Synthesis of palau’amide and its diastereomers: confirmation of its stereostructure

Four diastereomers of palau’amide (1-4), a cytotoxic cyclodepsipeptide, were synthesized. The ¹H NMR spectrum of 1 was identical to that of natural palau’amide. This established the complete stereostructure of palau’amide.     

Separation of Uranium Mixing with its Decayed Nuclides and its Activated Nuclides

Extractions of uranium from the acidic media, HCl and MNO₃ at different concentrations, by the tertiary amines, trilaurylamine, triisooctyllamine and trioctylamine were systematically investigated. In experiments, ²³²U was used as the tracer and aliquots of both phases after extractions were taken, ashed at 500°C, placed onto stainless steel planchets, and measured by a surface-barrier Si(Li) detector connected to an alpha spectrometer. One unique condition found useful for complete separation of uranium was that of the radioactive uranium present in 8 M HCl being extracted with 10% trilaurylamine in xylene. In that case, greater than 95% of the uranium could be extracted into the organic solution, whereas all of the radionuclides of a series of its decayed products, ²²⁸h, ²²⁴Ra, ²²⁰Rn, ²¹⁶Po and ²¹²Bi remained completely in the aqueous solution. The same procedure could also be used for the separation of uranium from a mixture with its activated nuclides. Plutonium-239 and Am were used as the tracers representing the activated nuclides of uranium. It was found that ²⁴¹Am was absolutely not extracted, but that ²³⁹Pu could be extracted with ≥95% efficiency from the medium of 8 M HCl into 10% trilaurylamine in xylene. However, ²³⁹Pu could be easily stripped using the solution mixture of 8 M HCl and 0.05 M NH₄I and excluded from the organic solution.     

A brief summary of electrochemistry: from its beginnings to its present challenges

Journal of Solid State Electrochemistry -     

树枝状大分子PAMAM合成及对蒙脱土插层改性和应用研究

有机阳离子改性蒙脱土已广泛应用于聚合物改性制备高性能聚合物。本文合成了不同代数G0(零代)、G2(二代)的树枝状大分子聚酰胺-胺(PAMAM),同时对G0、G2代PAMAM进行了季铵化改性,得到了PAMAM季铵盐,进一步用PAMAM季铵盐插层改性钠基蒙脱土(Na+-MMT)得到了PAMAM季铵盐改性蒙脱土(PAMAM/MMT)。XRD分析表明,PAMAM季铵盐己与Na+-MMT中的Na+进行了离子交换,同时提出了G0、G2代PAMAM季铵盐对MMT的双分子和单分子插层模型。进一步研究了PAMAM/MMT对聚碳酸酯(PC)的流变性能的影响规律,结果表明PAMAM/MMT可明显降低聚碳酸酯熔融剪切粘度,有利于提高其加工性能。     

青蒿素及其类似物的合成研究-由青蒿素降解产物重组青蒿素

青蒿素1是中药青蒿(Artemisia annua L.)中的抗疟有效成份,它具有与其他抗疟药完全不同的独特结构,近年来,李英等已报道了从青蒿素合成得一系列疗效更高的衍生物,而Schmid等和许杏祥等曾分别独立完成了青蒿素的合成。由于合成其它青蒿素衍生物的需要,我们计划发展较为实用的方法。鉴于目前易于获得天然的青蒿素,因此我们在研究全合成的同时,也探索利用由青蒿素获得接力中间体重组青蒿素和合成青蒿素衍生物。通过酸性降解研究,我们从青蒿素经两步可制得双酮酯化合物3,产率较高。该化合物保持青蒿素中原有的构型,因此是一个理想的接力中间体,本文报道由此化合物重组青蒿素的工作。     

Orientational ordering of a nematic liquid crystal and its mixture with its chain-perfluorinated analogue

The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using ¹³C NMR. The method of proton-encoded local field (PELF) spectroscopy in combination with off-magic-angle spinning (OMAS) of the sample was used. High resolution 2D spectra were obtained, from which the order parameters were calculated. Linear relations between the obtained order parameters and anisotropic chemical shifts determined by 1D ¹³C NMR were established and semi-empirical parameters were achieved. A 1:2 mixture of 7CPB and its chain-perfluorinated analogue (7PFCPB) showed interesting phase behaviour with the change of temperature. It was studied by the use of ¹³C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained from the 2D NMR method.     

Orientational ordering of a nematic liquid crystal and its mixture with its chain-perfluorinated analogue

The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using ¹³C NMR. The method of proton-encoded local field (PELF) spectroscopy in combination with off-magic-angle spinning (OMAS) of the sample was used. High resolution 2D spectra were obtained, from which the order parameters were calculated. Linear relations between the obtained order parameters and anisotropic chemical shifts determined by 1D ¹³C NMR were established and semi-empirical parameters were achieved. A 1:2 mixture of 7CPB and its chain-perfluorinated analogue (7PFCPB) showed interesting phase behaviour with the change of temperature. It was studied by the use of ¹³C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained from the 2D NMR method.     

Simple HPLC-UV determination of nucleosides and its application to the authentication of Cordyceps and its allies

A simple HPLC-UV method combined with a simple extraction procedure of nucleosides (adenosine, cordycepin, 2'-deoxyadenosine, guanosine and uridine) was developed and applied to the authentication of Cordyceps and its allies. The separation was performed on a C(18) column by isocratic elution with acetonitrile-water, and UV detection at 260 nm. The amounts of adenosine, cordycepin, 2'-deoxyadenosine, guanosine and uridine in Cordyceps were 0.28-14.15, 0.006-6.36, 0.01-0.14, 0.68-14.79 and 0.19-20.29 mg/g, respectively. Among the nucleosides studied, cordycepin was characteristically included in Cordyceps militaris (L.) Link. (CM), which is one of key Cordyceps allies, and might be a good marker for authenticating CM. The ratio of nucleosides to adenosine contents in Cordyceps seemed to be a useful marker for authentication and quality control of Cordyceps.     

Electrodeposition of rhenium and its alloys

The processes of electrodeposition of rhenium and its alloys with nickel from aqueous solutions are considered. The results of theoretical and experimental studies of the process of perrhenate ion reduction are analyzed: the data on the possible mechanisms of the cathodic process, participation of atomic hydrogen in it, potentials of transition of rhenium to different oxidation degrees. Codeposition of rhenium and nickel is discussed. The effect of complexation on the current efficiency of rhenium deposition is considered. Information of the sources of data discussed in this paper is provided.     

胞壁酰二肽(MDP)及其类似物的合成

本文报道胞壁酰二肽(MDP)及其类似物MDP[γ-Abu]^1、MDP-Oxalys的合成。应用一些新的合成方法和一种新型高效缩合剂, 简化了合成步骤, 提高了收率。     

Synthesis of Galactosylhydroxylysine and its Analogs

Synthesis of (--)-galactosylhydroxylysine (GHL, I), and its analogs (+)-2 and (+)-3, which are essential for development of assays for osteoporosis, is described starting from (2S,5R)-(+)-hydroxylysine (4).     

Ozonolysis of dipterocarpol and its derivatives

Oxidation of dipterocarpol and its derivatives with ozone gave compounds containing lactone, lactol, alkoxytetrahydrofuran, aldehyde, and methyl ketone fragments in the side chain, as well as 1,2,4-trioxolane fragment in the A ring. The molecular and crystalline structures of dipterocarpol were determined by X-ray analysis.     

Synthesis of Hemigossypol and its Derivatives

Hemigossypol (3), a sesquiterpene natural product, was previously isolated from Gossypium barbadense and was shown to display improved anti-fungal activity compared to gossypol (1), the disesquiterpene dimer of hemigossypol (3). Gossypol exhibits multiple biological activities. In order to study whether hemigossypol and its derivatives retain the various bioactivities of gossypol, we developed a short and convenient synthetic scheme to synthesize hemigossypol. This is the first de novo synthesis of this natural product. In addition derivatives of hemigossypol with various 2,5-alkyl substituents were synthesized. Modification of the synthetic scheme also afforded the natural product hemigossylic lactone (4) and its 2,5-substituted derivatives.     

Halonitromethylation of benzene and its derivatives

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2650–2651, November, 1988.