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COMMUNICATIONS TO THE EDITOR
as fast as 20' as a t 25', but upon addition of chloroform to prevent freezing and cooling with solid carbon dioxide it appeared to be instantane-
Vol. 68
were constant. The products of this hydrolysis were dextrin B-lal and maltose, the yields being 62 and 30% of the weight of dextrin B-la, reOW. spectively. Dextrin B-lal rotated 146.0' in The only hypothesis that seems t o accord with water and had a reducing power by the Goreall of these results is the one suggested by Liebhaf- Steele method equivalent to 12% of t h a t of glusky,' that the reactive halogen is in the form of cose. On treatment with the amylase of Asperhydrate. If these hydrates contain a number of gillus oryzae, the reducing power of dextrin R-la1 molecules (of water, like the solid Cl2.6H20, they increased about sixfold and the rotation decreased could involve the large heat of formation required t o +3S0. This hydrolysate after fermentation to explain the large negative temperature coef- with yeast did not reduce Fehling solution and ficient of the reaction. There is, of course, was levorotatory. After removal of the yeast and ample evidence that the number of "icebergs" concentration of the solution, a solid was obtained D in water; in water falls off rapidly from 0' t o room tempera- by addition of ethanol; [ C U ] ~ ~-32' ture. yield, 4.2% of the weight of dextrin A . This It has been difficult to secure sufficient repro- solid was acetylated and from the resulting prodducibility to give satisfactory quantitative data, uct levoglucosan triacetate was isolated ; yield, and since this may take some time, it seems ap- 0.6% of t h a t calculated for levoglucosan on the propriate 1.0 publish the above preliminary re- basis of waxy corp starch; [ c Y ] * ~ D-65.5' in sults. CHClB (c, 1); m. p. 110-111°,7 (mixed m. p. unchanged). On deacetylation, levoglucosan was (1) 1% A. Liebhafsky, Chef#. Rev., 17, 89 (1935). obtained in pure crystalline form and characterDEPARTMENI OF CHEMISTRY ized. Levoglucosan was also obtained from 1-NIVERSITY UF CALIFORNIA J. H. HILDEBRANDthe hydrolysate resulting from the action of the BERKELEY, C:ALIF RECEIVED APRIL 15, 1946 amylase from Aspergillus oryzae on dextrin B - l a without prior fermentation. Isolation was effected both by distillation and by fractional crysTHE ISOLATION OF LEVOGLUCOSAN FROM THE tallization after acetylation. Further work will ENZYMIC HYDROLYSATES OF WAXY CORN have to be carried out to determine whether the STARCH 1,G-anhydro linkage is formed during enzymic Sir: Waxy corn ~ t a r c h ' *has ~ , ~been subjected to fission of the substrate or actually occurs in waxy the consecutive action of @-amylase, a-amylase, starch. (7) Zemplbn, Gerecs and Valatin, Ber , 73, 576 (1940) @-amylase,and an amylase prepared from AsperRESEARCH FOUNDATION gillus oryzae in order to obtain information on its CORNINDUSTRIES EDNAM. MONTGOMERY XEWYORK17, N.Y. structure. REGIONAL RESEARCH LABORATORY The starch, pasted a t 80°, was first treated with SORTHERN OF AGRICULTURAL A N D INDUSTRIAL CHEMISTRY BUREAU @-wheat amylase4 free from a-amylase and mal- AGRICULTURAL RESEARCH ADMINISTRATIOT tase. Dextrin A5 and maltose, the end-products U. S. DEPARTMENT OF AGRICULTURE of this hydrolysis, were isolated in yields of 49 and PEORIA5, ILLISOIS G E. HILBLRT 4870, respcctively. RECEIVED MARCH 4, 1946 Dextrin A was then subjected to the action of a-malt-amylase,8 free from @-amylase and maltase, until no further increase in the reducing 6-CHLOROVANILLIN FROM THE CHLORITE OXIDATION OF LIGNIN power of the hydrolysate occurred. From this hydrolysate, dextrin B-1 was separated by the Sir: addition of ethanol to a concentration of 85% by I n a fundamental study of the reaction of lignin volume; after two reprecipitations the new dex- with sodium chlorite in acid solution, the original trin was dialyzed continuously against distilled filtrate from the preparation of holocellulose from water for nine hours. The liquor remaining after black spruce (Picea mariana) by means of sodium dialysis waij concentrated and the dextrin R-la chlorite in dilute acetic acid according to Wise and was recovered by precipitation with ethanol; co-workers' , 2 was investigated. The filtrate was yield, 44% of the weight of dextrin A ; [ff]"D further acidified with sulfuric acid and fraction+lCiO.l"' in water; reducing power 3.5 and S.006 ated. The steam lion-volatilc aldehyde fraction of that of glucose by Shaffer-Hartniann and Gore- was itlcntified as 6-chlorovanillin, colorless plates Steele methods, respectively. from ethanol melting a t 167-168'. (Anal. Dextrin %la was next submitted to the action Calcd. for CsH703Cl: C, 51.49; H, 3.78; C1, of @-amylaseuntil the rotation and reducing power 19.00; CH30, 16.63. Found: C, 51.34; H , 3.76; (1) Hixon and Sprague, I x d . E x g , Chem., 34, 959 (1942). C1, 19.19; CH30, 16.70.) The oxime, prepared ( 2 ) hfacMasters a n d Hilbert, ibid., 36, 958 (1944). by heating with a solution of hydroxylamine hy(3) Schopmeyer, Felton and Ford, ibid., 3 6 , 1168 (1943). (4) Hanes, Biochem. J . , 30, 174 (1936). ( 5 ) Cf.Haworth, Kitchen and Peat, J. Chem. SOL.,619-625'(1913). ( 6 ) Hanes, Ccn. J. Re.wnrch, 13B, 185-208 (1935).
+
(1) Wise, Ind. Eng. Chem., Anal. E d . , 17, 63-64 (1045). (2) Wise, Murphy and D'Addieco, Paper Trade J.,122, No. 2, 35
(1946).
NEWBOOKS
May, 1946
drochloride and sodium‘hydxaxide and recrystallizing the product from dilute ethanol, was obtained as colorless needles melting a t 177-178’. Raiford and Lichty3 synthesized 6-chlorovanillin and its oxime and recorded melting points of 167168’ and liso,respectively. Further work on the filtrates from the chlorite treatments of carefully analyzed samples of black spruce (Picea marianu), western red cedar (Thuja plicata), western hemlock (Tsuga heterophylla), (3) Raiford and Lichty. THISJOURNAL, 62, 4581 (1930).
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aspen (Populus sp.), loblolly pine (Pinus tueda) and slash pine (Pinus caribaea) and on the liquors from the chlorite treatments of a number of isolated lignins of various types from both harclwoods and softwoods is now in progress. The results of these experiments, together with theoretical considerations, will appear in future communications. THEINSTITUTE OF PAPER CHEMISTRY APPLETON, WISCONSIN IRWIK A . PEARL APRIL 3, 1946 RECEIVED
NEW BOOKS Journal of Colloid Science, VICTOR K. LAMER,Editor-inChief, et al. Academic Press, Inc., Publishers, 125 East 23rd St., New York 10, X. Y. Volume I, No. 1, January, 1916. Published bimonthly at $10.00 a year. This new publication, with Professor LaMer of Columbia University as Editor-in-chief, will contain original papers, letters to the Editor and book reviews. In addition to Professor LaMer the editors are T. R. Bolam of Edinburgh, E. F. Burton of Toronto, R. M. Fuoss of New Haven, H. K. Kruyt of Utrecht, J. W. McBain of Palo Alto, E. K. liideal of Cambridge, William Seifriz of Philadelphia, A. W. Thomas of New York, Arne ‘fiselius of Upsala and Harry B. Weiser of Houston, an impressive list. There is also a consulting committee composed of W. T. Astbury, J. J. Bikermann, W. Clayton, P. Debye, W. Feitknecht, Alexander Frumkin, William D. Harkins. Ernst A. Hauser, Wilfried Heller, J. N. Mukherjee, F. F. Nord and The Svedberg. The papers in the first number are: “Contraction and the C h e m p l Structure of the Muscle Fibril” by A. SzentGyorgi; Polarization and Permeability” by M. SpiegelAdolf and E. A. Spiegel; “Torsion in Protoplasm” by William Seifriz; “Adsorbed Nitrate Ions in Relation to Plant Growth” by H. Jenny; “Surface Films of Polymers” by D. J. Crisp; “Mono-dispersed Hydrophobic Colloidal Dispersions and Light-Scattering Properties. I.” by Victor K. LaMer and Marion D. Barnes; “Monodispersed Hydrophobic Colloid Dispersions and Light-Scattering Properties. 11.” by Marion D. Barnes and Victor K. LaMer; “The Method of Purifying and Concentrating Colloidal Dispersions by Electrodecantation” by Paul Stamberger; “Structure of Soap Micelles as Indicated by X-Rays and Interpreted by the Theory of Molecular Orientation. 11.” by William D. Harkins, Richard W. Mattoon and Myron L. Corrin. One wonders why there was not a paper on plastics in the first number and why there were two papers by the Editor-in-Chief. Plastics is a very important field in the colloid science of today. WILDERD. BANCROFT Colorimetry for Chemists. By M. G. MELLON,Ph.D., Sc.D., Professor of Analytical Chemistry, Purdue University. The G. Frederick Smith Chemical Company, 867 McKinley Avenue, Columbus, Ohio, 1945. 15.5, X 23 cm. 133 pp. 51 figs. Price, $1.00 for bound copies. Paper copies free on request. The still growing importance of optical methods for quantitative analysis is exemplified by this compact and
suggestive volume. After a careful delineation of the scope of colorimetric methods, there is a description of typical instruments, their manipulation and limitations. Much attention is devoted t o tabulation and plotting of experimental data, and the relative advantages of various co6rdinates are discussed. There is a section dealing with color analysis and psychophysical specification. The final chapter outlines a number of experiments designed for development of technical skill. The bibliography of two hundred and fifty references is well chosen and up t o date. Those who digest this booklet can undertake colorimetric and spectrophotometric procedures with added efficiency and confidence. GEORGES. FORBES L’Effet Soret. Diffusion Thermique dans Les Phases Condensdes. By S.R. DE GROOT,Doctor of Science. S. V. Soord-Hollandsche Uitgevers Maatschappij, Amsterdam, Holland, 1915. 191 pp. 42 illustrations. 15 X 23 cm. This book, the author’s doctoral thesis, reviews the experimental and theorctical literature on thc Soret cffcct and thermal diffusion in the liquid phase and coritains a report of the author’s own experimental moork on thermal diffusion in aqueous salt solutions. After an introductory chapter, the experimental procedures and results, which have been obtained in investigations of the pure Soret effect, are discussed in some tietail. Then follows a discussion of the thermal diffusion method of Clusius and Dickel, called the thermogravitational procedure by the author. Results of its application to liquid phase separations obtained by the author and other investigators are presented. The following chapters are devoted t o a lengthy review of the theoretical interpretation of the Sorct effect and thermal diffusion. The thermodynamic theories, analogous ro those of the thermo-electric effect a i d the relatiotis between thermoelectric potentials and Peltier heats, are presented in some detail. I t is shown how the Onsager reciprocal relations, based upon the principle of microscopic reversibility and the theory of fluctuations, may be used to supplement the purely phenomenological theory to yield significant results. The kinetic theories of the Soret effect are also presented, and the results which can be obtained from them are summarized. Unfortunately, no entirely adequate molecular theory of thermal diffusion exists except that of Chapman and Enskog for gases of low density, to which Maxwell-Boltzmann transport equation is applicable.
