Bonding and correlation analysis of various SiCO isomers

The structural properties for various SiCO isomers in the singlet and triplet states have been investigated using CASSCF methods with a 6-311 +G* basis set and also using three DFT and MP2 with same basis set for those systems except for the linear singlet state. The detailed bonding character is discussed, and the state-state correlations and the isomerization mechanism are also determined. Results indicate that there are four different isomers for each spin state, and for all isomers, the triplet state is more stable than the corresponding singlet state. The most stable is the linear SiCO ((3)Sigma(-)) species and may be refer-red to the ground state. At the CASSCF-MP2(full)/6-311+G* level, the state-state energy separations of the other triplet states relative to the ground state are 43.2 (cyclic), 45.2 (linear SiOC), and 75.6 kcal/mol (linear CSiO), respectively, whereas the triplet-singlet state excitation energies for each configuration are 17.3 (linear SiCO), 2.2 (cyclic SiCO), 10.2 (linear SiOC), and 18.5 kcal/mol (linear CSiO), respectively. SiCo ((3)Sigma(-)) may be classified as silene (carbonylsilene), and its COdelta- moiety possesses CO- property. The dissociation energy of the ground state is 42.5 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and falls within a range of 36.5-41.5 kcal/mol at DFT level, and of 23.7-28.9 kcal/mol at the wave function-correlated level, whereas the vertical IP is 188.8 kcal/mol at the CASSCF-MP2(full)/6-311+G* level and is very close to the first IP of Si atom. Three linear isomers (SiCO, SiOC, and CSiO) have similar structural bonding character. SiOC may be referred to the iso-carbonyl Si instead of the aether compound, whereas the CSiO isomer may be considered as the combination of C (the analogue of Si) with SiO (the analogue of CO). The bonding is weak for all linear species, and the corresponding potential energy surfaces are flat, and thus these linear molecules are facile. Another important isomer is of cyclic structure, it may be considered as the combination of CO with Si by the side pi bond. This structure has the smallest triplet state-singlet state excitation energy (similar to2.2 kcal/mol); the C-O bonds are longer, and the corresponding vibrational frequencies are significantly smaller than those of the other linear species. This cyclic species is not classified as an epoxy compound. State-state correlation analysis and the isomerization pathway searches have indicated that there are no direct correlations among three linear structures for each spin state, but they may interchange by experiencing two transition states and one cyclic intermediate. The easiest pathway is to break the Si-O bond to go to the linear SiCO, but its inverse process is very difficult. The most difficult process is to break the C-O bond and to go to the linear CSiO.

Dynamics of excited OCS investigated by resonance-enhanced multiphoton ionization

The predissociation decay behavior of molecule carbonyl sulfide (OCS) has been investigated by resonance-enhanced multiphoton ionization spectroscopy using the pump-probe technique of dichroic femtosecond lasers in real time. The lifetime of excited OCS around 74 720 cm(-1) by two-photon absorption of 268 nm, corresponding to upsilon(1)=1 of the Rydberg state [(2)Pi(1/2)]4ppi((1)Sigma(+)), is directly determined to be tau(D)=1071+/-11 fs. This picosecond decay process indicates that the excited state is predissociative. The temporal information of dissociation enriches the knowledge of the potential-energy surface of the associative excited state.

从Σ-协议到公共参考串模型下可否认零知识的高效编译器

给出公共参考串(CRS)模型下可否认零知识的一个正面结果:从Σ-协议到CRS模型下的可否认零知识的高效转化.由Pass在CRYPTO 2003中给出的下界可知,我们的编译器取得了最优的轮效率.此外,转化所增加的通信复杂度较小.

Theoretical studies on the reaction mechanism of palladium(0)-catalyzed addition of thiocyanates to alkynes

The reaction mechanism of the Pd(0)-catalyzed alkyne cyanothiolation reaction is investigated by MP2, CCSD(T) and the density functional method B3LYP. The overall reaction mechanism is examined. The B3LYP results are consistent with the results of CCSD(T) and MP2 methods for the isomerization, acetylene insertion and reductive elimination steps, but not for the oxidative addition step. For the oxidative addition, the bisphosphine and monophosphine pathways are competitive in B3LYP, while the bisphosphine one is preferred for CCSD(T) and MP2 methods.

Probing Charge Transport of Ruthenium-Complex-Based Molecular Wires at the Single-Molecule Level

A ruthenium(II) bis(sigma-arylacetylide)-complex-based molecular wire functionalized with thiolacetyl alligator clips at both ends (OPERu) was used to fabricate gold substrate-molecular wire-conductive tip junctions. To elucidate the ruthenium-complex-enhanced charge transport, we conducted a single-molecule level investigation using the technique-combination method, where electronic delay constant, single-molecular conductance, and barrier height were obtained by scanning tunneling microscopy (STM) apparent height measurements, STM break junction measurements, and conductive probe-atomic force microscopy (CP-AFM) measurements, respectively.

Structure and mechanical properties of extruded Mg-Gd based alloy sheet

The Mg-8Gd-2Y-1Nd-0.3Zn-0.6Zr (wt.%) alloy sheet was prepared by hot extrusion technique, and the structure and mechanical properties of the extruded alloy were investigated. The results show that the alloy in different states is mainly composed of alpha-Mg solid solution and secondary phases of Mg5RE and Mg24RE5 (RE = Gd, Y and Nd). At aging temperatures from 200 degrees C to 300 degrees C the alloy exhibits obvious age-hardening response. Great improvement of mechanical properties is observed in the peak-aged state alloy (aged at 200 degrees C for 60 h), the ultimate tensile strength (sigma(b)), tensile yield strength (sigma(0.2)) and elongation (epsilon) are 376 MPa, 270 MPa and 14.2% at room temperature (RT), and 206 MPa. 153 MPa and 25.4% at 300 degrees C, respectively, the alloy exhibits high thermal stability.

Reaction Mechanism of Palladium-Catalyzed Silastannation of Allenes by Density Functional Theory

The reaction mechanism of Pd(O)-catalyzed allenes silastannation reaction is investigated by the density functional method B3LYP. The overall reaction mechanism is examined. For the allene insertion step, the Pd-Si bond is preferred over the Pd-Sn bond. The electronic mechanism of the allene insertion into Pd-Si bond to form sigma-vinylpalladium (terminal-insertion) and sigma-allylpalladium (internal-insertion) insertion products is discussed ill terms of the electron donation and back-donation. It is found that the electron back-donation is significant for both terminal- and internal-insertion. During allene insertion into Pd-Si bond, internal-insertion is preferred over terminal-insertion. By using methylallene, the regio-selectivity for the monosubstituted allene insertion into Pd-Si and Pd-Sn bond is analyzed.

Regioselective Bis-Selenation of Allenes Catalyzed by Palladium Complexes: A Theoretical Study

The reaction mechanism of Pd(O)-catalyzed allene bis-selenation reactions is investigated by using density functional methods. The overall reaction mechanism has been examined. It is found that with the bulkier PMe3 ligand, the rate-determining step is the reductive elimination process, while allene insertion and reductive elimination processes are competitive for the rate-determining step with the PH3 ligand, indicating the importance of the ligand effect. For both cis and trans palladium complexes, allene insertion into the Pd-Se bond of the trans palladium complex using the internal carbon atom attached to the selenyl group is prefer-red among the four pathways of allene insertion processes. The formation of sigma-allyl and pi-allyl palladium complexes is favored over that of the sigma-vinyl palladium species. By using methylallene, the regioselectivity of monosubstituted allene insertion into the Pd-Se bond is analyzed.

Microphase-Separated Brushes on Square Platelets in PS-b-PEO Thin Films

In polystyrene-block-poly(ethylene oxide) thin square platelets can be obtained via fast solvent evaporation by controlling the tethering density (0.08 < sigma < 0.11). The tethering density of the brushes is proportional to the thickness of the PEO crystal and increases with increasing initial solution heating temperature (T-i). When T-i < T-m, where T-m is the melting point of PEO, brushes with microphase-separated structures are observed. The formation of microphase-separated brushes depends on two factors: the strong incompatibility between PS and noncrystalline PEO chains (attached to the crystalline PEO) and the weak interaction between PS-PS brushes.

Preparation and electrical properties of new oxide ion conductors Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8)

Ce6-xDyxMoO15-delta (0.0 <= x <= 1.8) were synthesized by modified sol-gel method. Structural and electrical properties were investigated by means of X-ray diffraction (XRD), Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The XRD patterns showed that the materials were single phase with a cubic fluorite structure. Impedance spectroscopy measurement in the temperature range between 350 degrees C and 800 degrees C indicated a sharp increase in conductivity for the system containing small amount of Dy2O3. The Ce5.6Dy0.4MoO15-delta detected to be the best conducting phase with the highest conductivity (sigma(t) = 8.93 x 10(-3) S cm(-1)) is higher than that of Ce5.6Sm0.4MoO15-delta (sigma(t) = 2.93 x 10(-3) S cm(-1)) at 800 degrees C, and the corresponding activation energy of Ce5.6Dy0.4MoO15-delta (0.994 eV) is lower than that of Ce5.6Sm0.4MoO15-delta (1.002 eV).

Preparation and Electrical Properties of New Oxide Ion Conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8)

A series of oxide ion conductors Ce6-xGdxMoO15-delta (0.0 <= x <= 1.8) have been prepared by the sol-gel method. Their properties were characterized by differential thermal analysis/thermogravimetry (DTA/TG), X-ray diffraction (XRD), Raman, IR, X-ray photoelectron spectroscopy (XPS), and AC impedance spectroscopy. The XRD patterns showed that the materials were single phase with a cubic fluorite structure. The conductivity of Ce6-xGdxMoO15-delta increases as x increases and reaches the maximum at x = 0.15. The conductivity of Ce4.5Gd1.5MoO15-delta is sigma(t) = 3.6 x 10(-3) S/cm at 700 degrees C, which is higher than that of Ce4.5/6Gd1.5/6O2-delta (sigma(t) = 2.6 x 10(-3) S/cm), and the corresponding activation energy of Ce4.5Gd1.5MoO15-delta (0.92 eV) is lower than that of Ce4.5/6Gd1.5/6O2-delta (1.18 eV).

Synthesis and Electrical Properties of New Solid State Electrolyte Materials Ce6-xHoxMoO15-delta(0.0 <= x <= 1.2)

Ce6-xHoxMoO15-delta(0.0 <= x <= 1.2) was synthesized by modified sol-gel method and characterized by differential X-ray diffraction(XRD), Raman, and X-ray photoelectron spectroscopy(XPS) methods. The oxide ionic conductivity of the samples was investigated by AC impedance spectroscopy. It shows that all the samples are single phase with a cubic fluorite structure. The solid solution Ce6-xHoxMoO15-delta(x=0.6) was detected to be the best conducting phase with the highest conductivity(sigma(t)=1.05x10(-2) S/cm) at 800 degrees C and the lowest activation energy(E-a=1.09 eV). These properties suggest that this kind of material has a potential application in intermediate-low temperature solid oxide fuel cells.

以金纳米粒子为探针比色法检测顺铂

研究简单且高灵敏度的检测广谱抗癌药物顺铂(cis-Pt)的新方法在临床上具有重要意义.无机纳米粒子由于具有特殊的光(电)学性质以及其它与形状或粒径有关的性质,近十年来已被广泛应用于各种生物分析和生物医学检测技术中[1,2].本文报道了一种以金纳米粒子表面等离子吸收带变化为基础,通过DNA与cis-Pt相互作用来检测溶液中cis-Pt浓度的新型比色法.1实验部分1.1试剂与仪器实验所用多肽(CALNN)、互补DNA(5′-GAGAGACCGAGAGAGAAA-3′)和多肽-DNA(CALNN-5′-AAAAATTTCTCTCTCGGTCTCTC-3′)均购自Alta Biosciences公司(UK);cis-Pt购自Sigma公司(USA).其它试剂均为分析纯;实验用水为18.2MΩ超纯水.JEOL2010电子透射显微镜(日本电子);紫外分光光度计UVMini-1240(日本岛津);AMX2-400核磁共振仪(布鲁克);X射线等离子质谱仪(英国热电).1.2表面修饰多肽/多肽-DNA的金纳米粒子...

Synthesis, structure and photochromic properties of a novel 1,6-hexanediamine trimolybdate supramolecular compound

A novel supramolecular compound 1,6-hexanediamine trimolybdate ((C6H18N2[Mo3O10], denoted as HDAMo) has been synthesized by a hydrothermal method and its structure has been characterized by elemental analyses, Fourier transform infrared (FT-IR) spectra, single-crystal X-ray diffraction (XRD) technique. This single crystal compound consists of protonated 1,6-hexanediamine (HDA) cations and polyoxometalate [Mo3O10](2-) anions. Its crystal structure belongs to monoclinic system (space group P2(1)/n) with a = 7.7508(14), b = 11.467(2), c = 16.167(3) angstrom, beta = 92.689(3)degrees, V = 143 5.3(5) angstrom(3), Z = 4 and D-ealc = 2.619 g cm(-3). The final statistics based on F-2 are GOF = 0.980, R-1 = 0.0261 and wR(2) = 0.0506 for I > 2 sigma(I). XRD analysis revealed that in the crystal structure of HDAMo, novel infinite [Mo3O10](2-) chains parallel to a axis are made up of distorted MoO6 octahedra connected by corners and edges. The protonated HDA cations occupy channels formed by [Mo(3)O3(10)](2-) Chains and exhibit strong hydrogen bond interactions to terminal and bridging oxo groups of the chains. The [Mo3O10](2-) chains linked through protonated HAD cations formed a one-dimensional network. The HDAMo compound shows novel photochromic properties, i.e., its color changes from white to reddish brown gradually under UV irradiation. XRD, FT-IR, ESR spectra and XPS are used to investigate the photochromic behavior of the compound.

Polyelectrolyte complexes of chitosan and phosphotungstic acid as proton-conducting membranes for direct methanol fuel cells

Polyelectrolyte complexes (PECs) of chitosan and phosphotungstic acid have been prepared and evaluated as novel proton-conducting membranes for direct methanol fuel cells. Phosphotungstic acid can be fixed within PECs membranes through strong electrostatic interactions, which avoids the decrease of conductivity caused by the dissolving of phosphotungstic acid as previously reported. Scanning electron microscopy (SEM) shows that the PECs membranes are homogeneous and dense. Fourier transform infrared spectroscopy (FTIR) demonstrates that hydrogen bonding is formed between chitosan and phosphotungstic acid. Thermogravimetric analysis (TGA) shows that the PECs membranes have good thermal stability up to 210 degrees C. The PECs membranes exhibit good swelling properties and low methanol permeability (P, 3.3 x 10(-7) cm(2) s(-1)). Proton conductivity (sigma) of the PECs membranes increases at elevated temperature, reaching the value of 0.024 S cm(-1) at 80 degrees C.