Short-Chain Branching in Polyethylene and Poly(vinyl Chloride) Using Pyrolysis Hydrogenation Gas Chromatography and 13C Nuclear Magnetic Resonance Analysis

This study compares the use of pyrolysis hydrogenation gas chromatography (PHGC) and ¹³C Fourier transform nuclear magnetic resonance (FTNMR) methods for the analysis of reference polyethylene (PE) samples, ethylene-α-olefin copolymers, and specially prepared poly(vinyl chloride) (PVC) samples which were reduced to their PE skeletal structures. The nature and relative quantities of the short branches along the polymer chains were determined using both techniques. Improved high-resolution PHGC data, obtained with a fused silica capillary separation column, gave results which were in satisfactory agreement with the ¹³C FTNMR data. This approach confirms that detailed microstructural information can be obtained with these methods by using carefully controlled experimental conditions and appropriate reference systems.     

Tentative Identification of the Reactive Species in the Reaction of Cp2 TiCl2 with Salts of Diacids

The tentative identification of the reactive species in the condensation of Cp₂ TiCl₂ with salts of diacids to form titanium polysters is made. The reactive species are believed to be the same for both aqueous solution and interfacial systems, i.e., R -CO₂ ^? and Cp₂ Ti²⁺ with reaction occurring in the aqueous phase. The condensation of Cp₂ TiCl₂ with disodium terephthalate in interfacial systems occurs via a pseudo-first-order reaction:

Rate = K[Cp₂ TiCl₂] The rate-determining step (s) is believed to be diffusion of CP₂ TiCl₂ into the aqueous layer and/or hydrolysis of Cp₂ TiCl₂     

Applicability of generic linear scoring mosels in the U.S. credit-union environment

Although credit-scoring models represent a widely used managerialaid for large financial intermediaries, the vast majority ofU.S. credit unions—relatively small cooperatively ownedretail intermediaries, constrained by sample and funding limitations—haveyet to adopt such techniques. Lovie & Lovie (1986) havetheorized that the flat-maximum effect or curve of insensitivityassociated with linear scoring models could be advantageousin areas of applied prediction such as credit scoring. In thiscontext, we reported the relative predictive power of genericcredit-scoring models versus customized models in an earlierpaper (Overstreet et al. 1992). Unfortunately, these findingswere not readily adaptable to the credit-union industry dueto a dated sample with incomplete credit-bureau information.Consequently, from 1988 to 1991, we gathered a refined databasefrom which to further develop and field-test generic scoringmodels in the credit-union environment. The results reportedherein not only confirm, but amplify, the relative predictivepower of such models found earlier. Relative costs and benefitsof generic versus customized models are modelled for a representativecredit union. Future research directions are set forth in theconclusions.     

Release of nitric oxide and iodine to the atmosphere from the freezing of sea-salt aerosol components

The known room-temperature, solution-phase reaction between nitrite ions and iodide ions, which occurs in acidic conditions (pH < 5.5), is shown to be accelerated when neutral aqueous solutions are frozen. The reaction is proposed to occur in liquid "micropockets" within the ice structure at temperatures between the freezing point and the eutectic temperature. The products, nitric oxide and molecular iodine, are known to play significant roles in atmospheric compositional change, and therefore, the results obtained here, which are not dependent on acidification, may impact on observed snowpack chemistry. Investigation of the effect of oxygen on the chemical processing indicates that a chain reaction mechanism is operative.     

Proton-induced grain boundary segregation in stainless steel

Abstract

A technique is developed which addresses the problem of irradiation assisted stress corrosion cracking of stainless steels in light water reactors using high energy protons to induce grain boundary segregation. These results represent the first grain boundary segregation measurements in bulk produced by proton irradiation of stainless steel. The technique allows the study of grain boundary composition with negligible sample activation, short irradiation time, rapid sample turnaround and at minimal cost. Scanning Auger electron microscopy is used to obtain grain boundary composition measurements of irradiated and unirradiated samples of ultra high purity (UHP) type 304L stainless steel and UHP type 304L steels with the additions of phosphorus (UHP + P) and sulphur (UHP + S). Results show that irradiation of all three alloys causes significant Ni segregation to the grain boundary and Cr and Fe away from it. Irradiation of the UHP + P alloy also results in segregation of P at the grain boundary from 5.3 to 8.7 at %, over 80 times the bulk value. No radiation-induced grain boundary segregation of S was measured in the UHP + S alloy. Results also indicate that the presence of P or S may enhance radiation-induced segregation of major alloying elements at the boundary. Comparison of irradiated and unirradiated regions of the UHP + P alloy indicate that while a prior thermal treatment segregates P to the grain boundary to 5.3 at %, the major element concentrations at the grain boundary are completely different from those under irradiation.     

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr (110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr₂CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.     

Characterization of aromatic-thiol π-type hydrogen bonding and phenylalanine-cysteine side chain interactions through ab initio calculations and protein database analyses

In this study, the aromatic-thiol π hydrogen bonding and phenylalanine-cysteine side chain interactions are characterized through both molecular orbital calculations on a C₆H₆-HSCH₃ model complex and database analyses of 609 X-ray protein structures. The aromatic-thiol π hydrogen bonding interaction can achieve a stabilization energy of 2.60 kcal mol^?1, and is stronger than the already documented aromatic-hydroxyl and aromatic-amino hydrogen bonds. However, the occurrence of the aromatic-thiol hydrogen bond is rather rare in proteins. This is because most of the thiol groups participate in the formation of either disulphide bonds or stronger S—H…O (or N) ‘normal’ hydrogen bonds in a protein environment. Interactions between the side chains of phenylalanine and cysteine residues are characterized as the phenyl(Phe)(HSCH₂-)(Cys) interaction. The bonding energy for such interactions is approximately 3.71 kcal mol-¹ and is achieved in a geometric arrangement with an optimal phenyl(Phe)-(HS-)(Cys) π-type hydrogen bonding interaction. The interaction is very sensitive to the orientation of the two lone electron pairs on the sulphur atom relative to the π electron cloud of the phenyl ring. Accordingly, the interaction configurations that can accomplish a significant bonding energy exist only within a narrow configurational space. The database analysis of 609 experimental X-ray protein structures demonstrates that only 268 of the 1620 cysteine residues involve such phenylalanine-cysteine side chain interactions. Most of these interactions occur in the form of π (aromatic)-lone pair(sulphur) attractions, and correspond to a bonding energy less than 1.5 kcal mol^?1. A few were identified as the aromatic-thiol hydrogen bond with a bonding energy of 2.0–3.6 kcal mol^?1.     

A Non-linear Singular Perturbation Problem Arising in the Study of Chemical Flow Reactors

This paper presents a method of obtaining the complete asymptoticsolution of boundary value problems of the form for x [0,1] where b(x) is strictly positive andfor small and positive. Physically, the problem arises in determiningthe steady-state concentration of a substance in a chemicalflow reactor. A "two-variable" expansion procedure is used.     

DISTRIBUTIONS OF FREE RADICALS AMONG AMINO ACIDS FROM LYOPHILIZED ULTRAVIOLET-IRRADIATED PROTEINS

Abstract— The effects of u.v.-irradiation at 254 nm upon lyophilized ribonuclease, lysozyme, insulin, and chymotrypsinogen have been investigated by electron spin resonance (ESR). enzymatic assay, and labeling of free radical sites with tritiated hydrogen sulfide (HST). The ESR signal of the irradiated protein diminishes on exposure to HST, and tritium becomes covalently bound to carbon. The distribution of tritium among the amino acids of each protein. studied as an indicator of the carbon free radical distribution, differs markedly from those observed previously to result from exposure to gamma radiation, electrical discharge. or hydrogen atoms. However, the earlier observation that the tritium distribution is influenced by protein conformation holds true as well for u.v.-irradiation. Moreover, the distributions of tritium among the amino acids of u.v.-irradiated proteins indicate a broad scattering of free radicals. Tyrosine and phenylalanine, residues that absorb light energy in the region of the wavelength employed, are not particularly important as radical carriers. Thus, for ribonuclease, these residues incorporated 3.8 and 1.5 per cent of the total tritium, but they absorb 51 and 12 per cent of the light, respectively. These results, together with the observed low recoveries of methionine, an amino acid that does not absorb at 254 nm, add weight to the concept that a migration of energy ensues after the initial absorption of light energy and that photolytic damage may thus be due to destruction of amino acids other than those initially absorbing the u.v.-radiation.