Novel 99mTc labeled σ receptor ligand as a potential tumor imaging agent

A novel ^99mTc labeled complex, [N-[2-((2-oxo-2-(4-(3-phenylpropyl)piperazin-1-yl)ethyl) (2-mercaptoethyl)amino)acetyl]-2-aminoethanethiolato]Technetium(V) oxide (PPPE-MAMA’-^99mTcO) ([ ^99m Tc]-2) has been designed and prepared based on the integrated approach. The corresponding rhenium complex (PPPE-MAMA’-ReO)(Re-2) has been prepared and characterized. In vitro competition binding assays show moderate affinity of Re-2 towards σ₁ and σ₂ receptors with K _i values of 8.67 ± 0.07 and 5.71 ± 1.88 μmol, respectively. Planar images obtained at 0.5 h, 4 h, 20 h after i.v. injection indicate the accumulation of [ ^99m Tc]-2 in MCF-7 human breast tumor bearing mice at 20 h. Furthermore, the accumulation of [ ^99m Tc]-2 has been inhibited at 20 h after co-injection of [ ^99m Tc]-2 plus haloperidol (1 mg/kg). Biodistribution studies of [ ^99m Tc]-2 display an in vivo tumor uptake of 0.14% ± 0.01% ID/g at 24 h post i.v. injection with a tumor/muscle ratio of 6.02 ± 0.87. The above results suggest that [ ^99m Tc]-2, derived from a previously published lead compound, retains certain tumor uptake and affinity for σ receptors. [ ^99m Tc]-2 may be used as a basis for further structural modifications to develop tumor imaging agents with high affinity for σ receptors.     

有机磷化合物的质谱研究(Ⅶ)——二氮二磷杂环戊烷衍生物的化学电离质谱

本文报道了七种4.5-二氧代-2-硫代-1,3,2,4-二氮二磷杂环戊烷衍生物的化学电离质谱(CIMS,甲烷为反应气),结果表明:CIMS中准分子离子MH~+为基峰离子;MH~+离子易发生失去H_2S,CO,C_3H_6等小分子的裂解,(M+C_2H_5)~+离子存在再断裂。     

Design and Theoretical Study of Nickel Catalysts for Syndiotactic Polyolefins

A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position.     

A highly sensitive assay for protein with dibromochloro-arsenazo-Al(3+) using resonance light scattering technique and its application

A simple, sensitive and selective method has been developed for the determination of protein using resonance light scattering (RLS) technique. The method is based on the interaction of protein and arsenazo-DBC-Al(3+) in the pH range of 5.0-7.0, which causes a substantial enhancement of the resonance scattering signal of arsenazo-DBC-Al(3+) in the wavelength range of 300-550 nm with the maximum RLS platform at 405-420 nm. With this method, 2.50-50.00 mug ml(-1) of bovine serum albumin (BSA) and 2.50-60.00 mug ml(-1) of human serum albumin (HSA) can be determined, and the detection limits, calculated three times the standard deviation (S.D.) of six blank measurements, for BSA and HSA were 123.4 and 89.6 ng ml(-1), respectively. Moreover, the method is free from interference from many amino acids and metal ions. The method, with high sensitivity, selectivity and reproducibility, was satisfactorily applied to the determination of total protein in human serum samples. Mechanism studies indicated that arsenazo-DBC-Al(3+) could bind to BSA depending mainly on electrostatic forces, which results in enhanced RLS in the arsenazo-DBC-Al(3+)-protein system.     

Highly efficient rhodium/monodentate phosphoramidite catalyst and its application in the enantioselective hydrogenation of enamides and alpha-dehydroamino acid derivatives

An easily prepared and highly efficient monodentate phosphoramidite ligand derived from BINOL, (S)-2,2'-O,O-(1,1'-binaphthyl)-dioxo-N,N-diethylphospholidine, was examined in the hydrogenation of both enamides and alpha-dehydroamino acid derivatives. The catalyst provided remarkably high enantioselectivities (up to 99.6% ee for enamides and >99.9% ee for alpha-dehydroamino acid derivatives).     

Micellar effects on the electrochemistry of dopamine and its selective detection in the presence of ascorbic acid

The electrochemistry of dopamine (3-hydroxytyramine) was studied by cyclic voltammetry at a glassy carbon electrode in the presence of cetyltrimethylammonium bromide (CTAB) and sodium dodecyl sulfate (SDS) micelles at different pH. The anodic peak potential (E(pa)) and peak current (I(pa)) were found to be remarkably dependent on the charge and the concentration of the surfactant. The E(pa) and I(pa) change abruptly around the critical micellar concentration (CMC) of the surfactants and reach a plateau above the CMC. The E(pa) at the plateau shifts to more positive values in the cationic CTAB micellar solution, e.g. from 180 mV vs SCE in aqueous solution at pH 6.8 to 410 mV in CTAB micelle, whilst it shifts to less positive values in the anionic SDS micellar solution, e.g. 150 mV at pH 6.8. Therefore, the overlapped anodic peaks of dopamine and ascorbic acid in the mixture of the two compounds in aqueous solutions can be separated in CTAB micelles since the micelle shifts the E(pa) of ascorbic acid to less positive values. The two peaks are separated by ca. 400 mV at pH 6.8 in CTAB micelle, hence dopamine can be determined in the presence of 100 times excess of ascorbic acid. In SDS micelle and in the presence of ascorbic acid, the I(pa) of dopamine is greatly enhanced due to the catalytic oxidation of the latter that enables quantitative determination of both compounds.     

风毛菊化学成分研究（Ⅰ）

从风毛菊中分离得到16种化合物,经光谱方法鉴定为山奈素-3-O-(6＂-O-巴豆酰)-β-D-葡萄糖甙(1)、槲皮素-3-O-(6＂-O-巴豆酰)-β-D-葡萄糖甙(2)、丁香甙甲醚(3))、山奈素-3-O-β-D-葡萄糖甙、槲皮素-3-O-β-D-葡萄糖甙、丁香甙、α-香树脂醇棕榈酸酯、β-香树酯醇棕榈酸酯、羽扇豆醇棕榈酸酯、羽扇豆醇乙酸酯、羽扇豆醇、β-谷甾醇、棕榈酸、二十四烷酸、二十六烷酸、二十五烷烃,其中(1)、(2)和(3)为新化合物。     

Two New ent-Kaurane Diterpenoids from Isodon xerophilus

In continuation of our research on diterpenoids in the Isodon species, several newcompounds"' were obtained from the leaves oflsodon xerophilus (C. Y. Wu et H. W. Li)H. Hara (Labiatae), a perennial shrub native to Yunnan province. Further fractionation ofthe EtOAc extract led to the isolation of tWo new enl-kauranoids, xerophilusin E (l) andxerophilusin F (2). This paper deals with the structUral elucidation of the newcompounds.Xerophilusin E (l), a minor constitUent, was obtained as p…     

Analysis of functional groups on the surface of plasma-treated carbon nanofibers

Plasma chemically modified carbon nanofibers were characterized by X-ray photoelectron spectroscopy with regard to the content of carbon, oxygen, and nitrogen and the contribution of carboxylic groups or ester, carbonyl and hydroxylic groups or ether on the surface. Unfortunately, X-ray photoelectron spectroscopy only provides an average value of the first 10 to 15 molecular layers. For comparison, depth profiles were measured and wet chemical methods were applied to estimate the thickness of the functionalized layer and the distribution of oxygen-containing functional groups within the near-surface layers. The results indicate that the fiber surface is covered by a monomolecular oxygen-containing layer and that plasma treatment allows a complete oxygen functionalization of the uppermost surface layer. The best conditions for plasma treatment found within the set of parameters applied to generate complete functionalization are: plasma gas O(2)/Ar ratio 1:1, gas pressure 1-1.5 hPa, plasma power 80 W, treatment time >or= 5 min. Additionally, three quick and easy methods are presented to estimate the efficiency of plasma treatment with regard to surface functionalization: pyrolysis, contact angle measurements, and light permeability measurements of aqueous carbon nanofiber suspensions.     

Novel photopolymerizable biodegradable triblock polymers for tissue engineering scaffolds: synthesis and characterization

For use in micro-patterned scaffolds in tissue engineering, novel diacrylated triblock macromers (PLA-b-PCL-b-PLA, PGA-b-PCL-b-PGA and PCL-b-PEO-b-PCL) were synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and gel permeation chromatography (GPC). All diacrylated polymers were designed as triblock copolymers and involved biodegradable blocks of relatively non-polar epsilon-caprolactone (CL) and polar monomers such as glycolide (GA), lactide (LA) or ethylene oxide (EO). All triblock polymers were prepared in molecular weights of a few kilo daltons via the anionic ring-opening polymerization (ROP) of the corresponding lactide, glycolide or caprolactone using stannous octoate [Sn(Oct)(2)] as catalyst. The polymers had low polydispersity indices, ranging from 1.23 to 1.56. Biodegradable polymeric networks were prepared with conversions of 72-84% via photopolymerization of the triblock diacrylated polymers with 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator. PLA-b-PCL-b-PLA copolymers crumbled easily and were not suitable for micro-patterning. PGA-b-PCL-b-PGA copolymers had higher water contact angles than PCL-b-PEO-b-PCL and were also cytocompatible with Fibroblasts 3T3.