Enzymatic Promiscuity： ＂Amano＂ Lipase AS-catalysed Synthesis of Naphthopyran Derivatives in Anhydrous Media

＂Amano＂ lipase AS（lipase from Aspergillus niger）, which naturally hydrolyzes triglycerides, was found promiscuously to catalyze multi-component reactions of aromatic aldehydes with malononitrile and β-naphthol to prepare naphthopyran derivatives in anhydrous organic solvents in moderate to good yields.     

Effect of the formation of secondary pores in zeolite ZSM-5 on the properties of molybdenum-zeolite catalysts for methane aromatization

A study is performed of 4% Mo/ZSM-5 (30) catalysts for methane aromatization prepared by solid-phase synthesis with mechanical mixing of a zeolite with MoO₃ followed by calcination at 550°C. Zeolite etched with sodium hydroxide solutions and dealuminated with aluminum nitrate solutions is used as a support. Catalytic studies of the catalysts are conducted. The effect of treating the initial zeolite on the properties of catalysts in methane aromatization is determined. The effect subsequently treating a zeolite support has on the acid sites of a catalyst is confirmed by means of temperature-programmed reduction and the temperature-programmed desorption of NH3. The formation of molybdenum ions in the +5 oxidation state during catalysis and the presence of graphitized carbon deposits on a spent catalyst’s surface are confirmed by EPR and temperature-programmed oxidation.     

Study of lithium ion exchange by two synthetic zeolites: Kinetics and equilibrium

We examined the exchange of univalent cations (Na+ and H+) retained on two commercially available synthetic zeolites with Li+ ions present in aqueous solutions in contact with the solids with a view to preparing effective controlled-release pharmaceutical forms. The studied zeolites were manufactured by Merck and featured channel diameters of 0.5 (Zeolite 5A, Ref. 1.05705.250, designated Z-05 in this work) and 1.0 nm (Zeolite 13X, Ref. 1.05703.250, designated Z-10 here). The XRD technique revealed that Z-05 possesses an LTA structure derived from that of sodalite and Z-10 a faujasite-type structure. Their exchange capacities were found to be 2.72 and 3.54 meq/g. The Z-Na + Li(+) / Z-Li + Na(+) and Z-H + Li(+) / Z-Li + H(+) ion-exchange processes were found to be reversible and their kinetic laws to obey the equation (-dC/dt) = k(a) x C(n) x (1-theta) - (k(d) x theta), with n = 1 for Z-10 and n = 2 for Z-05. Based on the equilibrium results, the overall processes involve one (with Z-05) or two single ion-exchange processes (with Z-10). In both cases, the equations that govern equilibrium are direct results of the kinetic laws. Thus, the first process-the one with only Z-05-involves the retention of Li+ cations at anionic sites on the outer surface of the solid and their access to the larger pores; the second process-which occurs with Z-10 only-involves the retention of lithium(I) cations within the zeolite channels. In both systems, the exchange with Li+ (from the aqueous solution) is easier than that with H+; this is consistent with our kinetic, equilibrium, and thermodynamic results.     

Investigation of the Interaction between Isoflavonoids and Bovine Serum Albumin by Fluorescence Spectroscopy

The interactions of bovine serum albumin （BSA） with three structurally related isoflavonoids, genistein, puerarin and daidzein, were studied under physiological conditions by fluorescence spectroscopic technique. The quenching mechanism of these compounds with BSA was suggested as static quenching and the binding constants were determined at different temperatures based on the fluorescence quenching results. The transfer efficiency of energy and distance between the acceptor and BSA were investigated on the basis of the mechanism of the Forster energy transference. According to the thermodynamic parameters it has been suggested that the acting force be mainly hydrophobic force. The comparison of binding potency of the three isoflavonoids to BSA showed that the substitution by 5-OH and 8-Glc could enhance the binding affinity. All these obtained in the work can make us better understand the mode of the action and pharmacological activities of the isoflavonoids.     

Fe48Co52 Alloy Nanowire Arrays： Effects of Magnetic Field Annealing

The effects of magnetic field annealing on the properties of Fe48Co52 alloy nanowire arrays with various interwire distances （Di=30-60 nm） and wire diameters （Dw=22-46 nm） were investigated in detail. It was found that the array＇s best annealing temperature and crys- talline structure did not show any apparent dependence on the treatment of applying a 3 kOe magnetic field along the wire during the annealing process. For arrays with small Dw or with large Di, the treatment of magnetic field annealing also had no obvious influence on their magnetic performances. However, such a magnetic field annealing constrained the shift of the easy magnetization direction and improved the coercivity and the squareness obviously for arrays with large Dw or with small Di. The difference in the intensity of the effective anisotropic field within the arrays was believed to be responsible for this different variation of the array＇s magnetic properties after magnetic field annealing.     

Laser Flash Photolysis on Electron Transfer Reactions between 1,8-Dihydroxyanthraquinone with Adenine and Cytosine

Electron transfer （ET） reactions between 1,8-dihydroxyanthraquinone （DHAQ） and two DNA bases, adenine （A） and cytosine （C）, have been investigated in CH3CN/H20 solution with nanosecond time-resolved laser flash photolysis. After irradiation at 355 nm, the triplet DHAQ is produced via intersystem crossing and reacts with two nucleobases. ET processes for both reactions have been definitely identified, in which two bases play a significant role of electron donor. Based on the measured decay dynamics of various intermediates and the corresponding quenching rates, an initial ET process followed by a secondary proton-transfer reaction is suggested for both the overall reactions. By plotting the observed quenching rate against the concentration of two DNA bases, the bimolecular quenching rate constants are determined as 9.0-10s L/（mol.s） for the 3DHAQ＊＋C reaction and 3.3x10^8 L/（mol.s） for the 3DHAQ＊＋A reaction, respectively.     

Improved Photovoltaic Performance of MEH-PPV/PCBM Solar Cells via Incorporation of Si Nanocrystals

We have studied the effect of silicon nanocrystals （SiNCs） as a third component on performance of organic bulk heterojunction solar cells composed of poly[2-methoxy,5-（2＇-ethylhexyloxy）-l,4-phenylene vinylene] （MEH- PPV）：[6,6]-phenyI-C61-butyric acid methyl ester （PCBM） blend film. By adding suitable amounts of SiNCs into MEH-PPV：PCBM blend, the device performance such as external quantum efficiency, short circuit current density （Js（）, and power conversion efficiency （PCE） improved. Incorporation of 2.5% SiNCs in the blend led to 13.6% improvement of Jsc, which in turn resulted in 18% improvement of PCE up to 2.28%. The improved performance was mainly due to the improvements both in the charge generation from the interface of MEH-PPV/SiNCs and the charge collection at the cathode.     

Synthesis and Crystal Structure of Tianagliflozin Triacetate

The title compound tianagliflozin triacetate 1 was synthesized and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic system(C27H31ClO8,Mr = 518.97),space group P21 with a = 5.3913(11),b = 16.137(2),c = 15.411(3) ,β = 94.15(3)°,V = 1337.3(5) 3,Z = 2,Dc = 1.289 g/cm3,F(000) = 548,μ = 0.190 mm-1,the final R = 0.0374 and wR = 0.0809 for 3981 observed reflections(I 2σ(I)).The structure of 1,triacetate of a highly potent SGLT2 inhibitor tianagliflozin,was unambiguously determined by single-crystal X-ray diffraction,which helped to confirm the desired β configuration at the anomeric center and the position where the deoxylation occurred.The two benzene rings in the lattice are basically orthogonal to each other.There are four intermolecular hydrogen bonds in the crystal,which helps to further stabilize the crystal.     

Theoretical Investigation on Interaction between Guanine and Luteolin

The interacting patterns of the luteolin and guanine have been investigated by using the density functional theory B3LYP method with 6-31＋G＊ basis set. Eighteen stable structures for the luteolin-guanine complexes have been found respectively. The results indicate that the complexes are mainly stabilized by the hydrogen bonding interactions. Meanwhile, both the number and strength of hydrogen bond play important roles in determining the stability of the complexes which can form two or more hydrogen bonds. Theories of atoms in molecules and natural bond orbital have also been utilized to investigate the hydrogen bonds involved in all the systems. The interaction energies of all the complexes which were corrected by basis set superposition error are 6.04-56.94 kJ/mol. The calculation results indicate that there are strong hydrogen bonding interactions in the luteolin-guanine complexes. We compared the interaction between luteolin and four bases of DNA, and found luteolin-thymine was the strongest and luteolin-adenine was the weakest. The interaction between luteolin and DNA bases are all stronger than luteolin-water.     

Facile Synthesis and Crystal Structures of New Ammonium Sulfonates （CA-DNBS and TEA-TMBS）

The title compounds, C12HIoN307SCI （I） and C15H27NO3S （II）, crystallize in the monoclinic system, space group P21/c with a = 7.3995（1）, b = 27.8489（6）, c = 9.8246（2）/, fl = 131.349（1）, V = 1519.82（5） A3, Z = 4, F（000） = 768, Rint = 0.033 and S = 1.03 for I, and in the orthorhombic system, space group Pbca with a = 8.6227（1）, b = 16.1480（4）, c = 23.8774（6）/, V= 3324.67（12） A3, Z = 8, F（000） = 1312, Rint = 0.024 and S = 1.04 for II. We have devised a convenient procedure for the synthesis of fused organic salts resulting from 1：1 proton-transfer, using an amine and a derivative ofbenzenesulfonic acid. The synthesized salts have a number of applications ranging from their consumption as eco-friendly solvents and catalysts in organic syntheses, to being used as efficient precursors for the production of sulfa drugs. Structures of compounds 3-chloroanilinium 2,4-dinitrobenzenesulfonate （CA-DNBS） and triethylaminium 2,4,6-trimethylbenzenesulfonate （TEA-TMBS） were determined by single-crystal X-ray diffraction studies and infrared spectroscopy.     

Synthesis,Crystal Structure and Anticoagulant Activity of 5-Chloro-N-[[（5S）-2-oxo-3-[4-（2- oxopyridin-1 （2H）-yl）phenyl] oxazolidin-5- yl] methyl] thiophene-2-carboxamide①

The title compound(zifaxaban 2, C20H16ClN3O4 S, Mr = 429.87) was synthesized and its crystal structure was determined by single-crystal X-ray diffraction. Zifaxaban crystallizes in monoclinic, space group P21 with a = 5.7900(12), b = 13.086(3), c = 12.889(3) A, β = 100.86(3)°, V = 959.1(3) A3, Z = 2, Dc = 1.489 g/cm3, F(000) = 444, μ = 0.342 mm-1, the final R = 0.0320 and wR = 0.0640 for 2717 observed reflections(I 2σ(I)). The absolute configuration of the stereogenic center in the title compound was confirmed to be S by single-crystal X-ray diffraction. Four existing intermolecular hydrogen bonds help to stabilize the lattice and the molecule in the lattice to adopt an L-shape conformation. Zifaxaban was slightly more active than rivaroxaban 1 in in vitro assay against human FXa and therefore is promising as a drug candidate.     

Two Novel Homochiral Enantiomorphic 3D Metal-organic Frameworks： Synthesis, Crystal Structure, Luminescent and SHG Properties

Two homochiral enantiomorphic 3D coordination polymers： （D-HAPA）2[Cd2Cs（D- HAPA）（m-BDC）4]＇（EtOH） （1D） and （L-HAPA）2[Cd2Cs（L-HAPA）（m-BDC）a]＇（EtOH） （1L） （APA = 2-amino-l-propanol, m-H2BDC = 1,3-benzenedicarboxylate）, have been assembled solvothermally respectively with the induction of enantiomorphic organic small molecules （D,L-APA）. 1L and 1I） crystallize in chiral space group P21 with Flack parameters of-0.012（13） and -0.07（3）, respectively, and have been characterized by satisfactory elemental analysis, FT-IR spectra, CD-spectra and single-crystal X-ray diffraction. They both exhibit sqp topological net, purple fluorescence and SHG activity.     

Synthesis,Crystal Structure and MMCT Property of a New Mixed-valence Cyanide-bridged Binuclear Complex

A new mixed-valence cyanide-bridged complex, Br3Fe(μ-NC)RuBr(dppm)2(dppm = bis(diphenylphosphino)methane), was obtained through the reaction between trans-(dppm)2ClRuCN and FeBr3. Its crystal structure was characterized. Electronic absorption spectra indicate the existence of metal-to-metal charge transfer(MMCT) and this complex is Class Ⅱ mixed valence complexes according to the classification of Robin and Day. Magnetic analysis shows it is paramagnetic.     

Three Inorganic-organic Composite Polyoxotungstates： Syntheses,Characterization and Structures of [Cu（2,2＇-bpy）2]5[α-PW11.5Cu0.5O40]·2H2O, [Co（2,2＇-bpy）2（N3）2]4H3[α-PW12O40]·3H2O and [Cu（2,2＇-bpy）2（4,4＇-bpy）]2[α-GeW12O40]-4H2O

Three new inorganic-organic composite polyoxotungstates [Cu（2,2＇-bpy）2]5[α-PW11.5Cu0.5O40]·2H2O 1, [Co（2,2＇-bpy）2（N3）2]4H3[α-PW12O40]·3H2O 2 and [Cu（2,2＇-bpy）2（4,4＇-bpy）]2[α-GeW12O40]-4H2O 3 （2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine） have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombic space group Pna21 with a = 27.847（3）, b = 21.597（2）, c = 20.1179（19）A, V= 12099（2）A^3, Z= 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1^- with a = 12.31150（10）, b = 16.1954（4）, c = 19.36290（10）A, α = 99.366（11）, β =105.168（8）, γ = 111.836（8）°, V = 3309.98（9）A3, Z = l, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858（4）, b = 20.943（6）, c = 15.598（5）A, β = 102.338（5）°, V= 4103（2）A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1-3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.     

A New 3D Metal-organic Framework with Tetranuclear Cadmium（II） Clusters： Synthesis,Structure, and Luminescent Property

A unique metal-organic framework [Cd2(L)1.5(μ3-OH)(H2 O)2 ]·2H2 O(1, H2 L = 2,5-dibenzoylterephthalic acid) has been synthesized under hydrothermal conditions, and characterized by single-crystal X-ray diffractions, elemental analyses, IR spectra and fluorescence spectrum. The compound is of triclinic system, space group P1, C33 H27 CdO14, Mr = 870.33, a = 12.2939(17), b = 12.5135(9), c = 13.2046(10), α = 115.3190(10), β = 96.9140(10), γ = 109.7950(10)°, V = 1641.6(3)3, Z = 2, Dc = 1.761 g/cm3, F(000) = 862, μ(MoK) = 1.366 mm-1, Rint = 0.0148, R = 0.0240 and wR = 0.0639 for 5995 observed reflections with I 2σ(I). X-ray analysis shows that the title complex exhibits a 3D framework with(412·63) topology, in which the tetra-nuclear [Cd4(μ3-OH)2 ] clusters act as 6-connected nodes, and the L ligands can be simplified to be linear connectors. Moreover, the thermal stability and fluorescence have been studied in detail.     

Asymmetric Synthesis, Antifungal Activity and Molecular Modeling of Iodiconazole Isomers

Iodiconazole is a novel antifungal agent that was developed in its racemic form. In order to investigate the ef- fects of the chiral center on the antifungal activity, R- and S-isomers of iodiconazole were prepared on the basis of the asymmetric Sharpless epoxidation. （S）-Iodiconazole was proved to have better antifungal activity than the （R）- isomer. The binding modes of the two isomers with lanosterol 14~z-demethylase were clarified by molecular dock- ing.     

Synthesis,Structure and Biological Activity of 5-Benzyl-4-amino-1,2,4- triazole-3-thione Schiff Base

A novel Schiff base was synthesized via 5-benzyl-4-amino-1,2,4-triazole-3-thione with 3-phenoxy-benzaldehyde under refluxing. The structure was characterized by elemental analysis, IR, 1H NMR, ESI-MS and single-crystal X-ray diffraction. This compound crystallizes in monoclinic, space group P21 /c with a = 16.0289(16), b = 5.8022(6), c = 20.542(2), β = 95.667(2)o, C22 H18 N4 OS, Mr = 386.46, V = 1901.1(3)3, Z = 4, Dc = 1.347 g/cm3, F(000) = 804, μ = 0.191 mm-1, the final R = 0.0453 and wR = 0.1307 for 2456 observed reflections with I 2σ(I). The crystal packing of the compound is stabilized by classical intermolecular N–H···S hydrogen bonds. Furthermore, the biological activity to four vegetable pathogens has been tested. The title compound exhibited good fungicidal activities to Gibberlla nicotiancola.     

Reaction Mechanism,Synthesis and Characterization of Urea-glyoxal （UG） Resin

The reaction mechanism of glyoxal （G） with urea （U） under weak acid condition was theoretically investigated at PW91/DNP/COSMO of quantum chemistry using density functional theory （DFT） method. The results show that the addition reaction of G with U under the conditions mainly involves the reactions of U with protonated glyoxal （p-G）, protonated 2,2-dihy- droxyacetaldehyde （p-G 1） and protonated bis-hemdiol （p-G2） to form two important carbocation reactive intermediates of C-p-UG and C-p-UG1, and two important hydroxyl compounds of UG and UG1. These compounds play important roles in the formation of UG resin. According to the result of quantum chemical calculation, UG resin was synthesized successfully under weak acid conditions. The UG resin was characterized by matrix assisted laser desorption ionization time of flight mass spectrometry （MALDI-TOF-MS）, ultraviolet and visible spectroscopy （UV-vis）, Fourier transform infrared spectroscopy （FT1R） and nuclear magnetic resonance spectroscopy （13CNMR and 1HNMR）. These instrumental analytical results agree with each other and further confirm the addition reaction pathway of glyoxal with urea proposed by quantum chemical calculation.     

Time-dependent Density Functional-based Tight-bind Method Efficiently Implemented with OpenMP Parallel and GPU Acceleration

The time-dependent density functional-based tight-bind （TD-DFTB） method is implemented on the multi-core and the graphical processing unit （GPU） system for excited state calcu-lations of large system with hundreds or thousands of atoms. Sparse matrix and OpenMP multithreaded are used for building the Hamiltonian matrix. The diagonal of the eigenvalue problem in the ground state is implemented on the GPUs with double precision. The GPU- based acceleration fully preserves all the properties, and a considerable total speedup of 8.73 can be achieved. A Krylov-space-based algorithm with the OpenMP parallel and CPU acceleration is used for finding the lowest eigenvalue and eigenvector of the large TDDFT matrix, which greatly reduces the iterations taken and the time spent on the excited states eigenvalue problem. The Krylov solver with the GPU acceleration of matrix-vector product can converge quickly to obtain the final result and a notable speed-up of 206 times can be observed for system size of 812 atoms. The calculations on serials of small and large systems show that the fast TD-DFTB code can obtain reasonable result with a much cheaper computational requirement compared with the first-principle results of CIS and full TDDFT calculation.     

Bonding of Hydroxyl and Epoxy Groups on Graphene： Insights from Density Functional Calculations

Density functional theory and GGA-PW91 exchange correlation function were performed to simulate the bonding behavior of hydroxyl and epoxy groups on the graphene surface. We compared the different binding energies for two epoxy groups, as well as one hydroxyl group and one epoxy group on all possible positions within a 6-fold ring, respectively. The calculated results suggest that two oxygen-containing groups always tend to bind with the neighboring carbon atoms at the opposite sides. Moreover, two hydroxyl groups on the meta position are unstable, and one of the hydroxyl groups easily migrates to the para position. In contrast to the disperse arrangement, the aggregation of multiply hydroxyl groups largely enhances the binding energy of every hydroxyl group. It is worth noting that the binding sites and hydrogen bonds play an important role in stability. Our work further points out the number of oxygen-containing groups and the location of oxide region largely influence the electronic properties of graphene oxide.