Characterization of C-H...π interactions in the structure of the CHClF(2)-HCCH weakly bound complex

The microwave spectra of four isotopologues of the CHClF(2)-HCCH dimer have been measured and used to determine the structure of the complex. An initial scan over the 7-18 GHz region using the chirped-pulse microwave spectrometer at the University of Virginia provided initial assignments of the (35)Cl and (37)Cl isotopologues, with two additional H(13)C(13)CH species assigned using the resonant cavity Balle-Flygare microwave spectrometer at Eastern Illinois University. For the most abundant isotopologue, the rotational constants and quadrupole coupling constants are: A = 3301.21(4) MHz, B = 1353.4268(19) MHz, C = 1153.7351(18) MHz, χ(aa) = 34.681(12) MHz, χ(bb) = -69.70(3) MHz, χ(cc) = 35.02(2) MHz and χ(ab) = -8.8(3) MHz, in good agreement with ab initio calculations at the MP2/6-311++G(2d,2p) level. The alignment of CHClF(2) with respect to acetylene reveals a C-Hπ interaction, with a secondary C-ClH-C interaction also present between the two monomers. The fitted distance between the CHClF(2) hydrogen atom and the center of the triple bond is 2.730(6) ?, the distance between the chlorine atom and the acetylenic hydrogen is 3.061(38) ?, and the C-Hπ angle is 148.2(6)°. In addition, the centrifugal distortion constants give an estimate of the binding energy for the weak interaction of about 4.9(5) kJ mol(-1), in reasonable agreement with several similar complexes.     

Decomposition pathways of C1C4 alcohols adsorbed on platinum (111)

The adsorption and decomposition of methanol, ethanol, propan-1-ol, propan-2-ol and butan-1-ol has been studied on clean, and oxygen pre-covered Pt(111) surfaces. Temperature Programmed Reaction Spectroscopy (TPRS), Surface Potential Measurements (ΔV), UPS and XPS were used to characterise the adsorbed layer as a function of temperature. Each alcohol adsorbed into two states, a monolayer phase and a multilayer phase which were distinguishable by TPRS and Spectroscopy measurements. The monolayer alcohol adsorption heats increased sequentially from methanol to n-butanol (11.5–15 kcal mole^?1). On the clean surface, less than 10% of the adsorbed monolayer dissociated, with 90% of the alcohol desorbing intact. Two competing dissociative pathways were observed: complete dissociation to adsorbed CO, H and C, and with propan-1-ol and butan-1-ol, scission of the CC bond nearest the CO group to form adsorbed CO, H and ethylidyne and propylidyne species respectively. The latter reaction probability was constant at 30% for n-propanol and n-butanol. In all cases the final desorption products were the parent alcohol, CO and H₂ with carbon remaining on the surface for the higher alcohols. Atomic oxygen removed hydrogen from the alcohols as water but did not change the final reaction products.     

Electron beam effects in auger analysis of physisorbed xenon

Adsorbed xenon on evaporated films of nickel and platinum has been analysed by Auger electron spectroscopy. The primary electron beam is shown to cause some surface heating resulting in a displacement of the isotherms. This temperature effect is the same for both metals and is due to the limiting thermal conductivity of the glass substrate. A further effect, the electron induced desorption (EID) of xenon is evidenced by a distortion of the isotherms at low equilibrium gas pressures. This effect is more clearly observed on platinum because the coverage is higher than on nickel. The EID cross-section for xenon on both metals is found to be 1 × 10^?17cm². The attenuation of the metal Auger peaks by the xenon overlayer is found to be less for platinum than for nickel. This difference is attributed to a lower packing density of xenon on the platinum surface.     

A molecular packing analysis of some ferrous porphyrin complexes

An analysis has been made of the applicability of various sets of nonbonded interaction potential parameters which do not consider hydrogen atoms explicitly, to represent molecular packing interactions in crystals of ferrous porphyrin complexes, which are models for deoxyhemoglobin. Ordered regions of the structures are well described, but disordered solvent or ligands cause difficulty.     

Studies using the CASSCF wavefunction

The CASSCF method of Roos, Taylor and Siegbahn has been implemented and extended. In addition to the super-Cl and two-step convergence method, a second-order convergence method is implemented. Further, CASSCF energy gradients are available. The CASSCF method is extended by second-order Epstein-Nesbet perturbation theory. Applications of these methods to the single-triplet splitting of CH₂ and also the determination of the fundamental frequencies of H₂O are reported.     

Irradiance,Photofrin® Dose and Initial Tumor Volume are Key Predictors of Response to Interstitial Photodynamic Therapy of Locally Advanced Cancers in Translational Models

The objective of the present study was to develop a predictive model for Photofrin^®-mediated interstitial photodynamic therapy (I-PDT) of locally advanced tumors. Our finite element method was used to simulate 630-nm intratumoral irradiance and fluence for C3H mice and New Zealand White rabbits bearing large squamous cell carcinomas. Animals were treated with light only or I-PDT using the same light settings. I-PDT was administered with Photofrin^® at 5.0 or 6.6 mg kg⁻¹, 24 h drug-light interval. The simulated threshold fluence was fixed at 45 J cm⁻² while the simulated threshold irradiance varied, intratumorally. No cures were obtained in the mice treated with a threshold irradiance of 5.4 mW cm⁻². However, 20–90% of the mice were cured when the threshold irradiances were ≥8.6 mW cm⁻². In the rabbits treated with I-PDT, 13 of the 14 VX2 tumors showed either local control or were cured when threshold irradiances were ≥15.3 mW cm⁻² and fluence was 45 J cm⁻². No tumor growth delay was observed in VX2 treated with light only (n = 3). In the mouse studies, there was a high probability (92.7%) of predicting cure when the initial tumor volume was below the median (493.9 mm³) and I-PDT was administered with a threshold intratumoral irradiance ≥8.6 mW cm⁻².     

The charactization of high-speed swept reflectometer for plasma diagnostics on the RFX reversed-field pinch

An ordinary mode IMPATT-based reflectometer operating over 26.5–110GHz has been developed for density diagnostic application on the RFX reversedfield pinch experimental fusion machine. The reflectometer uses polarization rotators located at the antennas for optimizing the polarization of the emitted E-field A sweep speed of 1.25ms for the full band is possible. Single subbands may be swept at a rate of 200us. The provision of polarization rotators and high-speed solid-state oscillators maximises the immunity of the system to the effects of high fluctuation frequencies and mode mixing due to high magnetic shear. The reflectometer uses an IMPATT oscillator system for the source which has not been used in previous reflectometer circuits. A previously unachievable temporal resulution is therefore available with this system. The reflectometer is the first to be developed for use on a reversed-field pinch (RFP) machine.Verification of reflectometer operation was achieved using plane metal targets to simulate the reflecting plasma cut-off layer. Targets were located at various distances from the antennas to cover the expected spatial reflection range. The theoretical and experimental characteristics were obtained by processing the intermediate frequency output of the detectors. Spurious signals are removed by calibrating the target data using residual fringe data. A zero-crossing detection algorithm was developed to accurately identify the beat fringes and to deduce the phase/frequency characteristic. Single subband and full sweep results are presented.     

The influence of bond flexibility and molecular size on the chemically selective bonding of In2O and Ga2O on GaAs(001)-c(2 x 8)/(2 x 4)

The surface structures formed upon deposition of In2O and Ga2O by molecular beam epitaxy onto the arsenic-rich GaAs(001)-c(2 x 8)/(2 x 4) surface have been studied using scanning tunneling microscopy and density functional theory. In2O initially bonds, with indium atoms bonding to second layer gallium atoms within the trough, and proceeds to insert into or between first layer arsenic dimer pairs. In contrast, Ga2O only inserts into or between arsenic dimer pairs due to chemical site constraints. The calculated energy needed to bend a Ga2O molecule approximately 70 degrees, so that it can fit into an arsenic dimer pair, is 0.6 eV less than that required for In2O. The greater flexibility of the Ga2O molecule causes its insertion site to be 0.77 eV more exothermic than the In2O insertion site. This result shows that although trends in the periodic table can be used to predict some surface reactions, small changes in atomic size can play a significant role in the chemistry of gas/surface reactions through the indirect effects of bond angle flexibility and bond length stiffness.     

A highly efficient procedure for 3-sulfenylation of indole-2-carboxylates

A highly efficient one-pot procedure for 3-sulfenylation of 2-carboxyindoles is described. Treatment of thiols with N-chlorosuccinimide at -78 degrees C in CH(2)Cl(2) affords sulfenyl chlorides in situ that readily react with 2-carboxyindoles to give 3-thioindoles in high yields. This new method is milder, produces less waste, and is compatible with a wide range of thiol and indole functionality. [reaction: see text]