US3599645A - Treatment of tobacco to reduce polyphenol content - Google Patents

Treatment of tobacco to reduce polyphenol content Download PDF

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US3599645A
US3599645A US808146A US3599645DA US3599645A US 3599645 A US3599645 A US 3599645A US 808146 A US808146 A US 808146A US 3599645D A US3599645D A US 3599645DA US 3599645 A US3599645 A US 3599645A
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tobacco
oxidative browning
water
curing
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William H Johnson
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RESEARCH Corp TECHNOLOGIES Inc A NONPROFIT CORP OF DE
North Carolina State University
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Assigned to UNIVERSITY OF NORTH CAROLINA, THE, (NORTH CAROLINA STATE UNIVERSITY) reassignment UNIVERSITY OF NORTH CAROLINA, THE, (NORTH CAROLINA STATE UNIVERSITY) ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: RESEARCH CORPORATION TECHNOLOGIES, INC., A NON-PROFIT CORP. OF DE.
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    • AHUMAN NECESSITIES
    • A24TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24BMANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
    • A24B15/00Chemical features or treatment of tobacco; Tobacco substitutes, e.g. in liquid form
    • A24B15/18Treatment of tobacco products or tobacco substitutes
    • A24B15/20Biochemical treatment

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  • the polyphenol content of tobacco is reduced with minimal effect F. the desired characteristics of the final tobacco which has been moistened by contact with water or water vapor so that the moisture content of the said tobacco is at least percent and is product by subjecting tobacco which has been moistened by contact with water or water vapor so that the moisture content of the said tobacco is at least 70 percent and is in the yellowed state to a short term of heating between about and about F. to initiate oxidative browning and thereafter holding the tobacco at a temperature between about 70 and about 1 10 F. until a major portion of the polyphenol content thereof is enzymatically oxidized.
  • the heating may be effected by infrared radiation or by contacting the tobacco with hot gases or hot water.
  • the tobacco may be treated either in whole leaf or in shredded form.
  • FIG. 2 I I I l J 5 IO I5 20 25 TIME (SECONDS) FIG. 2
  • FIG. 3 WILLIAM H. JOHNSON BY M ATTOR NEYK TREATMENT OF TOBACCO To REDUCE POLYPHENOL CONTENT
  • the invention relates to a method whereby the polyphenol compound content of tobacco may be substantially reduced.
  • the total phenol content of tobacco has been identified as an important contributor to tumorigenic activity of smoke condensate or to cilia toxicity of tobacco smoke.
  • polyphenols such as chlorogenic acid
  • present in tobacco have been identified as specific precursors of phenols and occur to levels of 6 to 7 percent of total weight.
  • the present invention provides a method whereby polyphenol compounds may be systematically reduced by amounts up to 85 percent of that originally present.
  • the object of the invention is accomplished by subjecting tobacco in the yellowed state during curing to a short term of heating at a temperature between about 140 and about 180 F. to initiate oxidative browning and thereafter holding the tobacco at a temperature between about 70 and about 1 10 F. until a major portion of the polyphenol content thereof is enzymatically oxidized.
  • FIG. 1 is a generalized flow sheet of the method of the invention
  • FIG. 2 is a graph of the oxidative browning initiating heat treatment of the invention.
  • FIG. 3 is a diagrammatic representation of an illustrative form of apparatus suitable for carrying out the oxidative browning initiating heat treatment of the invention.
  • the tobacco, after harvest, is yellowed (1, FIG. 1) under controlled temperature and humidity conditions, for example at 85 tol05 F. at 85 to 95 percent relative humidity during a period of about 24 to 72 hours, depending on maturity, leaf position on the stalk and the like.
  • controlled temperature and humidity conditions for example at 85 tol05 F. at 85 to 95 percent relative humidity during a period of about 24 to 72 hours, depending on maturity, leaf position on the stalk and the like.
  • major chemical reactions of the curing process have occurred such as starch hydrolysis, proteolysis and chlorophyll oxidation, and the leaf has a yellow color.
  • the yellow leaf is then turgor conditioned (2, FIG. 1) to a moisture content of 70 to 85 percent (wet basis) by passin'g air at a relatively humidity of 95-100 percent over the whole or the shredded leaf or by immersing the tobacco in water.
  • the latter is particularly effective and rapid if the tobacco is in the shredded state and requires no more than 3--5 hours.
  • the conditioned tobacco is then rapidly heated (3', FIG. 1). to a temperature in the range from about 140 to about 180 F.
  • the time of heating being longer at the lower temperatures.
  • the tobacco is heated to 180 F. in about 15 seconds and held at l 80 for about 5 seconds when it is rapidly cooled to about 75 F..At 160 F. the time at temperature should be about 10 seconds; while at 140 F., 15 to 20 seconds at temperature is desirable.
  • ln 'gene' ralfbptimal results are obtained by the shorter time of heating in the neighborhood of 180 F. J j
  • the tobacco is then quickly cooled to a temperature in the range from about 70 to about 110 F. where it is held for about 30 minutes (4, FIG. 1) for substantial completion (up to 85 percent or more) of the polyphenol oxidation reactions.
  • the thermal treatment for initiation of polyphenol oxidation can be effected by passing hot air through or over the tobacco, by irradiating thetobacco with infrared heat or by immersing the tobacco in hot water.
  • Treatment with hot water is particularly effective in obtaining rapid and closely controllable heat treatment.
  • a suitable heating apparatus is shown in FIG. 3 wherein an immersion tank 10 is provided with a hot water inlet 11 and outlet 12.
  • the tobacco 13 to be treated in whole leaf or shredded form, is passed through the body of water in the tank at the desired rate by means of conveyor 14 in cooperation with hold down flight 15.
  • the tobacco leaving the tank is quickly cooled to the temperature for carrying out the polyphenol oxidation reactions by the evaporative cooling action of a stream of air from conduit 16.
  • the tobacco is dried (5, FIG. 1) by heated air circulated on, over or through the tobacco or by freeze-drying the tobacco by the methods described in my application Ser. No. 707,064, filed Feb. 21, 1968.
  • the tobacco is reconditioned (6, FIG. 1) to safe handling moisture levels of about 12-20 percent (wet basis), for example, with humidified air at 70 F.
  • shredding of the leaf tobacco may be carried out before or after any stage in the treating process.
  • Oxidation of polyphenols, and particularly odiphenols, is associated or occurs simultaneously with oxidative browning, which is initiated at elevated temperatures.
  • the oxidation product of polyphenol oxidation contains protein and iron to give a high molecular weight compound.
  • denaturation and protoplasmic coagulation occur rapidly. It is considered that structural modifications occur in cytoplasmic membranes at these temperatures which permit commingling of oxidative enzymes, substrates and oxygen within the cell. This irreversible change in cytoplasmic membranes allows freer and more rapid movement of reactants for oxidative browning, including polyphenol oxidation.
  • a method of curing tobacco which comprises bringing tobacco in the yellowed state to a moisture content of at least 70 percent by contacting'the tobacco with a material consisting of water or water vapor, subjecting the thereby turgor conditioned tobacco to a temperature of from about 140 to about l80 F. for from about 5 to about 20 seconds to initiate oxidative browning with concurrent polyphenol oxidation and thereafter holding the tobacco at a temperature of from about to about'l 10 F. for from about 5 to about 30 minutes.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Tobacco Products (AREA)

Abstract

The polyphenol content of tobacco is reduced with minimal effect F. the desired characteristics of the final tobacco which has been moistened by contact with water or water vapor so that the moisture content of the said tobacco is at least 70 percent and is product by subjecting tobacco which has been moistened by contact with water or water vapor so that the moisture content of the said tobacco is at least 70 percent and is in the yellowed state to a short term of heating between about 140* and about 180* F. to initiate oxidative browning and thereafter holding the tobacco at a temperature between about 70* and about 110* F. until a major portion of the polyphenol content thereof is enzymatically oxidized. The heating may be effected by infrared radiation or by contacting the tobacco with hot gases or hot water. The tobacco may be treated either in whole leaf or in shredded form.

Description

United States Patent Inventor Appl. No.
Filed Patented Assignee William H. Johnson Raleigh, N.C. 808,146
Mar. 18, 1969 Aug. 17, 1971 Research Corporation New York, N.Y.
TREATMENT OF TOBACCO TO REDUCE OTHER REFERENCES Bulk Curing Of Bright Leaf Tobacco (pub.) Johnson,
Henson, Hassler & Watkins from Tobacco Science Mar. 1960 p. 22- 28 inc.
Primary Examiner-Melvin D. Rein Attorney-Stowe and Stowell ABSTRACT: The polyphenol content of tobacco is reduced with minimal effect F. the desired characteristics of the final tobacco which has been moistened by contact with water or water vapor so that the moisture content of the said tobacco is at least percent and is product by subjecting tobacco which has been moistened by contact with water or water vapor so that the moisture content of the said tobacco is at least 70 percent and is in the yellowed state to a short term of heating between about and about F. to initiate oxidative browning and thereafter holding the tobacco at a temperature between about 70 and about 1 10 F. until a major portion of the polyphenol content thereof is enzymatically oxidized. The heating may be effected by infrared radiation or by contacting the tobacco with hot gases or hot water. The tobacco may be treated either in whole leaf or in shredded form. v
YELLOWED TOBACCO LEAVES TURGOR I counmomns I ii irttttig TY 3 THERMAL lNITIATlON 0F POLYPHENOL OXIDATION )4 LOW TEMPERATURE POLYPHENOL OXIDATION RECONDITIONING PATENTEU AUGI H9?! 3,599,645
SHEET 1 BF 2 I YELLOWED TOBACCO LEAVES @imj TURGOR CONDITIONING Ll lfi fiij THERMAL INITIATION OF POLYPHENOL OXIDATION [EB Emi I/f4 LOW TEMPERATURE POLYPHENOL OXIDATION I S H R E DDINO L 1 DRYING JBEPQ IQ 6 RECONDITIONING mvsmon I WILLIAM H. JOHNSON BY M d fwefl ATTORNEYfi PATENTEDAHGIIIS?! 3 599 5 5 sum 2 OF 2 g. a a. 2 a
I I l J 5 IO I5 20 25 TIME (SECONDS) FIG. 2
INVENTOR FIG. 3 WILLIAM H. JOHNSON BY M ATTOR NEYK TREATMENT OF TOBACCO To REDUCE POLYPHENOL CONTENT The invention relates to a method whereby the polyphenol compound content of tobacco may be substantially reduced.
Recent investigations have indicated that certain polyphenol compounds such as chlorogenic acid, present in tobacco, are precursors of phenols. in tobacco smoke, particularly cigarette smoke, and a principal object of the invention is the provision of a method whereby such compoundsmay be substantially reduced in amount with minimal effects on the desired characteristics of the final tobacco product.
The total phenol content of tobacco has been identified as an important contributor to tumorigenic activity of smoke condensate or to cilia toxicity of tobacco smoke. Reference is made specifically to the book, Tobacco and Tobacco Smoke,. Academic Press, New York, 1967, by E. L. Wynder and E. Hofiman who give a rather complete account of work in the area of experimental tobacco carcinogenesis. Numerous tests have demonstrated tumor promoting activity for the phenolic fraction of smoke condensate whenapplied in skin tests on mice. Furthermore, the tumorigenic activity has been 'found higher for tobacco smoke condensate having higher 'levels of phenols.
In other studies, 1 percent concentrations of phenol were toxic to clam gill cilia; while 0.05 percent concentration induced total stasis, without recovery within a -minute observation period. The cilia, fine hairlike structures on the inner linings of the throat and lungs, play an important role in mucus transport and in the cleansing action of the lungs by propelling foreign matter back to the mouth where it can be expelled.
It, therefore, appears to be highly desirable in the interest of producing less hazardous cigarettes and other tobacco products that the phenolic content of tobacco smoke be reduced. Polyphenols, such as chlorogenic acid, present in tobacco have been identified as specific precursors of phenols and occur to levels of 6 to 7 percent of total weight. The present invention provides a method whereby polyphenol compounds may be systematically reduced by amounts up to 85 percent of that originally present.
' The object of the invention is accomplished by subjecting tobacco in the yellowed state during curing to a short term of heating at a temperature between about 140 and about 180 F. to initiate oxidative browning and thereafter holding the tobacco at a temperature between about 70 and about 1 10 F. until a major portion of the polyphenol content thereof is enzymatically oxidized.
The invention will be more particularly described with reference to the accompanying drawings in which:
FIG. 1 is a generalized flow sheet of the method of the invention;
FIG. 2 is a graph of the oxidative browning initiating heat treatment of the invention; and
I FIG. 3 is a diagrammatic representation of an illustrative form of apparatus suitable for carrying out the oxidative browning initiating heat treatment of the invention.
Typically the tobacco, after harvest, is yellowed (1, FIG. 1) under controlled temperature and humidity conditions, for example at 85 tol05 F. at 85 to 95 percent relative humidity during a period of about 24 to 72 hours, depending on maturity, leaf position on the stalk and the like. At the end of this step, major chemical reactions of the curing process have occurred such as starch hydrolysis, proteolysis and chlorophyll oxidation, and the leaf has a yellow color.
The yellow leaf is then turgor conditioned (2, FIG. 1) to a moisture content of 70 to 85 percent (wet basis) by passin'g air at a relatively humidity of 95-100 percent over the whole or the shredded leaf or by immersing the tobacco in water. The latter is particularly effective and rapid if the tobacco is in the shredded state and requires no more than 3--5 hours.
The conditioned tobacco is then rapidly heated (3', FIG. 1). to a temperature in the range from about 140 to about 180 F.
and for about 5 to 20 seconds,.as shown in FIG; 2, the time of heating being longer at the lower temperatures. In the illustrative example shown in FIG. 2, the tobacco is heated to 180 F. in about 15 seconds and held at l 80 for about 5 seconds when it is rapidly cooled to about 75 F..At 160 F. the time at temperature should be about 10 seconds; while at 140 F., 15 to 20 seconds at temperature is desirable. ln 'gene' ralfbptimal results are obtained by the shorter time of heating in the neighborhood of 180 F. J j
The tobacco is then quickly cooled to a temperature in the range from about 70 to about 110 F. where it is held for about 30 minutes (4, FIG. 1) for substantial completion (up to 85 percent or more) of the polyphenol oxidation reactions.
The thermal treatment for initiation of polyphenol oxidation can be effected by passing hot air through or over the tobacco, by irradiating thetobacco with infrared heat or by immersing the tobacco in hot water. v
Treatment with hot water is particularly effective in obtaining rapid and closely controllable heat treatment. A suitable heating apparatus is shown in FIG. 3 wherein an immersion tank 10 is provided with a hot water inlet 11 and outlet 12.
The tobacco 13 to be treated, in whole leaf or shredded form, is passed through the body of water in the tank at the desired rate by means of conveyor 14 in cooperation with hold down flight 15. The tobacco leaving the tank is quickly cooled to the temperature for carrying out the polyphenol oxidation reactions by the evaporative cooling action of a stream of air from conduit 16.
Following the polyphenol oxidation step, the tobacco is dried (5, FIG. 1) by heated air circulated on, over or through the tobacco or by freeze-drying the tobacco by the methods described in my application Ser. No. 707,064, filed Feb. 21, 1968. Following drying, the tobacco is reconditioned (6, FIG. 1) to safe handling moisture levels of about 12-20 percent (wet basis), for example, with humidified air at 70 F. As indicated in FIG. 1, shredding of the leaf tobacco may be carried out before or after any stage in the treating process.
Early shredding tends to facilitate handling and improve uniformity.
In the foregoing illustrative discussion of the method, conditions are described for achieving maximum reduction in polyphenol content under optimum conditions, with minimal effect on the desired characteristics of the tobacco product. First, the tobacco following harvest undergoes important biochemical transformations of the coloring phase of curing to achieve desired levels of sugars, breakdown of complex proteins, etc. This is important in achieving desirable flavor and smoke characteristics in the tobacco. Turgor conditioning, next, establishes high moisture levels for assuring an optimal oxidative reaction; since the biochemical reaction requires an aqueous state. This is followed by a rapid thermal treatment which elevates the tobacco temperature within seconds to about 140 to about 180 F. for a short term of heating to initiate oxidative browning.
Oxidation of polyphenols, and particularly odiphenols, is associated or occurs simultaneously with oxidative browning, which is initiated at elevated temperatures. There is indication that the oxidation product of polyphenol oxidation contains protein and iron to give a high molecular weight compound. At leaf temperatures above l35l40 F. denaturation and protoplasmic coagulation occur rapidly. It is considered that structural modifications occur in cytoplasmic membranes at these temperatures which permit commingling of oxidative enzymes, substrates and oxygen within the cell. This irreversible change in cytoplasmic membranes allows freer and more rapid movement of reactants for oxidative browning, including polyphenol oxidation.
Laboratory studies were conducted to determine the temperature range for most effectively initiating polyphenol oxidation. The temperature-time treatments as discussed were found to be optimal. Below F., the tests indicated less extensive modification in cytoplasmic membranes, basedon electrical conductivity and moisture permeability observations,'to give noticeably slower and less-extensive oxidative browning. ABove l80 F., the reaction was triggered; howreduce or tivation effects are not significant. Colorimetric observations have indicated that in most leaves complete oxidative browningis efi'ected within 5 to 25 minutes. For complete reaction in at least 95 percent of the tobacco, about 30 minutes should be provided.
Treatment, of tobacco varieties, Golden Wilt, Yellow Special A and Coker 239,by the method of the invention wherein the leaf tobacco was heated in 20 seconds to about 180 F. as in FIG. 2 to initiatepolyphenol oxidation and then allowed to brown at about 75 F. for 30 minutes resulted in uniform elimination of about 85 percent of the polyphenol content-of the tobacco expressed as chlorogenic acid.
I claim:
l. A method of curing tobacco which comprises bringing tobacco in the yellowed state to a moisture content of at least 70 percent by contacting'the tobacco with a material consisting of water or water vapor, subjecting the thereby turgor conditioned tobacco to a temperature of from about 140 to about l80 F. for from about 5 to about 20 seconds to initiate oxidative browning with concurrent polyphenol oxidation and thereafter holding the tobacco at a temperature of from about to about'l 10 F. for from about 5 to about 30 minutes.
2. A method of curing tobacco as defined in claim 1 wherein the yellowed tobacco is shredded before it is subjected to the oxidative browning initiatingheat treatment. 1
3. A method of curing tobacco as defined in 'claim 1 'wherein the tobacco is shredded afterit has been subjected to the oxidative browning initiating heat treatment.
4. A method of curing tobacco as defined in claim 1 wherein the yellowed tobacco is heated to oxidative browning initiat-,
ing temperature by immersion in hot water.
5. A method of curing tobacco as defined in claim 1 wherein the yellowed tobacco is heated to oxidative browning initiating temperature bypassing hot air through or over the tobacco.
6. A method of curing tobacco as defined in claim 4 wherein the heated tobacco is cooled to from about 70 to about 1 l0 F. by the evaporative cooling effect of a current of air.
7. A method as defined in claim 1 wherein the tobacco after oxidative browning is dried by low pressure sublimation of the water content thereof from the frozen condition.
8. A method as defined in claim 1 wherein the tobacco after oxidative browning is dried by passing a current of air through or over the tobacco.

Claims (7)

  1. 2. A method of curing tobacco as defined in claim 1 wherein the yellowed tobacco is shredded before it is subjected to the oxidative browning initiating heat treatment.
  2. 3. A method of curing tobacco as defined in claim 1 wherein the tobacco is shredded after it has been subjected to the oxidative browning initiating heat treatment.
  3. 4. A method of curing tobacco as defined in claim 1 wherein the yellowed tobacco is heated to oxidative browning initiating temperature by immersion in hot water.
  4. 5. A method of curing tobacco as defined in claim 1 wherein the yellowed tobacco is heated to oxidative browning initiating temperature by passing hot air through or over the tobacco.
  5. 6. A method of curing tobacco as defined in claim 4 wherein the heated tobacco is cooled to from about 70* to about 110* F. by the evaporative cooling effect of a current of air.
  6. 7. A method as defined in claim 1 wherein the tobacco after oxidative browning is dried by low pressure sublimation of the water content thereof from the frozen condition.
  7. 8. A method as defined in claim 1 wherein the tobacco after oxidative browning is dried by passing a current of air through or over the tobacco.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3845774A (en) * 1971-07-28 1974-11-05 T Tso Process for curing tobacco
US3927682A (en) * 1973-10-27 1975-12-23 Japan Tobacco & Salt Public Air-curing process of tobacco leaf
US3995646A (en) * 1974-03-04 1976-12-07 Debrunn Albert W Tobacco processing method
US4167191A (en) * 1977-09-27 1979-09-11 Brown & Williamson Tobacco Corporation Tobacco drying process
US4308876A (en) * 1979-02-16 1982-01-05 Airco, Inc. Methods and apparatus for expanding tobacco
US4448208A (en) * 1981-01-21 1984-05-15 Philip Morris Incorporated Tobacco extractor
US5826590A (en) * 1996-09-26 1998-10-27 Brown & Williamson Tobacco Corp. Method and plant for treating tobacco stems for the production of cut tobacco
WO2000002464A1 (en) * 1998-07-08 2000-01-20 Novozymes A/S Use of a phenol oxidising enzyme in the treatment of tobacco
US6298859B1 (en) 1998-07-08 2001-10-09 Novozymes A/S Use of a phenol oxidizing enzyme in the treatment of tobacco

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2224833A (en) * 1935-10-03 1940-12-10 Ig Farbenindustrie Ag Process of influencing the color of tobacco leaves
US3223090A (en) * 1963-09-11 1965-12-14 Brown & Williamson Tobacco Reconstituted tobacco products and method of making same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2224833A (en) * 1935-10-03 1940-12-10 Ig Farbenindustrie Ag Process of influencing the color of tobacco leaves
US3223090A (en) * 1963-09-11 1965-12-14 Brown & Williamson Tobacco Reconstituted tobacco products and method of making same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Bulk Curing Of Bright Leaf Tobacco (pub.) Johnson, Henson, Hassler & Watkins from Tobacco Science Mar. 1960 p. 22 28 inc. *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3845774A (en) * 1971-07-28 1974-11-05 T Tso Process for curing tobacco
US3927682A (en) * 1973-10-27 1975-12-23 Japan Tobacco & Salt Public Air-curing process of tobacco leaf
US3995646A (en) * 1974-03-04 1976-12-07 Debrunn Albert W Tobacco processing method
US4167191A (en) * 1977-09-27 1979-09-11 Brown & Williamson Tobacco Corporation Tobacco drying process
US4308876A (en) * 1979-02-16 1982-01-05 Airco, Inc. Methods and apparatus for expanding tobacco
US4448208A (en) * 1981-01-21 1984-05-15 Philip Morris Incorporated Tobacco extractor
US5826590A (en) * 1996-09-26 1998-10-27 Brown & Williamson Tobacco Corp. Method and plant for treating tobacco stems for the production of cut tobacco
WO2000002464A1 (en) * 1998-07-08 2000-01-20 Novozymes A/S Use of a phenol oxidising enzyme in the treatment of tobacco
US6298859B1 (en) 1998-07-08 2001-10-09 Novozymes A/S Use of a phenol oxidizing enzyme in the treatment of tobacco
JP2002520005A (en) * 1998-07-08 2002-07-09 ノボザイムス アクティーゼルスカブ Use of phenol oxidase in tobacco processing.
AU761885B2 (en) * 1998-07-08 2003-06-12 British American Tobacco (Investments) Limited Use of a phenol oxidising enzyme in the treatment of tobacco
JP2011010656A (en) * 1998-07-08 2011-01-20 Novozyme As Use of phenol oxidizing enzyme in treatment of tobacco
JP2014057603A (en) * 1998-07-08 2014-04-03 Novozyme As Use of phenol oxidase in processing tobacco

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DE2011967A1 (en) 1970-10-01
BE747434A (en) 1970-08-31
NL7003656A (en) 1970-09-22
FR2039044A5 (en) 1971-01-08
GB1233878A (en) 1971-06-03
SE360005B (en) 1973-09-17

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