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81.
Kreickmann T Diedrich C Pape T Huynh HV Grimme S Hahn FE 《Journal of the American Chemical Society》2006,128(36):11808-11819
The bis(benzene-o-dithiol) ligands H(4)-1, H(4)-2, and H(4)-3 react with [Ti(OC(2)H(5))(4)] to give dinuclear triple-stranded helicates [Ti(2)L(3)](4)(-) (L = 1(4)(-), 2(4)(-), 3(4)(-)). NMR spectroscopic investigations revealed that the complex anions possess C(3) symmetry in solution. A crystal structure analysis for (PNP)(4)[Ti(2)(2)(3)] ((PNP)(4)[14]) confirmed the C(3) symmetry for the complex anion in the solid state. The complex anion in Li(PNP)(3)[Ti(2)(1)(3)] (Li(PNP)(3)[13]) does not exhibit C(3) symmetry in the solid state due to the formation of polymeric chains of lithium bridged complex anions. Complexes [13](4)(-) and [14](4)(-) were obtained as racemic mixtures of the Delta,Delta and Lambda,Lambda isomers. In contrast to that, complex (PNP)(4)[Ti(2)(3)(3)] ((PNP)(4)[15]) with the enantiomerically pure chiral ligand 3(4)(-) shows a strong Cotton effect in the CD spectrum, indicating that the chirality of the ligands leads to the formation of chiral metal centers. The o-phenylene diamine bridged bis(benzene-o-dithiol) ligand H(4)-4 reacts with Ti(4+) to give the dinuclear double-stranded complex Li(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] containing two bridging methoxy ligands between the metal centers. The crystal structure analysis and the (1)H NMR spectrum of (Ph(4)As)(2)[Ti(2)(4)(2)(mu-OCH(3))(2)] ((Ph(4)As)(2)[(16]) reveal C(2) symmetry for the anion [Ti(2)(4)(2)(mu-OCH(3))(2)](2)(-). For a comparative study the dicatechol ligand H(4)-5, containing the same o-phenylene diamine bridging group as the bis(benzene-o-dithiol) ligands H(4)-4, was prepared and reacted with [TiO(acac)(2)] to give the dinuclear complex anion [Ti(2)(5)(2)(mu-OCH(3))(2)](2)(-). The molecular structure of (PNP)(2)[Ti(2)(5)(2)(mu-OCH(3))(2)] ((PNP)(2)[17]) contains a complex anion which is similar to [16](2)(-), with the exception that strong N-H...O hydrogen bonds are formed in complex anion [17](2)(-), while N-H...S hydrogen bonds are absent in complex anion [16](2)(-). 相似文献
82.
Optical Absorption in Periodic Graphene Superlattices: Perpendicular Applied Magnetic Field and Temperature Effects
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Melquiades de Dios‐Leyva Michael A. Hernández‐Bertrán Alvaro L. Morales Carlos A. Duque Huynh Vinh Phuc 《Annalen der Physik》2018,530(5)
A detailed study of the magneto‐optical absorption is presented for graphene superlattices (SLs) subjected to a perpendicular magnetic field. For a given temperature, this quantity exhibits a resonant peak structure whose characteristics depend on the magnetic field regime, circular polarization of light and SL barrier height. For the intermediate field regime, we demonstrated that the resonant peak structure of is directly correlated to the partial joint density of states. Specifically, the latter exhibits van Hove‐like singularities and peaks at energies where takes its maximum values. We also investigated the magnetoabsorption in the weak field regime for SLs exhibiting one and extra Dirac points in the absence of the field. It was found that for SLs with only one Dirac point, the absorption spectra consist of resonant peaks satisfying the same circular polarization dependent selection rule as that for pristine graphene, except for one of them. For SLs with extra Dirac points, the resonant peaks arise from transitions between singlet subbands or between doublet subbands and satisfy a circular polarization and peak intensity dependent selection rule. It was also found that the resonant structure of can be observed experimentally at room temperature in clean SLs. 相似文献
83.
Tetrazole Photoclick Chemistry: Reinvestigating Its Suitability as a Bioorthogonal Reaction and Potential Applications
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Dr. Zhengqiu Li Linghui Qian Prof. Dr. Lin Li Dr. Jan C. Bernhammer Prof. Dr. Han Vinh Huynh Prof. Dr. Jun‐Seok Lee Prof. Dr. Shao Q. Yao 《Angewandte Chemie (International ed. in English)》2016,55(6):2002-2006
The bioorthogonality of tetrazole photoclick chemistry has been reassessed. Upon photolysis of a tetrazole, the highly reactive nitrile imine formed undergoes rapid nucleophilic reaction with a variety of nucleophiles present in a biological system, along with the expected cycloaddition with alkenes. The alternative use of the tetrazole photoclick reaction was thus explored: tetrazoles were incorporated into Bodipy and Acedan dyes, providing novel photo‐crosslinkers with one‐ and two‐photon fluorescence Turn‐ON properties that may be developed into protein‐detecting biosensors. Further introduction of these photo‐activatable, fluorogenic moieties into staurosporine resulted in the corresponding probes capable of photoinduced, no‐wash imaging of endogenous kinase activities in live mammalian cells. 相似文献
84.
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
85.
86.
Tran TD Nguyen TT Do TH Huynh TN Tran CD Thai KM 《Molecules (Basel, Switzerland)》2012,17(6):6684-6696
A series of simple heterocyclic chalcone analogues have been synthesized by Claisen Schmidt condensation reactions between substituted benzaldehydes and heteroaryl methyl ketones and evaluated for their antibacterial activity. The structures of the synthesized chalcones were established by IR and 1H-NMR analysis. The biological data shows that compounds p?, f? and t? had strong activities against both susceptible and resistant Staphylococcus aureus strains, but not activity against a vancomycin and methicillin resistant Staphylococcus aureus isolated from a human sample. The structure and activity relationships confirmed that compounds f?, f? and t? are potential candidates for future drug discovery and development. 相似文献
87.
A new method enabling the determination of 15 priority carcinogenic polyaromatic compounds (PAC) proposed by the US National Toxicology Program (NTP) has been developed and applied to diesel exhaust particulates (DEP). The clean-up procedure consists of solid-phase extraction (SPE) and HPLC fractionation on silica phases followed by liquid-liquid extraction and chromatography on a polyvinylbenzene copolymer column. The method gives good recoveries for all PAC studied except dibenzo[a,j]acridine and dibenzo[a,h]pyrene, for which recovery values are below 80%. The use of GC-MS ion trap and its capacity to achieve single-ion storage enhanced the sensitivity of the method, enabling the detection of high-molecular-weight PAH in the low ng g(-1) concentration range. Intermediate polarity GC columns, e.g. BPX-50 or equivalent, enabled better separation, when applied to DEP analysis, than the generally used DB-5 apolar phase. This is observed mainly for separation of isomeric compounds belonging to the benzofluoranthene and dibenzopyrene families. The application of this method to DEP sampled from the exhaust of a diesel engine and in confined locations such as a tunnel has shown that all PAH of the NTP list could be detected, except dibenzo[a,h]pyrene. No dibenzacridine or dibenzocarbazole could be detected in such matrices. The method is sufficiently sensitive to be applicable to environmental exposure measurements in occupational health surveys. 相似文献
88.
Kaggwa GB Froebe S Huynh L Ralston J Bremmell K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(10):4695-4704
The adsorption of a polyacrylamide (MW 14600) and two polysaccharides (MW 9260 and 706 x 10(3)) onto model silica surfaces of different hydrophobicities was investigated. In all cases, adsorption adhered to the Freundlich isotherm, reflecting the heterogeneous character of the solid substrates. The latter strongly influenced the character of the adsorbed polymer, with morphologies from chainlike structures to thin films and patches being observed. Surface roughness, polymer type, and molecular weight also play roles in controlling adsorbed polymer morphology. Surface wettability is strongly influenced by the thickness of the adsorbed layer. 相似文献
89.
In supply chain management, one of the most critical problems which require a lot of effort to deal with is how to quantify and alleviate the impact of bullwhip effect – the phenomenon in which information on demand is distorted while moving upstream. Although it is well established that demand forecast, lead time, order batching, shortage gaming and price fluctuation are the main sources that lead to the bullwhip effect, the problem of quantifying bullwhip effect still remain unsolved in many situations due to the complex nature of the problem. In this research, a measure of bullwhip effect will be developed for a simple two-stage supply chain that includes only one retailer and one supplier in the environment where the retailer employs base stock policy for their inventory and demand forecast is performed through the first-order autoregressive model, AR(1). The effect of autoregressive coefficient and lead time on this measure will then be investigated. 相似文献
90.