Synthesis and Properties of Carbazole Main Chain Copolymers with Oxadiazole Pendant toward Bipolar Polymer Host: Tuning the HOMO/LUMO Level and Triplet Energy

Three new carbazole copolymers, poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-3,6-diyl)s (P1), poly(9-(2,5-diarene-[1,3,4]oxadiazole)-2, 7-carbazole-alt-9-(2-ethylhexyl)-3, 6-carbazole-diyl)s (P2), and poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-2,7-diyl)s (P3), were synthesized by the Suzuki coupling reaction

Synthesis, characterization, and electroluminescence of PPV copolymers containing electron and hole-transporting units

Three series of poly(phenylene vinylene) (PPV) derivatives containing hole-transporting triphenylamine derivatives [N-(4-octoxylphenyl)diphenylamine, N,N'-di(4-octyloxylphenyl)-N,N'-diphenyl-1,4-phenylenediamine, and N,N'-di(4-octoxylphenyl)-N,N'-diphenylbenzidine] (donor) and electron-transporting oxadiazole unit (2,5-diphenyl-1,3,4-oxadiazole) (acceptor) in the main chain were synthesized by improved Wittig copolymerization. The resulting donor-acceptor (D-A) polymers are readily soluble in common organic solvents, such as chloroform, dichloroethane, THF, and toluene.

Syndiotactically enriched 1,2-selective polymerization of 1,3-butadiene initiated by iron catalysts based on a new class of donors

A series of phosphoryl (P=O) contained compounds: triethylphosphate (a), diethyl phenyl phosphate (b), ethyldiphenylphosphate (c) triarylphosphates (d and h-m), triphenylphosphine oxide (e), phenyl diphenylphosphinate (f) and diphenyl phenylphosphonate (g) have been prepared. Iron catalysts, which are generated in situ by mixing the compounds with Fe(2-EHA)(3) and (AlBu3)-Bu-i in hexane, are tested for butadiene polymerization at 50 degrees C. Phosphates donated catalysts have been, unprecedently, found to conduct extremely high syndiotactically (pentad, rrrr=46.1-94.5%) enriched 1,2-selective (1,2-structure content=56.2-94.3%) polymerization of butadiene.

Synthesis and characterization of phenylene-thiophene all-conjugated diblock copolymers

Grignard metathesis (GRIM) polymerization for all-conjugated diblock copolymers comprising poly (2,5-dihexyloxy-1,4-phenylene) (PPP) and poly(3-hexylthiophene) (P3HT) blocks were systematically studied with LiCl as additive and 1,2-bis (diphenylphosphino) ethane nickel dichloride (Ni(dppe)Cl-2) or 1,3-bis(diphenylphosphino) propane nickel dichloride (Ni(dppp)Cl-2) as catalyst. It was found that the addition order of the monomers was crucial for the success of copolymerization. With the monomer addition in the order of phenyl and then thienyl Grignard reagents, all-conjugated PPP-b-P3HT diblock copolymers with different block ratios were successfully synthesized. In contrast, the inverted addition order only afforded a mixture containing both block copolymers and deactivated or end-capped homopolymers.

Constructing mixed-metal coordination polymers from copper(II)-pyridinedicarboxylate metalloligands

In the mixed-metal complex catena-poly[bis[diaquasilver(I)] [bis[aquacopper(II)]-mu(3)-pyridine-2,5-dicarboxylato-2': 1: 1'kappa N-5,O-2: O-5: O-5, O-5'-mu-pyridine-2,5-dicarboxylato-2: 1 kappa(4) N, O-2: O-5, O-5'-disilver(I)-mu(3)-pyridine-2,5-dicarboxylato-1: 1': 2 '' kappa(5) O-5, O-5': O-5: N, O-2-mu pyridine-2,5-dicarboxylato-1': 20 ''kappa(4) O-5, O-5': N, O-2] hexahydrate], {[Ag(H2O)(2)][AgCu(C7H3NO4)(2)(H2O)] center dot 3H(2)O}(n), a square-pyramidal Cu-II center is coordinated by two N atoms and two O atoms from two pyridine-2,5-dicarboxylate (2,5-pydc) ligands and a water molecule, forming a [Cu(2,5-pydc)(2)-( H2O)](2-) metalloligand. One Ag I center is coordinated by five O atoms from three 2,5-pydc ligands and, as a result, the [Cu(2,5-pydc)(2)(H2O)](2-) metalloligands act as linkers in a unique mu(3)-mode connecting Ag-I centers into a one-dimensional anionic double chain along the [101] direction.

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

Electrocatalytic reduction of 1,2-diiodoethane by anions of supramolecular complex of (beta-CD)(2)/C-60 in DMF solution

The homogeneous electrocatalytic reduction of 1,2-diiodoethane by anions of the supramolecular complex of (beta-CD)(2)/C-60 in DMF solution is reported. The results show that the trianion of (beta-CD)(2)/C-60 exhibits electrocatalytic behavior towards the reduction of 1,2-diiodoethane, whereas the diani on is unable to reduce the diiodoethane. The second-order catalytic rate constant in DMF solution was determined to be 3.1 x 10(5) M-1 s(-1) by analysis of voltammetric responses under pseudo-first-order conditions with respect to (beta-CD)(2)/C-60. The results suggest that the host beta-cyclodextrin molecules have little effect on the electrocatalytic ability of the encapsulated C-60 toward organic halides.

A new 1D metal-organic coordination polymer with blue fluorescent emission: [Cd-2(1,10 '-phen)(2)(betc)(H2O)](n)

A new coordination polymer [Cd-2(1,10'-phen)(2)(betc)(H2O)](n) (1) (betc = benzene-1,2,4,5-tetracarboxylate, 1,10'-phen = 1,10'-phenanthroline) was hydrothermally synthesized from CdCl2.2.5H(2)O, H(4)betc and 1,10'-phen at 160 degreesC. It was characterized by IR, XPS, TG and single-crystal X-ray diffraction. Compound 1 possesses infinite chair-like chains which construct 3D framework through pi-pi interactions and the hydrogen bond interactions. The fluorescent spectrum study shows that compound 1 exhibits blue fluorescent emission in the solid at room temperature.

导向剂法快速合成ZSM-5分子筛的方法

一种导向剂快读合成小晶粒ZSM-5分子筛的方法，主要包括导向剂制备、分子筛合成两步。第一步导向剂制备首先根据配料比将硅源与无离子水制成Ａ溶液后将模板剂加入，在搅拌下再将由无机酸碱调节适当碱度的铝源滴入均匀反应，按趁虚升温完成后，将合成液体中接近透明的部分分离出即为导向剂。分子筛的合成过程同导向剂相同，只是将原料配比中的有机胺模板剂由导向剂取代，晶化过程需６５－７５小时即可完成，得到平均粒径0.1μm的ZSM5分子筛。本发明制备简单，合成周期短。

Highly efficient green light emitting polyfluorene incorporated with 4-diphenylamino-1,8-naphthalimide as green dopant

The dopant/host methodology, which enables efficient tuning of emission color and enhancement of the electroluminescence (EL) efficiency of organic light emitting diodes (OLEDs) based on small molecules, is applied to the design and synthesis of highly efficient green light emitting polymers. Highly efficient green light emitting polymers were obtained by covalently attaching just 0.3-1.0 mol% of a green dopant, 4-(N,N-diphenyl) amino-1,8-naphthaliniide (DPAN), to the pendant chain of polyfluorene (the host). The polymers emit green light and exhibit a high photoluminescence (PL) quantum yield of Lip to 0.96 in solid films, which is attributed to the energy transfer from the polyfluorene host to the DPAN dopant unit. Single layer devices (device configuration: ITO/PEDOT/Polymer/Ca/Al) of the polymers exhibit a turn on voltage of 4.8 V, luminance efficiency of 7.43 cd A(-1), power efficiency of 2.96 lm W-1 and CIE coordinates at (0.26, 0.58). The good device performance can be attributed to the energy transfer and charge trapping from the polyfluorene host to the DPAN dopant unit as well as the molecular dispersion of the dopant in the host.

Direct electrochemistry and surface plasmon resonance characterization of alternate layer-by-layer self-assembled DNA-myoglobin thin films on chemically modified gold surfaces

Alternate layer-by-layer (L-by-L) polyion adsorption onto gold electrodes coated with chemisorbed cysteamine gave stable, electroactive multilayer films containing calf thymus double stranded DNA (CT ds-DNA) and myoglobin (Mb). Direct, quasi-reversible electron exchange between gold electrodes and proteins involved the Mb heme Fe2+/Fe3+ redox couple. The formation of L-by-L (DNA/Mb), films was characterized by both in situ surface plasmon resonance (SPR) monitoring and cyclic voltammetry (CV). The effective thickness of DNA and Mb monolayers in the (DNA/Mb)l bilayer were 1.0 +/- 0.1 and 2.5 +/- 0.1 mn, corresponding to the surface coverage of similar to65% and similar to89% of its full packed monolayer, respectively. A linear increase of film thickness with increasing number of layers was confirmed by SPR characterizations. At pH 5.5, the electroactive Mb in films are those closest to the electrode surface; additional protein layers did not communicate with the electrode. CV studies showed that electrical communication might occur through hopping conduction via the electrode/base pair/Mb channel, thanks to the DNA-Mb interaction. After the uptake of Zn2+, a special electrochemical behavior, where MbFe(2+) acts as a DNA-binding reduction catalyst in the Zn2+-DNA/Mb assembly, takes place.

3{1-[2-(-3-羟基-1-甲基-2-亚丁烯氨基)-苯亚氨基]-乙基}4-甲硫基-2,4-戊二烯-2-醇的不对称Schiff碱镍(Ⅱ)配合物的合成、结构和性质

由 5-(2-乙酰基-1-甲硫基-3-羰基-亚丁基)-丙二酸亚异丙酯 (1)与邻苯二胺及乙酸镍()经一步反应合成了3{1-[2-( -3-羟基-1-甲基-2-亚丁烯氨基)-苯亚氨基 ]-乙基} 4-甲硫基-2,4-戊二烯-2-醇(3)的不对称四齿 Schiff碱镍()配合物(2),X射线衍射结果表明,配合物 2属单斜晶系,P21/C空间群.a=1.1476(2)nm,b=1.1782(2)nm,c=1.4810(3)nm;β=111.73(2)°,V=1.8602(7)nm3,Z=4,Rf=0.0535.电化学(循环伏安)测定结果表明,该配合物在测定条件下(阳极峰电位为1.1)发生了不可逆的氧化-还原反应.

Synthesis and structural characterization of organolanthanide complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands

Reactions of anhydrous LnCl(3) (Ln = Nd, Gd, Dy, Er, Yb) with 2 equiv of LiCp' in THF afford the lanthanocene complexes Of CP'(2)Ln(mu-Cl)(2)Li(THF)(2) (CP' = eta(5)-t-BuC5H4, Ln = Nd (1), Gd (2), Dy (3), Er (4), Yb (5); Cp'= 1,3-eta(5)-t-Bu2C5H3, Ln = Nd (6), Gd (7), Dy (8), Er (9), Yb (10)). The molecular structures of 7 and 8 were characterized by X-ray crystallographic analysis. In these complexes, two Cp' ring centroids and two it-bridging chloride atoms around the lanthanide atoms form a distorted tetrahedron. The insertion of elemental chalcogen E (E = S, Se) into Li-C bonds of dilithium o-carborane in THF solution afforded dimers of dilithium. dichalcogenolate carboranes, [(THF)(3)LiE2C2B10H10Li(THF)](2) (E = S (12a), Se (12b)), which were confirmed by a crystal structure analysis. Reactions Of Cp'(2)Ln(mu-Cl)(2)Li(THF)(2) (1-10) with 12a or 12b gave dinuclear complexes of the formula [Li(THF)(4)](2)[Cp'(2)LnE(2)C(2)B(10)H(10)](2) (Cp'= eta(5)-t-BuC5H4, E = S, Ln = Nd (13a), Gd (14a), Dy (15a), Er (16a), Yb (17a); E = Se, Ln = Nd (13b), Gd (14b), Dy (15b), Er (16b), Yb (17b); Cp'= 1,3-eta(5)-t-Bu2C5H3 E = S, Ln = Nd (18a), Gd (19a), Dy (20a), Er (21a), Yb (22a); E = Se, Ln = Nd (18b), Gd (19b), Dy (20b), Er (21b), Yb (22b)). According to the X-ray structure analyses, the dianions of 13a and 13b contain two o-carborane dichalcogenolate bridges, and each CP'2Ln fragment is attached to one terminal and two bridging chalcogen ligands. The central Ln(2)E(2) four-membered ring is not planar, and the direct metal-metal interaction is absent.

Simultaneous determination of 2-aminothiazole, 2-aminobenzothiazole and 2-mercaptobenzothiazole by capillary electrophoresis with end-column amperometric detection

Capillary electrophoresis with amperometric detection is evaluated for the simultaneous determination of 2-aminothiazole (A), 2-amino-benzothiazole (AB), 2-mercaptobenzothiazole (AM). The cyclic voltammogram, hydrodynamic voltammogram, effect of pH, concentration of buffer and separation voltage on the separation and the detection were studied. The conditions were optimized as follows: 50 mM phosphate buffet; pH 6.0, 2s at 17.5 kV sample injection, separation at 17.5 kV, 1.2 V as detection potential. The method provided low detection limit as 0.5 mu M, 0.05 mu M and 0.01 mu M, wide linear range 2-200 mu M, 10-200 mu M and 0.025-100 mu M for A, AB, and AM, respectively. The variations in peak current and migration time for 15 consecutive injections of a standard containing 5 mu M each compound were 3.7, 2.1, and 3.9%, and 1.2, 0.8, and 1.2%, for A, AB and AM, respectively. This method was employed to analyze river water.