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41.
Alain Estve Adeline Bail Georges Landa Ahmed Dkhissi Marie Brut Mehdi Djafari Rouhani Jan Sudor Anne-Marie Gu 《Chemical physics》2007,340(1-3):12-16
Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior. 相似文献
42.
Khaled A. Aamer Gregory N. Tew 《Journal of polymer science. Part A, Polymer chemistry》2007,45(6):1109-1121
Supramolecular block‐random copolymers containing [Ir(terpy)2]3+ in the side chain were synthesized via postfunctionalization of a P(S‐b‐ACterpy) block copolymer. Absorbance and emission spectra compared to a model compound show that the polymer backbone has a minor effect on the polymer absorbance but produces a larger shift for the phosphorescence signals to higher wavelength. Dynamic light scattering of the metal complex containing copolymer studied in various solvents showed monomodal aggregation with decreasing aggregate size as the solvent dielectric constant increased. The copolymer precursor P(S‐b‐ACterpy) shows multimodal aggregation in different solvents with the major population consisting of single chains. This difference in behavior between the two polymers is attributed to the electrolytic nature of the complex and the amphiphilicity induced by the charged metal complex. Supramolecular copolymers like these will continue to have interesting self‐organizational properties and may find applications in multicomponent systems for photoinduced charge separation processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1109–1121, 2007 相似文献
43.
The hyperfine constants for muonium in elemental and binary inorganic solids suggest formation of three different families
of defect centre, with distinct electronic structures. The overall range of values, spanning nearly five orders of magnitude,
and their correlation with host properties such as band gap and electron affinity, reveal a deep-to-shallow instability which
has profound implications for the electrical properties of hydrogen impurity in electronic materials, both semiconducting
and dielectric. 相似文献
44.
Rodrigo París José Luis de la Fuente 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3538-3549
Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), 1H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007 相似文献
45.
The plastic deformation field near the horizontal surface of a half space of perfectly plastic material associated with an indenting rotating rigid tooth is studied using slip line theory. The tooth is one of many on a roll surface and indents first into the half-space material and then rotates about the roll center. A slip line field is proposed for the deforming plastic region and a solution scheme is outlined. The emphasis is on determining the shape of the deforming region, especially that of the free surface. The study has a potential application in roughness transfer in metal forming processing. 相似文献
46.
In this paper, an adaptive FE analysis is presented based on error estimation, adaptive mesh refinement and data transfer for enriched plasticity continua in the modelling of strain localization. As the classical continuum models suffer from pathological mesh-dependence in the strain softening models, the governing equations are regularized by adding rotational degrees-of-freedom to the conventional degrees-of-freedom. Adaptive strategy using element elongation is applied to compute the distribution of required element size using the estimated error distribution. Once a new mesh is generated, state variables and history-dependent variables are mapped from the old finite element mesh to the new one. In order to transfer the history-dependent variables from the old to new mesh, the values of internal variables available at Gauss point are first projected at nodes of old mesh, then the values of the old nodes are transferred to the nodes of new mesh and finally, the values at Gauss points of new elements are determined with respect to nodal values of the new mesh. Finally, the efficiency of the proposed model and computational algorithms is demonstrated by several numerical examples. 相似文献
47.
A nonclassical problem is considered for the transport equation with coefficients depending on the energy of radiation. The task is to find the discontinuity surfaces for the coefficients of the equation from measurements of the radiation flux leaving the medium. For this tomography problem, an optimization problem is stated and numerically analyzed. The latter consists in determining the radiation energy that ensures the best reconstruction of the unknown medium. A simplified optimization problem is solved analytically. 相似文献
48.
Leong‐Huat Gan Palaniswamy Ravi Bao Wei Mao Kam‐Chiu Tam 《Journal of polymer science. Part A, Polymer chemistry》2003,41(17):2688-2695
Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003 相似文献
49.
The sub-millisecond protonation dynamics of the chromophore in S65T mutant form of the green fluorescent protein (GFP) was
tracked after a rapid pH jump following laser-induced proton release from the caged photolabile compoundo-nitrobenzaldehyde. Following a jump in pH from 8 to 5 (which is achieved within 2 μs), the fluorescence of S65T GFP decreased
as a single exponential with a time constant of ∼90 μs. This decay is interpreted as the conversion of the deprotonated fluorescent
GFP chromophore to a protonated non-fluorescent species. The protonation kinetics showed dependence on the bulk viscosity
of the solvent, and therefore implicates bulk solvent-controlled protein dynamics in the protonation process. The protonation
is proposed to be a sequential process involving two steps: (a) proton transfer from solvent to the chromophore, and (b) internal
structural rearrangements to stabilize a protonated chromophore. The possible implications of these observations to protein
dynamics in general is discussed 相似文献
50.
A rigorous and systematic intercomparison of codes used for the retrieval of trace gas profiles from high-resolution ground-based solar absorption FTIR measurements is presented for the first time. Spectra were analyzed with the two widely used independent, retrieval codes: SFIT2 and PROFFIT9. Vertical profiles of O3, HNO3, HDO, and N2O were derived from the same set of typical observed spectra. Analysis of O3 was improved by using updated line parameters. It is shown that profiles and total column amounts are in excellent agreement, when similar constraints are applied, and that the resolution kernel matrices are also consistent. Owing to the limited altitude resolution of ground-based observations, the impact of the constraints on the solution is not negligible. It is shown that the results are also compatible for independently chosen constraints. Perspectives for refined constraints are discussed. It can be concluded that the error budget introduced by the radiative transfer code and the retrieval algorithm on total columns deduced from high-resolution ground-based solar FTIR spectra is below 1%. 相似文献