pH sensitivity of Si--C linked organic monolayers on crystalline silicon surfaces.

The electrochemical behavior of Si--C linked organic monolayers is studied in electrolyte-insulator-Si devices, under conditions normally encountered in potentiometric biosensors, to gain fundamental knowledge on the behavior of such Si electrodes under practical conditions. This is done via titration experiments, Mott-Schottky data analysis, and data fitting using a site-binding model. The results are compared with those of native SiO(2) layers and native SiO(2) layers modified with hexamethyldisilazane. All samples display pH sensitivity. The number of Si--OH groups on the alkylated samples is calculated to be less than 0.7 % of that of a pure SiO(2) insulator, which still causes a pH sensitivity of approximately 25 mV per pH unit in the pH range: 4-7. The alkylated samples hardly suffer from response changes during up- and down-going titrations, which indicates that very little oxide is additionally formed during the measurements. The pK(a) values of all samples with monolayers (4.0-4.4) are lower than that of native SiO(2) (6.0). The long-term drift (of approximately 1 mV h(-1)) is moderate. The results indicate that biosensors composed of alkylated Si substrates are feasible if a cross-sensitivity towards pH in the sensor signal is taken into account.     

Triazole: the Keystone in Glycosylated Molecular Architectures Constructed by a Click Reaction

The copper(I)‐catalyzed modern version of the Huisgen‐type azide–alkyne cycloaddition to give a 1,4‐disubstituted 1,2,3‐triazole unit is introduced as a powerful ligation method for glycoconjugation. Owing to its high chemoselectivity and tolerance of a variety of reaction conditions, this highly atom‐economic and efficient coupling reaction is especially useful for the effective construction of complex glycosylated structures such as clusters, dendrimers, polymers, peptides, and macrocycles. In all cases the triazole ring plays a key role by locking into position the various parts of these molecular architectures. The examples reported and briefly discussed in this short review highlight the use of this reaction in carbohydrate chemistry and pave the way to further developments and applications.     

聚丙烯腈高分子半导体纤维的研究——聚丙烯腈高分子半导纤维的制备及其半导体特性

经四氯化锡处理的聚丙烯腈纤维,在进一步热处理过程中可以成为一种高分子半导纤维。它具有如下四个特点:1.纤维电阻率在10~3—10~(12)欧姆·厘米范围内可以控制热处理温度而随意调节。2.水解处理干燥后纤维的电阻值基本不变。3.有足够的机械强度可以进行多种形式的加工。4.纤维的电阻-温度、电导率-频率依赖关系,直流伏-安特性的试验结果表明它具有有机半导体特性,是一种兼有良好电性能和力学性能的高分子半导纤维。     

丙烯腈在金属镁引发下的聚合动力学

研究了金属镁在硝酸溶液中引发丙烯腈的聚合反应。实验结果表明,聚合速度与金属镁的用量无关,并且当[HNO_3]>[AN]时服从下列关系式: R_p=1.91×10~5e~(-15000/RT)[Mg]~0[AN]~(2.2)[HNO_3]~(0.45) 丙烯腈-丙烯酸甲酯的共聚试验证明,聚合反应是按自由基机理进行。     

Synthesis, crystal structure and studies on properties of trisodium 5,3′,5′-trisulfonate-2,3,4,4′-tetrahydroxy-deoxybenzoin

A new water soluble compound trisodium 5,3′,5′-trisulfonate-2,3,4,4′-tetrahydroxy-deoxybenzoin (TTDB) was synthesized and characterized by IR, UV, ¹H NMR, and elemental analysis. The single crystal of TTDB was determined by X-ray single crystal diffraction. The scavenging effect of compounds on hydroxy radicals was detected by fluorescent spectrophotometry. The electrochemical behavior of compounds in nonaqueous solution DMF was carried out by means of cyclic voltammetry. The experimental result shows that the crystal [C₁₄H₁₇Na₃O₁₈S₃] belongs to monoclinic, space group C2/c with unit cell constants a = 1.4223(4) nm, b = 2.4327(8) nm, c = 1.3596(4) nm, α = 90°, β = 113.044(5)°, γ = 90°, Z = 8, V = 4.329(2) nm³, D _c = 1.925 mg/m³, F(000) = 2568, F _w = 638.43, R ₁ = 0.0950, wR ₂ = 0.2648. The half effective concentration EC₅₀ of scavenging hydroxy radicals of compound THDB is 53.1 μmol/L, while that of scavenging hydroxy radicals of compound TTDB is 47.3μmol/L. The electrochemistry redox processes of THDB and TTDB are different from each other. __________ Translated from Chemical Journal of Chinese Universities, 2005, 26(9) (in Chinese)     

Spectroscopic Interrogation of Layer-by-layer Assembled Films of Conjugated Polyelectrolytes

Layer-by-layer fluorescent conjugated polyelectrolyte films have been studied. The photoluminescence of conjugate polyelectrolytes was observed to be highly tunable during this film assembly process. Efficient photoinduced electron transfer from thus prepared highly luminescent film to a natural electron-transfer protein cytochrome c has also been observed.     

Anordnung und Orientierung kationischer Tenside auf ebenen Silicatoberflächen

Zusammenfassung Die n-Alkylammoniumderivate der glimmerartigen Schichtsilicate können als Modellsubstanzen für die Anordnung kationischer Tenside an Festkörpergrenzflächen herangezogen werden. Im ersten Teil der Arbeit wird die Darstellung durch Kationenaustausch aus den natürlichen Schichtsilicaten beschrieben. Es wird ausführlich auf die Fehlerquellen hingewiesen, die reproduzierbare Messungen erschweren.

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Summary The n-alkylammonium derivatives of mica-type layer silicates are suitable models for studies about the arrangement of cationic tensides at solid interfaces. Part I of the paper deals with the preparation of these compounds by a simple cation exchange reaction. Sources for errors in obtaining reproducible data are discussed in detail.

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Mit 1 Abbildung in 3 Einzeldarstellungen und 3 Tabellen     

Xyloketal G,a Novel Metabolite from the Mangrove Fungus <Emphasis Type="Italic">Xylaria sp.</Emphasis> 2508

A novel metabolite 1, named xyloketal G, was isolated from cultures of marine derived mangrove fungus Xylaria sp. 2508. Its structure was elucidated by analysis of spectroscopic data.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 22–23, January–February, 2005.     

Complete 1H and 13C NMR assignments of four new steroidal glycosides from a gorgonian coral Junceella juncea

Four new cholest-type steroidal glycosides, junceellosides A-D, isolated from the EtOH/CH(2)Cl(2) extracts of the South China Sea gorgonian coral Junceella juncea, were identified. Complete assignments of the (1)H and (13)C NMR chemical shifts for these compounds were achieved by means of one- and two-dimensional NMR techniques, including (1)H-(1)H COSY, HSQC, HMBC and NOESY spectra.     

Synthesis and herbicidal activities of methyl-1-(2,4-dichlorophenoxyacetoxy)alkylphosphonate monosalts

A series of 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5 and its corresponding phosphonate monosalts 6 were synthesized as potential herbicide. The phosphonate monosalts can be prepared from 1-(2,4-dichlorophenoxyacetoxy)alkylphosphonic acid dimethyl esters 5, which were synthesized by the condensation of O,O-dimethyl-1-hydroxyalkylphosphonates with dichlorophenoxyacetic chloride. This method provides a simple and efficient procedure for the synthesis of phosphonate derivatives containing sensitive groups to acid, base or water such as carboxylate ester bond; and the herbicidal activity of title compounds was evaluated in a set of experiments in greenhouse. Most of the compounds exhibited notable herbicidal activity.