EP4085769A1

EP4085769A1 - Method for improving aroma of cigarette product by using raspberry ketone glucoside

Info

Publication number: EP4085769A1
Application number: EP21878763.8A
Authority: EP
Inventors: Sheng LEI; Kai Wang; Lei Fu; Liang He; Rongfen QU; Jian Zhang; Juan Liu; Deshou MAO; Zhiyu Li
Original assignee: China Tobacco Yunnan Industrial Co Ltd
Current assignee: China Tobacco Yunnan Industrial Co Ltd
Priority date: 2021-03-15
Filing date: 2021-03-25
Publication date: 2022-11-09
Anticipated expiration: 2041-03-25
Also published as: WO2022193351A1; CN113100469B; EP4085769A4; EP4085769B1; CN113100469A

Abstract

The present invention discloses for the first time a method of improving the fragrance of cigarette products by using raspberry glycoside, flavors comprising raspberry glycoside are dispersed or dissolved in a solvent to form a flavor dispersion, and the flavor dispersion is added to cigarettes. The present invention uses raspberry glycoside as latent flavor of cigarettes for the first time, so as to solve the problems that flavors in the cigarettes are not stable enough, as well as the characteristic styles are not prominent. In the present invention, the flavor dispersion comprising raspberry glycoside is used in cigarette paper, tobacco shreds or reconstituted tobacco sheets. The mainstream and side-stream smoke in the cigarettes have the characteristic fragrance of raspberry ketone, and the fragrance is rich.

Description

TECHNICAL FIELD

The present invention belongs to the technical field of tobacco, and in particular, to a method of improving the smoking quality of mainstream smoke and characteristic smoke fragrance of side-stream smoke of cigarette products by using raspberry glycoside.

BACKGROUND

Reduction of tar and harm of cigarette products is the development trend of tobacco products; however, reduction of tar and harm may inevitably bring about shortage of tobacco fragrance, thus affecting consumer experience. Formula flavoring is an effective way to enhance smoking experience of tobacco products. There are many reports in the prior art that ordinary flavors and fragrances are added to tobacco shreds, cigarette paper and reconstituted tobacco sheets. However, ordinary flavors and fragrances used for flavoring in the prior art tend to volatilize and escape during online flavoring as well as transportation and storage, which may affect the effective flavoring rate of flavors and fragrances, bringing about poor fragrance stability of cigarette products. In addition, tobacco flavoring technologies in the prior art mainly focus on adjusting or improving sensory effect of mainstream smoke without paying attention to that of side-stream smoke; the fragrance of side-stream smoke can bring a pleasant smell and create a better smell environment for the surrounding non-smokers. Thirdly, the flavors and fragrances in the prior art, such as raspberry ketone, are insoluble in water, which can only be dissolved in ether or volatile oil, thus bringing security risks to the flavoring of tobacco.
Raspberry glycoside is a functional ingredient in raspberries with chemical name of 4-butanonylphenyl-β-D-glucopyranoside or raspberry ketone-β-D-glucopyranoside, the molecular formula is C₁₆H₂₂O₇ with CAS No. 38963-94-9. The structural formula of raspberry glycoside is shown in FIG.1 and FIG.2. Raspberry glycoside is white or off-white crystalline powder, easily soluble in polar solvents such as water and ethanol, without odor at room temperature. Raspberry glucoside has special physiological functions and biological activities, which can effectively hinder formation of tyrosinase and inhibit synthesis of melanin. It is reported in the prior art that raspberry glycoside is mainly used in cosmetics for advanced whitening, freckle removal, anti-aging and conditioning functions.
There is no report of the use of raspberry glycoside in tobacco to enhance the fragrance of cigarette products.

SUMMARY

The purpose of the present invention is to disperse or dissolve flavors comprising raspberry glycoside in a solvent to form flavor dispersions, and add to cigarettes, so as to enhance the recognition of cigarette products, improve the characteristic sense of side-stream smoke and the smoking quality of mainstream smoke, enhance the richness of product styles, and solve the problem that flavors and fragrances in the prior art are not stable enough, thus affecting the stability of cigarette quality.
The technical solutions of the present disclosure are as follows:
The present invention discloses a method of improving the fragrance of cigarette products by using raspberry glycoside. The flavors comprising raspberry glycoside are dispersed or dissolved in a solvent to form a flavor dispersion, and the flavor dispersion is added to the cigarette
Preferably, the flavor dispersion is added to cigarette paper, tobacco shreds or reconstituted tobacco sheets to improve the characteristic smoke fragrance of side-stream smoke and/or improve the smoking quality of mainstream smoke.
Preferably, the solvent is water, ethanol or a mixture of the both.
Preferably, the flavor dispersion also comprises other flavor ingredients.
Preferably, the other flavor ingredients comprise at least one selected from mogrosides, maple extractum, dihydroactinidiolide and strawberry aldehyde.
Preferably, the flavors in the flavor dispersion comprise: 1. raspberry glycoside and mogrosides, their mass ratio is (2-8): (1-3); or ② raspberry glycoside, mogrosides, maple extractum and dihydroactinidiolide, their mass ratio is (2-8): (1-3): (0.5-1): (0.05- 0.1); or ③ raspberry glycoside, mogrosides and strawberry aldehyde, their mass ratio is (2-5): (2-5): (0.1-0.3); or ④ raspberry glycoside, mogrosides, maple extractum and strawberry aldehyde, their mass ratio is (2-5):(2-5):(0.5-1):(0.1-0.3).
Preferably, the flavor dispersion further includes fillers and combustion improvers.
Preferably, the filler is light calcium carbonate.
Preferably, the combustion improver is an organic acid metal salt, which is selected from at least one of potassium citrate, potassium malate, potassium lactate and potassium acetate.
Preferably, the flavor dispersion is coated onto cigarette paper, the coating ratio of the flavor is 0.1wt%∼1wt% (i.e., the weight ratio of the flavor to the dry weight of the cigarette paper), the grammage of the obtained cigarette paper is 28-38 g/cm², and an air permeability is 30-100 CU.
The present invention has the following beneficial effects:

1. The present invention uses raspberry glycoside as latent flavor for the first time in cigarettes. In the present invention, the flavor dispersion comprising raspberry glycoside is added to cigarettes, so as to solve the problems such as flavors in the cigarettes are not stable enough, as well as the characteristic styles are not prominent.
2. The raspberry glycoside of the present invention is a heat-stable latent flavor, which is stable without smell found during storage and transportation in reconstituted tobacco sheets, cigarette paper or cigarette products. When heated or ignited for smoking, the raspberry glycoside can release characteristic components of raspberry ketones and produce characteristic fragrance of raspberries and blueberries with the functional effect of fusion and coordinating with original tobacco flavors, which can be adjusted to highlight the fragrance of berry-style characteristic, so as to improve the sensory smoking quality of cigarettes.
3. Other auxiliary flavor ingredients selected by the present invention are as follows: raspberry glycoside, mogrosides, maple extractum, dihydroactinidiolide, strawberry aldehyde, etc., any two or more of which can be selected according to the design of cigarette characteristic styles to be used flexibly in combination with raspberry glycoside, so as to further highlight the fragrance of different cigarette styles, and improve the sensory smoking quality. In addition to the above-mentioned flavor components, other flavor components can also be selected for blending with raspberry glycoside according to the needs of fragrance of cigarette characteristic style.
4. The pyrolysis products of the flavor dispersion comprising raspberry glycoside of the present invention contain characteristic fragrance ingredients such as raspberry ketone with a relatively high content. While raspberry ketone is volatile and unstable at room temperature, raspberry glucoside is stable at room temperature, which ensures the stability of tobacco flavor during storage and transportation. When smoking, the characteristic fragrance of raspberry and blueberry are rich, and the use of other flavor ingredients ensures the characteristic fragrance of mainstream and side-stream smoke, which can improve brand recognition while avoiding homogenization of Chinese cigarette products.
5. The flavor dispersion comprising raspberry glycoside of the present invention can be added to cigarette paper or tobacco shreds to improve the sensory effect of side-stream smoke fragrance. Compared with the ordinary cigarettes with added flavor in control samples, the mainstream and side-stream smoke components of the flavor dispersion comprise raspberry glycoside of the present invention have greater differences, especially the content of the characteristic fragrance of raspberry ketone in the side-stream smoke is obviously higher. When used for smoking cigarette products, the characteristic fragrance of raspberry ketone in the side-stream smoke can bring a pleasant smell to the surrounding non-smokers, so as to create a better environment for non-smokers.
6. The flavor dispersion comprising raspberry glycoside of the present invention can also be used in reconstituted tobacco sheets, which can also improve the characteristic fragrance of mainstream and side-stream smoke. At present, in the production of traditional reconstituted tobacco sheets, natural plants and their extracts are mainly used as flavor additives, fragrance substances contained in natural plants are widely used in the cigarette formulations of reconstituted tobacco sheets as they have the characteristics of imparting unique fragrance to cigarettes, so as to improve the smoking quality of cigarettes. The flavor dispersions of the present invention comprising raspberry glycoside can also be used in reconstituted tobacco sheets, which can also add unique fragrance to the reconstituted tobacco sheets and improve the smoking quality of cigarettes, so as to effectively improve the utilization rate of raw materials of cigarette blending formula, while reducing cigarette production costs.
7. The method of improving fragrance of cigarette products with the flavor dispersions comprising raspberry glycoside of the present invention is simple. The flavors and fragrances in the prior art, such as raspberry ketone, are insoluble in water, while raspberry glycoside is soluble in water, which is more environmentally friendly when used in cigarettes. Compared with traditional cigarette flavoring methods, the flavoring method of the present invention is more controllable, and the flavoring is uniform. The selected characteristic fragrance does not depend on cigarette blending formula, thus reducing the difficulty of cigarette blending formula and flavoring. The quality of the off-site processed products of cigarette brands can be guaranteed; meanwhile, the use value of low-grade tobacco sheets can be improved, the dependence of high-grade cigarettes on high-priced hemp pulp cigarette paper can also be reduced.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG.1 is a molecular formula of raspberry glycoside.
FIG.2 is a three-dimensional structural formula of raspberry glycoside.
FIG.3 is a thermogravimetry of raspberry glycoside.

DETAILED DESCRIPTION OF THE EMBODIMENTS

In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further illustrated below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention. The experimental methods that do not specify specific conditions in the following embodiments are generally in conventional conditions. Unless otherwise stated, the percentages and parts are calculated by mass.
Study on the thermal stability and pyrolysis behavior of raspberry glycoside. The pyrolysis steps of raspberry glycoside are as follows:
Accurately weigh 1.5 mg of raspberry glycoside and put into a special quartz tube for pyrolysis, place the quartz tube in the heating wire of a pyrolysis apparatus, the pyrolysis atmosphere: air; the total pyrolysis gas flow rate: 70mL/min; the temperature-rising program of the pyrolysis probe is as follows: ①Starting at 50°C (5s), rising to 350°C at 10°C/s (5s); ②Starting at 50°C (5s), rising to 600°C at 10°C/s (5s); ③Starting at 50°C (5s), rising to 900°C at 10°C/s (5s). After completion of the program, the gas chromatography injection port is connected, and the pyrolysis products are separated by gas chromatography and identified by mass spectrometry. The pyrolysis products without marking with a matching degree are greater than 800, the pyrolysis products are retrieved and identified by NIST98 standard spectral library, for substances with a peak area greater than 0.1%, semi-quantitative analysis of pyrolysis products is carried out by peak-area normalization method. (Pyrolysis of each raspberry glycoside sample needs to be done three times with three temperature ranges, i.e., simulating the heating temperature of 350°C, the smoldering temperature of 600°C for conventional cigarettes and the smoking temperature of 900°C respectively)
The conditions of gas chromatography-mass spectrometry are as follows:
The flow rate of the carrier gas He is set to: 1.0 mL/min; the temperature of the injection port: 230 °C; temperature-rising program: 50 °C (5 min), rising to 100 °C at 10 °C/min (1 min), rising to 280 °C at 15 °C/min (10 min); the split ratio is 1:10; mass spectrometry conditions are as follows: the interface temperature is 230 °C; electrospray ionization source (ESI) temperature: 250 °C; ionization energy: 70 eV; mass scanning range: 35-500 u.
The steps of the thermogravimetric analysis method are as follows:
Weigh (5.00±0.05) mg raspberry glycoside sample and place the sample in a thermogravimetric platinum crucible. At the airflow rate of 50mL/min, the temperature-rising program is as follows: from 30°C to 900°C (10min) at the rate of 10°C/min. Conduct DSC, TG/DTG analysis, as well as data collection and analysis.
The results of thermal stability and thermal cracking of raspberry glycoside are as follows:
As shown in Table 1 and FIG.3 below, analysis of the pyrolysis components of raspberry glycoside shows that 17 compounds are detected by pyrolysis at 350 °C, accounting for 62.69% of the total peak area. Among which ketones accounts for 50.11%, aldehydes 2.91%, acids 1.07%, phenols 0.76%, and others 7.58%. Others are mainly carbohydrates, including D-allose and 1,6-anhydro-β-D-glucose. Among which, raspberry ketone (47.64%), D-allose (7.01%), levoglucosenone (1.84%), 5-hydroxymethylfuraldehyde (1.28%), furaldehyde (0.84%), and p-hydroxybenzaldehyde (0.78%) are of relatively high content.
A total of 5 compounds are detected by thermal cracking at 600°C, accounting for 68.18% of the total peak area, among which ketones accounts for 65.45%, aldehydes 1.50%, acids 1.23%. Among which, raspberry ketone (65.45%), p-hydroxybenzaldehyde (1.04%), stearic acid (0.67%), palmitic acid (0.56%), 5-hydroxymethylfurfural (0.46%) are of relatively high content.
A total of 18 compounds are detected by thermal cracking at 900°C, accounting for 82.74% of the total peak area, among which ketones accounts for 79.88%, aldehydes 0.66%, acids 0.73%, phenols 0.30%, and others 1.06%. Others are mainly amine compounds, including 1-methylpentylamine, N-methyl ethylenediamine, 2-octylamine, 1,3-dimethylpentylamine and N-(2-methoxyethyl) methylamine. Among which, raspberry ketone (78.75%), 3,5-dihydroxy-2-methylpyran-4-one (0.74%), 2,3-dihydrobenzofuran (0.67%), p-hydroxybenzaldehyde (0.66%), and palmitic acid (0.61%) are of relatively high content.
It can be seen that, with rising of thermal cracking temperature, the peak area ratio of the fragrance substances produced by pyrolysis of raspberry glycoside is increasing, the proportion of ketones increases, especially that of raspberry ketones increases significantly, while the proportions of aldehydes, acids and phenols decrease, amines appear at 900°C in thermal cracking.
The above results indicate that, raspberry glycoside can be pyrolyzed to produce raspberry ketone, a characteristic fragrance ingredient, at different temperatures; the higher the pyrolysis temperature, the greater the content of raspberry ketone. This feature is not shown in most glycoside latent fragrance substances, when other glycosides with structures that are different from raspberry glycoside are pyrolyzed, the fragrance ingredients may be further pyrolyzed into non-characteristic odor ingredients, while fragrance ligands with maintained structures and properties are rarely obtained. As a comparison, Table 2 lists thermal cracking of nerol glucoside at different temperatures. The results show that the structure of the ligand nerol cannot be maintained at different temperatures, which is further pyrolyzed into acetamide. Thus, thermal cracking of nerol glucoside does not produce the characteristic odor of neroli.

FIG.3 shows thermogravimetric results of raspberry glycoside. It can be seen from FIG.3 that, raspberry glucoside samples begin to lose mass from 220 °C, due to cleavage of glycosidic bonds and generating raspberry ketones, allose and glucose ketones. When the temperature further rises, the generated raspberry ketone is pyrolyzed and sublimated, the mass loss rate is the largest, part of the primary cracking ingredients are further cracked, and the branched chains such as methoxyl, ethoxyl and carbonyl, etc. on the aromatic rings are removed, part of the branched chains are oxidized into macromolecular acids such as stearic acid and palmitic acid, part of the branched chains and aromatic rings are oxidized into furaldehyde, 5-hydroxymethylfuraldehyde and other aromatic substances; as the temperature continues to rise, the remaining fragrance substances begin to be carbonized at 370 °C. At 580 °C, the fragrance substances are completely carbonized, and the mass does not change any more.

Table 1 Thermal cracking results of raspberry glycoside at different temperatures

350°C		600°C		900°C
Substance	Relative content %	Substance	Relative content %	Substance	Relative content %
Raspberry ketone	47.64	Raspberry ketone	65.45	Raspberry ketone	78.75
D-Allose	7.01	p-Hydroxybenzaldehyde	1.04	3,5-Dihydroxy-2-methylpyran-4-one	0.74
Levogluconone	1.84	Stearic acid	0.67	2,3 -Dihydrobenzofuran	0.67
5-Hydroxymethylfu raldehyde	1.28	Palmitic acid	0.56	p-Hydroxybenzaldehyde	0.66
Furaldehyde	0.84	5-Hydroxymethylfuraldehyde	0.46	Palmitic acid	0.61
p-Hydroxybenzalde hyde	0.78	-	-	4H-pyran-4-one, 2,3-Dihydro-3,5-dihydroxy-6-methyl	0.29
Acetic acid	0.69	-	-	5-(4-Bromo-phenyl)-[1,3,4]oxa diazol-2-amine	0.23
1,6-Anhydro-β-D-Glucose	0.57	-	-	p-Methylphenol	0.18
p-Methylphenol	0.40	-	-	4-Ethylphenol	0.12
Palmitic acid	0.39	-	-	Parabanic acid	0.12
4-Ethylphenol	0.35	-	-	Maltol	0.10
2-Furancaboxaldeh yde-5-methyl	0.26	-	-	Cyclopropylcarbinol	0.09
Methyl maltol	0.19	-	-	1-Methylpentylamine	0.06
1-(2-Furanyl)-2-hy droxyethanone	0.15	-	-	N-Methylethylenediamine	0.04
Methylcyclopenten olone	0.11	-	-	(±)-3-Hydroxy-r-butyrolactone	0.03
4-Cyclopentene-1,3 -dione	0.11	-	-	2-Octylamine	0.02
Itaconic anhydride	0.06	-	-	1,3 -Dimethylpentylamine	0.02
		-	-	N-(2-Methoxyethyl)methylami ne	0.02
The total proportion of fragrance substances	62.69	The total proportion of fragrance substances	68.18	The total proportion of fragrance substances	82.74

Table 2 Thermal cracking results of nerol glycoside at different temperatures

350°C		600°C		900°C
Substance	Relative content %	Substance	Relative content %	Substance	Relative content %
Acetamide	42.23	Acetamide	78.46	Acetamide	84.35
D-Allose	31.89	D-Allose	5.84	D-Allose	3.26
2,5-Dimethylresorcinol	0.94	2,5-Dimethylresorcinol	0.78	2,5-Dimethylresorcinol	1.04
Stearic acid	0.15	-	-	(2 S) -2 -Amino-N-ethylpropionamide	0.04
The total proportion of fragrance substances	75.20	The total proportion of fragrance substances	85.08	The total proportion of fragrance substances	88.68

Embodiment 1, apply the flavor dispersion comprising raspberry glycoside to cigarette paper

Parts by mass of the flavor formula are as follows: raspberry glycoside 8g, and mogrosides 2g, as well as a small amount of filler and combustion improvers, which are dissolved in 100g of water to form a flavor dispersion containing raspberry glycoside. The flavor dispersion obtained containing raspberry glycoside is coated onto ordinary cigarette paper and dried, the grammage of the obtained cigarette paper is 38 g/m², and the air permeability is 60 CU. The content of flavor in the cigarette paper accounts for 0.5wt%.

Embodiment 2

The same as Embodiment 1 except for the flavor formula, parts by mass of the flavor formula of this embodiment is as follows: raspberry glycoside 7g, mogrosides 3g, maple extractum 0.5g, and dihydroactinidiolide 0.1g. The grammage of the obtained cigarette paper is 30 g/m² and an air permeability of 50 CU. The flavor content accounts for 0.8wt% of the cigarette paper.

Embodiment 3

The same as Embodiment 1 except for the flavor formula, parts by mass of the flavor formula of this embodiment is as follows: raspberry glycoside 4g, mogrosides 4g, and strawberry aldehyde 0.2g. The grammage of the obtained cigarette paper is 35 g/m² and an air permeability of 60 CU. The flavor content accounts for 0.4wt% of the cigarette paper.

Embodiment 4

The same as Embodiment 1 except for the flavor formula, parts by mass of the flavor formula of this embodiment is as follows: raspberry glycoside 3g, mogrosides 5g, maple extractum 0.5g, and strawberry aldehyde 0.2g. The grammage of the obtained cigarette paper is 33 g/m² and an air permeability of 50 CU. The flavor content accounts for 0.7wt% of the cigarette paper.

Embodiment 5: testing

Analyze and test the cigarette paper of Embodiment 1 and the ordinary cigarette paper of the control samples. Analysis method: pyrolysis analysis and cigarette smoke composition analysis

1. Pyrolysis analysis method

With reference to YQ/T-79 Technical Regulations on Tobacco Additives Thermal Pyrolysis (2016 ), the pyrolysis details are as follows:

(1) Pyrolysis conditions
Pyrolysis temperature-rising program: the initial temperature is 50 °C, rising to 350 °C, 600 °C and 900 °C at 30 °C/s, each for 5s; pyrolysis atmosphere: 9:91 (V/V) oxygen/nitrogen mixture; gas flow rate: 70 mL/min; temperature of pyrolyzer valve box: 280 °C; temperature of pyrolyzer transfer line: 280 °C; cold trap capturing temperature: -60 °C; cold trap injection conditions: temperature rising from -60 °C to 280 °C within 5min; cold trap system: fill the middle of the stainless steel tube with 2cm silicon oxide glass wool from both ends to the center.
(2) GC-MS conditions
The chromatographic column is made of an elastic quartz capillary; the stationary phase is 5% phenyl-95% methyl polysiloxane; the specification is [60m (length) × 0.25mm (inner diameter) × 1.0µm (film thickness)]; carrier gas flow, 1.5 mL/min; split ratio, 100:1; temperature-rising program: the initial temperature is 50°C, holding for 4 min, rising to 200°C at 4 °C/min, and rising to 280°C at 10 °C/min, holding for 15 min; mass spectrum transmission line temperature: 280°C; ion source temperature, 230°C; quadrupole temperature, 150°C; mass scanning range, 29∼450 amu;
(3) Data processing
The sample quality is corrected by using peak area, and the NIST 2014 mass spectrometry library is applied for retrieval and qualitative analysis.

2. Smoke analysis method: The cigarette paper of Embodiment 1 and ordinary cigarette paper are made into cigarettes, except for the cigarette paper, others such as tobacco shreds and filters are exactly the same.

(A) Instruments and reagents

Cerulean SM405-SV side-stream smoking machine; Agilent 6890-5973 gas chromatography-mass spectrometer; Buchi R-210 Rotary Evaporator; Elastic silica capillary column: DB-5MS 30m×0.25mm×0.25µm; methanol, dichloromethane, deuterated benzene and phenethyl acetate are all chromatographically pure.

(B) Collection and pretreatment of total particulate matters of side-stream smoke Firstly equilibrate cigarettes at (22±1) °C and relative humidity of (60±2)% for 48h, sort cigarettes by weight and suction resistance so as to pick out uniform cigarette samples. Smoke cigarettes with SM405-SV side-stream smoking machine, refer to YC/T 185-2004 for specific methods. Each glass fiber filter collects side-stream smoke from 4 cigarettes. Remove the fishtail cover, take 20mL of methanol, and clean the fishtail cover with a dropper containing methanol. Collect the methanol solution under vacuum condition (55°C, 300mbar), add with internal standard solution, and directly analyze by GC/MS.
(C) Collection and pretreatment of total particulate matters of mainstream smoke a. Smoke capturing:
Equilibrate cigarette samples at (22±1) °C and relative humidity of (60±2) % for 48h, select the cigarettes with average mass of ± 0.015g and average suction resistance ± 49Pa as test samples. Smoke cigarettes with a linear smoking machine, 10 cigarettes for each group, use a Cambridge filter with the diameter of 44mm to capture mainstream smoke particulate matters of the cigarettes, and connect two absorption bottles in series behind the catcher, each absorption bottle contains 10mL of methanol solution and captures gas compositions of mainstream smoke at low temperature (dry ice/isopropanol bath).

b. Particulate composition analysis

Put the Cambridge filters used for capturing the gas and particulate matters in the mainstream smoke of 10 cigarettes into a 4mL sample bottle, add 3mL of dichloromethane extractant, and accurately add 100µL internal standard solution (2 mg/mL), seal and extract with ultrasonic extraction for 30min, take out the extract, filter through a 0.45µm microporous membrane, analyze the filtrate by GC-MS, and quantitatively analyze the detected target ingredients with Selected Ion Monitoring (SIM).

c. Gas component analysis

After smoking the cigarette, use rubber suction bulbs to clean the absorption tubes in the two absorption bottles through suction for 5 times respectively, and add 100µL of internal standard solution to each absorption bottle accurately, after stirring evenly, take out 1mL of the solution in each of the two absorption bottles and mix uniformly for GC/MS analysis. The internal standard solution is double internal standard solution of deuterated benzene and phenethyl acetate. The DB-624 column method uses deuterated benzene as the internal standard, and the DB-5MS column method uses phenethyl acetate as the internal standard.

d. Chromatography mass spectrometry analysis

Take gas and particulate samples, inject the samples into the two columns of DB-5MS and DB-624 respectively for sample analysis, the specific chromatographic mass spectrometry analysis conditions are as follows: DB-5MS (60 m×1.0 µm×0.25 mm) method:
Temperature-rising program: $60 ° C \overset{2 ° C / \min}{\to} 250 ° C \overset{5 ° C / \min}{\to} 290 ° C (20 \min)$
; injection volume: 1 µL; injection-port temperature: 290°C; split ratio: 10:1; carrier gas: He, flow rate: 1.5 mL/min; transfer-line temperature: 290°C; ionization mode: ESI; ion-source temperature: 230°C; ionization energy: 70eV; quadrupole temperature: 150°C; mass scanning range of mass spectrometry: 26~400 amu; monitoring mode: full-scan mode and selected ion scan mode.
Timed events: CH₂Cl₂, 0 min detector on; 5 min detector off; 6 min detector on. CH₃OH, 0 min detector on; 4 min detector off; 5 min detector on.
DB-624 (60 m×1.4 µm×0.25 mm) method:
Temperature-rising program: $40 ° C (30 \min) \overset{2 ° C / \min}{\to} 160 ° C (1$
$\min) \overset{8 ° C / \min}{\to} 240 ° C (10 \min)$
; injection volume: 1µL; injection-port temperature: 220°C; split ratio: 10:1; carrier gas: He, flow rate: 1.0 mL/min; transfer-line temperature: 240°C; ionization mode: ESI; ion-source temperature: 230°C; ionization energy: 70eV; quadrupole temperature: 150°C; mass scanning range of mass spectrometry: 20∼350 amu; monitoring mode: full-scan mode and selected ion scan mode.
Timed events: methylene chloride, 0 min detector on; 12:10 min detector off; 13:90 min detector on. Methanol, 0 min detector on; 11:70 min detector off; 13:00 min detector on.

3. The testing results are as follows:
The pyrolysis results of the cigarette paper of Embodiment 1 at different temperatures are shown in Table 3 below.

Table 3 Pyrolysis results of the cigarette paper of Embodiment 1 at different temperatures

No. (#)	Retention time (min)	Compound	Peak area /mg Sample
No. (#)	Retention time (min)	Compound	350	600	900
1	5.38	Pyruvaldehyde	-	1.94E+06	1.78E+06
2	5.45	Formic acid	-	2.83E+06	2.14E+06
3	6.92	Hydroxyacetaldehyde	-	1.58E+06	3.53E+07
4	7.39	Acetic acid	1.33E+06	1.04E+07	3.21E+07
5	7.88	2-Pentanone	-	8.21E+05	5.73E+05
6	10	1-Hydroxyacetone	-	4.18E+07	2.91E+07
7	10.83	Propionic acid	-	5.74E+06	2.12E+06
8	11.22	2,3 -Pentanedione	-	3.62E+05	6.97E+05
9	13.17	3 -Pentene-2-one	-	7.12E+05	4.01E+05
10	14.38	Methyl acetate	-	3.15E+06	3.53E+06
11	14.51	Acetoin	-	5.17E+06	3.82E+06
12	15.03	Guaiacol	9.29E+05	2.13E+06	5.73E+06
13	15.17	Succinaldehyde	-	2.39E+07	2.91E+07
14	15.85	Cyclopentanone	-	5.19E+05	5.13E+05
15	16.8	3 -Furaldehyde	-	2.96E+05	4.05E+05
16	17.74	Furaldehyde	1.93E+06	5.13E+06	4.00E+06
17	18.52	Furfuryl alcohol	-	3.31E+06	4.16E+06
18	18.95	Acetoxy-2-propanone	-	3.91E+06	2.15E+06
19	19.74	Paraxylene	-	5.49E+05	4.39E+05
20	19.81	p-Hydroxybenzaldehyde	5.15E+05	2.43E+06	5.56E+06
21	19.99	Raspberry ketone	7.29E+05	1.73E+07	7.47E+06
22	20.13	Cyclopent-4-ene-1,3-dione	1.63E+05	5.08E+05	4.08E+05
23	21.29	2-Methyl-2-cyclopenten-1-one	1.56E+05	2.19E+06	1.87E+06
24	21.41	2(5H)-furanone	-	6.36E+06	5.11E+06
25	21.54	Butyrolactone	-	5.32E+06	2.83E+06
26	21.85	2-Cyclohexen-1-ol	-	2.73E+06	2.15E+06
27	22.08	1,2-Cyclopentanedione	-	1.01E+07	5.73E+06
28	23.86	5-Methylfurfural	9.63E+05	1.21E+06	6.58E+05
29	24.1	3-Methyl-2-cyclopenten-1-one	-	2.50E+06	1.01E+06
30	24.29	Phenol	-	1.95E+06	9.39E+05
31	24.46	3 -Methyl-2(5H)-furanone	-	8.14E+05	7.13E+05
32	25.12	2-Hydroxybutyrolactone	-	5.34E+06	1.95E+06
33	27.35	2,3-Dimethyl-2-cyclopenten-1-one	-	3.54E+06	9.90E+05
34	27.54	4-Methyl-5H-furan-2-one	-	7.70E+05	7.94E+05
35	27.73	2-Methylphenol	-	9.70E+05	9.10E+05
36	27.93	2-Hydroxy-3,4-dimethyl-2-cyclopenten-1-one	-	3.57E+06	2.99E+06
37	28.61	3-Methylphenol	1.53E+05	2.43E+06	1.17E+06
38	30.58	Maltol	6.33E+05	7.21E+05	8.65E+05
39	30.72	Ethylcyclopentenolone	-	4.75E+06	1.95E+06
40	31.8	2,4-Dimethylphenol	-	5.36E+05	2.77E+05
41	32.1	Palmitic acid	3.18E+05	1.25E+06	2.31E+06
42	33.11	2,3 -dihydroxybenzaldehyde	-	5.25E+05	9.10E+05
43	33.57	Catechol	-	5.34E+05	5.29E+05
44	34.82	1,4:3, 6-dihydrate-pyranoid glucose	-	3.01E+06	8.10E+06
45	36.31	Hydroquinone	-	9.90E+05	1.09E+06
46	37.77	2,3-Dihydro-1-indanone	-	6.41E+05	7.19E+05
47	37.9	3-Hydroxybenzaldehyde	9.63E+05	1.01E+06	9.39E+05

It can be seen from Table 3 that at 350° C, the pyrolysis products of the cigarette paper of Embodiment 1 containing raspberry ketone, guaiacol, p-hydroxybenzaldehyde, etc. are detected, showing that the added flavors have undergone pyrolysis reactions at 350°C, raspberry ketone is the characteristic pyrolysis product of raspberry glycoside, and guaiacol is the characteristic pyrolysis product of mogrosides. At 600°C and 900°C, the types of ingredients detected in the cigarette paper of Embodiment are the same, while the relative proportions of the ingredients change. The detected content of raspberry ketone is the highest at 600°C, and the detected content of guaiacol also increases with the rise of temperature.

The differences between pyrolysis products of the cigarette paper with added flavor of Embodiment 1 and ordinary cigarette paper of the control samples are compared at 900°C.

Table 4 Comparison of Pyrolysis of Cigarette Paper of Embodiment 1 with Control Samples at 900°C

No. (#)	Retention time (min)	Compound	Peak area /mg Sample		Peak area ratio
No. (#)	Retention time (min)	Compound	Cigarette Paper with added flavor	Control sample	Peak area ratio
1	5.38	Methy lglyo xal	1.78E+06	1.80E+06	0.99
2	5.45	Formic acid	2.14E+06	8.84E+05	2.42
3	6.92	Hydroxyacetaldehyde	3.53E+07	1.18E+07	2.99
4	7.39	Acetic acid	3.21E+07	1.70E+07	1.89
5	7.88	2-Pentanone	5.73E+05	4.73E+05	1.21
6	10	1-Hydroxyacetone	2.91E+07	1.08E+07	2.69
7	10.83	Propionic acid	2.12E+06	2.55E+06	0.83
8	11.22	2,3 -Pentanedione	6.97E+05	4.22E+05	1.65
9	13.17	3 -Penten-2-one	4.01E+05	3.91E+05	1.03
10	14.38	Methyl acetate	3.53E+06	2.34E+06	1.51
11	14.51	Acetoin	3.82E+06	2.18E+06	1.75
12	15.03	Guaiacol	5.73E+06	-
13	15.17	Succinaldehyde	2.91E+07	8.25E+06	3.53
14	15.85	Cyclopentanone	5.13E+05	7.07E+05	0.73
15	16.8	3 -Furaldehyde	4.05E+05	3.69E+05	1.10
16	17.74	Furaldehyde	4.00E+06	4.03E+06	0.99
17	18.52	Furfuryl alcohol	4.16E+06	4.13E+06	1.01
18	18.95	Acetoxy-2-propanone	2.15E+06	1.63E+06	1.32
19	19.74	Paraxylene	4.39E+05	8.10E+05	0.54
20	19.81	p-Hydroxybenzaldehyde	5.56E+06	-
21	19.99	Raspberry ketone	7.47E+06	-
22	20.13	Cyclopent-4-ene-1,3-dione	4.08E+05	4.95E+05	0.82
23	21.29	2-Methyl-2-cyclopenten-1-one	1.87E+06	1.94E+06	0.96
24	21.41	2(5H)-furanone	5.11E+06	3.95E+06	1.29
25	21.54	Butyrolactone	2.83E+06	3.12E+06	0.91
26	21.85	2-Cyclohexen-1-ol	2.15E+06	1.04E+06	2.07
27	22.08	1,2-Cyclopentanedione	5.73E+06	4.54E+06	1.26
28	23.86	5-Methylfurfural	6.58E+05	7.61E+05	0.86
29	24.1	3-Methyl-2-cyclopenten-1-one	1.01E+06	1.24E+06	0.81
30	24.29	Phenol	9.39E+05	8.44E+05	1.11
31	24.46	3 -Methyl-2(5H)-furanone	7.13E+05	5.78E+05	1.23
32	25.12	2-Hydroxybutyrolactone	1.95E+06	1.35E+06	1.44
33	27.35	2,3-Dimethyl-2-cyclopenten-1-one	9.90E+05	1.04E+06	0.95
34	27.54	4-Methyl-5H-furan-2-one	7.94E+05	8.85E+05	0.90
35	27.73	2-Methylphenol	9.10E+05	1.84E+06	0.49
36	27.93	2-Hydroxy-3,4-dimethyl-2-cyclopenten-1-one	2.99E+06	1.89E+06	1.58
37	28.61	3-Methylphenol	1.17E+06	1.68E+06	0.70
38	30.58	Maltol	8.65E+05	7.21E+05	1.20
39	30.72	Ethylcyclopentenolone	1.95E+06	2.17E+06	0.90
40	31.8	2,4-Dimethylphenol	2.77E+05	2.40E+05	1.15
41	32.1	Palmitic acid	2.31E+06	-
42	33.11	2,3 -Dihydroxybenzaldehyde	9.10E+05	3.32E+05	2.74
43	33.57	Catechol	5.29E+05	6.05E+05	0.87
44	34.82	1,4:3, 6-dihydrate-pyranoid glucose	8.10E+06	3.78E+06	2.14
45	36.31	Hydroquinone	1.09E+06	5.94E+05	1.84
46	37.77	2,3-Dihydro-1-indenone	7.19E+05	5.99E+05	1.20
47	37.9	3-Hydroxybenzaldehyde	9.39E+05	5.19E+05	1.81

It can be seen from Table 4 that at 900°C, guaiacol, p-hydroxybenzaldehyde, raspberry ketone, and palmitic acid are detected in the cigarette paper with added flavor of Embodiment 1, while none of these four ingredients is detected in the control samples.
Besides, other pyrolysis products of the cigarette paper with added flavor of Embodiment 1 are also quite different from the control samples. The pyrolysis products of the cigarette paper with added flavor of Embodiment 1 contain relatively high content of formic acid, hydroxyacetone, hydroxyacetaldehyde, succinaldehyde, 2,3-dihydroxybenzaldehyde, and didehydrated glucose pyranoid, while the content of cyclopentanone, paraxylene, dimethylphenol and other ingredients is low.
The analysis results of mainstream and side-stream smoke are similar. Compared with the control samples, the cigarettes prepared from the cigarette paper with added flavor of Embodiment 1 are detected of characteristic ingredients such as raspberry ketone, guaiacol, etc. in both the mainstream and side-stream smoke, while these ingredients are not found in the control samples. Comparison of characteristic fragrance ingredients in the mainstream and side-stream smoke of the cigarette paper with added flavor of Embodiment 1 is shown in Table 5 below. Table 5 Comparison of characteristic ingredients of mainstream and side-stream smoke of cigarettes (µg/piece)

Compound Mainstream smoke Side-stream smoke Ratio

Raspberry ketone 1.31 6.80 1:5.19

Guaiacol 0.27 1.17 1:4.33
According to experts' olfactory evaluation of the cigarettes, it can be known that the characteristic fragrance of raspberry and blueberry, etc. of raspberry ketone and guaiacol are more obvious in the side-stream fragrance.
It can be known that from the above testing that the characteristic ingredients such as raspberry ketone, guaiacol, etc. are detected in the pyrolysis products of the cigarette paper with added flavor of Embodiment 1, and the content of cigarettes in the mainstream and side-stream smoke is quite different. The distribution ratio of raspberry ketone as the pyrolysis ingredient of raspberry glycoside in the mainstream and side-stream smoke is 1:5.19, the distribution ratio of guaiacol as the pyrolysis ingredient of mogrosides in mainstream and side-stream smoke is 1:4.33. Thus, the characteristic fragrances of raspberry, blueberry, etc. in the side-stream smoke of the cigarettes prepared from the cigarette paper with added flavor of the present invention can be clearly felt, the sensory intensity is significantly stronger than the mainstream smoke. These fragrance in the side-stream smoke can bring a pleasant smell to the surrounding non-smokers so as to create a better environment for the non-smokers.
The testing results of the cigarette paper of Embodiments 2-4 are similar to that of the cigarette paper of Embodiment 1, the content of raspberry ketone and guaiacol in mainstream and side-stream smoke is also significantly higher, too.

Embodiment 6, apply the flavor dispersion comprising raspberry glycoside to tobacco shreds

The flavor formula is the same as that of Embodiment 1. Spray the flavor dispersion containing raspberry glycoside into tobacco shreds and dry, so as to obtain tobacco shreds with added flavor with a suitable moisture content. The flavor content accounts for 0.05wt% of the tobacco shreds.

Embodiment 7, apply the flavor dispersion comprising raspberry glycoside to tobacco shreds

The flavor formula is the same as that of Embodiment 2. The flavor content accounts for 0.07wt% of the tobacco shreds.

Embodiment 8, apply the flavor dispersion comprising raspberry glycoside to tobacco shreds

The flavor formula is the same as that of Embodiment 3. The flavor content accounts for 0.03wt% of the tobacco shreds.

Embodiment 9, apply the flavor dispersion comprising raspberry glycoside to tobacco shreds

The flavor formula is the same as that of Embodiment 4. The flavor content accounts for 0.06wt% of the tobacco shreds.

Embodiment 10: Testing

Test the tobacco shreds of Embodiment 6 and the cigarettes rolled from the tobacco shreds of Embodiment 6.The testing method and conditions are the same as those of Embodiment 5. The testing results are as follows: the distribution ratio of raspberry ketone as pyrolysis ingredient of raspberry glycoside in mainstream and side-stream smoke of cigarettes respectively in mainstream and side-stream smoke is 1:4.05, the distribution ratio of guaiacol as the pyrolysis ingredient of mogrosides in mainstream and side-stream smoke is 1:3.19. The results are basically similar to that of Embodiment 5.
Thus, the side-stream smoke of the cigarettes prepared by tobacco shreds with added flavor of the present invention can also clearly have the characteristic fragrances of raspberries and blueberries, etc. brought by the added flavor, so that the sensory intensity is significantly stronger than that of mainstream smoke, bringing a better and pleasant smell to non-smokers.

Embodiment 11, apply the flavor dispersions comprising raspberry glycoside to reconstituted tobacco sheets.

The flavor formula is the same as that of Embodiment 1. Spray the flavor dispersions containing raspberry glycoside into reconstituted tobacco sheets shreds and dry to obtain reconstituted tobacco shreds. The flavor content accounts for 0.5wt% of the tobacco shreds.
The testing method and conditions are the same as those of Embodiment 10. The testing results are as follows: the distribution ratio of raspberry ketone as pyrolysis ingredient of raspberry glycoside in mainstream and side-stream smoke of cigarettes respectively in mainstream and side-stream smoke is 1:4.58, the distribution ratio of guaiacol as the pyrolysis ingredient of mogrosides in mainstream and side-stream smoke is 1:3.92. The results show that the flavor dispersion comprising raspberry glycoside of the present invention used in reconstituted tobacco sheets can also add unique fragrance to the reconstituted tobacco sheets, so as to improve the quality of cigarette smoking and the utilization rate of raw materials of cigarette blending while reducing cigarette production costs.
The above has shown and described basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that, the present invention is not limited by the above-mentioned embodiments, what is described in the above-mentioned embodiments and the Description is only to illustrate the principle of the present invention, without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which all fall within the scope of what is claimed. The claimed scope of the present invention is defined by the appended claims and their equivalents.

Claims

A method of improving the fragrance of cigarette products with raspberry glycoside, wherein, a flavor comprising raspberry glycoside is dispersed or dissolved in a solvent to form a flavor dispersion, and the flavor dispersion is added to the cigarette.
The method according to claim 1, wherein, the flavor dispersion is added to cigarette paper, tobacco shreds or reconstituted tobacco sheets to improve the characteristic smoke fragrance of side-stream smoke and/or improve the smoking quality of mainstream smoke.
The method according to claim 1, wherein, the solvent is water, ethanol or a mixture of the both.
The method according to claim 1, wherein, the flavor dispersion further comprises other flavor ingredients.
The method according to claim 4, wherein, the other flavor ingredients comprise at least one selected from mogrosides, maple extractum, dihydroactinidiolide and strawberry aldehyde.
The method according to claim 5, wherein, the flavors in the flavor dispersion comprise: ①raspberry glycoside and mogrosides, their mass ratio is (2-8): (1-3); or ②raspberry glycoside, mogrosides, maple extractum and dihydroactinidiolide, their mass ratio is (2-8): (1-3): (0.5-1): (0.05-0.1); or ③raspberry glycoside, mogrosides and strawberry aldehyde, their mass ratio is (2-5): (2-5): (0.1-0.3); or ④raspberry glycoside, mogrosides, maple extractum and strawberry aldehyde, their mass ratio is (2-5):(2-5):(0.5-1):(0.1-0.3).
The method according to claim 6, wherein the flavor dispersion further comprises fillers and combustion improvers.
The method according to claim 7, wherein, the filler is light calcium carbonate.
The method according to claim 7, wherein, the combustion improver is an organic acid metal salt, which is selected from at least one of potassium citrate, potassium malate, potassium lactate and potassium acetate.
The method according to claim 2, wherein, the flavor dispersion is coated onto cigarette paper, the weight ratio of the flavor to the dry weight of the cigarette paper is 0.1wt%∼1wt%, the grammage of the obtained cigarette paper is 28-38 g/cm², and an air permeability is 30-100 CU.