James A. Harris

Synthesis of some furoic and thenoic esters of the methyl d-Glucopyranosides, and their stability to high-energy radiation

Abstract The esters obtained by complete esterificatlon of methyl D-glucopyranosides with, respectively, 2-furoyl chloride (β-, 1: α-, 2), 2-furanacryloyl chloride (β-, 3: α-, 4) 5-bromo-2-furoyl chloride (β-, 5: α-, 6) 2-thenoyl chloride (β-, 7: α-, 8) 5-methyl-2-thenoyl chloride (β-, 9: α-, 10) 5-bromothiopheneacryloyl chloride (β-, 11: α-, 12) and 2-thiopheneacryloyl chloride (β-, 13: α-, 14) were subjected to irradiation (2.8 x 1019 eV/gh) in the solid state to a dosage of 7.1 x 1020 eV/g. The e.s.r. spectra of irradiated (irr.) methyl α- and β- d -D-glucopyranoside and irr. esters 1-14 were examined to determine the nature of the radiation damage: those of the unsubstituted d -glucopyranosides contain one very strong doublet and one very strong singlet, indicating that cleavage of the C-I-O bond (doublet) and dehydrogenation of the C-I-H bond (singlet) had occurred. The e.s.r. spectra of irr. furoates 1 and 2 contain strong doublets. but those of 3-6 have none, showing that the glycosidic bonds in the latter are highly stable to radiation damage, but those in 1 and 2 are stable compared to that in methyl α- d -glucopyranoside. The e.s.r. spectra of the irr. thenoic esters indicated that glycosidic bonds to 11 and 12 are highly stable to radiation initiated cleavage (absence of doublets), those in 7-10 are fairly stable (weak doublets), and those in 13 and 14 are more stable (strong doublets) than that in methyl α- d -glucopyranoside (very strong doublet) Radiation-initiated, dehydrogenation reactions were decreased for 7 and 8 (very weak singlets), 9 and 10 (very weak, and weak singlets), and 11 and 12 (strong singlets). compared with those of methyl α- d -glucopyranoside, 13, and 14 (very strong singlets). The radiation stability of these esters may arise from intramolecular transfer of energy to the ester groups, and be followed by dissipation of the energy. The anomeric form of methyl d -glucopyranoside has no influence on the localization of the energy.

Ultraviolet Radiation in Treatments for Imparting Functional Properties to Cotton Textiles 1

The desirability of developing new methods for the chemical processing of textile materials has encouraged studies of ultraviolet radiation in textile finishing. Wrinkle-resastant cotton and flame- resistant cotton were prepared by processes that include photo-initiated, free-radical reactions resulting from ultraviolet radiation of cotton in the presence of reactive monomers. The influences of variables in the treatments were determined and optimum conditions identified. Other important findings on the chemistry and technology of ultraviolet radiation were observed.

Free radical addition of dialkyl phosphites to N,N-disubstituted amides of unsaturated fatty acids and screening of the products for antimicrobial activity.

Free radical addition of dibutyl phosphites to terminal and internal double bonds of monounsaturated amides was attained in high yield. The reaction was initiated by irradiation using Cobalt-60. Attempts to add diphenyl phosphite to the unsaturated amides failed with the amides being recovered unchanged. Similar attempts to add dialkyl phosphites to N-linoleoylmorpholine resulted in products that were deficient in phosphorus. Screening for antimicrobial activity againstEscherichia coli, Trichosporon capitatum, Trichoderma viride andCandida lipolytica indicated that terminal addition products may be more active than the internal addition products, with the former strongly inhibiting the growth of all four test organisms.

Limitations of Cold Sodium Sulfite Titration Methods for Free Formaldehyde in Textiles

One of the more important analytical methods for formaldehyde in a finished textile is the cold sodium sulfite analysis for free or unbound formaldehyde. Because this formaldehyde assay can represent the equilibrium formaldehyde in a finish or reagent and therefore that formaldehyde available for consumer exposure, values obtained should be free of bias. Interferences and limitations of cold sodium sulfite analyses for formaldehyde are detailed and techniques to surmount the limitations are presented.

Electron-spin resonance studies of oxidation photosensitized by ferric chloride, of some alcohols in rigid glasses

Abstract Ferric chloride-photosensitized oxidations of methanol, ethanol, 1-propanol ( 3 ), 2-propanol, 1-butanol ( 5 ), 2-methyl-1-propanol, 2-methyl-2-propanol ( 7 ), 1-pentanol, cyclopentanol, and cyclohexanol were conducted in the cavity of an e sr spectrometer at temperature between −150 and -196°, with high-pressure, mercury lamp as the light source except for rigid glasses of 7 plus ferric chloride, all of the photolyzed alcohols investigated generated e s r-detectable free-radicals. The effects of temperature of the concentrations of the radicals formed in the riged glasses indicated that the production of free radicals derived from alcohols involves an active intermediate trapped in the photolyzed, ferric chloride-alcohol rigid glass. In almost all classes, the intensities of the signals of the e s r-detectable radicals increased after photolysis was discontinued when the temperatures of the photolyzed, rigid galsses were increased, the intensities of the signals generated by the radicals increased initially, until radical recombinations became the predominant raection based on hyperfine splittings of the e s r spectra, a free-radical site could be assigned to the hydroxyl-bearing carbon atom of all of the alcohols investigated, except 3,5 and 7 . As the temperature of the rigid galsses were increased, changes in hyperfine splittings of the e s r spectra of the radicals derived from alcohols were observed, these changes probably reflect increased molecular motion of the photolyzed alcohols.

Fibrous Structure and Properties of Cotton-Poly(Butyl Methacrylate) Copolymers Prepared by Post-Irradiation Initiated Reactions

Graft copolymerization reactions of butyl methacrylate from aqueous methanol solutions with radiation-activated cotton cellulose fibers and fabrics were investigated. The effects of the initial concentration of long-lived free radicals (formed on the cellulose molecule at different radiation dosages) on the rate and extent of copolymerization of butyl methacrylate, with radiation-activated cellulose, and on the distribution of poly(butyl methacrylate) in the fibrous structure were determined. Copolymerization with cotton, containing the lowest initial concentration of free radicals of about one free radical per five to six cellulose molecules, gave a fibrous cotton copolymer which tended to have a layered structure. As the initial concentration of free radicals in cotton was increased, a fibrous copolymer with a higher degree of compactness of structure was obtained. The textile properties of fabric copolymers, which were crosslinked with dimeth yloldihydroxyethyteneurea, were determined.

Single Dyebath Application of Direct, Acid, and Basic Dyes to Cotton—Poly(Glycidyl Methacrylate) Fabrics

Cotton cellulose was macromolecularly modified by free-radical-initiated graft copolymerization with glycidyl methacrylate from aqueous methanol. The cotton—poly(glycidyl methacrylate) fabrics and chemically modified fabrics were dyed by single dyebath application of direct, direct plus acid, acid, basic, acid plus basic, and cuprophenyl dyestuffs. The colors of the dyed fabrics were matched with standard color plates. Modifications of the fabrics by reaction with allylamine, ammonia, p-anisidine, ethylenediamine, cyclo-hexylamine, N-cyclo-hexylpiperidine, methacrylamide, oxalic acid, o-phenylenediamine, phenylphosphinic acid, or sulfamide resulted in changes in colors of the dyed fabrics. However, the changes in colors of the fabrics were generally in strengths of hues rather than in color groupings.

Free radical addition of thiolacetic acid to esters and amides of unsaturated acids and screening of the products for antimicrobial activity.

Free radical addition of thiolacetic acid to terminal and internal double bonds of mono-and diunsaturated amides, as well as to unsaturated esters, was achieved by irradiation with Cobalt-60. Screening for antimicrobial activity againstStaphylococcus aureus, Escherichia coli, Aspergillus species,Torula species, andCandida albicans indicated that terminal addition products may be more active than internal addition products.

The specific electrical conductivity of the tissue fluids of desert Loranthaceae

MacDougal and Cannon 1 and MacDougal 2 suggested some years ago that the osmotic concentration of the tissue fluids of the two organisms is one of the fundamental variables in the relationship between plant parasite and host. Senn 3 has published one plasmolytic determination indicating higher concentration in a Viscum than in the leaves of the host tree and has secured similar results with other phanerogamic parasites. In the Jamaican montane rain-forest the concentration of the tissue fluids of the parasitic Loranthaceae is in general higher than those of the host. 4 The same relationship has been found to obtain in desert Loranthaceae. 5 As far as we are aware the relative electrolyte contents of the tissue fluids of parasite and host have not been determined heretofore. In August, 1920, we had the opportunity while carrying out work for the U. S. Department of Agriculture at Sacaton, Arizona to measure the specific electrical conductivity, K, as well as the osmotic concentration in atmospheres, P, calculated from the freezing point lowering, Δ, of the expressed sap of the leaves of the host trees and of the stems of the leafless Phoradendron californiczmz parasitic on the leguminous trees Acacia greggii and Olneya tesota and of the leaves of the leafy P. cockerellii parasitic on Populus wislizeni, Salix wriglztii and Fraxinus attenuata. Sap was extracted after antecedent freezing of the tissues in an ice and salt mixture 1 to facilitate extraction 2 and the constants determined on the centrifuged sap. Table I shows the average values of Δ and of P as determined from a published table. 3 For each comparison the osmotic concentration of the tissue fluids of the parasite is higher than that of the host. Thus the results of earlier investigations in Jamaica and Arizona are confirmed.

The accumulation of chlorides in the leaf tissue fluids of Egyptian cotton with the march of the season.

Among the physiological problems presented by the phenomenon of the differential absorption and tolerance in solution of chlorides and sulphates by the Egyptian and Upland types of cotton 1 is that of the change in the concentration of these anions with the march of the season. This problem is in reality twofold: (a) change in the concentration in one and the same organ with its development and senescence, and (b) the possible change in the concentrations found in the (leaf) tissues at as nearly as possible comparable stages of maturity at earlier and later periods in the development of the organism as a whole. The present discussion is limited to the latter phase. The more mature cotton plant does not lend itself readily to controlled laboratory experimentation. For this and other reasons a statistical method of attack seems desirable. The problem presents some difficulties, since concentrations based on unit volumes of tissue fluid may obviously be influenced by (a) errors of judgment or the errors of random sampling in the collection of leaves at earlier and later periods, 2 and by (b) the turgidity of the tissues at the time of collection of samples grown in field cultures. Table I shows the mean concentration of chlorides in terms of grams per liter of leaf tissue fluids from samples from the same plants in a first and second series of analyses 3 of the number (N) indicated based on cottoms grown in the Gila River Valley in southern Arizona. 4 Since the determinations of, the first and second series may be expected to be correlated, because of the influence of the individuality of the plants and of variation in the environmental conditions to which they are exposed, it is necessary to consider the correlation between the first and second determinations in calculating the probable errors of the difference between them.