Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone^® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.     

Electrophysiological Activity and Survival Rate of Rats Nervous Tissue Cells Depends on D/H Isotopic Composition of Medium

The deuterium content modification in an organism has a neuroprotective effect during the hypoxia model, affecting anxiety, memory and stress resistance. The aim of this work was to elucidate the possible mechanisms of the medium D/H composition modification on nerve cells. We studied the effect of an incubation medium with a 50 ppm deuterium content compared to a medium with 150 ppm on: (1) the activity of Wistar rats’ hippocampus CA1 field neurons, (2) the level of cultured cerebellar neuron death during glucose deprivation and temperature stress, (3) mitochondrial membrane potential (MMP) and the generation of reactive oxygen species in cultures of cerebellar neurons. The results of the analysis showed that the incubation of hippocampal sections in a medium with a 50 ppm deuterium reduced the amplitude of the pop-spike. The restoration of neuron activity was observed when sections were returned to the incubation medium with a 150 ppm deuterium content. An environment with a 50 ppm deuterium did not significantly affect the level of reactive oxygen species in neuron cultures, while MMP decreased by 16–20%. In experiments with glucose deprivation and temperature stress, the medium with 50 ppm increased the death of neurons. Thus, a short exposure of nerve cells in the medium with 50 ppm deuterium acts as an additional stressful factor, which is possibly associated with the violation of the cell energy balance. The decrease in the mitochondrial membrane potential, which is known to be associated with ATP synthesis, indicates that this effect may be associated with the cell energy imbalance. The decrease in the activity of the CA1 field hippocampal neurons may reflect reversible adaptive changes in the operation of fast-reacting ion channels.     

Sensitive Determination of 17β-Estradiol using a Magneto Sensor Based on Magnetic Molecularly Imprinted Polymer

The analysis of 17β-estradiol with high sensitivity and selectivity is extremely relevant to control the impacts that this compound can cause on health and the environment. Thus, we describe the development and application of a magneto carbon paste electrode based on magnetic molecularly imprinted polymer (MCPE-MMIP) for determination of 17β-estradiol. The analyte adsorbed on the MMIP was immobilized on the electrode surface by magnetic capture. The morphological and structural characterization of the obtained MMIP suggests that the material was effectively synthesized. MCPE-MMIP showed an improvement in the sensitivity for 17β-estradiol detection when compared to electrode configurations in the absence of this material. The optimum conditions (0.10 mol L⁻¹ phosphate buffer pH 7.0) were reached by differential pulse adsorptive stripping voltammetry (DPAdSV), in which the method presented linearity ranged from 0.06 to 175 μmol L⁻¹ with limits of detection and quantification of 0.02 and 0.06 μmol L⁻¹, respectively. The proposed sensor was applied effectively in the analysis of 17β-estradiol in river water and raw milk samples, exhibiting excellent recovery values (between 96.20 and 104 %), which were confirmed by HPLC analysis.     

Expanding the Ligand Classes Used for Mn(II) Complexation: Oxa-aza Macrocycles Make the Difference

We report two macrocyclic ligands based on a 1,7-diaza-12-crown-4 platform functionalized with acetate (tO2DO2A²⁻) or piperidineacetamide (tO2DO2AM^Pip) pendant arms and a detailed characterization of the corresponding Mn(II) complexes. The X−ray structure of [Mn(tO2DO2A)(H₂O)]·2H₂O shows that the metal ion is coordinated by six donor atoms of the macrocyclic ligand and one water molecule, to result in seven-coordination. The Cu(II) analogue presents a distorted octahedral coordination environment. The protonation constants of the ligands and the stability constants of the complexes formed with Mn(II) and other biologically relevant metal ions (Mg(II), Ca(II), Cu(II) and Zn(II)) were determined using potentiometric titrations (I = 0.15 M NaCl, T = 25 °C). The conditional stabilities of Mn(II) complexes at pH 7.4 are comparable to those reported for the cyclen-based tDO2A²⁻ ligand. The dissociation of the Mn(II) chelates were investigated by evaluating the rate constants of metal exchange reactions with Cu(II) under acidic conditions (I = 0.15 M NaCl, T = 25 °C). Dissociation of the [Mn(tO2DO2A)(H₂O)] complex occurs through both proton− and metal−assisted pathways, while the [Mn(tO2DO2AM^Pip)(H₂O)] analogue dissociates through spontaneous and proton-assisted mechanisms. The Mn(II) complex of tO2DO2A²⁻ is remarkably inert with respect to its dissociation, while the amide analogue is significantly more labile. The presence of a water molecule coordinated to Mn(II) imparts relatively high relaxivities to the complexes. The parameters determining this key property were investigated using ¹⁷O NMR (Nuclear Magnetic Resonance) transverse relaxation rates and ¹H nuclear magnetic relaxation dispersion (NMRD) profiles.     

Pourbaix diagrams in weakly coupled systems: a case study involving acridinol and phenanthridinol pseudobases

The thermodynamics of proton‐coupled electron transfer (PCET) in weakly coupled organic pseudobases was investigated using 2,7‐dimethyl‐9‐hydroxy‐9‐phenyl‐10‐tolyl‐9,10‐dihydroacridine (AcrOH) and 6‐phenylphenanthridinol (PheOH) as model compounds. Pourbaix diagrams for two model compounds were constructed using the oxidation potentials and the pK_a values obtained, respectively, from cyclic voltammetry and photometric titrations. Our comparative study reveals the importance of having the redox active –N center closer to –OH functionality on the thermodynamics of PCET process: PheOH exhibits a wider range of pH values (pH = 2.8 to 13.3) in which both the alcohol and the corresponding alkoxy radical are expected to coexist in solution. This result indicates that a concerted mechanism is more likely to be discovered in pseudobases analogous to PheOH. The thermochemical data also indicate that the concerted PCET mechanism cannot be achieved if water is used as the proton acceptor: assuming the pK_a of hydronium ions as ?1.7, the PCET involving PheOH or AcrOH as proton/electron donors and water as the proton acceptor is expected to follow the stepwise ET/PT mechanism. Copyright © 2015 John Wiley & Sons, Ltd.     

塔里木河流域中下游典型地物光谱变化规律

由于塔里木河流域中下游距离河道在垂直向的差别,以及气候与人为因素的影响,使植被的空间分布具有异构性.典型地物光谱变化的研究为中下游生态环境的遥感监测提供了基础,实验研究表明:绿色全荣植物中,棉花由于其具有明显绿峰、水分吸收谷和近红外的高反射峰而更加容易识别,其他植物主要差别则集中在550,680,1420 nm附近的反射峰、吸收谷和1920～2500 nm之间的反射率;与绿色植被相比,枯枝的光谱在可见光部分的绿峰和红光吸收谷不明显,但在可见光部分波形有所差别,而与流沙土壤光谱相比,各波段反射率变化较大;对比不同荣枯比例的植物光谱发现,同一种植物随着荣枯配比的变化,除可见光绿峰、近红外反射峰和各水分吸收谷变化外,最明显的是在近红外1420～1820 nm之间和短波红外1920～2500 nm之间反射率随着枯枝的比例增加而明显升高;关于土壤光谱,中下游各断面占主要类型的流沙土光谱相差不大,但是盐碱土和含有一定水分的盐碱土则变化较大,而且反射率基本低于流沙土,结壳土则除在近红外和短波红外部分变化更加平缓而有所差别外,其余波段接近流沙土;同样的土壤背景下,近红外和短波红外部分反射率的差别能够在一定程度上反映覆盖度的变化.     

水轮机导叶接力器电容式位移变送装置设计

针对现有的电位器拉线式水轮机导叶接力器位移变送装置中存在的接触不良、易磨损、输出信号不可靠的问题进行了分析.针对这些问题,运用电容式传感器原理,设计了一种新型水轮机导叶接力器电容式位移变送装置,该装置可以避免老式位移变送装置所存在的问题,能长期稳定可靠地实现线性测量水轮机导叶接力器的位移量.     

Hydroxyl radical electrochemically generated with water as the complete atom source and its environmental application

The most reactive hydroxyl radical （OH） was generated by electrochemical approach with safe water as the complete atom source. The direct evidence for OH formation was obtained by electron spin resonance method. The powerful OH electrochemically generated could effectively degrade organic pollutants and reduce the toxicity of wastewater. Electrochemical disinfection by OH was considerably efficient even without the aid of active chlorine. Bacteria inactivation of 99.99% was achieved for contact time of 30 min and current density of 5 mA·cm^-2, In comparison with active chlorine, OH is rather attractive as a promising environmentally benign disinfectant and opens a new route for microbial inactivation.     

氢化物发生无色散原子荧光分析法测定水中的砷和硒的含量

采用断续流动氢化物发生无色散原子荧光分析法同时测定水中的微量砷、硒,确定了仪器及氢化物产生的最佳实验条件。测定结果表明实际样品中砷的回收率在85%~110%之间;硒的回收率在92%~102%之间,样品测量值的相对标准偏差砷在1.1%~4.8%之间,硒在5.0%~5.9%之间。本方法可一次消化样品并同时测定砷、硒的含量,具有操作简单、快速、基体干扰少、灵敏度高、分析结果稳定可靠、节省试剂等特点,并且采用自动进样,适于大量样品的快速分析。     

阳离子聚合物对喷墨记录材料性能的影响

研究了不同阳离子聚合物聚二甲基二烯丙基氯化铵(PDMDAAC)和二甲基二烯丙基氯化铵－丙烯酰胺共聚物(PDMDAAC-AM)对喷墨记录材料的吸墨速度、清晰度以及耐水性能的影响。结果表明,当PDMDAAC和PDMDAAC-AM的添加量为每10mL涂布液中加入0.4mL时,喷墨记录材料的记录性能达到最佳。且通过扫描电镜照片显示,向喷墨记录材料的涂层中添加PDMDAAC-AM比添加相同量的PDMDAAC能得到更好的记录性能,可使喷墨记录材料的吸墨速度加快13倍、清晰度提高0.76%、耐水性能也得到明显的改善.