A Pair of 3D Homochiral Coordination Polymers with Open Channels Constructed by Lactic Acid Derivative Ligands and In-situ Formed Anions

With the help of in-situ formed CH_3COO- anion, a pair of 3D homochiral coordination polymers with open channels were constructed by the assembly of lactic acid derivative ligands, 1.4-DIB ligands and Cd（II） ions, namely [Cd3（（R）-CIA）2（CH3CO2）_2（1.4-DIB）2（H2O）2]·x（Guest）（1-D） and [Cd3（（S）-CIA）2（CH3CO2）2（1.4-DIB）2（H2O）2]·x（Guest）（1-L）. They contain 1D interesting ladder-like Cd-（R）-CIA（3-） chains and exhibit SHG-active behavior and photoluminescent property.

Synthesis and Crystal Structure of a Novel Bis(chlorido)-bridged One-dimensional Chain-like Copper(Ⅱ) Polymer

A copper（Ⅱ） complex [LCu2Cl4]n was synthesized by a new bis-Schiff base ligand containing quinoline unit, 1,4-bis[2-（4-fluorophenyl）iminomethyl-8-quinolinoxy]butane（L）. X-ray crystal structure shows that it is a binuclear complex, and the crystal belongs to the triclinic system, space group P1, with a = 9.387（2）, b = 9.968（2）, c = 10.291（2） ？, α = 87.532（3）, β = 63.762（2）, γ = 86.628（3）o, V = 862.1（3） ？^3, Z = 1, Dc = 1.640 Mg/m^3, F（000） = 428, R = 0.0416 and wR = 0.1141. Each Cu（Ⅱ） metal ion coordinates with a quinoline N atom, an imine N atom, an ether oxygen atom and three chlorides, forming a distorted six-coordinated octahedronal structure. Each copper（Ⅱ） complexation unit links with one of the adjacent ligand copper complexation units through the chlorido bridging groups, thus generating an infinite one-dimensional chain structure. Such 1D chains further construct a 2D network structure by π-π stacking interactions.

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3''-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L（o-bdc）]n（1） and [Zn L（mbdc）]_n·n H_2O（2）（L = 4？-（3-pyridyl）-3,2？：6？,3？？-terpyridine,H_2（o-bdc） = benzene-1,2-dicarboxylic acid,H_2（m-bdc） = benzene-1,3-dicarboxylic acid）,were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016（2）,b = 11.3815（11）,c = 19.8071（17） ？,β = 133.961（2）°,V = 4546.2（7） ？3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m^3,μ = 1.127 mm-1,F（000） = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 〉 2σ（I） and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003（14）,b = 11.9152（11）,c = 26.633（3） ？,β = 94.320（2）°,V = 4936.5（8） ？~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m^3,μ = 1.043 mm^（-1）,F（000） = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 〉 2σ（I） and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.

Crystal Structure of the Coordination Polymer of Sodium with Hydrazone Derivant of Acetoacetanilide

One new polymer, [Na（NPHSNPAB）（CH3OH）]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ^1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex： C（17）H（17）N4NaO9S, Mr = 476.39, triclinic system, space group P1, a = 8.8741（18）, b = 10.942（2）, c = 12.039（2） A, α = 65.74（3）, β = 77.49（3）, γ = 84.30（3）o, V = 1040.3（4） A3, Z = 2, Dc = 1.521 g/cm^3, λ = 0.71073 A, F（000） = 492, S = 1.106, R = 0.0614 and w R = 0.1423 for 2945 observed reflections with I 〉 2（I）. X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C–H···O, N–H···O, O–H···O, and O–H···S hydrogen bonds. Moreover, sodium（I） center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π···π stacking interaction in the polymer. The average bond distance of the two dicyclic units（3.768 A） indicated strong π···π stacking interaction. The complex displays greenyellow emission at room temperature.

Hydrothermal Syntheses, Crystal Structures and Fluorescence of a Copper(I) Polymer and a Salt with H_2SO_4 Based on a Pyrimidine Building Block

Based on the building block of 2-phenyl-4,6-di（pyridin-2-yl）pyrimidine （L = C20H14N4）, a Cu（I） polymer [（CuC20H14N4）（CuCl2）]∞ and a salt with H2SO4 [（C20H16N4）（HSO4）2] have been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction. In the Cu（Ⅰ） polymer, although the central metal ions of Cu（Ⅰ） directly coordinate with the building block L, they still do not assembly expected grid-type complexes and there exists a one-dimensional chain constructed through coordinate bonds. In the salt, hydrogen bonds along with two kinds of π…π supramoleuclar interactions fabricate two-dimensional （2D） networks which further generate a 3D supramolecular architecture via interlayer π…π interactions. Fluorescent spectra show that the L emits blue fluorescence and its Cu（Ⅰ） polymer and salt decrease the fluorescent intensity.

Stress-rupture measurements of cast magnesium strengthened by in-situ production of ceramic particles

We have introduced a polymer precursor into molten magnesium and then in-situ pyrolyzed to produce castings of metal matrix composites(P-MMCs)containing silicon-carbonitride(SiCNO)ceramic particles.Stress-rupture measurements of as-cast P-MMCs was performed at 350 ℃(0.69TM)to 450 ℃(0.78TM)under dead load condition corresponding to tensile stress of 2.5 MPa to 20 MPa.The time-to-fracture data were analyzed using the classical Monkman–Grant equation.The time-to-fracture is thermally activated and follows a power-law stress exponent exhibiting dislocation creep.Fractography analysis revealed that while pure magnesium appears to fracture by dislocation slip,the P-MMCs fail from the nucleation and growth of voids at the grain boundaries.

Moisture-proof and Enhanced Effect of Inorganic Coating on Porous Si_3N_4 Ceramic

Inorganic coating was fabricated on the surface of the porous Si3N4 ceramic by polymer derived（PD） and spraying technology, via using vinyl-polysilazane（PSN-1） as a preceramic polymer and Si3N4 and lithium aluminosilicate（LAS） powders as fillers. The phase and microstructure of the coatings were analyzed by X-ray diffraction（XRD） analysis and scanning electron microscopy（SEM）, respectively. The effect of the coatings on mechanical property and humidity resistance of the porous Si3N4 ceramic was investigated. The experimental results showed that we successfully fabricated the uniform and dense coating which preferably combined with the substrate upon the addition of fillers. The bending strength of the porous Si3N4 ceramic sprayed the coating increased by more than 18%, and the surface hardness increased by 1.7 times. The apparent porosity of the materials reduced by an average of 97.7%, and water absorption was below 0.5%. Therefore, the prepared coating with preferable density had an obviously moisture-proof and enhanced effect on the porous Si3N4 ceramic.

An unsymmetric constitutive equation for anisotropic viscoelastic fluid

A continuum constitutive theory of corotational derivative type is developed for the anisotropic viscoelastic fluid-liquid crystalline （LC） polymers. A concept of anisotropic viscoelastic simple fluid is introduced. The stress tensor instead of the velocity gradient tensor D in the classic Leslie-Ericksen theory is described by the first Rivlin-Ericksen tensor A and a spin tensor W measured with respect to a co-rotational coordinate system. A model LCP-H on this theory is proposed and the characteristic unsymmetric behaviour of the shear stress is predicted for LC polymer liquids. Two shear stresses thereby in shear flow of LC polymer liquids lead to internal vortex flow and rotational flow. The conclusion could be of theoretical meaning for the modern liquid crystalline display technology. By using the equation, extrusion-extensional flows of the fluid are studied for fiber spinning of LC polymer melts, the elongational viscosity vs. extension rate with variation of shear rate is given in figures. A considerable increase of elongational viscosity and bifurcation behaviour are observed when the orientational motion of the director vector is considered. The contraction of extru- date of LC polymer melts is caused by the high elongational viscosity. For anisotropic viscoelastic fluids, an important advance has been made in the investigation on the constitutive equation on the basis of which a seriesof new anisotropic non-Newtonian fluid problems can be addressed.

CHARGE TRANSFER POLYMERIZATION——THE POLYMERIZATION OF ACRYLONITRILE INITIATED BY CARBAZOLE AND ITS DERIVATIVES

The photopolymerization of acrylonitrile (AN) initited by aromatic tertiary amine, phenothiazine, diphenylsulfide triphenylphosphine, etc. are known to proceed by a charge transfer process with the formation of an exciplex. Recently we have briefly reported that the N-vinylcarbazole (VCZ) is an excellent photoinitiator for AN polymeriza-

Electromagnetic interference shielding properties of polymer derived SiC-Si3N4 composite ceramics

SiC-Si3N4 composite ceramics are successfully fabricated by pyrolysis of ferrocene-modified polycarbosilane(PCS) mixed with inert filler Si3N4 powders, followed by thermal treatment from 1100℃ to 1400℃ in Ar atmosphere. The porosity of SiC-Si3N4 ceramics decreases to 6.4% due to the addition of inert filler Si3N4. And the content and crystallization degree of free carbon and SiC derived from PCS are improved simultaneously with the increase of thermal treatment temperature. Finally, the free carbon and SiC interconnect, forming the conductive network. As a result, the electromagnetic interference(EMI) shielding performance of the as-prepared ceramic annealed at 1400℃ reaches up to 36 d B, meaning more than99.9% of EM energy is shielded. The low porosity and high EMI shielding performance enable SiC-Si3N4 composite ceramics to be a promising electromagnetic shielding and structural material.

Cationic conjugated polymers as signal reporter for label-free assay based on targets-mediated aggregation of perylene diimide quencher

Herein, we reported a new label-free and fluorescence turn-on biosensor based on cationic conjugated poly（9,9-bis（6＇-N,N,N-trimethylammonium）hexyl）fluorine phenylene）（PFP） and perylene diimide derivatives（PDI）. Cationic PFP, single-stranded nucleic acid and PDI were used as signal reporter, probe and fluorescence quencher, respectively. In the presence of nucleic acids, they form complexes with PFP and PDI through strong electrostatic attraction interactions, resulting in PDI aggregating on nucleic acids and fluorescence of PFP being quenched. When nucleic acids are hydrolyzed by enzymes or their conformation is changed via recognizing targets, the effective aggregation of PDI is disrupted and the quenching ability is decreased. Thus the fluorescence of PFP recovers significantly. By taking advantage of the mechanism, we construct a new biosensor for endonuclease and small molecules detection. Here, S1 nuclease and bisphenol A are used as model systems. The detection limit of the SI nuclease and BPA are1.0×10^-6U/mL and 0.05 ng/mL, respectively. Our method is sensitive, cost-effective and simple, and provides a new platform for bioanalysis.

Electromagnetic wave absorbing ceramics composites made of polymer-derived SiC with BN@CNTs pyrolyzed higher than 1200℃

Polymer-derived ceramics(PDCs)pyrolyzed at high temperatures are promising electromagnetic wave(EMW)absorption materials for aerodynamically heated parts of aircraft under harsh environments.Nev-ertheless,high-temperature pyrolysis results in a significant increase of electrical and dielectric proper-ties of the ceramics,causing extensive reflection of EMW.To address this challenge,boron nitride-coated carbon nanotubes(BN@CNTs)were fabricated and introduced into polymer-derived SiC(PDC-SiC)by py-rolyzing its precursor higher than 1200℃to form SiC-BN@CNT ceramic composites.The fabricated com-posites with 3 wt.%BN@CNTs pyrolyzed at 1200℃have an effective absorption bandwidth(EAB)of 4.2 GHz(8.2-12.4 GHz)at a thickness of 3.4 mm and the minimum reflection loss(RL min)of-57.20 dB.The ultra-broad EAB of 12.62 GHz(5.38-18 GHz)is obtained by simulation through periodic structure design-ing.The RL of the metamaterials was also measured using an arch testing method at a frequency range of 2-18 GHz and an EAB of 11.52 GHz(6.48-18 GHz)is obtained.The excellent absorption is attributed to the BN layer that limits the electrical conduction of the ceramic composites while retaining the high loss of CNTs.The introduction of BN@CNTs causes the refinement of SiC grains,which provides plenty of interfaces and enhances the interface polarization loss.This work successfully solves the problem that PDCs pyrolyzed at elevated temperatures cannot be used as EMW absorption materials by applying BN coating on CNTs served as absorbers for PDC-SiC.The results of this work greatly broaden the application scope of the PDC systems for EMW absorption.

Electrosynthesis and Characterization of Aminomethyl Functionalized PEDOT with Electrochromic Property

We herein report the electrosynthesis of an aminomethyl functionalized poly（3,4-ethylenedioxythiophene）（PEDOT） derivative, poly（2＇-aminomethyl-3,4-ethylenedioxythiophene）（PEDOT-Me NH2）, in CH2Cl2-Bu4NPF6（0.1 mol·L^-1） system containing 2% boron trifluoride diethyl etherate（BFEE）. The electrochemical behavior, structure characterization, thermal properties and surface morphology of this novel polymer were systematically investigated by cyclic voltammetry（CV）, Fourier-transform infrared spectroscopy（FTIR）, thermogravimetry（TG） and scanning electron microscopy（SEM）, respectively. Electrochemistry results demonstrated that PEDOT-Me NH2 film displayed good redox properties and high electrochemical stability. Besides, PEDOT-Me NH2 films exhibited the electrochromic nature with obvious color changing from purple in the reduced form to blue upon oxidation. By further investigation, kinetic studies revealed that PEDOT-Me NH2 film had decent contrast ratio（41.8%）, favorable coloration efficiency（152.1 cm^2·C^-1）, low switching voltages and moderate response time（2.4 s）. Satisfactory results implied that the obtained PEDOT-Me NH2 film is a promising optoelectronic material and holds promise for electrochromic devices and display applications.