Two-Dimensional Supramolecular from the Self-Assembly of Dissymmetrical Oxamidato-Bridged Heterometallic Trinuclear Building Blocks: Synthesis, Crystal Structure, and Magnetic Properties

Two heterometallic trinuclear complexes {[Cu(oxbp)]₂Co(H₂O)₂}1.5DMF0.5H₂O (complex 1) and {[Cu(oxbm)]₂Co(H₂O)₂}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]^– and [Cu(oxbm)]^–[H₃oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H₃oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm^–1 for complex 1 and 2, respectively.     

加氢处理催化剂载体中Y型分子筛组分对催化剂表面性质和催化性能的影响

应用ＸＲＤ，ＸＰＳ，ＩＲ－ＴＰＤ，ＣＯ２和ＮＯ吸附及正庚烷裂解和噻吩加氢脱硫脉冲微反等方法，研究了加氢处理催化剂载体经Ｙ型分子筛改性前后各种性质的变化，结果表明，载体经Ｙ型分子筛改性后，催化剂的Ｂ酸、正庚烷裂解活性和异构选择性明显提高，Ｙ型分子筛以分散的形式分布于γ－Ａｌ２Ｏ３表面，减少了载体表面的空位铝，该催化剂中有盯当一部分金属组分进入Ｙ型分子筛孔道与３其Ｂ酸位作用，与ＮｉＱ／γＡｌ２Ｏ３相比     

Fluorescent probes for detection of biothiols based on “aromatic nucleophilic substitution-rearrangement” mechanism

“Aromatic nucleophilic substitution-rearrangement (SNAr-rearrangement)” mechanism provided a powerful tool to design fluorescent probes for the discrimination between biothiols.     

Application of AMS <Superscript>14</Superscript>C measurements to criminal investigations

¹⁴C variations of atmospheric CO₂ as well as carbonaceous fraction of living materials, such as collagen from tooth and bone, tissue, skin, hair, nail, etc., of modern humans are influenced by ¹⁴C produced artificially by nuclear bomb tests in the atmosphere from late 1950s to early 1960s. By careful investigation of ¹⁴C concentration of tree rings and human body samples formed in this time intervals, we can establish a relationship of their ¹⁴C concentrations with calendar year. By applying this relation to a sample whose ¹⁴C concentration can be measured, we can estimate the formation age of the sample. In addition, sources of the chemicals that were used in some criminal cases can be possibly identified, by their carbon isotope ratios (¹³C/¹²C and ¹⁴C/¹²C). This method of age determination has been applied to a forensic study, i.e., two criminal cases of murder. For each case, by comparing the measured ¹⁴C abundances of several pieces of hair and one tooth (the third molar) from the body with the annual change on concentrations of bomb-produced ¹⁴C, the time of death of the body and the age of the victim were estimated. The estimated values were consistent with the real ones that were revealed by the confession of the real murderers.     

Syntheses,Characterization and Crystal Structures of Three Structurally Similar Dinuclear Schiff Base Cadmium(II) Complexes with Bridging Azide or Thiocyanate Ligands

Three novel Schiff base cadmium(II) complexes, derived from the end‐on (μ‐1,1‐N₃) azide or end‐to‐end (μ‐1,3‐NCS) thio cyanate bridges and similar tridentate Schiff base ligands, have been synthesized under similar synthetic procedures and their crystal structures determined by X‐ray diffraction methods. They are the dinuclear double end‐on azide‐bridged [Cd₂(L1)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 1 ), the dinuclear double end‐on azide‐bridged [Cd₂(L2)₂(N₃)₂(μ‐1,1‐N₃)₂] ( 2 ), and the dinuclear double end‐to‐end thiocyanate‐bridged [Cd₂(L3)₂(NCS)₂(μ_1,3‐NCS)₂] ( 3 ), where L1, L2 and L3 are three similar tridentate Schiff bases obtained by condensation of 2‐pyridylaldehyde with N,N‐diethylethane‐1,2‐diamine, of 2‐pyridylaldehyde with N‐isopropylethane‐1,2‐diamine, and of 2‐pyridylaldehyde with N,N‐dimethylpropane‐1,3‐diamine, respectively. Each cadmium(II) centre in the complexes is in a distorted octahedral coordination. There is a crystallographic inversion centre in each of the complexes. The similar small ligands used as the secondary ligands in the preparation of the cadmium(II) complexes with similar Schiff bases can result in similar structures.     

Alternating DNA and pi-conjugated sequences. Thermophilic foldable polymers

Foldable polymers with alternating single-strand deoxyribonucleic acid and planar conjugated organic perylene tetracarboxylic diimide units were found to self-organize into loosely folded nanostructures. Upon heating, the loosely folded structures become more ordered as evidenced by pi-stacking in the perylene segments. The folding and unfolding processes driven by the molecular interactions of adjacent perylenes were monitored in both aqueous and organic solutions. Heat-promoted folding, or inverse temperature behavior, which originates from positive enthalpy changes, was only observed in water. Therefore, we attributed this inverse temperature dependence to hydrophobic effects rather than pi-pi molecular orbital overlap between the perylene planes. These findings shed light on the design of new thermophiles in protein engineering as well as the construction of macromolecular-based nanodevices with actuator and sensory properties.     

咪唑-金属配合物的合成、性质及其与DNA的作用机理

Three hexakis（imidazole）metallo complexes of Co, Cd and Ni were synthesized and spectroscopically characterized. The crystal and molecular structures have been determined by X-ray crystallography analysis. The metal ions have an octahedral geometry with the MN6 chromophore. The electrochemical experimental results indicate that both [Co（Im）6]C12·2HCl·2H2O （1） and [Ni（Im）6]C12·4H2O （3） [Im=imidazole] could interact with DNA mainly by intercalation.     

Effects of various donor: acceptor blend ratios on photophysical properties in non-fullerene organic bulk heterojunctions

In this work, the donor:acceptor ratio effected photophysical properties of non-fullerene organic solar cells are comparatively investigated. Effective transportation of the photo-generated charge carriers can be obtained with the PDBD-T:ITIC ratio variation. There is no significant energy loss variation exists in the process of changing the D:A ratio.     

纳秒强激光场中苯电离产生高价离子的研究

用25 ns脉冲Nd-YAG 532 nm的激光，在1010～1011 W•cm－2的光场强度下，利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时，除观察到C2＋、C2H2+、C3H3+、C6H6+离子外，还观察到很强的Cq＋(q=1～3)高价离子.这些离子都有很高的平动能， C2＋的最可几平动能为12.9 eV， C3＋为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验，可以认为这些高价离子来源于含苯团簇的库仑爆炸过程.     

Studies on the Performance and Structure of Supported Catalysts for the Partial Oxidation of Methane to Syngas

The catalytic properties of several supported metal catalysts on different carriers were studied in the partial oxidation of methane (POM) to syngas. In our experiment, supported noble metal catalysts exhibited better performance than the other supported transition metal catalysts. The catalyst performances were significantly influenced by the d-electron configuration of the active metal components and the dispersion of active metal components on the support. A catalyst with a moderate number of unpaired electrons in the d-orbital of the active metal support without obvious acidity or redox activity (e.g. MgO) was suitable for POM performance. The Rh/SiO2 catalyst was the best in the POM reaction, among those investigated. Reaction conditions apparently also affected the POM performance of the catalyst. The conversion of methane and the selectivity for CO increased with the reaction temperature, and a high CH4/O2 ratio was not beneficial for POM performance.