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31.
A. G. Wikjord D. H. Page R. St. John Manley 《Journal of Macromolecular Science: Physics》2013,52(2):413-436
Macroscopic particles of various morphological forms are created by the crystallization of isotactic polystyrene from rapidly stirred solutions. Crystallization from trimethylbenzene over a 150° C temperature range produced spherical particles, globules, fibers, and rings depending upon the growth temperature. Crystallization from cyclohexanol (θ = 83.5°C) produced fibers in the temperature range of 85° to 140° C. Globular structures, similar to those formed by stirrer crystallization in trimethylbenzene developed during the Ziegler-Natta polymerization of styrene in trimethylbenzene between 25° and 75°C. Highly birefringent conical appendages appeared on many of the globules and fibers. The fibers often exhibited a skin-core effect with an average longitudinal and transverse orientation of the chain molecules in the skin and core, respectively. The skin frequently displayed periodic banded extinctions. All of these macrostructures consisted of a highly porous assembly of constituent microfibrillar units. It is believed that the morphogenesis of these structures involves the gradual aggregation of microfibrils under the influence of the flow patterns of the system. 相似文献
32.
Ion Grama Ronan Lauvergnat Émile Le Page 《Stochastic Processes and their Applications》2019,129(7):2485-2527
Let be a branching process in a random environment defined by a Markov chain with values in a finite state space . Let be the probability law generated by the trajectories of starting at We study the asymptotic behaviour of the joint survival probability , as in the critical and strongly, intermediate and weakly subcritical cases. 相似文献
33.
Lenhart JL van Zanten JH Dunkers JP Zimba CG James CA Pollack SK Parnas RS 《Journal of colloid and interface science》2000,221(1):75-86
Silane coupling agents are commonly applied to glass fibers to promote fiber/resin adhesion and enhance durability in composite parts. In this study, a coupling agent multilayer on glass was doped with trace levels of the dimethylaminonitrostilbene (DMANS) fluorophore. The fluorophore was immobilized on the glass surface by tethering the molecule to a triethoxy silane coupling agent, creating the DMANS/silane coupling agent molecule (DMSCA). DMSCA was then diluted with commonly used coupling agents and grafted to a glass microscope coverslip to create a model composite interface. A 53-nm blue shift in fluorescence from the immobilized DMSCA can be followed during cure of an epoxy resin overlayer, giving this technique potential to monitor the properties of the fiber/resin interface during composite processing. Contact angle measurements on these coupling agent layers were similar in the presence or absence of the DMSCA molecule, suggesting that trace levels of the fluorescent probe did not affect the structure of the layer. The immobilized DMSCA molecule behaved similarly to the DMANS precursor in solution. Both showed longer wavelength fluorescence in more polar environments. Copyright 2000 Academic Press. 相似文献
34.
Page T Nguyen HT Hilts L Ramos L Hanrahan G 《Analytical and bioanalytical chemistry》2012,403(8):2367-2375
This work reveals a computational framework for parallel electrophoretic separation of complex biological macromolecules and model urinary metabolites. More specifically, the implementation of a particle swarm optimization (PSO) algorithm on a neural network platform for multiparameter optimization of multiplexed 24-capillary electrophoresis technology with UV detection is highlighted. Two experimental systems were examined: (1) separation of purified rabbit metallothioneins and (2) separation of model toluene urinary metabolites and selected organic acids. Results proved superior to the use of neural networks employing standard back propagation when examining training error, fitting response, and predictive abilities. Simulation runs were obtained as a result of metaheuristic examination of the global search space with experimental responses in good agreement with predicted values. Full separation of selected analytes was realized after employing optimal model conditions. This framework provides guidance for the application of metaheuristic computational tools to aid in future studies involving parallel chemical separation and screening. Adaptable pseudo-code is provided to enable users of varied software packages and modeling framework to implement the PSO algorithm for their desired use. 相似文献
35.
Mithlesh Kumar R. M. Kadam T. K. Seshagiri V. Natarajan A. G. Page 《Journal of Radioanalytical and Nuclear Chemistry》2004,262(3):633-637
Thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) investigations were carried out on gamma irradiated SrBPO5 samples doped with CeO2 and co-doped with CeO2 and Sm2O3. On gamma-irradiation at room temperature, BO3
2–, O2
– and O– radicals were produced. It was seen that the O– radical ion disappeared in the sample annealed at 500 K. It is proposed that the recombination between trapped electrons and O– radical ions results in transfer of recombination energy to the impurity centre Ce3+ resulting in TSL glow peak at 485 K. In the case of co-doped samples energy transfer occurs between Ce3+ to Sm3+ resulting in increase in the intensity of glow peak at 485 K.The authors are grateful to Dr. V. K. Manchanda, Head, Radiochemistry Division, BARC for his keen interest and encouragement during the course of this work. 相似文献
36.
Page MJ Mahon MF Whittlesey MK 《Dalton transactions (Cambridge, England : 2003)》2011,40(31):7858-7865
Thermolysis of [Ru(PPh(3))(dppe)(CO)HCl] (dppe = 1,2-bis(diphenylphosphino)ethane) with the N-heterocyclic carbenes I(i)Pr(2)Me(2) (1,3-diisopropyl-4,5-dimethyl-imidazol-2-ylidene), IEt(2)Me(2) (1,3-diethyl-4,5-dimethyl-imidazol-2-ylidene) or ICy (1,3-dicyclohexylimidazol-2-ylidene) gave the cyclometallated carbene complexes [Ru(NHC)'(dppe)(CO)H] (NHC = I(i)Pr(2)Me(2), 4; IEt(2)Me(2), 5; ICy, 6). Dissolution of 4 in CH(2)Cl(2) or CHCl(3) gave the trans-Cl-Ru-P complex [Ru(I(i)Pr(2)Me(2))'(dppe)(CO)Cl] (7), which converted over hours at room temperature to the trans-Cl-Ru-CO isomer 7'. Chloride abstraction from 7 by NaBPh(4) under an atmosphere of H(2) produced the cationic mono-hydride complex [Ru(I(i)Pr(2)Me(2))(dppe)(CO)H][BPh(4)] (9), which could also be formed by protonating 4 with 1 eq HBF(4)·OEt(2). Treatment of 4 with excess HBF(4)·OEt(2) followed by extraction into MeCN produced the dicationic acetonitrile complex [Ru(I(i)Pr(2)Me(2))(dppe)(CO)(NCMe)(2)][BF(4)](2) (10). The structures of 6, 7, 7' and 10 have been determined by X-ray crystallography. 相似文献
37.
Jeffs L Arquier D Kariuki B Bethell D Page PC Hutchings GJ 《Organic & biomolecular chemistry》2011,9(4):1079-1084
By synthesising S-2-phenyl-N-(4-nitrophenyl)aziridine from S-phenylglycinol, it has been demonstrated that the aziridination of styrene by [N-(4-nitrobenzenesulfonyl)imino]phenyliodinane (nosyliminophenyliodinane, PhINNs) in the presence of S,S-2,2'-isopropylidene-bis(4-phenyl-2-oxazoline), catalysed by copper(II) triflate in CH(3)CN solution or heterogeneously by CuHY, has predominantly an R-configuration. The enantioselectivity of the aziridination of styrene by [N-arenesulfonylimino]-phenyliodinanes catalysed by copper-exchanged zeolite Y (CuHY), in conjunction with a chiral bis-oxazoline ligand, has been re-examined. In the case of PhINNs, it is shown that the product mixture of enantiomeric aziridines, on treatment with hexane, gives rise to a solid phase of low enantiomeric excess (ee) and a solution phase of high ee. Separation of the solid phase and recrystallisation afforded a true racemate (racemic compound), which has been confirmed by X-ray crystallography. The aziridine obtained from the solution phase could be recrystallised to produce the pure enantiomer originally in excess. A consequence of the new findings is that previous reports on the enantioselectivity of copper-catalysed aziridination, both in heterogeneous and homogeneous conditions, should be regarded with caution if the analytical procedure involved HPLC with injection of the enantiomeric mixture in a hexane-rich solvent. Such a method has been used in previous work from this laboratory, but has also been used elsewhere, following the procedure developed by Evans and co-workers when the (homogeneous) copper-catalysed aziridination by PhINTs was first discovered. Evidently, the change of substituent in the benzenesulfonyl group reduces the solubility in hexane, affording a solution phase of enhanced ee. 相似文献
38.
V. Natarajan T. K. Seshagiri A. G. Page 《Journal of Radioanalytical and Nuclear Chemistry》1994,187(2):123-129
Electron paramagnetic resonance (EPR) studies of -irradiated uranium doped BaCO3 have shown the formation of CO3
–, CO2
–, O3
– and O2
– ions. Thermally stimulated luminescence (TSL) glow curves of the -irradiated samples in the 300–600 K range have exhibited an intense peak around 360 K and a weak one around 440 K. The trap parameters for these peaks have been determined from TSL data. Spectral studies of the glow have revealed emission around 566, 583 and 590 nm characteristic of the uranate ion. From studies on the thermal stabilities of the radical ions, it has been inferred that the glow peak around 360 K is associated with the thermal destruction of O2
– ion and the peak around 440 K is associated with the thermal destruction of CO3
– ion. 相似文献
39.
40.
Wood JM Hinchliffe PS Davis AM Austin RP Page MI 《Chemical communications (Cambridge, England)》2002,(7):772-773
The alkaline hydrolysis of N-alpha-methoxycarbonyl benzyl-beta-sultam occurs 10(3) times faster than the corresponding carboxylate and with rapid D-exchange at the alpha-carbon: the pH rate profile indicates pre-equilibirum CH ionisation and together with formation of benzoyl formate as a product this suggests a novel mechanism for hydrolysis. 相似文献