On the uniqueness of solutions to linear complementarity problems

This paper characterizes the classU of all realn×n matricesM for which the linear complementarity problem (q, M) has a unique solution for all realn-vectorsq interior to the coneK(M) of vectors for which (q, M) has any solution at all. It is shown that restricting the uniqueness property to the interior ofK(M) is necessary because whenU, the problem (q, M) has infinitely many solutions ifq belongs to the boundary of intK(M). It is shown thatM must have nonnegative principal minors whenU andK(M) is convex. Finally, it is shown that whenM has nonnegative principal minors, only one of which is 0, andK(M)≠R ⁿ , thenU andK(M) is a closed half-space.     

The electron-poor phosphines P{C6H3(CF3)2-3,5}3 and P(C6F5)3 do not mimic phosphites as ligands for hydroformylation. A comparison of the coordination chemistry of P{C6H3(CF3)2-3,5}3 and P(C6F5)3 and the unexpectedly low hydroformylation activity of their rhodium complexes

The fluoroaryl phosphines P{C6H3(CF3)2-3,5}3 (La) and P(C6F5)3 (Lb) form the complexes trans-[MCl2(La)2] and trans-[MCl2(Lb)2](M = Pd or Pt) which have been isolated and fully characterised. 31P NMR studies of competition experiments show that the stability of trans-[PdCl2L2] is in the order L = Lb< La 相似文献   

Carboranethiol-modified gold surfaces. A study and comparison of modified cluster and flat surfaces

Four different carboranethiol derivatives were used to modify the surfaces of gold nanoparticles and flat gold films. The novel materials engendered from these modifications are extraordinarily stable species with surfaces that support self-assembled monolayers of 1-(HS)-1,2-C2B10H11, 1,2-(HS)2-1,2-C2B10H10, 1,12-(HS)2-1,12-C2B10H10, and 9,12-(HS)2-1,2-C2B10H10, respectively. Surprisingly, characterization of these materials revealed that a number of molecules of the carboranethiol derivatives are incorporated inside the nanoparticles. This structural feature was studied using a number of techniques, including X-ray photoelectron spectroscopy (XPS), UV-vis, and IR spectroscopies. Thermal desorption experiments show that carborane molecules detach and leave the nanoparticle surface mostly as 1,2-C2B10H10 isotopic clusters, leaving sulfur atoms bound to the gold surface. The surfaces of both the gold nanoparticles and the flat gold films are densely packed with carboranethiolate units. One carborane cluster molecule occupies an area of six to seven surface gold atoms of the nanoparticle and eight surface gold atoms of the flat film. XPS data showed that molecules of 1,12-(HS)2-1,12-C2B10H10 bind to the flat gold surface with only half of the thiol groups due to the steric demands of the icosahedral carborane skeleton. Electrochemical measurements indicate complete coverage of the modified gold surfaces with the carboranethiol molecules.     

The influence of solvation and finite temperatures on theWittig reaction: A theoretical study

The effects of the solvent and finite temperature (entropy) on the Wittig reaction are studied by using density functional theory in combination with molecular dynamics and a continuum solvation model. Standard gas-phase zero-temperature calculations are found to give similar results to previous studies. Gas-phase dynamics simulations allow the free energy profile of the reaction to be calculated through thermodynamic integration. The free energy profile is found to have a significant entropic barrier to the addition step of the reaction where only a small barrier was present in the potential energy curve. The introduction of the solvent dimethyl sulfoxide causes a change in the structure of the intermediate from the oxaphosphetane structure to the dipolar betaine structure. The overall reaction energy is changed only slightly. When the effects of both entropy and the solvent are included a significant entropic barrier to the addition reaction is obtained and the predicted intermediate again has the betaine structure.     

The calculation of excitation energies based on the relativistic two-component zeroth-order regular approximation and time-dependent density-functional with full use of symmetry

In the present work, we propose a relativistic time-dependent density-functional theory (TDDFT) based on the two-component zeroth-order regular approximation and a noncollinear exchange-correlation (XC) functional. This two-component TDDFT formalism has the correct nonrelativistic limit and affords the correct threefold degeneracy of triplet excitations. The relativistic TDDFT formalism is implemented into the AMSTERDAM DENSITY FUNCTIONAL program package for closed-shell systems with full use of double-group symmetry to reduce the computational effort and facilitate the assignments. The performance of the formalism is tested on some closed-shell atoms, ions, and a few diatomic molecules containing heavy elements. The results show that the fine structure of the excited states for most atoms and ions studied here can be accurately accounted for with a proper XC potential. For the excitation energies of the molecules studied here, the present formalism shows promise and the error encountered is comparable to that of nonrelativistic TDDFT calculations on light elements.     

Evaluation of two-dimensional gas chromatography-time-of-flight mass spectrometry for the determination of multiple pesticide residues in fruit

In recent years, comprehensive two-dimensional gas chromatography (GC x GC) has attained increasing attention for its outstanding separation potential and capability to solve demanding analytical tasks. Trace level analysis of pesticides residues in complex food matrices represents such a demanding task. For some commodities, such as baby food, the requirements on method detection limits are very strict and the unambiguous confirmation of the pesticide presence based on mass spectrometric detection is required. In this work, GC x GC coupled to time-of-flight mass spectrometry (TOF MS) has been evaluated for the determination of pesticides residues in fruit samples. Twenty modern pesticides with a broad range of physico-chemical properties were analysed in apple and peach samples. It has been demonstrated that the application of comprehensive two-dimensional gas chromatography brings distinct advantages such as enhanced separation of target pesticides from matrix co-extracts as well as their improved detectability. The limits of detection of the pesticides comprised in the study (determined at S/N = 5) ranged from 0.2 to 30 pg, injected with the exception of the last eluted deltamethrin, for which 100 pg could be detected. When compared to one-dimentional GC-TOF MS analysis under essentially the same conditions the detectability enhancement was 1.5-50-fold. Full mass spectral information by time-of-flight mass spectrometry and the deconvolution capability of the dedicated software allowed for reliable identification of most pesticides at levels below 0.01 mg/kg (< 10 pg injected) in fruit. Performance characteristics of the GC x GC-TOF MS method, such as linearity of calibration curves, repeatability of (summed) peak areas, as well as repeatability of first and second dimension retention times, were shown to fully satisfy the requirements for trace level analysis of the pesticide residues in food.     

Permethylated 6I-alkenoylamino-6I-deoxy β-cyclodextrin derivatives as modifiers of photoluminescence sensor response of porous silicon

A set of permethylated 6^I-(ω-alkenoyl)-6^I-amino-6^I-deoxy-β-cyclodextrin derivatives with different chain length of the alkenoyl group (used as a spacer) was synthesized. These derivatives were attached by photochemically activated hydrosilylation reaction to the surface of porous silicon. Photoluminescence response of the modified PS to controlled concentrations of various molecules in gas phase revealed strong host-guest interactions between β-cyclodextrin and the detected molecules. The strongest interaction was observed for aromatic molecules, which have the optimal size to fit into the β-cyclodextrin molecular cavity.     

Polypeptide-mediated silica growth on indium tin oxide surfaces

Herein, we describe the formation of silica structures on indium tin oxide (ITO) surfaces using poly-L-lysine (PLL) to template the condensation of silicic acid. Precisely controlled electrostatic fields were used to preposition PLL onto ITO surfaces. Subsequent polypeptide-mediated silicification resulted in the formation of silica with concentration gradients that followed the pattern of the externally applied electrostatic field used in the deposition of the PLL. The resulting silica structures were securely attached to the ITO surface. The technique described here offers an inexpensive and rapid method for the deposition of polypeptides on surfaces.     

EFFECTS OF DIETARY VITAMIN E AND SELENIUM ON LIGHT DAMAGE TO THE RAT RETINA*,†

Abstract—In this study we have investigated effects of dietary supplementation or deficiency in α-tocopherol (vitamin E) and selenium on acute light stress to albino rats. Selenium, which is an essential component of the enzyme glutathione peroxidase, and α-tocopherol are thought to be important in preventing in vivo lipid peroxidation. Before light stress, sections of paraffin embedded eyes show an intense yellow autofluorescent pigment localized in the retinal pigment epithelium (RPE) of the deficient rats which is barely visible in tissue sections from the supplemented rats. The fluorescent pigment is thought to be the result of damaging lipid peroxidation reactions. In addition the dcficient rats show increased electroretinogram (ERG) thresholds and decreased ERG-amplitudes compared to the supplemented rats. Acute 12 h light stress did not produce an increase in autofluorescent pigment in the RPE of the supplemented or deficient rats. The supplemented rats. however. showed marked light damage effects as measured by ERG-parameters. Contrary to our expectations, the deficient rats showed a lesser amount of light damage to the ERG than the supplemented rats. Our ERG results to date fail to implicate r-tocopherol levels or glutathione peroxidase activity as major factors in protecting the retina and pigment epithelium from damage after acute light stress.