EP4640078A1

EP4640078A1 - Aerosol-generating materials, consumables and aerosol provision systems

Info

Publication number: EP4640078A1
Application number: EP24172009.3A
Authority: EP
Inventors: Anthony Cunningham; Daniel Arthur; Jessica Sholl
Original assignee: Nicoventures Trading Ltd
Current assignee: Nicoventures Trading Ltd
Priority date: 2024-04-23
Filing date: 2024-04-23
Publication date: 2025-10-29
Also published as: WO2025224051A1

Abstract

The present invention relates to an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive. The invention also relates to consumables for use in an aerosol provision system, comprising an aerosol-generating material and a selectively releasable source of a nitrite-decreasing additive, as well as aerosol provision systems and uses of a selectively releasable source of a nitrite-decreasing additive to reduce the generation of tobacco-specific nitrosamines upon heating an aerosol-generating material.

Description

Technical Field

The present invention relates to an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive. The invention further relates to a consumable for use in an aerosol provision system, the consumable comprising an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive; and to aerosol provision systems comprising said consumable, as well as to kits comprising said consumable. The invention also relates to the use of a selectively releasable source of a nitrite-decreasing additive.

Background

Smoking articles such as cigarettes, cigars and the like burn tobacco during use to create tobacco smoke. Alternatives to these types of combustible articles release an inhalable aerosol or vapour by releasing compounds from a substrate material by heating without burning. These may be referred to as non-combustible smoking articles or aerosol generating articles.
One example of such a product is a heating device which releases compounds by heating, but not burning, a solid aerosolisable material. This solid aerosolisable material may, in some cases, contain a tobacco material. The heating volatilises at least one component of the material, typically forming an inhalable aerosol. These products may be referred to as heat-not-burn devices, tobacco heating devices or tobacco heating products. Various different arrangements for volatilising at least one component of the solid aerosolisable material are known.

Summary

In accordance with a first aspect of the invention, there is provided an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive.
In some embodiments, the selectively releasable source of the nitrite-decreasing additive is configured to release the additive no more than about 5 days before the intended heating of the aerosol-generating material in an aerosol provision system.
In some embodiments, the nitrite-decreasing additive is an antioxidant or a precursor to an antioxidant.
In some embodiments, the nitrite-decreasing additive is one or more selected from the group consisting of: sorbic acid, a sorbic acid salt, ascorbic acid, and an ascorbic acid salt. In some embodiments, the nitrite-decreasing additive is sorbic acid salt or ascorbic acid salt, wherein the sorbic acid salt or ascorbic acid salt is a salt selected from the group consisting of a lithium, sodium, potassium, magnesium, calcium or ammonium salt.
In some embodiments, the nitrite-decreasing additive is provided in encapsulated form. In some embodiments, the encapsulated nitrite-decreasing additive is provided in liquid form. In some embodiments, the encapsulated nitrite-decreasing additive is released in a temperature-dependent manner. In some embodiments, the encapsulated nitrite-decreasing additive is released upon being heated to a temperature within the range of from about 50°C to about 100°C.
In some embodiments, the nitrite-decreasing additive is present in an amount of about 0.01 to about 5 wt% based on the weight of the tobacco material. In some embodiments, the nitrite-decreasing additive is present in an amount of about 0.05 to about 3 wt% based on the weight of the tobacco material.
In accordance with a second aspect of the invention, there is provided a consumable for use in an aerosol provision system, the consumable comprising an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive.
In some embodiments, the consumable of the second aspect comprises an aerosol-generating material according to any embodiment of the first aspect.
In some embodiments, the selectively releasable source of the nitrite-decreasing additive is not included in the aerosol-generating material.
In some embodiments, the selectively releasable source of the nitrite-decreasing additive is not included in the aerosol-generating material, and the consumable comprises a first segment or chamber within which the tobacco material is held and a second segment or chamber within which the nitrite-decreasing additive is held, the consumable being configured to allow the nitrite-decreasing additive to contact the tobacco material only when the source of the nitrite-decreasing additive is released by the consumer before the consumable generates an inhalable aerosol.
In some embodiments, the nitrite-decreasing additive is present in an amount of from about 0.01 to about 5 wt% based on the weight of the tobacco material. In some embodiments, the nitrite-decreasing additive is present in an amount of from about 0.05 to about 3 wt% based on the weight of the tobacco material.
In some embodiments, the nitrite-decreasing additive is present in an amount of at least about 0.01 wt%, at least about 0.02 wt%, at least about 0.03 wt%, at least about 0.05 wt%, at least about 0.1 wt%, at least about 0.2 wt%, at least about 0.3 wt%, at least about 0.4 wt%, at least about 0.5 wt%, at least about 0.6 wt%, at least about 0.7 wt%, at least about 0.8 wt%, at least about 0.9 wt%, at least about 1 wt%, at least about 1.1 wt%, at least about 1.2 wt%, at least about 1.3 wt%, at least about 1.4 wt%, at least about 1.5 wt%, at least about 1.6 wt%, at least about 1.7 wt%, at least about 1.8 wt%, at least about 1.9 wt%, at least about 2 wt%, at least about 2.1 wt%, at least about 2.2 wt%, at least about 2.3 wt%, at least about 2.4 wt%, at least about 2.6 wt%, at least about 2.7 wt%, at least about 2.8 wt%, at least about 2.9 wt%, or at least about 3 wt% based on the weight of the tobacco material. Additionally or alternatively, the nitrite-decreasing additive is present in an amount of no more than about 5 wt%, no more than about 4.9 wt%, no more than about 4.8 wt%, no more than about 4.7 wt%, no more than about 4.6 wt%, no more than about 4.5 wt%, no more than about 4.4 wt%, no more than about 4.3 wt%, no more than about 4.2 wt%, no more than about 4.1 wt%, no more than about 4 wt%, no more than about 3.9 wt%, no more than about 3.8 wt%, no more than about 3.7 wt%, no more than about 3.6 wt%, no more than about 3.5 wt%, no more than about 3.4 wt%, no more than about 3.3 wt%, no more than about 3.2 wt%, no more than about 3.1 wt%, no more than about 3 wt%, no more than about 2.5 wt%, or no more than about 2 wt% based on the weight of the tobacco material.
In some embodiments, the nitrite-decreasing additive is present in a consumable in an amount of about 0.3 to about 20 mg. In some embodiments, the nitrite-decreasing additive is present in a consumable in an amount of from about 5 to about 20 mg.
In some embodiments, the nitrite-decreasing additive is present in a consumable in an amount of at least about 0.3 mg, at least about 0.5 mg, at least about 1 mg, at least about 1.5 mg, at least about 2 mg, at least about 2.5 mg, at least about 3 mg, at least about 3.5 mg, at least about 4 mg, at least about 4.5 mg, at least about 5 mg, at least about 5.5 mg, at least about 6 mg, at least about 6.5 mg, at least about 7 mg, at least about 7.5 mg, at least about 8 mg, at least about 8.5 mg, at least about 9 mg, at least about 9.5 mg, at least about 10 mg. Additionally or alternatively, the nitrite-decreasing additive is present in a consumable in an amount of no more than about 20 mg, no more than about 19 mg, no more than about 18 mg, no more than about 17 mg, no more than about 16 mg, no more than about 15 mg, no more than about 14 mg, no more than about 13 mg, no more than about 12 mg, no more than about 11 mg, no more than about 10 mg, no more than about 9 mg, or no more than about 8 mg, no more than about 20 mg, no more than about 20 mg, no more than about 20 mg.
In some embodiments, the tobacco material is cut rag tobacco or reconstituted tobacco.
In some embodiments, the consumable is rod shaped and has a mouth end and a distal end based on its intended use.
In some embodiments, the consumable is rod shaped and has a mouth end and a distal end based on its intended use and the selectively releasable source of the nitrite-decreasing additive is configured to release the nitrite-decreasing additive so that it is provided exclusively or in a greater concentration at a location toward the mouth end of the rod.
In some embodiments, the consumable is rod shaped and has a mouth end and a distal end based on its intended use and the selectively releasable source of the nitrite-decreasing additive is configured to release the nitrite-decreasing additive so that it is provided in a substantially consistent concentration throughout the rod.
In some embodiments, the nitrite-decreasing additive is an antioxidant or a precursor to an antioxidant.
In some embodiments, the nitrite-decreasing additive is one or more selected from the group consisting of: sorbic acid, a sorbic acid salt, ascorbic acid, and an ascorbic acid salt. In some embodiments, the nitrite-decreasing additive is sorbic acid salt or ascorbic acid salt, wherein the sorbic acid salt or ascorbic acid salt is a salt selected from the group consisting of a lithium, sodium, potassium, magnesium, calcium or ammonium salt.
In some embodiments, the nitrite-decreasing additive is provided in encapsulated form.
In some embodiments, the nitrite-decreasing additive is provided in liquid form.
In some embodiments, the nitrite-decreasing additive is present in an amount of 0.01-3 wt% based on the weight of the tobacco material. In some embodiments, the nitrite-decreasing additive is present in an amount of 0.01-1 wt% based on the weight of the tobacco material.
In accordance with a third aspect of the invention, there is provided an aerosol provision system comprising a consumable according to any embodiment of the second aspect of the invention.
In accordance with a fourth aspect of the invention, there is provided a kit comprising: an aerosol-generating consumable comprising an aerosol-generating material comprising tobacco material; and a dispenser comprising a nitrite-decreasing additive, wherein the dispenser may be used to combine the nitrite-decreasing additive and the tobacco material prior to use of the consumable.
In accordance with a fifth aspect of the invention, there is provided use of a selectively releasable source of a nitrite-decreasing additive to reduce the generation of tobacco-specific nitrosamines upon heating an aerosol-generating material.
In some embodiments, the nitrite-decreasing additive is released and contacts at least some of the aerosol-generating material no more than 5 days before the intended heating of the aerosol-generating material in an aerosol provision system.
In some embodiments, the aerosol-generating material comprises tobacco material or a tobacco extract.

Brief Description of the Drawings

Embodiments of the invention will now be described, by way of example only, with reference to the accompanying drawings, in which:

Figure 1 is a side-on cross-sectional view of an illustrative article for use in an aerosol provision system and comprising an aerosol-generating material according to the present disclosure; and
Figure 2 is a perspective illustration of a non-combustible aerosol provision device for generating aerosol from an article according to the present disclosure.

Detailed Description

In accordance with a first aspect of the invention, there is provided an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive.
Tobacco-Specific Nitrosamines (TSNAs) are generated when tobacco-containing aerosol generating materials are heated and they are understood to be formed by a process wherein secondary and tertiary amines react with nitrites and/or derivatives thereof. The inventors have found that the formation of TSNAs during heating can be reduced by treating the tobacco material with a nitrite-decreasing additive. Nitrites are precursors of nitrosating agents that react with amines to form TSNAs. Nitrites are present in tobacco material in very small quantities but are formed upon heating. By reducing nitrites, it is possible to reduce the nitrosation of amines to reduce TSNA formation.
As discussed in detail below, the effect of many of the proposed nitrite-decreasing additives may be relatively short-lived, lasting for time periods that are shorter than the normal time periods between the manufacture of a tobacco industry product and its use by a consumer. For that reason, it is proposed that the nitrite-decreasing additive be added to the tobacco material after manufacture of the product. To achieve this, the nitrite-decreasing additive is provided in a selectively releasable form. This keeps the nitrite-decreasing additive separate from the tobacco material until shortly before the intended use of the tobacco industry product. The user is able to trigger release of the nitrite-decreasing additive and to thereby reduce TSNA generation during use of the tobacco industry product.

Nitrite-Decreasing Additive

Nitrites are pre-cursors of nitrosating agents that react with amines to form TSNAs. Therefore, by reducing nitrites, the nitrosation of amines may be reduced to reduce the generation of TSNAs.
As used herein, the term nitrite-decreasing additive denotes a substance that reduces the nitrites present in tobacco material. This may be achieved by removing nitrites and/or by reducing the formation of nitrites. Several classes of compounds have been shown to mitigate nitrosamine formation.
As used herein, the term nitrite scavenger denotes a substance capable of reacting with nitrites. By reacting with nitrites, these nitrite scavenger compounds may be capable of decreasing the nitrites present in the tobacco material and thereby reduce TSNA formation.
Three different reaction mechanisms have been proposed for three main classes of compounds referred to herein as nitrite scavengers:

(1) Redox pathway
(2) Diazotization of primary amines
(3) Nitration of phenols (e.g., chlorogenic acid):

The nitrite scavenger may be one or more compounds which mitigate nitrosamine formation via any one of the above reaction pathways. In some embodiments, two or more nitrite scavenger compounds may be combined which mitigate nitrosamine formation via two or more of the above reaction pathways.
In some embodiments, the nitrite scavenger is an antioxidant or a precursor to an antioxidant. In some embodiments, the nitrite scavenger is one or more antioxidant selected from the group consisting of: ascorbic acid, an ascorbic acid salt, Vitamin E. Herein, reference to Vitamin E includes the individual compounds that are referred to as Vitamin E, including tocopherols such as α-tocopherol and tocotrienols such as δ-tocotrienol.
Ascorbic acid, also known as Vitamin C, can inhibit N-Nitrosamine formation by preventing the transfer of the nitroso group (O=N) from the nitrite to TSNA pre-cursors like nornicotine.
Antioxidant salts may be used as nitrite scavengers, such as those selected from the group consisting of a lithium, sodium, potassium, magnesium, calcium or ammonium salt.
In some embodiments, the nitrite scavenger is ammonia or a primary amine. For example, suitable primary amines include: primary alkyl amines such as methylamine and amino acids containing primary amines or thiol groups, such as L-cysteine, glycine, arginine, lysine and histidine, and primary aromatic amines such as aniline.
In some embodiments, the nitrite scavenger is a phenol or a phenolic acid, such as chlorogenic acid or derivatives thereof. Phenolic acids are usually divided into two main groups, namely benzoic acids and cinnamic acids. These compounds exist predominantly as hydroxybenzoic and hydroxycinnamic acids.
In some embodiments, the nitrite scavenger is one or more selected from the group consisting of: caffeic acid, ferulic acid, vanillic acid, p-coumaric acid, syringic acid and sinapinic acids.
An alternative approach to decreasing nitrites in tobacco material is to reduce their formation. The involves the use of a different class of nitrite-decreasing additives.
In some embodiments, the formation of nitrites may be reduced by the addition of an additive that prevents to the reduction of nitrates to nitrites by microorganisms. Such additives may be described as preservatives.
In some embodiments, the additive preventing the formation of nitrites in tobacco material include one or more of: sorbic acid, benzoic acid, or salts thereof (e.g., lithium, sodium, potassium, magnesium, calcium or ammonium salts thereof). In some embodiments, the nitrite-decreasing additive is or includes sorbic acid, potassium sorbate and/or sodium sorbate. In some embodiments, the nitrite-decreasing additive comprises a combination of one or more additive which acts as a nitrite scavenger, such as an antioxidant, and one or more additive which acts by preventing the formation of nitrites.
In some embodiments, the nitrite-decreasing additive comprises a combination of ascorbic acid or a salt thereof and sorbic acid or a salt thereof.
In some embodiments, the nitrite-decreasing additive is present in an amount of from about 0.01 to about 5 wt% based on the weight of the tobacco material. In some embodiments, the nitrite-decreasing additive is present in an amount of from about 0.01 to about 4 wt%, from about 0.01 to about 3 wt%, from about 0.01 to about 2 wt%, from about 0.01 to about 1.5 wt%, from about 0.01 to about 1.25 wt%, from about 0.01 to about 1 wt%, from about 0.01 to about 0.75 wt%, from about 0.1 to about 5 wt%, from about 0.1 to about 4 wt%, from about 0.1 to about 3 wt%, from about 0.1 to about 2 wt%, from about 0.1 to about 1 wt%, from about 0.5 to about 5 wt%, from about 0.5 to about 4 wt%, from about 0.5 to about 3 wt%, from about 0.5 to about 2 wt%, or from about 0.5 to about 1 wt% based on the weight of the tobacco material.
In some embodiments, the nitrite-decreasing additive is provided in solution. Suitable solvents include water and/or alcohols such as ethanol.

TSNAs

TSNAs are nitrosation products of endogenous pyridine alkaloids such as nicotine and nornicotine. The most commonly studied TSNA are:

Name Structure

N-nitrosonornicotine (NNN)

4-(methylnitrosoamino)-1-(3-pyridinyl)-1-butanone (NNK)

N-nitrosoanabsaine (NAB)

N-nitrosoanatabine (NAT)
TSNAs are naturally present at low levels, or not at all, in fresh green tobacco and increase during curing, storage, fermentation, and processing of harvested tobacco leaves, in particular, during the tobacco curing process, generally due to nitrosation of nicotine and related tobacco alkaloids.
TSNAs may be present in the aerosol generated when a tobacco-containing aerosol-generating material is heated, as a result of processes including thermogeneration (pyrosynthesis) of TSNAs and the transfer efficiency of TSNAs from the tobacco material to the aerosol emission (pyrorelease).
In some embodiments, contacting tobacco material with the nitrite-decreasing additive reduces the generation of TSNAs upon heating the tobacco material. By this it is meant that the aerosol generated from an aerosol-generating material that has been contacted with the selectively releasable nitrite-decreasing additive has a lower TSNA content than the aerosol generated from the same aerosol-generating material that has not been contacted with the nitrite-decreasing additive.
In some embodiments, contacting tobacco material with the nitrite-decreasing additive reduces the generation of one or more TSNA selected from:

(i) NNN;
(ii) NNK;
(iii) NAB; and/or
(iv) NAT

In some embodiments, contacting tobacco material with the nitrite-decreasing additive reduces the generation of one or both of:

(i) NNN; and
(ii) NNK.

In some embodiments, contacting tobacco material with the nitrite-decreasing additive reduces the generation of NNN.
In some embodiments, contacting tobacco material with the nitrite-decreasing additive reduces the generation of TSNAs by at least about 5 wt% compared to the TSNAs generated on heating an equivalent tobacco material that has not been contacted with the nitrite-decreasing additive. In some embodiments, contacting tobacco material with the nitrite-decreasing additive reduces the generation of TSNAs by at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 35 wt%, at least about 40 wt%, at least 45 wt% or at least about 50 wt% compared to the TSNAs generated on heating an equivalent tobacco material that has not been contacted with the nitrite-decreasing additive.

Selectively releasable source of the nitrite-decreasing additive

The inventors have found that the effect of contacting the tobacco material or aerosol-generating material with a nitrite-decreasing additive, may, in some embodiments, not be permanent and the effect of contacting the tobacco material or aerosol-generating material with the nitrite-decreasing additive may reduce over time following the initial contact. For example, ascorbic acid can react with N₂O₃, H₂NO₂ ⁺, and NOX, converting them to NO. However, under aerobic conditions, NO can oxidize to NO₂ and subsequently convert back to nitrosating agents (i.e., N₂O₃ or N₂O₄).
The provision of a selectively releasable source of nitrite-decreasing additive has been found to ensure that the treatment of the tobacco material or aerosol-generating material with the nitrite-decreasing additive is timed so as to be effective at reducing the generation of TSNAs when aerosol generating material is heated to generate an inhalable medium. The selective release of the nitrite-decreasing additive allows the additive to contact the aerosol-generating material shortly before the aerosol-generating material is heated to generate an aerosol, reducing the level of nitrites in the aerosol-generating material at the time the aerosol-generating material is heated.
In some embodiments, the selectively releasable source of the nitrite-decreasing additive is configured to release the nitrite scavenger no more than about 5 days, no more than about 4 days, no more than about 3 days, no more than about 2 days or no more than about 1 day before the intended heating of the aerosol-generating material in an aerosol provision system. In some embodiments, the selectively releasable source of the nitrite-decreasing additive is configured to release the additive no more than about 1 hour before the intended heating of the aerosol-generating material in an aerosol provision system, no more than about 30 minutes, no more than about 20 minutes, no more than about 15 minutes, no more than about 10 minutes, no more than about 5 minutes, no more than about 4 minutes, no more than about 3 minutes, no more than about 2 minutes, no more than about 1 minute, or no more than about 30 seconds before the intended heating of the aerosol-generating material in an aerosol provision system. In some embodiments, the selectively releasable source of the nitrite-decreasing additive is configured to release the additive immediately prior to heating of the aerosol-generating material. In some embodiments, the selectively releasable source of the nitrite-decreasing additive is configured to release the additive during heating of the aerosol-generating material in an aerosol provision system. For example, the nitrite-decreasing additive may be configured to release the additive as the aerosol-generating material is heated but before the aerosol-generating material reaches the temperature at which the aerosol is generated.
In some embodiments, the nitrite-decreasing additive is provided in encapsulated form.
The nitrite-decreasing additive may be encapsulated in an encapsulating material. In some cases, the encapsulating material comprises at least one of a polysaccharide material such as an alginate, carrageenan or pectin material; a cellulosic material; a gelatin; a gum; a protein material; a polyol matrix material; an amorphous solid; a gel; a wax; a polyurethane; polymerised, hydrolysed ethylene vinyl acetate, a polyester, a polycarbonate, a polymethacrylate, a polyglycol, polyethylene, polystyrene, polypropylene, polyvinyl chloride or a mixture thereof.
In some embodiments, the encapsulated nitrite-decreasing additive is released in a temperature-dependent manner. In some embodiments, the encapsulated nitrite-decreasing additive is released upon being heated to a temperature within the range of from about 50°C to about 100°C. This will mean that the additive is released almost as soon as the consumable is used. Alternatively, the release of the encapsulated nitrite-decreasing additive may be delayed until the tobacco is heated to a temperature at which the aerosol is generated, such as a temperature of at least 150°C, and optionally less than about 300°C, about 270°C or about 250°C.
Encapsulation can be used to reduce or prevent decomposition of the nitrite-decreasing additive during storage. Encapsulation can be used to reduce or prevent unintended volatilisation of the nitrite-decreasing additive during storage, and/or to prevent migration of the nitrite-decreasing additive within the aerosol-generating material before use. Encapsulation can be used to ensure that the nitrite-decreasing additive treatment of the aerosol-generating material occurs shortly before or as the aerosol-generating material is heated to generate an aerosol.
In some cases, the temperature-dependent release may be provided through use of an encapsulating material that melts, decomposes, reacts, degrades, swells or deforms to release the nitrite-decreasing additive at the release temperature. In other cases, heating may cause the encapsulated nitrite-decreasing additive to swell, causing rupture of the encapsulating material.
In some embodiments, the encapsulated nitrite-decreasing additive is provided in liquid form.
The encapsulated nitrite-decreasing additive may be provided in the form of capsules that are powders, granules or beads. In some cases, these capsules may be carried on a substrate. In some cases, the encapsulated nitrite-decreasing additive may be provided in the form of a matrix or an amorphous solid which surrounds, encapsulates or embeds the additive. The amorphous solid may comprise a polysaccharide matrix. The amorphous solid may be provided as a thin film. This thin film may be provided in shredded or sheet form, for example. In some cases, the encapsulated nitrite-decreasing additive may be present in a mixture of these forms, such as a combination of capsules and an encapsulating film.
In some embodiments, the nitrite-decreasing additive is selectively releasable by a user-actuated release mechanism.
In some embodiments, the nitrite-decreasing additive is encapsulated in a breakable capsule. The term "breakable capsule" refers to a capsule, wherein a shell can be broken by means of a pressure to release the core; more specifically a shell can be ruptured under the pressure imposed by the user's fingers (or any other pressure creating means) when the user wants to release the core of the capsule. In some embodiments, the capsule comprises a core as described above, and a shell. In some embodiments, the capsule may present a crush strength from about 4.5 N to about 40 N or to about 25 N.
In some embodiments, capsules may be substantially spherical and have a diameter of at least about 0.4 mm, 0.6 mm, 0.8 mm, 1.0 mm, 2.0 mm, 2.5 mm, 2.8 mm or 3.0 mm. The diameter of the capsules may be less than about 10.0 mm, 8.0 mm, 7.0 mm, 6.0 mm, 5.5 mm, 5.0 mm, 4.5 mm, 4.0 mm, 3.5 mm or 3.2 mm. Illustratively, the capsule diameter may be in the range of about 0.4 mm to about 10.0 mm, about 0.8 mm to about 6.0 mm, about 2.5 mm to about 5.5 mm or about 2.8 mm to about 3.2 mm. In some cases, the capsule may have a diameter of about 3.0 mm. These sizes are particularly suitable for incorporation of the capsule into a consumable.
In some embodiments, the breakable capsule has a core-shell structure.
In some embodiments, the total weight of a capsule may be in the range of about 1 mg to about 100 mg, suitably about 5 mg to about 60 mg, about 10 mg to about 50 mg, about 15 mg to about 40 mg, or about 15 mg to about 30 mg.
In some embodiments, the core comprises at least about 25% w/w nitrite scavenger, based on the total weight of the core.
In some embodiments, the barrier material is heat resistant. That is to say, in some embodiments, the barrier will not rupture, melt or otherwise fail at the temperature reached at the capsule site during heating of the article. In such embodiments, the additive is only released by positive action, such as rupture of the capsule, for example by the application of a compressive force, or puncture of the barrier material, for example using a blade or needle.
In some cases, the breakable capsule includes a barrier material which retains the nitrite-decreasing additive, and wherein the barrier material comprises one or more of a gelling agent, a bulking agent, a colouring agent, a plasticiser, and a filler material.
Suitably, the gelling agent may be, for example, a polysaccharide or cellulosic gelling agent, a gelatin, a gum, a gel, a wax or a mixture thereof. Suitable polysaccharides include alginates, dextrans, maltodextrins, cyclodextrins and pectins. Suitable alginates include, for instance, a salt of alginic acid, an esterified alginate or glyceryl alginate. Salts of alginic acid include ammonium alginate, triethanolamine alginate, and group I or II metal ion alginates like sodium, potassium, calcium and magnesium alginate. Esterified alginates include propylene glycol alginate and glyceryl alginate. In an embodiment, the barrier material is sodium alginate and/ or calcium alginate. Suitable cellulosic materials include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, cellulose acetate and cellulose ethers. The gelling agent may comprise one or more modified starches. The gelling agent may comprise carrageenans. Suitable gums include agar, gellan gum, gum Arabic, pullulan gum, mannan gum, gum ghatti, gum tragacanth, Karaya, locust bean, acacia gum, guar, quince seed and xanthan gums. Suitable gels include agar, agarose, carrageenans, furoidan and furcellaran. Suitable waxes include carnauba wax. In some cases, the gelling agent may comprise carrageenans and/or gellan gum; these gelling agents are particularly suitable for inclusion as the gelling agent as the pressure required to break the resulting capsules is particularly suitable.
The barrier material may comprise one or more bulking agents, such as starches, modified starches (such as oxidised starches) and sugar alcohols such as maltitol.
The barrier material may comprise a colouring agent which renders easier the location of the capsule within the tobacco industry product during manufacture. The colouring agent is preferably chosen among colorants and pigments.
The barrier material may further comprise at least one buffer, such as a citrate or phosphate compound.
The barrier material may further comprise at least one plasticiser, which may be glycerol, sorbitol, maltitol, triacetin, polyethylene glycol, propylene glycol or another polyalcohol with plasticising properties, and optionally one acid of the monoacid, diacid or triacid type, especially citric acid, fumaric acid, malic acid, and the like. The amount of plasticiser ranges from 1% to 30% by weight, preferably from 2% to 15% by weight, and even more preferably from 3 to 10% by weight of the total dry weight of the shell.
The barrier material may also comprise one or more filler materials. Suitable filler materials include starch derivatives such as dextrin, maltodextrin, cyclodextrin (alpha, beta or gamma), or cellulose derivatives such as hydroxypropyl methylcellulose (HPMC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), carboxymethyl cellulose (CMC), polyvinyl alcohol, polyols or mixture thereof. Dextrin is a preferred filler. The amount of filler in the shell is at most 98.5%, preferably from 25 to 95% more preferably from 40 to 80% and even more preferably from 50 to 60 % by weight on the total dry weight of the shell.
The capsule shell may additionally comprise a hydrophobic outer layer which reduces the susceptibility of the capsule to moisture-induced degradation. The hydrophobic outer layer is suitably selected from the group comprising waxes, especially carnauba wax, candelilla wax or beeswax, carbowax, shellac (in alcoholic or aqueous solution), ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, latex composition, polyvinyl alcohol, or a combination thereof. More preferably, the at least one moisture barrier agent is ethyl cellulose or a mixture of ethyl cellulose and shellac.
Methods of making the capsules include co-extrusion, optionally followed by centrifugation and curing and/or drying. Further details are disclosed in WO 2007/010407 A2 , the contents of which is incorporated herein by reference, in its entirety.

Aerosol-generating material

Aerosol-generating material is a material that is capable of generating aerosol, for example when heated, irradiated or energized in any other way. Aerosol-generating material may, for example, be in the form of a solid, liquid or semi-solid (such as a gel) which may or may not contain an active substance and/or flavourants.
The aerosol-generating material may comprise one or more active substances and/or flavours, one or more aerosol-former materials, and optionally one or more other functional material.
The aerosol-generating material may comprise a binder, such as a gelling agent, and an aerosol former. Optionally, a substance to be delivered and/or filler may also be present. Optionally, a solvent, such as water, is also present and one or more other components of the aerosol-generating material may or may not be soluble in the solvent.
In some embodiments, the aerosol-generating material may comprise or be in the form of an aerosol-generating film.
The aerosol-generating film may have a thickness of about 0.015 mm to about 1 mm. For example, the thickness may be in the range of about 0.05 mm, 0.1 mm or 0.15 mm to about 0.5 mm or 0.3 mm. The aerosol-generating material may comprise more than one film, and the thickness described herein may refer to the aggregate thickness of those films.
The aerosol-generating film may be continuous. For example, the film may comprise or be a continuous sheet of material. The sheet may be in the form of a wrapper, it may be gathered to form a gathered sheet, or it may be shredded to form a shredded sheet. The shredded sheet may comprise one or more strands or strips of aerosol-generating material.
The aerosol-generating film may be discontinuous. For example, the aerosol-generating film may comprise one or more discrete portions or regions of aerosol-generating material, such as dots, stripes or lines, which may be supported on a support. In such embodiments, the support may be planar or non-planar.
The aerosol-generating film may be formed by combining a binder, such as a gelling agent, with a solvent, such as water, an aerosol-former and one or more other components, such as one or more substances to be delivered, to form a slurry and then heating the slurry to volatilise at least some of the solvent to form the aerosol-generating film.
The slurry may be heated to remove at least about 60 wt%, 70 wt%, 80 wt%, 85 wt% or 90 wt% of the solvent.
The aerosol-generating material may comprise or be an "amorphous solid". In some embodiments, the aerosol-generating materiel comprises an aerosol-generating film that is an amorphous solid. The amorphous solid may be a "monolithic solid". The amorphous solid may be substantially non-fibrous. In some embodiments, the amorphous solid may be a dried gel. The amorphous solid is a solid material that may retain some fluid, such as liquid, within it. In some embodiments, the amorphous solid may, for example, comprise from about 50 wt%, 60 wt% or 70 wt% of amorphous solid, to about 90 wt%, 95 wt% or 100 wt% of amorphous solid.
The amorphous solid may be substantially free from (solid) botanical material. The amorphous solid may be substantially tobacco free.
The aerosol-former material may comprise one or more constituents capable of forming an aerosol. In some embodiments, the aerosol-former material may comprise one or more of glycerol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-butylene glycol, erythritol, meso-Erythritol, ethyl vanillate, ethyl laurate, a diethyl suberate, triethyl citrate, triacetin, a diacetin mixture, benzyl benzoate, benzyl phenyl acetate, tributyrin, lauryl acetate, lauric acid, myristic acid, and propylene carbonate.
The one or more other functional materials included in the aerosol-generating material may comprise one or more of pH regulators, colouring agents, preservatives, binders, fillers, stabilizers and antioxidants.

Tobacco material

In some embodiments, the aerosol generating material comprises tobacco material. The term "tobacco material" may include one or more of tobacco, tobacco derivatives, expanded tobacco, reconstituted tobacco, or tobacco-containing substitute materials.
The tobacco material may comprise one or more of ground tobacco, tobacco fibre, cut tobacco, tobacco leaf, tobacco lamina, extruded tobacco, tobacco stem, reconstituted tobacco and/or tobacco extract. The reconstituted tobacco material may comprise tobacco fibres, and may be formed by casting, a Fourdrinier-based paper making-type approach with back addition of tobacco extract, or by extrusion.
The aerosol generating material may comprise any type of tobacco, such as single grades or blends, cut rag or whole leaf. In some embodiments, the tobacco material is cut rag tobacco or reconstituted tobacco.
The tobacco material may comprise tobacco particle 'fines' or dust, expanded tobacco, stems, expanded stems, and other processed stem materials, such as cut rolled stems.
The tobacco used to produce tobacco material may be any suitable tobacco, such as single grades or blends, cut rag or whole leaf, including Virginia and/or Burley and/or Oriental.

Consumable

In accordance with a second aspect, there is provided a consumable for use in an aerosol provision system, the consumable comprising an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive.
As used herein a "consumable" is an article comprising or consisting of aerosol-generating material, part or all of which is intended to be consumed during use by a user. A consumable may comprise one or more other components, such as an aerosol-generating material storage area, an aerosol-generating material transfer component, an aerosol generation area, a housing, a wrapper, a mouthpiece, a filter and/or an aerosol-modifying agent. A consumable may also comprise an aerosol generator, such as a heater, that emits heat to cause the aerosol-generating material to generate aerosol in use. The heater may, for example, comprise combustible material, a material heatable by electrical conduction, or a susceptor.
In some embodiments, the consumable of the second aspect comprises an aerosol-generating material according to any embodiment of the first aspect.
In some embodiments, the selectively releasable source of the nitrite-decreasing additive is not included in the aerosol-generating material. In some embodiments, the selectively releasable source of the nitrite-decreasing additive is not included in the aerosol-generating material, and the consumable comprises a first segment or chamber within which the tobacco material is held and a second segment or chamber within which the nitrite-decreasing additive is held, the consumable being configured to allow the nitrite-decreasing additive to contact the tobacco material only when the source of the nitrite-decreasing additive is released by the consumer before the consumable generates an inhalable aerosol.
In some embodiments, the consumable is rod shaped and has a mouth end and a distal end based on its intended use.
Consumables, for instance those in the shape of rods, are often named according to the product length: "regular" (typically in the range of 68 to 75 mm, e.g., from about 68 mm to about 72 mm), "short" or "mini" (68 mm or less), "king size" (typically in the range of 75 to 91 mm, e.g., from about 79 mm to about 88 mm), "long" or "super-king" (typically in the range of 91 to 105 mm, e.g., from about 94 mm to about 101 mm) and "ultra-long" (typically in the range from about 110 mm to about 121 mm).
They are also named according to the product circumference: "regular" (about 23 to about 25 mm), "wide" (greater than about 25 mm), "slim" (about 22 to about 23 mm), "demi-slim" (about 19 to about 22 mm), "super-slim" (about 16 to about 19 mm), and "micro-slim" (less than about 16 mm).
In some embodiments, the consumable is rod shaped and has a mouth end and a distal end based on its intended use and the selectively releasable source of the nitrite-decreasing additive is configured to release the additive so that it is provided exclusively or in a greater concentration at a location toward the mouth end of the rod.
In some embodiments, the consumable is rod shaped and has a mouth end and a distal end based on its intended use and the selectively releasable source of the nitrite-decreasing additive is configured to release the additive so that it is provided in a substantially consistent concentration throughout the rod.
Figure 1 is a side-on cross-sectional view of a consumable or article 1 for use in an aerosol provision system. In the present case, the article comprises a consumable for a non-combustible aerosol provision system.
The article comprises an aerosol generating portion, in the present case a cylindrical aerosol-generating portion 2, and a mouthpiece 3 downstream from and connected to the aerosol-generating portion 2.
The aerosol-generating portion 2 comprises a rod or segment of aerosol-generating composition 20 wrapped in a rod wrapper 10.
In Figure 1, the rod of aerosol-generating composition 20 comprises one or more aerosol-generating material. In this embodiment, the aerosol-generating material is cut or shredded and formed into a rod segment.
The aerosol-generating portion 2 also comprises a capsule 21, which is a selectively releasable source of a nitrite-decreasing additive. In this embodiment, the nitrite-decreasing additive is the liquid core of a core-shell capsule 21. The shell may be ruptured to release the liquid comprising the nitrite-decreasing additive. The capsule 21 may be ruptured as a result of a compressive force applied to the capsule by the user. In other embodiments, the capsule 21 may be punctured or ruptured upon interaction with another part of the aerosol provision system, for example, upon insertion of the consumable into a device.
The article 1 also comprises a mouthpiece 3 which has a mouth end 3b and a distal end 3a that abuts the aerosol-generating portion 2.
The mouthpiece 3 illustrated in Figure 1 is located at the mouth end of the article 1 and comprises three elements, a mouthpiece body 14 downstream of a cooling section 13, and a hollow tubular element 15 downstream of the mouthpiece body 14. In other embodiments, one or two of these different mouthpiece elements may be omitted or duplicated, and/or the elements may be provided in a different sequence. For example, the hollow tubular element 15 may be omitted, and the mouthpiece body 14 may form the mouth end of the article. In some examples where the hollow tubular element 15 is omitted, the length of the mouthpiece body 14 may be increased, or a further body of material may be provided at the mouth end.
In an alternative arrangement that is not illustrated, the mouthpiece comprises a mouthpiece body at the mouth end of the mouthpiece, optionally comprising a plug of cellulose acetate tow or paper, and optionally including capsule. Adjacent to this mouthpiece body is a first tube, optionally formed from paper, which abuts at its other end a further tubular section, optionally comprising cellulose acetate.
In the mouthpiece shown in Figure 1, the cooling section 13, mouthpiece body 14 and hollow tubular element 15 are connected by a combining wrapping material 11.
As shown in Figure 1, tipping paper 9 is wrapped around the full length of the mouthpiece 3 and over part of the aerosol generating portion 2. The tipping paper 9 has an adhesive on its inner surface (not shown) to connect the mouthpiece 3 and rod 2. In the illustrated embodiment, the tipping paper 9 extends about 5 mm over the rod of aerosol generating material 2 but it can alternatively extend from about 3 mm to about 15 mm over the rod 2, or from about 4 mm to about 6 mm, to provide a secure attachment between the mouthpiece 3 and rod 2. In some embodiments the tipping paper may extend along the entire length of the rod of aerosol generating material.
In the illustrated embodiment, the article 1 is provided with first and second parallel rows of perforations 12 through the tipping material 9, the combining wrapping material 11 and the tube of the cooling section 13, providing ventilation into the mouthpiece 3 at the cooling section 13. The perforations 12 shown are formed as laser perforations, at positions about 18 mm and about 19 mm respectively from the downstream, mouth-end 3b of the mouthpiece 3. In other examples, the ventilation can be provided into the mouthpiece 3 at other locations.

Aerosol provision system

A third aspect of the invention provides, an aerosol provision system comprising a consumable according to any embodiment of the second aspect of the invention.
Combustible aerosol provision systems include cigarettes, cigarillos, cigars, and tobacco for pipes or for roll-your-own or for make-your-own cigarettes (whether based on tobacco, tobacco derivatives, expanded tobacco, reconstituted tobacco, tobacco substitutes or other smokable material).
Non-combustible aerosol provision systems that release compounds from an aerosol-generating material without combusting the aerosol-generating material, such as electronic cigarettes, tobacco heating products, and hybrid systems to generate aerosol using a combination of aerosol-generating materials.
In some embodiments, the delivery system is a non-combustible aerosol provision system, such as a powered non-combustible aerosol provision system.
According to the present disclosure, a "non-combustible" aerosol provision system is one where a constituent aerosol-generating material of the aerosol provision system (or component thereof) is not combusted or burned in order to facilitate delivery of at least one substance to a user.
In some embodiments, the non-combustible aerosol provision system is an electronic cigarette, also known as a vaping device or electronic nicotine delivery system (END), although it is noted that the presence of nicotine in the aerosol-generating material is not a requirement.
In some embodiments, the non-combustible aerosol provision system is an aerosol-generating material heating system, also known as a heat-not-burn system. An example of such a system is a tobacco heating system.
In some embodiments, the non-combustible aerosol provision system is a hybrid system to generate aerosol using a combination of aerosol-generating materials, one or a plurality of which may be heated. Each of the aerosol-generating materials may be, for example, in the form of a solid, liquid or gel and may or may not contain nicotine. In some embodiments, the hybrid system comprises a liquid or gel aerosol-generating material and a solid aerosol-generating material.
Typically, the non-combustible aerosol provision system may comprise a non-combustible aerosol provision device and a consumable for use with the non-combustible aerosol provision device.
In some embodiments, the disclosure relates to consumables comprising aerosol-generating material and configured to be used with non-combustible aerosol provision devices. These consumables are sometimes referred to as articles throughout the disclosure.
In some embodiments, the non-combustible aerosol provision system, such as a non-combustible aerosol provision device thereof, may comprise a power source and a controller. The power source may, for example, be an electric power source or an exothermic power source. In some embodiments, the exothermic power source comprises a carbon substrate which may be energised so as to distribute power in the form of heat to an aerosol-generating material or to a heat transfer material in proximity to the exothermic power source.
In some embodiments, the non-combustible aerosol provision system may comprise an area for receiving the consumable, an aerosol generator, an aerosol generation area, a housing, a mouthpiece, a filter and/or an aerosol-modifying agent.
In some embodiments, the consumable for use with the non-combustible aerosol provision device may comprise aerosol-generating material, an aerosol-generating material storage area, an aerosol-generating material transfer component, an aerosol generator, an aerosol generation area, a housing, a wrapper, a filter, a mouthpiece, and/or an aerosol-modifying agent.
Figure 2 shows an example of a non-combustible aerosol provision device 100 for generating aerosol from an aerosol-generating composition of an article or consumable 110, as described herein. For example, the article 110 may be the article 1 shown in Figure 1.
In broad outline, the device 100 may be used to heat a replaceable article 110 comprising the aerosol-generating composition as described herein, for instance an article as described elsewhere herein, to generate an aerosol or other inhalable medium which is inhaled by a user of the device 100. The device 100 and replaceable article 110 together form a system.
The device 100 comprises a housing 102 (in the form of an outer cover) which surrounds and houses various components of the device 100. The device 100 has an opening 104 in one end, through which the article 110 may be inserted for heating by a heating assembly. In use, the article 110 may be fully or partially inserted into the heating assembly where it may be heated by one or more components of the heater assembly. The article 110 is illustrated having a rod-shape, like the articles 1 illustrated in Figure 1.
The device 100 of this example comprises a first end member 106 which comprises a lid 108 which is moveable relative to the first end member 106 to close the opening 104 when no article 110 is in place. In Figure 2, the lid 108 is shown in an open configuration, however the lid 108 may move into a closed configuration. For example, a user may cause the lid 108 to slide in the direction of arrow "B".
The device 100 may also include a user-operable control element 112, such as a button or switch, which operates the device 100 when pressed. For example, a user may turn on the device 100 by operating the switch 112. This switch may also actuate the means for opening the container inserted into the device, in readiness for its use.
The device 100 may also comprise an electrical component, such as a socket/port 114, which can receive a cable to charge a battery of the device 100. For example, the socket 114 may be a charging port, such as a USB charging port.

Kit

A fourth aspect of the invention provides a kit comprising:

an aerosol-generating consumable comprising an aerosol-generating material comprising tobacco material; and
a dispenser comprising a nitrite-decreasing additive,
wherein the dispenser may be used to combine the nitrite-decreasing additive and the tobacco material prior to use of the consumable.

Use

A fifth aspect of the invention provides the use of a selectively releasable source of a nitrite-decreasing additive to reduce the generation of tobacco-specific nitrosamines upon heating an aerosol-generating material. Optionally, the aerosol-generating material comprises tobacco material.
In some embodiments, the nitrite-decreasing additive reduces the generation of one or more TSNA selected from:

(i) NNN;
(ii) NNK;
(iii) NAB; and
(iv) NAT

In some embodiments, the nitrite-decreasing additive reduces the generation of one or more TSNA selected from:

(i) NNN; and
(ii) NNK.

In some embodiments, the nitrite-decreasing additive reduces the generation of NNN.
In some embodiments, the nitrite-decreasing additive reduces the generation of TSNAs by at least about 5 wt% compared to the TSNAs generated on heating an equivalent tobacco material that was not treated with the nitrite-decreasing additive. In some embodiments, the nitrite-decreasing additive reduces the generation of TSNAs by at least about 10 wt%, by at least about 15 wt%, by at least about 20 wt%, by at least about 25 wt%, by at least about 30 wt%, by at least about 35 wt%, by at least about 40 wt%, by at least about 45 wt% or by at least about 50 wt% compared to the TSNAs generated on heating an equivalent tobacco material that was not treated with the nitrite-decreasing additive.

Examples

Apparatus

Smoking machine used in Example 1- Cerulean SM450RH 20-port linear smoking machine
Smoking machine used in Example 2 - Körber LM5E 5-port linear smoking machine Auto Analyzer System- Pulse Instrument Ltd
Spectrophotometer- Varian Cary 100
LC-MS/MS (High Performance Liquid Chromatography with tandem mass
spectroscopy) used in Example 1- LCMS 11 Agilent TQ 6470
LC-MS/MS used in Example 2 - SCIEX Triple Quad 4500
Injections- Hamilton 80530, Product code: 10130411, volume: 50µl
Devices- glo^™ Hyper
Consumables- Tobacco Heating Product (THP) consumables
Reagents and Materials

The nitrite-decreasing additive and solvents (other than water) used for injections were all purchased from Sigma-Aldrich and used without purification. Their CAS numbers are listed below:

Chemical	CAS number
L-Ascorbic acid	50-81-7
(+)-Sodium L-ascorbate	134-03-2
Trans-Ferulic acid	537-98-4
Sorbic acid	110-44-1
Vitamin E	10191-41-0
Ethanol (absolute, ≥99.8%)	64-17-5

Procedure

Testing was conducted on THP consumables that were stored for 48 hours before testing under ISO conditions (22°C/60% relative humidity (RH)). Two separate samples (pre-use and post-use) were generated for analysis, each sample contained 5 or 10 replicates, with each replicate using 3 or 5 consumables. Pre-use consumables have not been heated and post-use consumables, which were consumables that were heated using glo^™ Hyper THP device and puffed using the Cerulean SM450RH 20-port linear smoking machine or the Körber LM5E 5-port linear smoking machine. The smoke machine was programmed so that the consumables were heated for a full session (10 puffs/4 minutes) using the Health Canada Intense modified (HCIm) machine puffing regime.
Nitrite was tested for using Automated Spectroscopy. Initially the ground and homogenised tobacco was extracted with ultrapure water using a heated ultrasonic bath. The samples were left to cool to room temperature before being further diluted with ultrapure water, followed by being vortexed and syringe filtered. A portion of the filtrate was then reacted with sulphanilamide and N-(1-naphthyl)ethylenediamide dihydrochloride, which created a colour reaction, the sample was then analysed using a spectrophotometer at 540 nm.
To analyse and test tobacco products, smoking machines are used to ensure consistent sample generation to compare results. This is achieved by setting these machines to take specific volume puffs over a set time, known as smoking regimes, that are outlined in ISO standard 20778:2018. This particular study used the Health Canada Intense modified (HCIm) machine puffing regime (puff volume 55ml, puff duration 2 seconds, puff interval of 30 seconds and ventilation holes of the consumable are not blocked) (see T. J. J. Adamson, Food and Chemical Toxicology, 2018, 113, 337-344).

Example 1

In the first test, the following controls and nitrite-decreasing additive compositions were used:

Samples	Ratio	Solvent	Mass in 50ml (g)
No solvent control	-	-	-
Water control	-	Water	-
Ethanol control	-	Ethanol	-
Ascorbic Acid	2:1	Water	2.4964
Sodium Ascorbate	2:1	Water	2.4444
Ascorbic Acid w/Ferulic Acid	2:1 (15:0.5)	Water: Ethanol	2.4365, 0.082
Ferulic Acid	1:1	Ethanol	1.2116
Sorbic Acid	0.5:1	Ethanol	0.3119
Vitamin E	3:1	Ethanol	3.6146

Stock solutions were made up in 50 ml volumetric flasks for each nitrite-decreasing additive. The table directly above shows the mass of nitrite-decreasing additive that was added to the stock solutions, as well as the solvent used for each solution, which was determined by assessing what solvent each nitrite-decreasing additive was most soluble in. Amber tinted volumetric flasks were used to reduce the degradation of ascorbic acid, due to its light sensitivity, all other solutions were also made up in amber tinted bottles too to ensure consistency in the method.
Testing was conducted on THP consumables. They were injected using a 50 µl needle syringe, and, for each nitrite-decreasing additive, 60 consumables were each injected with a total volume of 50 µl. Before injections could commence the internal barrel of the syringe was cleaned with absolute ethanol (≥99.8%) five times, which also cleaned the inside of the needle. The plunger was removed and cleaned with absolute ethanol, and the external surface of the needle was also cleaned with absolute ethanol. A small segment of filter section from a THP consumable was inserted onto the needle, this ensured the needle remained in the tobacco section of the consumable to prevent the needle entering the cooling section. The needles were inserted through the centre tobacco section of the consumable. The injection was performed to distribute the additive as evenly as possible throughout the tobacco portion of the consumables.
In addition to the samples of nitrite-decreasing additive, control samples were also produced, each sample contained 60 consumables. The controls had either no solvent injected or only solvent (i.e., no nitrite-decreasing additive), to rule out the solvent being a factor behind any TSNA changes.
To ensure all samples were kept consistent a range of ±15 mg around the expected weight of an injection (varied depending on solvent) was used to determine an acceptable mass of the nitrite-decreasing additive injected into the consumable, if the weight was not in this range it was discarded. In addition, if the consumable was punctured by the needle or if too much spotting occurred on the paper, which is where the solvent absorbed onto the paper rather than into the tobacco, it was also discarded. Consumables were stored in labelled bags and conditioned for 19 days before emissions generation and analysis.

Tobacco-Specific Nitrosamine Analysis:

All samples were heated for a full session using glo^™ Hyper THP device and puffed using an automated constant volume linear smoking machine. The smoke machine was programmed so that the consumables were heated for a full session (10 puffs) using HCIm puffing regime.
When the consumables were heated the emissions formed were collected on a Cambridge filter pad, 5 consumables were heated for each pad, which was repeated 5 times. Cambridge filter pads are used in routine analytical machine smoking of tobacco products to collect the particulate phase of the smoke. The filter pad is combined with ammonium acetate and internal standard solution (NNN-d₄, NAT-d₄, NAB-d₄ and NNK-d₄), then extracted using a wrist action shaker. A portion of the extract is filtered, then analysed by LC-MS/MS with positive electrospray ionisation using a C18 guard and a C18 guard column.

Results and Discussion

The weight of the consumables was measured before and after every injection, so that the mass difference could be calculated.

The mean amounts of the NNN, NNK, NAB and NAT content in the THP emissions from those samples including a water-soluble nitrite-decreasing additive were as follows:

Additive	NNN [ng/item]	NNK [ng/item]	NAB [ng/item]	NAT [ng/item]
No solvent control	8.95	5.67	2.97	18.90
Water control	7.10	4.16	2.42	16.00
Ascorbic acid	6.80	4.49	2.18	14.28
Sodium ascorbate	6.95	4.52	2.25	15.60
Ascorbic acid w/Ferulic acid	8.17	5.33	2.54	16.36

The NNN values for both ascorbic acid and sodium ascorbate were very similar to those of the water control. One potential reason why no change in NNN compared to the water control was seen could be because ascorbic acid had decomposed. Alternatively, any nitrite-scavenging effect of the ascorbic acid on the tobacco material may have been short-lived, with the nitrites being replenished over time.
When the consumable was injected with ascorbic acid and ferulic acid, the NNN content increased. This was unexpected as ferulic acid was added in an attempt to stabilise the ascorbic acid.
Both ascorbic acid and ascorbic acid with ferulic acid increased the NNK content compared to the water control. Although an increase was seen in NNN for ascorbic acid with ferulic acid, this was not the case for just ascorbic acid.

The mean amounts of the NNN, NNK, NAB and NAT content in the THP emissions from those samples including ethanol-soluble nitrite-decreasing additives were as follows:

Additive	NNN [ng/item]	NNK [ng/item]	NAB [ng/item]	NAT [ng/item]
No solvent control	8.95	5.67	2.97	18.90
Ethanol control	8.97	5.91	2.98	18.76
Sorbic acid	7.97	4.44	2.74	17.56
Ferulic acid	8.50	5.34	2.79	17.58
Vitamin E	9.99	6.16	3.46	22.30

The addition of ethanol did not affect the NNN content. When ferulic acid was added to the consumable the NNN content was slightly lower, however, there was a large interquartile range resulting in most of the data overlapping with the ethanol control.
In contrast when sorbic acid was added, the NNN content was less than the NNN content in the control with ethanol.
The NNN content in the vitamin E sample increased in comparison to the ethanol control.
Of the exemplified nitrite-decreasing additives, sorbic acid was the most effective in decreasing NNK and ascorbic acid was the most effective at decreasing NNN, NAB, and NAT content.
Given the dynamic nature of the treated tobacco material, it was felt that the disappointing results seen in these tests could be due to the long delay between the tobacco treatment and the testing, during which, it was hypothesised, the effects of the additives could be wearing off as more nitrites are produced in the treated tobacco. It is also possible that the amount of the nitrite-decreasing additive added may have been too low. As a result, the amounts used were increased in the 2nd study (see below). Also, it was speculated that the location of the addition of the nitrite-decreasing additive could affect performance. As a result, a more localised injection of the additive was tested.

Example 2

In the second test, the intention was to reduce the time between treating the tobacco material with the nitrite-decreasing additive and testing. The following compositions were used:

Samples	Solvent	Mass in 50ml (g)
No solvent control	-	-
Water control	Water	-
Ethanol control	Ethanol	-
Ascorbic Acid	Water	6.055
Sodium Ascorbate	Water	6.811
Sorbic Acid	Ethanol	0.963

Samples were prepared using THP consumables following the same methodology as Example 1, except where noted.
A 50 µl syringe (cleaned as in Example 1) was used to inject a total volume of 50 µl into each consumable. The injection was performed to distribute 25 µl of the additive composition into the area extending up to 6 mm from the end of the tobacco rod abutting the mouth end cooling section of the consumable. The remaining 25 µl of the additive composition was injected to be distributed as evenly as possible throughout the remaining tobacco portion of the consumables.
Each sample contained 10 replicates.
Tobacco-Specific Nitrosamine Analysis:
All samples were heated for a full session using glo^™ Hyper THP device and puffed using an automated constant volume linear smoking machine. The smoke machine was programmed so that the consumables were heated for a full session (10 puffs) using HCIm puffing regime.
When the consumables were heated the emissions formed were collected on a Cambridge filter pad, 3 consumables were heated for each pad, which was repeated 10 times. Cambridge filter pads are used in routine analytical machine smoking of tobacco products to collect the particulate phase of the smoke. The filter pad is combined with ammonium acetate and internal standard solution (NNN-d₄, NAT-d₄, NAB-d₄ and NNK-d₄), then extracted using a wrist action shaker. A portion of the extract is filtered, then analysed by LC-MS/MS with positive electrospray ionisation without guard column.

Results and Discussion

Prior to analysis the consumables were stored at ISO conditions for 48 hours in sealed bags.

The mean amounts of the NNN, NNK, NAB and NAT content in the THP emissions from those samples including water-soluble nitrite-decreasing additives were as follows:

Additive	NNN [ng/item]	NNK [ng/item]	NAB [ng/item]	NAT [ng/item]
No solvent control	19.5	9.9	8.0	47.7
Water control	19.1	9.1	9.1	52.4
Ascorbic acid	10.1	6.0	4.4	26.6
Sodium ascorbate	10.7	7.3	5.1	29.9

The NNN values for ascorbic acid and sodium ascorbate were reduced by 47.1% and 44%, respectively, compared to the water control. The NNK values for ascorbic acid and sodium ascorbate were reduced by 34.1% and 19.8%, respectively, compared to the water control. The NAB values for ascorbic acid and sodium ascorbate were reduced by 51.6% and 44%, respectively, compared to the water control. The NAT values for ascorbic acid and sodium ascorbate were reduced by 49.2% and 42.9%, respectively, compared to the water control.
The mean amounts of the NNN, NNK, NAB and NAT content in the THP emissions from those samples including ethanol-soluble nitrite-decreasing additives were as follows:

Additive NNN [ng/item] NNK [ng/item] NAB [ng/item] NAT [ng/item]

No solvent control 19.5 9.9 8.0 47.7

Ethanol control 12.8 6.1 6.7 41.0

Sorbic acid 15.2 6.7 8.0 46.6
The NNN, NNK and NAT values for sorbic acid were reduced by 22.1%, 32.3% and 2.3%, respectively, compared to the no solvent control. No difference was seen in the NAB value compared to the no solvent control. However, the ethanol control performed better that the sorbic acid, suggesting that further refinement of the treatment with the additive may be required to improve the effect.
It is hypothesised that the effects of at least some of the nitrite-decreasing additives are short-lived, and have largely worn off where the sample consumables were tested 19 days after treatment of the tobacco material. In contrast, a delay of only 48 hours between treatment and testing saw the expected reductions in TSNAs.
Two factors may be at play here. Firstly, some of the nitrite-decreasing additives are relatively unstable and may lose efficacy over time. Secondly, and probably more importantly, the decrease in the nitrites in the tobacco material as a result of treatment with the additives is short-lived because more nitrites are being produced and replace those that have been removed by the treatment with the additives. Additionally, as noted above, it is possible that the amount of the nitrite-decreasing additive added may have been too low and/or that the location of the addition of the nitrite-decreasing additive was not optimised. Therefore, the use of higher amounts of nitrite-decreasing additive is expected to be more effective at reducing the generation of TSNAs.
The various embodiments described herein are presented only to assist in understanding and teaching the claimed features. These embodiments are provided as a representative sample of embodiments only and are not exhaustive and/or exclusive. It is to be understood that advantages, embodiments, examples, functions, features, structures, and/or other aspects described herein are not to be considered limitations on the scope of the invention as defined by the claims or limitations on equivalents to the claims, and that other embodiments may be utilised, and modifications may be made without departing from the scope of the claimed invention. Various embodiments of the invention may suitably comprise, consist of, or consist essentially of, appropriate combinations of the disclosed elements, components, features, parts, steps, means, etc., other than those specifically described herein. In addition, this disclosure may include other inventions not presently claimed, but which may be claimed in future.

Claims

An aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive.
The aerosol-generating material according to claim 1, wherein the selectively releasable source of the nitrite-decreasing additive is configured to release the nitrite-decreasing additive no more than 5 days before the intended heating of the aerosol-generating material in an aerosol provision system.
The aerosol-generating material according to claim 1 or claim 2, wherein the nitrite-decreasing additive is an antioxidant or a precursor to an antioxidant.
The aerosol-generating material according to any one of claims 1 to 3, wherein the nitrite-decreasing additive is one or more selected from the group consisting of:
sorbic acid, a sorbic acid salt, ascorbic acid, and an ascorbic acid salt.
The aerosol-generating material according to claim 4, wherein the sorbic acid salt or ascorbic acid salt is a salt selected from the group consisting of a lithium, sodium, potassium, magnesium, calcium or ammonium salt.
The aerosol-generating material according to any one of claims 1 to 5, wherein the nitrite-decreasing additive is provided in encapsulated form; preferably wherein the encapsulated nitrite-decreasing additive is provided in liquid form.
The aerosol-generating material according to claim 6, wherein the encapsulated nitrite-decreasing additive is released in a temperature-dependent manner; preferably wherein the encapsulated nitrite-decreasing additive is released upon being heated to a temperature within the range of from about 50°C to about 100°C.
The aerosol-generating material according to any one of claims 1 to 7, wherein the nitrite-decreasing additive is present in an amount of about 0.01 to about 5 wt% based on the weight of the tobacco material; preferably wherein the nitrite-decreasing additive is present in an amount of about 0.05 to about 3 wt% based on the weight of the tobacco material.
A consumable for use in an aerosol provision system, the consumable comprising an aerosol-generating material comprising tobacco material and a selectively releasable source of a nitrite-decreasing additive.
The consumable according to claim 9, comprising an aerosol generating material according to any one of claims 1 to 8.
The consumable according to claim 9, wherein the selectively releasable source of the nitrite-decreasing additive is not included in the aerosol-generating material.
The consumable according to claim 11, comprising a first segment or chamber within which the tobacco material is held and a second segment or chamber within which the nitrite-decreasing additive is held, the consumable being configured to allow the nitrite-decreasing additive to contact the tobacco material only when the source of the nitrite-decreasing additive is released by the consumer before the consumable generates an inhalable aerosol.
An aerosol provision system comprising a consumable as claimed in any one of claims 9 to 12.
A kit comprising:
an aerosol-generating consumable comprising an aerosol-generating material comprising tobacco material; and

a dispenser comprising a nitrite-decreasing additive,

wherein the dispenser may be used to combine the nitrite-decreasing additive and the tobacco material prior to use of the consumable.
Use of a selectively releasable source of a nitrite-decreasing additive to reduce the generation of tobacco-specific nitrosamines upon heating an aerosol-generating material, optionally wherein the nitrite-decreasing additive is released and contacts at least some of the aerosol-generating material no more than 5 days before the intended heating of the aerosol-generating material in an aerosol provision system, and/or wherein the aerosol-generating material comprises tobacco material or a tobacco extract.