Two New Flavone Glucosides from Serratula strangulata

Genus Serratula（Compositae）consists of about 70 species distributed throughout theworld[1]．Serratula species have been used as folk medicine to treat chickenpox,toxicosis,high cholesterol in China[2]. The phytochemical study of plant S．strangulata has not beenreported so far．In the course of our searching for biologically active substances from thisplant,two new flavone glucosides（1,2）were isolated．The present paper covers the isolationand structural elucidation of the two new compounds．     

Application of many-body green's functions to the calculation of molecular ionization potentials

We present a method for calculating the one-particle Green's function for molecules. The scheme is essentially that proposed by Schneider and Taylor [1]. The Green's function is obtained through the Dyson equation. Closed expressions result by using the functional derivation technique to truncate an infinite set of coupled equations. A physical interpretation of the approximation is given and a connection with the equations-of-motion method is pointed out. In a numerical application the ionization potentials are obtained for the molecules N₂, H₂O, NH₃ and CH₄.     

温和条件下用双组分催化剂催化CO2化学固定成环状碳酸酯

 发现四齿席夫碱铝配合物SalenAlCl和四正丁基碘化铵组成的双组分催化体系可以在室温和常压的温和条件下有效催化二氧化碳与环氧烷烃反应合成相应的环状碳酸酯。环氧烷烃的反应活性是环氧乙烷>环氧丙烷>1,2-环氧丁烷>环氧氯丙烷。提高反应温度有利于增加环加成反应速率。而在高于0.6MPa的压力条件下，增加CO2压力，反应速率略有提高。     

A New Approach to Producing Metaphosphates and Phosphorylating in Mild Conditions

Abstract

The fomation of monomeric metaphosphate has been postulated before, mainly i pyrolytic [1,2] or photolytic [3] fragmentation reactions. Meantime, these reactive intermediats are presumed to participate in the processes of electrophilic phosphorylation in living organisms [4]. In this connection it is reasonable that an active interest is being shown in the development of methods of generating metaphosphates in mild conditions [4–7] compatible with biological systems in order to simulate biological phosphoryl-transfer reactions.     

Hydrophobic Effects in Adsorptive Protein Immobilization

In an aqueous environment, noncovalent polar bonding (i.e., through ionic, charge transfer, or hydrogen bonds) may be assumed to be relatively weak because of thestrong chargesolvating and hydrogen-bonding ability of water. It has been suggested, the refore, that apolar (hydrophobic) forces may be the most important single factor providing the driving force for noncovalent intermolecular interactions in an aqueous milieu [1, 2]. However, in aqueous solutions electrostatic interaction may become important when the pertaining charges are shielded by accompanying hydrophobic groups from the quenching effect of water [1]. In this connection it may be pointed out that, on account of the low dielectric constant of the hydrophobic interior of a protein, intramolecular interaction of oppositely charged surface groups can be strong indeed [3].     

First observations of a spiral instability at the smectic A—cholesteric transition under an electric field

Archimedian spiral wave instabilities have been discovered in chemical [1] and biological systems [2]. We present here the first example of such an instability pattern, encountered in a physical medium [3]. This instability is directly observed by polarized optical microscopy, on a positive dielectric anisotropy smectic A sample with homeotropic organization between parallel glass slides. The arm of the spiral is probably constituted of a 180° Bloch wall, separating indistinguishable smectic domains, and incorporating progressively the helicity of the cholesteric phase, excluded from the smectic.     

Reactivity Ratios for Divinylbenzene and Ethylene Glycol Dimethacrylate Copolymerizations with Styrene and Methyl Methacrylate

The free radical copolymerization of styrene and other vinyl monomers to produce cross-linked, network polymers is of technological importance in the production of ion-exchange resins, packings for gas-liquid and gel permeation chromatography, cross-linked latex polymers, and other products. The principal multifunctional cross-linking monomers which are used in this connection are ethylene glycol dimethacrylate and divinylbenzenes, and accurate values for reactivity ratios in their reactions with bifunctional monomers are essential for the design of copolymerization processes and products.

Wiley and co-workers have reported reactivity ratios for the copolymerizations of these monomers with styrene and with methyl methacrylate [1]. In these studies the reactivity ratios were calculated from the raw data using a graphical “method of intersections” [2]. In this procedure the differential copolymer equation is put into the form     

Inclusion networks of a calix[5]arene-based exoditopic receptor and long-chain alkyldiammonium ions

[structure: see text]. Tail-to-tail connection of two cone calix[5]arene moieties by a rigid p-xylyl spacer affords the new exoditopic receptor 3 featuring two pi-rich cavities (assembling cores) in a centrosymmetric divergent arrangement, as established by a single-crystal X-ray analysis. 1H NMR complexation studies of 3 with alkyldiammonium ions support the formation of discrete bis-endo-cavity complexes and/or capsular assemblies along a polymer chain (polycaps), according to the length of the connector.     

First observations of a spiral instability at the smectic A—cholesteric transition under an electric field

Abstract

Archimedian spiral wave instabilities have been discovered in chemical [1] and biological systems [2]. We present here the first example of such an instability pattern, encountered in a physical medium [3]. This instability is directly observed by polarized optical microscopy, on a positive dielectric anisotropy smectic A sample with homeotropic organization between parallel glass slides. The arm of the spiral is probably constituted of a 180° Bloch wall, separating indistinguishable smectic domains, and incorporating progressively the helicity of the cholesteric phase, excluded from the smectic.     

PRIMARY PRODUCTS IN THE FLASH PHOTOLYSIS OF TRYPTOPHAN*

There has been considerable interest in the photochemistry of tryptophan in connection with ultraviolet inactivation of enzymes. Earlier flash photolysis work has demonstrated that the hydrated electron (e^-_aq) is an initial product in the irradiation of indole derivatives, accompanied by a longer-lived transient absorption near 500 nm attributed to an aromatic radical species[1–5]. Similar transients were observed in a recent flash photolysis study of lysozyme[6] in which it was proposed that inactivation is a consequence of electron ejection from 1 to 2 essential tryptophan residues in the active center. However, there has been uncertainty concerning the tryptophan radical structure and its relationship to the triplet state and radical spectra reported for tryptophan photolysis in low-temperature rigid media. This note reports a flash photolysis investigation of L-tryptophan (Trp) and 1-Methyl-L-tryptophan (1-MeTrp) undertaken to clarify these points. The flash photolysis apparatus and methods employed are described in Ref. [6].     

废弃塑料光催化转化制备低碳数有机化合物

大量废弃塑料引发了一系列的环境和生态问题,其转化和利用一直受到广泛关注.塑料中含有丰富的碳元素,但这些碳元素往往以惰性的C–C键和C–H键形式存在,因此如何利用这些碳资源成为一大难题和挑战.以往部分研究已经提供了塑料催化转化制备碳材料、化学品和燃料的可能性,但是自然界中的废弃塑料总量庞大,需要考虑其转化过程中的能量来源.地球上有丰富的太阳能资源,光催化过程有可能利用太阳能来实现温和条件下的废弃塑料转化.在以往的研究中,光催化塑料降解和光催化塑料重整过程主要关注的目标产物分别是CO₂和H₂.相较而言,光催化塑料转化制备低碳数有机化合物的过程有望助力碳循环经济的发展.近年来报道了一些光催化塑料转化制备低碳数有机化合物的研究工作,这些研究为获取和利用塑料中的碳资源提供了新的研究思路和策略.本文概括对比了光催化塑料降解、光催化塑料重整和光催化塑料转化制备低碳数有机化合物三种过程的差异,包括其中的目标产物和相应的反应活性物种.此外,本文总结了光催化塑料转化制备低碳数化合物的反应方法.简要地说,塑料可以经过光催化选择性氧化、氧化偶联和水解脱氢等策略来得到低碳数的化学品和燃料,涉及利用光催化氧化过程断裂塑料中的C–C键,利用水解过程断裂塑料的C–N和C–O键,以及利用光催化脱氢过程断裂中间产物的O–H键和N–H键等关键步骤.在光催化塑料转化到低碳数有机产物的文献报道中,主要涉及液固相反应体系和反应器,需要考虑反应溶剂的选择.水是理想的溶剂,但对塑料的溶解能力有限.当使用其他有机溶剂时,需要利用同位素标记实验验证产物中的碳物种来源.此外,实际废弃塑料上残留的其他杂质会影响光催化剂的吸光过程,降低光催化反应效率,因此亟需设计和开发合理的光反应器来提高对光能的利用率,实现塑料的高效转化.虽然塑料制备低碳数化学品和燃料的光催化转化策略已有研究报道,但未来仍需探索更加高效的转化路线.此外,塑料主要呈现高分子聚合物的结构,未来的研究可以借鉴对生物质等天然聚合物分子的转化策略.     

Catalytic Properties of Dendrtic PAMAMSA-Zinc Complexes in the Oxidation of Cyclohexene

Denrdrimer has many special properties different from ordinary polymers [1]. In the last few years, much of the research work concerning this kind of compound focuses on its synthesis and physical properties. As to its catalytic properties, several of the reports have been published [2]. We report here a new 1method of using the well-known dendrimer PAMAM[3] (polyamidoamine, G=1～4) and its modified product as the ligands for the coordination of Zn2+ to obtain some dendritic complexes. When these complexes was employed as the catalysts for the oxidation of cyclohexene, the results afforded us some exciting information     

A view and a review of the melting of alkali metal halide crystals

Summary A representational model, proposed to account for the physical changes that accompany the melting of alkali halides, was described in Part 1 [1]. The liquid is portrayed as undergoing continual dynamic structural reorganization of its constituent ions between individual small domains, zones of various regular, crystal-type arrays. These alternative arrangements are stabilized by the enthalpy of melting, which, in liquids, relaxes the restriction for solids that only the single, most stable, crystal structure can be present. The dynamic character of the melt accounts for its fluid character and the loss of long-range order [1, 2]. This model is extended here to consider the phase diagrams of binary, common ion, alkali halide mixtures comprehensively reviewed in [3]. Factors determining whether each of these yields a eutectic, or a solid solution, on cooling are discussed and several trends in the 70-phase diagrams are identified. Eutectic formation, involving maintenance of the liquid state below the melting points of the pure components, is ascribed to the participation, in an extended dynamic equilibrium, of additional domains having the regular structures characteristic of double salts. The known crystalline double binary halides [3], Li/Cs or Rb/F, Cl, Br or I, melt at temperatures well below those of the simpler pure component salts. It is concluded that the set/liq model for melting, proposed in [1, 2], accounts for some important properties of the phase diagrams presented in [3].     

ON THE MECHANISM OF FLUORESCENCE QUENCHING IN PYRENE- AND 3,4-BENZOPYRENE-1,3,7,9-TETRAMETHYLURIC ACID SYSTEMS

T he interaction between aromatic hydrocarbons and purine or its analogues has been widely noted in connection with the possibility of complex formation between carcinogens and DNA or its precursors. Weil-Malherbe[1], Boyland and Green[2] reported that 1,3,7,9-tetramethyluric acid (TMUA) solubilizes aromatic hydrocarbons in aqueous solution and exerts a strong quenching action on fluorescence of the hydrocarbons. The solubilization has been attributed to formation of a molecular complex [2]. Complex formation is now thought to be mainly due to van der Waal's force (polarization and dispersion force) rather than charge transfer ( CT ) one[2,3–5]. Van Duuren [3,5] examined fluorescence spectra of TMUA-hydrocarbon complexes both in solution and in potassium bromide pellets. In solution, the fluorescence spectrum of the complex showed no change in the position of the maximum and in intensity, when compared with that of the free hydrocarbon. In the solid state, however, a blue shift was observed for the fluorescence of the complex. From these results, it was concluded that the complex is entirely dissociated in solution and the fluorescence shift observed in the solid state is the result of the interaction in the excited state. The present note describes a new observation which is useful for understanding the mechanism of fluorescence quenching in the hydrocarbons-TMUA systems.     

On the tautomerism of 5-aminotetrazole

In order to study the connection between the structure of sulfanilamides and their antibacterial action, sulfanilamide derivatives of 1- and 2-methyl-5-aminotetrazoles and of 1,3-dimethyl-5-iminotetrazole have been synthesized. A study of their IR spectra has shown that 1-methyl-5-sulfanilimidotetrazole has the imide structure in the crystalline state and 2-methyl-5-sulfanilamidotetrazole the amide structure. The sulfanilamide derivatives of 1- and 2-methyl-5-aminotetrazoles possess a considerable antibacterial activity, while 1, 3-dimethyl-5-sulfanilimidotetrazole is inactive.For communication V, see [1].     

A calorimetric study of the glass transition kinetics in polyisoprene

The connection between the dielectric and calorimetric relaxation behaviours of synthetic polyisoprene Cariflex IR 305 is studied. A similar comparison of dielectric and dilatometric results was described in [1]. The heat capacity was measured during heating of samples prepared with different thermal history. Experimental results were compared with the heat capacity curves calculated for a model based on the multiparameter theory of Kovacs et al. [4]. The model considers the relaxation system as being composed of a set of subsystems characterized by different relaxation times. The distribution of relaxation times and their temperature dependence were taken from the diclectric measurement. The relaxation time of a subsystem from posed to depend, not only on the actual, temperature of the sample, but also on the deviation of this subsystem from equilibrium, or alternatively, on the deviation of the system as a whole. The comparison between the measured and modeled curves shows that both influences must be taken into account in order to explain the experimental results.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday.     

Total synthesis of (+)-tubelactomicin A. 2. Synthesis of the upper-half segment and completion of the total synthesis

[reaction: see text]. We have completed the total synthesis of natural (+)-tubelactomicin A (1), a 16-membered macrolide antibiotic. This Letter presents a highly efficient synthesis of the upper-half segment (C14-C24) and the completion of the total synthesis featuring a high-yielding Stille coupling for the connection of the upper-half and lower-half segments and Mukaiyama macrolactonization for the construction of the entire structure of 1.     

Studies of 1-azabicyclic compounds. III. The mannich reaction with 1, 2-dihydropyrrolizines

1, 2-Dihydropyrrolizines with position 5 unsubstituted react with aliphatic and cyclic secondary amines under mild conditions to give Mannich bases. The picrates are prepared, and some physical properties of the bases synthesized are described.For part II see [5].     

A Convenient and Easy-controlled Method for Preparation of 7,10-Bis(2,2,2-trichloroethyloxycarbonyl)-10-deacetyl Baccatin Ⅲ

Introduction The complex natural product paclitaxel(Tax-olR, 1a), first isolated from Taxus brevifolia[1], has an excellent clinical activity against ovarian and breast cancers[2] and shows promising results in the treatment of other cancers[3]. The structure-activity relationships(SAR) of taxoid derivatives have been extensively studied to search for the analogues bearing better physical, chemical and biological properties. One example is the discovery of TaxotereR(1b). The structures of Taxol and Taxotere are shown in Scheme 1.