CN113197323A

CN113197323A - Fragrance-carrying supramolecular gel based on gallic acid nicotine salt gelling agent

Info

Publication number: CN113197323A
Application number: CN202110516615.XA
Authority: CN
Inventors: 韩熠; 赵伟; 巩效伟; 杨柳; 张霞; 雷萍; 吕茜; 洪鎏; 申钦鹏; 刘凌璇; 秦云华; 陈永宽
Original assignee: China Tobacco Yunnan Industrial Co Ltd
Current assignee: China Tobacco Yunnan Industrial Co Ltd
Priority date: 2021-05-12
Filing date: 2021-05-12
Publication date: 2021-08-03
Anticipated expiration: 2041-05-12
Also published as: CN113197323B

Abstract

The invention belongs to the field of supramolecular gel, and particularly relates to aroma-carrying supramolecular gel based on a gallic acid nicotine salt gelling agent. The gel comprises a nicotine gallate gelling agent and a flavor substance and a solvent dispersed in the nicotine gallate gelling agent; the gallic acid nicotine salt gelling agent is a three-dimensional fiber network structure formed by self-assembly of a one-dimensional fiber network, and the one-dimensional fiber network structure is formed by connecting a plurality of gallic acid nicotine salt supermolecular structural units formed between gallic acid and nicotine. According to the invention, the gallic acid and nicotine are used for the first time to prepare the gelling agent with a supramolecular network structure and the fragrance-carrying supramolecular gel, the fragrance substance is stably fixed in the gel network at normal temperature, the storage stability of the fragrance component is effectively increased, and the common fixation and synergistic release of nicotine and the fragrance component are realized.

Description

Fragrance-carrying supramolecular gel based on gallic acid nicotine salt gelling agent

Technical Field

The invention belongs to the field of supramolecular gel, and particularly relates to aroma-carrying supramolecular gel based on a gallic acid nicotine salt gelling agent.

Background

The basic nicotine can be reacted with the carboxylic group of the organic acid to form a nicotine carboxylate. Nicotine comprises a pyridine ring and an azole ring, wherein the azole ring nitrogen is more basic and tends to react with the carboxyl group of carboxylic acid to form nicotine salt, while the pyridine ring nitrogen is less basic and substantially cannot be ionized and can only be bound to carboxylic acid by non-covalent action such as hydrogen bond. The tobacco leaf naturally contains various carboxylic acid nicotine salts, and the nicotine salts can be divided into 1:1 acid-base ratio, 2:1 acid-base ratio and 3:1 acid-base ratio according to the acid-base ratio of the formed nicotine salts. Wherein the common nicotine carboxylate comprises nicotine tartrate, nicotine gallate, nicotine malate, nicotine oxalate, and nicotine benzoate.

Studies have shown that two complex chemical reactions occur when nicotine is released from nicotine salts: the first reaction comprises dissociation and/or dehydration and decomposition of carboxylic acid anions; the second reaction involves proton transfer between different nicotine forms, disproportionation of a single protonated salt to a mixture of a double protic salt and free nicotine, and evaporation of the free nicotine to achieve a disproportionation equilibrium. Experiments prove that most nicotine salts can release nicotine in two different temperature ranges (110-. Specifically, there are 3 intervals for the temperature of nicotine released by heating of various nicotine salts: about 115 ℃ (evaporation/volatilization of non-protonated nicotine (free nicotine)), about 165 ℃ (disproportionation of monoprotonated nicotine salt), and about 200 ℃ (decomposition/dissociation of biprotonated nicotine salt).

The synthesized nicotine salt can be directly added into the electronic cigarette or the heating cigarette to achieve the effects of supplementing the nicotine amount and obtaining the physiological feeling similar to that of smoking and burning cigarettes. If the heating temperature of the tobacco leaves exceeds 250 ℃, the nicotine content in the smoke is similar to that in the smoke of the burning and sucking type cigarette. Meanwhile, when the heating temperature of the tobacco leaves does not exceed 350 ℃, the generation of harmful and potentially harmful ingredients (HPHCs) is obviously reduced compared with the smoking type cigarette. Importantly, the transfer rates of nicotine from the unprotonated (free) nicotine and nicotine carboxylate salts to the gas phase were comparable in the 250-300 ℃ range. Heating cigarettes avoids the high temperatures of tobacco combustion, delivering nicotine levels similar to smoking cigarettes, but with lower average levels of harmful components.

The current major problems and drawbacks of heating cigarettes:

the heating cigarette is different from the burning type cigarette and is characterized in that: the time required for heating the cigarette to preheat the cigarette to the working temperature (such as 300 ℃) is longer, so that the time for exposing the tobacco section to the temperature range of 125-250 ℃ is longer, and the nicotine salt can completely transfer the nicotine to the gas phase in the temperature range, on one hand, volatile flavor components are evaporated into the gas phase in a large amount along with the transfer of the nicotine in the preheating stage and then escape out of the cigarette, so that the flavor attenuation of the later section in smoking is serious; on the other hand, the tobacco itself contains a large amount of polycarboxylic acid nicotine salt (such as malic acid and gallic acid nicotine salt), and when the nicotine salt releases nicotine, due to the poor thermal stability of the polycarboxylic acid itself, the elimination reaction occurs due to dehydration or decarboxylation to form a weakly acidic product such as monocarboxylic acid (such as acetic acid), and in the process, the problems of small smoke amount at the front stage of smoking, mouth burning of smoke, obvious sour feeling and the like are caused due to the slow accumulation of moisture and acidity.

The reconstituted tobacco leaves have the characteristics of stronger plasticity, homogenization and higher adjustable level while keeping the active ingredients of the natural tobacco leaves, so the reconstituted tobacco leaves are one of the main tobacco section materials of the existing heating cigarettes. The tobacco section of the mainstream heating cigarette is manufactured by adopting a paper making method and a thick paste method. The papermaking process is influenced by the coating rate, the smoke amount and the fragrance amount of the papermaking process are slightly low, and the high-content (12% -20%) smoke agent is mainly coated on the surface of reconstituted tobacco and is easy to leach and absorb moisture. In order to improve the aroma amount of the reconstituted tobacco, refined processing such as tobacco solvent extraction, molecular distillation and the like is usually adopted to prepare tobacco extract with high aroma amount and high nicotine amount and add the tobacco extract into the coating liquid, so that the process is complicated and the manufacturing cost is high; in order to meet the loading function of the chip base, a more complex special chip base needs to be developed; the reconstituted tobacco has high surface viscosity and poor elasticity, and the difficulty of the subsequent shredding process is increased. The slurry water content (about 80%) of the reconstituted tobacco by the thick slurry method is high during forming, and the high water content needs to be removed during drying, so that loss of aroma components and smoke agents is easily caused. In conclusion, reconstituted tobacco for cigarette heating by a paper making method and a thick stock method mainly has the problems of leaching from tobacco sections, moisture absorption and the like caused by low aroma amount and smoke amount and high smoke agent, which directly affect the product quality and the smoking sensory quality.

The main problems and defects of the electronic cigarette liquid at present are as follows:

the nicotine originally used in e-cigarette smoke solutions was referred to as "free base" nicotine. The free base nicotine is volatile. As a result, when a consumer inhales the e-vaping sol, nicotine is likely to be released from the aerosol particles in gaseous form, deposited in the oral/upper respiratory tract, and absorbed by the blood. Absorption in the mouth/upper respiratory tract is slower than in conventional cigarettes, and pharmacokinetic studies have shown that they are closer to Nicotine Replacement Therapy (NRT) products than in conventional cigarettes. For this reason, tobacco solutions containing nicotine salts have been introduced. Nicotine salts are less volatile than free base nicotine. Pharmacokinetic studies have shown that nicotine carboxylates can deliver nicotine through the lungs, increasing the rate of absorption without exceeding the maximum nicotine concentration of conventional cigarettes, while having acceptable subjective satisfaction and ease of smoking. Currently, a nicotine salt that is representative in commercially available electronic cigarettes is nicotine benzoate.

Although nicotine salts have been widely used in electronic cigarette liquid, the current electronic cigarettes containing nicotine salts still have the following major problems in the sense of sense: when the nicotine salt is heated and decomposed to form free nicotine and delivered to atomized steam, the release behavior of the nicotine by mouth is inconsistent with that of the aroma component, the key aroma component and the nicotine are difficult to realize the synergistic delivery, and the nicotine can not bring matched characteristic aroma while bringing the physiological satisfaction of the nicotine, so that the sensory feelings of the nicotine and the aroma substance are weak, mutually cover or even mutually repel, especially for the volatile characteristic aroma substance, the nicotine and the aroma substance can not be stably released (usually the release amount by mouth is gradually reduced) in the whole smoking process, and the discordance is particularly obvious. For this reason, it is probably because: from the material aspect, the nicotine salt and the essence flavor in the tobacco liquid belong to different systems, the nicotine salt and the essence flavor belong to a nicotine release system, the essence flavor belongs to a flavor release system, a medium which can connect the nicotine salt and the flavor release system into a whole does not exist in the tobacco liquid, and the nicotine salt and the flavor release system respectively have the atomizing behaviors at the same atomizing temperature; from an organoleptic point of view, nicotine salts mainly provide suitable physiological satisfaction and relaxation, flavors and fragrances mainly provide inhalation and eating flavors with characteristic tastes through evaporation, and the organoleptic characteristics are also separated during smoking because of different atomization behaviors of the two. Another common problem with electronic cigarettes is: in the process of storing the cigarette liquid or the cigarette cartridge, the problem of volatilization loss of the aroma components is inevitable, and even in a closed cigarette cartridge, the problem of deterioration of aroma substances is also inevitable. Although the volatile aroma components can be wrapped by the microcapsule technology at present, because the microcapsule uses carbohydrate such as cyclodextrin and the like as a wall material, burnt taste and uncomfortable feeling caused by the adhesion of the wall material on a heating element can be generated at the heating temperature of the electronic cigarette. The stabilization of flavor substances, particularly volatile flavor substances, in cigarette liquid is still a major problem to be solved in the electronic cigarette at present.

Disclosure of Invention

In order to overcome the defects of the heated cigarettes and the electronic cigarettes, the invention discloses a nicotine salt gelling agent-based aroma-carrying supramolecular gel for the first time, which takes a fiber network formed by self-assembly of a small amount of nicotine salt gelling agent as a substrate, carries a large amount of solvent (smoke agent) dissolved with aroma substances, and can be applied to the fields of the heated cigarettes and the electronic cigarettes by utilizing the inherent high aroma-carrying amount, high solvent (smoke agent) carrying amount, thermal reversible property and supramolecular network structure stability different from the conventional nicotine salt molecules of the gel.

Interpretation of terms:

supramolecular gels: supramolecular gels are composed of small molecules (M), commonly referred to as small molecular weight gelling agents (LMWGs)_wLess than 3000). These compounds immobilize solvent molecules by allowing LMWGs to self-assemble by various non-covalent interactions (such as hydrogen bonding, pi-pi stacking, electrostatic interactions, complexation, and hydrophobic interactions, etc.) to form self-assembled fiber networks (SAFINs) when formed into supramolecular gels. Physical gels derived from small molecular weight organogelators (LMOGs) are generally thermoreversible (reversible sol-gel transformation occurs upon heating and cooling). Upon cooling of the gelling agent containing solution, growth of one-dimensional (1D) fibers is promoted, which self-assemble into complex three-dimensional (3D) SAFINs in a manner that allows the solvent molecules to be immobilized therein by capillary action to form a gel.

The present invention provides in a first aspect a flavor-bearing supramolecular gel based on a nicotine gallate gelling agent, the gel comprising a nicotine gallate gelling agent and a flavor substance and a solvent dispersed in the nicotine gallate gelling agent;

the gallic acid nicotine salt gelatinizer is a three-dimensional network structure formed by self-assembly of one-dimensional fibers, the one-dimensional fiber structure is formed by connecting a plurality of gallic acid nicotine salt supramolecular structural units formed between gallic acid and nicotine, and the gallic acid nicotine salt supramolecular structural units are connected as follows:

the forming principle of the gallic acid nicotine salt gelling agent is as follows: the nicotine and the carboxylic acid molecules are combined into a supermolecular structural unit through a synthon, then the supermolecular structural unit is connected into a one-dimensional fiber structure through intermolecular force such as hydrogen bond, and then the one-dimensional fiber structure is self-assembled to form a three-dimensional network structure.

Preferably, the fragrance substance is selected from: one or more of jasmone, anisyl ketone, zingerone, muscone, civetone, nerolidol, farnesol, beta-caryophyllenol, beta-santalol, alpha-santalol, jasmal, vanillin, ethyl vanillin, piperonal, cinnamaldehyde, methyl laurate, ethyl laurate, methyl myristate, ethyl myristate, geranyl benzoate, linalyl benzoate, phenylacetic acid and beta-caryophyllene.

Preferably, the organic solvent is selected from ethyl acetate or a mixed solvent of ethyl acetate and 1, 2-propylene glycol.

The second aspect of the invention provides a preparation method of a fragrance-carrying supramolecular gel based on a gallic acid nicotine salt gelling agent, which comprises the following steps:

step 1, preparing a gelling agent: respectively dissolving gallic acid and nicotine in a mixed solvent of water and ethanol according to a molar ratio of 2:1, stirring at room temperature until the gallic acid and nicotine are completely dissolved to respectively obtain a gallic acid solution and a nicotine solution, fully mixing the two solutions to obtain a mixed solution, heating the mixed solution to reflux, reacting for more than 30min, performing rotary evaporation, and drying a product obtained by the rotary evaporation at 30-40 ℃ for 20-30 h to obtain a gallic acid nicotine salt gelling agent;

step 2, preparation of gel:

dissolving the fragrant substance with organic solvent to obtain a fragrant substance-containing solvent; and then adding the flavor-containing substance solvent into the gallic acid nicotine salt gelling agent obtained in the step 1, dissolving the substance by heating and stirring or ultrasonic treatment, and then standing in an ice water bath to form gel.

The ice-water bath temperature is preferably: 0-5 degrees Celsius, such as 0 degrees Celsius, 1 degree Celsius, 2 degrees Celsius, 3 degrees Celsius, 4 degrees Celsius, 5 degrees Celsius.

Preferably, in the step 1, the volume content of water in the mixed solvent of water and ethanol is less than 20%; the mass volume ratio of the gallic acid to the mixed solvent of water and ethanol is 1g: 20-30 mL, the mass volume ratio of the nicotine to the mixed solvent of water and ethanol is 1g: 100-300 mL, the rotary evaporation temperature is 50-60 ℃, and the rotary evaporation pressure is 150-170 mbar.

In the step 1, a mixed solvent of water and ethanol is selected as a solvent, the reason that the gallic acid can be dissolved in the ethanol is that a small amount of water is added to promote partial ionization of the carboxylic acid and prevent salt forming reaction after excessive water is added and the carboxylic acid is completely ionized.

Nicotine is soluble in ethanol. In step 1, ethanol can be used alone to dissolve nicotine.

Preferably, in the step 2, the mass-to-volume ratio of the flavor substance to the organic solvent is 1g: 20-30 mL, the mass-to-volume ratio of the gallic acid nicotine salt gelling agent to the flavor substance-containing solvent is 1g: 20-30 mL, the temperature of the ice water bath is 4 ℃, and the standing time in the ice water bath is 1-3 h. Since the amounts of fragrance and gelling agent required are relatively small and the amount of solvent is relatively large, it is easier to handle in practice with a mass to volume ratio.

Theoretically, ethanol could be replaced by methanol or acetone, but methanol is more toxic and acetone is too volatile and therefore is not generally used.

Since the formation of the gallic acid nicotine salt gellant exhibits moderate polarity overall with the synergistic effect of hydrogen bonding and pi-pi stacking as driving forces, the flavor material of the present invention is selected to be a moderately polar material and the organic solvent is selected to be an ethyl acetate-1, 2-propanediol mixed solvent.

The fragrant substance is a medium polar substance and belongs to a semi-volatile fragrant substance. Standing in ice water bath to maintain the stability of semi-volatile fragrant substances.

More preferably, the organic solvent is more preferably a mixed solvent of ethyl acetate and 1, 2-propanediol, considering that ethyl acetate is volatile and less polar and thus makes uniform dispersion thereof in a moderately polar nicotine gallate gelling agent somewhat difficult (e.g., requires heating).

The organic solvent is selected from a mixed solvent of ethyl acetate and 1, 2-propylene glycol, and has the following reasons: the gelling agent is generally medium-polarity and is easy to form a uniform system with a mixed solvent of ethyl acetate and 1, 2-propylene glycol which are medium-polarity solvents when being heated; secondly, the moderate polar fragrant substance has higher solubility in the mixed solvent of the moderate polar solvent ethyl acetate and 1, 2-propylene glycol; thirdly, the gelling agent is medium in polarity, so that gel is easily formed in a mixed solvent of ethyl acetate and 1, 2-propylene glycol which are solvents with similar polarity, and the gelation failure caused by phase separation during cooling gelation is avoided; and fourthly, 1, 2-propylene glycol can be used as a smoke agent.

Further preferably, the volume ratio of ethyl acetate to 1, 2-propanediol in the mixed solvent of ethyl acetate and 1, 2-propanediol is (2:8) to (4:6), in which case the solubility in the gelling agent and the fragrance material is better.

The key or difficulty of the preparation process of the invention is to avoid the formation of nicotine salt, and the method mainly adopts the following method to avoid salt formation:

1. according to the invention, the organic solvent is used for replacing water, so that the ionization reaction of carboxylic acid in the gallic acid is reduced to avoid the formation of nicotine salt;

2. in a conventional process for preparing a nicotine salt: direct heating to promote acid-base neutralization. The invention adopts reflux and rotary evaporation to prevent violent salt forming reaction so as to prepare the gelling agent.

3. In a conventional process for preparing a nicotine salt: the freeze drying method is adopted to rapidly remove free or crystal water contained in the nicotine salt. The invention adopts a rotary evaporation method to remove the solvent ethanol in the reaction system to obtain the gelling agent.

In a third aspect, the present invention provides the use of a gel comprising a flavour and a nicotine gallate gelling agent as described in the first aspect, for the heating of a non-burning cigarette or e-cigarette.

Preferably, when the gel is used in a cigarette which is not combusted by heating, the release time of nicotine is effectively prolonged, so that the physiological feeling brought by nicotine is more continuous, the problem of leaching or moisture absorption of a smoke agent is avoided, and the phenomenon that the fragrance is lost too fast is also avoided;

when the gel is used in an electronic cigarette, the aroma component and nicotine can be stabilized, and the synergistic release of the aroma component and nicotine during heating and atomization is ensured.

The way the gel is used in an electronic cigarette is: the nicotine salt gel microparticles are added into a tobacco liquid solvent (smoking agent) system or a tobacco liquid, or the nicotine salt fragrance-carrying gel is directly dispersed in the tobacco liquid solvent (smoking agent) or the tobacco liquid to form a uniform system, so that the fragrance-generating components and nicotine are stabilized, and the synergistic release of the fragrance-generating components and nicotine during heating and atomization is ensured.

The principle of the invention is as follows:

the invention obtains the gelling agent by selecting specific gallic acid carboxylate to react with nicotine and controlling the reaction conditions, such as solvent type, heating mode, post-treatment mode, reactant proportion and other factors.

The supramolecular synthons constituting the supramolecular building blocks capable of forming stable gels are key to the formation of the above-mentioned gelling agents. According to the concept of crystal engineering, if the same type of supramolecular interaction can be reliably and reproducibly created between basic building blocks (molecules) with specific functional groups, the non-covalent bonds connecting these basic building blocks are called supramolecular synthons. Increasing the hydrogen bonding sites facilitates the assembly of the gelling agent molecules into a gel network.

Gallic acid (3,4, 5-trihydroxybenzoic acid) was chosen as the carboxylic acid source for the synthesis of nicotine hydroxy aromatic acid salt gelling agent. Gallic acid contains 3 phenolic hydroxyl groups.

When 2mol of gallic acid is mixed with 1mol of nicotine, the trans-structure of L-nicotine remains unchanged, wherein 1 molecule of gallic acid attacks the nicotine pyridine ring from the side to form pyridine nitrogen-carboxylic acid hetero synthon (figure 1), and another 1 molecule of gallic acid attacks the pyrrole ring in the cis direction with the pyridine ring to form pyrrole nitrogen-carboxylic acid charge assisted hydrogen bond (N-carboxylic acid charge assisted hydrogen bond)⁺…H-O^-) A hetero synthon (3 in fig. 2), and the pyridine ring is parallel to the benzene ring of gallic acid that attacks the pyrrole ring. The supermolecular structural units are connected with each other through hydrogen bonds (6 in figure 2) between phenolic hydroxyl groups to form a 1-dimensional hydrogen bond network, and the face-to-face pi-pi stacking effect (7 in figure 2) between pyridine rings and benzene rings which are parallel to each other is favorable for the structural stability. Supramolecular building blocks and 1-dimensional hydrogen bonding network are shown in FIG. 2Shown in the figure.

According to the theory of molecular engineering, gelation needs to satisfy the following conditions in 3 respects: (1) the strong and directional supramolecular action promotes the aggregation of gelling agent molecules to form fibers; (2) the ability to wind or interweave into fibers (i.e., the ability to form SAFINs); (3) a factor preventing pure crystallization of the gelling agent. The various hydrogen-bonded supramolecular synthons described above promote (1) and (2), while long hydrocarbon chains can promote (3).

The method for measuring the critical gelation concentration CGC is a test tube inversion method: adding gelling agents with different masses into a test tube added with 1g of solvent, heating until the gelling agents are completely melted, standing at room temperature, inverting the test tube until the material is not deformed after condensation, and regarding the material as gel formation, wherein the minimum mass percent of the gelling agents required for forming the gel is the critical gelation concentration of the gelling agents.

Sol-gel transition temperature T_gelThe determination method is a falling ball method: 0.5g of the gel was placed in a test tube (15mmx100mm) and a glass bead having a mass of 214.6mg was placed on the gel surface. The test tube was heated by immersion in an oil bath, the temperature recorded when the glass ball fell to the bottom of the test tube being T_gel。

Compared with the prior art, the invention has the following beneficial effects:

1. the invention uses gallic acid and nicotine to prepare a gelling agent with a supramolecular network structure and a fragrance-carrying supramolecular gel for the first time, and the gel realizes the common fixation and the synergistic release of nicotine and fragrant components.

The critical gelation concentration CGC of the gelling agent is calculated to be 0.80 wt%, namely when the gel is formed, the minimum mass fraction of the gelling agent in the gel is 0.80 wt%. The sol-gel transition temperature (T) of the gelling agent was determined_gel) The temperature is 86 deg.C, and the material is in sol or solution state at 86 deg.C or higher under atmospheric pressure, and the material is in gel state at 86 deg.C or lower. Because of the inherent thermal reversible property of the supramolecular gel, the fragrance substance (especially the semi-volatile fragrance substance) is encapsulated by the nicotine salt gel network in the supramolecular gel, and only when the heating temperature is more than or equal to T_gelWhen the temperature is lower than the above range, the gel will melt to become sol or solutionT_gelIn the meantime, the molten sol or solution undergoes reversible gelation and returns to a gel state. Therefore, the fragrant substance is stably fixed in the gel network at normal temperature, and the storage stability of the fragrant component is effectively improved.

2. The inherent high load rate of the supramolecular gel to a solvent (a smoke agent) and a fragrant substance dissolved in the supramolecular gel can make up the problem of insufficient fragrance and smoke of a heated cigarette, and realize effective supplement of the fragrance and the smoke; in particular, the semi-volatile flavor substances are fixed in the nicotine salt gel releasing nicotine in the high-temperature stage, so that the volatile loss of the flavor in the preheating stage or the low-temperature heating stage can be reduced, and the decayed flavor can be supplemented in the later stage in the suction.

3. Unlike the conventional polybasic carboxylic acid nicotine salt, in the gallic acid nicotine salt gelling agent, carboxyl groups, pyridine nitrogen and pyrrole nitrogen form heterogeneous synthons, and supermolecular structural units formed by the synthons are self-assembled into a stable fiber network, so that the number of free carboxyl groups is reduced, even free carboxyl groups do not exist, the opportunity that the heated cigarette generates volatile monocarboxylic acid due to dehydration and decarboxylation in a preheating stage or a low-temperature heating stage is inhibited, and the phenomena of small smoke amount at the front stage of smoking, mouth burning of smoke, obvious sour feeling and the like caused by slow accumulation of moisture and acidity are reduced.

4. One of the intrinsic properties of supramolecular gels is: the amount of gellant used is extremely small, while the amount of gel loading substance is extremely large (e.g., one molecule of gellant can bind thousands of molecules of solvent). Thus, the net effect is that a small amount of nicotine salt gelling agent can be combined with the aroma component dissolved in the solvent by fixing a large amount of solvent. In the field of heating cigarettes, such advantages are reflected in: because the coating rate of the traditional coating liquid is not high, the using amount of the coating liquid is increased or tobacco extract is added to obtain enough aroma amount and smoke amount, and the gel is loaded with high content of smoke agent and aroma component, the coating amount of the applied gel is lower than that of the applied coating liquid, which is beneficial to reducing raw material and manufacturing cost.

5. In addition, the 1, 2-propylene glycol used as the solvent of the gel is a smoke agent, the smoke agent is locked in the gel at normal temperature, the problem of smoke agent leaching or moisture absorption is not easy to occur, and the too fast loss of fragrance is avoided.

6. Because the nicotine salt gel is more stable than pure nicotine salt in structure, the upper limit of the release temperature of nicotine is higher than that of nicotine in the conventional nicotine salt, so that the release loss of nicotine before 210 ℃ can be reduced, the release time of nicotine is effectively prolonged, and the physiological feeling brought by nicotine is more continuous.

7. Due to the inherent thermoreversible characteristic of the supramolecular gel, when the gel is applied to the reconstituted tobacco for the heated cigarette, the gel is heated and melted to be converted into sol or solution and then applied to the reconstituted tobacco, and then the sol or solution is cooled to be gelatinized and combined with the reconstituted tobacco, so that the processing of the reconstituted tobacco and the formation of the gel are synchronous, and the working procedures are reduced.

8. The nicotine salt gel is used as a carrier of the flavor substance and the smoke agent, the requirement on the loading function of the reconstituted tobacco sheet base is reduced, and the use of a large amount of loading fillers is reduced.

9. For the reconstituted tobacco by the thick paste method, even if higher moisture needs to be removed during drying, because the fragrant substances and the smoke agent are fixed in the gel, the loss of the fragrant substances and the smoke agent can be effectively avoided while the moisture is removed by adopting measures such as low-temperature multi-stage drying and the like.

10. The conventional reconstituted tobacco has high surface viscosity and poor elasticity due to the fact that a large amount of smoke agents are applied to the surface of the reconstituted tobacco, and provides high requirements for a subsequent shredding process.

11. Since the raw materials for preparing the gelling agent are nicotine and carboxylic acid per se, and no other components are added, no residue is left after heating or no bad smell is generated by adhesion to the heat generating element.

12. When the nicotine salt gel is applied to the electronic cigarette, the nicotine salt gel microparticles are added into a cigarette liquid solvent (smoking agent) system or a cigarette liquid, or the nicotine salt-loaded gel is directly dispersed in the cigarette liquid solvent (smoking agent) or the cigarette liquid to form a uniform system, so that the aroma component and the nicotine are stabilized, and the synergistic release of the aroma component and the nicotine during heating and atomization is ensured. In addition, the nicotine salt supermolecule aroma-carrying gel obtained by regulating the adaptability of the nicotine salt gelling agent and the aroma-carrying substances has the characteristics of high aroma-carrying capacity, high solvent (smoke agent) carrying capacity, thermal reversibility and the like. The invention uses a gel medium to associate the originally separated nicotine salt system and the flavor system to form a new substance form (gel) and to associate the originally separated physiological satisfaction and relaxation to the characteristic taste of the mouth-eating taste to form a new comprehensive sensory perception (resulting from the synergistic release of nicotine and flavor substances). Through the recombination of the substance level and the sensory level, the nicotine and the aroma components are released synergistically, so that the synergistic sensory experience is obtained.

13. The known temperature range for releasing nicotine from nicotine salt comprises two intervals of 110-125 ℃ and 160-210 ℃. When the nicotine salt gel is used for replacing nicotine salt in electronic cigarettes, due to the structural stability of the supramolecular gel, nicotine is equivalently fixed by the gel structure, the rapid release of the nicotine is prevented, and the release temperature T of the nicotine_nicThe range is higher than that of the conventional nicotine salt and is close to or consistent with the working temperature of the electronic cigarette, the nicotine inhalation amount at the working temperature of the electronic cigarette is improved, and the nicotine release duration is longer.

14. The specific fragrance-carrying supermolecule gel system comprehensively matches the factors such as the thermal stability of the nicotine salt gelling agent, the nicotine release temperature interval, the volatility of fragrance substances fixed by the gel, the properties of a solvent and the like. In particular, the present invention fixes a semi-volatile fragrant substance with good thermal stability (T)_gelHigh value) and release of nicotine (T) in the high temperature region_nicHigher value) can overcome the defect that a large amount of semi-volatile flavor substances are released in the front section of smoking and the fragrance in the rear section of smoking is thin.

15. When the nicotine salt gel is applied to the electronic cigarette, when the electronic cigarette is not sucked or used, the melted gel is condensed to be gelled due to the heat reversible characteristic of the gel, so that the nicotine is re-stabilized through the recovery of the nicotine salt gelling agent network, and the flavor substance is re-fixed in the gel to be stabilized, thereby reducing the loss of the nicotine and the flavor substance in the process of warming and cooling the electronic cigarette.

16. Interconversion of gel and solution/sol phases is only related to disassembly and assembly of supramolecular structural units, chemical components are not changed in the phase change process, and stability and consistency of sensory experience of the electronic cigarette are facilitated.

17. The reconstituted tobacco loaded with the coating liquid is high in fragrance loading, high in smoke generation and low in coating weight. The traditional reconstituted tobacco is of a type with low aroma loading, low smoke generation and high coating weight. The concrete expression is as follows: when the coating liquid is cooled to be gelatinized, the fragrant substances and the smoke agent are locked in the gel and separated from the moisture, and the moisture outside the gel can be removed during subsequent heating and drying to control the moisture content, so that the loss of the perfume in the gel is avoided, and the amount of the coating liquid applied to reach the required fragrance amount and smoke amount is lower. The novel HNB reconstituted tobacco with high fragrance amount and high smoke amount different from the conventional HNB reconstituted tobacco is prepared by adopting the high-proportion gel coating liquid (namely the gel occupation ratio in the coating liquid is high, namely the coating liquid takes gel as the main component, so that the coating amount is reduced), the fixed spice and the smoke agent can be fully utilized, the coating amount is greatly reduced, the utilization rate of the coating liquid is increased, and the application value of the gel is embodied. In the conventional coating liquid, the perfume and the smoke agent are not locked in the medium, and when the coating liquid is heated and dried to control the water content, the perfume, the water and the smoke agent are all in an open state, so that the water is removed and part of fragrant substances and the smoke agent are removed, so that the loss is compensated by adding high-content perfume (such as 7-8%) and the smoke agent (such as 20%), and as a result, the amount of the coating liquid applied to reach the required amount of perfume and smoke agent is higher, and the waste is larger.

Drawings

FIG. 1 is a schematic diagram of a pyridine-carboxylic acid synthon according to the present invention.

Fig. 2 shows gallic acid nicotine salt supramolecular structural units and a fiber network.

Detailed Description

The present invention will be described below with reference to specific examples, but the embodiments of the present invention are not limited thereto. The experimental methods not specified in the examples are generally commercially available according to the conventional conditions and the conditions described in the manual, or according to the general-purpose equipment, materials, reagents and the like used under the conditions recommended by the manufacturer, unless otherwise specified. The starting materials required in the following examples and comparative examples are all commercially available.

Example 1

A preparation method of flavor-carrying supramolecular gel based on gallic acid nicotine salt gelling agent comprises the following steps:

step 1, preparing a gelling agent: respectively dissolving gallic acid and nicotine in a mixed solvent of water and ethanol according to a molar ratio of 2:1, wherein the mass volume ratio of the gallic acid to the mixed solvent of the water and the ethanol in which the gallic acid is dissolved is 1g:28mL, and the mass volume ratio of the nicotine to the mixed solvent of the water and the ethanol in which the nicotine is dissolved is 1g:210mL, stirring at room temperature until the gallic acid is completely dissolved to respectively obtain a gallic acid solution and a nicotine solution, fully mixing the two solutions to obtain a mixed solution, heating the mixed solution to reflux, reacting for more than 30min, carrying out rotary evaporation at 170mbar and 53 ℃, and drying the rotary evaporated product at 36 ℃ for 24 hours to obtain the gallic acid nicotine salt gelling agent. In the mixed solvent of water and ethanol, the volume ratio of water to ethanol is 1: 5.

Step 2, preparation of gel:

dissolving the fragrant substance in a mixed solvent of ethyl acetate and 1, 2-propylene glycol to obtain a fragrant substance-containing solvent, wherein the mass-volume ratio of the fragrant substance to the mixed solvent of ethyl acetate and 1, 2-propylene glycol is 1g:22 mL. In the mixed solvent of ethyl acetate and 1, 2-propylene glycol, the volume ratio of ethyl acetate to 1, 2-propylene glycol is 3: 7.

Weighing a certain amount of 0.88g of the gallic acid nicotine salt gelling agent prepared in the step 1, placing the gelling agent into a test bottle, adding 20mL of the solvent containing the aroma substances (which indicates that the amount of the gelling agent is fixed, solvents with different volumes can be fixed, and the 20mL refers to the highest solvent amount that the 0.88g of the gelling agent can be fixed) into the test bottle, dissolving the solvent by heating and stirring or ultrasonic waves, and standing the solution in an ice-water bath at the temperature of 2 ℃ for 2.5 hours to form the aroma-loaded supramolecular gel.

The supramolecular building blocks and 1-dimensional hydrogen bonding network forming the gallic acid nicotine salt gelling agent of step 1 are shown in fig. 2, each synthon has been labeled in fig. 2: 2 is a pyridine nitrogen-carboxylic acid hetero synthon, 3 is a pyrrole nitrogen-carboxylic acid charge assisted hydrogen bond (N)⁺…H-O^-) Hetero synthons, 6 is a hydrogen bond between phenolic hydroxyl groups, and 7 is a face-to-face pi-pi stacking interaction between pyridine rings and benzene rings in parallel.

Example 2

This example provides the use of the flavor-loaded supramolecular gel prepared in example 1 of the invention in heating cigarettes

The nicotine salt supermolecule gel can be applied in the manufacturing process of reconstituted tobacco for heating cigarettes by a paper-making method and reconstituted tobacco for heating cigarettes by a thick pulp method respectively, and can be applied with single gel or mixed gels of different types according to actual application.

Heating reconstituted tobacco for cigarettes by a paper-making method:

the first method is as follows: adding the fragrant supramolecular gel prepared in the example 1 into a certain amount of smoke agent (1, 2-propylene glycol, glycerol or a mixture of the two in a certain proportion), wherein the mass ratio of the fragrant supramolecular gel to the smoke agent is 5:1, heating to 90 ℃, melting the gel to be a sol state or a solution, uniformly mixing to prepare a mixed coating liquid containing the molten gel and the smoke agent, and spraying the mixed coating liquid onto a tobacco sheet substrate prepared by a papermaking method by adopting a spraying process. The reconstituted tobacco to which the mixed coating liquid is applied is cooled to room temperature, and the molten gel is gelatinized and uniformly dispersed in the smoke agent. Removing water in the reconstituted tobacco to a proper water content through one or more times of drying, and then performing shredding and rolling processing.

The preparation process of the mixed coating liquid containing the molten gel and the smoke agent has the following characteristics:

1. another preparation is to heat the flavor-bearing supramolecular gel to a molten state to convert it to a sol state or solution, and then add a heated amount of a smoke generator. In the embodiment, the scheme is not adopted, so that the phenomenon that the molten gel is condensed to form a sol-gel mixture due to insufficient melting caused by cooling after the smoke agent is added into the molten gel is avoided, and meanwhile, the energy consumption of two-step heating is reduced;

2. the mass ratio of the added spice to the added smoke agent in the conventional heating cigarette is usually 1: 4-1: 2.5, but a large amount of fragrant substances are lost in the actual production process, and the final actual ratio is lower than the ratio. The gel of example 1, in which the smoke generating agent was fixed, can greatly reduce the amount of smoke generating agent added, and at the same time, since the fragrance material was fixed by the gel, the loss of fragrance material in the subsequent drying and water removal process was reduced, and the amount of fragrance was increased by increasing the gel ratio.

The second method comprises the following steps: the flavor-bearing supramolecular gel prepared in example 1 is heated to 90 ℃ and melted to be converted into a sol state or a solution, and the melted gel is directly sprayed on a tobacco sheet base prepared by papermaking method as a coating liquid by a spraying process according to the amount of smoke required by a final product, the amount of smoke agent fixed by the gel and the viscosity of the melted gel. And cooling the reconstituted tobacco applied with the coating liquid to room temperature, and enabling the molten gel to generate gelation effect and be uniformly dispersed on the surface of the reconstituted tobacco. Then, the cut tobacco and the rolling processing are carried out.

Heating reconstituted tobacco for cigarettes by a thick paste method:

the first method is as follows: the application of the above gel is concentrated in the subsequent stages of shaping (casting) and drying. The method specifically comprises the following steps: after the reconstituted tobacco is molded by a thick paste method and dried to remove higher moisture, the gel is heated to 90 ℃ to be melted and converted into a sol state or solution, and the sol state or solution is directly used as a coating liquid and sprayed on the reconstituted tobacco by adopting a spraying process;

or adding the aroma-carrying supramolecular gel prepared in the example 1 into a certain amount of smoke agent (1, 2-propylene glycol, glycerol or a mixture of the two in a certain proportion), wherein the mass ratio of the aroma-carrying supramolecular gel to the smoke agent is 5:1, heating to 90 ℃, melting the gel to form a sol state or a solution, uniformly mixing to prepare a mixed coating liquid containing the molten gel and the smoke agent, and spraying the coating liquid onto the reconstituted tobacco by adopting a spraying process. And cooling the reconstituted tobacco applied with the coating liquid to room temperature, and enabling the molten gel to generate gelation effect and be uniformly dispersed on the surface of the reconstituted tobacco or in the smoke agent. Removing water in the reconstituted tobacco to a proper water content through one or more times of drying, and then performing shredding and rolling processing.

Because the moisture content of the reconstituted tobacco leaves by the thick pulp method is higher and the smoke generation amount is not high, the proportion of the additional smoke generation agent is properly increased compared with that of the tobacco leaves by the paper-making method.

The second method comprises the following steps: the aroma-carrying supramolecular gel prepared in example 1 was used as a component of the slurry. The method specifically comprises the following steps: mixing tobacco raw materials, adhesive, smoke agent and the like, crushing into powder with a certain mesh number, adding a certain amount of water, adding the fragrance-carrying supermolecule gel prepared in the example 1 at 50-60 ℃, and fully stirring to form uniform slurry. And then uniformly spreading the mixture on a circulating metal belt, heating to 85 ℃ (the temperature of a thick pulp method can be slightly lower than the sol-gel transition temperature, because the mixture is heated on one metal belt, the temperature is quickly raised) to melt the gel in the pulp, then gradually cooling, gelatinizing the molten gel, simultaneously drying, dehydrating and solidifying the pulp in multiple stages, and finally stripping to obtain the reconstituted tobacco.

The reason is as follows: firstly, mixing at 50-60 ℃ is a common temperature condition for pulping, so that the mixing uniformity of the pulp can be ensured; the slurry mixed with the gel is laid on the metal belt in the subsequent manufacturing process, so that the contact area between the gel and a heating area is increased, the gel can be ensured to be rapidly and uniformly melted at 85 ℃, on one hand, the gel can be uniformly distributed in the reconstituted tobacco, and on the other hand, the loss of flavor substances in the process is reduced; and the subsequent gradual cooling ensures that dehydration and gelation are synchronously and uniformly carried out.

Example 3

This example provides the use of the aroma-bearing supramolecular gel prepared in example 1 in electronic cigarettes.

The nicotine salt supramolecular gel can be applied to electronic cigarettes in 2 ways, and a single gel or different types of mixed gels can be adopted according to the actual application.

The method comprises the following steps: after drying the fragrance-carrying supramolecular gel prepared in the example 1 in a drying oven at the constant temperature of 40 ℃ for 24-36h, grinding the dried gel into uniform microparticles, adding a certain amount of the aerosol into a certain amount of smoking agent for electronic cigarettes according to a certain proportion, fully stirring, wherein the smoking agent is a mixed solvent of glycerol and 1, 2-propylene glycol in a volume ratio of 1.2:1, the mass ratio of the fragrance-carrying supramolecular gel to the smoking agent is 1:120, and directly adding the mixture as a smoking agent containing the fragrance-carrying gel or as an auxiliary material into a finished cigarette liquid to be uniformly mixed to obtain the cigarette liquid containing the fragrance-carrying gel.

The smoke agent in the electronic cigarette is equivalent to a dispersion medium of gel, the proportion of the smoke agent is not too low, and the addition amount of the gel is reduced as much as possible on the premise of ensuring the fragrance amount and the smoke amount.

The second method comprises the following steps: the gel itself, in which a large amount of 1, 2-propanediol is fixed, is used as the gel-state atomizing material.

Under the condition of the heating temperature of the electronic cigarette, the cigarette liquid containing the gel is subjected to gel melting macroscopically, gel network disassembly and separation of a supramolecular structural unit until the supramolecular synthon is broken microscopically, and the nicotine locked by the gel is released and is released along with the fragrance substance and the smoke agent to be inhaled; when smoking is stopped or not used, the melted gel undergoes gelation again due to the thermo-reversible nature of the supramolecular gel, and nicotine and carboxylic acid molecules recombine to form supramolecular synthons, thereby forming supramolecular building blocks which further assemble into a fiber network to immobilize the condensed flavor and smoke producing agents therein.

Example 4

step 1, preparing a gelling agent: respectively dissolving gallic acid and nicotine in a mixed solvent of water and ethanol according to a molar ratio of 2:1, wherein the mass volume ratio of the gallic acid to the mixed solvent of the water and the ethanol in which the gallic acid is dissolved is 1g:25mL, and the mass volume ratio of the nicotine to the mixed solvent of the water and the ethanol in which the nicotine is dissolved is 1g:250mL, stirring at room temperature until the gallic acid is completely dissolved to respectively obtain a gallic acid solution and a nicotine solution, fully mixing the two solutions to obtain a mixed solution, heating the mixed solution to reflux, reacting for more than 30min, carrying out rotary evaporation at 160mbar and 50 ℃, and drying the rotary evaporated product at 36 ℃ for 25h to obtain the gallic acid nicotine salt gelling agent. In the mixed solvent of water and ethanol, the volume ratio of water to ethanol is 1: 6.

Step 2, preparation of gel:

dissolving the fragrant substance in ethyl acetate to obtain a fragrant substance-containing solvent, wherein the mass volume ratio of the fragrant substance to the ethyl acetate is 1g:22 mL. Weighing a certain amount of 0.88g of the gallic acid nicotine salt gelling agent prepared in the step 1, placing the gelling agent into a test bottle, adding 20mL of the solvent containing the aroma substances (which indicates that the amount of the gelling agent is fixed, solvents with different volumes can be fixed, and the 20mL refers to the highest solvent amount that the 0.88g of the gelling agent can be fixed) into the test bottle, dissolving the solvent by heating and stirring or ultrasonic waves, and standing the solution in an ice-water bath at the temperature of 2 ℃ for 2.5 hours to form the aroma-loaded supramolecular gel.

Claims

1. A flavor-bearing supramolecular gel based on a nicotine salt of gallic acid gelling agent, characterized in that the gel comprises a nicotine salt of gallic acid gelling agent and a flavor substance and an organic solvent dispersed in the nicotine salt of gallic acid gelling agent;

2. flavor-carrying supramolecular gel based on nicotine gallate gelling agent as claimed in claim 1, characterized in that the flavor substance is selected from: one or more of jasmone, anisyl ketone, zingerone, muscone, civetone, nerolidol, farnesol, beta-caryophyllenol, beta-santalol, alpha-santalol, jasmal, vanillin, ethyl vanillin, piperonal, cinnamaldehyde, methyl laurate, ethyl laurate, methyl myristate, ethyl myristate, geranyl benzoate, linalyl benzoate, phenylacetic acid and beta-caryophyllene.

3. The flavor-bearing supramolecular gel based on a nicotine gallate gelling agent as claimed in claim 1, wherein the organic solvent is selected from ethyl acetate or a mixed solvent of ethyl acetate and 1, 2-propanediol.

4. A preparation method of flavor-carrying supramolecular gel based on gallic acid nicotine salt gelling agent is characterized by comprising the following steps:

step 2, preparation of gel:

5. The preparation method according to claim 4, wherein in the step 1, the volume content of water in the mixed solvent of water and ethanol is less than 20%; the mass volume ratio of the gallic acid to the mixed solvent of water and ethanol is 1g: 20-30 mL, the mass volume ratio of the nicotine to the mixed solvent of water and ethanol is 1g: 100-300 mL, the rotary evaporation temperature is 50-60 ℃, and the rotary evaporation pressure is 150-170 mbar.

6. The preparation method according to claim 4, wherein in the step 2, the mass-to-volume ratio of the flavor substance to the organic solvent is 1g:20 to 30mL, the mass-to-volume ratio of the gallic acid nicotine salt gelling agent to the flavor-containing solvent is 1g:20 to 30mL, the temperature of the ice water bath is 4 ℃, and the standing time in the ice water bath is 1 to 3 hours.

7. The method for producing a gel containing a flavorant and a nicotine gallate gelling agent according to claim 4, wherein the flavorant is selected from the group consisting of: one or more of jasmone, anisyl ketone, zingerone, muscone, civetone, nerolidol, farnesol, beta-caryophyllenol, beta-santalol, alpha-santalol, jasmal, vanillin, ethyl vanillin, piperonal, cinnamaldehyde, methyl laurate, ethyl laurate, methyl myristate, ethyl myristate, geranyl benzoate, linalyl benzoate, phenylacetic acid and beta-caryophyllene.

8. The method for producing a gel containing a flavorant and a nicotine gallate gelling agent according to claim 4, wherein the organic solvent is ethyl acetate or a mixed solvent of ethyl acetate and 1, 2-propanediol.

9. Use of a gel comprising a flavorant and a nicotine gallate gelling agent of claim 1, wherein the gel is used in a non-burning cigarette or an electronic cigarette.

10. Use of a gel comprising a flavorant and a nicotine gallate gelling agent according to claim 9, wherein when the gel is used in heating a non-combustible cigarette, the gel will

The release time of nicotine is effectively prolonged, the physiological feeling brought by nicotine is more continuous, the problem of leaching or moisture absorption of a smoke agent is avoided, and the too fast loss of fragrance is also avoided;