JP2006061142A - Filter for eliminating active oxygen and method for eliminating active oxygen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a filter for eliminating active oxygen and to provide a method for eliminating active oxygen. <P>SOLUTION: In the filter for eliminating active oxygen, a filter substrate comprises a water-soluble chitosan-manganese complex as an oxygen radical remover. When the filter for eliminating the active oxygen is used as a filter pipe for eliminating the active oxygen, oxygen radical can be removed by feeding water in a prescribed amount immediately before smoking to a filter-containing section containing the water-soluble chitosan-manganese complex. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a filter for removing active oxygen and a method for removing active oxygen. More particularly, the present invention relates to an active oxygen removing filter and an active oxygen removing method that are particularly useful as a tobacco filter.

It is a well-known fact that cigarette smoke contains various harmful substances such as tar, nicotine, benzpyrene, and amines. In addition, oxygen radicals generated during tobacco smoking cause various damages to cellular components such as proteins and membrane components, as well as DNA that constitutes genes. It is considered to be one of the main factors that cause arteriosclerosis and blur, including diseases and cerebrovascular diseases.
Upon smoking of tobacco is estimated to include suction once per 10 ¹⁴ oxygen radicals. It has been found that cancers such as pharyngeal cancer, esophageal cancer, and lung cancer caused by smoking are often caused by the above-mentioned various harmful substances contained in cigarette smoke, particularly oxygen radicals generated in large quantities.

  Conventionally, in order to remove various harmful substances in tobacco smoke, filters having various constituents have been provided. Many of these are intended to physically adsorb and remove harmful substances such as tar, and it can be said that they do not have sufficient functions to remove oxygen radicals, which is considered to be one of the main factors. For example, various pipes with increased activated carbon capacity are commercially available, all of which have the ability to adsorb and remove tars and harmful substances and have a certain degree of decomposition ability. It is expected. However, conventional conventional filters cannot remove oxygen radicals (for example, Patent Documents 1, 2, and 3). In addition, disposable water pipes have been put on the market, but such water pipes have little ability to remove oxygen radicals. Furthermore, pipes containing enzymes and vitamins are also known, but the enzymes and vitamins contained in these pipes do not have the ability to remove oxygen radicals. However, superoxide dismutase (SOD) and catalase (CAT) are known as enzymes having the ability to remove oxygen radicals, but these enzymes are unstable and are used for removing activated oxygen. When used as a filter, there is a big problem in stability, and it must be said that practical use is difficult.

  Various filter materials for reducing various harmful substances in tobacco smoke have been proposed (for example, Patent Document 4). It must be said that none of these filter materials has sufficient performance to remove oxygen radicals.

Therefore, development of a filter for removing active oxygen capable of removing particularly harmful oxygen radicals from tobacco smoke is demanded.
JP-A-5-23158 JP-A-6-343448 JP 7-39361 A JP 2000-236864 A

  In order to solve the above problems, the present inventor has eagerly studied the influence of oxygen radicals on cells and a filter material that can effectively eliminate harmful oxygen radicals, and further stabilizes it when used in tobacco filters. As a result of examining the ability to scavenge oxygen radicals and the ability to eliminate oxygen radicals during smoking, it was found that a filter material containing a water-soluble chitosan manganese complex can effectively and efficiently remove such oxygen radicals, and the present invention has been completed. .

  This invention removes harmful oxygen radicals, particularly from tobacco smoke, lowering the carcinogenicity of tobacco, preventing aging of blood vessels, arteriosclerosis including heart disease and cerebrovascular disease, blur, etc. An object of the present invention is to provide a filter for removing active oxygen and a method for removing active oxygen that can prevent diseases and provide peace of mind to the health of smokers and those around them.

  In order to achieve the above object, the present invention provides an activated oxygen removal filter comprising a filter base material containing a water-soluble chitosan manganese complex as an oxygen radical removing agent.

As a preferred embodiment of the present invention, the water-soluble chitosan manganese complex further includes a predetermined amount of water, more preferably about 0.3 to 1.0 ml / filter. There is provided a filter for removing activated oxygen. As another preferred embodiment, there is provided an activated oxygen removing filter comprising a water-soluble chitosan manganese complex at a ratio of 0.1 μg to 1 mg / filter volume (cm ³ ).

  As another embodiment of the present invention, there is provided an activated oxygen removing filter pipe comprising an activated oxygen removing filter-containing section including the activated oxygen removing filter and a moisture-containing section.

  As another embodiment, the present invention provides an activity comprising removing oxygen radicals by supplying a predetermined amount of water to the water-soluble chitosan manganese complex portion of the activated oxygen removal filter portion immediately before smoking. A method for removing oxygenated oxygen is provided.

  The activated oxygen removing filter according to the present invention is characterized in that the filter base material contains a water-soluble chitosan manganese complex as an oxygen radical removing agent. Further, the activated oxygen removing filter of the present invention is further provided with a predetermined amount of moisture.

  As a filter substrate that can be used in the activated oxygen removal filter of the present invention, any substrate that is generally used as a filter substrate can be used. For example, cellulose, Various natural or synthetic fibers such as polypropylene, polyamide, acetate, polystyrene, and polyvinyl alcohol can be used. A desirable base material is good in water retention.

The water-soluble chitosan manganese complex that can be used in the activated oxygen removal filter of the present invention is, for example, a high molecular weight polymer composed of chitosan oligosaccharide composed of two or more glucosamines that constitute chitosan, It is preferable that one manganese is bonded to each glucosamine to form a complex. The number of constituent sugar chitosans is generally 2-6, preferably 3-5, and more preferably 4 chitosan oligosaccharides.
The water-soluble chitosan manganese complex can be produced by a method known in the technical field. For example, after suspending chitosan in water and adding an aqueous manganese acetate solution with stirring to this, the precipitate obtained by stirring and reacting for a predetermined time is collected by filtration, washed thoroughly with distilled water, and washed with saturated saline. It can be produced by thoroughly washing again with distilled water. The obtained precipitate is suspended in distilled water and neutralized with acetic acid, hydrochloric acid, sulfuric acid or fatty acid, so that it becomes water-soluble. Therefore, it can be stored by adding ethanol or lyophilizing.

The amount of the water-soluble chitosan manganese complex used in the present invention is 0.1 μg to 1 mg / filter volume (cm ³ ), preferably 1 μg to 20 μg / filter volume (cm ³ ).

  The filter of the present invention is preferably stored in a solid phase state until use, and converted to an aqueous phase for use to optimize the reaction. However, it is possible to coexist. In addition, the water-soluble chitosan manganese complex is stable at 40 ° C. for 3 years or more, and can sufficiently remove most of the stored oxygen radicals when used. Furthermore, when the filter of the present invention is used, other harmful substances such as tar, nicotine, benzpyrene, amines and the like can also be dissolved and removed in the aqueous phase. In addition, the filter may contain a compound for removing tars, such as activated carbon.

  The filter according to the present invention preferably removes oxygen radicals by supplying water to a portion containing a water-soluble chitosan manganese complex from a filter portion containing water immediately before smoking. As a result, the water-soluble chitosan manganese complex is dissolved in water, and oxygen radicals can be efficiently erased.

  Therefore, when the filter of the present invention is applied to a smoking device such as a pipe, it is preferable that the moisture is supplied from the portion containing moisture to the portion containing the water-soluble chitosan manganese complex immediately before smoking. In addition, the filter can be attached to a tobacco pipe or directly attached to a tobacco, or can be used by supplying moisture before use. Thus, the filter of the present invention can be used as an active oxygen removing filter pipe attached to a tobacco filter. The filter of the present invention can be used, for example, as an active oxygen removing filter pipe having an embodiment shown in the accompanying drawings.

  The filter of the present invention can also be attached to a mask or the like, so that it can be used to eliminate or reduce the harm caused by tobacco smoke of passive smokers. Furthermore, this filter can be used for removing oxygen radicals contained in various smokes by attaching to a filter such as an air cleaner, a vacuum cleaner, an air conditioner, etc.

Hereinafter, the present invention will be described in more detail with reference to experimental examples and examples. However, the present examples do not limit the present invention in any way.
(Experimental materials and experimental methods)
As the oxygen radical scavenging compound, a water-soluble chitosan manganese complex, which is a manganese complex in which glucosamine as a constituent sugar is composed of two or more oligosaccharides, was used. This water-soluble chitosan manganese complex can be produced, for example, by the method described in the following examples.
The measurement of the oxygen radical was performed based on the method of Nakayama et al. (Carcinogenesis, 4,765-769, 1983). That is, tobacco smoke was drawn with an aspirator, and oxygen radicals were trapped in 6 ml of dimethylsulfoxide solution. To this was added 3 ml of 100 mM sodium phosphate buffer (pH 7, 4) containing 50 μM nitroblue tetrazolium (NBT), 10 μM EDTA and 0.06% Triton X-100. After mixing well, absorption at 560 nm was measured, and the amount of oxygen radicals was calculated from a calibration curve. As a control, a solution to which NBT was not added was used.

(Experiment 1)
A pipe (1) in which a water-soluble chitosan manganese complex is fixed to a filter having the structure shown in FIG. 1 invented in order to efficiently eliminate oxygen radicals generated from tobacco smoke, and a filter containing a certain amount of water is attached to the water phase. ) And a pipe (2) fitted with a moisture-free filter.
In FIG. 1, (a) of the filter compartment containing 1 mg of the water-soluble chitosan manganese complex is common to the pipe (1) and the pipe (2). In addition, in (a) part, 50 mg of activated carbon was included, and tar was removed. Measurement of oxygen radicals in the smoke was performed according to the method of Nakayama et al. (Gann, 75, 95-98, 1984). That is, after sucking tobacco smoke with an aspirator, the amount of oxygen radicals dissolved in the aqueous solution was measured. As a result, as shown in Table 1, the removal rate of oxygen radicals in the pipe (1) was almost complete at 95% or more, whereas it was only 5 to 15% in the pipe (2). . Thus, the high oxygen radical removal effect was confirmed by immobilizing water-soluble chitosan manganese complex on a filter and adding water just before smoking.

(Experiment 2)
It is well known that cigarette smoke contains a variety of carcinogens such as benzpyrene, and the risk of lung cancer increases when chronic inflammatory stimuli are applied. Among them, oxygen radicals that are generated in large amounts are also known to be a direct factor of cell cancer. Oxygen radicals generated by tobacco smoke cause cleavage of DNA in cells (Nature 314, 462-464: 1985), and after DNA is separated from cells by an alkaline elution method, the frequency of DNA cleavage can be measured. Therefore, the oxygen radical scavenging ability of the filter according to the present invention was examined by measuring the protection rate against DNA cleavage of cells. As a result, when the water-soluble chitosan manganese complex is contained in the filter according to the present invention, as shown in FIG. 2, most of the DNA cleavage is protected as compared with the filter not containing this. It has been found. Note that SOD and catalase (CAT) were used as positive substances, and water-soluble chitosan and heat-treated SOD were used as negative substances.

1.79 g of shellfish-derived chitosan was suspended in 200 ml of water, and an aqueous solution containing 0.613 g of manganese acetate was added thereto with stirring, followed by further stirring for 60 minutes for reaction. In the reaction, the amount of manganese in the supernatant of the reaction solution was measured (ICP emission spectrophotometer (SPS7000A, Seiko Denshi Kogyo, Chiba)) to determine the end point. The insoluble part was collected by filtration and washed thoroughly with water. When this insoluble material was suspended in a saturated saline solution, manganese was not present in the supernatant. From this, it was confirmed that this insoluble matter was a chitosan manganese complex. Yield 227g.
The chitosan manganese complex thus obtained was suspended in 100 ml of water, and 0.65 g of acetic acid was added to completely dissolve it. This solution was freeze-dried to prepare a water-soluble chitosan manganese complex. Yield 2.30 g, manganese content 3.2%.

The oxygen radical scavenging ability is determined by a cytochrome c reduction method in an oxygen radical generating system by the xanthine-xanthine oxidase method [McCord, JM and Fridich, I (1969) J Biol Chem. , 244: 6049-6055)]. That is, 500 μl of phosphate buffer (300 mM, pH 7.8), 500 μl of xanthine aqueous solution (0.3 mM), 1000 μl of water, 500 μl of cytochrome c (60 μM), and 200 μl of 10 ⁻⁸ M xanthine oxidase are added to 300 μl of specimen. Then, the time change of the absorbance at 550 nm was measured. The final concentration (IC ₅₀ ) of the sample that inhibits this change in absorbance by 50% is indicated by the concentration of the sample, and is defined as the ability to scavenge oxygen radicals. The results (IC ₅₀ ) by this method are as shown in Table 2.

As shown in FIG. 3, the filter of the present example has a water-soluble chitosan manganese complex in which the main body 1 includes a filter compartment 3 containing moisture and a water-soluble chitosan manganese complex 1 mg / cm ³ adjacent to the filter compartment 3. Oxygen in the smoke entering from the smoke inflow section when moisture is transferred from the filter section 3 to the filter section 2 by suction from the suction section 5 comprising the filter section 2 or blown out from the end 4 of the filter section 3 In this type of filter, radicals are eliminated in the filter section 2 and other harmful substances in the smoke are dissolved and removed in the aqueous phases of both the filter section 3 and the filter section 2.

  As shown in FIG. 4, the filter of the present embodiment includes a tubular pipe body 9 having a cigarette attachment portion 12 for fitting the cigarette 19, a moisture-containing filter section 21 adjacent to the tobacco attachment portion 12, and It consists of a water-soluble chitosan manganese complex-containing filter compartment 20 provided on the side opposite to the tobacco attachment portion 12. A partition wall 22 is provided between the water-containing filter compartment 21 and the water-soluble chitosan manganese complex-containing filter compartment 20, and a suction part 34 is provided on the opposite side of the partition wall 22. In use of this filter, the water-containing chitosan manganese complex-containing filter passes through the holes 16 in the partition wall portion 22 by sucking or blowing out from the tobacco attachment portion 12 through the suction end 13 in use. When the smoker sucks in the cigarette fitted in the cigarette mounting portion 12 from the suction end, the oxygen radicals in the cigarette smoke are erased, and other harmful substances in the tobacco smoke, such as tar and nicotine. Benzpyrene and amines are removed by the water in the filter compartment 21 and the filter member in the filter compartment 20.

  As shown in FIG. 5, the filter of the present embodiment has a tobacco filter body 3 adjacent to the tobacco leaf portion and the tobacco leaf portion, a moisture-containing filter compartment 28, and a portion of the filter compartment 28 adjacent to the tobacco leaf portion. And a filter end 29 adjacent to the opposite side of the water-soluble chitosan manganese complex-containing filter section 27, and when the tobacco is ignited and inhaled, the water first contains water from the water-containing filter section 28. It is comprised so that oxygen radical may be erase | eliminated from the smoke of the tobacco which moves to the filter division 27 containing a chitosan manganese complex and flows in.

  The filter of this example is composed of a filter section and a filter end containing a water-soluble chitosan manganese complex adjacent to the tobacco leaf portion and the tobacco leaf portion, and a small amount of water is dripped from the filter end before sucking tobacco. When the cigarette is lit and sucked from the end of the filter, oxygen radicals are erased from the cigarette smoke.

The invention's effect

  The water-soluble chitosan manganese complex-containing filter of the present invention can almost completely remove oxygen radicals in tobacco smoke that could hardly be removed so far. Can protect against smoke damage.

FIG. 4 is a cross-sectional view showing a filter used in Experiment 1. The graph which shows the protective effect of the filter of this invention with respect to the cutting | disconnection of a DNA strand by an oxygen radical. In addition, when (1) contains nothing, (2) includes SOD 10 μg / cm ³ , (3) includes CAT 10 μg / cm ³ , and (4) includes water-soluble chitosan manganese complex 1 mg / cm ³ When (5) contains heat-treated SOD, (6) shows the case containing 1 mg / cm ³ of water-soluble chitosan. The longitudinal cross-sectional view which shows the filter used in Experiment 1. FIG. FIG. 6 is a longitudinal sectional view showing a filter used in Example 3. FIG. 6 is a longitudinal sectional view showing a filter used in Example 4.

Explanation of symbols

(A) Water-soluble chitosan manganese complex-containing filter compartment (b) Moisture-containing filter compartment (c) Tobacco 1 Filter body 2 Water-soluble chitosan manganese complex-containing filter compartment 3 Water-containing filter compartment 5 Suction part 9 Cylindrical pipe body 11 Moisture Contained filter member 12 Cigarette attachment part 13 Suction end 15 Bulkhead desk 16 Hole 17 Bulkhead 18 Central hole 19 of cigarette 20 Water-soluble chitosan manganese complex-containing filter section 21 Water-containing filter section 22 Partition section 27 Water-soluble chitosan manganese complex containing Filter section 28 Moisture-containing filter section 29 Filter section 30 Tobacco leaf section 34 Suction section 35 Tube 36 Tobacco filter body

Claims (8)

  A filter for removing activated oxygen, wherein the filter substrate contains a water-soluble chitosan manganese complex as an oxygen radical scavenger.   2. The activated oxygen removal filter according to claim 1, further comprising a predetermined amount of moisture.   3. The activated oxygen removing filter according to claim 1 or 2, wherein the predetermined amount of water is 0.3 to 1.0 ml / filter. The activated oxygen removing filter according to any one of claims 1 to 3, wherein the water-soluble chitosan manganese complex is contained at a rate of 0.1 µg to 1 mg / cm ³ . Oxygen removal filter.   An activated oxygen removing filter pipe comprising the activated oxygen removing filter according to any one of claims 1 to 4.   6. The activated oxygen removing filter pipe according to claim 5, wherein the pipe is composed of a filter containing section containing the activated oxygen removing filter and a moisture containing section containing the moisture. Activated oxygen removal filter pipe.   7. The activated oxygen removal filter pipe according to claim 5, wherein a predetermined amount of moisture can be supplied from the moisture-containing compartment to the filter-containing compartment immediately before smoking. Filter pipe for oxygen removal.   A filter containing the water-soluble chitosan manganese complex of the activated oxygen removing filter according to any one of claims 1 to 4 or the activated oxygen removing filter pipe according to any one of claims 5 to 7. An activated oxygen removing method comprising removing oxygen radicals by supplying a predetermined amount of moisture to a containing compartment immediately before smoking.

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