BIO-CATALYTIC FILTER - MACRIS BASIL

Title:

BIO-CATALYTIC FILTER

Document Type and Number:

WIPO Patent Application WO/2000/002647

Kind Code:

A1

Abstract:

Retention of the harmful and carcinogenic substances acetaldehyde, acetone, acrolein, benzene, benzo[$g(a)]pyrene, 1,3 butadiene, 2-butanone, hydrogen sulphide, isoprene, methanethiol, nitric oxide and toluene from tobacco smoke, indoor and outdoor air and engine exhaust, using a mixture of the biological catalysts (enzymes) superoxide dismutase and peroxidase together with methemoglobin, immobilized on a conventional solid matrix.

Inventors:

MACRIS BASIL (GR)
TSIROPOULOS GEORGE (GR)

Application Number:

PCT/GR1999/000025

Publication Date:

January 20, 2000

Filing Date:

July 09, 1999

Export Citation:

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Assignee:

MACRIS BASIL (GR)
TSIROPOULOS GEORGE (GR)

International Classes:

A24D3/14; B01D53/85; (IPC1-7): B01D53/85; A24D3/02; A24D3/14

Domestic Patent References:

WO1996000019A1

1996-01-04

Foreign References:

US4414988A	1983-11-15
US4049673A	1977-09-20
US5279963A	1994-01-18
CH609217A5	1979-02-28

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Claims:

CLAIMS

1.

A filter (BCF I), made of conventional materials, was enriched with the biological catalysts superoxide dismutase, peroxidase and methemoglo bin (Fe3, for the retention of different harmful compounds. The latter compounds exist in the tobacco (cigarette) smoke, in the outdoor and indoor air and in the engine exhaust.

2.	The tested harmful compounds were partially or totally removed by BC <BR> <BR> F I and comprised acetaldehyde, acetone, benzene, benzo [a] pyrene, 1,3 butadiene, 2butanone, hydrogen sulphide, isoprene, methanethiol, nitric oxide and toluene.

3.	Acetaldehyde, a harmful compound3, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 89. 1%, 91. 1%, 93.5% and 95.5%, respectively.

4.

Acetone, a harmful compound4, was removed by BCF I from the gase ous phase of smoke of the cigarettes KENTUCKY 1R3F, KENTUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGI CAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 97. 8%, 97. 6%, 99. 8% and 99. 8%., respectively.

5.

Acrolein, a harmful compound5, was removed by BCF I from the gase ous phase of smoke of the cigarettes KENTUCKY 1R3F, KENTUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGI CAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 97.7%, 97. 6%, 99. 8% and 99. 8%, respectively 6. Benzene, a harmful compound6, was removed by BCF I from the gase ous phase of smoke of the cigarettes KENTUCKY 1R3F, KENTUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGI CAL FILTER) Lights (average of 2nd, 4th and 6 puff) by 99. 7%, 99. 6%, 99. 9% and 99. 9%., respectively 7. Benzo [a] pyrene, a harmful compound2, was removed by BCF I from the solid phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of the first 6 puffs) by 6. 1 %, 4.7%, 29.4% and 23.8%, respectively 8.1, 3 Butadiene, a harmful compound7, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 94.0%, 94.7%, 97.4% and 98. 4%., respectively 9.2Butanone, a harmful compound8, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2nd, 4 and 6th puff) by 99.6%, 99.7%, 99.6% and 99.5%, respectively lO. Isoprene, a harmful compoundi°, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 98.0%, 97.0%, 98.8% and 99.3%, respectively 11.Methanethiol, a harmful compound¹¹, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 97.5%, 97.6%, 98.8% and 98.4%, respectively 12. Nitric oxide, a harmful compound12, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2"d, 4'and 6i'puf by 18. 3%, 16.9%, 25.5% and 45.1%, respectively 13. Toluene, a harmful compoundl3, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KEN TUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2nd, 4th and 6th puff) by 98.6%, 97.3%, 98.9% and 97.4%, respectively 14. Hydrogen sulfide, a harmful compoundl4, was removed by BCF I from the gaseous phase of smoke of the cigarettes KENTUCKY 1R3F, KENTUCKY 1R4F, BF (BIOLOGICAL FILTER) Full Flavor and BF (BIOLOGICAL FILTER) Lights (average of 2"d, 4'and 6i'puf by 92. 1%, 90.7%, 91.5% and 97.7%, respectively 15. Besides cigarettes, the BCF 1 has the potential to be applied in appara tus and systems designed to remove harmful compounds such as . acetaldehyde, acetone, acrolein, benzene, benzo [a] pyrene, 1,3 butadiene, 2butanone, hydrogen sulphide, isoprene, methanethiol, nitric oxide and toluene from the outdoor and indoor air as well as in the en gine exhaust.

Description:

DESCRIPTION BIO-CATALYTIC FILTER This invention refers to the development of a filter from conventional mate- rials, on which specific biological catalysts (oxidoreductases, methemoglo- bin) have been immobilized. This filter removes harmful substances con- tained in tobacco smoke, indoors and outdoors polluted air and engine ex- haust.

Tobacco smoking addiction is more prevailing worldwide than alcohol and drugs put togetherl causing serious health problems and killing more peo- ple. Despite this, the number of people that smoke cigarettes increases every day.

There are numerous substances in the cigarette smoke. Among the harmful ones are2 : ammonia, benzopyrene, dimethylnitrosamine, catechol, meth- ylquinolines, methylnaphthalene, nitrosopyrrolidine, quinoline, pyrene, hy- drogen cyanide, pyridine, nicotine, hydrazine-6. 2-naphthylamine, hydrogen cyanide, phenols. Also, as harmful substances have been reported acetalde- hyde3, acetone4, acroleins, benzene6, 1,3 butadiene, 2-butanoneg, free radi- cals9, isoprenei°, methanethiolll, nitric oxide12, carbon monoxide 2, tolu- enel3, hydrogen sulphide14 and peroxides9.

In the outdoor (atmospheric) and indoor (interior) polluted air there are many harmful gases. In the atmospheric air, the most important are: ben- zene6, 1,3 butadiene, nitric oxide1, carbon dioxide16, lead17, carbon mon- oxide2, polycyclic aromatic hydrocarbon hydrocarbonsl8 and ozone'9.

Among indoor air pollutants, besides nitrogen dioxide and carbon monox- ide, are asbestos20, pesticides21, radon gas22, cigarette smoke, formalde- hyde23 and several volatile organic toxic compounds.

Finally, the main exhaust gases from combustion of fossil fuels in engines are carbon monoxide2, simple (1,3 butadiene7) and cyclic hydrocarbons (benzene2).

The Diagram A depicts a cigarette with the conventional and the BC-F I filter. The BC-F I consists of 200 mg of conventional materials (activated carbon particles) on which the enzymes and hemoglobin have been immo- bilized (adsorbed).

Enzymes Superoxide dismutase (SOD). It was prepared from cells of the yeast Sac- charomyces cerevisiae. The intracellular enzyme was partially purified with organic solvents, lyophilized and stored in the freezer.

Peroxidase (Horse Radish Peroxidase, HRP). The enzyme was a product of the Sigma Chemical Co., USA.

Hemoglobin It was a commercial product (methemoglobin), provided by the ffARIlVVX BV Co., Holland. It contained (, mole/gr) : Methemoglobin (MetHb) > 36 and Oxyhemoglobin (OxyHb) < 4.5.

Cigarettes The cigarettes KENTUCKY 1R3F (research cigarettes, tobacco health re- search, University of Kentucky, Code 1R3F, tar 15.0 mg/cigarette, nicotine 1.16 mg/cigarette) and KENTUCKY 1R4F (research cigarettes, tobacco health research, University of Kentucky, Code 1R4F, tar 9.2 mg/cigarette, nicotine 0.8 mg/cigarette), internationally recognized as reference ciga- rettes, were used. For comparison reasons, the cigarettes with a biological filter (BIOLOGICAL FILTER) BF Full Flavor (SEKAP Co., Athens, Xanthi, Greece, tar 14.0 mg/cigarette, nicotine 1.0 mg/cigarette) and BF Lights (SEKAP Co., Athens, Xanthi, Greece, tar 8.0 mg/cigarette, nicotine 0.7 mg/cigarette)..

Enrichment of filter with enzymes and hemoglobin The enzymes and hemoglobin were immobilized by adsorption on conven- tional materials (activated carbon particles) in the form of a water solution.

The latter contained 100 Units of SOD, 100 Units of HRP and 2 mg hemo- globin. Following adsorption, the materials were dried under vacuum at 35°C and assembled on the cigarette filter as shown in Diagram A.

Analytical methods Cigarette smoke contains gaseous and solid compounds. The latter were separated with the aid of the special filter Cambridge, located between the filter and the syringe used for sampling (Diagram B) Gases. Samples of 35 ml were taken at the 2nd, 4 and 6th puff. The puffs were separated by one minute intervals and each puff lasted 2 sec. This method was preferred over the collection of puffs in a special container (balloon) due to significant losses of measured compounds encountered with the latter device.

Gas Chromatography - Ultraviolet Spectroscopy (GC-UV). A new appa- ratus24 was employed for the determination of the gaseous substances ac- etaldehyde, acetone, benzene, 1,3 butadiene, 2-butanone, hydrogen sul- fide, isoprene, methanethiol, nitric oxide and toluene. For quantitative comparison reasons, the analysis was carried out under the same condi- tions, that is: Chromatography column: PRP3,8 cm length, 1.6 mm diameter Carrying gas : Nitrogen, 10 ml/min Temperature range : 55-130°C (10 °C/min) 130-160°C (4 °C/min)

Sample volume: 450 1 (room temperature) Detector: UV spectrophotometer (166-330 nm) Solid substances. They are contained in the tar collected on an appropriate filter (Cambridge) during the first 6 puffs. The benzo [α]pyrene was deter- mined as reported in the literature25 The results appear in the Figures la (la/l, la/2, la/3, la/4), lb (lb/l, lb/2, 1 b/3, 1 b/4), 1 c (1 c/1, 1 c/2, 1 c/3), 2a (2a/ 1, 2a/2, 2a/3, 2a/4), 2b (2b/l, 2b/2,2b/3, 2b/4), 2c (2c/l, 2c/2, 2c/3), 3 and 4. The comparison of constituents in the smoke was made between cigarettes with the conventional and BC-F I filter.

Three replicates, randomly designed, were used in measurement. In all meas- urements, the standard deviation was practically < 10%.

In the Figures la-lc and 2a-2c a comparison was made between KEN- TUCKY IR3F and BF Full Flavor and between KENTUCKY IR4F and BF Lights, respectively. The results concern the retention of the harmful compounds acetaldehyde, acetone, acrolein, benzene, 1,3 butadiene, 2- butanone, hydrogen sulfide, isoprene, methanethiol, nitric oxide and toluene by the BC-F I filter during the 2nd, 4th and 6th puffs is concerned. The Figure 3 shows the retention of benzo [a] pyrene by the BC-F I filter during the first six puffs. Finally, in the Figure 4, the average retention of harmful constitu- ents in the smoke of tested cigarettes by BC-F I is depicted.

LITERATURE 1. Consequences of Cigarette, Alcohol and Other Drug Use. 1998.

ColumbialHCA Healthcare Corporation, Galen Healthcare. Inc., USA (http :// www. columbia. hca. com/) 2. U. S. Department of Health and Human Services, Public Health Services, Publication nos. (PHS) 79-50066,81-50156 and 82-50179 3. Sprince, H 1985. Protective action of sulfur compounds against al- dehyde toxicants of cigarette smoke 1985.. Eur. J. Respir. Dis.

Suppl., 139: 102-12 4. Charbonneau, M.; Brodeur, J., du Souich, P., Plaa, G. L. 1986. Cor- relation between acetone-potentiated CCl4-induced liver injury and blood concentrations after inhalation or oral administration. Toxi- col. Appl. Pharmacol., 84: 286-94 5. Hoffmann, D., Melikian, A. A., Brunnemann, K. D. Studies in to- bacco carcinogenesis. 1991. IARC Sci Publ, 105: 482-4 6. Hoffmann, D., Melikian, A. A., Wynder, E. L. Scientific challenges in environmental carcinogenesis. 1996. Prev. Med, 25: 14-22, 7. Hallberg, L M., Bechtold, W. E., Grady, J., Legator, M. S., Au, W. W. 1997. Abnormal DNA repair activities in lymphocytes of

workers exposed to 1, 3-butadiene. Toxicol., 113: 247-52, 1996; Mu- tat. Res., 383: 213-21 8. Chen, H. F., Hee, S. S. 1995. Ketone EC50 values in the Microtox test. Ecotoxicol. Environ. Saf. 30 (2): 120-3 9. Pryor, W. A. 1997. Cigarette smoke radicals and the role of free radicals in chemical carcinogenicity. Environ. Health Perspect, 105 (4): 875-82 10. Melnick, R. L., Sills, R. C., Roycroft, J. H., Chou, B. J., Ragan, H. A., Miller, R. A. 1996. Inhalation toxicity and carcinogenicity of iso- prene in rats and mice: comparisons with 1,3-butadiene. Toxicol., 113: 247-52 ll. Finkelstein, A., Benevenga, N. J. 1986. The effect of methanethiol and methionine toxicity on the activities of cytochrome c oxidase and enzymes involved in protection from peroxidative damage. J.

Nutr. 116 (2) : 204-1 S 12. Yoshie, Y., Ohshima, H. 1997. Synergistic induction of DNA strand breakage by cigarette tar and nitric oxide. Carcinogenesis, 18 (7) : 1359-63 13. Flanagan, R. J., Ruprah, M., Meredith, T. J., Ramsey, J. D. 1990.

An introduction to the clinical toxicology of volatile substances.

Drug Saf. 5 (5): 359-83 14. Guidotti, T. L. 1966. Hydrogen sulphide. Occup Med (Oxf), 46 (5) ; 367-71 15. Menzel, D. B. 1992. Antioxidant vitamins and prevention of lung disease. Ann. N. Y. Acad. Sci. 669: 141-55 16. Pool, B. L., Janowsky, I., Klein, P., Klein, R. G., Schmezer, P., Vogt- Leucht, G., Zeller, W. J. 1998. Effects of S02 or NOx on toxic and genotoxic properties of chemical carcinogens. I. In vitro studies.

Carcinogenesis, 9 (7): 1237-45 l7. Schaefer, M. 1994. Children and toxic substances: confronting a major public health challenge. Environ. Health Perspect 102 (2): 155- 6 18. Nebert, D. W. 1981. Genetic differences in susceptibility to chemi- cally induced myelotoxicity and leukemia. Environ. Health Perspect 39: 11-22 l9. Menzel, D. B. 1984. Ozone: an overview of its toxicity in man and animals. J. Toxicol. Environ. Health 13 (2-3): 183-204 20. Koshi, K., Kohyama, N., Myojo, T., Fukuda, K. 1991. Cell toxic- ity, hemolytic action and clastogenic activity of asbestos and its sub- stitutes. Ind. Health 29 (2) 37-56 21. al Saleh, I. A. 1994. Pesticides : a review article. J. Environ. Pathol.

Toxicol. Oncol. 13 (3): 151-61

22. Piao, C. Q., Hei, T. K. 1993. The biological effectiveness of radon daughter alpha particles. I. Radon, cigarette smoke and oncogenic transformation. Carcinogen. 14 (3): 497-501 23. Restani, P., Galli, C. L. 1991. Oral toxicity of formaldehyde and its derivatives. Crit. Rev. Toxicol, 21 (5): 315-28 24. Lagesson-Andrasko, L., Lagesson, V., Andrasko, J. 1998. The use of Gas-Phase spectra in the 168-330. Wavelength region for analyti- cal purposes. 1. Qualitative Measurements. Anal. Chem. 70 (5): 819- 826 25. Kershaw, J. R. 1996. Fluorescence spectroscopic analysis of benzo [a]pyrene in coal tar and related products. Fuel, 75 (4): 522-524

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