Absolute Rate Constants for the Addition of the 1‐(tert‐Butoxy)carbonylethyl Radical onto Cyclic Alkenes in Solution

Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical ^.CHMeCO₂(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain.     

Low-temperature Heat Capacities and Thermodynamic Properties of Hydrated Sodium Cupric Arsenate [ NaCuAsO4·1.5H2O(s)]

Low-temperature heat capacities of the solid compound NaCuAsO4 · 1.5H2O(s) were measured using a precision automated adiabatic calorimeter over a temperature range of T = 78 K to T = 390 K. A dehydration process occurred in the temperature range of T = 368-374 K. The peak temperature of the dehydration was observed to be TD = (371.828±0.146) K by means of the heat-capacity measurement. The molar enthalpy and entropy of the dehyperimental values of heat capacities for the solid(Ⅰ) and the solid-liquid mixture(Ⅱ) were respectively fitted to two polynomial equations by the least square method. The smoothed values of the molar heat capacities and the fundamental thermodynamic functions of the sample relative to the standard reference temperature 298.15 K were tabulated at an interval of 5 K.     

Reactions of bis(hexamethylbenzene)iron(0) with carbon monoxide and with unsaturated hydrocarbons

Thermal decomposition of bis(hexamethylbenzene)iron(0) in the presence of carbon monoxide yields a novel carbonyl iron complex, [C₆(CH₃)₆]Fe(CO)₂. The cyclohexadiene complex [C₆(CH₃)₆]Fe(C₆H₈) is obtained from reaction of bis(hexamethylbenzene)iron(0) with either 1,3-cyclohexadiene or benzene, and the yield is much greater in the presence of hydrogen gas. Interaction of bis-(hexamethylbenzene)iron(0) with 2-butyne induces a catalytic cyclotrimerization to give more hexamethylbenzene. Kinetic and isotope distribution studies indicate that the primary step in these reactions is not a direct loss of one ring ligand, but rather an insertion of the iron center into one of the ligand methyl CH bonds, leading to a benzyl hydride complex species. Mechanisms for the subsequent reactions of this iron hydride species are proposed.     

Application of the essential work of fracture concept to nanostructured polymer materials

The first part of the paper deals with a critical discussion of the methodical basis of essential work of fracture (EWF) concept with respect to the specimen geometry (especially the notch depth) and application to polymers. In the second part, an in situ testing device, which combines a tensile testing machine with an optical strain-field measuring system, has successfully demonstrated possibility of characterization of fracture behaviour of polystyrene-polybutadiene block copolymers and block copolymer/homopolymer blends as examples of nanostructured polymer materials. It has been shown that knowledge of the time evolution of the strain field close to the crack tips leads to a simple verification of the basic precondition for the applicability of the EWF concept, the precondition “plastic zone coalescence-before-stable crack propagation”.     

Synthesis of β-ketoenamine donors having O, N, Se/Te donor functionalities and their reaction chemistry with Pd(II) and Pt(II) metal ions

Monoanionic tridentate ligands LH_a and LH_b containing ONSe and ONTe donor sequences and their Pd²⁺ and Pt²⁺ derivatives were synthesized and characterized. The formation of a five- and a six-membered ring around the central metal atom and associative phenomena in solutions provide extra stability to the metal complexes.     

Quantitative determination of UV filters in sunscreen lotions using microemulsion electrokinetic chromatography

Microemulsion electrokinetic chromatography (MEEKC) has been applied to the separation of some UV filters (Eusolex 4360, Eusolex 6300, Eusolex OCR, Eusolex 2292, Eusolex 6007, Eusolex 9020, Eusolex HMS, Eusolex OS, and Eusolex 232) commonly used in sunscreen lotions. Use of a MEEKC buffer with a mixed surfactant system to stabilize the oil droplets and an organic modifier in the aqueous phase allowed separation of most of the selected analytes in a single run in a system fitted with a diode array detector recording three wavelengths (240 nm, 300 nm, and 380 nm) simultaneously. The microemulsion employed consisted of 2.25 g of SDS, 0.75 g of Brij 35, 6.6 g 1‐butanol, 0.8 g n‐octane, 17.5 g 2‐propanol, and 72.1 g of 10 mM borate buffer (pH 9.2). Detection limits from 0.65 to 6.0 μg/mL were obtained and the calibration plots were linear over at least one order of magnitude for all analytes. The developed method could be applied to the determination of UV filters in several sun protection products including lotions, milks, and oils. Comparison of the obtained data with those from an HPLC method described in the literature showed acceptable agreement.     

Cystine and cysteine analysis as the same phenylthiocarbamyl derivatives by HPLC in protein hydrolyzates

Summary A new approach is described, and a novel explanation presented, for the high performance liquid chromatographic analysis of cystine and cysteine as their phenylthiocarbamyl derivatives. PTC cystine and cysteine have been eluted with the same retention times and molar responses, most probably due to electrophilic attack of phenylisothiocyanate on cystine resulting in the scission of the disulfide bond yielding two moles of cysteine. Further, total PTC cystine and cysteine have been measured both in model solutions and in standard protein hydrolyzates (lysozyme, bovine albumin, ribonuclease) with the same linearity as the other ineteen amino acids. The reproducibility of the measurements, at the 250–750 pmole level, proved to be 4.1% (Relative Standard Deviation %) or less.     

ansa-Metallocene derivatives XXXIII. 2-Dimethylamino-substituted bis-indenyl zirconium dichloride complexes with and without a dimethylsilyl bridge: syntheses, crystal structures and properties in propene polymerization catalysis

Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH₃)₂N-C₉H₆)₂ZrCl₂, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH₃)₂Si(2-(CH₃)₂N-C₉H₅)₂ZrCl₂, were prepared by reaction of the corresponding ligand lithium salts with ZrCl₄ in toluene. Diffractometric structure determinations reveal C₂-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH₃)₂Si(2-(CH₃)₂N-C₉H₅)₂ZrCl₂ catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me₂Si-bridged bis(indenyl)ZrCl₂ complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species.     

A new algorithm for the fixed-node quantum Monte Carlo method

A novel algorithm is proposed for the fixed-node quantum Monte Carlo (FNQMC) method.In contrast to previous procedures,its "guiding function" is not optimized prior to diffusion quantum Monte Carlo (DMC) computation but synchronistically in the diffusion process The new algorithm can not only save CPU time,but also make both of the optimization and diffusion carried out according to the same sampling fashion,reaching the goal to improve each other This new optimizing procedure converges super-linearly,and thus can accelerate the particle diffusion During the diffusion process,the node of the "guiding function" changes incessantly,which is conducible to reducing the "fixed-node error" The new algorithm has been used to calculate the total energies of states X3B1 and a1A1 of CH2 as well as π-X2B1 and λ-2A1 of NH2 The singlet-triplet energy splitting (λEsT) in CH2 and π energy splitting in NH2 obtained with this present method are (45 542±1.840) and (141.644±1.589) kJ/mol,respectively The calculated