Three new lanthanide coordination polymers containing isophthalate and 1,10-phenanthroline

Three lanthanide coordination polymers were prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. [Pr₂(mBDC)₃(phen)(H₂O)]_n·0.5nH₂O (1) (mBDC=isophthalate, phen=1,10-phenanthroline) exhibits two kinds of metal environments (coordination numbers 7 and 8). In complex 1, mBDC ligands adopt the tetradentate (bridging and bridging) coordination mode and connect Pr ions into an undulating layer, and a 3D supramolecular structure is formed via hydrogen bonds between adjacent layers. [Tb₄(mBDC)₆(phen)]_n (2) has three types of metal environments (coordination numbers 6, 7 and 8) and is composed of a 3D network formed by mBDC linking Tb ions via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. There are two kinds of small quadrilateral channels along the a-axis. [Er₄(mBDC)₆(phen)]_n (3) is isostructural to complex 2.     

Metastasis-suppressor KAI1/CD82 induces homotypic aggregation of human prostate cancer cells through Src-dependent pathway

To investigate the functional role of KAI1/CD82, a metastasis suppressor for human prostate cancer, in the regulation of homotypic cell adhesion, we transfected KAI1 cDNA into DU 145 human prostate cancer cells and established stable transfectant clones with high KAI1/CD82 expression. The KAI1 transfectant cells exhibited significantly increased homotypic cell aggregation in comparison with the control transfectant cells. This aggregation of the KAI1 transfectants was further enhanced upon exposure to anti-CD82 antibody, suggesting that KAI1/CD82 may be involved in the intracellular signaling for the cell adhesion. Among several signal pathway inhibitors tested, PP1, an inhibitor of Src family kinases, significantly suppressed homotypic aggregation of the KAI1 transfectant cells. Ligation of KAI1/CD82 with anti-CD82 antibody increased endogenous Src kinase activity of the KAI1 transfectant cells. When different types of src expression constructs were retransfected into the KAI1-transfected DU 145 cells, kinase-negative mutant src transfectant cells exhibited much lower homotypic aggregation than the mock cells transfected with an empty vector. Moreover, homotypic aggregation of the mutant src transfectant cells was not enhanced by KAI1/CD82 ligation with anti- CD82 antibody. These results suggest that Src mediates the intracellular signaling pathway of KAI1/CD82 for the induction of homotypic adhesion of human prostate cancer cells.     

Improved expression by cytomegalovirus promoter/enhancer and behavior of vascular endothelial growth factor gene after myocardial injection of naked DNA

Direct injection of the vascular endothelial growth factor (VEGF) gene plasmid DNA into the myocardium was shown to induce development of new blood vessels to increase the circulation in the heart of patients with coronary artery diseases. However, such angiogenic gene therapy (via naked DNA) was limited by low level of gene expression. Furthermore, the temporal and spatial characteristics of VEGF gene transfer in the heart are not known. In this study, we demonstrated that a plasmid vector, containing the human cytomegalovirus immediate early (HCMV IE) promoter and enhancer, induces greater expression of gene in the rat heart monitored by gene fused to the chloramphenicol acetyl transferase (CAT) reporter, than four different viral and cellular promoters. Interestingly, expression of VEGF121 protein showed an earlier peak, a shorter duration, and a wider distribution than that of CAT only. Therefore, a plasmid vector with an HCMV IE promoter/enhancer provides clear advantages over other previously developed plasmids. Furthermore, expression profile of VEGF121 gene may provide useful information in the design of angiogenic gene therapy in the heart.     

Synthesis of some dibenzodiazepinone derivatives as potent and m2-selective antimuscarinic compounds

Two series of 5-[[4-[4-(dialkylamino)butyl]-l-cyclohexyl]acetyl], and 5-[(dialkylamino)acyl]-10,11-dihydro-5H- dibenzo[b,e][1,4]diazepin-11-ones were synthesized as potential m2-selective ligands 1,2. Their affinity and selectivity for the muscarinic cholinergic receptor m-AChR subtypes were determined. Replacing a nitrogen with CH in the piperidine ring of 5-[[4-[4-(dialkylamino)butyl]-l-piperidinyl]acetyl]-10,11-dihydro-5H-dibenzo-[b,e][1,4]diazepin-11-ones 3 significantly altered the affinity and selectivity to the muscarinic receptor subtypes.     

硝酸镧与冠醚(2, 2)配合物的晶体及电子结构研究

用X-射线单晶衍射法测定了硝酸镧与冠醚(2,2)配合物的晶体结构,发现其具有与报道的Eu(NO_3)_3(2,2)配合物不同的配位方式.晶体属于三斜晶系,空间群P(?),晶胞参数为a=10.312(2)(?);b=12.745(3)(?);c=8.917(2)(?);α=103.79(2)°;β=112.73(2)°;γ=83.68(2)°;V=1049.5(5)(?)~3;F(000)=587.88;Z=2.结构用重原子法解出;R值为0.0292.用INDO法计算了配合物的净电荷分布,电子结构、键级.结果表明,镧与配位原子间的键具有一定程度的共价性.镧的5d轨道对共价性的贡献最大,而4f轨道基本上不参与成键.La-N比La-O(醚)间存在较强的作用,增大了配合物的稳定性.     

A novel thin-layer amperometric detector based on chemically modified ring-disc electrode and its application for simultaneous measurements of nitric oxide and nitrite in rat brain combined with in vivo microdialysis

A novel thin-layer amperometric detector (TLAD) based on chemically modified ring-disc electrode and its application for simultaneous measurements of nitric oxide (NO) and nitrite (NO₂⁻) in rat brain were demonstrated in this work. The ring-disc electrode was simultaneously sensitive to nitric oxide (NO) and nitrite (NO₂⁻) by modifying its inner disc with electropolymerized film of cobalt(II) tetraaminophthalocyanine (polyCoTAPc)/Nafion and its outer ring with poly(vinylpyridine) (PVP), respectively. The ring-disc electrode was used to constitute a novel TLAD in radial flow cell for simultaneous measurements of NO and NO₂⁻ in rat brain combined with techniques of high performance liquid chromatography (HPLC) and in vivo microdialysis. It was found that the basal concentration of NO in the caudate nucleus of rat brain is lower than 1.0×10⁻⁷ mol l⁻¹, NO₂⁻ concentration is 5.0×10⁻⁷ mol l⁻¹ and NO exists in brain maybe mainly in the form of its decomposed product.     

Patterned and controlled polyelectrolyte fractal growth and aggregations

Two-dimensional patterned and controlled polyelectrolyte aggregations (e.g., tree-like ramified structures) created by microcontact printing have been demonstrated and discussed. Polyelectrolyte-micropatterned aggregations on surfaces were controlled by the micropattern size and shape of PDMS stamps. The formation of aggregates was dependent on the ink and surface conditions, and the aggregates consisted of two distinct layers; strongly adsorbed, primary uniform layers and weakly adsorbed, secondary aggregation layers positioned on top of the primary layers. The adsorption of the primary layers was strong enough not to be washed away, while the aggregated secondary layers were easily removed by washing. The aggregation of secondary layers showed typical tree-like ramified structures of fractal growth and aggregation. Directional and confined stamping led to directing and confining the growth of the fractal polyelectrolyte clusters, respectively. The micropatterned primary uniform layers were not removed by extensive washing, and they were identified by selective nickel plating and charged particle selective adsorption in which the surface formed positive and negative micropatterns. These functional and patterned surfaces have great potentials for advanced devices and sensors.     

磷脂酰胆碱与牛血清白蛋白相互作用的FT-IR研究

利用傅立叶变换红外(FT-IR)和拉曼(FT-Raman)光谱研究了高浓度磷脂酰胆碱(PC)与牛血清白蛋白(BSA)的相互作用,及Eu3＋对该作用的影响.FT-IR结果显示,PC/BSA混合体系中二者的相互作用主要发生在PC头部极性基团,且这一作用随BSA含量的增加而增强,作用后蛋白质二级结构中α螺旋的比例有所增加. FT-Raman光谱说明PC与BSA的相互作用影响磷脂CH链的排列有序程度. PC/BSA/Eu3＋体系的红外光谱显示, Eu3＋与PC的磷氧键发生了强相互作用,并使蛋白α螺旋的比例进一步增加.     

二氧化铈还原表面上水煤气变换反应机理

采用原位红外，程序升温脱附，脉冲表面反应技术研究了ＣｅＯ２还原表面在中温变换反应条件下表面物种的生成及脱附，并根据研究结果归纳出水煤气变换反应机理。     

Sesquiterpene esters from the fruits of Celastrus orbiculatus

Three new beta-dihydroagarofuran sesquiterpene esters, 6 alpha-acetoxy-9 beta-benzoyloxy-1 beta-cinnamoyloxy-8 beta-butanoyloxy-beta-dihydroagarofuran (1), 6 alpha-acetoxy-9 beta-benzoyloxy-1 beta-cinnamoyloxy-8 beta-(2-methylbutanoyloxy)-beta-dihydroagarofuran (2), and 6 alpha-acetoxy-1 beta,8 beta-dibenzoyloxy-9 beta-hydroxy-beta-dihydroagarofuran (6), together with three known compounds (3-5) were isolated from the fruits of Celastrus orbiculatus THUNB. Their structures were elucidated on the basis of spectroscopic methods. Compound 4 showed moderate activity in inhibiting LPS-induced nitric oxide production in murine macrophage RAW264.7 cells with an IC(50) value of 43.7 microM.