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United States Patent: 4,055,191 Other References "Tobacco & Tobacco Smoke," Wynder et al., Academic Press 1967, New York, pp. 521-527. Alteration of Cigarette Smoke Composition 1, Influence of Certain Additives, from "Tobacco Science" Mag., pp. 78"81. Primary Examiner: Howell; Kyle L. Assistant Examiner: Millin; V. Attorney, Agent or Firm: Hendershot; Michael L., Ross, Jr.; J. Bowen, Parent Case Text Page 2 of 23 This application is a continuation-in-part of U.S. patent application, Ser. No. 458,355, filed Apr. 5, 1974, now abandoned. What is claimed is: 1. A smoking tobacco composition comprising tobacco, palladium in an amount of from about 0.001 to about I weight percent based on the weight of the tobacco, and an inor ani_c_nra~salt in an amount of from about 0.25 to about 0.75 weight percent calcu a1°tec~as added nitrate nitrogen 2. The composition of claim 1 wherein the concentration of palladium is from about 0.01 to about 0.1 weight percent and the concentration of nitrate salt is from about 0.25 to about 0.6 weight percent calculated as added nitrate or nitrite nitrogen, based on the weight of said tobacco. 3. The composition of claim 2 wherein the nitric oxide releasing compound is a nitrate salt of a metal selected from Groups Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, and the transition metals of the Periodic Table. 4. The composition of claim 3 wherein the nitric oxide releasing compound is selected from the group of alkali and alkaline earth metal nitrate salts. 5. The composition of claim 4 wherein the nitrate is a salt of a metal selected from the http:// 164.195.100.11/netacgi/nph-Parser?Sect1=PTO1 &Sect2=HIT.../405519 2/ 13/01

' United States Patent: 4,055,191 Page 23 of 23 to Control 3050cm.sup.-1 of PCAH to Sample Cigarettes Cigarettes Dry Solids Weight Basis 2960cm.sup.-1 Control , IR Basis Control 30.5 53.2 1.74 100 0.258 100 A 28.1 44.3 1.58 91 0.206 75 B 20.7 32.1 1.55 89 0.187 72 *Ratio of absorbance peaks appearing at wavelengths of 3050cm.su 2960cm.sup.-1. **M=1000. I 1Jie+.re ShGppiny Cart ~ Hum6er Help http://164.195.100.11/netacgi/nph-Parser?Sect1=PTO1 &Sect2=HIT.../405519 2/13/01

United States Patent: 4,055,191 Page 4 of 23 20. The composition of claim 19 wherein the nitrate is an alkali or alkaline earth metal nitrate. 21. The composition of claim 20 wherein the nitrate is magnesium nitrate. 22. The composition of claim 21 wherein the palladium is added to the tobacco in the form of (NH4).sub.2 PdCl.sub.6. 23. The composition of claim 21 wherein the salt is ammonium tetrachloropalladate. 24. A smoking tobacco composition comprising a. a blend of tobaccos containing up to about 21 percent by weight reconstituted tobacco; b. magnesium nitrate, in an amount of from about 0.25 to about 0.75 weight percent calculated as added nitrate nitrogen based on the weight of the tobacco; and c. palladium, in an amount of from about 0.01 to about 0.1 weight percent based on the weight of the tobacco. 25. The composition of claim 24 wherein the palladium is in the form of palladium hexachloropalladate. 26. A smoking tobacco composition which comprises the product of the process of mixing tobacco and an aqueous solution of a palladium salt in an amount of from about 0.01 to about 0.1 weight percent calculated as palladium and an inorganic nitrate salt in an amount of from about 0.25 to about 0.75 weight percent calculated as added nitrate nitrogen, said weight percents of palladium and nitrate salt being based on the total weight of the tobacco in the smoking composition. 27. The composition of claim 26 wherein the nitrate salt is magnesium nitrate and the palladium salt is selected from the group of ammonium hexachloropalladate and ammonium tetrachloropalladate. 28. The composition of claim 27 wherein the aqueous solution is the casing solution. This invention relates to smoking compositions containing tobacco and having associated therewith a combination of a catalytic agent and an additive capable of http://164.195.100.11/netacgi/nph-Parser?Sect1=PTO1 &Sect2=HIT.../405519 2/ 13/01

United States Patent: 4,055,191 Page 20 of 23 Sample B, is further borne out by the observations with the other cigarettes in that the rate of regression with the others was quite low (15% or less), and that a considerable number of new papillomas were found at necropsy. No tumors were observed in either of the acetone or non-test control groups and therefore they do not appear in the Table. TABLE III Papillomas and Carcinomas Observed During Experiment and at Necrospsy During Experiment Control A B Animals with tumor total 20 17 1 Regressed* 0 1 1 Tumors observed Total 38 34 Regressed 6 4 1 At Necropsy Animals with papilloma only Confirmation 9 12 0 New 0 2 1 papillomas Confirmed 18 25 0 New 10 9 1 Animals with carcinoma Confirmed** 10 5 0 New 1 0 0 Carcinomas Confirmed 18 5 0 New 4 0 0 Total*** Tumor-positive animals 21 19 2 Tumors 52 43 2 Effective number of animals 50 48 43 % Incidence (Tumor +/Eff.) 42% 40% 4.7% *Positive papilloma which disappeared and was not found at necro **Confirmed as carcinoma, whether original visual observation ha "papilloma," "possible carcinoma," or "probable Totals include animals (or tumors) counted as regressions plus a necropsy findings. http://164.195.100.11/netacgi/nph-Parser?Sect1=PTO1&Sect2=HIT.../405519 2/13/01

United States Patent: 4,055,191 Page 3 of 23 group of calcium, magnesium and zinc. 6. The composition of claim 5 wherein the nitrate is magnesium nitrate hexahydrate. 7. The composition of claim 2 wherein the palladium is in the form of finely divided metallic palladium. 8. The composition of claim 7 wherein the palladium is present as palladium black. 9. The composition of claim 2 wherein the palladium is in the form of a palladium salt thermally decomposable to metallic palladium. 10. The composition of claim 9 wherein the palladium salt is a water-soluble salt. 11. The composition of claim 10 wherein the water-soluble palladium salt is selected from the group of a nitrate salt, a halide salt, a diamine complex of palladium or a palladate salt. 12. The composition of claim 11 wherein the salt is ammonium hexachloropalladate. 13. The composition of claim 12 wherein the nitric oxide releasing compound is magnesium nitrate hexahydrate. 14. The composition of claim 10 wherein the salt is ammonium tetrachloropalladate. 15. A cigarette containing the tobacco composition of claim 1. 16. A cigar containing the tobacco composition of claim 1. 17. A pipe tobacco containing the tobacco composition of claim 1. 18. The process for making the composition of claim 1 comprising admixing a catalytic quantity of palladium, said nitrate and tobacco to provide a uniform dispersion of said palladium and said nitrate throughout said tobacco. 19. A smoking tobacco composition comprising: a. tobacco, and b. a catalytic mixture consisting, essentially of palladium, in an amount of from about 0.01 to about 0.1 weight percent based on the weight of the tobacco and a non-toxic inorganic nitrate salt in an amount of from about 0.25 to about 0.75 weight percent calculated as added nitrate nitrogen based on the weight of the tobacco. http://164.195.100.11/netacg'i/nph-Parser?Sect1=PTO1 &Sect2=HIT.../405519 2/13/01

United States Patent: 4,055,191 Page 1 of 23 US PATENT & TRADEMARK t]FFICE PAT"1~NT FULL `l"ZX.'i" AND 1M.AGI~ 1)A"I'ASASV Home Boolean Manual I View Shopping Cart Humber Help Add to Shopping Cart (1of1) cUnited States Patent 4,055,191 Norman et al October 25 1977 . , ............ _.._...._.........._..._..._............_ , Tobacco composition Abstract The amount of polycyclic aromatic hydrocarbons in tobacco smoke is reduced and a substantially diminished biological activity of the tobacco smoke condensate when evaluated on experimental animals following conventional protocol is achieved by adding to the tobacco palladium, either in metallic or salt form, and an inorganic nitric oxide generating compound. Inventors: Norman; Vello (Raleigh, NC); Bryant, Jr.; Herman G. (Durham, NC) Assignee: Liggett & Myers Incorporated (Durham, NC) Appl. No.: 619536 Filed: October 3, 1975 Current U S Class: 131/334; 131/342 . . N Intern'1 Class: A24B 015/02; A24B 015/04 0 00 Field of Search: 131/9,17 R,17,140 rn co:- References Cited [Referenced Byl .......... .. ......... , ... .~a U.S. Patent Documents nv 3572348 Mar., 1971 Norman et al. 131/17. 1,180,320 Foreign Patent Documents Jun., 1959 FR 131/17. http://164.195.100.11/netacgi/nph-Parser?Sect1=PTO1&Sect2=HIT.../405519 2/13/01

United States Patent: 4,055,191 Page 16 of 23 STEMS WEIGHT %* NITROGEN** Control 84 11 5 -- -- A 84 11 5 0.05 -- B 74 21 5 0.05 0.50 *The palladium was added to the blend in the form of (NH.sub.4). PdCl.sub.6. **The final tobacco blend prior to the addition of nitrate conta weight percent native nitrate nitrogen. The added nitrate nitrog provided to the blend in the form of magnesium nitrate hexahydra ****Reconstituted tobacco sheet The above control and Samples A-B most closely approximate the composition of the samples in Example I. The following tabulated data, determined by conventional laboratory techniques, represents certain chemical and physical properties of sample cigarettes selected from the 240,000 cigarettes above, prepared for biological testing. SAMPLE CONTROL - A B Cigarette weight (grams) 1.146 1.111 1.130 Length (mm) 85 85 85 Circumference (mm) 25 25 25 Pressure Drop (cmH.sub.2 0) 4.5 4.3 3.7 Burn Rate (mm/min) 4.93 4.84 5.03 Moisture (wt.%) 11.2 11.4 12.0 Number Puffs 9.7 9.9 9.6 SMOKE STREAM PROPERTIES TMP* (mg/cigarette) 31.8 31.8 29.8 H20 (mg/cigarette) IV o 4.1 4.2 00 . 4.1 i Nicotine (mg/cigarette) O~. te 1.63 1.67 1.27 4~6 NFDS** (mg/cigarette) .la 26.1 25.9 24.4 v *Total particulate matter (wet smoke) _ **Nicotine free dry solids ` NFDS = TPM - (Nicotine 30 H.sub.2 http://164.195.100.11/netacgi/nph-Parser?Sect1=PTO1&Sect2=HIT.../405519 2/13/01

United States Patent: 4,055,191 Page 11 of 23 propylene glycol and sugars to which a solution of ammonium hexachloropalladate and a sufficient amount of water to solubilize the requisite amount of nitrate compound have been added. Such a solution can be conveniently atomized on uncut tobacco strip, or by conventional casing apparatus. Palladium black can be applied on tobacco in the form of a suspension in casing or water or in dry powder from containing the requisite amount of palladium by any convenient means such as atomization or dusting. When palladium black is used, a convenient method of application of the additive to the tobacco is to dry blend the palladium, ground tobacco, a fibrous material and a binder. Dry blending, as in a conventional double cone blender effectively distributes the palladium over the surface of the tobacco including the pores within the tobacco surface which are large enough to accept the palladium particles. When required, dry blending is followed by wet mixing with water and casing materials in proportions sufficient to provide the resulting mixture with the appropriate consistency for conventional reconstituted tobacco sheet manufacturing operations. The sheet is then cut into strips and a solution of nitrate compound in water is applied to the strips. This is followed by a drying step if the tobacco moisture level needs to be adjusted. This material can be used in cigarette manufacture as such or it can be blended in any desired proportion with regular tobacco. The fibrous material which is a constituent of the dry blend can be, for example, .alpha. -cellulose or fibrous tobacco stem material. The binder portion of the dry blend may be sodium carboxymethyl cellulose, or a natural gum such as guar gum. The casing materials used in the wet mixing step are usually glycerin and propylene glycol. Of course, any other known fibrous material, binder or casing materials known to be useful in combination with tobacco products can be used in combination with or in place of those herein set forth. The weight proportions of the additives described above for use in reconstituted tobacco sheets are within the following approximate weight ranges. The proportions shown are within the usual range required to provide useful tobacco products. MATERIAL WEIGHT % Fibrous 4-8 Binder 1-20 Casing Comprising: about 3-9 a) glycerin 4-6 b) propylene glycol 0.5-2 http://164.195.100.11/netacgiinph-Parser?Sect1=PTOl&Sect2=HIT.../405519 2/13/01

United States Patent: 4,055,191 Page 10 of 23 eliminators of PCAH, particularly at levels compatible with acceptable taste and smell of cigarette smoke. Thus, when these nitrate salts are used in accordance with the practice of the present invention, i.e., in the presence of palladium, the amount of nitrate required to decrease the PCAH of the tobacco smoke is lowered significantly thereby allowing for the production of cigarettes that are more desirable from a taste and smell standpoint, yet have a significant reduction in the PCAH content of their tobacco smoke. In the practice of the present invention, the proportion of nitrate associated with palladium and tobacco in the smoking composition is below 0.8%, and preferably is in the range of from about 0.25to about 0.75%, calculated as added nitrate nitrogen. Although the amount of reduction of PCAH yield that is due to the nitrate can be increased as the level of nitrate is increased, the taste and aroma of smoke becomes progressively more obnoxious as the nitrate level is increased. Hence, in combination with palladium, we prefer to operate in the 0.25 to 0.60% added nitrate nitrogen range. The incorporation of the additives of the present invention may take place at any time prior to the final packaging of the tobacco product. In the case of cigarette tobacco they may be incorporated before or after blending of the various tobaccos if, in fact, blended tobacco is employed, and the additives may be applied to one or all of the blend constituents. The additives should be well dispersed throughout the tobacco so that they will be uniformly effective during the entire period during which the composition is smoked. Furthermore, it is important to ensure that the dispersion effectively contacts a maximum volume of smoke which is drawn in by the user. Since the catalytic activity of the palladium is most likely a surface phenomenon, the greatest likelihood of maximum contact between the smoke being drawn in by the user and the palladium is obtained when the area/volume ratio of the palladium particles is maximized for a given weight of palladium. For this reason, if the palladium is applied as metallic palladium black its particle size should preferably be smaller than about 100 U.S: mesh. Water-soluble palladium salts such as hexachloropalladates, tetrachloropalladates, nitrates, chlorides or diamine complexes have the advantage that they can be applied as a dilute solution which facilitates the achievement of good dispersion throughout the tobacco matrix. N o.. c"w; ; The calcium, magnesium and zinc nitrates are very soluble in water and can be applied ~. as a relatively concentrated solution which avoids the excessive wetting of tobacco a+ and yet assures good distribution throughout the tobacco mass. ~::- 3 ~_-.. . We have found that the combination of palladium and a nitrate compound is most efficiently applied in a conventional casing solution such as one comprising glycerin, http://164.195.100.11/netacgi/nph-Parser?Sect1=PTO 1 &Sect2=HIT.../405519 2/ 13/01

United States Patent: 4,055,191 Page 17 of 23 The smoke condensates from the above-prepared cigarettes were assayed for their respective potencies in the induction of epidermal tumors in mice according to the following procedure. The above cigarettes were stored in the laboratory, and before smoking were equilibrated in a cabinet at laboratory temperature and 58% relative humidity. They were then smoked, for the purpose of collecting condensate, on an L&M.sup.TM wheel-type smoker as described in Tobacco Science, Vol. IX, pp 112-115, (1965). The cigarettes were smoked utilizing techniques commonly accepted for such procedures, that is, one 35 ml. puff per minute, to a butt-length of 30 mm. Smoke condensate was collected at liquid air temperature in a two-trap train, with overall yield determined by increase in weight of the traps. The condensate was removed from the traps with acetone, and the acetone removed under reduced pressure at a temperature of 40.degree.-50.degree. C. The final "dry" condensate was dissolved in an equal weight of acetone to give the solution for application. For each test group, 50 young adult HalICR female albino mice, age 8-12 weeks, were housed in clear plastic cages, seven or eight per cage. There were three condensate- treated groups, and two controls: a vehicle control painted with acetone only and a non-test control. The animals were maintained on Wayne Lab Blox food pellets (Alhid Mills, Inc., Chicago, Illinois) and water ad lib. The laboratory was maintained at a temperature of 75.degree. F and a relative humidity of 50%. At the start of the experiment, the animals had an average weight of 27 grams and each animal was individually identified by cage number and toe clipping. The condensates were applied 5 days a week for 79 weeks, with a fresh batch of smoke condensate being prepared for each day of application. The test procedure involved the clipping of hair from the dorsal test area prior to each test painting. The non-test control animals were hair-clipped only at the time of necropsy. Individual test paintings had a target weight of 100 mg (range 90-110) of the test solution, five times per week, except during the first 2 weeks when the target was 80 mg. Animal health was continuously monitored and any seriously ill animals werre sacrificed whenever necessary. The weights of the animals were measured monthly throughout the experiments. During the experiment, the changes in animal body weight were not significantly different among the cigarette groups and lagged only slightly behind the controls, as expected. http://164.195.100.11/netacgi/nph-Parser?Sectl=PTO1&Sect2=HIT.../405519 2/13/01