WO2011075970A1 - 一种含有生物组合物的复合滤嘴 - Google Patents

一种含有生物组合物的复合滤嘴 Download PDF

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WO2011075970A1
WO2011075970A1 PCT/CN2010/071732 CN2010071732W WO2011075970A1 WO 2011075970 A1 WO2011075970 A1 WO 2011075970A1 CN 2010071732 W CN2010071732 W CN 2010071732W WO 2011075970 A1 WO2011075970 A1 WO 2011075970A1
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biological composition
filter
carrier
tow
composite filter
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PCT/CN2010/071732
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English (en)
French (fr)
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施丰成
朱立军
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川渝中烟工业公司
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Priority to EP10838536.0A priority Critical patent/EP2517584B1/en
Publication of WO2011075970A1 publication Critical patent/WO2011075970A1/zh

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    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters

Definitions

  • the invention relates to a composite filter containing a biological composition, in particular to a biological composition formed by cobalt porphyrin and ginkgo biloba extract in a cigarette filter, belonging to a cigarette filter additive and a filter processing technology.
  • the cigarette filter is used to filter substances harmful to the human body in the cigarette smoke, and the retention rate of the tar is about 35%.
  • Existing fiber filter rods are mainly made of acetate tow or polypropylene fiber tow material, and the filtration effect depends on their molecular structure and physicochemical properties. Due to its structural and physicochemical properties, there are deficiencies in terms of filtration effect.
  • Acetate fiber tow filter media has a negative charge, while many particles in cigarette smoke also have a negative charge. There are about 2 ⁇ 10 9 negatively charged particles in the flue gas.
  • the filter Due to the repulsive action of the same charge, the filter mainly intercepts the particulate matter in the cigarette smoke by mechanical blocking and diffusion deposition; due to the lack of reactive groups
  • the partial polarity structure of the fiber tow can only have a certain affinity for the more polar substances containing oxygen atoms in the flue gas compound, such as aldehydes and lactones in the carboxy compounds, and the furan and phenolic substances in the heterocyclic compounds. Therefore, there is a certain selective filtering effect.
  • the adsorption capacity of weakly polar compounds and trace metal elements of harmful carbon radicals, aromatic hydrocarbons and propylene in cigarette smoke is low.
  • the polypropylene fiber tow filter material is a high molecular saturated alkane compound without any negatively charged groups, and its molecular structure is stable and its physicochemical properties are inert. Its hydrophobic group is a non-polar structure, and has no polar structure with high affinity to polar smoke components.
  • the change in pressure drop does not affect the selective filtering of the polar components of the flue gas, so the polarity in the flue gas
  • the molecular molecule retention rate is low, and the molecular interception performance of the low-boiling spicy stimulating gas substance in the cigarette smoke is poor.
  • cigarette smoke contains a variety of harmful components, especially free radicals, condensed aromatic hydrocarbons, and tobacco-specific nitrosamines that may cause cancer.
  • the above-mentioned conventional cigarette filters cannot effectively filter out these substances.
  • a function-enhancing cigarette filter which, by adding a relevant composition to the filter, can selectively remove harmful components in the cigarette smoke on the one hand, and impart a harmless aroma component in the smoke on the other hand.
  • the smooth passage of the cigarette filter is enhanced, the production cost is low, and industrialization is easy.
  • Porphyrins have a unique structure, the molecules have rigidity and a large face, and the periphery The position and orientation of the functional group are controllable, enabling it to have an efficient recognition function for molecular size, traits, functional groups and chiral isomers.
  • it has been used in chromatographic separation analysis, sensors, simulated enzyme analysis, and construction of receptors in the field of analytical chemistry.
  • the stationary phase of porphyrin derivatives has been successfully applied HPLC, CE, etc. Kibbey et al. ( Kibbey CE, Meyerhoff ME.
  • This type of stationary phase is used to pre-enrich carcinogenic PAHs
  • the study is more stable than the fiber-based stationary phase.
  • the good recognition of porphyrins for PAHs is based on the strong ⁇ - ⁇ between PAHs and porphyrins rich in ⁇ electrons. Role, this effect not only has the ⁇ - ⁇ effect of face-to-face, but also the ⁇ - ⁇ effect of face-to-edge ( Chen S, Fetzer JC, Meyerhoff ME. Fresenius J Anal Chem, 2001 (3-4): 385-392. Yutaka S, Masaki M, Junichi O, et al. Anal Sci, 1991, 7(5): 805-806. Mifune M, Shimomura Y, Saito Y, Et al. Bull Chem Soc Jpn, 1998, 71(8): 1825-1829. ).
  • Ginkgo biloba extract has been used as a Chinese herbal medicine for thousands of years in China.
  • the internationally recognized quality index of Ginkgo biloba extract is more than 24% for flavonoids and 6% for lactones.
  • Studies have shown that the main active components of antioxidants in Ginkgo biloba extract are flavonoids and lactones.
  • the substance has no obvious antioxidant effect ( ⁇ et al. The chemical constituents and antioxidant activities of Ginkgo biloba leaves. Chinese natural medicine, 2008, 6(1): 26-29.), the reducing hydroxyl (-OH) functional group contained in the molecule directly exerts an antioxidant effect.
  • Quercetin in flavonoids blocks and terminates the free radical chain reaction chain by acting as a hydrogen atom donor, which can directly scavenge free radicals and hydrogen peroxide, effectively antagonize the damage of free radicals to unsaturated fatty acids, and reduce Lipid peroxide content, while increasing the activity of superoxide dismutase (Li Yuhua et al. The role of Ginkgo biloba extract[J]. Chinese Health, 2008, 16(11): 529.).
  • the structure has stronger antioxidant activity than the dihydric phenol; 3
  • the number of phenolic hydroxyl groups in the molecule and the number of hydrogen bonds that can be formed are positively correlated with the antioxidant activity of the molecule, and are important factors for the strong antioxidant activity of flavonoids (Zhao Jihong et al. Structural factors of antioxidant activity of flavonoids) Journal of North China University of Technology, 2001, 13(1): 36-44.).
  • flavonoids By changing the hydroxy substitution of flavonoids, making flavonoids
  • the electron spin density distribution of the semiquinone radical is more uniform, and the chemical modification increases the number of phenolic hydroxyl groups of the flavonoid compound and the number of intramolecular hydrogen bonds to increase the antioxidant activity of the flavonoid compound.
  • the stationary phase has high selectivity and good separation performance when measuring fused aromatic hydrocarbons and fullerene hydrocarbons.
  • Ginkgo biloba extract has high antioxidant activity.
  • the application of the composition to the cigarette filter can better filter out harmful components and form a function-enhancing cigarette filter.
  • the object of the present invention is to provide a filter for removing harmful substances in cigarette smoke to reduce the harm of smoking to the human body.
  • the cigarette filter of the present invention is obtained by adding a carrier to which a biological composition is adhered to a tow filter rod to form a composite filter.
  • Its biological composition is composed of cobalt porphyrin and ginkgo biloba extract.
  • the invention includes the following:
  • a composite filter comprising a biological composition, characterized in that the tow filter plug of the filter comprises a biological composition which, when the biological composition is adhered to the carrier, is formed during the formation of the tow filter rod The carrier to which the biological composition is adhered is added to the tow filter plug to form.
  • a method of preparing a composite filter comprising a biological composition comprising the steps of:
  • Polycyclic aromatic hydrocarbons generally have characteristic fluorescence excitation spectra and fluorescence emission spectra.
  • the increase in fluorescence intensity of 3,4-benzo[a]pyrene and the red shift of the fluorescence spectrum indicate that 3,4-benzo[a]pyrene interacts with cobalt porphyrin.
  • the binding constant (K) to NNN, NAB, NNK, and NAT is 1.4 ⁇ 10 4 , respectively. 1.1 ⁇ 10 4 , 5.8 ⁇ 10 3 , 3.4 ⁇ 10 3 , ie the binding capacity is NNN, NAB, NNK and NAT, indicating that porphyrins form a new complex with TSNAs, and there is a strong interaction between them. .
  • No. 1 is a cigarette (blank control cigarette) to which no biological composition is added
  • No. 2 is a cigarette to which a biological composition is added (the same below), wherein The mass ratio of the cobalt porphyrin to the ginkgo leaf extract is 1:3;
  • NNK is 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone
  • NNN is N- Nitroso nornicotine
  • NAB is N-nitroso-shamrock
  • NAT is N-nitroso neonicotinine.
  • the toxicity test of the cigarette and the blank control cigarette using the filter of the present invention was carried out, and the results showed that the mutagenicity and toxicity of the cigarette using the filter of the present invention were lower than that of the blank control cigarette.
  • the response of the mice during the test was: smoking No.1 Cigarette mice are more excited and active when they smoke the first ten cigarettes. They are quieter in the future. During the smoking process, the ears, mouth, four toes, and tail of the mice are congested, and the body sweats. Before death, they often appear as chaos and convulsions. In comparison, smoking No.2 Cigarette mice have longer quiet periods, delayed death, stable breathing, and no congestion in the ears, mouth, nose, throat, four toes, and tails. The survival rate and the LD50 and the number of deaths from smoking of the cigarettes using the filter of the present invention were higher than those of the blank control cigarettes, and the smoke toxicity was decreased (Table) 3).
  • mice After the acute toxicity test of passive smoking, the histopathological observation of mice was carried out. The smoking of the blank control cigarette was 100%. The lung tissue and venules of the mice were hyperemia, and the cigarettes using the filter of the present invention only reached 46.7%.
  • the median lethal dose of No.1 tar is 141.42 ⁇ g/ml, No.2 tar
  • the median lethal dose was 213.35 ⁇ g/ml, which was much higher than that of No. 1 cigarette, so the cytotoxicity of the cigarette tar using the filter of the present invention was much lower than that of the blank control cigarette.
  • the tar-induced micronucleus rate of the blank control group was 2.33 ⁇ , and the No.1 group 5.00 ⁇ No.2 group 3.92 ⁇ , compared with the blank control, the positive result was obtained, but There was no significant difference between No.1 and No.2. That is, the cigarette to which the filter of the present invention is applied does not produce new toxic side effects after adding the biological composition, and can reduce the damage to the lung to some extent.
  • Figure 2 is a spectrum diagram of the interaction between porphyrins and TSNAs, (A)(B)(C)(D) NNN, NAB, NNK, NAT interaction spectra, where B-H and B-L represent NNN, NAB, NNK, NAT in cobalt porphyrin The spectral curve of the amount of addition is gradually increased.
  • Figure 3 is a schematic diagram of the structure of a binary composite filter.
  • the binary composite filter of the present invention is composed of a tow filter rod 1 (after the biological composition is adhered to the carrier, uniformly added to the tow filter rod when the tow filter rod is molded), and no biological composition is added.
  • the tow filter rod 2, the inner layer paper 3, the outer layer paper 4 and the like are partially composed, and the main feature thereof is that the carrier to which the biological composition is adhered is uniformly added to the tow filter rod.
  • the present invention is implemented as follows:
  • a certain amount of cobalt porphyrin and ginkgo biloba extract is dissolved in a certain amount of 95% ethanol, a certain amount of polyvinylpyrrolidone is added, and the mixture is thoroughly stirred, and adhered to the carrier in a certain ratio, and then added The amount was uniformly added to the tow filter rod 1 to prepare a binary composite filter.
  • the mass ratio of the cobalt porphyrin and the ginkgo biloba extract in the biological composition is 1:1 to 80, preferably 1:1 to 50, more preferably 1:1 to 30, most preferably 1:1 to 10.
  • a further solution is: the ratio of the biological composition to ethanol is: 1 g biological composition: 10-100 ml ethanol, more preferably 1 g Biological composition: 10-50 ml ethanol, most preferably 1 g biological composition: 10-20 ml ethanol.
  • a further solution is:
  • the mass ratio of the polyvinylpyrrolidone to the biological composition is from 1:1 to 50, preferably from 1:1 to 20, most preferably from 1:1 to 10.
  • a further solution is that the carrier is activated carbon, green plant particles, silicates.
  • a further solution is that the mass of the biological composition is 0.1 ⁇ to 5.0 ⁇ of the mass of the carrier.
  • a still further solution is that the carrier to which the biological composition is adhered added to the tow filter plug is added in an amount of from 3 to 30 mg per branch.
  • a still further solution is that the method of adding the carrier to which the biological composition is adhered to the tow filter plug is to control the amount of the carrier, which is added to the tow filter plug by dropping .
  • the tow filter rod may be a filter rod of a cellulose acetate tow or a polypropylene fiber tow material commonly used in the art, or may be a filter rod of other materials.
  • a further solution is: preparing the binary composite filter, uniformly adding a carrier to which the biological composition is adhered when the tow filter rod is molded, and making the tow filter rod 1 through the inner layer of the paper 3 and not adding The material is used to make a tow filter rod 2, and on the composite filter forming machine, the tow filter rod 1 and the tow filter rod 2 are combined into a binary composite filter through the outer layer of paper 4.
  • the binary composite filter tipping paper is butt-joined with the tobacco portion wrapped with the cigarette paper on the cigarette machine, and the tow filter rod 1 is placed between the tow filter rod 2 and the cigarette shreds.
  • the cobalt porphyrin used in the present invention is purchased from ALFA and has a content of 96%.
  • Ginkgo biloba extract is purchased from Ningbo Lihua Pharmaceutical Co., Ltd., containing flavonoids. 24%, lactone 6%.
  • the technical scheme for preparing the binary composite filter described above and the specific process steps for preparing the binary composite filter described below are also applicable to the preparation of a multi-component composite filter composed of a plurality of filter rods.
  • Sensory evaluation, detection of harmful components of cigarette smoke and biological test the results show that: the cigarettes using the filter of the invention, the smoke is coordinated, the irritation is relieved, the taste is comfortable; the release effect of harmful components of flue gas is reduced and biology
  • the test tests all achieved the effects described in the Summary of the Invention.

Abstract

本发明涉及一种含有生物组合物的复合滤嘴，该滤嘴的丝束滤棒中包含一种生物组合物，其通过将该生物组合物粘附于载体后，在丝束滤棒成型时，将粘附了生物组合物的载体添加到丝束滤棒中形成。其中生物组合物由钴卟啉和银杏叶提取物组成，其质量比例=1∶1~80。采用该滤嘴不仅可以明显降低卷烟烟气中的自由基、苯并[a]芘、烟草特有亚硝胺等有害成分的释放量，而且可使卷烟的急性毒性、亚慢性毒性、细胞毒性及致突变性均低于对照卷烟，同时对卷烟的吸食品质无不良影响。

Description

一种含有生物组合物的复合滤嘴 技术领域
本发明涉及一种含有生物组合物的复合滤嘴，特别是钴卟啉和银杏叶提取物形成的生物组合物在卷烟滤嘴中的应用，属于卷烟滤嘴添加剂及滤嘴加工技术。
背景技术
卷烟滤嘴用于过滤卷烟烟气中对人体有害的物质，对焦油的截留率在35%左右。现有纤维滤棒主要是由醋酸纤维丝束或聚丙烯纤维丝束材料制成，其过滤效果取决于它们的分子结构和物理化学性质。由于受其结构和物理化学性质的限制，就过滤效果而言，均存在不足之处，醋酸纤维丝束滤材带有负电荷，而卷烟烟气中许多颗粒也带有负电荷，每毫升卷烟烟气中约有2×109个负电荷颗粒，由于相同电荷的排斥作用，这种滤嘴主要以机械阻挡和扩散沉积截留卷烟烟气中的粒相物质；由于受缺少活性基团的限制，纤维丝束含有的部分极性结构只能对烟气化合物中含有氧原子的极性较强的物质如羧基化合物中醛酮及内酯，杂环化合物中呋喃和酚类物质等有一定亲和力，从而有一定的选择性过滤作用。而对卷烟烟气中有害的碳自由基、芳香烃及丙烯类的弱极性化合物和微量金属元素吸附能力较低。聚丙烯纤维丝束滤材是高分子的饱和烷烃化合物，不带任何负电荷基团，其分子结构稳定、物理化学性质表现为惰性。其疏水基团是非极性结构，没有与极性烟气成分有高度亲和力的极性结构，压降的变化不影响对烟气极性组分的选择性过滤作用，因此对烟气中极性物质分子截留率低，对卷烟烟气中低沸点的辛辣刺激杂气物质分子截留性能差。
众所周知，卷烟烟气中含有多种有害成分，尤其是可能致癌的自由基、稠环芳烃、烟草特有亚硝胺等，上述的传统卷烟滤嘴不能有效地滤除这些物质。
所以需要一种功能加强的卷烟滤嘴，通过在滤嘴中添加相关的组合物，一方面能选择性地去除卷烟烟气中的有害成分，另一方面能让烟气中的无害香味成分顺利通过，同时要求这种功能加强的卷烟滤嘴制作方便、生产成本低以及易于实现工业化。
卟啉类化合物具有独特结构，分子具有刚性和较大表面（ face ） ，周边（ edge ） 功能团的位置和方向可控，使其具有高效识别功能，可进行分子大小、性状、功能团及手性异构体的识别。目前，在分析化学领域中已用于色谱分离分析、传感器、模拟酶分析及构筑受体等方面。在色谱分析中，卟啉类衍生物的固定相已成功应用于 HPLC 、 CE 等。 Kibbey 等（ Kibbey CE, Meyerhoff ME.Anal Chem,1993,65(17): 2189-2196. ）首次合成了卟啉类固定相 H2CPTPP 、 SnCPTPP 、 InCPTPP ， 并成功用于 PAHs 的分离。此后 ， 又制备了 ProP-silica 固定相（ Xiao J,Kibbey CE,Coutant DE, et al. J Liq Chromatogr Rel Technol,1996,19:2901- 2932. ）及 MProP-silica 固定相（ Chen S, Meyerhoff ME.Anal Chem,1998,70(13): 2523- 2529. ） , 获得了更好的分子形状选择性。这类固定相用于预富集致癌性 PAHs 的研究，比纤维类固定相更稳定。卟啉类化合物对于 PAHs 的良好识别性，其原理是利用富含 π 电子的 PAHs 与卟啉类化合物间强烈的 π-π 作用，这种作用不仅有 face-to-face 的 π-π 作用，还有 face-to-edge 的 π-π 作用（ Chen S, Fetzer JC,Meyerhoff ME. Fresenius J Anal Chem, 2001(3-4):385-392.Yutaka S, Masaki M,Junichi O,et al.Anal Sci,1991, 7(5):805-806. Mifune M, Shimomura Y, Saito Y, et al.Bull Chem Soc Jpn,1998,71(8): 1825- 1829. ）。
银杏叶提取物作为中草药在中国已有几千年的历史。国际上一般公认的银杏叶提取物的质量指标为含黄酮类24%以上、内酯类6%以上，研究表明，银杏叶提取物中抗氧化作用的主要活性成分为黄酮类物质，内酯类物质无明显抗氧化作用（牟玲丽等.银杏叶的化学成分及其抗氧化活性.中国天然药物, 2008, 6(1): 26-29.），其分子中含有的还原性羟基（-OH）功能基团可直接发挥抗氧化作用。黄酮类中的槲皮素通过起一种氢原子供体的作用阻断和终止自由基连锁反应链，可直接清除自由基和过氧化氢，有效地拮抗自由基对不饱和脂肪酸的破坏，降低脂质过氧化物含量，同时提高过氧化物歧化酶的活性（李玉华等. 银杏叶提取物的作用[J]. 中国保健,2008,16(11):529.）。
化学发光法测定了黄酮类清除O2·的效果，对其结构与清除O2·活力之间的关系研究表明， 4' -OH 和2，3位双键是清除O2·的主要活性部位(邹耀红等. 黄酮类化合物清除活性氧自由基性能的研究[J].常熟高专学报，2001,15(2):47-50.), 3' ， 4' - 邻二羟基是其具有清除自由基活性的关键结构,其他位上的羟基起一定作用（胡春等. 用化学发光法研究黄酮化合物对 O2· 和 ·0H 的 清除. 无锡轻工大学学报, 1996, 15(3):194-198.）。
结构化学和量子化学半经验计算方法研究了黄酮类化合物抗氧化活性的结构因素，研究结果表明： ① 在分子内形成半醌式自由基时所需能量△ HOF 较低，其形成的自由基较稳定，从而具有较高的抗氧化活性； ② 电子自旋密度分布的均匀性，是抗氧化性较强的重要原因，含邻二酚羟基的 黄酮 形成的半醌式自由基，电子自旋密度分布比较均匀，而且分子中半醌式基团与邻位酚羟基形成分子内氢键使体系能位降低，因而黄酮类化合物中具有邻二羟基酚的结构比含间二羟基酚的抗氧化活性强；③ 分子中的酚羟基数目和可以形成氢键的数目与分子的抗氧化活性呈正相关，是黄酮类化合物具有强抗氧化活性的重要因素 ( 赵继红等 . 黄酮类化合物抗氧化活性的结构因素 . 北方工业大学学报 ,2001,13(1):36-44.) 。通过改变 黄酮 的羟基取代、使 黄酮 半醌式自由基的电子自旋密度分布更加均匀、用化学修饰增加黄酮类化合物的酚羟基数量以及形成分子内氢键的数目等途径可提高黄酮类化合物抗氧化活性。
根据卟啉类化合物具有独特结构特点，作为 HPLC 固定相测定稠环芳烃、富勒烃等时有很高选择性、较好分离性能；银杏叶提取物具有较高的抗氧化活性。将其组合物应用于卷烟滤嘴中，可以较好地滤除有害成分，形成功能加强的卷烟滤嘴。
 技术问题
本发明的目的在于提供一种对卷烟烟气中有害物质截留效果好的滤嘴，以减轻吸烟对人体的危害。
技术解决方案
本发明的卷烟滤嘴是将粘附了生物组合物的载体添加到丝束滤棒上，制成复合滤嘴。其生物组合物是钴卟啉和银杏叶提取物组成的。
本发明包括以下内容：
1. 一种含有生物组合物的复合滤嘴，其特征在于该滤嘴的丝束滤棒中包含一种生物组合物，其通过将该生物组合物粘附于载体后，在丝束滤棒成型时，将粘附了生物组合物的载体添加到丝束滤棒中形成。
2. 制备含有生物组合物的复合滤嘴的方法，该方法包括以下步骤：
（1）制备钴卟啉、银杏叶提取物生物组合物，然后将该组合物溶解于乙醇中，得到生物组合物的乙醇溶液，在溶液中加入聚乙烯吡咯烷酮，充分搅匀；
（2）将步骤（1）得到的混合物粘附于载体上，
（3）在丝束滤棒成型时均匀添加粘附了生物组合物的载体，
（4）然后使用内层盘纸分别卷制添加了粘附生物组合物的载体的丝束滤棒和不添加生物组合物的丝束滤棒，
（5）最后，在复合滤嘴成型机上，通过外层盘纸将丝束滤棒和丝束滤棒复合成复合滤嘴。
3. 上述的含有生物组合物的复合滤嘴在卷烟中的应用。
 有益效果
并进行了相关的测试如下：
a. 荧光猝灭法测定钴卟啉与3,4-苯并[a]芘相互作用
多环芳烃一般都具有特征的荧光激发光谱和荧光发射光谱，我们通过荧光猝灭法测定了钴卟啉与3,4-苯并[a]芘作用大小，结果表明：随着钴卟啉浓度的增加，3,4-苯并[a]芘的荧光强度下降，荧光光谱发生红移（参见附图1），说明3,4-苯并[a]芘与钴卟啉发生了相互作用。
b. 紫外分光光度法测定钴卟啉与烟草特有亚硝胺相互作用
我们又根据卟啉化合物有紫外吸收，并且在 413nm 附近有特征吸收峰的特点，通过紫外分光光度法测定了钴卟啉与烟草特有亚硝胺（ TSNAs ， NNN 、 NAB 、 NNK 、 NAT ）作用大小，结果表明：随着 TSNAs 的加入，卟啉类物质的特征吸收峰（ 413nm ）强度降低，且随着加入的 TSNAs 浓度增加，其强度逐渐降低，并出现了新的复合物特征峰（ 438 nm ），其峰的强度随着加入的 TSNAs 浓度增加而逐渐增加，紫外光谱发生红移（参见 附 图 2 ），与 NNN 、 NAB 、 NNK 、 NAT 的结合常数（ K ）分别为 1.4×104 、 1.1×104 、 5.8×103 、 3.4×103 ，即结合能力大小依次为 NNN 、 NAB 、 NNK 、 NAT ，表明卟啉类与 TSNAs 形成了新的复合物，它们之间存在较强的作用。
c. 卷烟烟气中自由基、3,4-苯并[a]芘、烟草特有亚硝胺释放量测定
测定了空白对照卷烟与应用本发明滤嘴的卷烟 烟气中自由基、3,4-苯并[a]芘、烟草特有亚硝胺释放量并计算滤除效率，结果见表1，从表中可以看出，与空白对照卷烟相比，应用本发明滤嘴卷烟的烟气中上述有害成分明显降低，降低率最高可达66.89%，最低达到30.36%。
表1 卷烟烟气有害成分测定结果及滤嘴效率
气相自由基
（相对单位）		 固相自由基
（相对单位）		 3,4- 苯并 [a] 芘 (ng/ 支 ) NNK
(ng/ 支 )		 NNN
(ng/ 支 )		 NAB
(ng/ 支 )		 NAT
(ng/ 支 )
No.1 8.73 8.31 14.50 5.50 9.09 1.07 11.74
No.2 6.08 5.60 9.80 3.30 3.01 0.43 6.53
降低率（ % ） 30.36 32.61 32.41 40.00 66.89 59.81 44.38
注：No.1为未添加生物组合物的卷烟（空白对照卷烟）， No.2添加了生物组合物的卷烟（下同）,其中 钴卟啉与银杏叶提取物的质量比为1：3；
NNK 为 4- （甲基亚硝胺基） -1- （ 3- 吡啶基） -1- 丁酮， NNN 为 N- 亚硝基降烟碱， NAB 为 N- 亚硝基假木 贼碱， NAT 为 N- 亚硝基新烟碱 。
d. 生物学测试
进行了应用本发明滤嘴的卷烟与空白对照卷烟的毒性检测，结果表明：应用本发明滤嘴的卷烟的致突变性和毒性均低于空白对照卷烟。
  1. （a） 鼠伤寒沙门氏菌 / 哺乳动物微粒体酶试验（ Ames 试验）
Ames 试验结果见表 2 ，从表中可以看出在 100-500 之间的 3 个剂量上均有具有抑制作用，致突变性减小。
表 2 Ames 试验掺入法样品致突变检测结果（ X±SD ） (+S9)
组别 受试焦油剂量（ μg/ 皿 ) 菌落回复数 ( 个 / 皿 ) 抑制率 (%)
No.1 100 64.8±11.8
300 83.2±12.0
500 107.2±9.7
No.2 100 42.8±10.0 49.66
300 53.2±9.8 47.85
500 70.4±10.5 42.45
溶剂 +S9 20.5±2.4
（ b ）小鼠被动吸烟急性毒性试验及肺病理组织学观察
小鼠在试验过程中的反应表现为：吸食 No.1 卷烟的小鼠，在吸前十支卷烟时，较为兴奋、活跃，以后较为安静，吸烟过程中小鼠的耳、嘴、四趾、尾充血，身体出汗，死亡前多表现为乱窜、抽搐；相比较而言，吸食 No.2 卷烟的小鼠，安静的时间较长、死亡时间延迟、呼吸平稳，并且耳、嘴、鼻、喉、四趾、尾的充血没有空白卷烟明显。吸食应用本发明滤嘴的卷烟的存活率和半数致死吸烟量及开始死亡吸烟量均高于空白对照卷烟，其烟气毒性降低（表 3 ）。
表3 被动吸烟小鼠急性毒性结果
组别 实验小鼠总数（只） 存活率 (%) 半数致死吸烟量 ( 支 ) 开始死亡吸烟量 ( 支 )
No.1 60 33.3 49 35
No.2 60 40.0 54 44
被动吸烟急性毒性试验结束后，进行了小鼠病理组织学观察，吸食空白对照卷烟的是 100% 的小鼠肺组织和小静脉充血，而吸食应用本发明滤嘴的卷烟只达到 46.7% 。
  1. （b） 中性红细胞毒性试验
从表 4 可以看出， No.1 焦油半数致死量为 141.42 μg/ml ， No.2 焦油 半数致死量为 213.35μg/ml ，远远高于 No.1 卷烟，因此应用本发明滤嘴的卷烟焦油的细胞毒性远低于空白对照卷烟。
表4 中性红细胞毒性试验结果
组别 半数细胞致死量 (LD50,μg/ml)
No.1 141.42
No.2 213.35
（ d ）亚慢性毒性试验
大鼠被动吸烟 30 天后，分别用天平称重，发现包括阴性对照在内的三组之间没有明显变化，均未达到显著性水平。之后处死大鼠，取大鼠的呼吸道及肺，进行了病理学观察，发现 No.1 卷烟组大鼠重度周围型肺气肿，而 No.2 卷烟组大鼠轻度周围型肺气肿。将取完血液的大鼠的胸骨髓取出，进行了微核试验，结果见表 5 ，从表中可看出，空白对照组焦油诱发微核率为 2.33 ‰， No.1 组 5.00 ‰ No.2 组 3.92 ‰，与空白对照相比，达到阳性结果，但是 No.1 和 No.2 之间无显著性差异。即应用本发明滤嘴的卷烟添加生物组合物后没有产生新的毒副作用，能够在一定程度上减轻对肺的损伤。
表5 大鼠骨髓嗜多染性红细胞微核发生率
组别 观察细胞数（个） 微核数（个） 微核率 ( ‰ )
空白组（阴性对照） 12000 28 2.33
No.1 12000 60 5.00
No.2 12000 47 3.92
附图说明
下列附图描述了本发明相关测试的实验结果及滤嘴结构示意图
图 1 为 卟啉类化合物与苯并芘相互作用光谱图， Ksv = (5.27 ± 0.31) × 105 。
图 2 为 卟啉类化合物与 TSNAs 相互作用光谱图，（ A ）（ B ）（ C ）（ D ）分别为与 NNN 、 NAB 、 NNK 、 NAT 相互作用光谱图，其中 B-H 及 B-L 表示 钴卟啉中 NNN 、 NAB 、 NNK 、 NAT 的加入量逐渐增加时的光谱曲线。
图 3 为二元复合滤嘴结构示意图。
 本发明的最佳实施方式
下面结合附图3对本发明给予更详细说明。
本发明所述二元复合滤嘴由丝束滤棒1（是将生物组合物粘附于载体后，在丝束滤棒成型时均匀添加于丝束滤棒中）、未添加生物组合物的丝束滤棒2、内层盘纸3、外层盘纸4等部分组成，其主要特征是将粘附了生物组合物的载体均匀添加到丝束滤棒上。
本发明是这样实现的：
将一定量的钴卟啉和银杏叶提取物溶解于一定量的95%的乙醇中，加入一定量的聚乙烯吡咯烷酮，充分搅匀，将其以一定比例粘附于载体上，再以一定添加量均匀地添加到丝束滤棒1中，制作二元复合滤嘴。
更进 一步的方案是：所述的生物组合物中钴卟啉和银杏叶提取物的质量比例为 1:1~80 ，优选 1∶1~50 ，更优选 1∶1~30 ，最优选 1∶1~10 。
更进一步的方案是：生物组合物与乙醇的比例为： 1g 生物组合物 :10-100ml 乙醇，更优选 1g 生物组合物 :10-50ml 乙醇，最优选 1g 生物组合物 :10-20ml 乙醇。
更进一步的方案是： 聚乙烯吡咯烷酮与生物组合物的质量比为：1：1～50，优选1：1～20，最优选1：1～10。
更进一步的方案是：所述载体为活性炭、绿色植物颗粒、硅酸盐类。
更进一步的方案是：所述的生物组合物的质量为载体质量的 0.1‰~5.0‰ 。
更进一步的方案是：所述添加到丝束滤棒中的粘附了生物组合物的载体的添加量为 3-30mg/ 支 。
更进一步的方案是：所述将粘附了生物组合物的载体添加到丝束滤棒中的方法为控制载体的量，通过下落加到丝束滤棒中 。
更进一步的方案是：所述的将丝束滤棒可以是本领域常用的醋酸纤维丝束或聚丙烯纤维丝束材料的滤棒，也可以是其他材料的滤棒。
更进一步的方案是：制作所述的二元复合滤嘴，在丝束滤棒成型时均匀添加粘附了生物组合物的载体，通过内层盘纸3，制作丝束滤棒1和不添加物质制作丝束滤棒2，在复合滤嘴成型机上，通过外层盘纸4将丝束滤棒1和丝束滤棒2复合成二元复合滤嘴。
最后，在卷烟机上将二元复合滤嘴用水松纸与用卷烟盘纸包裹的烟丝部分对接成一体，并将丝束滤棒1置于丝束滤棒2和卷烟烟丝之间。
本发明所使用的 钴卟啉购自 ALFA 、含量 96% ，银杏叶提取物购自宁波立华制药有限公司，含黄酮 24% 、内酯 6% 。
以上描述的制备二元复合滤嘴的的技术方案和以下描述制备二元复合滤嘴的具体工艺步骤，同样适用于制备多个滤棒复合而成的多元复合滤嘴。
本发明的实施方式
实施例：称取5.0g钴卟啉、15.0g银杏叶提取物，将其溶解于400ml的95%乙醇中，加入5g聚乙烯吡咯烷酮，充分搅拌均匀后，粘附于40kg的载体上，再将该载体以6mg/支的量添加到丝束滤棒中，制作二元复合滤嘴，然后卷烟。进行感官评吸、卷烟烟气有害成分检测及生物学试验检测，结果表明:应用本发明滤嘴的卷烟，烟香协调，刺激性减轻，口感舒适；烟气有害成分释放量降低效果和生物学试验检测均达到了发明内容中描述的效果。

Claims (1)

1. 一种含有生物组合物的复合滤嘴，其特征在于该滤嘴的丝束滤棒中包含一种生物组合物，其通过将该生物组合物粘附于载体后，在丝束滤棒成型时，将粘附了生物组合物的载体添加到丝束滤棒中。
2. 根据权利要求 1 所述的含有生物组合物的复合滤嘴，其特征在于该复合滤嘴是二元复合滤嘴，其通过将含有生物组合物的丝束滤棒与未添加生物组合物的另一段丝束滤棒复合而成。
3. 根据权利要求 1 所述的含有生物组合物的复合滤嘴，其特征在于所述生物组合物由钴卟啉和银杏叶提取物组成。
4. 根据权利要求 3 所述的含有生物组合物的复合滤嘴，其特征在于所述钴卟啉和银杏叶提取物的质量比例为 1∶1~80 ，生物组合物质量为载体质量的 0.1‰~5.0‰ ，粘附了生物组合物的载体在丝束滤棒中的添加量为 3~30mg/ 支。
5. 根据权利要求 4 所述的含有生物组合物的复合滤嘴，其特征在于该生物组合物中钴卟啉和银杏叶提取物的质量比例为 1∶1~50 。
6. 根据权利要求 5 所述的含有生物组合物的复合滤嘴，其特征在于该生物组合物中钴卟啉和银杏叶提取物的质量比例为 1∶1~10 。
7. 制备含有生物组合物的复合滤嘴的方法，该方法包括以下步骤：
（1） 制备钴卟啉、银杏叶提取物生物组合物，然后将该组合物溶解于乙醇中，得到生物组合物的乙醇溶液，在溶液中加入聚乙烯吡咯烷酮，充分搅匀；
（2） 将步骤（1）得到的混合物粘附于载体上；
（3） 在丝束滤棒成型时均匀添加粘附了生物组合物的载体；
（4） 然后使用内层盘纸分别卷制添加了粘附生物组合物的载体的丝束滤棒和不添加生物组合物的丝束滤棒；
（5） 最后，在复合滤嘴成型机上，通过外层盘纸将丝束滤棒和丝束滤棒复合成复合滤嘴。
8. 根据权利要求 7 所述的复合滤嘴的制备方法，其特征在于所述生物组合物由钴卟啉和银杏叶提取物组成，其质量比例为 1∶1~80 ，生物组合物质量为载体质量的 0.1‰~5.0‰ ，粘附了生物组合物的载体在丝束滤棒中的添加量为 3~30mg/ 支。
9. 根据权利要求 8 所述的复合滤嘴的制备方法，其特征在于该生物组合物中钴卟啉和银杏叶提取物组成的质量比例为 1∶1~10 。
10. 权利要求 1 － 9 所述的含有生物组合物的复合滤嘴在卷烟中的应用。
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CN101708072A (zh) 2010-05-19
EP2517584B1 (en) 2015-09-02

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