Alumina as an Efficient Catalyst for the Preparation of Sulfonyl Hydrazides and Sulfonyl Semicarbazides Under Solvent-free Conditions

Sulfonyl hydrazide and sulfonyl semicarbazide derivatives exhibit variety of bactriostatic activity and also are important compounds as blowing agents in cellular rubber and plastics. Different methods for the preparation of these compounds are reported for example, sulfonyl semicarbazides are prepared by reaction of a sul- fonyl hydrazides with urea or cyanic acid , reaction of sulfinic acid salt with azodicarbonamide in water, and reaction of sulfonyl chloride and semicarbazide. In lots of these methods the yields are not high, the solvents are toxic （pyridine） and also the starting materials are not commericaly available. We now report a modified and convenient procedure for the preparation of these compounds under solvent-free condition.     

New Approach to the Synthesis of C-Glycosides

C-glycosides are important carbohydrate mimetics and have gained considerable attention because ot their attractive biological activities as pharmaceutical targets and their resistance to enzymatic degradation in vivo. Consequently, a large number of C-glycosides have been synthesized for their bioactivity investigation, and various synthetic methodologies have been developed. As a continuation of the synthesis of novel C-glycoside derivatives using exo-glycals as the precursor, we wish to present herein new approaches to the synthesis of C-aryl aminoglycoside via the 1,3-dipolar cycloaddition （Scheme 1 ） and C-disaccharides by Suzuki cross-coupling reaction （Scheme 2）, and the synthesis of dihydropyrimidinonyl （DHPM） glycoside by the three component Biginelli reaction （Scheme 3）.     

The Preparation of Some Novel Indazole Derivatives by Using Chalcones

1 Introduction Indazole and its derivatives have little biological significance and have not been found in natural products due to the difficulty for living organisms to construct an N-N bond. Indazole derivatives exhibit variety of pharmacological properties such as anti-inflammatory, antidepressant, antitumor, antiarthritic and analgesic activities~([1]). Different synthetic pathways generate these compounds. For instance, ring closure of pyrazole moiety, addition of hydrazine derivatives t…     

Solid State Polymer Electrolytes for Dye-sensitized Solar Cell

1 Introduction Over the past decade,Dye-sensitized solar cells (DSSCs) have been intensively investigated as potential alternatives to conventional inorganic photovoltaic devices due to their low production cost and high energy conversion[1-4]. This type of solar cell has achieved an impressive energy conversion efficiency of over 10%,whose electrolyte is a voltaic organic liquid solvent containing iodide/triiodide as redox couple.However,the use of a liquid electrolyte brings difficulties in the practical application of DSSCs because of leakage and evaporation.It is well-known that ionic liquids having unique properties,such as nonvolatility,chemical and electrochemical stabilities,high ionic conductivity and gel-forming properties with polymer.Therefore,ionic liquids have attracted great attention in DSSCs due to their remarkable properties.The poly(theylene oxide) (PEO) is classical polymer matrix for solid polymer electrolyte.Based on this knowledge,our group introduced PEO-imidazole ionic liquid oligomer to electrolyte in DSSCs[2]. The gel electrolytes are also used to replace the liquid electrolytes.The gel electrolytes made from physically cross-linked gelators are unstable and have trouble in permeating into the pores of TiO2 electrodes.Our group introduced the quaternization reaction of two constituents of latent chemically cross-linked gel electrolyte precursors to overcome the permeating problem[3]. Pyridine group in organic molecules or poly(vinylpyridine) contained in the electrolyte not only can improve the open-circuit photovoltage,but also can be the reaction sites of quaternization reaction.The poly (4-vinylpyridine-co-acrylonitrile) has been synthesized and applied in the chemical gel electrolyte[4]. In this study,the copolymer of 4-vinylpyridine and oligo ethylene glycol methyl ether methacrylate was synthesized and used to form all solid state electrolyte or quasi solid state electrolyte with multifunctional halogen derivatives in DSSCs.     

Preparation of dicholesteryl-derivatives: The effect of spatial configuration upon gelation

To investigate the effect of spatial configuration on the gelation properties of low molecular mass gelators(LMMGs),four novel di-cholesteryl derivatives have been specially designed and synthesized by introducing the cis-/trans-isomers of butene diacid and the optical isomers of D/L-phenylalanine into the linker between two cholesteryl moieties.These isomers have been denoted as MaDC,FaDC,MaLC and FaLC,respectively.The gelation properties of the compounds were examined in 26 organic solvents,and it was found that the trans-configuration is more favorable for the gelation,but the chirality of the linker shows little effect to the gelation.FaDC has the strongest gelation ability among the four isomers.Interestingly,FaDC and FaLC display phase-selective gelation of benzene,toluene and xylene from their mixtures with water at room temperature,which establishes a foundation for the purification of water contaminated by oil or aromatic solvents.SEM and CD spectroscopy studies revealed that the spatial configuration of the linkers of the gelators affects significantly the aggregation mode,the morphologies and the chirality of the network of the gels.Moreover,the different aggregation behaviors also have an impact on mechanical properties of the gels,which are consistent with the results from rheological studies.Furthermore,temperature-and concentration-dependent 1 H NMR and FTIR measurements demonstrated that intermolecular hydrogen bonding and-stacking are the main driving forces for the formation of the gels.     

Molecular crystals based on 9,10-distyrylanthracene derivatives with high solid state fluorescence efficiency and uniaxial orientation induced by supramolecular interactions

Two 9,10-distyrylanthracene (DSA) derivatives CNDSA and t-BUDSA were designed and synthesized, and their photophysical properties and crystal structures were investigated. Compared to DSA, the maximum emission peaks of the two compounds showed red-shift not only in THF solution, but also in crystals, because the introduction of electron-withdrawing substituents to DSA leads to more dispersion of the electrons in the molecules. The two crystals of CNDSA and t-BUDSA show strong fluores- cence with the efficiency F of 45% and 33%, respectively, which may be resulted from no obvious-interactions between molecules inside the crystal due to the large distance between the two adjacent molecules and nearly no overlap between the central anthracene planes. The analysis of crystal structures of the two compounds indicated that the molecules are arranged in the same conformation and orientation in their crystals, i.e. uniaxially oriented packing crystal, because of the supramolecular interac- tion of CH/ in the two crystals and additional C-H···N interactions in CNDSA.     

Application of the annexation principle to the thermodynamic property study of ternary metallic melts In-Bi-Cu and In-Sb-Cu

Based on the phase diagrams, measured activities and the annexation principle, calculating models of mass action concentrations for In-Bi-Cu and In-Sb-Cu melts have been formulated. Calculated results not only agree well with practical values, but also obey the mass action law, showing that the deduced model can reflect the structural reality of given melts and that the annexation principle is applicable to these two ternary metallic melts. So long as there is one from three binary systems constituting the ternary melts, in which the activities of one component exhibit positive deviation relative to Raoultian behavior, heterogeous melts inevitably would form, so heterogeneous calculating model should be used to calculate their mass action concentrations. On the contrary, if all the binary melts are homogeneous and their activities exhibit negative deviation with respect to the Raoult's law, then the ternary melts formed from them will certainly be homogeneous,hence single phase model should be applied.     

Optimization of hypocrellin B derivative amphiphilicity and biological activity

To satisfy the dual requirements of the fluent transportation in blood and the affinity to the target tissues of vascular diseases, hypocrellin derivatives with optimized amphiphilicity are expected. In this work, 3-amino-l-propanesulfonic acid and 4-amino-l-butanesulfonic acid substituted hypocrellin B, named compounds 1 and 2, were designed, synthesized in high yields and characterized. Besides greatly strengthened red absorption, the maximum solubility of compound 2 in phosphate buffered saline （PBS） is 4.2 mg/mL which is just enough to prepare an aqueous solution for intravenous injection in clinically acceptable concentration, while the partition coefficient between n-octanol and PBS, 5.6, benefits the cell-uptake and biological activity as well. Furthermore, EPR measurements reveal that the photosensitization activities of the two compounds to generate semiquinone anion radicals, superoxide anion radicals and singlet oxygen are a little bit higher than those of taurine substituted hypocrellin B （THB）, but the photodynamic activities to human lung cancer A549 cells are several times that of THB, mainly due to increases in lipophilicity and cell-uptake.     

Preventing False Trips of Zone 3 Protection Relays in Smart Grid

While remote zone 3 protection relays are essential to power systems, their false trips are also one of main causes related to cascading blackouts. Although many methods have been developed on traditional power systems to address this issue, the past cascading failure events showed the ineffectiveness of these methods.With the development of Smart Grid(SG), new agent-based methods have been proposed to address this issue by utilizing SG real-time communications. We found that these solutions simply assume ideal communication networks and do not consider the effect of practical network constraints and resource management. In this paper,we propose several solutions to address practical network resource management and constraints, and further improve the agent-based solutions in order to prevent the false tripping of zone 3 relays in various conditions. We also analyze the potential issues of these solutions, and point out the future investigation in this direction.     

Effect of bromization on the properties of a series of sub-stituted 1,8,15,22-tetra(2,4-ditertbutylphenoxy) phthalocyanines

As a novel kind of functional dyes, phthalocyanines and metallophthalocyanines have been attracting the at-tention of many scientists for many years. Recently, the chemistry of Pcs has been undergoing a renaissance because Pcs and many of their derivatives exhibit theirproperties for potential application in materials science[1,2 One of the main questions in the field of phthalocya-nines research is to modify the molecular structure re-placing the benzene-spherical hydrogen atoms by various s…     

竹红菌素类光动力药物

竹红菌素作为一类新型的光动力药物,与卟啉类化合物相比,具有化学组成单一、易纯化等优点．文章综述了近年来竹红菌素类光动力药物的研究进展,包括竹红菌素的化学修饰和物理包裹,并对其未来的研究方向作了展望．     

Modified Dye for Water-Fast Ink-Jet Printing

A quaternary ammonium compound containing amino acid residue was synthesized by Converting 3-chloro-2-hydroxy-propyalkyldimethylammonium chlorides into its epoxide derivatives, then attaching an amino acid to the epoxide derivatives synthesized a quaternary ammonium compound containing amino acid residue. Modified dyes were prepared by the ionotropy of anionic dyes with the quaternary ammonium compound containing amino acid residue. It was discovered that the modified dyes exhibited an excellent pH controllable solubility. These modified dyes have good water solubility at pH> 8.0, but they were water insoluble at pH < 6.5. On the printing paper, modified dyes in water-based ink-jet print ink could convert to water insoluble form and give prints excellent water fastness.     

一些有机染料和中间体的SHG效应

采用固体粉末方法，测试了苯系偶氮、嘧啶、吡啶酮、四氢喹啉甲川型染料，以及中间体共６２个有机分子的ＳＨＧ效应，发现其中１４个品种具有ＳＨＧ活性。考察了影响ＳＨＧ效应的有关因素，发现电子效应基本一致的硝基和氰基取代染料，呈现出完全不同的ＳＨＧ性质。说明电子效应并不是影响有机分子ＳＨＧ活性的唯一因素，ＰＰＰ－ＭＯ理论计算结果也证实了这点。     

生物活性多甲氧基黄酮羧酸和氨基酸衍生物的合成及其结构表征

多甲氧基黄酮(PMFs)是一类存在于柑橘属植物中具有显著抗癌、抗炎和抗氧化等生物活性的天然产物。为了提高多甲氧基黄酮类化合物的水溶性和药用价值,以2种来源丰富且抗癌活性高的多甲氧基黄酮橘皮素和川陈皮素为底物,分别经过氧丙酮氧化得到多甲氧基黄酮醇[3-羟基橘皮素(7)和3-羟基川陈皮素(8)],化合物7和化合物8分别在K₂CO₃和N,N-二甲基甲酰胺条件下与氯乙酸乙酯进行Williamson反应,生成了多甲氧基黄酮羧酸酯类衍生物,再经碱性水解合成了2种未见文献报道的多甲氧基黄酮羧酸衍生物[橘皮素-3-O-乙酸(1)和川陈皮素-3-O-乙酸(2)]。化合物1和化合物2在CH₂Cl₂作溶剂、1-(3-二甲基丙胺)-3-乙基碳二亚胺盐酸盐为缩合剂和4-N,N-二甲氨基吡啶为辅助剂的条件下,分别与2种不同的氨基酸甲酯盐酸盐发生缩合反应,得橘皮素和川陈皮素的氨基酸甲酯衍生物,然后经水解反应得到了4种新型多甲氧基黄酮氨基酸衍生物3～6。对所合成的化合物用¹H NMR、¹³C NMR和MS等方法进行了结构表征。     

Photophysics, photochemistry and photobiology of hypocrellin photosensitizers

Hypocrellins are novel photosensitizers from China, which are demonstrated to have significant anti- tumor and anti-virus activity and to be potential photo- dynamic therapy (PDT) agents. As compared with hemato- porphyrin, the only approved photosensitizer, hypocrellins have several advantages, such as easy preparation and easy purification, high triplet quantum yield, high singlet-oxygen quantum yield, high phototoxicity but low dark toxicity, and rapid clearance from normal issues. This article reviews briefly the photophysics, photochemistry and photobiology of hypocrellins on the basis of the domestic and international research results.     

Photochemistry of hypocrellin derivatives under aerobic conditions

Hypocrellins are a novel type of photosensitizers. A series of new hypocrellin B (HB) derivatives have been synthesized to overcome their limitations, i.e. to improve their red absorption and amphiphilicity. The generation of reactive oxygen species (including Superoxide anion radical, hydroxyl radical and singlet oxygen) is investigated in the presence of oxygen. The chemical structures of HB derivatives affect not only the generation efficiencies of Superoxide and hydroxyl radicals, but also quantum yields of singlet oxygen.     

烷氧基铜酞菁的合成及溶解性的研究

用固相法合成了2种烷氧基取代的铜酞菁金属配合物.采用红外光谱、紫外一可见光谱对所合成的化合物进行了表征,同时也进行了溶解性的研究.结果表明:2种配合物红外光谱相似,最大吸收波长分别为720和668 nm;2种配合物均能溶于二氯甲烷、乙酸乙酯,解决了酞菁在有机溶剂中的溶解性问题,为其进一步应用提供了依据.     

Photochemistry of hypocrellin derivatives under anaerobic conditions

To improve the red absorption and solubility of hypocrellin, we have synthesized a series of hypocrellin B derivatives. The photochemistry of these new compounds in anaerobic media has been investigated by using electronic paramagnetic resonance (EPR) and spectrophotometric methods. The semiquinone anion radicals can be produced by self-electron transfer on irradiation, with the formation efficiency and EPR hyperfine structures of the semiquinone anion radicals dependent on the structures of the derivatives. When an electron donor is present, the electron transfer from electron donor to hypocrellin B derivatives enhanced the production of the corresponding semiquinone anion radical; in addition, the semiquinone anion radical and hydroquinone can be detected spectrophotometrically. Structural modifications exert little effect on the absorption position of semiquinone anion radical and hydroquinone, but influence their formation efficiency significantly.     

富勒烯生物分子衍生物合成的研究进展

富勒烯生物分子衍生物的合成是改善富勒烯水溶性的重要策略,本文对几大类富勒烯生物分子衍生物的合成进行了综述,还讨论并提出了这类物质的研究前景和展望。