Synthesis and Characterization of Cerium Tetraphenylporphyrin Nitrate and Molecular Recognition for NO

Cerium （III） tetraphenylporphyrin nitrate Ce（TPP）NO3 was synthesized by using meso- tetraphenylporphyrin （TPP） and Ce（NO3）.6H20 in mixture solution of CHC13 and C2HsOH （V：V=1：1）. The complex was characterized by UV-Vis, FT-IR, conventional fluorescence, MALDI-TOF-MS, and ^1H NMR spectral techniques. The structure of complex was proposed viaSpectral analyses, in which tetraphenylporphyrin was coordinated to a cerium ion in a tetradentate fashion, while one nitrate was coordinated to the same cerium ion. After bubbling NO to the solution of Ce（TPP）NO3 in CH2Cl2, spectral analyses suggested that Ce（TPP）NO3 could interact with NO to form a novel complex of Ce（TPP）（NO）NO3, and NO was coordinated to the center cerium ion. When nitrogen was poured into the Ce（TPP）（NO）（NO3） solution, the complex could be reduced to Ce（TPP）NO3.     

Synthesis and characterization of high molecular weight poly(1,2-propylene carbonate-<Emphasis Type="Italic">co</Emphasis>-1,2-cyclohexylene carbonate) using zinc complex catalyst

Using supported multi-component zinc dicarboxylate catalyst,poly（1,2-propylene carbonate-co-1,2-cyclohexylene carbonate）（PPCHC） was successfully synthesized from carbon dioxide（CO₂） with propylene oxide（PO） and cyclohexene oxide（CHO）.The conversion of epoxides dramatically increased up to 89.7%（yield:384.2 g of polymer per g of Zn） with increasing reaction temperature from 60℃to 80℃.The optimized reaction temperature is 80℃.The chemical structure,the molecular weight,as well as thermal and mechanical properties of the resulting terpolymers were investigated extensively. When CHO feed content（mol%） is lower than 10%,the PPCHC terpolymers have number average molecular weight（M_n） ranging from 102×10³ to 202×10³ and molecular weight distribution（MWD） values ranging from 2.8 to 3.5.In contrast to poly（propylene carbonate）（PPC）,the introduction of small amount of CHO leads to increase in the glass transition temperature from 38.0℃to 42.6℃.Similarly,the mechanical strength of the synthesized terpolymer is greatly enhanced due to the incorporation of CHO.These improvements in mechanical and thermal properties are of importance for the practical application of PPC.     

Theoretical Investigation on the Absorption and Emission Properties of the Three Isomers of Bis（thiocyanato）（2,2^1-bipyridyl）platinum（ll）

This paper presents a Density Functional or Time Dependent Density Functional （DFT/TDDFT） study of the molecular and electronic structures, optical absorption and emission spectra of three linkage isomers： bis（isothiocyanato-S）（2,2^1-bipyridyl） platinum（II） （[Pt（SCN）2（bpy）]）, （isothiocyanato-S）（thiocyanato-N）-（2,2^1-bipy- ridyl） platinum（II） （[Pt（SCN）（NCS）（bpy）]）, and bis（thiocyanato-N）（2,2^1）-bipyridyl）platinum（II） （[Pt（NCS）2（bpy）]）, in which different coordination ligands based on the N- and S-coordination of the thiocyanato ligands control the luminescent color. The electronic structures were studied using the B3LYP functional. Optimized geometries Were compared to the experimentally observed structures. TDDFT calculation was carded out to investigate the excited singlet and triplet states. Calculations have been performed both in vacuo and in solvents, using a polarized continuum model （PCM） to account for solute-solvent interactions. Inclusion of the solvent led to a significant energy change, and as a consequence, the computed spectrum calculated in the presence of the solvent was in good agree- ment with the experimental determinations. The first two absorptions were found to originate from mixed plati- num-SCN （or NSC） to bipyridyl-n＊ transitions rather than pure metal-to-ligand-charge-transfer （MLCT） transitions, whereas the higher-energy bands arose from intraligand n→π＊ transitions. The stretching frequencies of C≡N have been calculated both in the ground and excited states, which are relative to the charge transition during the excitation. In addition, different sizes of basis sets were also discussed in this paper.     

BSA Hybrid Synthesized Polymer

Bovine serum albumin （BSA）, a naturally occurring biopolymer, was regarded as a polymeric material to graft to an acrylic acid （AA）-N-vinyl pyrrolidone （NVP） copolymer to form a biomacromolecular hybrid polymer. The hybrid polymer can be blended with polyethersulfone （PES） to increase the hydrophilicity of the PES membrane, which suggested that the hybrid polymer might have a wide application in the modification of biomaterials.     

Facile synthesis of α-difluoromethyl α-propargylamines from CF2H-substituted N-tert-butanesulfinyl ketimines

Stereoselective approach for preparation ofα-difluoromethylα-propargylamines has been developed.1,2-Addition of lithium acetylides to diverse chiral difluoromethylated（S）-N-tert-butanesulfinyl ketimines by using Ti（OⁱPr）₄ as catalyst and THF as solvent afforded N-tert-butanesulfinamides in good to excellent yields（51-93%） and good diastereoselectivities（dr.85:15 to 93:7）.The N-tert -butanesulfinyl group can be readily cleaved under mild acidic condition（4 mol/L HCl in dioxane） to provide the correspondingα-difiuoromethylα-propargylamine in excellent yields（90-95%）.     

Production of octyl levulinate biolubricant over modified H-ZSM-5： Optimization by response surface methodology

The present study highlighted the use of modified H-ZSM-5 （Meso-HZ-5） as heterogeneous catalyst for the synthesis of octyl levulinate biolubricant by catalytic esterification of biomass derived renewable levulinic acid （LA） with n-octanol. The process variables such as catalyst loading （X1）, n-octanol to LA molar ratio （X2） and reaction temperature （X3） were optimized through response surface methodology （RSM）, using Box-Behnken model. Analysis of variance was performed to determine the adequacy and significance of the quadratic model. The yield of octyl levulinate was obtained to be 99% at optimum process parameters. The developed quadratic model was found to be adequate and statistically accurate with correlation value （R2） of 0.9971 to predict the yield of octyl levulinate biolubricant. The study was also extended on the validation of theoretical and experimental data, including catalyst reusability.     

In situ generation of biodegradable poly(p-dioxanone) micro-particles by polymerization in supercritical carbon dioxide

Ring-opening suspension polymerization of p-dioxanone（PDO） in supercritical carbon dioxide（scCO₂） was investigated in the presence of poly（caprolactone）-perfluropolyether-poly（caprolactone）（PCL-PFPE-PCL）.The molecular weight,yield and particle morphology of poly（p-dioxanone）（PPDO） were studied.The stabilizer was effective to stabilize the ring-opening polymerization（ROP） of PDO in scCO₂,leading to the formation of resorbable microparticles in a"one pot"procedure.The mean size of PPDO microparticles obtained from suspension polymerizations was sensitive to the rate of agitation and the stabilizer concentration.The method to generate PPDO microparticles has overcome its unprocessable drawback with common organic solvents and provided new product form for biomedical applications.     

Geometries, Electronic Structures, and Electron Detachment Energies of Small Boron Sulfide Anions： A Density Functional Theory Investigation

A density functional theory investigation on the geometries, electronic structures, and electron detachment energies of BS, BS2, B（BS）2 and B（BS）3 has been performed in this work. The linear ground-state structures of BS （C∞v, ^1∑^＋） and BS2^- （O∞h, ^1∑g^＋） prove to be similar to the previously reported BO and BO2 with systematically lower electron detachment energies. Small boron sulfide clusters are found to favor the formation of -B=S groups which function basically as a-radicals and dominate the ground-state structures of the systems. The perfect linear B（BS）2^-（D∞h, ^3∑g） and beautiful equilateral triangle B（BS）3^- （D3h,^2A1”） turn out to be analogous to the well-known C2v BH2 and O3h BH3, respectively. The electron affinities of BS, BS2, B（BS）2 and B（BS）3 are predicted to be 2.3, 3.69, 3.00 and 3.45 eV, respectively. The electron detachment energies calculated for BS^-, BS2^-, B（BS）2^-, and B（BS）3^- may facilitate future photoelectron spectroscopy measurements to characterize the geometrical and electronic structures of these anions.     

Lewis Base Organocatalyzed Enantioselective Hydrosilylation of α-Keto Ketimines

A chiral Lewis base organocatalyzed enantioselective hydrosilylation ofa-keto ketimines was investigated.The reactions afforded various enantioenriched a-amino ketones with good yields（up to 95％） in moderate to good enantioselectivities（up to 98％ e.e.）.Furthermore,one of the products was reduced to a chiral 1,2-amino alcohol.Following cyclization of it with triphosgene generated a cannabinoid receptor 1 （CB 1） inhibitor with good diastereoselectivity.     

Synthesis and Spectroscopic Properties of Cyclotriphosphazenes Containing 6-（4-Hydroxyphenyl）-2,2′-bipyridine Side Groups

Two novel cyclotriphosphazene derivatives containing 6- （4-hydroxyphenyl）-2,2′-bipyridine （hopbp） side groups, N3 P3 （dobp） 2 （hopbp） 2 （ 1 ） and N3 P3 （dobp） （hopbp） 4 （2） （ dobp = 2,2′-dioxybiphenyl）, were synthesized and characterized. These compounds display strong fluorescent emission both in solution and in solid state. Their absorption and emission spectra are sensitive to proton： the addition of HBF4 to the methanol and dichloromethane solution（9： 1, volume ratio） of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum, and the process was also characterized by isosbestic points of absorption spectra at 267, 287 and 313 nm.     

Practical copper-catalyzed N-arylation of amines with 20% aqueous solution of n-Bu4NOH

N-Arylation of a wide variety of amines with phenylboronic acid catalyzed by copper acetate under 20%aqueous solution of n-Bu₄NOH was accomplished in good to excellent yields（up to 92%） and substrate conversions（up to 96%）.     

Double emulsion droplets as microreactors for synthesis of magnetic macroporous polymer beads

An easy method is presented to fabricate monodisperse magnetic macroporous polymer beads（MMPBs）. Waterin-oil high internal phase emulsion（HIPE） is prepared by emulsifying aqueous iron ions solution in an oil phase containing monomers. The HIPE is introduced into a simple microfluidic device to fabricate monodisperse（water-in-oil）-in-water double emulsion droplets. The droplets serve as microreactors to synthesize Fe3O4 nanoparticles and are on-line polymerized to form MMPBs. The prepared MMPBs display uniform size, interconnected porous structure, superparamagnetic behavior and uniform distribution of Fe3O4 in polymer matrix. The MMPBs are characterized by scanning electron microscopy（SEM）, Fourier transform infrared spectroscopy（FTIR）, X-ray diffraction（XRD）, transmission electron microscopy（TEM）, vibrating sample magnetometry（VSM）. We believe that this method is a universal technique in preparing macroporous nanocomposite beads.     

二个钴5-磺酸基水杨酸、邻菲罗啉配合物的合成、次级合成与结构

Cobait（Ⅱ） nitrate reacted with 1,10-phenanthroline （phen） and 5-sulfosaiicylic acid （H3ssal） to yield the cobait（Ⅰ） complex [Co（phen）2（H2O）2]（Hssal）o4H2O （1） and the reaction of 1 with copper acetate led to a novel complex [Co（phen）（H2O）4][Cu2（ssal）2（phen）2]·5H2O （2）. These two complexes were cationanion species and the cationic motif [Co（phen）2（H2O）2]^2＋of 1 could be converted to [Co（phen）（H2O）4]^2＋ in the formation process of new anion [Cu2（phen）2（ssal）2]^2- of 2. In both complexes abundant hydrogen bonds construct different supramolecular architectures, thus the conversion reaction can provide a new path to create novel supramolecular network.     

Enantioselective synthesis of functionalized fluorinated dihydropyrano [2,3-c]pyrazoles catalyzed by a simple hi functional diaminocyclohexane-thiourea

Enantioselective synthesis of functionalized fluorinated dihydropyrano[2,3-c]pyrazoles has been achieved via a diaminocyclohexane-thiourea catalyzed cascade Michael addition and Thorpe-Ziegler type cyclization in high yields （up to 98%） with moderate to good enantioselectivity （up to 90% ee）.     

Antitumor Compound Identification from Zanthoxylum bungeanum Essential Oil Based on Composition-activity Relationship

The chemical composition of Zanthoxylum bungeanum（Z bungeanum） essential oi1（39 batches） was analyzed by gas chromatography-mass spectrometry（GC-MS） analysis（23 ingredients）, and the antitumor activity against HeLa cells was detected via the MTT[3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyltetrazolium bromide] assay. Two composition-activity relationship（CAR） models, generalized regression neural network（GRNN） and support vector regression（SVR） were respectively used to calculate the mean impact value（MIV） so as to identify bioactive com- pounds. Among them 9 ingredients（peaks 4, 15, 7, 8, 13, 3, 16, 9 and 11） were selected due to their high absolute MIVs. All of them have been confirmed with potential antitumor activity by previous researches. The CAR model combined with MIV was expected to be a credible tool for the active compound identification from herbs.     

Electrochemical Method to Characterize Multidrug Resistance

Multidrug resistance（MDR） is a main factor to make the failure of chemotherapy. It is closely related to the over-expression of P-glycoprotein（P-gp）, multidrug resistance protein（MRP） and breast cancer resistance protein（BCRP）. Herein we reported a novel method to characterize MDR, taking advantage of the electrochemical properry of chemotherapeutic drugs. Meanwhile, the definition of accumulation phase and retention phase has been improved. Furthermore, with specific modulators introduced to inhibit the relevant efflux pumps, the exact protein that mainly works in the cells employed in this study can be identified.     

Selective Hydrogenation of Avermectin Catalyzed by Iridium-Phosphine Complexes

A series of new iridium complexes, IrCl（COD）（TMOPP） （1） [COD=1,5-cyclooctadiene, TMOPP=tris（4- methoxyphenyl）phosphine], IrCl（COD）（TFMPP） （2） [TFMPP = tris（4-trifluoromethylphenyl）phosphine], IrCl（COD）（BDNA） （3） [BDNA= 1,8-bis（diphenylphosphinomethyl）naphthalene], IrCl（COD）（BISBI） （4） [BISBI= 2,2＇-bis（diphenylphosphinomethyl）biphenyl] and IrCl（COD）（BDPB） （5） [BDPB= 1,2-bis（diphenylphosphinomethyl）benzene], were synthesized and characterized by NMR spectra and elemental analyses. In order to obtain the relationships between complex structures and their catalytic properties, IrCl（COD）（DPPM） （6） [DPPM = bis（diphenylphosphino）methane], IrCl（COD）（DPPE） （7） [DPPE= 1,2-bis（diphenylphosphino）ethane], IrCl（COD）（DPPP） （8） [DPPP=1,3-bis（diphenylphosphino）propane] and IrCl（COD）（TPP） （9） [TPP=triphenylphosphine], were also synthesized according to the reported methods. The hydrogenation results showed that the low electronic density at the central metal was favorable to increase the catalytic activity for the hydrogenation of avermectin, but decrease the selectivity to ivermectin. The complex with a large chelating ring and a bulky chelating backbone would easily cause the cleavage of C-O bond in avermectin to give a byproduct avermectin aglycon.     

Activation free energy of Zn（Ⅱ）,Co（Ⅱ） binding to metallo-β-lactamase ImiS

In an effort to understand the recombination of a B2 metallo-β-lactamase（MβL）,the binding of metals to apo-ImiS was studied by isothermal titration calorimetry and fluorescence spectra.The binding of Zn（Ⅱ）,Co（Ⅱ） to apo-lmiS resulted in activation free energies △G_≠~θ values of 93.719 and 92.948 kJ mol~（-1）,respectively,and increasing of fluorescence intensity at maxima emission of 340 nm.     

（Salen）Ti（Ⅳ）-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a （salen）Ti（Ⅳ） complex formed in situ from the reaction of Ti（OPr-i）4 and the chiral Schiff base derived from （1R,2R）-（＋）-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity （up to 73% ee）.