Ultrastructural alterations in the ventricular myocardium of the adult Italian newt (Lissotriton italicus) following exposure to nonylphenol ethoxylate

Nonylphenols ethoxylates (NPEs) are surface active agents (surfactants) commonly used in cleaning products, in industrial processes, agricultural formulations and paints. They are found in sewage, municipal wastewaters and industrial effluents, and as contaminants in water bodies. Accumulating data suggest that exposure to NPEs can adversely affects functional properties of the neurologic, reproductive, immune, and endocrine systems. In order to examine whether NPEs exert similar damaging effects on the cardiovascular system, we used an amphibian model to examine the ultrastructural alterations of the ventricular myocardium following exposure to NPEs. Adult Lissotriton italicus in the aquatic phase were exposed to NPE10 (100 μg/L, ppb) for 96 h. Heart specimens were collected from a total of 10 individuals and processed for scanning and transmission electron microscopy. Our ultrastructural examinations demonstrated that amphibian ventricle is susceptible to the effects of NPEs. The most pronounced alterations were observed in the membrane compartments of both myocardial and endothelial cells as demonstrated by the presence of swollen mitochondria with disrupted cristae and dilated rough endoplasmic reticulum. We suggest that destabilization of the lipid milieu within membranes might represent one of the potential mechanisms by which NPEs exert their toxic effects on amphibian heart.     

一种新型芴类衍生物的光谱性质研究

合成了具有大π共轭性的对称型芴类衍生物9,9-二(2-乙基已基)-2,7-二(2-(4-甲氧基)苯-2,1-乙烯基)芴(简写为MO-Flu-MO)。通过元素分析、质谱、紫外-可见光谱和红外光谱对其进行了表征。测试了该染料在乙腈、二氯甲烷、四氢呋喃和正己烷4种不同极性溶剂中的线性吸收光谱和单光子荧光谱。结果发现溶剂效应对吸收光谱和荧光光谱表现出不同程度的影响,对产生这些光谱行为的主要原因进行了讨论。     

The Synthesis, X-ray Crystal Structure and Optical Properties of Novel 5-aryl-3-ferrocenyl-1-pyridazinyl-pyrazoline Derivatives

A series of novel 5-aryl-3-ferrocenyl-1-pyridazinyl pyrazoline derivatives was synthesized by the reaction of ferrocenyl chalcone and 3-chloro-6-hydrazinylpyridazine in 10-65% yields. The compounds were characterized using IR, (1)H NMR, HRMS spectroscopic techniques and representative compounds 3c and 4c were assigned based on the X-ray crystallographic structure. The absorption and fluorescence characteristics of the compounds were investigated in chloroform, tetrahydrofuran and acetonitrile, respectively. The results showed that the absorption maxima of the compounds varied from 323 to 327 nm depending on the groups bonded to benzene and pyridazine ring. The maximum emission spectra of compounds in CHCl(3) were dependent on groups in pyridazine ring in which a strong donating-electron group such as propoxyl group on pyridazine ring in N-1 position of pyrazoline made the emission wavelength of 4a-4e small red shifte than that of compounds 3a-3e with chlorine group. The intensity of absorption and fluorescence was also correlated with substituent on aryl ring in C-5 position of pyrazoline. In addition, the absorption spectra of these compounds changed very little, but the fluorescence spectra had much change with increasing solvent polarity.     

MALDI-based intact spore mass spectrometry of downy and powdery mildews

Fast and easy identification of fungal phytopathogens is of great importance in agriculture. In this context, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has emerged as a powerful tool for analyzing microorganisms. This study deals with a methodology for MALDI-TOF MS-based identification of downy and powdery mildews representing obligate biotrophic parasites of crop plants. Experimental approaches for the MS analyses were optimized using Bremia lactucae, cause of lettuce downy mildew, and Oidium neolycopersici, cause of tomato powdery mildew. This involved determining a suitable concentration of spores in the sample, selection of a proper MALDI matrix, looking for the optimal solvent composition, and evaluation of different sample preparation methods. Furthermore, using different MALDI target materials and surfaces (stainless steel vs polymer-based) and applying various conditions for sample exposure to the acidic MALDI matrix system were investigated. The dried droplet method involving solvent evaporation at room temperature was found to be the most suitable for the deposition of spores and MALDI matrix on the target and the subsequent crystallization. The concentration of spore suspension was optimal between 2 and 5?×?10(9) spores per ml. The best peptide/protein profiles (in terms of signal-to-noise ratio and number of peaks) were obtained by combining ferulic and sinapinic acids as a mixed MALDI matrix. A pretreatment of the spore cell wall with hydrolases was successfully introduced prior to MS measurements to obtain more pronounced signals. Finally, a novel procedure was developed for direct mass spectra acquisition from infected plant leaves. Copyright ? 2012 John Wiley & Sons, Ltd.     

乙二醇分子间氢键结构与溶剂效应

采用密度泛函理论在B3LYP/6-311++G** (范德华校正)水平上研究乙二醇在气相中分别与乙腈、丙酮、四氢呋喃、水、乙二醇形成氢键二聚体的结构性质,根据PCM 极化统一场模型讨论氢键溶剂效应。结果表明,五种氢键二聚体分子中的氢键属于红移氢键,溶剂使氢键二聚体分子的偶极矩变大,并对OH振动频率的影响不大。     

乙二醇分子间氢键结构与溶剂效应

采用密度泛函理论在B3LYP/6-311++G~(**)水平上研究乙二醇在气相中分别与乙腈、丙酮、四氢呋喃、水、乙二醇形成氢键二聚体的结构性质,根据PCM(polarized continuum model)极化统一场模型讨论氢键溶剂效应.结果表明,五种氢键二聚体分子中的氢键属于红移氢键,溶剂使氢键二聚体分子的偶极矩变大,并对OH振动频率的影响不大.     

溶剂极性对1，5-二羟基蒽醌分子双质子转移过程的影响

具有激发态分子内双质子转移特性的分子在荧光传感器、激光材料、生物分子探针等领域具有广泛的应用. 羟基蒽醌作为蒽醌类化合物是自然界中广泛存在且具有质子转移特性的次级代谢物,其衍生物已被广泛研究并成功应用于染料、免疫增强和抗癌药物. 近年来,1,5-二羟基蒽醌(1,5-DHAQ)作为一种具有两个分子内氢键的羟基蒽醌衍生物受到了广泛的关注. 本文采用飞秒瞬态吸收光谱结合含时密度泛函理论方法研究了溶剂极性对1,5-DHAQ分子激发态分子内双质子转移过程的影响. 1,5-DHAQ分子在甲苯、四氢呋喃和乙腈溶剂中的稳态荧光光谱表明,溶剂极性的改变对1,5-DHAQ的荧光峰位置产生了影响. 瞬态吸收光谱表明,溶剂极性的增大加快了质子转移的速率. 超快动力学拟合结果表明,溶剂极性的增大有助于加快1,5-DHAQ分子中的激发态分子内双质子转移过程. 此外,通过理论计算得到的势能曲线分析表明质子转移的能垒随着溶剂极性的增加而逐渐减小,从而促进1,5-DHAQ分子激发态分子内双质子转移过程的发生,这进一步验证和解释了实验结果. 本工作有助于开发和合成更稳定、高效的羟基蒽醌衍生物.     

Influence of solvent basicity on DMABN photophysics

¹H‐NMR resonance measurements of 4‐(dimethylamino)benzonitrile (DMABN), dissolved in dichloromethane at temperatures over the range 300–195 K, confirm that the electronic charge transfer from its dimethylamino group to its cyano group increases with increasing dipolarity of the solvent and hence that the twisted internal charge transfer form of DMABN can be directly created by excitation of its electronic ground state. However, in tetrahydrofuran and 1,4‐dioxane, the DMABN molecules form complexes with the solvent, hindering charge transfer and reducing the electron‐releasing capability of the dimethylamino group. Irradiating a dilute solution of DMABN with an intensity as low as 7.8 × 10¹³ photons/s causes the formation of 4‐(methylamino)benzonitrile as photoproduct. The emission spectra of DMABN exhibit an isoemission point at a wavelength that is shifted with an increase in solvent dipolarity. The high efficiency with which the photoproduct is obtained seems to depend on the basicity of the solvent and challenges some former photophysical conclusions not considering this fact and drawn by using stronger irradiation sources, as well as the potential use of DMABN‐like compounds as solvent viscosity probes. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of preparation method on properties of lithium salt-poly(ethylene oxide) polymer electrolytes

The effects of using different sources of precursor poly(ethylene oxide) (PEO) and acetonitrile solvent on the physical and electrochemical properties of lithium salt-PEO polymer electrolytes were investigated. Although no differences were found due to the use of different types of PEO, the purity of the acetonitrile solvent was found to be critical in controlling the properties of the polymer product. Acetonitrile of nominally relatively low purity produced polymer electrolytes exhibiting largely crystalline type behaviour while the use of nominally high purity solvents gave polymers which were apparently completely amorphous at temperatures above about 50°C. Transport number measurements gave values for the lithium ions of 0.4 at 132°C for the largely crystalline materials and 0.3 at 112°C for the amorphous polymers. Analysis of the acetonitrile solvents revealed the presence of water in the nominally high purity grades and it has been confirmed that water contamination is responsible for the production of the low melting temperature form of the polymer complex.     

Effect of Non‐Ideal Mixed Solvents on Dimensions of Poly(N‐Vinylpyrrolidone) and Poly(Methyl Methacrylate) Coils

An addition of a small amount of non‐solvent tetrahydrofuran (THF) to good solvent water gave rise to a strong solvent power for poly(N‐vinylpyrrolidone) (PVP). It was found that PVP coils in mixtures of water and THF first swelled as the fraction of THF was increased, and then the coils contracted after a critical composition of the solvent mixture based on the measurement of dilute solution viscosities. It was reached that the power of the mixed solvents was not the simple average of the power of individual components. The influence of the non‐ideal mixing of water and THF on the power of these mixtures for PVP and the dimensions of PVP coils was taken into account. Especially the formation of pseudo‐clathrate hydrate structure with the composition φ _THF ≈ 0.44 was found to be an important factor to change the solvation and dimensions of PVP coils. Some other solvent mixtures for PVP and poly(methyl methacrylate) (PMMA) were also found to be non‐ideal mixtures. The viscosities of these solvent mixtures could show positive or negative deviation from the values obtained from the addition rule. It was shown again that the influence of the non‐ideality of these solvent mixtures on the dimensions of polymer coils was great. The action of mixed solvents changed the dimension of polymer coils, not only because of excluded volume effects but also because of the different molecular interactions present in these mixed solvents.     

分子印迹聚合反应中功能单体与模板分子间作用力的光谱分析

要获得吸附性能良好的非共价型分子印迹聚合物,聚合前模板分子与功能单体的结合程度至关重要。而相关研究报道较少。文章采用紫外光谱并结合红外光谱分析法,研究了模板分子穿心莲内酯与功能单体丙烯酰胺(AM)在3种溶剂乙腈、四氢呋喃和乙酸乙酯中相互作用力的大小。实验结果发现,穿心莲内酯与AM在乙腈溶剂中,224nm处的紫外吸收峰发生蓝移,蓝移5nm,且吸收峰增强,红外光谱中O—H伸缩振动峰发生蓝移,蓝移近8cm-1,N—H伸缩振动峰蓝移近6cm-1,表明两者之间发生较强的蓝移氢键作用力;而它们在另两种溶剂中作用力很微弱。因此,加入功能单体后光谱改变越大分子间作用力越强,识别点的选择性越好,由此制备的分子印迹聚合物吸附性能越好。     

分子印迹聚合反应中致孔剂选择的紫外光谱分析

在制备分子印迹聚合物的过程中,模板分子与功能单体的结合程度直接影响到分子印迹聚合物的吸附性能,适宜的致孔剂对模板分子与功能单体之间的作用力影响巨大.采用紫外光谱分析法,研究了模板分子香兰素与功能单体丙烯酰胺(AM)在3种致孔剂乙腈、四氢呋喃和乙酸乙酯中相互作用力的大小.实验结果发现,香兰素与AM在乙腈致孔剂中,227nm处的紫外吸收峰发生蓝移,蓝移5nm,且吸收峰增强,表明两者之间发生较强的氢键作用力;而它们在另两种致孔剂中作用力很微弱.因此,加入功能单体后光谱改变越大分子间作用力越强,由此制备的分子印迹聚合物的吸附性能越好.     

借助功能阳离子实现敏化发光的铕配合物的溶剂效应的研究

在离子缔合型铕配合物Eu(tta)₄·DEASPI中,借助功能阳离子DEASPI的电荷转移激发态可以实现对铕离子的单光子与双光子的敏化发光,其能量传递遵循Förster机制。将Eu(tta)₄·DEASPI溶解于多种有机溶剂中(丙酮、DMF、乙醇和乙腈),发现溶剂效应对于该能量传递体系的影响非常显著。借助光谱测量,发现在乙腈溶液中能量传递效率远高于其他三种溶剂。本文对造成溶剂效应的多种因素进行了详细的分析。     

Solvent Polarity and Excitation Wavelength Dependence of the Dual Fluorescence in N,N-Diethyl-4-Nitrosoaniline

Dual fluorescence in N,N-Diethyl-4-nitrosoaniline (DENA) has been studied employing absorption, excitation and emission spectroscopic techniques and computational methods. The absorption and fluorescence spectra of DENA were measured in solvents of various polarities at room temperature. The emission spectra of DENA were found to exhibit a single emission band in non polar solvent (cyclohexane) and in a highly polar solvent (acetonitrile). In the contrary, two emission bands were observed in medium polar solvents (tetrahydrofuran, 1,2-dichloroethane and dichloromethane) whereby the short (local excited; LE) and long (charge transfer; CT) emission maxima correspond to the emission maxima of the compound observed in cyclohexane and acetonitrile solutions, respectively. Moreover, the two emission bands have shown strong excitation wavelength dependence, and area normalization resulted in an iso-emissive point. The two emission maxima were in addition found to correspond to two excitation maxima in 3D fluorescence spectra. Further, two minima were obtained in potential energy surface calculation of DENA. From the experimental and computational results it was concluded that the dual fluorescence may be attributed to the presence of two different ground state structural conformers of DENA in equilibrium that are stabilized through solute-solvent interaction.     

MALDI-TOF MS对难溶聚芳酰胺PA6T的分析表征

选用五种样品试剂三氟乙酸、四氢呋喃、甲酸、乙腈、60%乙腈/5%三氟乙酸和两种不同的制样方法,采用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)表征难溶性聚合物聚对苯二甲酸己二酰胺(PA6T)的结构和分子量。发现以60%乙腈/5%三氟乙酸为样品试剂所得谱图的分子质量范围和信噪比最大,且溶剂法一步点样优于无溶剂法制样。获得了离子液体中合成产物PA6T的链结构,表明其主链为线性,未发现环状聚合物的存在,存在三种端基结构聚合体： 两端均为氨基或羧基、或一端为氨基另一端为羧基。采用MALDI-TOF MS和SEC两种方法对比测量了PA6T的平均分子量和分子量分布指数,表明MALDI-OF MS测得的平均分子量低于SEC法,分子量分布指数也低于SEC法,这是由于MS处理数据时忽略了低分子量部分,且高分子量部分因难以离子化而无法得到引起的。对于难溶的聚芳酰胺类聚合物的结构和分子量及其分布表征,MALDI-TOF MS仍不失为一个好方法。     

Coexistence of solvated electrons and solvent valence anions in negatively charged acetonitrile clusters, (CH3CN)-n(n=10-100)

Anion photoelectron spectroscopy of acetonitrile cluster anions, (CH3CN)(-)(n) (n=10-100), successfully demonstrates the competitive coexistence of two different anionic species: a solvated electron and a solvent-bound valence anion. The distinctly different nature of these anions is revealed by hole-burning-type photoelectron spectroscopy and relative photodetachment cross section measurements. This unusual coexistence is attributed to the closely lying nature of their anionic states at just the number of solvent molecules sufficient to almost complete the first solvation layer.     

Size characterization of metal oxide nanoparticles in commercial sunscreen products

There is an increase in the usage of engineered metal oxide (TiO₂ and ZnO) nanoparticles in commercial sunscreens due to their pleasing esthetics and greater sun protection efficiency. A number of studies have been done concerning the safety of nanoparticles in sunscreen products. In order to do the safety assessment, it is pertinent to develop novel analytical techniques to analyze these nanoparticles in commercial sunscreens. This study is focused on developing analytical techniques that can efficiently determine particle size of metal oxides present in the commercial sunscreens. To isolate the mineral UV filters from the organic matrices, specific procedures such as solvent extraction were identified. In addition, several solvents (hexane, chloroform, dichloromethane, and tetrahydrofuran) have been investigated. The solvent extraction using tetrahydrofuran worked well for all the samples investigated. The isolated nanoparticles were characterized by using several different techniques such as transmission electron microscopy, scanning electron microscopy, dynamic light scattering, differential centrifugal sedimentation, and x-ray diffraction. Elemental analysis mapping studies were performed to obtain individual chemical and morphological identities of the nanoparticles. Results from the electron microscopy techniques were compared against the bulk particle sizing techniques. All of the sunscreen products tested in this study were found to contain nanosized (≤100 nm) metal oxide particles with varied shapes and aspect ratios, and four among the 11 products were showed to have anatase TiO₂.     

On-target separation of analyte with 3-aminoquinoline/α-cyano-4-hydroxycinnamic acid liquid matrix for matrix-assisted laser desorption/ionization mass spectrometry

3-Aminoquinoline/α-cyano-4-hydroxycinnamic acid (3AQ/CHCA) is a liquid matrix (LM), which was reported by Kumar et al. in 1996 for matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. It is a viscous liquid and has some advantages of durability of ion generation by a self-healing surface and quantitative performance. In this study, we found a novel aspect of 3AQ/CHCA as a MALDI matrix, which converges hydrophilic material into the center of the droplet of analyte-3AQ/CHCA mixture on a MALDI sample target well during the process of evaporation of water derived from analyte solvent. This feature made it possible to separate not only the buffer components, but also the peptides and oligosaccharides from one another within 3AQ/CHCA. The MALDI imaging analyses of the analyte-3AQ/CHCA droplet indicated that the oligosaccharides and the peptides were distributed in the center and in the whole area around the center of 3AQ/CHCA, respectively. This 'on-target separation' effect was also applicable to glycoprotein digests such as ribonuclease B. These features of 3AQ/CHCA liquid matrix eliminate the requirement for pretreatment, and reduce sample handling losses thus resulting in the improvement of throughput and sensitivity.     

The Solvent Effect on Spin Exchange in Long-Chain Nitroxide Biradicals

Intramolecular electron spin exchange, as a function of temperature and the solvent viscosity, polarity and relaxation properties of the solvent molecules, has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two long-chain flexible nitroxide biradicals existing in fluid solutions in three spectroscopically different spatial conformations. Certain thermodynamic parameters of the conformational rearrangements were calculated from the EPR spectra. Spin exchange in two biradicals dissolved in five different alcohols was compared with that in a nonpolar solvent (toluene), polar protic (water) and aprotic (acetonitrile), and with thermodynamic characteristics of the solvents. Distinct correlations were found between macroscopic (solvent viscosity, polarity) and microscopic (solvent longitudinal relaxation time) characteristics of solvents, and thermodynamic parameters of the intramolecular conformational transitions. Authors' address: Van Anh Tran, Institute of Physical and Theoretical Chemistry, Graz University of Technology, Technikerstrasse 4, 8010 Graz, Austria     

Mechanism of sulfur transfer from 1,2,4‐dithiazolidine‐3,5‐diones to triphenylphosphines

The mechanism of sulfurization of substituted triphenylphosphines with 4‐(3‐ and 4‐substituted)‐1,2,4‐dithiazolidine‐3,5‐diones in acetonitrile, dichloromethane, tetrahydrofuran and toluene at 25 °C was studied. The reaction pathway involves rate‐limiting initial nucleophilic attack of the phosphorus at sulfur followed by fast decomposition of the phosphonium intermediate to the corresponding phosphine sulfide, phenylisocyanate and carbonylsulfide. From the Hammett correlations and from the solvent dependency, it was concluded that the transition‐state structure is very polar and resembles the zwitter‐ionic intermediate. The extent of P–S bond formation and S–S bond cleavage is very similar in the solvents series, but the latter gradually decreases with the decreasing polarity of the solvent. Copyright © 2013 John Wiley & Sons, Ltd.