B COMPLEX VITAMINS In Sugar Cane and Sugar Cane Juice
N T H E United States the two most inexpensive sources of energy-producing foods are cereal products and cane sugar (6). In recent years workers have repeatedly demonstrated that important B complex vitamins, which are found in unprocessed cereal products, are greatly reduced in quantity during processing (1, 3, 4, 8, 1S, 18). The essential facts were recognized many years ago by those who advocated the advantages of whole-wheat flour (9, 10). Investigators have clearly demonstrated that refined sugar is devoid of thiamine (6, 7, 11, 13, 19) and presumably of other vitamins. The present investigation of the water-soluble B complex vitamins of sugar cane and sugar cane juice was undertaken to discover to what extent the processes of sugar refining create this nutritional disparity by removing or destroying certain vitamins naturally associated with sugar in the cane.
I
William I?.Jackson1 and Thomas J. Macek MERCK k COMPANY, INC., RAHWAY, N. J .
waxing. All samples were stored under refrigeration until assayed. In Cuba a total of thirty-six different samples of juice were similarly collected from an equal number of different varieties of cane. I n addition, representative pieces of whole sugar cane were collected from thirty-nine different varieties. All juices and canes were preserved as described. I n both Louisiana and Cuba the samples were collected from plantations in different parts of the state and island, respectively, and thus are representative of several types of soils. The age of the cane varied from 3 months to 2 years, and both plant and ratoon type were sampled. For the most part the Louisianan and Cuban canes were 9 and 11 months old, respectively. On arrival at the laboratory the preserved juices were immediately assayed for sucrose, thiamine, riboflavin, niacin, pantothenic acid, and biotin. The pieces of whole cane were freed of their wax coating, and a portion of each piece was pulped with the aid of a mechanical saw, a knife, and finally a laboratorytype meat grinder. A weighed quantity of the fresh pulp was pressed on a Carver laboratory press, and the juice was col-
EXAMINATION OF SUGAR CANES AND JUICES
The samples of cane juices and canes used in the present investigation were collected in Louisiana and Cuba. I n Louisiana ten samples of juices were taken from three varieties of caneLe., Canal Point 28-19, Coimbatori 281, and Coimbatori 290; two additional samples were obtained from mixed canes direct from the crusher. The canes were freshly cut in the field, and the juices were immediately expressed in a laboratory crusher or in factory crushers. The juices were preserved by the addition of 2 0 3 0 % alcohol. Samples of whole sugar cane, consisting of two or three segments from both the top and bottom of several canes, were also taken directly from the field and preserved by
TABLEI. SUCROSE AND VITAMIN CONTENTS EXPRESSED FROM SUGAR CANE Variety of Cane
Za 6= Za 1" la
izh ...
Badilla Baragu& Canalpoint Coimbatori Cristalina
lb 35
2b 2) 2a
Fajardo
lb
6b 20 1b
158 lb
... 36a , . ,
b
Louisianan Cane Juiaes 18.24 0.062 0.039 14.83 0.099 0.052 15.38 0.084 0.055 13.85 0.049 0,049 11.41 0.136 0.071 11.41 0.049 0,038 14.76 o . m o 0.053 18.24 0.136 0.077 Cuban Cane Juices 20.19 0.179 0.112 18.66 0.229 0.070 16.41 0.259 0.070 16.66 0.197 0.110 16.80 0.095 0.075 16.61 0.255 0.140 19.69 0.141 0.086 17.23 0.180 0 081 19.67 0.103 0.059 17.27 0.186 0.082 19 41 0.133 0.062 10.25 0.086 0.051 17.87 0.179 0.083 23.04 0.359 0.174
2.84 2.71 3.76 5.41 5.80 2.53 3.70 5 80 1.65 1.76 2.28 3.04 2.53 1.27 1.20 1.38 1.60 1.53 1.60
0.76 1.69 3.34
0.721 0.829 0.703 0,861 1.063 0.657 0.834 1.063
Present address, Wyeth Incorporated, Philadelphia, Pa.
TABLE 11. SUCROSE AND VITAMINCONTENTS OF WHOLE SUGARCANES
O F JUrCES
Vitamins, Micrograms/Gram of Juice No. of Samples ' ThiPantoor Sucrose, amine Ribo- thenio Species HC1 flavin acid Niacin Biotin
C.P. 28-19 c o . 281 co. 290 Mixed Mixed Minimum Average Maximum
Mayaguez MediaLuna Palma POJ SantaCruz Minimum Average Maximum a Samples.
1
Variety of Cane
0.034 0.034 0.025 0.022 0.028 0.022 0.031 0.038
C.P. 28-19 c o . 281 c o . 290 Minimum Average Maximum Badilla BaraguB Canal Point Coimbatori Cristalina Fajardo Mayaguez Media Luna Palma POJ Santa Crus Uba
0.975 0,030 0.814 0.033 0.768 0.038 0.797 0.042 0.538 0.020 0.914 0.041 0.813 0,027 0.956 0.028 0.697 0,025 0.720 0.029 0.718 0.027 0.530 0.016 0.765 0.030 1.06 0.045
Minimum Average Maximum
Vitamins, Micrograms/Gram of Cane ThiPantoNo. ,of Sucrose, amine Ribo- thenic Species % HC1 flavin acid Niacin Biotin
.. .. .. .. .. .. 1
3 2 2 2 1
6 2 3 15 1 1
..
39
..
Louisianan Whole Canes 11.66 0.328 0.203 11.08 0.499 0.250 11.84 0.332 0.202 0.245 0.149 .. 0.398 0.222 0.576 0.261
0.040 0.042 0.027
1.93 3.36 4.27
1.38 1.60 0.988 0.851 1.31 1.62
Cuban Whole Canes 14.50 0.300 0.230 11.21 0.428 0.309 12.82 0.415 0.169 12.98 0.623 0.237 12.48 0.565 0.189 11.81 0.475 0.185 13.89 0.342 0.227 10.23 0.375 0.301 15.22 0.348 0.216 10.92 0.451 0.245 15.10 0.334 0.396 12.44 0.194 0.212
1.68 1.27 2.16 2.33 1.51 0.950 1.39 2.00 1.30 1.12 1.41 2.13
1.95 1.75 1.74 1.31 1.12 1.80 1.79 2.04 1.67 1.38 1.51 1.68
0.073 0.037 0.071 0.054 0.027 0.071 0.054 0.065 0.046 0.047 0.044 0.044
5.30 12.24 18.95
0.543 1.41 3.47
0.888 1.56 3.03
0.009 0.050 0.106
... . . ..
0.194 0.129 0.420 0.241 0.793 0.396
3.61 2.81 3.78
0.023 0.036 0.048
Species. d
261
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
262
TABLE 111. VITAMINCONTENTS OF INDIVIDUAL VARIETIESO F CUBAN WHOLESUGARCANE
Variety of cane Badilla Baragu4 Baraguh 469 1.29 Baragu4 470 C.P. 29-116 C.P. 29-320 Co. 213 Co. 281 Cristalina (Preston) Cristalina (Espana) Fajardo 916 Mayaguez 7 Mayaguez 28 Mayagues 42 Mayaguez 49 Mayagues 62 Mayaguez 234 Medis Luna 318 Media Luna 4-17 Palma 19 Palma 32 (thin) Palma 32 (thick) POJ 22 POJ 2714 (Palma) POJ 2714 (Jatibonico) POJ 2714 (Rayada) POJ 2714 (Sport) POJ 2714 (Sport) POJ 2725 (Palma) POJ 2725 (Espana) POJ 2725 (Jatibonico) POJ 2727 (Preston) POJ 2727 (Jatibonico) POJ 2878 (Preston) POJ 2878 (Espana) POJ 2878 Preston) POJ 2883 {Violeta) Santa Crus 124 U ba
Av. Vitamin Content Micrograms/Gram of Chne ThiPantoAge, Sucrose, amine Ribo- thenic Soid ~ i Biotin ~ HC1 flavin M ~ , % 1.95 0.073 11 14.50 0,300 0.230 1 .e8
ij
lg:ig :!g0.202 :
11 11 11 24 11 ll
9.91 12.25 13.40 13.00 12.95 12,55
11
~:~~~1.74 ;:\2.52
t::::
0.585 0.245 0.650 0,595 o,713
0,389 0.205 0.133 0.345 o,208 0.129
2.16 2.15 1.20 3.47 1,68
1.70 1.78 1.30 1.32 1,35
0.038 0.075 0.068 0.045 o,026 0.063
11 11 11 11 11 12 11 11
12.40 11.81 12.45 18.95 13.50 10.82 11.40 16.20 9.60 10.85 15.70
0.418 0.475 0.363 0.269 0.357 0.223 0,360 0.478 0.470
0.170 0.185 0.150 0.162 0 357 0.223 0.220 0.223 0.230
1.35 0.95 0.78 1.27 2.31 0.58 1.88 1.52 2.18
0.89 1.80 1.25 1.29 1.89 1.53 1.72 3.02 2.08
0.027 0.071 0.068 0.041 0 056 0'070 0.056 0.034 0.045
11 11 24 12 3 12 11 12 24 11 24 11 12 17 12 11 11
13.20 0.385 0.218 10.78 0.313 0.355 13.10 0.300 0.283 8.92 0.418 0.235 7.90 0.478 0.164 8.92 0.343 0.230 14.56 0.360 0.193 11.37 0.403 0.158 16.10 0.387 0.187 5.30 0.791 0.520 10.52 0.410 0.148 8.25 0.383 0.352 14.15 0.793 0.158 12.00 0.642 0.277 8.73 0.343 0.195 15.10 0.334 0,396 12.44 0.194 0.212
0.99 1.15 1.23 0.54 1.57 0.99 1.00 0.83 1.30 1.50 0.87 1.23 0.98 1.87 0.79 1.41 2.13
1.15
0.062 0.052 0.106 0.038 0,009 0.022 0.062 0.078 0.041 0.030 0.050 0.054 0.038 0.036 0.028 0.044 0.044
11 11
0 0
1.73 1.55 1.32 1.04 1.15 1.06 1.25 1.70 2.38 1.10 1.18 1.18 2.00 0.91 1.51 1.68
TABLE IV. AVERAGE VITAMINDISTRIBUTION IN TOPAND BOTTOM PORTIONS OF SUGAR CASES
ThiamineHC1 Riboflavin Pantothenic acid Niacin Biotin Sucrase, %
-Louisianan Cane-Cuban TOP Bottom Top, Microg;ams Microgra& Micrograms Per g. Per lb. Per g. Per lb.' Per g. Per lb. cane s u c r o ~ e cane sucrose cane sucrose 0.333 1491 0.498 1791 0.429 2274 0.258 1154 0.194 737 0.258 1284
CanBottom Micrograhs Perg. Per lb. cane sucrose 0.394 1361 0.223 850
3.99 17941 1.37 6164 0.034 154 10.09
1.29 4653 1.45 5263 0.050 179 13.16
2.61 9367 1.21 4614 0.035 138 12.82
1.51 1.71
7345 8224 224 11.32
0.051
lected. The marc from the pressing was recovered, macerated with acidulated water for 30 minutes a t room temperature, again pressed, and the extract was collected. This process of maceration and pressing was repeated twice. I n all, the pulp was subjected to four hydraulic pressings. Cbntrol tests showed that this treatment was sufficient to extract all the vitamins as well as all the sugar. The juice and extracts were combined and adjusted by the addition of acidulated water so that each gram of combined extract represented a definite weight of fresh pulped cane. These extracts were then assayed for sucrose and the vitamins.
Vol. 36, No. 3
to a modification of the Snell and Wright method for niacin, The assays for sucrose and for the B complex vitamins were averaged and tabulated into groups according to the variety of cane. Averaged assays for juices and whole cane appear in Tables I and 11, respectively. data on the average assays for the in~ More i complete ~ dividual varieties of Cuban cane, rather than for groupings of similar varieties, appears in Table 111. Table IV compares the sucrose and vitamin contents of the bottom and top portions of sugar cane in terms of averaged values. The vitamin contents of Louisianan and Cuban juices and canes are comparedin Table V. RESULTS AND CONCLUSIONS
Sugar canes vary greatly in sucrose content in different countries, in different parts of the same country, and from time to time in the same locality. The maximum sucrose content of Louisianan cane is usually about 12%; the average content of Cuban cane is between 13 and 14q7,. I n the present study the average sucrose content for the Louisianan samples was 11.5 and for the Cuban, 12.30J0. The bottom segments of the canes were generally richer in sucrose than the top segments. On the other hand, the top segments were generally richer in vitamins than the bottom ones (Table IV). The results in Table I11 indicate that the vitamin content differs from one variety to another. This variation likewise occurs between the groupings of Cuban varieties as shown in Table 11; between these groupings no uniform correlation was apparent in respect to sucrose and vitamin content. Except for pantothenic acid where the reverse is true, a comparison of the average vitamin values per pound sucrose (Table V) shows that Cuban cane is richer in the B complex vitamins than Louisianan. This was probably true because the Cuban samples were more mature than the Louisianan. Because of climatic conditions Louisianan cane is usually cut before it reaches full maturity. From Table V it is b o evident that biotin and riboflavin occur in lesser amounts than does thiamine hydrochloride in sugar cane and juice, whereas niacin and pantothenic acid are found in greater amounts.
TABLEV. VITAMINCONTENTSOF LOUISIANANAND CUBAN JUICES AND CANE(Mo. VITAMINPER POUND SUCROSE) Y L o u i s i a n a n Samples-Cuban SamplesJuice Whole Cane Juice Whole Cane Av. Max. Av. Max. Av. Mas. Av. Max. Thiamine HC1 1.57 2.2o o. 29 o. 54 2.o5 17.95 o. 46 1 , Riboflavin 0.92 1.17 0.17 0.28 1.07 4.92 0.22 0.44 Pas,henic 13.73 19.61 12.03 23.06 6.03 22.74 4.42 9.87 5.39 7.89 2.68 4.23 6.77 32.60 1.99 3.32 $ ;;;: 0.15 0.20 0.09 0.130.20 0.420.080.12
ASSAY METHODS
ACKNOWLEDGMENT
Sucrose determinations were made following a modified Jackson-Gillis method for Clerget sucrose (16). The values in the tables are given as per cent by weight. Thiamine hydrochloride was determined by Connor and Straub's modification (3) of the thiochrome method. Assay samples were treated with the enzyme claras? to hydrolyze any co-carboxylase that might be present. Riboflavin was determined microbiologically by the method of Snell and Strong (IQ), pantothenic acid according to Strong, Feeney, and Earle (I?'), niacin according to Snell and Wright (16), and biotin according
So many people contributed to the success of this work that it is hardly possible to mention all. However, special thanks are due to the following members of the scientific staff of Merck & Company R. T. Major, Director of Research, E. H. Meiss, B. Martin, E. Benditt, M. Gunness, B. Moore, J. Cross, J. L. Stokes, J. A. Elder, W. C. Fulmer, and J. Young. Walter Godchaux and W. Bondurant, Godchaux Sugars, Inc., H. J* Jacobs, South Coast Corporation, and J. T. Landry, Supreme Sugar Refinery, cooperated in providing samples and for work on the Louisianan canes. George Deschapelle and Jose Maria Zayas, of Havana, made it possible for the material to be taken from Cuba with a mini-
March, 1944
INDUSTRIAL AND ENGINEERING CHEMISTRY
mum of trouble and delay. A. C. Matthews, Central Palma; E. Miller, Compafiia Arucarera Atlantica del Golfo; F. Adair Monroe, Compafiia Cubana; H. J. Schreiber, Ingenio JatibonN O ; Percy A. Staples Hershey Corporation of Cuba; J. D. Stephenson, Central V)ioleta; N. N. Trinler, Central Preston; George T. Walker, Central Espana; and B. A. Sample, of Havana, provided facilities of all kinds and splendid hospitality. Special thanks are due F. A. Monroe, whose influence was of tremendous help in many difficult situations. The Coca Cola Corporation of Havana made available, without chargel mobile refrigerating facilities which made possible the collection of samples from all over the island. Leonard Wickenden, of New York, provided valuable connections in Louisiana and Cuba. LITERATURE CITED
(1) Andrews, J. S.,
Boyd, H. M., and Terry, D. E., Cereal Chem.,
19,55 (1942). (2) Baker, A. Z.,Wright, M. D., and Drummond, J. C., J. SOC. Chem. Id.,56, 191 (1937). (3) Connor, R. T., and Straub, G. J., IND. ENG.CEEM.,ANAL.ED., 13, 380 (1941). (4) Copping, A. M.,and Roscoe, M. H., ,Biochem. J., 31, 1879 (1937).
263
(6) Cowgill, 0.R., J. Am. Med. Assoc., 113, 2146 (1939). (6) Zbid., 122, 437 (1943). (7) Daniel, E. P., and Munsell, H. E., U. 8. Dept. Agr., iMisc. Pub. 275 (1937). (8) Harris, L. J., and Leong, P. C.,J . SOC.C h m . Id.,56, 195 (1937). (9) Lapicque, L., and Chaussin, J., C m p t . rad., 166,300 (1917). (10) Moore, C. V.,and Brodie, J. L., Arch. Pediat., 42, 572 (1925). (11) Nelson, E. M.,and Jones, D. B., J . Agr. Research, 41,749(1930). (12) Pyke, M.,J . SOC.Chem. Id.,58, 338 (1939). (13) Sherwood, R. C., Nordgren, R., and Andrews, J. S., Cered Chem., 18,811 (1941). (14) Snell, E. E.,and Strong, F. M., IND. ENG.CHEM.,ANAL. ED., 11, 346 (1939). (16) Snell, E. E., and Wright, L. D., J. Biol. Chem., 139,676 (1941). (16) Spencer, G. L., and Meade, G. P., Handbook for Cane Sugar Manufacturers and Their Chemists, 7th ed., p. 234,New York, John Wiley t Sons, 1929. ENG.CHE~M., (17) Strong, F. M., Feeney, R. E., and Esrle, A., IND. ANAL.ED., 13,566 (1941). (18) Thomas, J. M.,Bina, A. F., and Brown, E. B., Cereal Chem., 19, 173 (1942). ENG.CREM.,33, 718 (1941). (19) Williams, R.R.,IND. PRSSS~NTBIII before the Division of Sugar Chemistry and Technology a t the CHEMICAL SOCIIITY,Pittsburgh, Pa. 106th Meeting of the AMERICAN
Corrosivity of Lubricating Oils EXISTENT AND POTENTIAL GEORGE W. WATERS‘ AND HUGH D. BURNHAM* Shell Oil Company, Inc., Wood River, Ill.
T
HE fundamental Bearing corrosion is analyzed into two concepts: ‘‘exOn the other hand requ&tes for coristent corrosivity” which occurs by virtue of the instanevery lubricant can cause rosion are a corroditaneous chemical state of a lubricant, and “potential corimmediate corrosion to: a ble and vulnerable metal rosivity” which occurs under conditions, representative degree, varying from zero surface, and the presence of those of service, which lead to the simultaneous oxidato relatively great magnition of the oil. The effects upon both types of corrosivity tude. This “existent corroof corrosive bodies, generally acidic. of temperature, time, nature of oil,concentrationof reactsivity” (EC) is defined as Corrosion of the bearants, and physical factors of tests are described. The imthe corrosion caused by ings of an internal cornportant functioh of protective lacquer films in preventing a lubricant under concorrosion and the interference with their action by deditions which lead to bustion engine by lubricating oil occurs in service tergents are demonstrated. no, or insignificant, change under conditions which efeither chemically or physifect simultaneously other cally, other than that chemical changes in the lubricant. In general, an unused oil condirectly associated with the occurrence of corrosion. Thus, tains no corrosive bodies; however, when an oil-metal system is an undoped, fresh oil would be expected to have very low aged under conditions representative of service, corrosion will EC, whereas the same oil after a period of service may have occur t o a degree dependent upon the oil and the severity of the developed an appreciable EC. Existent corrosivity is expressed fundamental factors. This tendency of an oil to become corroin the same units as potential corrosivity; however, the apparasive, called “potential corrosivity” (PC), is defined the extus and conditions of memurement necessarily differ markedly. tent of corrosion which occurs during the service life of the oil. Although the potential corrosivity of a lubricant is influenced Some liberty is taken in this definition since the corrosion which by the initial characteristics of the oil, it win depend to a major occurs in service is a function of the conditions, and varies not degree upon the conditions of aging. I n service, corrosion is only with type of engine but Over different units of the same inseparable from and dependent upon the oxidation of the oil. type. However, standard engine tests have been devised and Hence, in the laboratory, conditions of test for potential corrosivlimits assigned to permissible corrosion; potential corrosivity, ity should promote the oxidation of the lubricant. Herein lies therefore, is not an imaginary concept. Potential corrosivity a fundamental difference between potential corrosivity and pertains to fresh oils and is most accurately measured in the enexistent corrosivity; for the latter the maximum separation of &e. Laboratory tests, however, which age an oil under the variables is sought. Although existent corrosivity is useful in a conditions representative of service, predict with reasonable fundamental study, potential corrosivity remains more imaccuracy its potential COrrOSiVity. Potential COrrOSiVity is exportant practically since the quality of a lubricant is determined pressed as the milligram weight loss per square centimeter BUSby its performance in service, tained by the metal under the selected conditions.
* Present address, Shell Oil Company, Inc., 50 West 50th Street, New York 20, N. Y. 3 Present address, Lieutenant, Ordnance Department, The Proving Center, Aberdeen Proving Ground, Md.
APPARATUS FOR MEASURING CORROSIVITY
The corrosion and stability (C and 5) apparatus and test used to evaluate potential corrosivity were described elsewhere (8);
