Synthesis, conductivity and photosensitivity of 2-D conjugated polymers of metalporphyrazine with sulfur bridges

The title polymers PMS₈Pz, M=Mn^II, Fe^II, Co^II, Ni^II, Cu^II, Zn^II, were synthesized by reaction of 2, 3, 5, 6-tetracyano-1, 4-dithiin with corresponding metal salts, respectively. The structure and properties of these polymers were characterized by elemental analysis, transmission electron microscope, DTA, IR, UV-Vis, fluorescence and EPR spectra. It has been found that these conjugated polymers have the property of intrinsic semiconductor. The conductivity σ_298K of these polymers is in the range of 10⁻⁹≈10⁻³ S·cm⁻¹ under pressure 10.63 MPa and incrementals in the metal order Mn<Co<Fe<Zn<Cu<Ni. The photosensitivity of the MS₈Pz to the CdS-PVA films is incrementals in the metal order Zn<Mn<Co<Fe<Cu<Ni. Supported by the National Natural Science Foundation of China and by the Approach Fund of State Key Laboratory of Coordination Chemistry in Nanjing University Peng Zhenghe: born in Apr. 22, 1945, Professor     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

Subsolidus phase relations in the system MgO-ZnO-SiO2 at high pressure

The subsolidus phase relations were determined experimentally in the system MgO-ZnO-SiO2 at 1.0 GPa and 1 200℃, by use of the high-pressure apparatus "piston-cylinder". The results showed characteristics of the phases assemblage different from that in similar ternary systems. It is impossible to form complete Mg2SiO4-Zn2SiO4 olivine and Mg2Si2O6-Zn2Si2O6 pyroxene solid solution. This is controlled by the properties of Zn2+ with an outer layer of electron (Ar)3d10, different from others transition metal ions, like Fe2+ , Ni2+ , Co2+ .     

Summer monsoon and dust signals recorded in the Dasuopu firn core, central Himalayas

In September 1997, a 15-m firn core was recovered from an elevation of 7 000 m a. s.l. from the Dasuopu Glacier in the central Himalayas. The analysis of δ18O values and major ion (Ca2+ , Mg2+ , NH4+ , SO42- and NO3-) concentrations shows that average annual accumulation is 0.75 m (water equivalent) in the Dasuopu firn core. The seasonal variations of δ18O values and major ion concentrations in the core indicate that present summer monsoon and dust signals are recorded with high-resolution in the Dasuopu Glacier. δ18O in precipitation are controlled by amount effect in summer monsoon season, more negative δ18O is representative of summer monsoon signal in snow layers. Higher concentrations of Ca2+ , Mg2+ , SO42- and NO3-are dominated by spring dust storm imput derived from the arid and semi-arid desert regions in central Asia. Also EOF analysis verifies that high spring concentrations of major ions are consistent. Due to the possibly different sources, the secondary variations of NH4+ and NO3- are negatively relevant with that of Ca2+ and Mg2+ .     

稀土氧化物掺杂对TiO2/沸石光催化性能的影响

以钛酸丁酯和稀土氧化物为原料, 采用溶胶 凝胶法制备了镧、 钕和镱稀土离子掺杂TiO₂/沸石光催化剂. 通过XRD和IR方法对样品进行表征, 研究了不同沸石粒径及不同稀土氧化物掺杂量(质量分数)对农药敌敌畏光催化降解性能的影响. 结果表明, 当沸石最佳粒径为0.15 mm, La³⁺掺杂量质量分数为3.0%时（以TiO₂质量计）, 稀土离子的掺杂可显著提高TiO₂//沸石的光催化降解性能.     

Nitric oxide suppresses stomatal opening by inhibiting inward-rectifying K<Stack><Subscript>in</Subscript><Superscript>+</Superscript></Stack> channels in <Emphasis Type="Italic">Arabidopsis</Emphasis> guard cells

We explore nitric oxide （NO） effect on K^＋in, channels in Arabidopsis guard cells. We observed NO inhibited K^＋in, currents when Ca^2＋ chelator EGTA （Ethylene glycol-bis（2-aminoethylether）-N,N,N′,N;tetraacetic acid） was not added in the pipette solution; K^＋in currents were not sensitive to NO when cytosolic Ca^2＋ was chelated by EGTA. NO inhibited the Arabidopsis stomatal opening, but when EGTA was added in the bath solution, inhibition effect of NO on stomatal opening vanished. Thus, it implies that NO elevates cytosolic Ca^2＋ by activating plasma membrane Ca^2＋ channels firstly, then inactivates K^＋in, chartnels, resulting in stomatal opening suppressed subsequently.     

Mechanisms of peroxynitrite-induced [Ca2+]i increase in single neuronal cell

The mechanism of peroxynitrite (ONOO⁻)-induced [ca²⁺]_i increase in single MN9D cell (Dopaminergic neuroblastoma cell line) was studied by using Fura-2 microfluorometric technique. The results show that ONOO⁻ caused a rapid increase of [Ca²⁺]_i when ONOO₋ was puffed to the cell. Removing Ca²⁺ from the bath or using calcium channel antagonist (CdCl₂, Nifedipine) greatly inhibited the [Ca²⁺]_i increase induced by ONOO⁻¹, suggesting that the opening of L-Ca²⁺ channel makes a great contribution to the [Ca²⁺]_i increase. The effect of sulfhydryl reductive agent (DTT) on ONOO⁻-induced [Ca²⁺]_i increase suggests that ONOO⁻-activating L-Ca²⁺ channel is partly related to its oxidative speciality.     

Bi~(3+)/Yb~(3+)共掺GdVO_4近红外发光性能研究

使用高温固相法制备了一种新的Bi3+,Yb3+共掺杂GdVO4量子裁剪近红外发光材料,该材料在波长为250~400nm的紫外光激发下发射出很强的近红外光(900~1100nm).由于体系中Bi3+离子的引入,相对于Gd0.9Yb0.1VO4,Gd0.87Yb0.1Bi0.03VO4在989nm处的近红外发光强度提高近120%,且其激发峰也从323nm红移至341nm,整个激发谱带更宽,更有利于实际应用.由于Yb3+离子既可以利用基质中的VO3-4电荷迁移态跃迁的能量,也可以同时利用Bi3+的1S0-3P1能级跃迁传递能量,相对于目前报道的理论量子裁剪效率最高的YVO4:Bi3+,Yb3+,GdVO4:Bi3+,Yb3+无论其近红外发光强度还是可见光发光强度强度皆有提升,是一种很有希望的紫外宽带激发近红外发光材料.     

Antilocalization sensing of interactions between two-dimensional electrons and surface species

We apply antilocalization measurements to experimentally study the interactions and exchange between InAs surface accumulation electrons and local magnetic moments of the rare earth ions Sm3?,Gd3?,Ho3?,and Dy3?,of the transition metal ions Ni2?,Co2?,and Fe3?,and of Fe3O4nanoparticles and Fe3?-phthalocyanine deposited on the surface.The influence of the deposited species on the surface electrons is observed through the changes in the spin–orbit scattering and magnetic spin-flip scattering rates,which carry information about magnetic interactions.Experiments indicate a temperature-dependent magnetic spin-flip scattering for Ho3?,Dy3?,Ni2?,and Co2?.Concerning the spin–orbit scattering rate,we observe an increase,except for the cases of Ni2?,Fe3?,Fe3O4nanoparticles and Fe3?-phthalocyanine.We also observe an increase in SO scattering in another system where we study the interactions of Au nanoparticles and ferromagnetic Co0.6Fe0.4nanopillars and an In0.53Ga0.47As quantum well.Experimental results are analyzed and compared to theoretical models.Our method provides a controlled way to probe the quantum properties of two-dimensional electron systems,either on the surface of InAs or in a quantum well.     

Determination of crystal structure of omphacite

The chemical formula of omphacite was expressed with (MⅡ MⅠ ) (Si, AI)2O6. Cations that occupied the MⅡ site were large cations such as Ca or Na, and (Na/(Na+Ca)) ratio ranged from 0.2 to 0.8; the 6-coordinated MⅠ site accommodated cations such as Mg, Fe2+, Al, Fe3+ ,and(AI/(AI+Fe3+)) ratio was more than 0.5. Omphacite space groups reported were C2/ c, P2, P2/n, P2/c, cell parameters are α0 = 0.9600-0.9630 nm,b0 = 0.8750-0.8830 nm,c0 = 0.5230-0.5290 nm,β = 106°40′-107°10'. The sample was picked up from the eclogites in Zhucheng County, Shangdong Province. The intensity data were collected with the RIGAKU RASA Ⅱ -S four-circle single crystal diffractometer.The correct structure model was obtained by using the Patterson method and Fourier synthesis, SHELX-76 program, structure refinement with 905 independent diffraction points (| F0 |> 3σ |F0 |). After the structure parameter refinement, the R-factor reduced to 0.0515. The crystal structure analysis indicates that omphacite has a new space group-Pn space group.     

Studies on the interaction of DNA and Ru (1,10-phenanthroline)2− (dipyrido[3,2−a:2′,3′−c]phenazine)2+

The interaction of Ru(phen)₂(dppz)²⁺(phen=1,10-phenanthroline,dppz=dipyrido[3,2−1:2′,3′−c]phenazine) and the calfthymus DNA were studied with fluorescence and ultraviolet visible absorption spectroscopy. The ultraviolet visible absorption spectrum of Ru(phen)₂(dppz)²⁺ calfthymus DNA, and their interaction demonstrated that Ru(phen)₂(dppz)²⁺ intercalated into the double helix of DNA via the ligand dppz. Fe(CN)₆ ⁴⁻ and NaCl can not quench the fluorescence of Ru(phen)₂(dppz)²⁺-DNA, which was in agreement with the intercalation mode. Foundation item: Supported by National Natural Science Foundation of China Biography: LING Lian-sheng (1972-), male, PhD, candidate.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Molecule modification and mass deposition induced by the implantation of low energy Fe+ ion beams into amino acids

Fe⁺ ion beams with the energy of 110 keV were implanted into films of L(+)-cysteine (HSCH₂CH(NH₂)COOH). One of the single crystals grown in hydrochloric acid solution with the implanted samples through slow evaporation was structurally characterized by the X-ray crystallography. The crystal is monoclinic, space group C2, with a = 1.8534(4) nm, b = 0.5234(1) nm, c = 0.7212(1) nm, β= 103.72°, V = 0.67965(3) nm³, Z = 4, F(000) = 144.0, D{clac} = 1.763 g · cm⁻³, μ(MoK _a = 1.06 mm⁻¹, T = 293(2) K. R = 0.0379, wR = 0.0835 for 660 observed reflections (I > 2σ(I)). The structural formula of the crystal compound is (CH₂CH(NH₂)NO₂)ClFe (M _r = 180.38 u). Products of heavy ion beam irradiation were purified and it was directly confirmed that the implanted Fe⁺ ions had been deposited in the novel molecules. The same doses of Fe⁺ ion beams of the same energy were implanted into films of L(+)-cysteine hydrochloride monohydrate. FTIR spectroscopy of the implanted samples proved that some of the original molecules were seriously damaged and significant modifications were induced.     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.     

Effects of metal ions on recombinant calcineurin A subunit

Effects of metal ions on activities and solution conformations of calcineurin A subunit have been examined. The ability of several metal ions to activate calcineurin A has been tested with Ni²⁺> Mn²⁺> Mg²⁺/Ca²⁺. The corresponding CD spectra and intrinsic fluorescent emission spectra show that calcineurin A exists in different metal ion-dependent conformation states. Effects of the different concentritions of Ni²⁺ on activities and solution conformations of calcineurin A have been tested too. Results indicate that effects of these metal ions to activate calcineurin are due to their conformational changes.     

Near-infrared to visible up-conversion emissions of Er^3＋ doped Al2O3 powders derived from the sol-gel method

The Er3 doped Al2O3 powders were prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3.5H2O]. The different phase structure, including three crystalline types of (Al,Er)2O3 phases, γ, θ, α, and two Er-Al-O phases, ErAlO3 and Al10Er6O24, was obtained with the 1 mol% Er3 doped Al2O3 powders at the different sintering temperatures of 600―1200℃. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the 2H11/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3 , were detected by a 978 nm semiconductor laser diodes excitation. The phase structure and OH content had evident influence on the up-conversion emissions intensity. The maximum intensities of both the green and red emissions were obtained respectively for the Er3 doped Al2O3 powders sintered at 1200 ℃, which was composed mainly of α-(Al,Er)2O3, less of ErAlO3 and Al10Er6O24 phases, and with the least OH content. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er3 doped Al2O3 powders.     

A breakthrough of researching reservoir adsorption gas and its significance

GC-C-MS on linear isotope analysis equipment makes it possible to measure the hydrocarbon gases at the level of 10 -3-10 -2 μL- By applying this technique the carbon isotopes of C1-C3 of the adsorbed gas from the Triassic oil sand bed of the Aican-l Well in the Turpan-Hami basin were analysed. The δ13C values of C1-C3, are -55.1‰, -38.6‰ and -35.0‰ respectively. In terms of geochemical characteristics of natural gases and crude oils, in combination with basinal geological backgrounds, it is considered that the reservoir adsorbed gas was formed by crude-oil biodegradation, absorbed by reservoir rocks and its oil-gas source is related with the Permain (perhaps including the Carboniferous). The adsorbed gas is obviously different from the Jurassic coal-generated oil and gas.     

异丙醇-硫酸铵-PAN双水相萃取光度法测定镍(Ⅱ)

研究了异丙醇水溶液与(NH4)2SO4的双水相体系下,螯合剂PAN(1-(2-吡啶偶氮)-2-萘酚)与Ni 2+以及吐温80形成的缔合物在两相间的分配行为.结果表明,该缔合物的最大吸收波长为562nm,与PAN和异丙醇水溶液的混合液相比,最大吸收发生了97nm红移.应用该缔合物体系分离测定镍时,其线性范围为0.10~0.60mg/L,线性相关系数为0.999 2,表观摩尔吸光系数为1.7×105 L·mol-1·cm-1.利用该方法萃取测定Ni(Ⅱ)时,干扰离子铅(Ⅱ)、锌(Ⅱ)、铝(Ⅲ)、锰(Ⅱ)、钼(Ⅶ)、Fe(Ⅲ)、铬(Ⅶ)不被萃取,实现Ni(Ⅱ)与上述干扰离子的分离.     

非活性马尾藻对水中Cd2+和Ni2+的生物吸附及脱附研究

【目的】以马尾藻粉为生物吸附剂,研究其在静态实验中对Cd2＋ 和Ni2＋ 的吸附及脱附能力,并对吸附速度、动力学、重金属选择性和吸附剂再生等问题进行探讨.【方法】采用单因素法分析pH 值、初始浓度、平衡离子类型等条件因素对重金属吸附容量的影响,采用准一级和准二级动力学模型对Cd2＋ 、Ni2＋ 的吸附数据进行拟合.【结果】Cd2＋ 的最佳吸附条件为pH 值4.5、初始浓度500mg/L、平衡离子为NO3ˉ,Ni2＋ 的最佳吸附条件为pH 值3.0、初始浓度900mg/L、平衡离子为Clˉ;Cd2＋ 、Ni2＋ 的吸附平衡到达时间分别为50min和25min;准二级动力学模型对吸附数据的拟合效果更好,相关系数（犚2 ）均大于0.99;对混合溶液中不同重金属的选择性吸附顺序为Pb2＋ 〉Ni2＋ 〉Cd2＋ 〉Mn2＋ ;1.0mol/L HCl对Cd2＋ 、Ni2＋ 的理论洗脱率均可达到99%.【结论】马尾藻粉对Cd2＋ 和Ni2＋ 的吸附容量大,吸附条件温和,重金属脱附率高,是一种性能良好的生物吸附剂.     

Mechanism of selective separation on the surface of ionic sieve of removal of lead

This note describes a kind of ionic sieve with high selectivity to remove trace lead in water, in which stannic molybdopyrophosphate is used to be the substrate. The mechanism of selective separation on the surface of ionic sieve of removal of lead was explored by analyzing fourier transformation infrared spectra (FTIR), X-ray photoelectron spectrometry (XPS) and the results of selective adsorptivity experiment. The investigation suggests that in the process of synthesizing ionic sieve the olation reactions occur in solid phase by thermodynamic recrystallization and the adsorption units with special selectivity to lead are formed by chemical modification. After the ion exchange for Pb²⁺, the oaltion reactions not only keep the microstructures of adsorption units from collapse, but also provide lead cavties with special selectivity to lead ion that are capable of having special binding “memory effect” to Pb²⁺ by SnO₃ ²⁻ and P₂O₇ ⁴⁻ groups on the surface of this ionic sieve. Meanwhile, the selective separation capacity is a kind of weak chemical effect that is relative to the valence electron state of the adsorbed ion directly and tightly.