Synthesis and derivatisation of a novel spiro[1-benzofuran-2,4'-piperidin]-3-one scaffold

The synthesis of a novel spiro[1-benzofuran-2,4'-piperidin]-3-one scaffold has been achieved in five steps with an overall yield of 47%. The versatility of the spiropiperidine scaffold in the context of library synthesis is exemplified by selective and sequential derivatisation of the amino and aryl bromide functional groups, including the development of multi-step telescope reaction matrices.     

Synthesis of constrained analogues of cholecystokinin/opioid chimeric peptides

In our ongoing research on the synthesis of constrained analogues of CCK/opioid chimeric peptides, a bicyclic dipeptide mimetic for Nle-Asp was designed and synthesized. Starting from β-allyl substituted aspartic acids, the terminal double bond was oxidized resulting in spontaneous cyclization to form racemic hemiaminals. Allylation of the hemiaminals afforded 5-allyl substituted proline analogues, which on oxidation, Horner-Emmons olefination, asymmetric hydrogenation, and bicyclization afforded bicyclic dipeptide mimetics for Nle-Asp. Constrained CCK/opioid peptide analogues containing bicyclic dipeptide mimetics for Nle-Gly, Nle-Asp, and homoPhe-Gly were then synthesized and analyzed at both the CCK and opioid receptors.     

First synthesis of perfluorinated corrole and its mn=o complex

A novel perfluorinated corrole, 2,3,7,8,12,13,17,18-octafluoro-5,10,15-tris(pentafluorophenyl)corrole, and its manganese(III) and oxomanganese(V) derivatives have been synthesized. The perfluorinated manganese corrolate exhibited excellent reactivity and stability in the catalytic oxidation of alkenes with iodosylbenzene.     

CH3(2A′)自由基与臭氧反应机理的量子化学研究

用量子化学UMP2方法，在6-311++G**基组水平上研究了CH3(2A′)自由基与臭氧反应机理，全参数优化了反应过程中反应物、中间体、过渡态和产物的几何构型，在UQCISD(T)/6-311++G**水平上计算了它们的能量；并对它们进行了振动分析，以确定中间体和过渡态的真实性；同时应用经典过渡态理论计算了反应的速率常数，并与实验值进行了比较, CH3自由基与臭氧反应速率常数的理论计算结果为: 4.73×10－14 cm3•molecule－1•s－1，与实验报导的结果(k=2.52×10－14 cm3•molecule－1•s－1)很接近，同时发现CH3(2A′)自由基与O3的反应是强放热反应.     

Kinetics of the Reduction of Cupric Ion in Ammonia Solution by Sulfur Dioxide

The reduction of cupric ion in ammonia solution by aqueous sulfur dioxide was studied. Each run was carried out at constant initial cupric concentration, stirred rate and total mixed gas flow rate. The effect of temperature, partial pressure of sulfur dioxide in gas phase and cupric ion concentration of the solution was investigated. The reaction of Cu³⁺+SO₂(aq.)→Cu⁺+SO₄^2? was carried out by bubbling mixed gas (SO₂/N₂) through the aqueous ammonia complex of copper (II). The color change for the system was from deep blue, green, yellow to white. The pH values in the system changed from 10 to 4. The product of the reaction was identified by the analyses of IR spectrum and X-ray diffraction, having the formula of 7Cu₂SO₃· 2CuSO₃·3(NH₄)₂SO₃·24H₂O. The kinetic model of the reduction was proposed as: –d[Cu²⁺]/dt = k exp(–E/RT)[Cu²⁺]α[SO₂%] According to the experiments, the parameters were determined as: α=1.64±0.03, þ=1.20, E=13.7 Kcal/mol and k = (1.77±0.20)×10¹⁰ (g-equ./?)^?0.64min^?2.     

Three Novel Triterpenoids from the Aerial Part of Helwingia chinensis

Three novel triterpenoids named chinenols A – C ( 1 – 3 ), together with two known compounds, glutin‐5‐en‐3β‐ol ( 4 ) and daucosterol ( 5 ), were isolated from the aerial part of Helwingia chinensis Batal . The structures of 1 – 3 were determined on the basis of their HR‐EI‐MS, IR, ¹H‐ and ¹³C‐NMR (DEPT), and 2D (HMQC, HMBC, NOESY) data. Compounds 1 – 3 and 5 showed inhibition activity in an antibacterial assay.     

Smectic Bimetallomesogens: Synthesis and Mesomorphic Properties in Oxygen-Bridged Dicopper and Divanadyl Complexes

The synthesis and mesomorphic properties of a homologous series of N-(3-hydroxypropyl)-4-alkoxylsalicylaldimine, N-(3-hydroxypropyl)-4-(4′-alkoxybenzoxy)salicylaldimine, and their dicopper(II) and di-oxovanadium(VI) complexes are reported. Copper complexes exhibited monotropic smectic A phases; however, vanadyl complexes showed no mesomorphism. A systematic comparison revealed that the meso-genie behaviors of these bimetallic complexes are induced by the weak intermolecular force and determined mainly by the central metal. The effects on the structural variations near the metal central cores and side chain density are also discussed.     

偶氮胂酸型荧光试剂测定铝的研究

比较了５种新试剂及偶氮胂－Ｉ的铝铬合物的荧光性能，讨论了试剂结构与性能之间的关系。试验出７－〔（４－甲基－２－胂酸基苯）偶氮〕－８－羟基喹啉－５－磺酸为铝的优良荧光试剂，并用其测定茶叶、含茶叶饲料，以及大白鼠排泄物中的铝和水样中的铝，结果满意。