Product Design
Subject: Monthly Development Summary - Research Directorate
Abstract
Summarizes work on Phillip Morris research and development projects. Reports progress in the ART-STEM study, with the exposure of stems to citric acid and supercritical Co2. Evaluates organic acids and potassium salts for sidestream reduction. Mentions use of CORESTA smoking machine in the odor modification program. Summarizes TSNA precursor research. Studies sensory effects on taste and odor modification. Discusses varied cigarette paper design projects, including CaCo2 paper, Ecusta prepared magnesite, dolomite paper, Aromatek applied paper, and paper incorporating vanillin release compound. Notes that the initial results of Dr. Helena Chum's work with flax fiber cigarette paper are "extremely exciting because they suggest that eventually we may be able to systematically design cigarette paper parameters so as to optimize cigarette taste characteristics."
Fields
- Author
- Charles, James L., Ph.D. (PM, R&D VP, Pharmacologist, Industry Expert)Vice President of Research and a scientist for Philip Morris, Inc. Vice President of Research for Philip Morris, Inc. in 1986 and then again from 1992 to 1993.
- Recipient
- Houghton, Kenneth S., Ph.D. (Senior VP of R&D at Philip Morris)Defense
- Hypothesis
- Sidestream constituent yieldsModification of selected sidestream smoke constituents in response to health concerns.
- Use of additives
Modification of tobacco products through use of additives and measuring effects on dependence, behavior, and toxicity.- Use of filters, paper, and ventilation
Modification of tobacco products through use of filters, paper, and ventilation, and measuring effects on dependence, behavior, and toxicity.- Use of tobacco processing/ blends
Modification of tobacco products through changes in tobacco processing and use of blends, and measuring effects on dependence, behavior, and toxicity.- Sensory effects
Technologies used to measure, control, or alter sensory effects - Use of additives
- Keyword
- Flavor (Taste)
- Menthol delivery (Smoke menthol, menthol yield)
- Nicotine manipulation
- Pyrolysis
- Secondhand Smoke (Sidestream smoke, SS)
- Sensory response
- Sidestream visibility
- Tobacco taste (Attribute measure)
- Menthol delivery (Smoke menthol, menthol yield)
- Additive
- Ammoniasee also: Ammonium bicarbonate, Ammonium carbonate, Ammonium chloride, Ammonium hydroxide, Ammonium sulfide, Diammonium phosphate, and Urea
- Carbon dioxide
- Citric acid
- Magnesium carbonate
- Vanillin
- Ammonia
see also: Ammonium bicarbonate, Ammonium carbonate, Ammonium chloride, Ammonium hydroxide, Ammonium sulfide, Diammonium phosphate, and Urea- Menthol
- Carbon dioxide
- Smoke Constituent
- Acids
- Alkaloids
- ammonia
- Carbon dioxide
- Hydrogen cyanide (HCN)
- Menthol
- Nicotine
- Nitric oxides
- Nitrosamines (N-nitrosamines)
- Alkaloids
- Design Component
- Ash appearance
- Casing
- Cellulose acetate filter (CA filter, Conventional filter)
- Flax paper (Flax wrapper)
- Humectant
- Magnesium oxide paper
- Woodpulp wrapper
- Casing
- Operation/Project
- Project 1904
- Project ART (Denicotinized cigarette)
- Project OSIRIS
- Project ART (Denicotinized cigarette)
- Named Organization
- COMARK
- Coresta (Industry-affiliated Int'l scientific/research group)
An international organization whose objective is "to improve cooperation in scientific research and tobacco." Consists of 186 member companies/institute from 54 countries, including tobacco, paper and filter companies, and universities engaged in tobacco research.- DUPONT
- Eastman Kodak Co. (Kodak) (Cigarette filter mfg from 1950s to 1994.)
Manufacturers of quality control equipment for cigarette packaging- ECUSTA
- ELECTRONIC TECHNOLOGY IN IMAGING
- GENEBANK
- Kimberly-Clark Corp. (Specializes in the tobacco reconstitution process)
Specializes in the tobacco reconstitution process and in helping the tobacco companies control their nicotine- NELSON
- NY POLYTECHNIC
- PERKIN ELMER
- Pfizer Flavor & Fragrance Product Group (C.A.L.) (supplier of tobacco extracts in 1993)
A New Jersey supplier of tobacco extracts in 1993- R.J. Reynolds Tobacco Co. (Cigarette manufacturer (Camel, Winston, Doral))
Cigarette manufacturer (Camel, Winston, Doral)- RSA
- SOLAR ENERGY RESEARCH INST
- SUGARMAN
- Usda, U.S. Dept of Agriculture
- WATTENS
- CALLERY CHEMICAL
- Coresta (Industry-affiliated Int'l scientific/research group)
- Brand
- Ambrosia
- CABIN
- Marlboro (PM)
- CABIN
- Subject
- Filters (Design)
- Paper (Design)
- additives
- acids (additives)
- Humectants
- Menthol (Additives)
- nicotine technology
- Particle Size (Technology)
- Sensory Effects—Impact (Effects)
- Test/Smoke Machine (Testing)
- Secondhand Smoke/Constituents
- Paper (Design)
Document Images
h%(enthol Studies - The modified tow mentholator is running well. Calibration runs were
completed to determine tow residence times. Samples of tow were mentholated with residence
times varying from 15 to 130 seconds. The mentholation rate was determined to be 0.041 mg
menthol/g tow - sec residence time. Jay Pierotti is currently working on developing a method
for estimating the quantity of inentholl on the tow.surface versus menthol inside the fiber.
Continued research on application methods for the GMC'menthol release compound prompted
a number of studies in support of providing quantitative application levels and in support of
qualifying the latest large scale preparative batch of GMC from Lee laboratories.
The amount of GMC (Sugarman) on filler was determined in nine samples of tobacco after
spray application in the Semi-works batch cylinder. The average recovery of the GMC was
99% with respect to the target concentration, with a negligible amount found on the cylinder
walls after spraying.
Filler samples submitted by L. Haws were analyzed for ethanol to model equipment to be used
for ethanol removal after GMC spray application.
Methods were developed and samples analyzed for the determination of benzene, menthyl
chloride, and pyridine in Sugarman.
In addition, selective ion electrode fluoride determination were conducted on sugarman, no
fluoride was detected.
Operations Support - Pellets of sludge from reconstitution processes were analyzed to
determine the concentration of eight elements. These samples were also analyzed for residual
nicotine.
Two charcoal samples from Cabin Milds filters were found to be plant-based charcoal after
comparison with a coal-based charcoal and a coconut-based charcoal. The particle size of the
charcoal within the inner filter was about 0.2mm in diameter while the charcoal within the
middle filter space was about 1.8mm in diameter.
A foil-paper laminate was examined to determine the depth of penetration into the paper of the
Na silicate-based glue. The glue was located'close to the foil-paper interface, but it was not
uniformly thick. The glue was not detected on the outer side of the paper.
German certification continues for the PMI export materials not covered by the first round of
testing. A certificate of analysis was issued for each of the materials used in both the export
and domestic formulations.
-11-
Specifications were completed for a fourth vendor and a meeting with that vendor was held on
site discussing the contents of the specifications as regards their materials. The written
specifications and associated methodology was very favorably received and some additional
samples/methods/protocol exchanges are planned. Work continues on the FRG Direct
Materials and the Dry Flavors.
A method has been developed to monitor low levels of ammonia in environments were ETS is
present. The method offers ease of use and relative high sensitivity and precision. A special
report is in preparation. This method is currently being used to pressure the ammonia levels for
Project PACT.
Commerciali7ation of GMC and Polymic - Analysis of GMC batches 003R and 004 is in
progress. Using an alternate HPLC method, additional peaks were observed. These are a- and
(!-anomers of the known isomers of GMC as well as other minor isomers of GMC not
previously observed. All of this data has been reviewed and work is in progress to better define
the GMC anal'ysis by HPLC.
Callery Chemical has developed a promising synthesis of the PoIyMIC monomer. Full details
were received in early June. Their process uses potassium hexamethyldisilazide to form the
potassium enolate of acetone which is isolated as a solid and in turn is reacted with menthyl
chloroformate to form the desired monomer in good yield. Callery willl be carrying out some
additional research in June and issuing a final status report about the 1st of July.
A final review has been completed with Eastman Kodak on their work directed to finding an
improved synthesis of the PoIyMIC monomer. Kodak was unable to find any process which
they feel would be suitable. Effective mid-June they have stopped all work on this project.
Flavo Release TechnologX - Aromatek 150 (ethyl vanillin glucoside) was recrystallized from
aqueous methanol and aqueous ethanoL The solids obtained from these recrystallizations were
examined by Scanning Electron Microscopy. The samples were forwarded to Flavor
Development for evaluation.
3,4,6-Tri-O-acetyl-D-glucal was reacted with vanillin to give 4'-formyl-2'-methoxyphenyl 4,6-
di-O-acetyl-2,3-didehydro-2,3-dideoxy-D-erythro-hexoside. The purification and conversion
of this material to the unacetylated hexoside are in progress.
The reactions of 2-oxo-(3-ionol with di-t-butyl dicarbonate, methyl oxalyl chloride and oxalyl
chloride to obtain t-butyl-3-oxo-R-ionyl carbonate, methyl 3-oxo-p-ionyl oxalate and di-3-oxo-
(3-ionyl oxalate respectively have been carried out. All of these oxoionyl derivatives are
designed to: release megastigmatrienone on pyrolysis. Purification of these materials for
pyrolytic and subjective evaluation is currently in progress.
-12-
R.S.A. Company has been contracted to devel'op: a laboratory scale synthesis of vanillin
chloroformate which can be used to prepare a large variety of vanillin release compounds. The
research was begun on 6/13 and initial trials have been encouraging. An interim status report
will be sent on 6/25.
All analytical work has been completed for Vanil-3 (the large scale production of CR-2910 at
Aldrich) and the material has been released for internal evaluation.
Flavor Chemistry - Work continues on the recovery of organic components from the ART
process water column effluent. A total of 35g of organic neutrals, obtained from Stage I water
column effluent, was fractionated on i kilogram of silica gel to provide 8 fractions of
increasing polarity. Of these, 7 have been characterized by odor profiling and subjective
smoking as follows:
Fraction 2 (1.6g)
odor: fruity (non-citrus), honey, spicy, tea, green-herbal.
flavor tea-sweet, bright topnotes, good mouth feel.
Fraction 3 (7.3g)
odor woody, hay, fresh tobacco smoke.
flavor. sweet, flue-cured roasted, peppery, increased impact.
Fraction 4 (11.3g)
odor tea, sweet, hay, honey-floral.
flavor. full, rounded with sweet roasted note, peppery.
Fraction 5 (6.8g)
odor: tea/hay, honey, musty, pungent.
fliavor. full, blended sweet with salivation, good mouth feel.
Fraction 6 (3.3g)
odar: tea/hay, honey, sweet.
flavor. peppery tongue-bite, salivating, sour, lbts of mouth feel.
Fraction 7 (3.4g)
odor fruity (non-citrus), honey, sweet, hay, nutty.
flavor high amplitude, full-rounded, bitter.
Fraction 8 (0.9g)
odor. burnt-smoky, sweet, honey.
flavor peppery, musty, lots of mouth feel.
-13-
The subjective smoking information was obtained using nicotine-free cigarettes injectedd
with 3SOppm of each fraction.
Inorganics as Novel Tobacco lkiaterials Additives - Smoking studies have been completed on
a number of "mag carbonates", and the results are extremely encouraging with many giving
excellent sidestream reduction and a few with extremely high subjective ratings. One of the
best leads to date has been a magnesite, MgCO, , produced by the hydrothermal treatment of a
Reheis Mg(OH), paste in a CO, atmosphere. High-basis weight (63 g/m' ) handsheets of this
material have been prepared and are pending smoking d'ata. The preparation of this material
was reproduced and the sample submitted for papermaking. An additional sample containing
47% magnesite and 53% Mg(OH)2 was also prepared by the hydrothermal treatment of Reheis
Mg(OH)2 paste in a COt atmosphere and submitted for papermaking.
A high surface area "mag carbonate" generated from the pyrolysis of an ammonium magnesium
carbonate gave significant sidestream reduction with acceptable ash. Work with this system is
continuing.
A number of inorganic samples have been generated and either have been or will be submitted
for paperntaking. These include; 1) a sample from the large scale synthesis (11 liter reaction)
of the material from the magnesium methyl carbonate matrix study which gave the most
promising smoking results, 2) a freeze-dried sample of one of the samples from the same
magnesium methyl carbonate matrix study that was found unsuitable for handsheet preparation
due to excessive drainage times, 3) a 1:1 mixture of "mag carbonate" and calcium carbonate
prepared by reacting a suspension of calcium carbonate in magnesium methyl carbonate with
water and potassium hydroxide, 4) a 19:1 mixture of hydromagnesite and Mg(OM prepared by
reacting aqueous KOH with hydromagnesite, 5) a potassium magnesium carbonate generated
from the pyrolysis of a potassium ammonium magnesium carbonate, 6) two sol-gel CaCO,
samples, one with a surface area of 312 m= /g at 200 ° C, and 7) two "mag carbonate" samples,
one generated at N.Y. Polytechnic and the other in-house by an aqueous sol-gel route.
As a possible replacement for monopotassium phosphate, the hexasodium and hexapotassium
salts of phytic acid [myo-inositol-hexakis-(dihydrogen phosphate)] were prepared in solution.
The aim is to mimic the contribution of the soluble phosphate additives without consumption
by the formation of inert insoluble phosphate phases.
Cigarette Design - Last month we reported on a series of Kimberly-Clark cigarette wrappers
made from wood pulp. Cigarettes were fabricated with these wrappers and were found to have
equivalent puff counts to controls made with conventional flax wrappers. During this period,
we repeated this test with wood-pulp wrappers supplied by Wattens. Again we found no
significant differences in puff counts between the two wrappers. Additionally, we examined
the puff counts reported in the CI database for our competitors' brands made with wood pulp.
-14-
Cigarette design modeling showed no significant differences between their puff counts and
comparable cigarettes fabricated from flax wrappers.
Filter Research and Development - In addition to developing methods of acetylating paper
webs, we are also acetylating pulped wood fibers and making hand sheets from these. This has
been successfully accomplished on a laboratory scale. We are also seeking outside vendors
who can provide acetylated pulp and produce continuous sheets of web with it. Recent
discussions with USDA proved promising, and we are exploring the possibility of obtaining a
large-scale sample of acetylated pulp from them for producing a small bobbin of web material
for large-scale filter making and testing.
Nicotine Antibody: Several experiments were conducted to determine the cause of the varia-
tion observed in the ELISA to measure nicotine. One ELISA plate was shaken during each of
the incubation periods and one was not shaken. The plate that was shaken exhibited higher
absorbance readings than the stationary plate; however, the shaken plate had more variation in
the data.
/df
PC: Directors
Research Fellow
