalate fibers. The mass of DNA filaments representing 10 mg for a conventional cigarette filter.
En milieu de sels fluorés à 0,1 % de KF, NaF, Na2P03F dans un rapport deIn the midst of fluorinated salts containing 0.1% KF, NaF, Na2PO3F in a ratio of
1:1:1.1: 1: 1.
Taux d'humidité : 7 ± 2%Humidity level: 7 ± 2%
PH : environ 8. PH: about 8.

Claims

Revendications claims
1. Procédé de filtration d'action sélective, chimique directe, anticancérigène, destiné à filtrer les produits toxiques, en particulier les hydrocarbures polycycliques aromatiques (HPA) tel que le benzo(a)pyrène (BaP) et les nitrosamines, contenus dans la fumée de tabac d'une cigarette ; ledit procédé comprenant l'étape de maîtriser le taux des produits toxiques par rapport à celui de la nicotine de manière à ce que la réduction du taux à la sortie du filtre soit supérieure à un seuil prédéterminé, (de sorte que la nicotine et les arômes du goût pour la satisfaction et le plaisir des fumeurs sont conservés).1. Filtering process of selective action, direct chemical, anticarcinogenic, intended to filter toxic products, in particular polycyclic aromatic hydrocarbons (HPA) such as benzo (a) pyrene (BaP) and nitrosamines, contained in smoke tobacco from a cigarette; said method comprising the step of controlling the level of toxic products relative to that of nicotine so that the reduction in the rate at the outlet of the filter is greater than a predetermined threshold, (so that the nicotine and the aromas taste for satisfaction and pleasure of smokers are preserved).
2. Procédé de filtration selon la revendication 1 tel que pour maîtriser le taux des produits toxiques par rapport à celui de la nicotine, notamment le taux des hydrocarbures polycycliques aromatiques (HPA) ) et des nitrosamines, ledit procédé comprend les étapes suivantes : - l'étape de capter tout ou partie des produits toxiques au moyen d'un principe actif agissant sur lesdits produits toxiques selon des processus moléculaires comparables à ceux selon lesquels réagit l'ADN et/ou l'ARN de la cellule humaine vis à vis desdits produits toxiques,2. A filtration method according to claim 1 such that to control the level of toxic products compared to that of nicotine, in particular the level of polycyclic aromatic hydrocarbons (HPA)) and of nitrosamines, said method comprises the following steps: - l step of capturing all or part of the toxic products by means of an active principle acting on said toxic products according to molecular processes comparable to those by which the DNA and / or RNA of the human cell reacts with respect to said products toxic
- l'étape de contrôler les conditions opératoires du filtre en opérant en milieu sensiblement non aqueux et de pH basique, de préférence supérieur ou égal à 8,the step of controlling the operating conditions of the filter by operating in a substantially non-aqueous medium and of basic pH, preferably greater than or equal to 8,
- l 'étape d'ajuster la masse du principe actif de telle sorte qu'elle soit supérieure ou égale à 0,1 % de la masse du filtre de la cigarette et de préférence supérieure ou égale à 1 % de la masse du filtre. - The step of adjusting the mass of the active ingredient so that it is greater than or equal to 0.1% of the mass of the filter of the cigarette and preferably greater than or equal to 1% of the mass of the filter.
3. Procédé selon la revendication 2 tel que ledit principe actif est composé de molécules constituées d'un ou plusieurs cycles azotés ou heterocycles azotés, et particulièrement des hétéroaromatiques azotés, notamment de pentacycles ou d'hexacycles ou d'une association des deux ; ledit principe actif se présentant sous la forme : - d'une chaîne desdites molécules et/ou3. Method according to claim 2 such that said active principle is composed of molecules consisting of one or more nitrogen rings or nitrogen heterocycles, and in particular nitrogen heteroaromatics, in particular pentacycles or hexacycles or a combination of the two; said active principle being in the form: - a chain of said molecules and / or
- desdites molécules liées dans un arrangement chimique commun à une fibre, notamment une fibre composée d'acétate de cellulose.- Said molecules linked in a chemical arrangement common to a fiber, in particular a fiber composed of cellulose acetate.
4. Procédé selon la revendication 3 tel que la molécule du principe actif est de l'ADN et/ou de l'ARN et/ou un dérivé de l'ADN ou de l'ARN, comme par exemple l'adénosine triphosphate (ATP), l'adénosine monophosphate cyclique (AMP), l'adényl-cyclase.4. Method according to claim 3 such that the molecule of the active principle is DNA and / or RNA and / or a derivative of DNA or RNA, such as for example adenosine triphosphate (ATP ), cyclic adenosine monophosphate (AMP), adenyl cyclase.
5. Filtre de cigarette d'action sélective, chimique directe, anti-cancérigène, destiné à filtrer particulièrement les hydrocarbures polycycliques aromatiques (HPA), notamment le benzo(a)pyrène (BaP), ainsi que les nitrosamines, en conservant le taux de nicotine et les arômes du goût pour la satisfaction et le plaisir du fumeur ; ledit filtre comportant un principe actif composé de molécules constituées d'un ou plusieurs cycles azotés ou heterocycles azotés, et particulièrement des hétéroaromatiques azotés, notamment de pentacycles ou d'hexacycles ou d'une association des deux ; ledit principe actif se présentant sous la forme :5. Cigarette filter for selective action, direct chemical, anti-carcinogenic, intended to filter particularly polycyclic aromatic hydrocarbons (HPA), in particular benzo (a) pyrene (BaP), as well as nitrosamines, while retaining the rate of nicotine and flavor aromas for the satisfaction and pleasure of the smoker; said filter comprising an active principle composed of molecules consisting of one or more nitrogen rings or nitrogen heterocycles, and in particular nitrogen heteroaromatics, in particular pentacycles or hexacycles or a combination of the two; said active principle being in the form:
- d'une chaîne desdites molécules et/ou- a chain of said molecules and / or
- desdites molécules liées à une fibre dans un arrangement chimique commun, notamment une fibre composée d'acétate de cellulose ; la masse desdits cycles ou heterocycles azotés et particulièrement des hétéroaromatiques azotés étant au moins égale ou supérieure à 0,1 % de la masse totale du filtre ; lesdits cycles ou heterocycles azotés et particulièrement des hétéroaromatiques azotés opérant dans un milieu sensiblement non-aqueux et ayant un pH basique ,- said molecules linked to a fiber in a common chemical arrangement, in particular a fiber composed of cellulose acetate; the mass of said nitrogenous cycles or heterocycles and particularly of nitrogenous heteroaromatics being at least equal to or greater than 0.1% of the total mass of the filter; said nitrogenous cycles or heterocycles and particularly nitrogenous heteroaromatics operating in a substantially non-aqueous medium and having a basic pH,
(de sorte qu 'il est ainsi possible de réduire de manière substantielle, à la sortie du filtre, le taux des hydrocarbures polycycliques aromatiques par rapport à la nicotine, notamment de plus de 90 %, en conservant le taux de nicotine et les arômes du goût pour la satisfaction et le plaisir du fumeur ).(so that it is thus possible to substantially reduce, at the outlet of the filter, the level of polycyclic aromatic hydrocarbons compared to nicotine, in particular by more than 90%, by keeping the rate nicotine and flavor aromas for the satisfaction and pleasure of the smoker).
6. Filtre selon la revendication 5 tel que les molécules sont constituées en polymère au sens large. 6. Filter according to claim 5 such that the molecules are made of polymer in the broad sense.
7. Filtre selon l'une quelconque des revendications 5 ou 6 tel que le principe actif est exclusivement constitué desdites molécules et/ou desdits polymères.7. Filter according to any one of claims 5 or 6 such that the active principle consists exclusively of said molecules and / or said polymers.
8. Filtre de cigarette selon l'une quelconque des revendications 5 à 7 tel que la masse desdits cycles ou heterocycles azotés, et particulièrement des hétéroaromatiques azotés, est au moins égale ou supérieure à 1 % de la masse totale du filtre8. Cigarette filter according to any one of claims 5 to 7 such that the mass of said nitrogenous cycles or heterocycles, and in particular nitrogenous heteroaromatics, is at least equal to or greater than 1% of the total mass of the filter
9. Filtre de cigarette selon l 'une quelconque des revendications 5 à 8 tel que le taux d'humidité du filtre est compris entre 5 et 10%9. Cigarette filter according to any one of claims 5 to 8 such that the humidity of the filter is between 5 and 10%
10. Filtre de cigarette selon l'une quelconque des revendications 5 à 9 tel que le pH du filtre est supérieur à 810. Cigarette filter according to any one of claims 5 to 9 such that the pH of the filter is greater than 8
11. Filtre de cigarette selon l'une quelconque des revendications 5 à 8 tel que la molécule du principe actif est de l'ADN et/ou de l'ARN et/ou un dérivé de l'ADN ou de l'ARN, comme par exemple l'adénosine tπphosphate (ATP), l 'adénosine monophosphate cyclique ou l'adén l- cyclase,11. A cigarette filter according to any one of claims 5 to 8 such that the molecule of the active principle is DNA and / or RNA and / or a derivative of DNA or RNA, such as for example adenosine tπphosphate (ATP), cyclic adenosine monophosphate or adén l-cyclase,
(de sorte que les produits toxiques cancérigènes, contenus dans la fumée de tabac, affectant les molécules d'ADN et/ou d'ARN de la cellule humaine, sont captes par le filtre selon des processus moléculaires comparables à ceux selon lesquels lesdits produits toxiques agissent sut l'ADN et/ ou l'ARN de la cellule humaine)(so that the toxic carcinogenic products, contained in tobacco smoke, affecting the DNA and / or RNA molecules of the human cell, are captured by the filter according to molecular processes comparable to those according to which said toxic products act on the DNA and / or RNA of the human cell)
12. Filtre selon l'une quelconque des re\ endications 5 à 11 tel que la molécule du principe actif est additionnée, sur l 'un au moins des cycles azotés ou heterocycles azotés et particulièrement des hétéroaromatiques azotés, d'au moins une fonction choisie dans un groupe comprenant les fonctions :12. Filter according to any one of claims 5 to 11 such that the molecule of the active principle is added, on at least one of the nitrogen cycles or nitrogen heterocycles and particularly nitrogen heteroaromatics, to at least one selected function in a group including functions:
- aminé NH2,- NH2 amino,
- cétone, aldéhyde,- ketone, aldehyde,
- méthyle, - alcène, alcyle ou aryle, sur l'un au moins des cycles azotés ou heterocycles azotés, et particulièrement des hétéroaromatiques azotés.- methyl, - alkene, alkyl or aryl, on at least one of the nitrogen rings or nitrogen heterocycles, and in particular nitrogen heteroaromatics.
13. Filtre selon l'une quelconque des revendications 5 à 12 tel qu'au moins une molécule du principe actif est additionnée d'un ou plusieurs sucres tels que le ribose ou le désoxyribose.13. Filter according to any one of claims 5 to 12 such that at least one molecule of the active principle is added with one or more sugars such as ribose or deoxyribose.
14. Filtre selon l'une quelconque des revendications 5 à 13 tel qu'au moins une molécule du principe actif est additionnée d'une ou plusieurs fonctions acides, notamment de l'acide phosphorique (H3P04) pentavalent et/ou d'une autre molécule comportant un phosphore trivalent.14. Filter according to any one of claims 5 to 13 such that at least one molecule of the active principle is added with one or more acid functions, in particular phosphoric acid (H3PO4) pentavalent and / or another molecule containing a trivalent phosphorus.
15. Filtre selon l'une quelconque des revendications 5 à 14 telle que la polymérisation s'effectue au sens large au niveau des cycles azotés, soit des heterocycles azotés et particulièrement des hétéroaromatiques azotés et/ou des fonctions additionnées et/ou des acides et/ou des sucres. 15. Filter according to any one of claims 5 to 14 such that the polymerization is carried out in the broad sense at the level of the nitrogen cycles, ie nitrogen heterocycles and particularly nitrogen heteroaromatics and / or added functions and / or acids and / or sugars.
16. Filtre selon l'une quelconque des revendications 5 à 15 tel que la molécule du principe actif comporte un ou plusieurs atomes et/ou une ou plusieurs molécules et/ou un ou plusieurs radicaux et/ou un ou plusieurs ions d'un halogène, tel que notamment le fluor.16. Filter according to any one of claims 5 to 15 such that the molecule of the active principle comprises one or more atoms and / or one or more molecules and / or one or more radicals and / or one or more ions of a halogen , such as in particular fluorine.
17. Filtre selon l'une quelconque des revendications 5 à 16 tel que la molécule du principe actif est en milieu de sels halogènes, notamment en milieu de sels de fluorure de sodium NaF.17. Filter according to any one of claims 5 to 16 such that the molecule of the active principle is in the middle of halogenated salts, in particular in the middle of sodium fluoride salts NaF.
18. Filtre selon l'une quelconque des revendications 5 à 17 tel que lesdites fibres sont partiellement halogénées, tel que notamment par le fluor, et/ou sont dans un milieu comportant des atomes, des molécules, des radicaux ou des ions d'un halogène, tel que notamment le fluor.18. Filter according to any one of claims 5 to 17 such that said fibers are partially halogenated, such as in particular by fluorine, and / or are in a medium comprising atoms, molecules, radicals or ions of a halogen, such as in particular fluorine.
19. Procédé de fabrication d'un filtre comportant des molécules et/ou des fibres selon l'une quelconque des revendications 5 à 18 ; ledit procédé comprenant l'étape d'extruder et/ou de rouler ensemble lesdites molécules et/ou lesdites fibres.19. A method of manufacturing a filter comprising molecules and / or fibers according to any one of claims 5 to 18; said method comprising the step of extruding and / or rolling together said molecules and / or said fibers.
20. Dispositif de filtration comportant des molécules et/ou des fibres selon l 'une quelconque des revendications 5 à 19.20. A filtration device comprising molecules and / or fibers according to any one of claims 5 to 19.
21. Dispositif de filtration selon la revendication 20 tel que lesdites molécules et/ou lesdites fibres sont incorporées dans des compartiments séparés.21. A filtration device according to claim 20 such that said molecules and / or said fibers are incorporated in separate compartments.
22. Dispositif de filtration selon l'une quelconque des revendications 20 ou 21 tel que lesdites molécules et/ou lesdites fibres se présentent selon un état physique gélatineux, liquide ou gazeux.22. A filtration device according to any one of claims 20 or 21 such that said molecules and / or said fibers are in a gelatinous, liquid or gaseous physical state.
23. Application du dispositif de filtration selon l'une quelconque des revendications 20 à 22 à la filtration sélective de produits toxiques.23. Application of the filtration device according to any one of claims 20 to 22 to the selective filtration of toxic products.
24. Cigarette comportant un dispositif de filtration selon l'une quelconque des revendications 20 à 22. 24. Cigarette comprising a filtration device according to any one of claims 20 to 22.
EP00962594A 1999-09-13 2000-09-08 Filtering method and filter consisting of nitrogen-containing cycles or heterocyles such as dna or rna designed in particular for filtering tobacco smoke and cigarette containing such a filter Expired - Lifetime EP1213977B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9911552A FR2798302B1 (en) 1999-09-13 1999-09-13 FILTER COMPOSED OF NITROGEN HETEROCYCLES SUCH AS DNA, IN PARTICULAR FOR THE FILTRATION OF TOBACCO SMOKE, CIGARETTE COMPRISING SUCH A FILTER
FR9911552 1999-09-13
PCT/FR2000/002493 WO2001019210A1 (en) 1999-09-13 2000-09-08 Filtering method and filter consisting of nitrogen-containing cycles or heterocyles such as dna or rna designed in particular for filtering tobacco smoke and cigarette containing such a filter

Publications (2)

Publication Number Publication Date
EP1213977A1 true EP1213977A1 (en) 2002-06-19
EP1213977B1 EP1213977B1 (en) 2003-11-26

Family

ID=9549884

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00962594A Expired - Lifetime EP1213977B1 (en) 1999-09-13 2000-09-08 Filtering method and filter consisting of nitrogen-containing cycles or heterocyles such as dna or rna designed in particular for filtering tobacco smoke and cigarette containing such a filter

Country Status (8)

Country Link
US (1) US6866045B1 (en)
EP (1) EP1213977B1 (en)
JP (1) JP4808881B2 (en)
AT (1) ATE254858T1 (en)
AU (1) AU7426300A (en)
DE (1) DE60006832D1 (en)
FR (1) FR2798302B1 (en)
WO (1) WO2001019210A1 (en)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1614457A1 (en) * 2003-04-16 2006-01-11 Nissei Bio Co., Ltd. Method for removing harmful substances and filter for removing harmful substances
US20050016555A1 (en) * 2003-07-24 2005-01-27 Lyles Mark B. Nucleic acid based filters
CN101166432A (en) * 2005-04-28 2008-04-23 日生生物股份有限公司 Cigarette filter tip capable of removing bad materials
US20090183745A1 (en) * 2005-10-12 2009-07-23 Nissei Bio Company, Limited Cigarette Filter
JPWO2007083370A1 (en) * 2006-01-18 2009-06-11 日生バイオ株式会社 Air conditioner filter that can remove harmful substances
JP5317394B2 (en) * 2006-05-30 2013-10-16 株式会社ダイセル Tobacco filter material and tobacco filter
WO2008036388A2 (en) * 2006-09-22 2008-03-27 New York University Methods and products for neutralizing the harmful effects of combustion products
JP2008030039A (en) * 2007-08-13 2008-02-14 Nissei Bio Kk Method for removing harmful substance and filter for removing harmful substance
JP2008068254A (en) * 2007-08-13 2008-03-27 Nissei Bio Kk Method and filter for removing harmful substance
US9192193B2 (en) 2011-05-19 2015-11-24 R.J. Reynolds Tobacco Company Molecularly imprinted polymers for treating tobacco material and filtering smoke from smoking articles
US10731018B2 (en) 2015-08-11 2020-08-04 Arizona Board Of Regents On Behalf Of The University Of Arizona Antioxidant polydihydropyridazine and polypyridazine foams from 1,2,4,5-tetrazine
US10619023B2 (en) 2015-08-11 2020-04-14 Arizona Board Of Regents On Behalf Of The University Of Arizona Green chemistry method of synthesizing polymer structures that can function as a built-in antioxidant
US10851192B2 (en) 2015-08-11 2020-12-01 Arizona Board Of Regents On Behalf Of The University Of Arizona Dihydropyridazine-based antioxidants and uses thereof
WO2017172882A1 (en) * 2016-03-29 2017-10-05 The Arizona Board Of Regents On Behalf Of The University Of Arizona Pyridazine and pyridazinone based foam filtration materials for removal of nucleophiles, electrophiles, and metals
WO2018005864A1 (en) 2016-06-29 2018-01-04 The Arizona Board Of Regents On Behalf Of The University Of Arizona Method of formation of a robust network of foam through diels-alder reaction
US10633517B2 (en) 2017-03-10 2020-04-28 Arizona Board Of Regents On Behalf Of The University Of Arizona Hydrogenated tetrazine-based antioxidants and free radical reaction inhibitors and uses thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3982897A (en) 1972-09-25 1976-09-28 Israel Herbert Scheinberg Filter and detector and methods of using same in the removal and detection of carbon monoxide from, and in, a gas stream
GB1503879A (en) * 1976-02-19 1978-03-15 Scheinberg I Preparation and method of use of compounds and compositions effective for removal conversion and detection of carbon monoxide
WO1982002820A1 (en) * 1981-02-18 1982-09-02 Pruss Guenter Tobacco smoke filter
US4498485A (en) * 1982-08-05 1985-02-12 Hem-Sub, Inc. Interferon and interferon inducers combined with tobacco products
JPS60151397U (en) * 1984-03-21 1985-10-08 ピツプフジモト株式会社 smoking pipe
JPS6258981A (en) * 1985-04-08 1987-03-14 近藤　昭子 Structure of tobacco filter part
US4735218A (en) * 1984-09-09 1988-04-05 Kondo Akiko Tobacco filter
EP0434339A3 (en) 1989-12-18 1991-10-09 R.J. Reynolds Tobacco Company Cigarette and cigarette filter element therefor
US5105834A (en) 1989-12-18 1992-04-21 R.J. Reynolds Tobacco Company Cigarette and cigarette filter element therefor
US5746231A (en) 1993-01-11 1998-05-05 Craig Lesser Tobacco smoke filter for removing toxic compounds
RU2123271C1 (en) 1994-06-27 1998-12-20 Ставридис Иоаннис Method of manufacturing filter for tobacco smoke, filter, cigarette, and method of filtering tobacco smoke
LU88544A1 (en) 1994-10-07 1996-04-29 G L A D S A Anticarcinogenic treatment for cigarette filters or the like

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0119210A1 *

Also Published As

Publication number Publication date
ATE254858T1 (en) 2003-12-15
FR2798302B1 (en) 2001-12-21
FR2798302A1 (en) 2001-03-16
JP2003509033A (en) 2003-03-11
JP4808881B2 (en) 2011-11-02
DE60006832D1 (en) 2004-01-08
EP1213977B1 (en) 2003-11-26
US6866045B1 (en) 2005-03-15
AU7426300A (en) 2001-04-17
WO2001019210A1 (en) 2001-03-22

Similar Documents

Publication Publication Date Title
EP1213977B1 (en) Filtering method and filter consisting of nitrogen-containing cycles or heterocyles such as dna or rna designed in particular for filtering tobacco smoke and cigarette containing such a filter
US7025067B2 (en) Activated charcoal filter for effectively reducing p-benzosemiquinone from the mainstream cigarette smoke
KR100265506B1 (en) Filter cigarette
US20110155154A1 (en) Smoking Article with Tobacco Beads
FR2542581A1 (en) METHOD AND ENVELOPE OF A SMOKING ARTICLE FOR REDUCING THE AUXILIARY CURRENT OF SMOKE
US8011373B2 (en) Method of treating tobacco extract solution to reduce magnesium ions and method of manufacturing a treated tobacco material
CN111655051A (en) Biodegradable filter to improve taste
EP0436599A1 (en) Tobacco smoke filters and process for production thereof
CN104270968A (en) Liquid tobacco compositions
CA2464149A1 (en) Cigarette filter and filter-tipped cigarette
EP1541044B1 (en) Filter for cigarette
EP1541043B1 (en) Filter for cigarette
CN1897833B (en) Tobacco smoke filter
BE1020864A3 (en) COMBINATION IN THE FORM OF POWDER HAVING PRESERVATIVE PROPERTIES, RETENTRICE OF WATER AND TEXTURANT.
CN202026791U (en) Multi-element composite filter stick
FR2459011A1 (en) METHOD OF AROMATING TOBACCO SMOKE, CIGARETTE TIP FOR IMPLEMENTING SAID METHOD AND APPLICATION OF THE PROCESS
US20050016555A1 (en) Nucleic acid based filters
CA3211812A1 (en) Liquid composition for inhalation for electronic cigarettes
JP2001352963A (en) Cigarette filter and cigarette therewith
CH649007A5 (en) TOBACCO SMOKE FILTER.
CH622687A5 (en) Smokeable substance
CN101166432A (en) Cigarette filter tip capable of removing bad materials
FR2767649A1 (en) Method of production of non-tobacco cigarettes
JP2017513518A (en) Additive-carrying composition
EP4544927A1 (en) Filter for smoking article containing lyocell tow, manufacturing method, and smoking article comprising same

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: 20020409

AK Designated contracting states

Kind code of ref document: A1

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

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20020903

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

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: IE

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: 20031126

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20031126

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: 20031126

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: 20031126

Ref country code: NL

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: 20031126

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: 20031126

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 60006832

Country of ref document: DE

Date of ref document: 20040108

Kind code of ref document: P

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: FRENCH

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040226

Ref country code: DK

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: 20040226

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: 20040226

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

Ref country code: DE

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: 20040227

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040309

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040317

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
LTIE Lt: invalidation of european patent or patent extension

Effective date: 20031126

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

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: 20040908

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

Ref country code: CH

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

Effective date: 20040930

Ref country code: BE

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

Effective date: 20040930

Ref country code: LI

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

Effective date: 20040930

Ref country code: MC

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

Effective date: 20040930

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: 20040827

BERE Be: lapsed

Owner name: *MAILLARD FREDERIC

Effective date: 20040930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

BERE Be: lapsed

Owner name: *MAILLARD FREDERIC

Effective date: 20040930

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

Ref country code: PT

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

Effective date: 20040426

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20110127 AND 20110202

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

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

Ref country code: GB

Payment date: 20120925

Year of fee payment: 13

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

Ref country code: FR

Payment date: 20121026

Year of fee payment: 13

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130908

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140530

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

Ref country code: GB

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

Effective date: 20130908

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

Ref country code: FR

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

Effective date: 20130930