Highly Active New α-Diimine Nickel Catalyst for Polymerization of Ethylene

A new α-diimine ligand 1a, bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2a, {bis[N,N′-（4-tert-butyl-2,6-dimethylphenyl）imino]-2,3-butanediylidene}dibromo- nickel were successfully synthesized, and characterized by 1H NMR, 13C NMR, Fourier transform infrared spectroscope（FTIR）, elemental analysis and X-ray photoelectron spectroscopy（XPS）. α-Diimine ligand 1b, bis[N,N′-（2,6- dimethylphenyl）imino]-2,3-butanediylidene and its corresponding Ni（II） complex 2b, {bis[N,N′-（2,6-dimethyl- phenyl）imino]-2,3-butanediylidene}dibromonickel were also synthesized and characterized for comparison. The pre-catalyst 2a with sterically bulky, electron-donating group tert-butyl, activated by diethylaluminum chloride （DEAC） and tested in the polymerization of ethylene, was very highly active[2.01×107 g PE/（mol Ni？h？0.1 MPa）] and led to a very highly branched polyethylene（ca. 35―103 branches/1000 C）. The state of the polyethylene obtained varied from plastic, elastomer polymers to the oil-like hyperbranched polymers.

A New Cadmium(Ⅱ) Coordination Polymer Extended through Hydrogen Bonds and π-π Stacking Interactions: Synthesis and Photoluminescence Property

A new coordination polymer, {[Cd(OPY)(tdc)(HO)]·H2 O}n(OPY = 4,4?-(oxybis(4,1-phenylene))dipyridine, H2 tdc = thiophene-2,5-dicarboxylic acid), has been synthesized hydrothermally based on a V-shaped ligand OPY. The structure was fully characterized by elemental analysis, FT-IR spectroscopy, and X-ray single-crystal diffraction analysis. In1, two OPY ligands and one water molecule acted as terminal ligands coordinating to Cdcation to form [Cd(OPY)HO]units, which are then linked by tdc2-ligands to generate a one-dimensional chain. Every two adjacent chains linked by extensive O–H···O hydrogen bonds constitute one-dimensional double-chains, and such chains are extended into two-dimensional layers via O–H···N hydrogen bonds. These layers are further connected to form a three-dimensional supramolecular architecture via π-π stacking interactions. In addition, the thermal stability and solid state fluorescence property of 1 were also investigated.

A Three-dimensional Self-penetrating Co(Ⅱ) Coordination Polymer Containing a 2D → 3D Parallelly Polycatenated Subnet

Hydrothermal assembly of Co2＋ ion, a bis-imidazole ligand BIMB（BIMB = 1,4-bis（imidazol-1-yl）benzene） and a rigid bidentate linker 2,6-naphthalenedicarboxylic acid（H2ndc）, yields a novel three-dimensional（3D） self-penetrating coordination polymer {[Co（BIMB）（ndc）]·H2O}n（1）. Complex 1 exhibits {6~5.8} topology and contains a 2D → 3D parallel polycatenated substructure. In addition, solid-state UV-vis absorption spectra of 1 were also investigated.

Two Polymorphs of the Inclusion Compound [(n-C_4H_9)_4N]^+·(C_(13)H_9O_3)^-·H_2O

Two polymorphs of the inclusion compound [（n-C4H9）4N]＋＇（C13H903）H2O have been prepared and characterized by X-ray crystallography. Polymorph 1： triclinic P1, a = 13.4982（2）, b = 13.5743（2）, c = 17.1996（2） A, at = 67.045（1）,β = 77.845（1）, γ= 88.762（1）°, V = 2830.43（7） A3, Z = 4, R = 0.0491, wR= 0.1276; Polymorph 2： tetragonal P43, a = b = 13.53690（1） A, c = 30.8491（8） A, V = 5653.02（16） A3, Z = 8, R = 0.0448, wR = 0.0984. In these two crystal structures, the hydrogen-bonded ribbons built of 4,4＇-dihydroxybenzophenone （DHBP, C13H1003） anions and water molecules are orderly arranged to generate two-dimensional host layers, with tetrabutylammonium cations contained between the layers to form the sandwich-like inclusion compounds. The structures of 1 and 2, which exist as two polymorphs, both display the similar packing pattern and hydrogen-bond linking model.

Facile synthesis of Sb@Sb2O3/reduced graphene oxide composite with superior lithium-storage performance

Sb-based materials have been considered one of the most promising anode electrode materials for lithium-ion batteries,whereas they were commonly synthesized through time-consuming and costly processes.Here,Sb@Sb2O3/reduced graphene oxide(Sb@Sb2O3/rGO)composite was successfully synthesized by a facile one-pot chemical method at ambient temperature.Based on the XRD and TGA analysis,the mass fractions of Sb and Sb2O3 in the Sb@Sb2O3/rGO composite are ca.34.05%and 26.6%,respectively.When used as an alternative electrode for lithium ion batteries,a high reversible capacity of 790.9 mA·h/g could be delivered after 200 cycles with the capacity retention of 93.8%at a current density of 200 mA/g.And a capacity of 260 mA·h/g could be maintained even at 2000 mA/g.These excellent electrochemical properties can be attributed to its well-constructed nanostructure.The Sb and Sb2O3 particles with size of 10 nm were tightly anchored on rGO sheets through electronic coupling,which could not only alleviate the stress induced by the volume expansion,suppress the aggregation of Sb and Sb2O3 particles,but also improve the electron transfer ability during cycling.

Synthesis of O-glycosylα-aryl nitrones

α-Aryl nitrone are one of the most useful kinds of nitrones and have been extensively explored in recent years.However,the sugar moieties have not been introduced into these molecules before.We presented here an efficient synthesis ofα-aryl nitrone Oglycosides via condensation of N-substituted hydroxylamine and aryl aldehydes glycosides in benzene.

Preparation of a Novel Acid Doped Polyaniline Adsorbent for Removal of Anionic Pollutant from Wastewater

Polyaniline(PANI) was one of the most extensively studied adsorbents due to its low cost and good environmental stability. The objective of the current study was to improve the selective capabilities of PANI for anionic dyes. We found that the acid doped PANI prepared with hydrochloric acid and p-toluenesulfonic acid(PTSA) could selectively adsorb anionic dyes. It exhibited very good selectivity for OG dye, the mechanism was proposed based on the chemical interaction of PANI with the sulfonate group of the dyes. The effects of solution p H, initial dye concentration, and different HCl/PTSA mole ratios on the adsorption capacity of OG have been investigated. Kinetic simulations indicated that the adsorption process could be well represented by pseudo-second-order kinetic plots. The isothermal adsorption curve fitting also showed that the adsorption process could be well described by the Langmuir isothermal equation. The results showed that acid doped PANI could be employed as a promising adsorbent for anion removal from dye wastewater.

Construction of TiO_(2)-covalent organic framework Z-Scheme hybrid through coordination bond for photocatalytic CO_(2) conversion

In this work,a covalent organic framework(COF),which is constructed by the building blocks of[5,10,15,20-tetrakis(4-aminophenyl)porphinato]copper(Ⅱ)(CuTAPP)and p-benzaldehyde,is employed to integrate with TiO_(2) for the purpose of establishing a Z-scheme hybrid.Within the system,isonicotinic acid performs the role of a bridge that connects the two components through a coordination bond.Further photocatalytic application reveals the hybrid framework is able to catalyze CO_(2) conversion under simulated solar light,resulting in CO production rate of 50.5 μmol g^(-1)·h^(-1),about 9.9 and 24.5 times that of COF and pristine TiO_(2),respectively.The ameliorated catalytic performance owes much to the por-phyrin block acting as photosensitizer that augments the light absorbance,and the establishment of Z-scheme system between the inorganic and orga nic comp on ents that enhances the separati on of the carriers.In addition,the chemical bridge also ensures a steady usage and stable charge delivery in the catalysis.Our study sheds light on the development of versatile approaches to covalently in corporate COFs with inorga nic semic on ductors.

Structures and Properties Characterization of Acrylonitrile-butadiene-styrene /Organo-palygorskite Clay Composites

Palygorskite （PGS） and vinyl tris-（2-methoxyethoxy） silane （KH-172） modified palygorskite （OPGS） were used to prepare acrylonitrile-butadiene-styrene （ABS）/clay composites. Thermal stability of the composites was evaluated by using thermogravimetric analysis （TGA）. The morphology of the fractured surface and the degree of dispersion of the clay in the ABS matrix were observed by scanning electron microscopy （SEM）. X-ray diffraction （XRD） analysis results showed the variation of the crystal structure. Measurements of the tensile properties of the ABS/clay composites proved that the ABS/OPGS composited material represented the most excellent tensile property, because of good compatibility and dispersion of ABS with OPGS.

Layered AI-substituted Cobalt Hydroxides/GO Composites for Electrode Materials of Supercapacitors

In this work, Al-substituted a-Co（OH）2/GO composites with supercapacitive properties were prepared by chemical co-precipitated method in which cobalt nitrate and aluminum nitrate were used as the raw material, and graphite oxide was employed as carrier. The as-prepared materials were characterized by X-ray diffraction （XRD）, field emission scanning electron microscopy （FESEM） and fourier transform infrared spectroscopy （FF-IR）. Cyclic voltammetry （CV） and galvanostatic charge/discharge measurements showed that the Al-substituted a-Co（OH）2/GO electrode material had excellent electrochemical capacitance. The specific capacitance of 1137 F·g-11 was achieved in 6 mol/L KOH solution at a current density of 1 A·g-1 within a potential range of 0-0.5 V. Moreover, only 12% losses of the initial specific capacitance were found after 500 cycles at a current density of 1 A·g-1.

Tumor targeting of HPMA copolymer conjugates containing sulfadiazine groups

To develop new tumor targeting macromolecular conjugates,poly（HPMA）-SD-APMA-DTPA（HPMA：N-（2-hydroxypropyl）- methacrylamide;APMA：N-（3-ammopropyl）methacrylamide;DTPA：diethylenetriaminepentaacetic acid;SD：sulfadiazine） was synthesized and characterized.The poly（HPMA）-SD-DTPA conjugates were radiolabeled with the radionuclide ^（99m）Tc and tested for uptake by cultured H22 cells in vitro.DTPA-^（99m）Tc（radiotracer 1） and poly（HPMA）-DTPA-^（99m）Tc（radiotracer 2） were also synthesized and characterized for comparison.The uptake of poly（HPMA）-SD-DTPA-^（99m）Tc（radiotracer 3,34.76%） was significantly higher than that of poly（HPMA）-DTPA-^（99m）Tc（16.40%）,indicating that uptake of the poly（HPMA）-SD-DTPA-^（99m）T was active binding.The uptake of poly（HPMA）-DTPA-^（99m）Tc was significantly higher than that of DTPA-^（99m）Tc（2.98%）, suggesting that uptake of the poly（HPMA）-DTPA-^（99m）T was passive binding.The data suggest that the poly（HPMA）-SDAPMA -DTPA conjugates might be useful as tumor targeting macromolecular conjugates.

Synthesis of Copillar[5]arene by Co-oligomerization of Different Monomers and Its Application to Supramolecular Polymer Gel

A copillar[5]arene derivative with different repeating units was synthesized by co-oligomerization of different alkyl ethers.Copillar[5]arene-based supramolecular polymer gel was formed by a self-inclusion complexing in acetonitrile.The supramolecular polymer gel was driven by the C-H•πinteractions,and presented two phases as time went on,and finally,constructed the supramolecular organic framework.Notably,the supramolecular polymer gel showed reversible gel-sol phase transitions upon heating and cooling.Meanwhile,the transparent films formed by the supramloecular gel show the potential application in the field of anti-acid rain materials.

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Disilver Complex with Pyrazinyl Oxime Ligand

A novel binuclear Ag（I） complex [Ag2（C6H6NaO）2（C6H7N3O）2]·2CH3CN （1） was synthesized by the evaporation reaction of silver nitrate and （E）-1-（pyrazin-2-yl）ethanone oxime （HL）. The complex was characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction analysis. It crystallizes in the monoclinic space group C2/c with a = 22.7089（3）, b = 11.5443（7）, c = 16.1468（4）/A, β = 127.7150（10）°, V= 3348.6（2） A^3, Dc = 1.675 g/cm^3, Mr = 844.42, Z = 4, F（000） = 1696.0,μ = 1.226 mm^-1, the final R =0.0250 and wR = 0.070. The coordination around the silver（I） atom is a distorted trigonal-bipyramidal geometry involving one protonated pyrazinyl oxime ligand （HL）, one deprotonated oxime ligand （L^-） and one CH3CN solvate molecule in the asymmetric unit of complex 1.

Interventional Radionuclide Therapy of Hepatocellular Carcinoma： Assessment of Intratumoral Retention of HPMA Copolymers

To develop new radiopharmaceuticals for the interventional radionuclide therapy of recurrent hepatocellular carcinoma, poly（HPMA）-APMA-DTPA[HPMA=N-（2-hydroxypropyl） methacrylamide; APMA=N-（3-aminopropyl）methacrylamide; DTPA=diethylenetriaminepentaacetic acidl was synthesized by free radical precipitation polymerization in acetone/dimethylsulfoxide with N,N＇-azobis（isobutyronitrile） as the initiator. The copolymers were characterized with nuclear magnetic resonance（NMR） spectroscopy and gel permeation chromatography（GPC, Mn=2.2xl04, Mw/Mn=l.38）. Subsequently, poly（HPMA）-APMA-DTPA was conjugated with 99mTC radionuclide. Prolonged retention of poly（HPMA）-APMA-DTPA conjugate within the tumor tissues was demonstrated by single-photon emission computed tomography computed tomography（SPECT-CT） at 1, 2, 4 and 24 h following intra-tumoral injection of the conjugate to hepatocellular carcinoma xenografts in mice. DTPA-99mTc was also synthesized and characterized for comparison. The data suggest that the poly（HPMA）-APMA-DTPA conjugates might be useful for the interventional radionuclide therapy of recurrent hepatocellular carcinoma in humans.

Synthesis and Crystal Structure of a Novel Dinuclear Copper(Ⅱ) Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper（Ⅱ） complex [CuL（NO3）]2·2MeOH was obtained by the coordination reaction of Cu（NO3）2·3H2O with ligand HL （HL=N-（methyl-2-benzimidazol- methylidene）-2-hydroxyaniline）. The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535（3）, b=10.009（3）, c=10.666（4） , α=104.303（4）, β=100.105（4）, γ=115.917（4）o, V=839.0（5） 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F（000）=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper（Ⅱ） complex units [CuL（NO3）]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper（Ⅱ） units.

Synthesis and Crystal Structure of 2-O-(2-hydroxyethyl)-D-glucose

The title compound, 2-O-（2-hydroxyethyl）-D-glucose （CsH1607, Mr= 224.21）, has been synthesized and its structure was characterized by using NMR spectrum and X-ray single-crystal diffraction. This molecule crystallizes in the monoclinic system, space group P21, with a = 8.399（17）, b = 6.620（14）, c = 9.81（2） A, β = 115.110（17）°, V= 493.7（18） A3, Z = 2, Dc = 1.508 mg/m3,/1 = 0.13 mm-1, F（O00） = 240, the final R = 0.0464 and wR = 0. l 15 for 152 ] observed reflections （1 〉 2a（I））. X-ray crystal structure analysis revealed that the conformation of the pyranosyl ring existed in a slightly distorted act chair conformation （Cremer-Pople puckering parameters of Q = 0.573（4） A, 0 = 6.7（3）0 and = -5.2（2）°）. The molecule exists as a monomer in the solid state, whose conformation is stabilized via multiple inter- and intramolecular hydrogen bonds.

A New Facile Route to Chlorination of Alcohols via Lewis Acid AlCl₃

Halogenated aluminates AlCl3, applied as efficient chlorination reagent for hydroxyl groups of substitution alcohols is described. Primary and secondary benzylic alcohols could be transformed into corresponding aromatic halides with almost complete conversion and unique selectivity. As chlorination reagent, AlCl3 has an incomparable advantage over others, such as low material cost, commercial availability as well as convenient product isolation.

Preparation of ZnO/GO composite material with highly photocatalytic performance via an improved two-step method

ZnO/graphene oxide（ZnO/GO） composite material,in which ZnO nanoparticles were densely coated on the GO nanosheets,was successfully prepared by an improved two-step method and characterized by IR, XRD,TEM,and UV-vis techniques.The improved photocatalytic property of the ZnO/GO composite material,evaluated by the photocatalytic degradation of methyl orange（MO） under UV irradiation,is ascribed to the intimate contact between ZnO and GO,the enhanced adsorption of MO,the quick electron transfer from excited ZnO particles to GO sheets and the activation of MO molecules viaπ-πinteraction between MO and GO.

Novel biomonitoring method for determining five classes of legacy and alternative flame retardants in human serum samples

Flame retardants(FRs)are ubiquitous in environment and biota and may pose harm to human health.In recent years,concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices.In this study,we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs,including polychlorinated naphthalenes(PCNs),short-and middle-chain chlorinated paraffins(SCCPs and MCCPs),novel brominated flame retardants(NBFRs),and organophosphate esters(OPEs)in human serum.Serum samples were prepared by liquid-liquid extraction using ethyl acetate,and purified with Oasis®HLB cartridge and Florisil–silica gel columns.Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry,highresolution gas chromatography coupled with high-resolution mass spectrometry,and gas chromatography coupled with quadrupole time-of-flight mass spectrometry,respectively.The proposed method was validated for linearity,sensitivity,precision,accuracy,and matrix effects.Method detection limits for NBFRs,OPEs,PCNs,SCCPs,and MCCPs were 4.6×10^(–4)–8.6×10^(–2),4.3×10^(–3)–1.3,1.1×10^(–5)–1.0×10^(–4),1.5,and 9.0×10–1 ng/mL,respectively.Matrix spike recoveries ranged from 73%–122%,71%–124%,75%–129%,92%–126%,and 94%–126%for NBFRs,OPEs,PCNs,SCCPs,and MCCPs,respectively.The analytical method was applied for detection of real human serum.CPs were the dominant FRs in serum,indicating CPs were widely presented in human serum and should be pay more attention for their health risk.

In-situ incorporation of Copper （Ⅱ） porphyrin functionalized zirconium MOF and TiO2 for efficient photocatalytic CO2 reduction

As one of the highly effective methods to prepare catalysts for photocatalytic reduction of CO2 into valueadded chemicals,using metalloporphyrin as light-harvesting mixed ligand to modify metal-organic framework(MOF)is very valuable since it can greatly improve the prophyrin dispersibility and consequently inhibit its potential agglomeration.Herein,we employed a one-pot synthetic strategy to chemically immobilize Cu(II)tetra(4-carboxylphenyl)porphyrin(CuTCPP)into UiO-66 MOF structure through coordination mode.Meanwhile,in-situ growth of TiO2 nanoparticles onto the MOF is actualized with the generation of CuTCPP c UiO-66/TiO2(CTU/TiO2)composites.Under Xe lamp irradiation(λ>300 nm),the catalytic result presents that an optimal value of 31.32 μmol g^-1 h^-1 CO evolution amount,about 7 times higher than that of pure TiO2 was obtained through the photocatalysis.It is supposed owning to a consistent augment of light absorption derived from chemically implanted porphyrin derivative,which is simultaneously functioning with an efficacious separation of photo-induced carries given by the newly engendered composites between MOF and TiO2,an effective catalytic activity and approving recyclability of CTU/TiO2 can be achieved in the photocatalytic reduction of CO2 into CO.