Reactivity difference between protolytic forms of some macrocyclic chromium(III) complexes in ligand substitution and electron transfer processes

The review provides insight into the mechanism of ligand substitution and electron transfer (from chromium(III) to iron(III)) by comparison of the reactivity of some tetraazamacrocyclic chromium(III) complexes in the conjugate acid-base forms. Use of two geometrical isomers made possible to estimate the influence of geometry and protolytic reactions in trans and cis position towards the leaving group on the rate enhancement. Studies on the reaction rates in different media demonstrated the role played by outer sphere interactions in a monodentate ligand substitution.     

Bionanoscience at the plant virus-inorganic chemistry interface

Bionanoscience is an inter-disciplinary area of research that sits at the interface of chemistry, biology, materials science, engineering and medicine. During the past 10 years the suitability and applicability of using plant viruses as building blocks, synthons, scaffolds or templates in bionanoscience/technology have begun to be explored. This short review describes how the plant Cowpea mosaic virus can be functionalised on its outer surface to form electroactive nanoparticles, can be used to construct monolayers on solid surfaces and multilayer arrays by a bottom-up, layer-by-layer approach, and how it can template mineralization processes to give new routes to monodisperse nanoparticles. Potential applications of virus-derived nanoparticles include nanoelectronics, sensory devices, catalysis, photonics and medical applications from imaging to the targeting and delivery of therapeutic agents.     

Directing iridium-catalyzed C-C bond formation by selection of the ancillary ligands: Polymerization and cyclotrimerization of alkynes

The ability of organoiridium derivatives of catalyzing oligomerization and polymerization of terminal alkynes is markedly influenced by the nature of non-participative ligands coordinated to the metal. The dimeric species [Ir(cod)Cl]₂ and [Ir(cod)(OMe)]₂ (cod = 1,5-cyclooctadiene) as well as the phosphine complexes HIr(cod)(PR₃)₂ (PR₃ = PPh₃, P(p-MeOC₆H₄)₃, P(o-MeOC₆H₄)Ph₂, PCyPh₂) catalyze the polymerization reaction, whereas the diphosphine derivatives HIr(cod)(P-P) (P-P = Ph₂P(CH₂)_nPPh₂ (n = 1-4), o-C₆H₄(PPh₂)₂) promote the regioselective formation of 1,2,4-trisubstituted benzenes. On the other hand, the iridium complexes with nitrogen chelating ligands Ir(cod)(N-N)X and Ir(hd)(N-N)X (hd = 1,5-hexadiene; N-N = 1,10-phenanthroline and substituted derivatives; X = halogen) catalyze alkynes polymerization. In most cases one catalytic reaction predominates over the other possible routes, so that polymerization often takes place in the absence of oligomerization side reactions, and conversely cyclotrimerization is rarely accompanied by formation of either polyene or dimers.     

Synthesis, stability and reactivity of palladium(0) olefin complexes bearing labile or hemi-labile ancillary ligands and electron-poor olefins

An overview of the general features of electron-poor olefin stabilized palladium(0) complexes bearing labile and hemi-labile ancillary ligands is presented. In particular, we have summarized the synthetic methodologies, the ligands commonly used, and the characterization of such complexes. The behavior of these species in solution is also described with particular attention to their fluxional rearrangements and reactivity. Thus, olefin exchange reactions are described and a comprehensive order of coordinative capability of the most widely used electron-poor alkenes is presented. The reactions of the title complexes dealing with olefin isomerization, oxidative addition, and formation of palladacyclopentadiene derivatives are eventually reported together with their main structural characteristics.     

嗜卷书虱气调抗性形成过程中能源物质的积累与利用

报道了嗜卷书虱对高二氧化碳,低氧气调抗性形成过程中能源物质的积累以及抗性形成后在气调胁迫下能源物质的利用情况。结果表明随着抗性水平的提高。嗜卷书虱体内甘油三酯,多糖以及游离氨基酸含量均显升高。在气调胁迫环境下,嗜卷书虱抗性品系能源物质的消耗率明显低于敏感品系,甘油三酯的积累以及在气调摁迫下缓慢消耗可能是其抗气调性的主要内在机理之一。     

毛乌素沙地3种优势植物对模拟降水量变化的水分平衡研究(英文)

未来全球变化 ,尤其降水变化的进一步加剧 ,将对毛乌素沙地陆地生态系统分布格局和生产力带来巨大影响。为了预测未来变化 ,提出合理的对应策略 ,实验选择毛乌素沙地 3种优势灌木、半灌木为研究对象 ,人工控制 4种降水量水平来探讨水分平衡对全球降水量变化的响应。结果表明 ,沙地蓄水量和不同沙层深度含水量季节变化明显受到不同施水量和 3种植物种类的影响。 3种植物沙地蓄水量和不同深度沙层含水量随着施水量的增加逐渐增大 ,并且不同施水量和植物沙地含水量随深度增加逐渐增大。在同一施水量处理下的蓄水量和同一深度含水量均大体为杨柴 (HedysarummongolicumTurcz.) >沙柳 (SalixpsammophilaC .WangetCh .Y .Yang) >油蒿 (Artemisiaordosi caKrasch .) ;3种植物的蒸发量和蒸腾量季节变化明显受到施水量的影响。随着施水量的增加 ,即 15 7 5、315 0、472 5和 6 30 0mm ,蒸发总量依次为 12 3.6 6、2 5 8.6 8、376 .30、45 8.5 7mm ;蒸腾总量 ,油蒿分别为 5 0 .80、6 8.93、10 8.39、16 3.36mm ;沙柳分别为 47.37、6 8.17、93.6 5、135 .97mm ;杨柴分别为 46 .73、6 7.37,86 .0 7、10 9.6 4mm。蒸发量显著大于蒸腾量     

小麦叶片老化期间的内肽酶与H_2O_2的关系(英文)

研究了H2 O2 和蛋白水解酶在小麦 (TriticumaestivumL .cv.Yanmai15 8)叶片老化过程中的关系。小麦叶片老化期间 ,H2 O2 含量高的叶片中内肽酶活力也高。老化后期 ,内源H2 O2 迅速累积 ,内肽酶活力迅速上升 ;通过内肽酶同工酶电泳可检测到新增一种活力较强的内肽酶。用外源H2 O2 处理全展旗叶的内肽酶粗提液 ,随着H2 O2 浓度的升高 ,内肽酶活力先上升后下降。     

高赖氨酸蛋白基因导入水稻及可育转基因植株的获得

构建了一个植物高效表达质粒,使来源于四棱豆（Psophocarpus tetragonolobus(L.)DC)的高赖氨酸蛋白基因（lys）受控于单子叶植物ubiqutin强启动子下表达。用基因枪法将其导入水稻(Oryza sativa L.)幼胚诱导的愈伤组织,经潮霉素抗性筛选,得到可育的再生植株。经PCR和Southem blotting检测,表明该基因已整合到水稻的基因组织。GUS组织化学染色表明转基因水稻植株的叶、茎和根中均有gus基因的表达。测定112株转基因水稻叶片中赖氨酸叶量,大部分植株有不同程度的提高,最高幅度为16．04％。     

莲胚芽叶绿素合成对光照的依赖性

被子植物的叶绿素合成需要光照,但是莲（Nelumbo nucifera Gaertn.)胚芽却一直被猜测具有在黑暗中合成叶绿素的能力,因为莲胚芽变绿是在四重覆盖物（子叶、种皮、果皮和莲蓬）包被下几乎不大可能秀光的环境中发生的,本实验从正反两个方面否定了这种可能性;首先对处于发育早期的莲蓬进行遮光处理。结果发现莲胚芽虽然可以继续发育,但是它的叶绿素合成却受到严重抑制。积累了大量合成叶绿素的前体,并且这些前体主要与依赖光的原叶绿素酸酯氧还酶（LPOR）结合在一起;其次不依赖光的原叶绿素酸酯氧还酶（DPOR）的编码基因在物种间高度保守,但是用PCR的方法在功基因组中却扩增不同源序列,表明莲胚芽不大可能具有在黑暗中合成叶绿素所必需的酶。两方面实验结果表明,莲胚芽的叶绿素合成只能通过依赖光的途径进行。     

利用超快时间分辨技术对光系统Ⅱ核心天线CP43和CP47的动力学荧光光谱的分析

采用超快时间分辨荧光光谱装置对光系统Ⅱ核心天线CP43和CP47进行了研究 ,并在 5 14.5nm激光激发下获得了它们的动力学荧光光谱。CP43和CP47的荧光光谱范围分别为 6 40～ 780nm和 6 30～ 775nm ,并且它们分别在约 6 80nm和 6 91nm处有最大峰 ,在这两个峰值处的荧光寿命分别约为 3.5 4ns和 3.2 2ns。通过理论计算认为在CP43和CP47中 ,叶绿素a的荧光发射效率分别约为 38.3%和 40 .6 %。讨论了类胡萝卜素到叶绿素a分子的能量传递 ,认为在CP43和CP47中 ,类胡萝卜素到叶绿素a分子的能量传递时间常数分别为 9.6× 10 11s-1和 1.3× 10 12s-1,能量传递效率分别为 47.5 %和 6 6 .5 % ,并且估计在这两种核心天线中 ,类胡萝卜素分子和叶绿素a分子的外周间距分别约为 0 .110nm和 0 .0 85nm。