注凝成型制备氧化锆增韧氧化铝陶瓷

采用低毒单体N,N-二甲基丙烯酰胺(DMAA)制备了氧化锆增韧氧化铝(ZrO2/Al2O3,ZTA)陶瓷,氧化铝与氧化锆的质量比为3∶1,浆料的固相体积分数为50 vol%。讨论了不同干燥方式对干燥速率以及坯体性能的影响,研究了不同成型温度对坯体性能的影响。通过研究发现,在湿热烘箱中干燥的坯体强度最高,成型温度应控制在65℃附近。通过对不同单体含量的坯体烧结后陶瓷性能的对比,发现单体的加入量为10wt%左右较好,通过与干压成型陶瓷性能的对比,发现注凝成型得到的陶瓷强度和韧性分别提高了42.2%和23.5%,达到640 MPa和6.3MPa.m1/2,通过扫描电镜图片分析发现,注凝成型制得的陶瓷结构更均匀。     

PDMAA/Clay纳米复合水凝胶的制备与性能

以无机黏土为交联剂,采用偶氮二异丁腈(AIBN)为引发剂制备了新型的聚N,N ＇-二甲基丙烯酰胺/黏土(PDMAA/Clay)纳米复合水凝胶,作为对比,采用过硫酸钾(KPS)为引发剂制备了相对应的水凝胶.对两种纳米复合水凝胶的结构、形态、溶胀行为和力学性能等进行了研究.试验表明,黏土的结晶结构均已被破坏,黏土规整的片层被剥离并在凝胶中无序分布,起到交联剂的作用.随着黏土含量的增加,水凝胶的溶胀速率和溶胀度降低.采用AIBN制备的PDMAA/Clay水凝胶具有更好的韧性及更高的断裂强度,其断裂伸长率可达1 800％以上,而KPS制备的水凝胶的断裂伸长率在1 200％左右.     

Distribution and cycle of arsenic compounds in the ocean

In order to understand the distribution and the cycle of arsenic compounds in the marine environment, the horizontal distributions of arsenic(V) [As(V)], arsenic(III) [As(III)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) in the Indian Pacific Oceanic surface waters have been investigated. This took place during cruises of the boat Shirase from Tokyo to the Syowa Station (15 November–19 December 1990), of the tanker Japan Violet from Sakai to Fujayrah (28 July–17 August 1991) and of the boat Hakuho-maru from Tokyo to Auckland (19 September–27 October 1992). Vertical distributions of arsenic in the west Pacific Ocean have also been investigated. The concentration of As(V) was found to be relatively higher in the Antarctic than in the other areas. Its concentration varied from 340 ng dm^?3 (China Sea) to 1045 ng dm^?3 (Antarctic). On the other hand, the concentrations of the biologically produced species, MMAA and DMAA, were extremely low in the Antarctic and southwest Pacific waters. Their concentrations in Antarctic waters were 8 ng dm^?3 and 22 ng dm^?3 and those in the southwest Pacific were 12 ng dm^?3 and 25 ng dm^?3. In the other regions the concentration varied from 16 ng dm^?3 (China Sea) to 36 ng dm^?3 (north Indian Ocean) for MMAA and from 50 ng dm^?3 (east Indian Ocean) to 172 ng dm^?3 (north Indian Ocean) for DMAA. As a result, with the exception of Antarctic and southwest Pacific waters, the percentages of each arsenic species in the surface waters were very similar and varied from 52% (east Indian Ocean) to 63% (northwest Pacific Ocean) for As(V), from 22% (northwest Pacific Ocean) to 27% (east Indian Ocean) for As(III) and from 15% (northwest Pacific Ocean) to 21% (north and east Indian Oceans) for the methylated arsenics (MMAA+DMAA). These percentages in Antarctic waters were 97%, 0.2% and 2.8%, respectively, and those in the southwest Pacific Ocean were 97% for As(V)+As(III) and 3% for MMAA+DMAA. The very low concentrations of the biologically produced species in Antarctic waters and that of methylated arsenic in southwest Pacific waters indicated that the microorganism communities in these oceans was dominated by microorganisms having a low affinity towards arsenic. Furthermore, microorganism activity in the Antarctic was also limited due to the much lower temperature of the seawater there. The vertical profile of inorganic arsenic was 1350 ng dm^?3 in surface waters, 1500 ng dm^?3 in bottom waters with a maximum value of 1700 ng dm^?3 at a depth of about 2000 m in west Pacific waters. This fact suggested the uptake of arsenic by microorganisms in the surface waters and the co-precipitation of arsenic with hydrated heavy-metal oxides in bottom waters. The suggested uptake of inorganic arsenic and subsequent methylation was also supported by the profile of DMAA, with a high concentration of about 26 ng dm^?3 in surface water and a significant decrease to a value of 9 ng dm^?3 at a depth of 1000 m.     

Possible key intermediates in arsenic biochemistry: Synthesis and identification by liquid chromatography electrospray ionization mass spectrometry and high resolution mass spectrometry

Arsenic is a type 1 carcinogen and its toxicity is critically dependent on chemical speciation. However, after decades of research, the biogenesis of at least fifty naturally occurring arsenic species is still not well understood.Here, based on experimental work, it is proposed a set of pathways for the formation of multiple arsenic species that might help to clarify the present situation.These are focused on the thiol protein arsenic bond and on its interaction with reactive metabolites. In fact, arsenic bound to glutathione interacting with sulfur adenosyl methionine (SAM), MethylCB₁₂ and AdoCB₁₂, forms a number of complexes that might be key intermediates in arsenic biochemistry. These include dimethylarsino glutathione (DMAG) m/z 412 [M + H]⁺, synthesized non-enzymatically from glutathione and cacodylate. Trimethylarsonio glutathione (TMAG) m/z 426 [M]⁺ synthesized from DMA, GSH and SAM, apparently by a classical Challenger methylcarbonium attack. Tetramethyl arsonium ion m/z 135 [M]⁺ is formed in a third step, apparently by carbanion methylation. The presence of trimethylarsine oxide (TMAO) m/z 137 [M + H]⁺ is attributed to the hydrolysis of TMAG or TMA, or to carbanion methylation of dimethylarsinoyl glutathione (m/z 428 [M]⁺) formed from cacodylate and GSH. Cantoni type attacks of DMAG on SAM were unsuccessful, eventually due to competition of the trivalent S⁺ atom of SAM for the As^III atom attack. The presence of dimethylarsonio diglutathione (DMADG m/z 717 [M]⁺), is suggested to result from a GS^- attack on dimethylarsenoyl glutathione (m/z 428 [M + H]⁺). The presence of dimethylarsenoyladenosine (m/z 372 [M + H]⁺), trimethylarsenosugar adenine (m/z 370 [M]⁺), and dimethylthioarsenosugar adenine (m/z 388 [M + H]⁺), is explained by the synthesis of the pecursor dimethylarsonio-adenosine glutathione DMAAG (m/z 661 [M]⁺), a likely source of oxo-and trimethylated arsenosugars, as well as of thio-arsenosugars by the cleavage of its S-C bond. The results gathered suggest that cell vacuoles might play a major role in arsenic metabolism, and that the dominance of oxo-As sugars, in algae extracts, may be supported by a mechanism of synthesis independent of DMAAG (m/z 661).They also offer an explanation for the reason why arsenobetaine, and tetramethylarsonium are loosely bound to biotic tissues. Four arsenic species new to science, to the best of our knowledge, and a number of known arsenic compounds were synthesized in this work, identified by HPLC–ESI-MSⁿ and FTICR–ESI-MS, and suggestions regarding their mechanisms of synthesis were advanced. These results provide a framework for arsenic biochemistry which may explain the origin of a significant part of arsenic known metabolites.     

光化学合成快速响应聚(N,N-二甲基丙烯酰胺-co-N-异丙基丙烯酰胺)水凝胶

通过光化学合成方法分别在高温(50℃)和室温(28℃)下实现了N,N-二甲基丙烯酰胺(DMAA)和N-异丙基丙烯酰胺(NIPAm)的交联共聚,制备了两种不同结构的P(DMAA-co-NIPAm)共聚物水凝胶.对两种温度下制备的P(DMAA-co-NIPAm)共聚物水凝胶的网络结构、溶胀与消溶胀速率和温度敏感性等方面进行了比较研究.结果发现,50℃下制备的P(DMAA-co-NIPAm)共聚物凝胶具有较为疏松的网络结构和相对较快的溶胀速率及温度响应特性.光化学合成方法较传统的热聚合制备方法具有简便、快捷的特点,合成过程仅需2 min.     

(NIPAAm)类三元共聚及IPN水凝胶的合成与温敏性能的研究

采用自由基聚合法合成了P(AAm-co-NIPAAm-co-DMAA)三元共聚水凝胶和P(NIPAAm-co-AAm)/PDMAA互穿聚合物网络(IPN)水凝胶。研究了两种水凝胶的温敏及溶胀性能,并考察了DMAA含量对两种凝胶性能的影响。结果表明,P(AAm-co-NIPAAm-co-DMAA)三元共聚水凝胶和P(NIPAAm-co-AAm)/PDMAA互穿聚合物网络(IPN)水凝胶都具有热缩温敏性,DMAA的摩尔分数增加(7%～22%),两种水凝胶的LCST从40℃升高到45℃;三元共聚水凝胶平衡溶胀比(SR)由8.33提高至14.50,IPN水凝胶平衡溶胀比(SR)由5.61提高至11.66;两种水凝胶都能在30min内达到消溶胀平衡,并且失水率在80%左右。IPN水凝胶的凝胶形态稳定性较三元共聚水凝胶明显提高。     

Environmental application of elemental speciation analysis based on liquid or gas chromatography hyphenated to inductively coupled plasma mass spectrometry—A review

In recent years the number of environmental applications of elemental speciation analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. The analytical characteristics, such as extremely low detection limits (LOD) for almost all elements, the wide linear range, the possibility for multi-elemental analysis and the possibility to apply isotope dilution mass spectrometry (IDMS) make ICP-MS an attractive tool for elemental speciation analysis. Two methodological approaches, i.e. the combination of ICP-MS with high performance liquid chromatography (HPLC) and gas chromatography (GC), dominate the field. Besides the investigation of metals and metalloids and their species (e.g. Sn, Hg, As), representing “classic” elements in environmental science, more recently other elements (e.g. P, S, Br, I) amenable to ICP-MS determination were addressed. In addition, the introduction of isotope dilution analysis and the development of isotopically labeled species-specific standards have contributed to the success of ICP-MS in the field. The aim of this review is to summarize these developments and to highlight recent trends in the environmental application of ICP-MS coupled to GC and HPLC.     

Sensitivity of microarray based immunoassays using surface-attached hydrogels

A promising pathway to improve on the sensitivity of protein microarrays is to immobilize the capture antibodies in a three dimensional hydrogel matrix. We describe a simple method based on printing of an aqueous protein solution containing a photosensitive polymer and the capture antibody onto a plastic chip surface. During short UV-exposure photocrosslinking occurs, which leads to formation of a hydrogel, which is simultaneously bound to the substrate surface. In the same reaction the antibody becomes covalently attached to the forming hydrogel. As the capture antibodies are immobilized in the three-dimensional hydrogel microstructures, high fluorescence intensities can be obtained. The chip system is designed such, that non-specific protein adsorption is strongly prevented. Thus, the background fluorescence is strongly reduced and very high signal-to-background ratios are obtained (SBR > 6 for c_BSA = 1 pM; SBR > 100 for c_BSA > 100 pM). The kinetics of antigen binding to the arrayed antibodies can be used to determine the concentration of a specific protein (for example the tumor marker β₂-microglobulin) in solution for a broad range of analyte concentrations. By varying size and composition of the protein-filled hydrogel microstructures as well as adjusting the extent of labeling it is possible to easily adapt the surface concentration of the probe molecules such that the fluorescence signal intensity is tuned to the prevalence of the protein in the analyte. As a consequence, the signal tuning allows to analyze solutions, which contain both proteins with high (here: upper mg mL⁻¹ range) and with very low concentrations (here: lower μg mL⁻¹ range). This way quantitative analysis with an exceptionally large dynamic range can be performed.     

宽带下视雷达信号模拟器的研制

分析了宽带下视雷达目标回波的特点及散射中心截面积的确定方法，地杂波回波的特点及其概率密度函数，功率谱函数，提出了一种通用的雷达信号模拟器模型，采用ＰＣ机ＤＭＡ控制方式实现了一个宽带下视雷达信号模拟器。解决了硬件设计和软件算法中的关键技术问题，并获得了良好的性能指标。     

The Contrasting Behaviour of Arsenic and Germanium Species in Seawater

The vertical profiles of inorganic arsenic [As(III)+As(V)], monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), inorganic germanium and monomethylgermanium (MMGe) were investigated at three sampling stations in the Pacific Ocean. In addition, the concentrations of these species in various surface waters have also been determined. The vertical profile of both inorganic arsenic and germanium displayed low concentrations, 1100 to 1450 ng dm³ for inorganic arsenic and <0.7 to 2 ng dm³ for inorganic germanium, in the surface zone. The concentrations of inorganic arsenic increased with depth to maximum concentrations that varied from 1500 to 2200 ng dm³ at a depth of 2000 m and then slowly decreased to concentrations that varied from 1300 to 1900 ng dm³ at a depth of 5000 m. On the other hand, the vertical profiles of inorganic germanium displayed a relatively constant concentration (4 to 8 ng dm³) from a depth of 2000 m to 5000 m. These vertical profiles of inorganic germanium were linearly correlated with those of silicate with a Ge/Si molar ratio of 0.715×10⁶. Both MMAA and DMAA displayed maximum concentrations in surface water and abruptly dropped with depth from 0 to 200 m. The concentration in surface water was 12 ng dm³ for MMAA and varied from 48 to 185 ng dm³ for DMAA. At depths >200 m, MMAA and DMAA were generally at comparable concentrations of about 3 ng dm³. In the case of MMGe, it was uniformly distributed throughout the water column at a concentration of approximately 16 ng dm³, indicating that MMGe was not involved in the biogeochemical cycling of inorganic germanium. In deep waters (>200 m), the concentrations of both inorganic arsenic and germanium increased from the southern Tasman Sea to the north. The increase in inorganic arsenic concentration was linearly correlated with that of phosphate and the increase in inorganic germanium concentration was linearly correlated with that of silicate, with apparent δAs/δP and δGe/δSi molar ratios of 4.53×10³ and 0.73×10⁶, respectively. © 1997 by John Wiley & Sons, Ltd.