CN1073387C - Low free radical and low toxicity cigarette and its prodn. method - Google Patents

Low free radical and low toxicity cigarette and its prodn. method Download PDF

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CN1073387C
CN1073387C CN 95116865 CN95116865A CN1073387C CN 1073387 C CN1073387 C CN 1073387C CN 95116865 CN95116865 CN 95116865 CN 95116865 A CN95116865 A CN 95116865A CN 1073387 C CN1073387 C CN 1073387C
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cigarette
free radical
gaseous phase
pipe tobacco
filter tip
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CN1145206A (en
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忻文娟
赵保路
侯京武
王平
田宁亚
齐伟成
吕东军
曹伏军
董建信
周骏
吴树起
孟惠英
瞿冬芬
张文元
黄俊华
金涧
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Beijing Cigarette Factory, Shanghai Tobacco Group
Institute of Biophysics of CAS
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BEIJING CIGARETTE FACTORY
Institute of Biophysics of CAS
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Abstract

The present invention relates to a gas-phase free radical scavenger for a cigarette, particularly to a cigarette with low free radical and low toxicity and a production method thereof. The gas-phase free radical scavenger is prepared from tea polyphenol and vitamine C in preferable proportion of 1: 1.

Description

Low free radical and low toxicity cigarette and production method thereof
The present invention relates to a kind of cigarette gaseous phase free radical scavenger, low free radical and low toxicity cigarette and production method thereof.Or rather, the present invention relates to a kind of low free radical and low toxicity cigarette and production method of making as the cigarette free radical scavenger with Tea Polyphenols, vitamin C and bluish dogbane thereof.
Smoking to the harm of health by many investigation and experiment confirm.
When world national governments advocate smoking cessation and legislation ban on opium-smoking and the opium trade, scientist and tobacco scientific workers are actively making great efforts the harm of research reduction cigarette, development is low poisons and the nonhazardous cigarette, it is little to be intended to solve comprehensive ban on opium-smoking and the opium trade effect, the contradiction that aspects such as the consumer is numerous, the economic benefit of smoking and social benefit, smoking and health exist.
In the production of cigarettes field,, generally be to adopt the cigarette filter technology for eliminating the noxious material in the cigarette.The cigarette filter great majority are made by NACF or acetate fiber filter material, and this respect can be referring to CN2174854Y and CN/088763A.Another kind of means are at pipe tobacco itself, promptly pipe tobacco are carried out specially treated, referring to CN1045515A.CN2132392Y discloses a kind of activated carbon fiber composite cigarette filter tip capable, and its filter fiber is formed by the fiber composite butt joint of two sections unlike materials at least.
But, the above-mentioned commonsense method that removes the noxious material in the cigarette does not all have from dealing with problems in essence.In fact, along with free radical medical science and the biological development of free radical, epidemiology survey confirms: free radical is the most serious product of harm in the cigarette.It can directly or indirectly be attacked, damaging cells, and can cause the generation of various diseases.Free radical is a carcinogenic substance, can cause cancer.This is noted by the country of some science prosperity.
In recent years, aspect the research of cigarette free radical, be confined to inquire in theory in the world, radicals scavenging is technical in cigarette does not become effective, and up to now, does not see the report of low free radical and low toxicity cigarette as yet.
The research that reduces free-radical contents in the cigarette is very a forward position and a complicated problem, does not solve in the world so far at all.Some research institutions only concentrate on the tar in the research of cigarette free radical, and tar content reaches the purpose that reduces free radical in the cigarette to reduce.
Therefore, be starved of:
1. set up the accurate detection of a cover and confirm in the cigarette and the free radical kind and the method for character, particularly gaseous phase free radical that produce in the smoking process;
2. study its mechanism, and work out efficiently harmful targetedly free radical scavenger of nontoxic attached effect on this basis human body harm;
3. darker because of hazard ratio solid phase (tar phase) the free radical extent of injury of gaseous phase free radical, it is more difficult to remove, therefore, research object and sweep-out method must be based on gaseous phase free radicals, and should set up the free radical scavenger adding method that adapts to modern cigarette process technical conditions.But fact proved, be very difficult.
Task of the present invention is to solve above-mentioned prior art problems, and a kind of low free radical and low toxicity cigarette and production method thereof are provided.
Free radical comprises solid phase free radical and gaseous phase free radical two parts in the cigarette, by the research of cryotronics spin resonance (ESR) method, find that the solid phase free radical mainly is polycyclic aromatic hydrocarbon free radical and quinone/semiquinone (Q/QH) free radical, wherein the Q/QH free radical accounts for 85% greatly, and this type free base is easy to be oxidized to oxygen radical.Mostly free radical in the gas phase is instantaneous unstable the existence, can not directly observe with the ESR spectrometer, and the inventor has set up with spin catching agent PBN or DMPO and unsettled radical-scavenging lived and changed into a kind of spin adduct that can use the ESR wave spectrum to detect.That is: adopt spin capture (DMPO or PBN) and ESR technology to combine and distinguish gaseous phase free radical.Assert that through test it is alkoxy radical and alkyl diradical.
Discover that gaseous phase free radical and solid phase free radical all are the free radicals that human body is had serious harm in the cigarette, but gaseous phase free radical has stronger oxidisability, and the solid phase free radical has certain reproducibility.Cigarette smoke is the Main Ingredients and Appearance in consumer's suction body, is the main path of harmful free radical harmful to human.
At These characteristics, on the strategy of cigarette radicals scavenging, be target with comprehensive removing cigarette free radical, serve as basic to remove gas phase.
Scavenger requires efficiently, has no side effect, and is pointed to free radical in the cigarette, technical feasible at cigarette producing process, and has better economic.
Through experimental study, the inventor finds, selects cigarette radicals scavenging agent prescription: Tea Polyphenols, vitamin C and bluish dogbane can suppress the cigarette toxin effectively as main component, particularly reduce gaseous phase free radical in the cigarette.
For this reason, determine the technology path of following removing free radical: add bluish dogbane medicinal extract and remove the solid phase free radical in pipe tobacco, add free radical scavenger and remove its gaseous phase free radical in filter tip, the two coordinates to remove free radical in the cigarette comprehensively.Experiment showed, that above-mentioned three kinds of components have removes the effect concertedness preferably.Use single component to remove effect and be lower than composite components removing effect.Just be based on above discovery, just finishing the present invention.
The present invention relates to a kind of low free radical and low toxicity cigarette, it is characterized in that the filter tip of cigarette is mixed and made into finite concentration and active carbon with Tea Polyphenols and vitamin C.According to the another embodiment of the present invention scheme, when cigarette throwing, soak into pipe tobacco, to obtain to fall the optimum synergistic effect of low smoke and non-toxic with bluish dogbane medicinal extract.
Remove in the prescription at gaseous phase free radical, Tea Polyphenols and ascorbic percentage by weight are 1: 1.The purity of Tea Polyphenols is preferably 60-95%, is higher than the upper limit 95%, and it is uneconomical to purify; And being lower than lower limit 60%, practical function is insufficient.Accounting for pipe tobacco gross weight 1-5 ‰ according to the content that experiment showed, scavenger is advisable.
Term " Tea Polyphenols " is a kind of green-tea extract, is actually the blocking agent of lipid peroxidation free chain reaction.
Should be pointed out that Tea Polyphenols, bluish dogbane and ascorbic combination as free radical scavenger basis of the present invention are necessary.If only select wherein a kind of for use, though the effect of falling low smoke and non-toxic is also arranged, effect is insufficient.That is to say the arithmetic sum height of the combination of these three kinds of compositions of employing than the efficient of using these three kinds of compositions to obtain respectively separately.Facts have proved that use radicals scavenging technology of the present invention, the gas phase clearance rate can reach 26.8%.
The method of soaking into pipe tobacco with bluish dogbane medicinal extract illustrates that it is for referencial use that this patent related content is incorporated into this paper at this in all United States Patent (USP)s 06/711,620 of the inventor.
The radicals scavenging effect is measured by the following method:
Radicals scavenging solution is sprayed onto on the pipe tobacco equably dries cigarette.Make reference system with the cigarette of the same race that does not add bluish dogbane, make trapping agent with PBN or DMPO and collect gaseous phase free radical, detect with the ESR method, pretending with the ESR wave spectrum of the cigarette that added scavenger and reference system cigarette free radical respectively is the relative value of free-radical contents, under the same conditions, the linearity of the wave spectrum of these two kinds of cigarette is identical with live width.Free radical scavenging activity calculates as follows:
E=(HO-HX)/HO * 100% wherein HO is that the reference system peak is strong, and HX is that to add the peak of sample of scavenger strong.
Following examples are intended to illustrate the present invention, are not that it is limited.
Embodiment 1
Tobacco leaf at first enter the damping machine steam get damp again to outlet temperature be 75 soil 5 ℃, moisture improves 4-5%, then through cutting sharp operation separately with the blade tip of tobacco leaf and phyllopodium, phyllopodium is through after wetting once more, enter the wind dispensing machine, blade is separated with stalk, and blade after the separation and blade tip (general designation blade) enter blade and handle pipeline processes, and stalk enters stalk and handles pipeline processes.
It is the same that white flank part in the blended type cigarette production is beaten the leaf pre-treating method.Beat blade behind the leaf and enter burley tobaccos and handle pipeline processes, before prewired cabinet, begin to mix, obstruct to enter and obstruct the processing pipeline processes with the flue-cured tobacco blade.
That is to say that blended type cigarette production throwing process is through forming three streamlines after the above-mentioned preliminary treatment: flue-cured tobacco blade processing streamline, stalk are handled streamline, white rib is handled streamline.
The burley tobaccos blade at first enters material in the white rib charger adding, bluish dogbane medicinal extract among the present invention mixes, dissolves with other cigarette charging, by nozzle mixed liquor is sprayed onto blade surface, white rib blade after reinforced enters white rib drying machine, dry under 140-110 ℃ of condition, moisture content of outlet is 8-12%., enter white rib table material charger for the second time add different feed liquid, mix with following flue-cured tobacco blade after reinforced then thereafter.
The reinforced thing of bluish dogbane is 1%-2% to the feeding quantity of whole tobacco leaves.
The flue-cured tobacco blade adds the flue-cured tobacco feed liquid through first Perfuming machine, afterwards, is mixed into leaf storing cabinet with above-mentioned white rib blade, stores 8 hours under relative humidity 65-75%, temperature 25-30 ℃ condition.Enter the filament cutter chopping behind the leaves storage, about leaf silk width 0.8MM, the leaf silk enters the cut-tobacco drier oven dry, 55 ± 5 ℃ of moisture content of outlet 12.5%, temperature through after the online expansion.
Stalk is fully wetting through profit stalk machine, steaming stalk machine; moisture reaches 32 soil 1%, temperature is 75 ± 5 ℃; enter the silk cutting machine chopping; stem thickness 0.15-0.18MM; in the stem charger, add the stem feed liquid then; the stem that adds feed liquid expands through expanded tower, and the leaf silk with the dryer outlet mixes at last, enters second Perfuming machine and adds spices.So far the pipe tobacco production process finishes, and pipe tobacco enters in the cut tobacco storing cabinet and stores for future use.
With formula rate is that (East Asia, Chinese Hangzhou Tea Polyphenols factory produces Tea Polyphenols (95%), trade mark GTP-104B, Tea Polyphenols purity is 95%): to be 3 ‰ concentration with the feeding quantity to tobacco leaf mix with an amount of activated carbon powder, water and adhesive the gaseous phase free radical scavenger of vitamin C (100%)=1: 1.The feed liquid that is made into is a carrier, makes filter stick on filter rod forming machine, is combined into cellulose acetate filter rod then and is exclusively used in the filter tip of removing gaseous phase free radical.
Prop up with above-mentioned pipe tobacco and the special-purpose filter tip cigarette cigarette that is added with bluish dogbane medicinal extract, produce low free radical and low toxicity cigarette.
Calculate according to above-mentioned free radical scavenging activity computing formula, the gas phase clearance rate reaches 26.8%.
Embodiment 2
According to the pipe tobacco of embodiment 1, the ratio of the active ingredient shown in the employing table 2 prepares the low degree-of-freedom low-toxic cigarette, the results are shown in table one and table two.
Following table three has provided the heat-resistant stable test of prescription.The result shows: under the cigarette producing process condition, the scavenger component can not take place to decompose and cause that scavenger content descends.
Test data 1 bluish dogbane is to the removing effect of free radical
The cigarette that props up (reference) and adding bluish dogbane with the cigarette that does not add bluish dogbane props up the removing effect that (sample) detects gaseous phase free radical, and clearance rate is 11.5%.Handle by statistics, have the difference (P<0.05) of conspicuousness, concrete ESR result such as table one:
Label Reference Sample
1 10.0 7.5
2 9.9 6.8
3 9.6 5.0
4 8.4 7.2
5 7.9 8.2
6 9.0 8.3
7 8.1 4.9
8 7.9 10.7
9 9.6 9.4
10 7.0 11.7
11 10.1 11.2
12 10.2 8.2
13 5.0 9.2
14 5.9 8.9
15 13.8 6.9
16 11.2 8.7
17 8.2 18.3
18 10.0 8.9
19 10.1 9.9
Label Reference Sample
20 10.6 6.0
21 8.2 6.7
22 10.6 9.5
23 8.2 4.6
24 7.5 13.5
25 10.7 7.7
26 10.3 9.8
27 8.4 12.7
28 10.2 10.9
29 8.9 7.3
30 10.0 10.2
31 10.2 12.2
32 5.3 8.9
33 16.0 6.3
34 16.3 7.8
35 10.4 8.8
36 8.4 11.8
37 22.6 6.3
38 14.3 6.9
Label Reference system Sample
39 15.4 3.3
40 9.4 3.4
41 10.4 4.9
42 12.8 3.5
43 13.9 5.7
44 12.0 5.4
45 6.5 8.2
46 10.6 5.0
47 12.5 6.7
48 15 10.7
49 15.1 15.5
50 9.58 14.3
51 9.8 12.0
52 8.3 9.4
53 9.9 11.2
54 10.7 3.5
55 9.0 11.2
56 8.8 7.4
57 6.4 9.1
Label Reference system Sample
58 8.6 6.1
59 9.1 10.0
60 9.1 10.8
61 13.5 6.5
62 11.3 17.6
63 13.3 8.1
64 10.6 7.3
65 7.5 9.1
66 12.2 11.9
67 8.6 5.9
68 2.1 6.3
69 4.9 8.1
70 4.0 8.1
71 4.9 8.1
72 6.0 8.9
73 7.2 7.8
74 7.6 5.7
75 12.8 13.8
76 7.4 8.0
On average (N=76) reference: 9.755 ± 3,180 samples: 8.631 ±, clearance rate E=11.5%P<(0.05)
Test data 2--in the gaseous phase free radical scavenger component
Tea Polyphenols and ascorbic ratio test
Experimental results show that: Tea Polyphenols and the C that supports one's family not are cigarette gas phase base scavengers preferably, but the proportioning difference of the two is removed the effect difference, and table two has been listed as the Tea Polyphenols of cigarette gaseous phase free radical scavenger and ascorbic proportioning test data.
Tea Polyphenols (95%): vitamin C (100%)
The relation of each effective ingredient and removing effect in the table two scavenger prescription:
Label Tea Polyphenols Vitamin C Clearance rate %
1 0.14 1.00 19.2
2 0.28 1.00 20.7
3 1.00 1.00 23.5
By table two as can be seen: when Tea Polyphenols purity is 95%, vitamin C purity is 1005, the two relatively is to have best removing effect at 1: 1 o'clock.
Test data 3--gaseous phase free radical scavenger temperature tolerance
Test
Be the stability of check gaseous phase free radical scavenger in the cigarette process allowed temperature range, adopt the FONTON method to carry out the heatproof experiment, investigate it to OH, free radical and O 2The influence of radicals scavenging effect.The results are shown in Table three:
The heatproof stability test of table three prescription:
Condition Decline to OH. radicals scavenging effect To O 2The decline of radicals scavenging effect
140 ℃ 10 minutes 0.0 4.1
120 ℃ 10 days 10.7 18.7
Table three data show; Under the cigarette producing process condition, the scavenger component can not decompose and cause the decline of removing effect.
Test data 4--the gaseous phase free radical scavenger is at filter tip
Middle addition small-scale test
The gaseous phase free radical scavenger is added in the filter tip, be rolled into cigarette with the pipe tobacco that adds bluish dogbane and prop up, prop up contrast, detect removing effect the smoking gaseous phase free radical with the cigarette that does not add bluish dogbane.Result such as following table four:
Table four: the addition small-scale test data of gaseous phase free radical in filter tip
Numbering Blank 1‰ 1% 3‰
1 2 132 121 116 98 96 94 82 77
3 4 111 111 96 93 91 86 73.5 72.5
5 6 107 102 88 87 82 81 72 68
7 8 101 99 87 84 81 80 65 65
9 10 93 93 81 78.7 79 78 65 62
11 12 88 86 76 75 74.5 73 62 60
13 14 85 83 74 73.3 73 64.7 58.5 57
15 16 83 82 72.7 69 63.3 63 55.5 51.5
Experiment date: 1994.4.18
Numbering Blank 1‰ 1% 3‰
17 18 878 77 61 58.7 62 61
19 20 75 75 56 51 57.5 57
21 22 74 69 45 44 56 55
23 24 67 66
25 26 65 64
27 28 64 63
29 30 62 58
31 53
Summary sheet four data are also carried out statistical analysis, draw following result:
Label Scavenger addition in the filter tip Clearance rate % The P value
1 Contain 1% gaseous phase free radical scavenger 12.42% <0.05
2 Contain 5 ‰ gaseous phase free radical scavenger 21.6% <0.05
3 Contain 1 ‰ gaseous phase free radical scavenger 10.99% < 0.05
By above data as can be seen:
1. add the gaseous phase free radical scavenger and can remove gaseous phase free radical in the cigarette effectively in filter tip, add the experiment of gaseous phase free radical scavenger with the past work in pipe tobacco and compare, removing under the identical situation of effect, the scavenger consumption can reduce greatly.Cost is reduced, more meet the cigarette producing process condition.
2. it is proportional between scavenger addition 1 ‰ to 5 ‰ that gaseous phase free radical is removed effect, reaches at 1% o'clock and reduce on the contrary.It is too high, less economical to consider that addition surpasses this limit production cost, selects 3 ‰ to be base value when production application, and the existing like this effect of removing preferably has better economic again.
The special-purpose filter tip type approval test of test data 5--gaseous phase free radical scavenger
According to above-mentioned result of the test,, carry out industrial experiment at the special-purpose filter tip of the compound removing gaseous phase free radical of Mudanjiang filter tip factory.
Special-purpose filter tip preparation method that is: with the concentration of 3% (scavenger accounts for the pipe tobacco weight ratio), is mixed itself and an amount of activated carbon, water and adhesive with aforementioned, makes filter stick on filter forming machine, is combined into the special-purpose filter tip of removing gaseous phase free radical then.
Use special-purpose filter tip, be rolled into cigarette with the pipe tobacco that adds bluish dogbane and prop up,, detect removing effect the cigarette gaseous phase free radical with the activated carbon that does not add scavenger/acetate fiber binary composite filter tip (blank) contrast.Result such as following table five:
Table five: the cigarette by the preparation of low free radical and low toxicity cigarette production method is removed the effect comparing data with common binary composite filter tip cigarette: (being added with the identical pipe tobacco of bluish dogbane)
Numbering Common binary composite filter tip Special-purpose filter tip
1 40.4 45.6
2 37.0 43.4
3 32.2 32.6
4 31.2 32.4
5 30.8 30.6
6 30.0 28.0
7 30.0 27.0
8 29.8 26.6
9 29.0 25.6
10 28.8 24
11 28.6 23.6
12 28.4 23
13 28.0 22.6
14 27.8 22.2
15 27.6 21.8
16 27.4 21.6
17 27.2 21.4
18 27.2 20.2
19 270 19.8
20 26.4 19.6
21 26.0 19.6
22 25.6 19.0
23 25.6 19.0
24 24.0 18.8
25 23.0 18.8
Numbering Common binary composite filter tip Special-purpose filter tip
26 22.8 18.3
27 22.6 18.0
28 21.8 17.6
29 21.4 17.4
30 20.2 17.2
31 19.8 17.0
32 19.6 17.0
33 19.6 17.0
34 19.4 16.8
35 19.0 16.5
36 19.0 16.2
37 18.8 15.8
38 18.4 15.6
39 17.8 15.5
40 17.8 15.4
41 17.6 15.3
42 17.4 15.0
43 17.4 15.0
44 17.3 14.9
45 16.8 14.8
46 16.7 14.6
47 16.7 14.4
48 16.6 14.3
49 16.2 14.2
50 16.2 14.1
Experiment date: 1994.12.30.
Numbering Common binary composite filter tip Special-purpose filter tip
51 16.1 14.0
52 15.4 14.0
53 15.3 13.9
54 15.2 13.8
55 15.0 13.6
56 15.0 13.2
57 14.6 12.9
58 14.4 12.8
59 14.0 12.8
60 13.4 12.8
61 13.2 12.6
62 13.1 12.4
63 12.7 12.4
64 12.6 12.1
65 12.4 12.0
66 12.2 11.8
67 11.8 11.7
68 11.7 11.6
69 11.6 11.2
70 11.4 10.8
71 10.9 10.8
72 10.6 10.5
73 10.2 10.4
74 10.0 10.2
75 9.8 10.1
Numbering Common binary composite filter tip Special-purpose filter tip
76 9.8 9.6
77 9.4 9.1
78 9.1 8.2
79 8.5 8.0
80 8.2 78
81 7.8 7.7
82 7.5 7.4
83 7.0 7.3
84 6.7 7.1
85 5.8 7.0
86 5.4 6.9
87 4.7 6.5
88 4.4 6.4
89 4.0 5.8
90 5.4
91 5.4
92 4.6
93 3.8
94 3.4
95
96
97
98
99
100
Mathematical statistics result shows: gaseous phase free radical is removed special-purpose filter tip and is reduced 14.5% than common activated carbon binary composite filter tip gaseous phase free radical, P<(0.05).Activated carbon+acetate fiber binary composite filter tip that this test shows and be used to reduce at present the cigarette oxious component both at home and abroad compares, and the special-purpose filter tip of gaseous phase free radical scavenger has tangible removing cigarette gaseous phase free radical effect.
Remarks: all be added with bluish dogbane in this test pipe tobacco, as radix 0.

Claims (4)

1. a low free radical and low toxicity cigarette is characterized in that the filter tip of cigarette is mixed and made into finite concentration and active carbon with Tea Polyphenols and vitamin C, wherein soaks into pipe tobacco with 1%-2% bluish dogbane medicinal extract in cigarette throwing.
2. according to the described cigarette of claim 1, wherein Tea Polyphenols and the vitamin C concentration that accounts for pipe tobacco weight 1 ‰-5 ‰ is mixed with an amount of active carbon, water and adhesive.
3. according to the described cigarette of claim 1, wherein the weight ratio of Tea Polyphenols and vitamin be 1: 1 as cigarette gaseous phase free radical scavenger.
4. method of producing low free radical and low toxicity cigarette, it may further comprise the steps:
In the process of production of cigarettes, bluish dogbane medicinal extract is mixed with other cigarette charging thing, dissolving, by the cigarette charging nozzle mixed liquor is sprayed onto wetting tobacco leaf surface, tobacco leaf after the above-mentioned reinforced processing is at 25-30 ℃, store 4-8 hour under the condition of relative humidity 65-70%, the reinforced thing of bluish dogbane is 1% for the feeding quantity of tobacco leaf, at the rolled cigarette packaging process, pipe tobacco enters cigarette machine, adopting the gaseous phase free radical scavenger is 1 ‰-5 ‰ concentration to the feeding quantity of pipe tobacco, with the proper amount of active carbon powder, the feed liquid that water and adhesive are made into is a carrier, on filter rod forming machine, make filter stick, be combined into the special-purpose filter tip of removing gaseous phase free radical with cellulose acetate filter rod then, with above-mentioned pipe tobacco and special and the filter tip cigarette Cigarette that is added with bluish dogbane medicinal extract, randomly through the packing machine packing, it is characterized in that described free radical scavenger is Tea Polyphenols and vitamin C, its proportioning is 1: 1.
CN 95116865 1995-09-13 1995-09-13 Low free radical and low toxicity cigarette and its prodn. method Expired - Lifetime CN1073387C (en)

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