EP3107409A1 - Utilisation d'une composition renfermant du 1,3-propanediol comme e-liquide - Google Patents
Utilisation d'une composition renfermant du 1,3-propanediol comme e-liquideInfo
- Publication number
- EP3107409A1 EP3107409A1 EP15717542.3A EP15717542A EP3107409A1 EP 3107409 A1 EP3107409 A1 EP 3107409A1 EP 15717542 A EP15717542 A EP 15717542A EP 3107409 A1 EP3107409 A1 EP 3107409A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- nicotine
- propanediol
- composition
- electronic cigarette
- propylene glycol
- 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
Links
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Classifications
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/10—Chemical features of tobacco products or tobacco substitutes
- A24B15/16—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes
- A24B15/167—Chemical features of tobacco products or tobacco substitutes of tobacco substitutes in liquid or vaporisable form, e.g. liquid compositions for electronic cigarettes
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B15/00—Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
- A24B15/18—Treatment of tobacco products or tobacco substitutes
- A24B15/28—Treatment of tobacco products or tobacco substitutes by chemical substances
- A24B15/30—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances
- A24B15/32—Treatment of tobacco products or tobacco substitutes by chemical substances by organic substances by acyclic compounds
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24F—SMOKERS' REQUISITES; MATCH BOXES; SIMULATED SMOKING DEVICES
- A24F40/00—Electrically operated smoking devices; Component parts thereof; Manufacture thereof; Maintenance or testing thereof; Charging means specially adapted therefor
- A24F40/10—Devices using liquid inhalable precursors
Definitions
- the present invention relates to the use of a composition containing 1,3-propanediol as an electronic cigarette liquid. It also relates to an electronic cigarette liquid composition comprising 1,3-propanediol, as well as nicotine and / or at least one flavor, and an electronic cigarette containing this composition.
- the e-cigarette market is currently developing significantly as it allows the consumer to maintain the ritual associated with the use of cigarettes without suffering the deleterious effects of the harmful substances it contains.
- the electronic cigarette or e-cigarette runs on electricity without burning. It produces a mist of fine particles, commonly called vapor or artificial smoke, visually resembling the smoke produced by burning tobacco.
- This vapor can be flavored (aroma of tobacco, mint, fruit, chocolate, etc.) and contain or not nicotine.
- the aerosol contains, according to the available data, far fewer deleterious substances to health than tobacco smoke, in particular no solid particles, tar, other carcinogens, or monoxide. of carbon (CO).
- the e-cigarette has three main parts contained in a plastic or metallic envelope:
- the battery is most of the time the largest part of the e-cigarette on the disposables.
- Reusable cigarettes are "low voltage" batteries (accumulators), rechargeable by USB cable or charger.
- the tube housing the battery is screwed onto the cartridge containing the liquid.
- an indicator light usually a red or blue diode - is placed at the other end of the battery tube.
- the e-liquid storage device may take the form of a cartridge (generally made of silicone, PMMA or stainless metal) or a tank (in particular PMMA / polyethylene, borosilicate glass or stainless metal) optionally supplemented with a device for collecting the liquid by capillarity (in particular silica, fiberglass, ceramic metal fabric, nylon thread or borosilicate fiber) in contact with the vaporization system.
- the atomizer makes it possible to convert the e-liquid into fog simulating smoke. It consists of a spiral or wire mesh that forms a heating resistor. It is more and more often integrated in the refillable cartridge. A micro-valve sensitive to depression caused by inspiration or a manually triggered contactor allows the battery to feed the atomizer.
- the e-cigarette can be single-use or reusable.
- the e-liquids used are mainly composed of the following constituents:
- Some e-liquids may also contain significant amounts of ethanol (> 1%).
- Some products may be free of synthetic propylene glycol.
- the objective is in this case to be able to claim products of exclusively vegetable origin. This objective is achieved, however, to the detriment of the longevity of heating resistors, which clog very quickly.
- the quality of the emitted smoke is far from adequate in terms of vapor density, and the organoleptic properties of the liquids are strongly modified, since the release of the flavors in the absence of propylene glycol is made less immediate.
- the exclusive use of glycerol forces to load the product with water, in order to reduce the viscosity of the e-liquid and thus facilitate the filling of the e-cigarette.
- propylene glycol in a larger quantity than glycerol is most often preferred, which does not allow manufacturers to claim a natural origin of their products.
- propylene glycol is obtained according to one of the most energy-consuming processes in the world. petrochemical and de facto has a strong environmental footprint (Eissen & al, Angew Chem Int, Ed., 2002, 41, 414-436) which results in high energy consumption and high production of volatile organic compounds (VOCs). ) and waste.
- the synthetic propylene glycol is obtained from propylene oxide according to a continuous hydration process, according to the following scheme: + poig ⁇ ycois
- propylene glycol is accompanied by the formation of secondary products (di-, and tri- and tetrapropylene glycols) and unconverted propylene oxide (Petrochemical Processes: Major Oxygenated, Chlorinated and Nitrated Derivatives - Alain Chauvel, Gilles Lefebvre - TECHNIP Editions - p26), horn illustrated below:
- propylene glycol is di- and tripropylene glycol, as well as propylene oxide whose residual content according to the producers is of the order of 5 to 10 ppm ( Propylene Glycol - CIR Expert Panel, June 28-29, 2010 - Draft Report).
- propylene oxide is classified by North American and European environmental agencies as a carcinogenic compound and mutagenic in animals and as a probable carcinogen in humans. Therefore, it is important to limit exposure to this compound.
- the Report and Expert Opinion on the e-Cigarette published by the French Office for Tobacco Prevention (OFT) in May 2013 stresses the need to ensure the absence of carcinogenic contaminants in e-liquids.
- PDO of plant origin is today produced industrially by fermentation of glucose. It is currently used as an intermediate resin synthesis, as a solvent, humectant, preservative in the food industry, cosmetics, pharmaceuticals and personal care products, and as a component of hydraulic fluids, antifreezes, brake fluids, coolants, as a component of cleaning liquids, detergents, co-solvent paints, and solvents in the printing ink industry. Also, to the knowledge of the Applicant, the PDO has never been described as constituting e-liquids.
- the present invention thus relates to the use of a composition containing 1,3-propanediol and at least one additive selected from the group consisting of glycerine, nicotine, a substitute of nicotine and aroma as an electronic cigarette liquid.
- an electronic cigarette liquid composition comprising 1,3-propanediol, as well as at least one compound selected from nicotine, a nicotine substitute and a flavor.
- It also relates to the use of 1,3-propanediol in an electronic cigarette liquid containing or not nicotine, to improve the tingling of the groove felt by a user of said liquid and / or the ease of aspiration of the vapor produced by said liquid and use of 1,3-propanediol in an electronic cigarette liquid containing nicotine, to improve the bioavailability of nicotine.
- thermolysis co-products It also relates to a use of 1,3-propanediol, optionally in the presence of glycerin, in an electronic cigarette liquid to enhance the aromatic power and a use of 1,3-propanediol, optionally in the presence of glycerin, in a liquid of electronic cigarette to limit or to suppress the formation of thermolysis co-products.
- the term "electronic cigarette” means all devices equipped with electrical means producing steam and delivering nicotine and / or aroma.
- This definition therefore includes, in particular, personal vaporizers (VPs), nicotine delivery systems (ENDS for “Electronic Nicotine Delivery System”, or ENDD for “Electronic Nicotine Delivery Device”), as well as electronic cigars, electronic pipes and electronic shisha, tobacco-based cigarettes that are heated or contain a flavor of tobacco obtained by maceration.
- VPs personal vaporizers
- ENDS Electronic Nicotine Delivery System
- ENDD Electronic Nicotine Delivery Device
- plant-based compound a compound comprising at least 95% biobased carbon, as determined by ASTM standard D6866-12 (Standard Test Methods for Determining the Biobase Content of Solid, Liquid, and Gaseous Samples Using Radiocarhon Analysis).
- the invention relates to the use of a composition containing PDO as an electronic cigarette liquid (hereinafter, "e-liquid").
- e-liquid an electronic cigarette liquid
- the PDO can be synthetic or, according to a preferred embodiment of the invention, it can be obtained from vegetable raw materials and referred to herein as "PDO of plant origin”.
- the PDO of plant origin is obtained by fermentation.
- the PDO of plant origin can be obtained by fermentation of glucose, in the presence of a native bacterium or genetically modified, selected in particular from strains of Klebsiella (including pneumoniae), Clostridium (including butyricum), Citrobacter (including freundii), Serratia and Escherichia coli, preferably Escherichia coli, and more preferably Escherichia coli K-12.
- a native bacterium or genetically modified selected in particular from strains of Klebsiella (including pneumoniae), Clostridium (including butyricum), Citrobacter (including freundii), Serratia and Escherichia coli, preferably Escherichia coli, and more preferably Escherichia coli K-12.
- a genetically modified strain is described in US application 2012/258521.
- the bio-based glucose used to produce PDO is usually derived from sugar or starchy plants such as sugar cane, maize, wheat, potato, sugar beet, rice,
- the glucose is derived from non-genetically modified plant varieties, such as sugar cane or beet.
- glucose is derived from non-food lignocellulosic biomasses such as wood, straw, palm bunchees, bagasse, and non-genetically modified maize stalks.
- the product of the fermentation can be recovered, and the PDO purified, by membrane filtration, electrodialysis, concentration or rectification, for example, or by a combination of these techniques.
- the PDO can in particular be purified by distillation, an operation which makes it possible to reach a purity of 99.8%.
- the impurities present at 0.2% are water and propanol-1 (Chatterjee et al., Glycerol to Propylene Glycol / Department of Chemical & Biomolecular Engineering Senior Design Reports (CEE), University of Pennsylvania - April 12, 2011 ), a compound devoid of toxicity.
- the PDO may represent from 50 to 99% by weight, preferably from 60 to 95% by weight, more preferably from 70 to 90% by weight, relative to the total weight of the composition.
- the composition used according to the invention may also contain propylene glycol.
- the latter may be of synthetic or vegetable origin (that is to say obtained from vegetable raw materials).
- the propylene glycol may in particular be obtained by hydrogenolysis of sorbitol or vegetable glycerol (New and Future Developments in Catalysis: Catalytic Biomass Chemistry - S. Suib Editor / Elsevier - 2013, pp 13-17 or by hydrogenation of vegetable lactic acid (J. Van Haveren & others Bulk Chemicals from Biomass, BioFPR, november 1, 2007. pp 41-57).
- the biosourced glycerol used to produce propylene glycol may be of animal or plant origin, preferably plant-based.
- Vegetable glycerol is derived from the hydrolysis (acidic or basic) of vegetable oils or their alcoholysis (transesterification). These oils belong in a non-limiting manner to the group of oils of soya, palm, palm kernel, copra, rapeseed, sunflower, corn germ, cotton, olive, sesame, rice bran, flax, castor oil, avocado, peanut, safflower, grapeseed, or tall oil. It is preferred to use glycerol from non-genetically modified plant varieties, such as palm, rapeseed, sunflower, or copra oils.
- the sorbitol or biosourced lactic acid used to produce propylene glycol of plant origin is generally derived from sugar or starchy plants such as sugar cane, corn, wheat, potato, sugar beet, rice, or sorghum.
- sugar or starchy plants such as sugar cane, corn, wheat, potato, sugar beet, rice, or sorghum.
- sorbitol or lactic acid from non-genetically modified plant varieties such as sugar cane or beet is used.
- sorbitol or lactic acid is obtained from non-food lignocellulosic biomasses such as wood, straw, palm bunchees, bagasse, and non-genetically modified maize stalks.
- the propylene glycol may represent from 2 to 50% by weight, preferably from 10 to 40% by weight, more preferably from 20 to 30% by weight, relative to the total weight of the composition.
- the composition used as e-liquid contains no or little glycerin, that is to say it contains from 0 to 40% by weight of glycerol, preferably from 0 to 20% by weight. by weight, for example from 0 to 5% by weight of glycerin or from 5 to 20% by weight of glycerin. It has indeed been observed, as indicated above, that the absence of glycerine makes it possible to avoid the formation of undesirable by-products when heating the glycerine.
- composition used according to the invention may additionally contain at least one compound chosen from nicotine, a nicotine substitute (typically a non-addictive molecule but with a sensory effect close to that of nicotine) and an aroma.
- a nicotine substitute typically a non-addictive molecule but with a sensory effect close to that of nicotine
- Nicotine can be of synthetic or plant origin and should preferably meet the criteria of purity described in the US Pharmacopoeia (USP) and European (PE) in force. It can in particular be extracted from tobacco leaves or obtained by chemical synthesis.
- the nicotine concentration in the composition according to the invention may range from 0 to 50 mg / ml, preferably from 2 to 20 mg / ml.
- the composition used according to the invention has an aroma content of less than 10% by weight.
- Flavorings may also be flavor of plant or synthetic origin such as those registered in the food and / or pharmaceutical, especially those listed in Regulation EU No 872/2012 of 1 October 2012 and in the US Pharmacopoeia ( USP) and European (PE) in force.
- the concentration of flavors can range from 0 to 30% by weight, preferably from 1 to 8% by weight, more preferably from 2 to 5% by weight, relative to the total weight of the composition.
- the composition used according to the invention may also comprise water and / or an alcohol such as ethanol and / or at least one dye.
- the water and the alcohol may each represent from 0 to 20% by weight, preferably from 1 to 10% by weight, relative to the total weight of the composition.
- the dyes may be dyes of vegetable or synthetic origin, such as those approved in the food and / or pharmaceutical fields and in particular those listed in the EU Regulation No. 1331/2008 and in the US and European Pharmacopoeias (USP) ( PE) in force.
- the concentration of flavors can range from 0 to 30% by weight, preferably from 1 to 8% by weight, more preferably from 2 to 5% by weight, relative to the total weight of the composition.
- the composition does not comprise ethanol and / or does not comprise no water, except that possibly contained in the raw materials that the composition contains.
- water can promote the development of pathogenic microorganisms of microbial origin and its use generally requires the use of preservatives or the production of a sterilizing microfiltration.
- the addition of water to e-liquids induces a transformation of nicotine base into protonated nicotine.
- the protonated form of nicotine is significantly less bio ⁇ assimilable, and in fact less addictive, than nicotine base.
- 1,3-propanediol makes it possible to formulate very fluid e-liquids without having to add osmosis water, in which the nicotine is present in base form and in its highly bioavailable form, which clearly improves the control. delivery of nicotine, especially during smoking cessation.
- the composition according to the invention has a kinematic viscosity at 20 ° C. of less than 200 mPas / s, preferably less than 100 mPa.s, more preferably less than 75 mPa.s, better still less than 60 mPa.s. said viscosity being greater than 30 mPa.s, preferably greater than 40 mPa.s and more preferably greater than 50 mPa. s.
- the invention also relates to an electronic cigarette containing the composition as described above. This is generally arranged in a cartridge secured to a receptacle housing a power supply system connected to a device for atomizing the composition.
- thermolysis coproducts It also relates to the use of 1,3-propanediol, optionally in the presence of glycerin, in an electronic cigarette liquid to limit or to suppress the formation of thermolysis coproducts.
- the mixture is analyzed by gas chromatography coupled to mass spectrometry according to the method described in the publication by Cao et al. (Cao XL, Corriveau J. An isotope dilution headspace method with gas chromatography-mass spectrometry for determination of propylene oxide in Food Addit Contam Part A Chem Anal Control Expo Risk Assessment 2009 Apr; 26 (4): 482-6.
- the biobased carbon content of the mixture is equal to
- Example 2 The procedure is identical to Example 1, but replacing propylene glycol vegetable by the 1, 3-propanediol provided by DuPont Tate & Lyle & LLC under reference Zemea ® propanediol.
- the biobased carbon content of the mixture is equal to
- the biobased carbon content of the mixture is equal to
- Example 2 The procedure is identical to Example 1, but replacing the propylene glycol and the glycerol of vegetable origin with PDO of plant origin according to Example 2.
- the biobased carbon content of the mixture is equal to
- e-liquid compositions prepared in Examples 1 to 4 are evaluated by a trained panel of 10 persons equipped with a Joytech TM brand cigarette and eCab TM model (December 2013 model). Each tank is filled with an identical amount of e-liquid (1 ml).
- each panelist blinds a test on the basis of 8 successive puffs spaced 20 seconds and each induced by heating 2 seconds. The evaluation is based on the rating, on a scale of 1 to 10, of the criteria of vapor density and aromatic power felt.
- the passage from one product to another is done by each panelist as follows: 5 minutes after the last aspiration, the panelist rinses his mouth with 2 glasses of water of 100 ml then quenches with 50 ml of water. A rest period between each assessment is set at 10 minutes.
- propylene glycol of plant origin (Example 1) has substantially the same properties as synthetic propylene glycol (Example 3).
- PDO (Example 2) has a significantly higher vapor density and aromatic power, which is further increased in the absence of glycerin (Example 4).
- synthetic propylene glycol it also makes it possible to produce e-liquid compositions having a small footprint environmental and free of undesirable impurities such as propylene oxide and its derivatives, or even acrolein.
- the product A is then similarly carried out to prepare the product B corresponding to a mixture consisting of 5.50 kg of propylene glycol, 4.00 kg of glycerin, 50 g of osmosis water and 162.6 g of nicotine.
- a sample of 200g of B is made for analysis.
- the kinematic viscosity of products A, B, C and D is then measured.
- a proton NMR spectrum (Nuclear Magnetic Resonance) is taken on an Avance Brucker brand apparatus (500 MHz), products A, B, C, D previously dissolved in D 2 0 (deuterated water). .
- the goal is to measure the percentage of protonated nicotine in the products.
- This NMR quantification of the proton is carried out on the basis of a calibration curve covering the protonated nicotine concentration range of between 5 and 95%.
- 1,3-propanediol product C in which no addition of osmosis water has been made, has a very advantageous viscosity ( ⁇ 60 mPa / s), resulting in a fluidity making it easy to fill an electronic cigarette tank.
- the product A has a very high viscosity, greater than 400 mPa / s.
- This type of viscous solution is not usable as e-liquid since it can not be poured at room temperature into the tank body of an electronic cigarette.
- product B has a fluidity comparable to that of products C and D. It corresponds to the currently commercial solutions present on the e-liquid market.
- 1,3-propanediol makes it possible very advantageously to prepare very fluid e-liquids without having to add osmosis water, thus without preservatives or without having to engage a sterilizing microfiltration.
- 1,3-propanediol ensures the delivery of nicotine in base form (non-protonated) and thus in highly bioavailable form.
- Example 7 Influence of the nature of the solvent on the sensory properties of the e-liquid and the ease of suction of the vapor
- the e-liquid compositions B, C and D prepared in Example 6 are evaluated by a trained panel of 40 persons (male, age between 25 and 49 years), equipped with a Joytech TM brand cigarette and eCab TM model (December 2013 model). Each tank is filled with an identical amount of e-liquid (1 ml).
- each panelist performs a blind test on the basis of 8 successive puffs spaced 20 seconds and each induced by heating 2 seconds.
- the passage from one product to another is done by each panelist as follows: 5 minutes after the last aspiration, the panelist rinses his mouth with 2 glasses of water of 100 ml then quenches with 50 ml of water. A rest period between each assessment is set at 10 minutes. The evaluation is based on the rating, on a scale of 1 to 10, of the following criteria:
- 1,3-propanediol associated with nicotine induces a throat hit superior to a conventional product consisting of glycerine, propylene glycol, water and nicotine (Product B).
- 1,3-propanediol alone induces a significant "throat hit” in the absence of nicotine and significantly greater than product B.
- Example 8 Olfactory and gustative evaluation of 1,3-propanediol formulations with or without nicotine and without glycerol
- a formulation based on nicotine and 1,3 propanediol containing 15 mg / ml of nicotine is prepared.
- This formulation and a formulation comprising 1,3 propanediol are blinded to an evaluation.
- olfactory by an expert oenologist specialized in tasting and olfactory characterization of beverages and alcohols.
- the assessment includes several distinct techniques, such as those used in the context of the evaluations of large scale alcohols:
- Phase 1 tasting in the mouth in a neutral tulip glass
- each product is left in the glass.
- First time the product is poured into the glass and then felt.
- Second time the glass is covered with a neutral paper and we feel the glass 12 hours after being left to rest.
- Third step the paper is removed from the glass for two days (this operation is carried out when one sips brandies to observe the degradations related to the penetration of the air which generally leads to degradations).
- test product is placed in the palm of the hand. Before this phase, the hands are rinsed with demineralised water so as not to have recurring tastes (skin odor, saponic taste associated with a classic wash or rinsing with tap water to have bleach notes). Then the product is felt, and in a second time the product is heated by a massage action in the palm of the hand - Phase 3: tasting on the tip of the finger and in the mouth.
- Phase 4 tasting aerosols from the vaporization of products consumed using an electronic cigarette.
- the equipment used meets the following characteristics:
- variable voltage battery set at 3.2 V
- the notes detected in the nose or mouth do not predict the heartbeat notes detected during the vaping of the product.
- thermogravimetric TGA
- DTA differential thermal analysis
- Thermogravimetric analysis is a method of thermal analysis in which changes in the physical and chemical properties of materials are measured as a function of temperature. ATG can provide information on physical phenomena, such as vaporization or combustion. Similarly, information on chemical phenomena such as dehydration or decomposition can be obtained.
- DTA differential thermal analysis
- Thermogravimetric Analyzer was used to jointly determine product vaporization temperatures, enthalpy values, and non-vaporized product rates at 350 ° C. The conditions of analysis are as follows:
- temperature range 25 to 350 ° C (temperature conditions representative of normal use as well as misuse of an electronic cigarette). Between each analysis, the apparatus is cleaned by heating at 600 ° C under air flow, to remove any traces of residue. vaporized and deposited on the crucible, the balance arms or the walls of the oven.
- glycerol vaporizes at 260 ° C with 27.3% uncharacterized residue formation (possibly related to a thermal decomposition product);
- propylene glycol vaporizes at a temperature of 174 ° C. without any thermal decomposition
- 1,3-propanediol vaporizes at a temperature of 189 ° C. without any thermal decomposition
- the nicotine is vaporized at a temperature of 190 ° C., producing a residue after evaporation of 1.08%, related to the presence in the nicotine of a non-vaporizable heavy compound;
- the 1,3-propanediol and the nicotine vaporize simultaneously at 202 ° C. (1 single peak of vaporization observed in ATD) without giving rise to decomposition and / or without reacting with each other.
- 1,3-propanediol and nicotine In contrast, the vaporization temperatures of 1,3-propanediol and nicotine alone are almost equivalent. Therefore, a formulation based on 1,3-propanediol and nicotine is perfectly suited to ensure a constant delivery of nicotine in aerosol form unlike glycerol or propylene glycol based formulations or their mixture.
- 1,3-propanediol is a thermally stable solvent for nicotine that vaporizes without interacting with nicotine.
- Example 10 Evaluation of nicotine stabilization in nicotine base form by RN ⁇ ⁇ It is clearly demonstrated in the literature that the most vaporizable form of nicotine is the nicotine base form, i.e. an unprotected nicotine. Nicotine is indeed a molecule that is very sensitive to the acid-base conditions of its environment. Thus, at acidic pH to neutral, it is present in one or more protonated forms that are difficult to vaporize. On the other hand, at basic pH, nicotine is stabilized in base form easily vaporizable and therefore more suitable to be administered in aerosol form.
- the stabilization of nicotine was evaluated by comparing a nicotine formulation as presently on the market, ie formulated in a propylene glycol mixture. and glycerine to a 1,3-propanediol formulation.
- the method employed is based on the use of proton magnetic resonance spectrometry ( 1 R NMR) analysis.
- This technique makes it possible to identify the hydrogen atoms in a molecule.
- the signals obtained are partly a function of the environment in which the hydrogen atoms are considered.
- this technique was previously used by chemists to characterize matrices containing nicotine, including tobacco.
- these studies were still focused on a portion of the protons of the pyrrolidine ring of nicotine, particularly the methyl group. The latter gives in NMR a characteristic signal whose chemical shift is a function of the acidic or basic pH of the formulation.
- the NMR analyzes are carried out using a BRUKER spectrometer of 400 MgHz (Ultrashield Plus magnet) equipped with an Avance III console and a BBOF (broadband + fluorine) probe.
- a calibration was carried out by measuring the chemical shifts of the target hydrogen atoms of nicotine solutions at different pHs of between 1 and 10.
- deuterated solutions D 2 0
- pH 1 HCl
- pH 7 phosphate
- other pHs citrate
- the nicotine is in an environment with a pH of less than 8, rather between 7 and 8. In fact, at this pH value, the basic and mono-protonated nicotine forms coexist.
- the nicotine formulated in 1,3-propanediol is essentially present in its most vaporizable form and is therefore most easily delivered by a personal vaporizer.
- Example 11 Evaluation of the aromatic power and throat hit of flavored and nicotinated formulations based on 1,3-propanediol or propylene glycol.
- the e-liquid compositions A and B are evaluated by a trained panel of 20 people (male, age between 25 and 49 years), equipped with an electronic cigarette consisting of i) a tank-atomizer of brand Aspire TM model Nautilus (tank-atomizer: Pyrex tank associated with a BDC atomizer of 1.6 Ohm, air inlet of variable diameter 0.9 / 1.1 / 1.4 / 1.8 mm) and ii) an Eleaf TM brand battery, model iStick (2200 mA / h capacity) and variable voltage (3.0 to 5.0 V).
- the conditions of use are as follows:
- Each panelist blinds a test on the basis of 3 sets of puffs spaced one minute apart, consisting of 4 successive puffs spaced 5 seconds apart and each induced by heating for 2 seconds.
- the evaluation is based on scoring, on a scale of 1 to 10, the criteria of aromatic power and throat hit.
- the passage from one product to another is done by each panelist as follows: 5 minutes after the last aspiration, the panelist rinses his mouth with 2 glasses of water of 100 ml then quenches with 50 ml of water. A rest period between each assessment is set at 10 minutes.
- the key points to evaluate are:
- throat hit throat that is to say the effect of internal tingling of the throat classically obtained when a smoker inhales a puff of conventional cigarette. Effect also felt when an electronic cigarette user craves a nicotine-rich aerosol.
- the nicotine formulation based on 1, 3-propanediol is clearly superior in terms of feeling of throat tingling and aromatic power to a formulation based on propylene glycol;
- 1,3-propanediol allows a better delivery of nicotine and a potentiating effect of aromas.
- 1,3-propanediol advantageously allows in terms of safety and cost, to consider lightened formulations in aroma and nicotine.
- Example 12 (comparative): Evaluation of the thermal stability of glycerinated compositions based on 1,3-propanediol or propylene glycol
- the 20% GV-40% PDO mixture leads to a co-vaporization of 1,3-propanediol and glycerol, which constitutes an advantage in terms of homogeneity of the aerosol produced by this mixture;
- the set of propylene glycol-based formulations leads to the appearance in ATD of exothermic peaks characteristic of intermolecular reactions. There is therefore hot chemical interaction (303-304 ° C) between the constituents of the formulation.
- These results are similar to those of Jensen et al (R. Paul Jensen, BS Wentai Luo, J. Pankow, RM Strongin, DH Peyton, Hidden Formaldehyde in E-cigarettes Aerosols, New England Journal of Medicine, 372; 392-3.93, January 22,2015) and Bekki et al (K. Bekki, S. Uchiyama, K Ohta, Y. Inaba, H. Nakagome, N.
- thermolysis of propylene glycol and glycerine leads to the formation of volatile aldehydes such as formaldehyde, acetaldehyde and acrolein, which react in situ with the glycols present in the e-liquids (propylene glycol and glycerol) to form heavy acetal compounds;
- the set of propylene glycol-based formulations leads to the presence of non-vaporizable residues at 350 ° C. corresponding to the formation of heavy secondary compounds whose content is between 0.6 and 1.7%;
- 1,3-propanediol-based formulations do not lead to exothermic reactions.
- the constituents of the formulations are therefore stable at high temperature.
- 1,3-propanediol stabilizes glycerol;
- the formulations based on 1,3-propanediol have very low levels of non-vaporizable residues at 350 ° C, between 0.01 and 0.3%.
- 1,3-propanediol-glycerol formulations are stable unlike propylene glycol-glycerol formulations, which lead to the formation of heavy secondary compounds.
- the thermal stability of the formulations is an essential pre-requisite of the formulations intended for personal vaporizers, with a view to guaranteeing their innocuity under the conditions of use and misuse of these devices.
Abstract
Description
Claims
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FR1451970A FR3015186A1 (fr) | 2014-03-11 | 2014-03-11 | Utilisation d'une composition renfermant du 1,3-propanediol comme e-liquide |
FR1456453A FR3015187B1 (fr) | 2014-03-11 | 2014-07-04 | Utilisation d'une composition renfermant du 1,3-propanediol comme e-liquide |
PCT/FR2015/050599 WO2015101760A1 (fr) | 2014-03-11 | 2015-03-10 | Utilisation d'une composition renfermant du 1,3-propanediol comme e-liquide |
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US10244793B2 (en) | 2005-07-19 | 2019-04-02 | Juul Labs, Inc. | Devices for vaporization of a substance |
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US10159282B2 (en) | 2013-12-23 | 2018-12-25 | Juul Labs, Inc. | Cartridge for use with a vaporizer device |
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JP4327909B2 (ja) * | 1996-11-13 | 2009-09-09 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | 組み換え生物による1,3―プロパンジオールの生産方法 |
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CN101084801A (zh) * | 2003-04-29 | 2007-12-12 | 韩力 | 一种非可燃性电子喷雾香烟 |
US8227217B2 (en) | 2009-11-17 | 2012-07-24 | Tsinghua University | Methods and genetically engineered micro-organisms for the combined production of PDO, BDO and PHP by fermentation |
ITMI20112290A1 (it) * | 2011-12-16 | 2013-06-17 | Dks Aromatic Srl | Composizione per sigarette elettroniche |
US20140088044A1 (en) * | 2012-09-21 | 2014-03-27 | Basil Rigas | Product comprising a nicotine-containing material and an anti-cancer agent |
ITBO20130706A1 (it) * | 2013-12-20 | 2015-06-21 | Sino Business Ltd | Composizione per sigarette elettroniche |
CN105377065A (zh) * | 2013-04-10 | 2016-03-02 | 斯诺商业有限公司 | 电子吸烟替代装置 |
KR20230013165A (ko) * | 2013-05-06 | 2023-01-26 | 쥴 랩스, 인크. | 에어로졸 장치를 위한 니코틴 염 제제 및 그 방법 |
CN105078930A (zh) * | 2014-05-16 | 2015-11-25 | 北京中卫神农慢性病医学研究院有限公司 | 一种烟雾药剂及其制备方法 |
CN104983064B (zh) * | 2015-06-05 | 2016-06-01 | 浙江中烟工业有限责任公司 | 一种电子烟烟液及其制备方法 |
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FR3015186A1 (fr) | 2015-06-26 |
FR3015187A1 (fr) | 2015-06-26 |
CN106455675A (zh) | 2017-02-22 |
GB201512314D0 (en) | 2015-08-19 |
WO2015101760A1 (fr) | 2015-07-09 |
DE112015000032T5 (de) | 2015-11-19 |
FR3015187B1 (fr) | 2017-02-17 |
US20160262443A1 (en) | 2016-09-15 |
EP3107409B1 (fr) | 2018-02-14 |
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