Tri-component diblock copolymers of poly(ethylene glycol)–poly(ε-caprolactone-<Emphasis Type="Italic">co</Emphasis>-lactide): synthesis,characterization and loading camptothecin

Biodegradable tri-component diblock copolymer was synthesized by bulk copolymerization of ε-caprolactone (CL) and D, L-lactide (LA) in the presence of methoxy poly(ethylene glycol) (MePEG), using stannous octoate as catalyst. Their chemical structure and physical properties were investigated by GPC, NMR, DSC, TGAand XRD. The increase of CL/LA ratio in the diblock copolymer leads to lower T _g, higher decomposition temperature and crystallinity. Nanoparticles formulated from MePEG–poly(CL-co-LA) (PCAE) possess spherical structure, which was characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The DLS results indicate that the particle size increased with the increase of CL/LA ratio and the hydrophobic fragment length in the copolymer. The drug encapsulation efficiency and the drug release behavior in vitro conditions of camptothecin were measured by high performance liquid chromatography (HPLC). The encapsulation efficiency can be achieved as high as 84.4% and the release behavior can be made well-controlled. MePEG–poly(CL-co-LA) nanoparticles might have a great potential as carriers for hydrophobic drugs.     

Substituenteneffekte auf die C–C-Bindungsstärke, 8. Standardbildungsenthalpien und Spannungsenthalpien von 1,1,2,2-Tetraethylethylenglykol-dimethylether und D,L-1,2-Dimethyl-1,2-diphenylethylenglykol-dimethylether

Effects of Substituents on the Strength of C - C Bonds, 8¹. - Heats of Formation and Strain of 1,1,2,2-Tetraethylethylene Glycol Dimethyl Ether and D,L .-1,2-Dimethyl-l,2-diphenylethylene Glycol Dimethyl Ether The heats of combustion of the title compounds 1 and 2 were measured calorimetrically with the result (kcal mol ^-1, s. d. in parentheses) ΔH°_c = − 1880.1 (± 0.6) and − 2373.3 (± 1.4). The heat of vaporisation of 1 ΔH^v = 14.3 (± 0.3) and the heat of sublimation of 2 ΔH^sub = 27.2 (± 0.5) were derived from their temperature dependance of the vapor pressure. The latter were determined between 30 and 80°C using a flow method. The resulting standard heats of formation ΔH°_t(g) = −122.4 (± 0.7) and −43.8 (±1.5) for 1 and 2 correspond to a strain enthalpy (_s) of 15.9 and 8.0 kcal mol^-1, respectively. The steric strain of the dimethoxyethanes 1 and 2 is about one fourth lower than the strain of the corresponding dimethylethanes 3 and 4 bearing the same substituents. Thus, a methoxy group causes less steric stress than a methyl group.     

薄层色谱法在香兰素合成中的应用

应用薄层色谱法对愈创木酚、3－甲氧基－4－羟基扁桃酸和香兰素进行了分析，以硅胶GF254作为吸附剂，从几种溶剂系统中选出氯仿：乙酸乙酯：正丙醇：冰乙酸：水＝20：1：1：1：2溶液作为展开剂。建立了 香兰素的薄层扫描定量分析方法，测定波长为500nm，参比波长为570nm，线性范围为0．31－6．2μg。     

富勒烯四甲氧基衍生物的合成与表征

富勒烯四甲氧基衍生物的合成与表征甘良兵，周胜，姜剑峰，黄春辉（北京大学化学与分子工程学院，北京，１００８７１）武轶，吕木坚，潘景歧（北京微量化学研究所）（北京大学分析测试中心）关键词Ｃ＿６０衍生物，甲氧基，四氮杂环十二烷富勒烯化学是目前人们研究的热门...     

Tocopherols and Triterpenoids from Sida acuta

A new tocopherol derivative, 7_a‐methoxy‐α‐tocopherol ( 1 ), and a new taraxastane triterpene, taraxast‐1,20(30)‐dien‐3‐one ( 5 ), together with four known compounds, β‐tocopherol ( 2 ), α‐tocopherol ( 3 ), α‐tocospiro B ( 4 ) and taraxasterone ( 6 ) were isolated from the whole plant of Sida acuta. Their structures were elucidated by spectral analysis including MS, 1D and 2D‐NMR spectroscopy. Among those compounds, compounds 1 , 2 , and 3 showed significant antioxidant effect (EC₅₀ = 86.9, 68.2, and 70.9 μM, respectively) in the DPPH radicals scavenging activity assay.     

Highly Regio- and Stereoselective Synthesis of β-Halohydrins from Epoxides Catalyzed with Ceric Ammonium Nitrate

Ce(IV) as ceric ammonium nitrate can effectively catalyze ring opening of epoxides with halides under very mild conditions and easy procedure to give the corresponding β-chloro-and β-bromohydrins in excellent yields. The reactions occur with both substituted and unsubstituted quaternary ammonium halides and with high regio- and stereoselectivity. The reaction of optically active styrene oxide with chloride ion was found to be highly stereospecific and afforded the corresponding β-halohydrin in 96% ee.     

Enantioseparation of chiral aromatic acids by multiple dual mode counter‐current chromatography using hydroxypropyl‐β‐cyclodextrin as chiral selector

This work concentrates on extending the utilization of multiple dual mode (MDM) counter‐current chromatography in chiral separations. Two aromatic acids, 2‐(6‐methoxy‐2‐naphthyl)propionic acid (NAP) and 2‐phenylpropionic acid (2‐PPA), were enantioseparated by MDM counter‐current chromatography using hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as chiral selector. The two‐phase solvent systems consisting of n‐hexane/ethyl acetate 0.1 mol/L phosphate buffer pH 2.67 containing 0.1 mol/L HP‐β‐CD (7.5:2.5:10 for NAP and 7:3:10 for 2‐PPA, v/v/v) were used. Conventional MDM and modified MDM were compared according to peak resolution under current separation mechanism. The influence of elution time after the first‐phase inversion and number of cycles for MDM were investigated. Peak resolution of NAP and 2‐PPA increased from 0.62 to 1.05 and 0.72 to 0.84, respectively, using optimized MDM conditions. Being an alternative elution method for counter‐current chromatography, MDM elution greatly improved peak resolution in chiral separations.     

Synthesis of 7‐Alkoxy/Hydroxy‐α‐methyltryptamines

Abstract

A simple method for the preparation of 7‐alkoxy/hydroxy‐α‐methyl‐DL‐tryptamines is reported. The key steps of the synthesis are the Japp–Klingemann coupling of 2‐piperidone‐3‐carboxylic acid 3 with diazonium salts 4, the Fischer‐type cyclization of hydrazones 5 to β‐carboline derivatives 6 and their hydrolysis to title compounds 8.     

Electrospray Ionization Mass Spectra of Amino Acid Methyl Ester 5′-Phosphoramidates of 2′,3′-Isopropylideneuridine

Amino acid methyl ester phosphates were synthesized and determined by using positive-ion mode electrospray ionization mass spectrometry(ESIMS) in combination with multistage tandem mass spectrometry. The fragmentation pathways were investigated, and it was observed that most fragment ions contained the phosphoryl group. It was interesting to observe that the fragmentation pathways of the protonated molecule show some differences when compared with those of the sodium ion adduct. The methoxy group of amino acid methyl ester can migrate from the carbonyl group to the phosphoryl group in the sodium ion adduct.