加有“引浪板”的固定式气动型波能转换装置水动力性能的计算

寻找和利用新能源是目前人们普遍感兴趣的问题。海洋波浪能作为一种新的再生型替代能源正引起人们极大的注意。本文对波能转换装置中的一种——侧向开口固定式气动型波能转换装置的性能进行了理论计算,对以往常规形式的转换装置的开口形式进行了改进,加装了“引浪板”。通过理论计算证明,加装“引浪板”后,气室的转换性能有了较大的提高,找到了“引浪板”的最佳倾角,并与试验结果进行了比较。计算采用格林函数法,通过内外场的匹配求解流场。文中所用方法具有一定的普遍意义。     

Strukturelle Abwandlungen an N-Acetylneuraminsäuren, 8 Synthese von 7-, 8-, 9-Desoxy- und 4,7-Didesoxyneuraminsäure

The 7- and 8-Iodnonulosonic acid derivatives1 and2 react with tributyltinhydride-AIBN to the 7- and 8-deoxy-N-acetylneuraminic acid derivatives3 a and4 a which after hydrolysis give the 7-deoxy-N-acetylneuraminic acid3 b (5-N-acetamido-3,5,7-trideoxy--D-galacto-2-nonulopyranosidonic acid=7-Deoxy-Neu5Ac) and 8-deoxy-N-acetylneuraminic acid4 b (5-N-acetamido-3,5,8-trideoxy--D-galacto-2-nonulopyranosidonic acid=8-Deoxy-Neu5Ac). The 4,8,9-tris-(t-butyldimethylsilyl)-N-acetylneuraminic acid derivative5 a yields after transformation to the 7-O-acetyl compound5 b and partial removing of the protecting groups the derivative5 c. Further reaction with theMitsunobu-reagent and methyliodide affords the 9-Iodocompound6 a which turned to the 8-O-acetylderivative6 b. Subsequent reduction by means of tributyltinhydride yields first the 9-deoxyderivative7 a and after hydrolysis the 9-deoxy-N-acetylneuraminic acid7 b (5-N-acetyl amido-3,5,9-trideoxy-D-glycero--d-galacto-2-nonulopy-ranosidonic acid=9-Deoxy-Neu5Ac). Another synthesis of7 b follows the route8 f 8 g 7 c. The Deoxy-N-acetylneuraminic acid3 b could be prepared also by an alternative procedure using the methyl--8,9-methylethylen-4-O-t-butyldimethylsilyl-N-acetylneuraminic acid methylester8 a via the intermediate compounds8 d and8 e. Application of the 8,9-O-methylethyliden-N-acetylneuraminic acid derivative8 opens an approach to the xanthogenates8 a and8 b which could be reduced to the deoxy-N-acetylneuraminic acid derivatives9 a and10 a. Hydrolysis of10 a yields the 4,7-dideoxy-N-acetylneuraminic acid10 b (5-N-acetamido-3,4,5,7-tetradeoxy--D-lyxo-2-nonulopyranosidonic acid=4,7-Dideoxy-Neu5Ac).

     

Angle‐resolved XPS of fluorinated and semi‐fluorinated side‐chain polymers

Angle‐resolved XPS data (elemental quantification and high‐energy‐resolution C 1s) are presented for ten polymers with side‐chains of the form ? OCO(CF₂)_yF, ? COO(CH₂)₂OCO(CF₂)_yF (y = 1, 2, 3) and ? COO(CH₂)_x(CF₂)_yF (x = 1, y = 1, 2, 3; x = 2, y = 8). Particular attention was paid to charge compensation and speed of data acquisition, with co‐addition from multiple fresh samples to give spectra with good energy resolution and good signal‐to‐noise ratio free from the effects of x‐ray‐induced degradation. Water contact angles for the polymers are also reported. The XPS data demonstrate preferential surface segregation of fluorine‐containing groups for all but the shortest side‐chain polymer, where the ? OCOCF₃ side‐chain either does not surface segregate or is too short for surface segregation to be detectable by angle‐resolved XPS. In the other polymers studied the relative positions of functional groups in the side‐chains correlate with the angle‐resolved behaviour of the corresponding C 1s components. This shows that the surface side‐chains are oriented towards the polymer surface. For the ? COO(CH₂)₂OCO(CF₂)_yF (y = 1) side‐chain, the angle‐resolved C 1s data suggest reduced ordering and linearity compared with y = 2 and 3. For any particular series of polymers, e.g. ? COO(CH₂)_x(CF₂)_yF, the water contact angles increase with y, consistent with burying of the hydrophilic ester groups as y increases. For any particular value of y the sequence of water contact angles is ? COO(CH₂)_x(CF₂)_yF > ? OCO(CF₂)_yF ～ ? COO(CH₂)₂OCO(CF₂)_yF, suggesting greater ordering and density of fluorocarbon species at the surface of the ? COO(CH₂)_x(CF₂)_yF side‐chain polymers compared with the other polymers studied. For the ? COO(CH₂)₂(CF₂)₈F polymer a water contact angle of 124° is measured, which is greater than that of poly(tetrafluoroethene). The ? COO(CH₂)₂OCO(CF₂)F polymer is unusual in that it shows a particularly low water contact angle (83° ), suggesting that the probe fluid is able to sense both ester groups, consistent with the reduced ordering of the side‐chain detected by angle‐resolved XPS. Copyright © 2004 John Wiley & Sons, Ltd.     

Growth dynamics and structural variations of a friable metal deposit during its contact deposition from aqueous solutions

A model is proposed for describing dynamics of contact exchange of metals, which takes into account the side process of hydrogen evolution. The contact exchange dynamics and structural characteristics of the deposit are considered as functions of the concentration of ions that undergo reduction in solution and the cementation EMF. The consideration makes allowance for different densities of microelements and the effect of the solution stirring by hydrogen evolving concurrently.     

Self-assembly and micellization of amphiphilic rod-coil block oligomer at the mica-water interface

In this paper, in situ atomic force microscopy has been used to investigate the micellization and self-assembling structure of an amphiphilic rod-coil block oligomer (EO16OPV) containing a conjugated oligo(phenylene vinylene) dimer and poly(ethylene oxide) at the mica-water interface. It is found that EO16OPV molecules have strong adsorption and aggregation properties on mica. In the wide concentration range from above the critical micelle concentration (cmc) to far below the cmc, a closely packed layer of stripe-like micelles with two preferred orientations can be formed at the mica-water interface. A cylindrical micelle structure for the stripes is proposed. We demonstrate that the stripe-like micelles formed on mica originate from different micellization processes at solution concentrations above and below the cmc. The origins of the strong micellization properties and oriented arrangement of the stripes are also discussed.     

Chemical Reactivity of Polypyrrole and Its Relevance to Polypyrrole Based Electrochemical Sensors

One of the most frequently used conducting polymers, polypyrrole, can take part in chemical processes with typical components of ambient media: oxygen, acids, bases, redox reactants, water, and organic vapors; it can also incorporate nonreactive ions and surfactants from solutions. The influence of such processes on changes of the polymer structure, composition and on possible degradation is analyzed. The benefits and disadvantages of such processes for analytical characteristic of polypyrrole based electrochemical sensors are considered. This discussion is focused on potentiometric ion sensors, where polypyrrole is either a receptor membrane or an ion‐to‐electron transducer placed between a solid state electrode support and a typical ion‐selective membrane.     

Studies on the Model Synthesis of the Brassinolide and Dolicholide Side Chains

A stereoselective synthesis of brassinolide and dolicholide, which involves construction of the side chain enantiomers by a highly stereoselective aldol reaction of aldehyde 5 with the anion of a-silyloxy ketone 6 is described.     

EXPRESSION OF A PARTIAL SYNTHETIC HUMAN TNF cDNA IN E. coli

A recombinant human tumour necrosis factor (rhTNF) cDNA was constructed. The TNF gene was isolated from a human genomic gene library. There are four exons in the TNF gene. The fourth exou codes for 140 amino acids of the TNF matured protein which is composed of 157 amino acids. A major portion of the fourth exon was isolated and then ligated to a synthesized DNA fragment coding for the remaining amino acids. The partial synthetic hTNF (rhTNF) cDNA thus generated was subcloned into a vector and successfully expressed in E. coli. 5-1 fer1entator was used to produce rhTNF. About 20g (wet weight) of bacterial pellet per liter medium and 106—10~7 units of cytotoxicity to L929 cells per milliliter medium were obtained. rhTNF was purified by HPLC and dried with a freeze dryer, rhTNF with a purity of about 95% in the form of white powder was obtained. The sequence of ten amino acids at the amino terminus of the rhTNF was determined. The result showed that it was identical with that of the natural human TNF.     

Phase behaviour of lyotropic liquid crystalline side chain polymers in aqueous solutions

Amphiphilic lyotropic liquid crystalline surfactants are synthesized displaying 10-undecenoic acid as hydrophobic and ethyleneglycol units as hydrophilic parts of the molecules. By addition reaction of the monomeric surfactants with poly [oxy(methylsilylene)], the surfactants are attached as side chains to the siloxane main chain. The phase behaviour of a polymer-water system and the corresponding monomer-water system is investigated by polarizing microscopy. The monomeric surfactant exhibits a liquid crystallineM ₁-phase of hexagonally packed, rod-like micelles in a concentration range of 49 to 70% surfactant. The liquid crystalline state of the polymeric surfactant is more stable, which is indicated by a broader temperature- and concentration range (35%–90% polymer surfactant). At lower concentration aM ₁-phase exists, which is separated by a cubic phase from a lamellarG-phase at higher concentration of the polymer surfactant. Compared to the monomeric system, the increased stability of the polymeric mesophase can be understood by the restriction of motions of the amphiphiles due to the linkage to the polymer main chain.Dedicated to Prof. Dr. F. H. Müller.The authors are greatly indebted to Wacker Chemie, D-Burghausen, FRG for kindly delivering the poly(hydrogensiloxane).     

Crystallization mechanism of regioregular poly(3‐alkyl thiophene)s

The crystallization properties of three regioregular poly(3‐alkyl thiophene)s (P3ATs) are studied: poly(3‐hexyl thiophene) (P3HT), poly(3‐octyl thiophene) (P3OT), and poly(3‐dodecyl thiophene) (P3DDT). The morphology of the isothermally crystallized samples is a whisker type. The values of the enthalpy of fusion of ideal crystals (ΔH), determined from the melting point depression in the polymer–diluent system, are 99, 73.6, and 52 J/g for P3HT, P3OT, and P3DDT, respectively. The values of the equilibrium melting point (T), determined from the Hoffman–Weeks extrapolation procedure, are 300, 230, and 180 °C for P3HT, P3OT, and P3DDT, respectively. From the linear extrapolation of the P3AT data, the T and ΔH values of unsubstituted polythiophene are predicted to be 400 °C and 139 J/g, respectively. The crystallization kinetics of these polymers are studied with differential scanning calorimetry, and the Avrami exponents vary between 0.6 and 1.4, indicating one‐dimensional heterogeneous nucleation with linear growth. As the P3AT whiskers are produced from the chain‐folding process, the Lauritzen–Hoffman growth rate theory is applied to analyze the temperature coefficient of the crystallization rate data. Graphical plots indicate a transition from regime I to regime II during isothermal crystallization for all the P3ATs studied. The fold surface energy and the work of chain folding calculated from the slopes of the graphical plots decrease with an increase in the number of carbon atoms of the side chain. The primary crystallization process of the side‐chain crystallization is very fast and is attributed to the zipping effect of the main‐chain crystals. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2073–2085, 2002