Syntheses and characterization of 16‐arm star and star diblock copolymer and AB8 9‐miktoarm star copolymer via NMRP and ROP from dendritic multifunctional macroinitiators

A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB₈ 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB₈ 9‐miktoarm star copolymers were cleaved by treating with Me₃SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007.     

正丁基苝四羧酸二酰亚胺的晶型和性能研究

文章合成了N,N'-二正丁基苝四羧酸二酰亚胺,并纯化、调晶,进行了IR、元素分析、X射线等测定.分析该化合物在DMF中的紫外光谱(最大吸收波长524.80 nm)、荧光光谱(最大发射波长539.0 nm)、Stokes位移(数值15 nm)等光谱性质.在400～700 nm范围内,α晶型薄膜紫外-可见吸收出现很强的吸收峰,且由β型变为α型,最大吸收波长有明显的红移(545 nm变为580 nm).X射线粉末衍射也反映出α晶型的2θ在26.0°处衍射峰CPS为2 508,β型在25.2°为1 891.α,β晶型作为电荷产生材料制得的功能分离型有机光导体,在光源滤波波长λ=532 nm曝光下,测得含α,β感光体达到饱和电位的时间分别为46,93.98 s,光衰电位(5.3千伏电压负充电电晕,1～2 s后的表面电位)分别为727和525 V,半衰曝光量分别为4.32,4.34μJ·cm-2,残余电位分别为30和45 V等光导性能数值.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.     

枸橼酸莫沙必利的合成

分别以邻羟基对氨基苯甲醇钠，对氟苯甲醛，邻苯二甲酰亚胺为起始原料，制得3个中间体，用其中2个中间体经偶合，环化后与第3个中间体反应，再经成盐制得产品，其摩尔总收率为31．5％。     

Vibrational spectra of (NH4)3ZnCl5

IR and Raman spectra of (NH₄)₃ZnCl₅ have been recorded. The observed spectra have been analysed on the basis of the vibrations of ZnCl ₄ ²⁻ and NH ₄ ⁺ ions. The appearance of multiple Raman bands indicates the presence of two different types of ammonium ions. The effect of anisotropic crystalline field over the ZnCl₄ and NH₄ tetrahedra is also discussed. The assignment of internal modes has been verified by the potential energy distribution calculations.     

Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

Solvent effects in the fluorination of 1,2-dichloro-1,1-difluoroethane (R-132b) to 2-chloro-1,1,1-trifluoroethane (R-133a)

Trichloroethylene has been found to act as a rate enhancing co-factor in the liquid phase, tantalum (V) halide catalyzed, fluorine-for-chlorine exchange reaction of 1,2-dichloro-1,1-difluoroethane (R-132b) to 2-chloro-1,1,1-trifluorethane (R-133a). Several trifluoromethyl substituted benzenes have also been found to be rate-enhancing solvents.     

111In–L–LDL and 153Gd–L–LDL as radiotracers for detection of AR4‐2J rat pancreatic tumors

Pancreatic cancer has an extremely poor prognosis, due, in part, to lack of methods for early diagnosis. The present study was designed to evaluate the potential of labeling low‐density lipoprotein (LDL) with a radionuclide using a lipid chelating agent, bis(stearylamide) of diethylenetriaminepentaacetic acid (L), to detect pancreatic tumors by gamma‐scintigraphy. Previous studies indicated that the difficulty of visualization of pancreatic tumors was due to their poor vascularization. This study compares the ability of two radiotracers, ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL to target highly vascularized rat pancreatic tumors (AR4‐2J) implanted in nude mice. Biodistribution studies showed that the tumor uptake of ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL tracers was twofold and fivefold higher respectively than with the controls (¹¹¹In citrate and ¹⁵³Gd citrate respectively). These tracers would thus be suitable for scintigraphic imaging. We show here that LDL could be employed as a delivery system for tracers such as ¹¹¹In or ¹⁵³Gd when these two radionuclides are complexed by a lipid‐chelating anchor, and that ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL enabled better visualization of the pancreatic tumor tissues, with a better result with ¹⁵³Gd–L–LDL. Copyright © 2004 John Wiley & Sons, Ltd.     

Solution 1H and 13C NMR of new chiral 1,4‐oxazepinium heterocycles and their intermediates from the reaction of 2,4‐pentanedione with α‐L‐amino acids and (R)‐(—)‐2‐phenylglycinol

The reaction of 2,4‐pentanedione ( 1 ) with (R)‐(—)‐2‐phenylglycine methyl ester ( 2 ), (R)‐(—)‐2‐phenylglycinol ( 3 ) and the proteinogenic amino acids (2S,3R)‐(—)‐2‐amino‐3‐hydroxybutyric acid (L ‐threonine) ( 4 ) and (R)‐(—)‐2‐amino‐3‐mercaptopropionic acid (L ‐cysteine) ( 5 ) methyl esters was investigated. The corresponding enamines 6 , 7 and 8 were isolated and characterized spectroscopically whereas 9 , which is unstable, was transformed in situ into 13 . Treatment of 7 , 8 and 9 with boron trifluoride etherate afforded the new [1,4]oxazepines 10 , 11 and [1,4]thiazepine ( 12 ) as their BF₃O^? salts. The structures of the enamines and their corresponding seven‐membered heterocycles were assessed by 1D and 2D NMR spectroscopy. Variable‐temperature experiments revealed different molecular mobility behavior among these heterocycles. Copyright © 2003 John Wiley & Sons, Ltd.