Gd替代对La0.6-xGdxSr1.4MnO4磁性和输运性质的影响

随着x的增加，多晶La0.6-xGdxSr1.4MnO4（x=0, 0.1, 0.2, 0.4, 0.6）的零场冷却 曲线从类自旋玻璃型转变成顺磁型，并且每条零场冷却 曲线都有一在20K的拐点。这一行为可以从Gd和Mn各自对材料总磁性的不同贡献来理解。另外，在所有的样品中，从100K到室温，都观察到了热激活导电行为。由于Mn-Mn间强的反铁磁耦和，直到外场达到50 kOe，都没有观察到明显的磁电阻效应。     

Effects of the sever on two-stage gyro-TWT amplifiers

The effects of the sever on two-stage gyro-TWT amplifiers were characterized by a self-consistent slow time scale model. Utilization of a sever was demonstrated to be capable of inducing additional launching losses as well as ballistic bunching effects. In addition, some electrons could bunch on an electron phase equal to 3π/2 at the beginning of the second stage as a result of a large and sharp change of the wave’s phase if the modulation of the electron beam in the first stage was strong. Calculated results further indicated that the performance was more sensitive to the position of sever than the length of the sever. Asymmetric interaction structures with the first stage being shorter than the second stage demonstrated higher saturated powers and wider bandwidths along with exhibiting more resistance to the velocity spread of the electron beam.     

气缸垫对机体受力和缸套变形影响的实验研究

某四缸柴油机在试制中出现机体裂纹现象，为保证内燃机正常工作，机体裂纹问题急待处理．应用力学理论对此进行分析，得出机体裂纹是由机体受力不均匀引起的结论．同时采用实验应力分析方法，对两种四缸柴油机机体进行了对比实验研究，在实验中发现了缸垫对机体受力和缸套变形的影响，从而提出了一种有效的改进方法，使机体的应力有明显下降，并不再出现裂纹，也未出现漏油、漏气和活塞拉缸等不良现象，大大提高了产品可靠性．     

Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C–H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.     

Synthesis,structure and characterization of two new metal–organic coordination polymers based on the ligand 5‐iodobenzene‐1,3‐dicarboxylate

Two new coordination polymers (CPs) formed from 5‐iodobenzene‐1,3‐dicarboxylic acid (H₂iip) in the presence of the flexible 1,4‐bis(1H‐imidazol‐1‐yl)butane (bimb) auxiliary ligand, namely poly[[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ²N³:N^3′](μ₃‐5‐iodobenzene‐1,3‐dicarboxylato‐κ⁴O¹,O^1′:O³:O^3′)cobalt(II)], [Co(C₈H₃IO₄)(C₁₀H₁₄N₄)]_n or [Co(iip)(bimb)]_n, (1), and poly[[[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ²N³:N^3′](μ₂‐5‐iodobenzene‐1,3‐dicarboxylato‐κ²O¹:O³)zinc(II)] trihydrate], {[Zn(C₈H₃IO₄)(C₁₀H₁₄N₄)]·3H₂O}_n or {[Zn(iip)(bimb)]·3H₂O}_n, (2), were synthesized and characterized by FT–IR spectroscopy, thermogravimetric analysis (TGA), solid‐state UV–Vis spectroscopy, single‐crystal X‐ray diffraction analysis and powder X‐ray diffraction analysis (PXRD). The iip²⁻ ligand in (1) adopts the (κ¹,κ¹‐μ₂)(κ¹, κ¹‐μ₁)‐μ₃ coordination mode, linking adjacent secondary building units into a ladder‐like chain. These chains are further connected by the flexible bimb ligand in a trans–trans–trans conformation. As a result, a twofold three‐dimensional interpenetrating α‐Po network is formed. Complex (2) exhibits a two‐dimensional (4,4) topological network architecture in which the iip²⁻ ligand shows the (κ¹)(κ¹)‐μ₂ coordination mode. The solid‐state UV–Vis spectra of (1) and (2) were investigated, together with the fluorescence properties of (2) in the solid state.     

Synthesis,structure, and DNA-binding properties of manganese(II) and zinc(II) complexes with tris(<Emphasis Type="Italic">N</Emphasis>-methylbenzimidazol-2-ylmethyl)amine ligand

Tris(N-methylbenzimidazol-2-ylmethyl)amine (Mentb) and its two complexes, [Mn(Mentb)(DMF)(H₂O)](pic)₂ 1 and [Zn(Mentb)(pic)](pic) 2 (pic = picrate), have been synthesized and characterized by physico-chemical and spectroscopic methods. Single crystal X-ray diffraction revealed that the two complexes have different structures. In complex 1, the coordination sphere around Mn(II) is distorted octahedral, whereas in complex 2 the coordination sphere around Zn(II) is distorted trigonal bipyramidal. The DNA-binding properties of the free ligand and its two complexes have been investigated by electronic absorption, fluorescence, and viscosity measurements. The results suggest that the ligand and its two complexes bind to DNA via an intercalation binding mode, and their binding affinity for DNA follows the order 1 > 2 > ligand.     

A Schiff base ligand <Emphasis Type="Italic">N</Emphasis>-(2-hydroxylacetophenone)-3-oxapentane-1,5-diamine and its nickel(II) complex: synthesis,crystal structure,antioxidation, and DNA-binding properties

A new Schiff base ligand N-(2-hydroxylacetophenone)-3-oxapentane-1,5-diamine (HL) and its Ni complex, [Ni₂(L)₂(NO₃)₂], have been synthesized and characterized by physicochemical and spectroscopic methods. The X-ray crystal structure of [Ni₂(L)₂(NO₃)₂] shows it to be a dinuclear 2:2 complex, in which each Ni(II) atom is in a distorted octahedral geometry. The two Ni(II) atoms are dibridged by two phenoxo ligands, forming a Ni₂O₂ parallelogram-type moiety. The interactions between free HL and the complex with calf thymus DNA have been investigated, and the binding constant and linear Stern–Volmer quenching constant suggest that the two compounds bind to DNA via the intercalation mode. The binding affinity of the complex was higher than that of HL. Antioxidant assays in vitro showed that the Ni(II) complex possesses significant antioxidant activity.     

Using an on-line microdialysis/HPLC system for the simultaneous determination of melamine and cyanuric acid in non-dairy creamer

The recent revelation of melamine (MEL) contamination in foodstuffs in China has rocked the international public health community. Many food categories have been involved in this scandal, including non-dairy creamer (NDC). In this study, we investigated the use of hollow-fiber microdialysis (MD) sampling coupled on-line with high-performance liquid chromatography (HPLC) as an alternative to sample pretreatment for the direct determination of MEL and its analogue cyanuric acid (CYA) in NDC. After MD sampling, the dialysate was injected on-line into the chromatographic system for analysis of MEL and CYA with UV detection at 203 nm. We monitored the effects of various parameters affecting the MD efficiency, namely the characteristics of the MD probe membrane, the flow-rate and the nature of the polarity modifier in the perfusion stream, and the addition of salt in the sample solution. The optimal enrichment efficiency for collecting MEL and CYA from aqueous NDC samples occurred with MD sampling using a hollow polysulfone MD fiber and MeOH as the perfusate at a flow rate of 10 μL min⁻¹. The optimized chromatographic conditions involved using a reversed-phase phenyl column and a mobile phase of 5 mM phosphate buffer in 10% (v/v) MeOH, buffered at pH 6.5. Detection was linear in the concentration range from 0.02 to 5 ppm for MEL and from 2 to 100 ppm for CYA, with detection limits of 1 ppb for MEL and 30 ppb for CYA. The volume of perfusate required to extract MEL and CYA from the NDC solution was only 21 μL. The total MD sampling time was 2.1 min. This method allows the sensitive, eco-friendly, and rapid determination of MEL and CYA in NDC—a risk food for economically motivated adulteration.     

Total synthesis of optically active lycopladine A by utilizing diastereoselective protection of carbonyl group in a 1,3-cyclohexanedione derivative

We successfully synthesized two enantiomers of bicyclic enones, (7R,7aR)- and (7S,7aS)-9, from the hemiacetal 2a, which we first synthesized from the symmetrical diketone 1a via diastereoselective carbon-oxygen bond formation between one of the carbonyl groups and the chiral alcohol on the C2 side chain in a 2,2-disubstituted 1,3-cycloalkanedione derivative. We also report the total synthesis of natural (+)-lycopladine A [(+)-6] from (7R,7aR)-9 and the formal synthesis of unnatural (-)-lycopladine A [(-)-6] from (7S,7aS)-9.