Electron Transfer Reactions in RB90745, A Bioreductive Drug Having Both Aromatic N-Oxide and Nitroarene Moieties

The bifunctional hypoxia-specific cytotoxin RB90745, has a nitroimidazole moiety attached to an imidazo[1,2,-a]quinoxaline mono-N-oxide with a spacer/linking group. The reduction chemistry of the drug was studied by pulse radiolysis using the one electron reductant CO₂^˙-. As N-oxides and nitro compounds react with CO₂^˙- at diffusion controlled rates, initial reaction produced a mixture of the nitro radical (λ_max 410 nm) and the N-oxide radical (λ_max 550 nm) in a few microseconds. Subsequently an intramolecular electron transfer (IET) was observed (k = 1.0 ± 0.25 × 10³ s^-1 at pH 5-9), from the N-oxide to the more electron-affinic nitro group. This was confirmed by the first order decay rate of the radical at 550 nm and formation at 410 nm, which was independent of both the concentration of the parent compound and the radicals. The rates of electron transfer and the decay kinetics of the nitro anion radicals were pH dependent and three different pK_aS could be estimated for the one electron reduced species: 5.6 (nitroimidazole group) and 4.3, and 7.6 (N-oxide function). The radicals react with oxygen with rate constants of 3.1 × 10⁷ and 2.8 × 10⁶ dm³ mol^-1 s^-1 observed at 575 nm and 410 nm respectively. Steady state radiolysis studies indicated four electron stoichiometry for the reduction of the compound.     

Degradation of bis(2-ethylhexyl) phthalate constituents under methanogenic conditions

The degradation of bis(2-ethylhexyl) phthalate (DEHP) and its intermediary hydrolysis products 2-ethylhexanol (2-EH) and mono(2-ethylhexyl) phthalate (MEHP) was investigated in a methanogenic phthalic acid ester-degrading enrichment culture at 37°C. 2-Ethylhexanoic acid (2-EHA), a plausible degradation product of 2-EH, was also studied. The culture readily degraded 2-EH via 2-EHA to methane which was formed in stoichiometric amounts assuming complete degradation of 2-EH to methane and carbon dioxide. MEHP was degraded to stoichiometric amounts of methane with phthalic acid as a transient intermediate. DEHP remained unaffected throughout the experimental period (330 days).Abbreviations 2-EH 2-ethylhexyl alcohol - 2-EHA 2-ethylhexanoic acid - BBP butylbenzyl phthalate - Be-CoA benzoyl Coenzyme A - CoA Coenzyme A - DEHP bis(2-ethylhexyl) phthalate - MEHP mono(2-ethylhexyl) phthalate - MSW municipal solid waste - PA phthalic acid - PAE phthalic acid ester - TMS trimethylsilyl derivative     

五大连池火山色木槭叶功能性状特征

植物功能性状反映了植物对生长环境的响应和适应, 是连接植物与环境的桥梁, 研究植物功能性状特征及其随坡向的变化规律, 对认识不同微地形生境下植物群落空间格局形成及适应机制具有重要意义。本文以五大连池不同历史年代的8座火山共有树种色木槭(Acer mono)为研究对象, 测定了9类叶功能性状, 研究了植物叶功能性状在火山间及火山坡向间(阴坡-阳坡)的变化规律, 以期揭示生境对火山植物主要叶功能性状的影响, 以及阴阳坡植物生存策略的变化, 初步探讨了植物对环境的适应机制。结果表明: (1)坡向的变化是造成色木槭叶功能性状差异的重要原因; (2)火山间叶功能性状的差异反映了它们具有不同的资源环境, 色木槭生长主要受氮元素的限制; (3)南北坡向及火山间叶片厚度与叶面积均呈极显著的正相关关系, 叶片厚度与比叶面积在不同火山间均呈显著的正相关关系, 这与色木槭在火山土壤条件下的自我保护密切相关, 色木槭通过这些指标间的功能调节来适应环境的变化, 并形成最佳功能组合。五大连池不同历史年代火山的色木槭采用增加植物叶片叶干物质浓度、叶面积、叶片厚度、叶氮和叶磷浓度提高固碳能力, 通过降低比叶面积和氮磷比来适应干旱、土壤养分贫瘠的环境。     

Size structure of current-year shoots in mature crowns

Characteristics of current-year shoot populations were examined for three mature trees of each of three deciduous broad-leaved species. For first-order branches (branches emerging from the vertical trunk) of the trees examined, lengths or diameters of all current-year shoots were measured. Total leaf mass and total current-year stem mass of first-order branches were estimated using an allometric relationship between leaf or stem mass and length or diameter of current-year stems. For each tree, the number of current-year shoots on a first-order branch was proportional to the basal stem cross-sectional area of the branch. On the other hand, first-order branches had shoot populations with size structures similar to each other. As a result, the leaf mass of a first-order branch was proportional to the basal stem cross-sectional area of the branch, being compatible with the pipe-model relationship. All current-year shoot populations had positively skewed size structures. Because small shoots have a larger ratio of leaf mass to stem mass than large shoots, first-order branches had an extremely large ratio of leaf mass to current-year stem mass. This biased mass allocation will reduce costs for current stem production, respiration and future radial growth, and is beneficial to mature trees with a huge accumulation of non- photosynthetic organs. The allometric relationships between leaf mass and basal stem diameter and that between leaf mass and current-year stem mass of first-order branches were each similar across the trees examined. Characteristics of shoot populations tended to offset inter-species diversity of shoot allometry so that branch allometry shows inter-species convergence.     

四种北方阔叶树种苗木对土壤镉胁迫的生长反应与抗性比较

采用盆栽方法,研究了4种北方阔叶树种茶条槭、山梨、五角槭和山荆子一年生苗木对土壤镉胁迫的生长反应和抗性.采用土壤和风化砂混合物作为栽培基质,设计5种土壤镉浓度梯度处理(对照、10、50、100、200mg·kg^-1).结果表明,低浓度处理(≤50mg·kg^-1)刺激各树种苗木的地径、树高生长,其中茶条槭在10mg·kg^-1处理下地径和苗高增加幅度最大,分别为对照的135.8%和146.0%;随着镉处理浓度的增加,地上部生长量下降,茶条槭在最高浓度处理下,生长量降低最大,地径和苗高仅分别为对照的241%和280%.叶片和新枝生物量变化存在较大种间差异,茶条槭和山梨在低浓度处理时总体上表现增加;山荆子新枝生物量增加,叶生物量减少;五角槭表现一致减少.最高浓度处理时,叶和新枝生物量受影响最大的是茶条槭,分别为对照的4.6%和7.3%;其次为五角槭,分别为对照的5.7%和7.9%;山梨和山荆子受影响的幅度相对较小.新根生物量除山梨外,其它3个树种苗木的生物量表现一致下降,其中下降幅度以茶条槭最大,最高浓度处理仅为对照的2.3%.山梨在低浓度处理下,新根生物量有所增加,分别为对照的125.5%和117.1%.     

Human heat shock protein 70 (Hsp70) as a peripheral membrane protein

While a significant fraction of heat shock protein 70 (Hsp70) is membrane associated in lysosomes, mitochondria, and the outer surface of cancer cells, the mechanisms of interaction have remained elusive, with no conclusive demonstration of a protein receptor. Hsp70 contains two Trps, W90 and W580, in its N-terminal nucleotide binding domain (NBD), and the C-terminal substrate binding domain (SBD), respectively. Our fluorescence spectroscopy study using Hsp70 and its W90F and W580F mutants, and Hsp70-?SBD and Hsp70-?NBD constructs, revealed that binding to liposomes depends on their lipid composition and involves both NBD and SBD.