Photoassisted "gate-lock" fluorescence "turn-on" in a new Schiff base and coordination ability of E-Z isomers

Rapid photoresponse (1.0-8.0 min) through fluorescence "turn-on" signaling displayed by a novel Schiff base (L) creating "gate lock" via intramolecular C-H···N interaction in photoisomerized product (L') has been described. Coordination chemistry of pre- and postirradiated species demonstrated a drastic change in the reactivity which has been supported by NMR, HRMS, UV-vis, emission, electrochemical, and complexation studies.     

Convergence of approximations to the primal problem in plasticity under conditions of minimal regularity

Summary. This work considers semi- and fully discrete approximations to the primal problem in elastoplasticity. The unknowns are displacement and internal variables, and the problem takes the form of an evolution variational inequality. Strong convergence of time-discrete, as well as spatially and fully discrete approximations, is established without making any assumptions of regularity over and above those established in the proof of well-posedness of this problem. Received June 8, 1998 / Published online July 12, 2000     

Study on 222–226Th Isotopes in the Cranking Framework

The yrast spectra, quadrupole moments, quadrupole deformation parameters (β ₂), non-axiality parameters (γ), root mean-square radii for protons and neutrons, occupation probabilities, moment of inertia (I), and B(E2) transition probabilities are calculated for ^222–226Th in the cranked Hartree–Bogoliubov framework. The calculations employ a quadrupole-quadrupole plus pairing model of residual interaction operating in a reasonably large valence space outside the ¹⁶⁴Pb core. Our calculations reproduce qualitatively the observed yrast spectra in ^222–226Th up to spin 20⁺. The calculated results indicate that the non-axiality parameter decreases as one moves along the yrast states. The observed increase in deformation from ²²²Th to ²²⁶Th is due to the increase in the occupation of low-k components of $(2g_{9/2})_{\pi }$ and $(1j_{{15/2}})_{\nu }$ orbits. The model parameters reproduce not only the moment of inertia, deformation, and transition probabilities but also the proton and neutron pairing gaps and are the most appropriate for cranking studies in this region.     

构象差异凝胶电泳检测亚甲基四氢叶酸还原酶基因A1298C多态性

建立构象差异凝胶电泳(conformation difference gel electrophoresis,CDGE)检测亚甲基四氢叶酸还原酶(methylenetetrahydrofolate reductase,MTHFR)基因A1298C多态性的方法。分别用PCR-CDGE和PCR-RFLP对10例样本的MTHFR基因A1298C多态性进行分型。CDGE结果显示有8例样本表现为迁移率慢的1条带,1例样本表现为迁移率快的1条带,1例样本表现为2条带。酶切结果显示AA基因型有8例,AC基因型和CC基因型各1例。CDGE和酶切结果的对比显示二者的结果是一致的。CDGE是一种可以对MTHFR基因A1298C多态性分型的方法。     

Alternative formulations of isotropic hardening for Mises materials, and associated variational inequalities

This work provides insight into aspects of classical Mises–Hill plasticity, its extension to the Aifantis theory of gradient plasticity, and the formulations of both theories as variational inequalities. Firstly, it is shown that the classical isotropic hardening rule, which is dissipative in nature, may equally well be characterized via a defect energy—and, what is striking, this energetically based hardening rule mimics dissipative behavior by describing loading processes that are irreversible. A second aspect concerns the equivalence between the conventional form of the flow rule and its formulation in terms of dissipation. This equivalence has been previously established using the tools of convex analysis (cf., e.g., Han and Reddy, Plasticity: mathematical theory and numerical analysis, Springer, New York, 1999)—in the current work this equivalence is derived directly from the constitutive equations and the specific form of the dissipation, without recourse to such machinery. Variational inequalities corresponding to the dissipative and energetic forms of the flow rule are derived; these inequalities involve only the displacement and plastic strain and are well suited to computational studies. Finally, it is shown that the framework developed for the classical theory is easily extended to incorporate the gradient-plasticity theory of Aifantis (Trans ASME J Eng Mater Technol 106:326–330, 1984).      

Routing vehicles to minimize fuel consumption

We consider a generalization of the capacitated vehicle routing problem known as the cumulative vehicle routing problem in the literature. Cumulative VRPs are known to be a simple model for fuel consumption in VRPs. We examine four variants of the problem, and give constant factor approximation algorithms. Our results are based on a well-known heuristic of partitioning the traveling salesman tours and the use of the averaging argument.     

Heteroleptic dipyrrinato complexes containing 5-ferrocenyldipyrromethene and dithiocarbamates as coligands: selective chromogenic and redox probes

Six heteroleptic dipyrrinato complexes [Ni(fcdpm)(dedtc)] (1), [Ni(fcdpm)(dipdtc)] (2), [Ni(fcdpm)(dbdtc)] (3), [Pd(fcdpm)(dedtc)] (4), [Pd(fcdpm)(dipdtc)] (5), and [Pd(fcdpm)(dbdtc)] (6) (fcdpm = 5-ferrocenyldipyrromethene; dedtc = diethyldithiocarbamate; dipdtc = diisopropyldithiocarbamate; dbdtc = dibutyldithiocarbamate) have been synthesized and characterized by elemental analyses and spectral (ESI-MS, IR, (1)H, (13)C NMR, UV-vis) and electrochemical studies. Crystal structures of 1, 2, 4, and 5 have been authenticated by X-ray single-crystal analyses. Nickel-based complexes 1-3 display selective chromogenic and redox sensing for Hg(2+) and Pb(2+) ions, while palladium complexes 4-6 display selective chromogenic and redox sensing only for Hg(2+). Electronic absorption, ESI-MS, and electrochemical studies indicated that sensing arises from interaction between 1-3 and Hg(2+)/Pb(2+) through sulfur of the coordinated dithiocarbamates, while it arises from the pyrrolic nitrogen of fcdpm and dithiocarbamate sulfur from 4-6 and Hg(2+). Different modes of binding between Ni and Pd complexes have further been supported by theoretical studies. The receptor-cation binding constants (K(a)) and stoichiometry between probes and Hg(2+)/Pb(2+) have been estimated by the Benesi-Hildebrand method and Job's plot analysis. Detection limits for 1-3 toward Hg(2+)/Pb(2+) and 4-6 for Hg(2+) have been found to be reasonably high.     

Modeling of polycrystals using a gradient crystal plasticity theory that includes dissipative micro-stresses

This study investigates thermodynamically consistent dissipative hardening in gradient crystal plasticity in a large-deformation context. A viscoplastic model which accounts for constitutive dependence on the slip, the slip gradient as well as the slip rate gradient is presented. The model is an extension of that due to Gurtin (Gurtin, M. E., J. Mech. Phys. Solids, 52 (2004) 2545–2568 and Gurtin, M. E., J. Mech. Phys. Solids, 56 (2008) 640–662)), and is guided by the viscoplastic model and algorithm of Ekh et al. (Ekh, M., Grymer, M., Runesson, K. and Svedberg, T., Int. J. Numer. Meths Engng, 72 (2007) 197–220) whose governing equations are equivalent to those of Gurtin for the purely energetic case. In contrast to the Gurtin formulation and in line with that due to Ekh et al., viscoplasticity in the present model is accounted for through a Perzyna-type regularization. The resulting theory includes three different types of hardening: standard isotropic hardening is incorporated as well as energetic hardening driven by the slip gradient. In addition, as a third type, dissipative hardening associated with plastic strain rate gradients is included. Numerical computations are carried out and discussed for the large strain, viscoplastic model with non-zero dissipative backstress.