Stepwise bidentate coordination of the novel indolylphosphine ligands HL (1, HL = P(C(6)H(5))(2)(C(9)H(8)N)(diphenyl-2-(3-methylindolyl)phosphine); 2, HL = P(C(6)H(5))(C(9)H(8)N)(2)(phenyldi-2-(3-methylindolyl)phosphine); and 3, HL = P(C(6)H(5))(C(17)H(12)N(2))(di(1H-3-indolyl)methane-(2,12)-phenylphosphine)) to the ruthenium cluster Ru(3)(CO)(12) is demonstrated. Reactions of 1-3 with Ru(3)(CO)(12) led to the formation of Ru(3)(CO)(11)(HL) (4-6), in which HL is mono-coordinated through the phosphorus atom. The X-ray structures of 4-6 show that the phosphorus atom is equatorially coordinated to the triruthenium core. In all cases, gentle heating of Ru(3)(CO)(11)(HL) resulted in the formation of Ru(3)(CO)(9)(mu-H)(mu(3),eta(2)-L)(7-9) in which the NH proton of the indolyl substituent had migrated to the ruthenium core to form a bridging hydride ligand. The X-ray structure of Ru(3)(CO)(9)(mu-H)[mu(3),eta(2)-P(C(6)H(5))(2)(C(9)H(7)N)] (7) shows the deprotonated nitrogen atom of the indolyl moiety bridging over the face of the triruthenium core, bonding to the two ruthenium metal centers to which the phosphorus atom is not bound. The phosphorus atom is forced to adopt an axial bonding mode due to the geometry of the indolylphosphine ligand. Cluster electron counting and X-ray data suggest that the indolylphosphine behaves as a six-electron ligand in this mode of coordination. Compounds 4-9 have been characterized by IR, (1)H, (13)C and (31)P NMR spectroscopy. 相似文献
Three subcommittees of the American Society for Testing and Materials (ASTM) are developing standards on various aspects of radiation processing. Subcommittee E10.01 “Dosimetry for Radiation Processing” has published 9 standards on how to select and calibrate dosimeters, where to put them, how many to use, and how to use individual types of dosimeter systems. The group is also developing standards on how to use gamma, electron beam, and x-ray facilities for radiation processing, and a standard on how to treat dose uncertainties. Efforts are underway to promote inclusion of these standards into procedures now being developed by government agencies and by international groups such as the United Nations' International Consultative Group on Food Irradiation (ICGFI) in order to harmonize regulations and help avoid trade barriers.
Subcommittee F10.10 “Food Processing and Packaging” has completed standards on good irradiation practices for meat and poultry and for fresh fruits, and is developing similar standards for the irradiation of seafood and spices. These food-related standards are based on practices previously published by ICGFI.
Subcommittee E10.07 on “Radiation Dosimetry for Radiation Effects on Materials and Devices” principally develops standards for determining doses for radiation hardness testing of electronics. Some, including their standards on the Fricke and TLD dosimetry systems are equally useful in other radiation processing applications. 相似文献
The hydride transfer reaction between OD+ and C3H6 has been studied experimentally and theoretically over the center of mass collision energy range from 0.21 to 0.92 eV using the crossed beam technique and density functional theory calculations. The center of mass flux distributions of the product ions at three different energies are highly asymmetric, with maxima close to the velocity and direction of the precursor propylene beam, characteristic of direct reactions. In the hydride transfer process, the entire reaction exothermicity is transformed into product internal excitation, consistent with mixed energy release in which the hydride ion is transferred with both the breaking and forming bonds extended. At higher collision energies, at least 85% of the incremental translational energy appears in product translation, providing a clear example of induced repulsive energy release. Compared to the related reaction of OD+ with C2H4, reaction along the pathway initiated by addition of OD+ to the C=C bond in propylene has a critical bottleneck caused by the torsional motion of the methyl substituent on the double bond. This bottleneck suppresses reaction through an intermediate complex in favor of direct hydride abstraction. Hydride abstraction appears to be a sequential process initiated by electron transfer in the triplet manifold, followed by rapid intersystem crossing and subsequent hydrogen atom transfer to form ground state allyl cation and HOD. 相似文献
In a sophomore/junior-level experiment suitable for intermediate organic or instrumental analysis, ring-substituted acetophenones were electrochemically reduced to form radical anions that then decompose in a manner determined by the ring substituent. Cyclic voltammetry was used to identify the electron-transfer (ET) mechanism, which was an electron transfer followed by a chemical reaction (EC). The product of the reaction was often electroactive (ECE) in the potential window defined by the acetonitrile/Bu4NPF6 solvent/supporting electrolyte. Products of the following decomposition were estimated with computer modeling (DFT) to estimate the likelihood of various decomposition pathways. Selection of the ring substituent or switching potential (Egw) allows the instructor to ask students to assign the mechanism for a single reduction or a complete ET mechanism, matching the difficulty of this experiment to the level of audience preparation. 相似文献
A simple method to generate an effective electron-ion interaction pseudopotential from the energy wave number characteristic
obtained by first principles calculations has been suggested. This effective potential has been used, in third order perturbation,
to study the effect of three-body forces on the lattice dynamics of noble metals. It is found that three-body forces, in these
metals, do play an important role. The inclusion of such three-body forces appreciably improves the agreement between the
experimental and theoretical phonon dispersion curves. 相似文献
One-dimensional (1H, 13C, DEPT), and two-dimensional (COSY, HETCOR) NMR experiments are used to assemble the chemical structures of monoterpene unknowns assigned to senior instrumental analysis students. Students were asked to use their knowledge of NMR to deduce the structure of their assigned compound. 相似文献
Protein adhesion plays a major role in determining the biocompatibility of materials. The first stage of implant integration is the adhesion of protein followed by cell attachment. Surface modification of implants (surface chemistry and topography) to induce and control protein and cell adhesion is currently of great interest. This communication presents data on protein adsorption (bovine serum albumin and fibrinogen) onto model hydrophobic (CH(3)) and hydrophilic (OH) surfaces, investigated using a quartz crystal microbalance (QCM) and grazing angle infrared spectroscopy. Our data suggest that albumin undergoes adsorption via a single step whereas fibrinogen adsorption is a more complex, multistage process. Albumin has a stronger affinity toward the CH(3) compared to OH terminated surface. In contrast, fibrinogen adheres more rapidly to both surfaces, having a slightly higher affinity toward the hydrophobic surface. Conformational assessment of the adsorbed proteins by grazing angle infrared spectroscopy (GA-FTIR) shows that after an initial 1 h incubation few further time-dependent changes are observed. Both proteins exhibited a less organized secondary structure upon adsorption onto a hydrophobic surface than onto a hydrophilic surface, with the effect observed greatest for albumin. This study demonstrates the ability of simple tailor-made monochemical surfaces to influence binding rates and conformation of bound proteins through protein-surface interactions. Current interest in biocompatible materials has focused on surface modifications to induce rapid healing, both of implants and for wound care products. This effect may also be of significance at the next stage of implant integration, as cell adhesion occurs through the surface protein layer. 相似文献
We describe a spectrometer for pulsed ENDOR at 140 GHz, which is based on microwave IMPATT diode amplifiers and a probe consisting of a TE011 cavity with a high-quality resonance circuit for variable radiofrequency irradiation. For pulsed EPR we obtain an absolute sensitivity of 3x10(9) spins/Gauss at 20 K. The performance of the spectrometer is demonstrated with pulsed ENDOR spectra of a standard bis-diphenylene-phenyl-allyl (BDPA) doped into polystyrene and of the tyrosyl radical from E. coli ribonucleotide reductase (RNR). The EPR spectrum of the RNR tyrosyl radical displays substantial g-anisotropy at 5 T and is used to demonstrate orientation-selective Davies-ENDOR. 相似文献
A method for measuring relative displacements on structures subjected to simulated seismic-base excitations is presented. This method uses a group of strain gages, mounted end-to-end and wired in series, as the sensor. Because the sensors are mounted directly to the structure, problems associated with the motion of the mounting hardware are avoided. Prior to their use in dynamic applications, static tests were performed to verify that strain-gage sensors give relative displacement readings that are as accurate as those obtained with conventional displacement transducers. These tests also showed that the hysteresis loops measured with the strain-gage sensors were smaller than those measured with the conventional displacement transducers. At similar load levels, the relative displacement results measured during dynamic tests were similar to those measured during static tests. 相似文献