Formulation of unrestricted and restricted Hartree–Fock–Bogoliubov equations

The Hartree–Fock–Bogoliubov (HFB) method, dealing with Bogoliubov orbitals, which consist of particle and hole part, can provide states with pair correlations associated with Cooper pairs. The dimension of HFB Fock matrices can be reduced by restrictions of spin states of Bogoliubov orbitals similarly to ordinary Hartree–Fock (HF) equations such as restricted HF (RHF), unrestricted HF (UHF), and generalized HF (GHF). However, there are few studies of moderate restricted HFB equations such as UHF‐based HFB equations. In this article, formulation and calculations of restricted HFB equations are described. The solutions of general and restricted HFB equations are compared. Pair correlations taking account of restricted and general HFB equations are discussed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Effect of nitrogen on mechanical,oxidation and structural behaviour of Ti–Si–B–C–N nanocomposite hard coatings deposited by DC sputtering

Ti–Si–B–C–N film was deposited by DC magnetron sputtering at different argon and nitrogen ratios such as N₂/Ar = 1 : 5, 2 : 4, 3 : 3, 4 : 1 and 5 : 0. The formation of TiN and TiB phases was observed because of incorporation of nitrogen. The hardness, modulus, microstructure, structure and bond formation with different nitrogen contents during the deposition were studied by nanoindentation, scanning electron microscope, X‐ray diffraction and X‐ray photoelectron spectroscopy, respectively. The oxidation kinetics of Ti–Si–B–C–N was investigated. The nitrogen incorporation during deposition influences different properties of the coating. Hardness and modulus decreased, and microstructure showed very fine grain presence, and film changes to fully amorphous because of incorporation of nitrogen in the film. Copyright © 2016 John Wiley & Sons, Ltd.     

Spectroscopical UV–Vis implications of an intramolecular η2–Mg coordination in bacteriochlorophyll–a from the Fenna–Matthews–Olson complex

Chlorophylls and their related compounds prominently feature a Mg²⁺ ion in the center of a porphyrine, with an intermolecular fifth coordination usually observed to place the ion out of the macrocyclic plane. Herein, we assess the role of a potential intramolecular η²–(C = C)Mg interaction and compare it to the intermolecular coordination from the Hystidine groupt to Mg²⁺ for Bacterichlorophyll–a (Bchl–a), the main photosynthetic pigment in the Fenna–Matthews–Olson complex present in green and purple bacteria. The influence of this fifth coordination on the UV‐Vis spectroscopy (CAM‐B3LYP/cc‐pVDZ), and the concomitant change in geometry around Mg in Bchl–a from planar to pyramidal is assessed by the quantum theory of atoms in molecules based non–covalent interactions scheme and through energetic analysis via natural bond orbital population methods at the M06‐2X/cc‐pVDZ and compared to the reference multi–hapto compound, magnesocene, Cp₂Mg.     

Synergistic Effect between Metal–Nitrogen–Carbon Sheets and NiO Nanoparticles for Enhanced Electrochemical Water‐Oxidation Performance

Identifying effective means to improve the electrochemical performance of oxygen‐evolution catalysts represents a significant challenge in several emerging renewable energy technologies. Herein, we consider metal–nitrogen–carbon sheets which are commonly used for catalyzing the oxygen‐reduction reaction (ORR), as the support to load NiO nanoparticles for the oxygen‐evolution reaction (OER). FeNC sheets, as the advanced supports, synergistically promote the NiO nanocatalysts to exhibit superior performance in alkaline media, which is confirmed by experimental observations and density functional theory (DFT) calculations. Our findings show the advantages in considering the support effect for designing highly active, durable, and cost‐effective OER electrocatalysts.     

Geminal approach to vibronic models of superconductivity in crystals. I. The Jahn–Teller effect

Electronic geminals constructed as linear combinations of binary products of site functions are used to formulate a vibronic model of superconductivity in crystals that is based upon the approximation of independent correlated electron pairs obtained variationally from an electron‐pair Hamiltonian and the Jahn–Teller effect. The cyclic symmetry of the system is taken into account and the geminals are sorted into doubly degenerate pairs. The Herzberg–Teller expansion of the pair Hamiltonian in terms of vibrational modes leads directly to the Jahn–Teller effect. A contact transformation of the vibronic Hamiltonian containing only linear terms lowers the energy of the system by a second‐order term associated with the Jahn–Teller stabilization energy. A possible model for superconductivity in solids is proposed on the basis of the Jahn–Teller effect. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Preparation and characterization of MPEG–PCL diblock copolymers with thermo‐responsive sol–gel–sol phase transition

MPEG–PCL diblock copolymers consisting of methoxy polyethylene glycol (MPEG, 750 g/mol) and poly(?‐caprolactone) (PCL) were synthesized by ring‐opening polymerization. Aqueous solutions of the synthesized diblock copolymers were prepared by dissolving the MPEG–PCL diblock copolymers at concentrations in the range of 0–20 wt %. When the PCL molecular weight was 3000 or greater, the polymer was only partially soluble in water. As the temperature was increased from room temperature, the diblock copolymer solutions showed two phase transitions: a sol‐to‐gel transition and a gel‐to‐sol transition. The sol‐to‐gel phase transition temperature decreased substantially with increasing PCL length. The sol–gel–sol transition with the increase in temperature was confirmed by monitoring the viscosity as a function of temperature. The temperature ranges of the phase transitions measured by the tilting method were in full agreement with those determined from the viscosity measurements. The maximum viscosity of the copolymer solution increased with increasing hydrophobicity of the diblock copolymer and with increasing copolymer concentration. X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses revealed that the diblock copolymers exhibited crystalline domains that favored the formation of an aggregated gel because of the tight aggregation and strong packing interactions between PCL blocks. Scanning electron micrographs of the diblock copolymer solutions in the sol state showed interconnected polyhedral pore structures, whereas those of the gel state revealed a fibrillar‐like morphology. Atomic force microscope (AFM) studies of the sol and gel surfaces showed that the sol surface was covered with fine globular particles, whereas the gel surface was covered with particles in micron‐scale irregular islets. These findings are consistent with uniform mixing of the diblock copolymer and water in the sol state, and aggregation of PCL blocks in the gel state. In conclusion, we confirm that the MPEG–PCL diblock copolymer solution exhibited a sol–gel–sol transition as a function of temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5413–5423, 2006     

Structure–activity relationship of N‐heterocyclic carbene–Pd(II)–imidazole complexes in Suzuki–Miyaura coupling between 4‐methoxyphenyl chloride and phenylboronic acid

A series of N‐heterocyclic carbene–PdCl₂–imidazole [NHC–Pd(II)–Im] complexes were synthesized and the structure of most of them was unambiguously determined by X‐ray single‐crystal diffraction. The structure–activity relationship of these complexes was investigated for the Suzuki–Miyaura coupling between 4‐methoxyphenyl chloride and phenylboronic acid, and the effect of the NHCs and Im moieties were fully discussed. The sterically hindered IPr‐based complex showed the highest catalytic activity. Copyright © 2013 John Wiley & Sons, Ltd.     

The chemical composition and bonding structure of B–C–N–H thin films deposited by reactive magnetron sputtering

The chemical composition and bonding structures of B–C–N–H films fabricated by medium frequency magnetron sputtering, with N₂+CH₄+Ar gas mixture sputtering the boron target, were investigated. XPS and FTIR spectrometric analyses show that the increase of CH₄ flow rate during deposition causes an increase of the C content in the films. The increase in the CH₄ flow rate promotes an increase in the B–C, C–N single and C?N double bonds which are the components of the hybridized B–C–N bonding structure. From the results of Raman spectroscopy analysis, it is seen that the intensity of the D band of the films' Raman spectrum decreases with increasing CH₄ flow rate, indicating a decrease of the sp²‐phase content or the sp² C cluster size. The decreases of I_D/I_G also reflect the formation of more boron‐ or nitrogen‐ bound sp³‐coordinated carbons in the films. Copyright © 2009 John Wiley & Sons, Ltd.     

On the Validity of Stokes–Einstein and Stokes–Einstein–Debye Relations in Ionic Liquids and Ionic‐Liquid Mixtures

Stokes–Einstein (SE) and Stokes–Einstein–Debye (SED) relations in the neat ionic liquid (IL) [C₂mim][NTf₂] and IL/chloroform mixtures are studied by means of molecular dynamics (MD) simulations. For this purpose, we simulate the translational diffusion coefficients of the cations and anions, the rotational correlation times of the C(2)? H bond in the cation C₂mim⁺, and the viscosities of the whole system. We find that the SE and SED relations are not valid for the pure ionic liquid, nor for IL/chloroform mixtures down to the miscibility gap (at 50 wt % IL). The deviations from both relations could be related to dynamical heterogeneities described by the non‐Gaussian parameter α(t). If α(t) is close to zero, at a concentration of 1 wt % IL in chloroform, both relations become valid. Then, the effective radii and volumes calculated from the SE and SED equations can be related to the structures found in the MD simulations, such as aggregates of ion pairs. Overall, similarities are observed between the dynamical properties of supercooled water and those of ionic liquids.     

Shaping Microcrystals of Metal–Organic Frameworks by Reaction–Diffusion

When components of a metal–organic framework (MOF) and a crystal growth modulator diffuse through a gel medium, they can form arrays of regularly‐spaced precipitation bands containing MOF crystals of different morphologies. With time, slow variations in the local concentrations of the growth modulator cause the crystals to change their shapes, ultimately resulting in unusual concave microcrystallites not available via solution‐based methods. The reaction–diffusion and periodic precipitation phenomena 1) extend to various types of MOFs and also MOPs (metal–organic polyhedra), and 2) can be multiplexed to realize within one gel multiple growth conditions, in effect leading to various crystalline phases or polycrystalline formations.     

Baeyer–Villiger oxidation of cyclohexanone by molecular oxygen with Fe–Sn–O mixed oxides as catalysts

Fe–Sn–O mixed oxides were synthesized and used as catalysts for Baeyer–Villiger oxidation of cyclohexanone, which showed both high catalytic activity and selectivity. X‐ray powder diffraction and scanning electron microscopy suggested that the Fe–Sn–O catalysts had a tetragonal structure with a grain size of 29.3 nm. An ε‐caprolactone yield as high as 98.8% was obtained in a small‐scale experiment (5 mmol of cyclohexanone). In a scale‐up test (20 mmol of cyclohexanone), the cyclohexanone conversion and ε‐caprolactone yield were 96.7 and 96.5%, respectively. In addition, the catalysts can be reused five times without any major decline in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Pressure–Volume–Temperature properties of polyolefin liquids and their melt miscibility

The pressure–volume–temperature (P–V–T) properties of a number of metallocene-produced polyolefins were measured experimentally at 10 MPa ≤ P ≤ 200 MPa and 30°C ≤ T ≤ 220°C in a dilatometer-type P–V–T apparatus. These included ethylene copolymers typical of linear low density polyethylene, with several α-olefins as comonomers and a wide range of comonomer content. The experimental P–V–T data were correlated with the equations of state from the Sanchez–Lacombe and Flory–Orwoll–Vrij theories. The solubility parameter map of the polyolefins, at atmospheric pressure, was established on the basis of the thermodynamic data. As the temperature increases, the solubility parameter of the polyolefin decreases. The solubility parameters of copolymers of ethylene with propylene, butene, hexene, and octene under constant temperature are all more or less the same at equal weight percent of comonomer. As the incorporation of branches increases, the solubility parameter decreases. The melt miscibility of the polyolefin blends can be predicted to design various blend products for specific applications from this solubility parameter map. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2835–2844, 1999     

Preparation of Si–C–N–Fe magnetic ceramics from iron‐containing polysilazane

A new type of hyperbranched polysilazane containing iron (PSZI) compound was synthesized by the polycondensation of silazane lithium salts with FeCl₃, and the structure of the PSZIs was investigated by IR, NMR and elemental analyses. The PSZIs were pyrolyzed under nitrogen, argon or NH₃, and magnetic ceramics could be obtained. The ceramic yields of the PSZIs were higher than those of their corresponding silazanes, and the PSZIs or silazanes with reactive groups containing Si? H, ? CH?CH₂ or higher branched structures had higher yields. The magnetism of the ceramics could be controlled by a pyrolytic atmosphere and temperature: the saturation magnetization M_s ranged from 20 to 100 emu g^?1 and coercivity H_c ranged from 463 to 50 Oe. The transformation of the magnetic loop of the PSZIs pyrolyzed at different temperatures under NH₃ was quite different from those under nitrogen. It was shown by X‐ray diffraction measurements that the magnetic crystalline form could exist as Fe₄N, Fe(0) or Fe₃N depending on temperature under NH₃, but under a nitrogen atmosphere Fe(0) was nearly the only magnetic crystalline form from 600 to 1100 °C. By dipping or spin‐coating of the PSZI solution, then through pyrolysis under nitrogen, argon or NH₃, thin uniform magnetic ceramic films could be fabricated on the substrates. Copyright © 2003 John Wiley & Sons, Ltd.     

Screening potential antagonists of epidermal growth factor receptor from Marsdenia tenacissima via cell membrane chromatography model assisted by HPLC–ESI–IT–TOF–MS

Marsdenia tenacissima, or Tongguanteng in Chinese, is a traditional Chinese herb and has a broad application in clinical practice for its pharmacological effects of treating asthma, pneumonia, tonsillitis, pharyngitis tumors, etc. However, few studies have reported the screening of the active components of this medicine for tumor therapy. In this work, a two‐dimensional analytical system was developed to screen antagonists of epidermal growth factor receptor (EGFR) from M. tenacissima. A fraction was retained on the EGFR cell membrane chromatography (CMC) column, separated and identified as tenacissoside G (TG), tenacissoside H (TH) and tenacissoside I (TI) by two‐dimensional HPLC–IT–TOF–MS. Molecular docking and 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyl‐2‐H‐tetrazolium bromide (MTT) assay were carried out to assess the activity of TS (including TG, TH and TI). Molecular docking results showed that the binding mode of TS on EGFR is similar to that of gefitinib. The MTT assay demonstrated that gefitinib and TS (especially TI) could inhibit the growth of EGFR highly expressed cell lines in a dose‐dependent manner in the range of 5–50 μmol/L. In conclusion, the two‐dimensional EGFR/CMC–HPLC–IT–TOF–MS system could be a useful approach in drug discovery from traditional Chinese medicines for searching for potential antitumor candidates.     

Conformational study on telaprevir by HPLC–DAD–MS and theoretical calculation

Telaprevir is a potent, selective, peptidomimetic inhibitor of the hepatitis C virus (HCV) NS3‐4A serine protease. it is used for the treatment of HCV infection in combination with peginterferon alfa and ribavirin. In the present work, the E–Z isomerization process of telaprevir in solution was revealed by online HPLC–DAD (diode array detector)–MS, variable‐temperature and variable‐gradient experiments. The molecular geometry information of the two isomers was established by molecular mechanics calculations, and good correlation between the two isomers' UV–vis spectra and their molecular geometry information was also discovered. In addition, it was revealed by molecular docking that the two isomers have different affinities to HCV NS3?4A protease, and the Z isomer, the minor form of telaprevir in solution, is the more effective inhibitor of HCV NS3?4A protease. The investigation can provide more structure information about telaprevir in solution and in the binding process of HCV NS3?4A protease.