γ-radiolysis of acetylated cotton cellulose: An ESR study

The nature and behavior of free radicals induced in acetylated cotton celluloses irradiated with γ-rays have been studied by electron spin resonance (ESR) spectroscopy. Dehydrogenation and deacetylation appear to be responsible for the free radicals observed from samples irradiated at 77°K. The degree of substitution enhanced the yield of acetyl radicals when the samples were irradiated at 77°K and adversely affected the overall radical concentration when irradiation was done at 300°K. In addition, the ESR spectra of samples irradiated under vacuum at 300°K were more intense than those obtained from samples irradiated in air. The nature, yield, and post-irradiation behavior of the primary radicals are discussed in the light of the ultimate chemical effects observed.     

Zirconium(IV) fluorosulphates : Preparation and characterization

Zr(SO₃F)₄, (A); ZrO(SO₃F)₂, (B); Zr(O₂CCH₃)₂, (SO₃F)₂, (C); and Zr(O₂CCH₃)₃SO₃F, (D) have been prepared and characterized (elemental analysis,i.r. Spectra and thermal analysis). The SO₃F groups are bidentate in (A) – (C) but have C_3V symmetry in D where all the three oxygen atoms of SO₃F group are coordinated in an equivalent manner. (A) – (D) are good Lewis acids and form coordination complexes with pyridine, triphenylphosphine oxide and 2,2′-bipyridyl. The thermal decomposition of the fluorosulphates is complex.     

Peptides—XXXVII: Synthesis of the 1–37 fragment of a lysozyme analogue

Combination of the protected peptide fragments 1–16, 17–26 and 27–37 to yield the 1–37 portion of a lysozyme analogue is described. The fragments were combined using DCCI with the addition of HONSu, and the products purified mainly by gel filtration.     

The integration of certain products of the multivariableH-function with a general class of polynomials

The authors present six general integral formulas (four definite integrals and two contour inegrals) for theH-function of several complex variables, which was introduced and studied in a series of earlier papers by H. M. Srivastava and R. Panda (cf., e.g., [25] through [29]; see also [14] through [18], [20], [24], [32], [34], [35], [37], and [38]). Each of these integral formulas involves a product of the multivariableH-function and a general class of polynomials with essentially arbitrary coefficients which were considered elsewhere by H. M. Srivastava [21]. By assigning suiatble special values to these coefficients, the main results (contained in Theorems 1, 2 and 3 below) can be reduced to integrals involving the classical orthogonal polynomials including, for example, Hermite, Jacobi [and, of course, Gegenbauer (or ultraspherical), Legendre, and Tchebycheff], and Laguerre polynomials, the Bessel polynomials considered by H. L. Krall and O. Frink [9], and such other classes of generalized hypergeometric polynomials as those studied earlier by F. Brafman [3] and by H. W. Gould and A. T. Hopper [8]. On the other hand, the multivariableH-functions occurring in each of our main results can be reduced, under various special cases, to such simpler functions as the generalized Lauricella hypergeometric functions of several complex variables [due to H. M. Srivastava and M. C. Daoust (cf. [22] and [23])] which indeed include a great many of the useful functions (or the products of several such functions) of hypergeometric type (in one and more variables) as their particular cases (see,e. g., [1], [10] and [39]). Many of the aforementioned applications of our integral formulas (contained in Theorems 1, 2 and 3 below) are considered briefly. Further usefulness of some of these consequences of Theorems 1 and 2 in terms of the classical orthogonal polynomials is illustrated by considering a simple problem involving the orthogonal expansion of the multivariableH-function in series of Jacobi polynomials. It is also shown how these general integrals are related to a number of results scattered in the literature. 0261 0262 V     

Interaction of chloroform with aniline, o-toluidine and N,N-dimethyl aniline

Heats of mixing aniline, o-toluidine, and N,N-dimethyl aniline with chloroform have been determined by an adiabatic calorimeter. The results have been examined for molecular interactions between them, and they indicate that aniline and o-toluidine are associated through hydrogen bonds. Enthalpy of bond formation in a 1:1 complex has also been determined.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Organic solid-state reactions

The role of voids and cracks in solid-state reaction between 8-hydroxyquinoline and phthalic anhydride has been investigated. 8-hydroxyquinoline reacts with phthalic anhydride both in solution and in solid state, forming a 1:1 yellow-colored complex. X-ray diffraction studies prove that the complex obtained from the solid-state reaction is the same as that obtained from solution. Several techniques have been used to study the kinetics of the reaction in the solid state. Kinetic studies by capillary technique showed that surface migration is the mode of diffusion of reactant concerned. Dilatometric technique confirms the formation of cracks and voids in the systems and shows that the reaction is propagated through the channels.     

Syntheses of the first N-mono- and N,N'-dipolyfluoroalkyl-4,4'-bipyridinium compounds

Reactions of 4,4'-bipyridine (1) with excess of polyfluoroalkyl iodides (2a-d) at 100-110 degrees C, under neat conditions, led to the formation of monoquaternary salts (3a-d) in > 90% yields. Salts 3a-d were metathesized with LiN(SO2CF3)2 either in water or water/acetone mixtures to form ionic liquids (4a-d), respectively, in > 88% yields. When 1 was reacted with 2.5 equivalent of 2a-c in DMF at 110 degrees C, the diquaternary salts 5a-c were formed in > 85% yields. Alternatively, 5a-c were also synthesized by heating a mixture of 3a-c and 2a-c (1.25 equivalent) in DMF. The metathesis reaction of 5a-c with LiN(SO2CF3)2 produced dicationic ionic liquids (6a-c) in > 86% yield.     

Rapid separation of phenylthiohydantoin amino acids: ambient pressure ion-mobility mass spectrometry (IMMS)

An electrospray ionization (ESI) ambient pressure ion-mobility spectrometer (APIMS) interfaced to an orthogonal reflector time-of-flight mass spectrometer (TOFMS) was evaluated for the first time as a detector for the identification of phenylthiohydantoin (PTH)-derivatized amino acids, the final products in the Edman sequencing process of peptides and proteins. The drift and flight times of the twenty common PTH amino acids were characterized by a well-defined 2-D mobility/mass spectral pattern. The combination of mobility/mass modes of analysis gave rise to a unique trend-line formation for the series of PTH amino acids. In addition, each PTH amino acid had a unique reduced mobility constant K(o), thus enabling the differentiation of all the amino acid derivatives including the PTH-leucine and PTH-isoleucine isomers. More importantly it was shown that it was possible to resolve a complete reference mixture of PTH amino acids in a single experimental run in less than 1 min. Detection limits for the PTH amino acids were found to range from 1.04 to 3.52 ng; indicating that the limits of detection were less than 17.0 pmol for all of the PTH amino acids.