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.     

Seasonality of cavitation and frost fatigue in Acer mono Maxim.

Although cavitation is common in plants, it is unknown whether the cavitation resistance of xylem is seasonally constant or variable. We tested the changes in cavitation resistance of Acer mono before and after a controlled cavitation–refilling and freeze–thaw cycles for a whole year. Cavitation resistance was determined from ‘vulnerability curves’ showing the percent loss of conductivity versus xylem tension. Cavitation fatigue was defined as a reduction of cavitation resistance following a cavitation–refilling cycle, whereas frost fatigue was caused by a freeze–thaw cycle. A. mono developed seasonal changes in native embolisms; values were relatively high during winter but relatively low and constant throughout the growing season. Cavitation fatigue occurred and changed seasonally during the 12‐month cycle; the greatest fatigue response occurred during summer and the weakest during winter, and the transitions occurred during spring and autumn. A. mono was highly resistant to frost damage during the relatively mild winter months; however, a quite different situation occurred during the growing season, as the seasonal trend of frost fatigue was strikingly similar to that of cavitation fatigue. Seasonality changes in cavitation resistance may be caused by seasonal changes in the mechanical properties of the pit membranes.     

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.     

五角枫种群表型多样性

为揭示五角枫种群的表型分化程度、变异模式及地理变异规律,以山西19个种群为研究对象,采用巢式方差分析、相关分析、聚类分析等方法从形态学角度对五角枫种群的叶片、果实、种子等23个表型性状进行了系统分析。结果表明:(1)五角枫23个表型性状中除果柄长、着生痕、种子长/宽以外,其余20个表型性状在种群间和种群内均存在显著和极显著差异。(2)19个种群的平均变异系数为18.07。叶片、果实、种子的平均表型变异系数依次为:果实19.78%叶片18.77%种子10.25%。(3)五角枫种群间表型分化系数(VST)均值为48.82%,种群内变异(51.18%)与种群间变异(48.82%)基本相当。叶片、果实、种子表型分化系数的平均值为:叶片58.08%果实41.24%种子25.87%。(4)五角枫叶片、果实和种子的信息多样性指数(H)为:叶片6.1079果实5.9118种子5.2855;多样性指数平均值(D)分别为:果实0.9967叶片0.9961种子0.9948。(5)主成分分析结果显示:五角枫种群表型多样性基本来源为:叶片贡献率果实贡献率种子贡献率。(6)五角枫表型变异呈现出以经度和纬度变异并存的趋势,少数表型性状与经度和纬度呈现显著或极显著相关。(7)利用欧氏距离对五角枫种群进行UPGMA聚类分析,将五角枫19个种群划分为两大类群。五角枫种群具有较高的表型多样性,种群间和种群内均存在丰富的表型变异,与其遗传特点和分布生境等密切相关,研究结果为今后五角枫种质资源的保护和利用奠定了基础。     

Production of extracellular PETase from Ideonella sakaiensis using sec-dependent signal peptides in E. coli

Poly(ethylene terephthalate) (PET) is the most commonly used polyester polymer resin in fabrics and storage materials, and its accumulation in the environment is a global problem. The ability of PET hydrolase from Ideonella sakaiensis 201-F6 (IsPETase) to degrade PET at moderate temperatures has been studied extensively. However, due to its low structural stability and solubility, it is difficult to apply standard laboratory-level IsPETase expression and purification procedures in industry. To overcome this difficulty, the expression of IsPETase can be improved by using a secretion system. This is the first report on the production of an extracellular IsPETase, active against PET film, using Sec-dependent translocation signal peptides from E. coli. In this work, we tested the effects of fusions of the Sec-dependent and SRP-dependent signal peptides from E. coli secretory proteins into IsPETase, and successfully produced the extracellular enzyme using pET22b-SP_MalE:IsPETase and pET22b-SP_LamB:IsPETase expression systems. We also confirmed that the secreted IsPETase has PET-degradation activity. The work will be used for development of a new E. coli strain capable of degrading and assimilating PET in its culture medium.     

Interrelationships between two-dimensional phase diagrams and mean molecular area-mole fraction curves in mixed monolayers

Both two-dimensional phase diagrams and mean molecular area (A)—mole fraction(x₂^π) curves have been investigated for various types of mixed monolayer systems. Two-dimensional phase diagram analysis and the behavior of A−x₂^π curves were found to be in good agreement with each other. From this result it was concluded that we should consider both phase diagrams and A−x₂^π curves of a mixed monolayer system in order to understand the behavior of the A−x₂^π curves.     

Characterization of the interaction of a mono‐6‐thio‐β‐cyclodextrin‐capped CdTe quantum dots–methylene blue/methylene green system with herring sperm DNA using a spectroscopic approach

Novel, water‐soluble CdTe quantum dots (QDs) capped with β‐cyclodextrin (β‐CD) and ~ 4.0 nm in diameter were synthesized in aqueous solution, and characterized using transmission electron microscopy (TEM). A fluorescence‐sensing system based on the photoinduced electron transfer (PET) of (mono‐6‐thio‐β‐CD)–CdTe QDs was then designed to measure the interaction of phenothiazine dyes [methylene blue (MB) and methylene green (MG)] with herring sperm DNA (hsDNA). This fluorescence‐sensing system was based on a fluorescence “OFF–ON” mode. First, MB/MG adsorbed on the surface of (mono‐6‐thio‐β‐CD)–CdTe QDs effectively quenches the fluorescence of (mono‐6‐thio‐β‐CD)–CdTe QDs through PET. Then, addition of hsDNA restores the fluorescence intensity of (mono‐6‐thio‐β‐CD)–CdTe QDs, because hsDNA can bind with MB/MG and remove it from the as‐prepared (mono‐6‐thio‐β‐CD)–CdTe QDs. In addition, detailed reaction mechanisms of the (mono‐6‐thio‐β‐CD)–CdTe QDs–MB/MG–hsDNA solution system were studied using optical methods, by comparison with the TGA–CdTe QDs–MB/MG–hsDNA solution system. Copyright © 2014 John Wiley & Sons, Ltd.