Thermoanalytical studies of rubber oxidation catalyzed by metallic ions

The effects of several metallic ions on the oxidation of natural rubber were studied by differential scanning calorimetry (DSC). The activation energy of oxidation was evaluated from DSC curves. Cobalt, manganese, iron and copper ions decreased the activation energy of oxidation. Nickel, zinc and tin ions did not affect the activation energy. The effective ions are those which are able to undergo one-electron transfer redox reaction with hydroperoxide. Based on the activation energy values, the catalytic activities of metallic ions are: Co > Mn > Cu ? Fe > Ni ? Zn ? Sn.     

Tetracarbonyliron adducts of Cp2Cr2(CO)4(μ-η2-P2). Syntheses and crystal structures of Cp2Cr2(CO)4P2[Fe(CO)4] m (m=1 and 2)

Cp₂Cr₂(CO)₄( - ² - P₂), 1, reacts with one molar equivalent of Fe₂(CO)₉ in THF to yield the mono- and di-iron complexes, Cp₂Cr₂(CO)₄P₂[Fe(CO)₄], 2, (16.5% yield) and Cp₂Cr₂(CO)₄P₂[Fe(CO)₄]₂, 3, (16.9% yield), as dark magenta brown and dark greenish brown crystals, respectively. Both complexes were characterized by single-crystal X-ray diffraction analysis. Crystal data –2: space group =P2₁/c,a=17.024(1) Å,b=8.180(1) Å,c=30.891(2) Å, =100.953(5)°,V=4223.4(7)ų,Z=8, 3743 observed reflections,R _F=0.033; 3: space group P1,a=10.209(2) Å,b=10.212(2) Å,c=15.989(3) Å, =106.93(1)°, =91.87(1)°, =119.50(1)°,V=1356.5(4) ų,Z=2, 3489 observed reflections,R _F=0.029.     

Aldol reaction under solvent-free conditions: highly stereoselective synthesis of 1,3-amino alcohols

[formula: see text] A method for the highly stereoselective synthesis of 1,3-amino alcohols based on the indium trichloride-catalyzed Mukaiyama aldol reaction of keto ester (R,S)-1 under solvent-free conditions has been developed. The high selectivity observed can be explained on the basis of the shielding of one face by a remote substituent.     

Polymerization behavior of 1,2,2,6,6-pentamethyl-4-piperidinyl m-isopropenyl-α,α-dimethylbenzyl carbamate

Copolymers of 1,2,2,6,6-pentamethyl-4-piperidinyl m-isopropenyl-α,α-dimethylbenzyl carbamate (CB) with styrene (S) and with methyl methacrylate (MMA) were synthesized using AIBN as initiator. S–CB copolymers made from feed ranging from 0.45–0.94 mole fractions S and MMA-CB copolymers made from feed of 0.34–0.88 mole fractions MMA were used to determine the monomer reactivity ratios r₁ and r₂. The structure of S–CB copolymers was inferred to be mainly of a random nature and in the MMA–CB copolymerization system there is a stronger tendency to form alternating copolymers. © 1993 John Wiley & Sons, Inc.     

Terminality,normality, and transversality conditions

The maximum principle distinguishes between two phases of the optimal control problem. Some of the stated conditions are to be satisfied at points other than endpoints and some conditions are to be satisfied specifically at the endpoints. This paper utilizes the first set of conditions from the maximum principle to reexamine the second set. In the process, a new necessary condition to be satisfied at the endpoints is obtained. This condition is for certain cases easier to apply than the transversality conditions, yields additional information which may be of computational advantage, and lends itself quite naturally to an exposition of abnormal solutions. The relationship of the new condition to the transversality conditions and a discussion on normality are included. Several examples are given to illustrate the results.This research was supported in part by NASA under Grant NGR-03-002-224 and NSF Science Faculty Fellowship. The authors are indebted to Professors G. Leitmann, G. Basile, and E. Cliff for their helpful comments and suggestions.     

The mechanism of antiparallel <Emphasis Type="Italic">β</Emphasis>-sheet formation based on conditioned self-avoiding walk

By introducing an additional hydrogen bond to hydrogen bond interaction in the force field of the CSAW (Conditioned Self-Avoiding Walk) model, we investigate into the mechanism of antiparallel β-sheet formation based on the folding of a short polyalanine in gas phase. Through our numerical simulation, we detect the possible presence of a transient helix during β-sheet formation, whose presence is shown to have slowed the formation of β-sheets by an order of magnitude. While we observe the mechanisms of nucleation, zipping and induction that drives the formation of a β-sheet, we uncover a new mechanism that involves transient β-turns and short β-sheets during the formation of long β-sheets. Our results have enabled us to provide an overview on the mechanisms of β-sheet formation via two main folding pathways: slow folding through the intermediate state of transient helix, and fast folding from the nucleation of β-turn.