Effect of pure and mixed solvents on the solubility, crystal growth and morphology of ethyl p-dimethylamino benzoate (EDMAB): An organic nonlinear optical material

The effects of pure and mixed solvents of ethanol and acetone on solubility, nucleation and growth of ethyl p-dimethylamino benzoate (EDMAB) were investigated. It was found that solubility of EDMAB increased as the volume ratio of acetone increased in the mixed solvent. Growth experiments were performed at 32 °C using pure and mixed solvents with different volume ratios of ethanol and acetone. Bulk single crystals of EDMAB were grown-in the experiment conducted using mixed solvent of 25% acetone and 75% of ethanol, whereas thin platelet crystal of EDMAB was obtained in the experiment conducted using pure ethanol. The acetone rich system resulted in uncontrolled nucleation with large number of tiny crystals, possibly due to high vapor pressure of acetone. The grown crystals were subjected to various analytical studies such as powder X-ray diffraction, Vickers microhardness, dielectric studies as a function of frequency and optical transmission and the powder Kurtz method.     

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。     

PSSS50-b-PNIPAM300嵌段共聚物在二元溶剂中自组装的NMR研究

本文结合核磁共振（NMR）、动态光散射（DLS）和透射电子显微镜（TEM）等表征方法,对自主合成的聚阴离子型温敏嵌段共聚物—聚（苯乙烯磺酸钠）-b-聚（N-异丙基丙烯酰胺）（PSSS₅₀-b-PNIPAM₃₀₀）在纯水、水/甲醇以及水/丙酮三种溶剂中的温度响应性和自组装行为进行了系统研究.结果发现PNIPAM链段在水/丙酮以及水/甲醇二元溶剂中的临界溶解温度（LCST）比在纯水溶液中略低,而在水/丙酮体系中的塌缩程度却明显低于纯水和水/甲醇体系.同时,PSSS₅₀-b-PNIPAM₃₀₀在不同溶剂体系中的聚集形貌也存在显著差异,表明加入有机溶剂小分子可以有效地调控温敏嵌段共聚物在水溶液中的自组装过程和聚集形貌.     

Simple low-loss waveguide bends using ARROW effect

A new concept for reducing bend loss in dielectric planar waveguides is presented. It is based on the introduction of a set of antiresonant reflecting optical waveguides (ARROWs) on the outside of the bent core and defined in the same fabrication step as the main bend. It has been ascertained by simulation that the bending loss can be significantly reduced. The method is compatible with other bend-lossreduction strategies, as well as with different waveguiding structures, such as rib and buried waveguides and fibers.This revised version was published online in August 2005 with a corrected cover date.     

Imperviousness of the hydrophobic silica aerogels against various solvents and acids

The experimental results on the imperviousness of the silica aerogels against various organic solvents and acids, are reported. Various types of hydrophobic silica aerogels were prepared using methyltrimethoxysilane (MTMS); tetraethoxysilane (TEOS) with ethyltriethoxysilane (ETES) and phenyltriethoxysilane (PTES) as co-precursors. The organic solvents used were: methanol, ethanol and acetone, and the acids used were: hydrochloric acid (HCl), nitric acid (HNO₃) and sulphuric acid (H₂SO₄). The imperviousness of the aerogels against these solvents and acids were tested with the variation of the percentage of organic solvents and acids in water from 10 to 100% and was characterized by the contact angle measurements. It was observed that in all the cases, the contact angle decreased with an increase in the percentage of solvent in water. While there was no absorption of the solvent up to 20% in water by the ETES and PTES modified aerogels, the MTMS-based aerogels showed the imperviousness up to 60% of the solvent in water. The MTMS aerogels were also impervious against all the three acids up to 100%, while the ETES and PTES modified aerogels could withstand only up to 80% of acids in water.     

用纳米压痕法分析溶剂对聚醚醚酮(PEEK)力学性能的影响

Poly (ether ether ketone)(PEEK) is a high-performance semi-crystalline thermoplastic polymer.Exposure of the polymeric surface to solvents can have a strong effect like softening/swelling of polymeric network or dissolution.In this study,nano-indentation analysis was performed to study the effect of acetone on the surface mechanical properties of PEEK using different exposure time.The experiments were performed with a constant loading rate (10 nm/s) to a maximum indentation displacement (1000 nm).A 30-second hold segment was included at the maximum load to account for any creep effects followed by an unloading segment to 80% unloading.The indentation hardness and the elastic modulus were computed as a continuous function of the penetration displacement in the continuous stiffness mode (CSM) indentation.The experimental data showed that the peak load decreased from ~5.2 mN to ~1.7 mN as exposure time in solvent environment increased from 0 to 18 days.The elastic modulus and the hardness of PEEK samples also displayed a decreasing trend as a function of exposure time in the solvent environment.Two empirical models were used to fit the experimental data of hardness as a function of exposure time which showed a good agreement with the experimental values.     

银纳米线表面等离激元波导的能量损耗

金属纳米结构的表面等离激元可以突破光学衍射极限,为光子器件的微型化和集成光学芯片的实现奠定基础.基于表面等离激元的各种基本光学元件已经研制出来.然而,由于金属结构的固有欧姆损耗以及向衬底的辐射损耗等,表面等离激元的传输能量损耗较大,极大地制约了其在纳米光子器件和回路中的应用.研究能量损耗的影响因素以及如何有效降低能量损耗对未来光子器件的实际应用具有重要意义.本文从纳米线表面等离激元的基本模式出发,介绍了它在不同条件下的场分布和传输特性,在此基础上着重讨论纳米线表面等离激元传输损耗的影响因素和测量方法以及目前常用的降低传输损耗的思路.最后给出总结以及如何进一步降低能量损耗方法的展望.表面等离激元能量损耗的相关研究对于纳米光子器件的设计和集成光子回路的构建有着重要作用.     

纳米ZnO墨水的溶剂及浓度优化及其在钙钛矿太阳能电池中的应用

纳米金属Zn O作为界面缓冲材料能够有效提高基于有机金属卤化物-甲基碘化铵的钙钛矿(PVSK)太阳能电池的水氧稳定性,是溶液制备高稳定性钙钛矿太阳能电池的一个关键技术。而在器件的制备过程中,Zn O分散溶剂的渗透可能导致下层钙钛矿薄膜的结构物性发生变化,从而对器件性能造成显著的影响。为解决该问题,本文详细分析了不同极性有机溶剂对Zn O分散性的影响,研究了不同溶剂对PVSK/PCBM薄膜的吸收光谱和晶体结构的影响,最终获得了甲醇-正丁醇混合溶剂的体积比为1∶1、Zn O质量浓度为10 mg·m L-1的优化分散体系,为进一步开展全溶液法制备钙钛矿太阳能电池提供了重要指导。     

Effect of dielectric properties of solvents on the quality factor for a beyond 900 MHz cryogenic probe model

A previous report by Kelly et al. [J. Am. Chem. Soc. 124 (2002) 12013] indicated that the ionic conductivity of aqueous solution produces a significant contribution to the sensitivity loss in high-resolution NMR equipped with a cryogenically cooled probe. The loss in a sample solution contains two contributions: one from the ionic conductivity and the other from the dielectric loss; the latter is especially important at high frequencies such as above 900 MHz. Here, we investigated the effect of the dielectric conductivity on the quality factor of a 930 MHz cryogenic probe model; in particular, it deals with the ionic aqueous solutions and organic solvents commonly used for NMR in biological research and the chemistry of natural compounds. The sample quality factor, Qs, at first increases with the real part of the relative dielectric permittivity epsilon' and then saturates. In the case of polar organic solvents, the transverse electric field on the sample decreases with epsilon', resulting in an increase of Qs. In the case of non-polar organic solvents, the dielectric conductivity is so small that the gradient of the increase is steep, resulting in much larger Qs though the epsilon' is small. The effect of the transverse electric field is negligible if the epsilon' becomes large, thus the loss for ionic aqueous solution is mainly governed by a loop current induced in the sample solution. As the induced electromotive force is independent of the epsilon', the Qs is saturated at high values of epsilon'. Based on the Qs obtained with the cryogenic probe model, the sensitivity for the cryogenic probe is expected to be as follows: the loss in sensitivity by loading water is more than 66%, i.e., the effect of the dielectric conductivity of water is remarkable at high frequencies; polar organic solvent suffers much larger losses, which is due to the enhancement of the effective sample resistance by the effect of epsilon'; a non-polar organic solvent is nearly free of the sensitivity loss as the dielectric conductivity is negligible; the reverse micelle behaves similarly.     

Concerted SN2 mechanism for the hydrolysis of acid chlorides: comparisons of reactivities calculated by the density functional theory with experimental data

DFT computations have been performed in acetone and water solvents in order to investigate the mechanism of hydrolysis of acid chlorides. Acetyl chloride and chloroacetyl chloride hydrolyze via concerted, one‐step S_N2 mechanism, with the attack of water at the sp² hybridized carbon atom of the C?O group, and the transition state (TS) has distorted tetrahedral geometry. Solvent molecules act as general base and general acid catalysts. The TS of chloroacetyl chloride is tighter and less polar than the TS of acetyl chloride. The structure of the S_N2 TS for the hydrolysis of benzoyl chlorides changes with the substituents and the solvent. Tight and loose TSs are formed for substrates bearing electron withdrawing (e‐w) and electron donating (e‐d) groups, respectively. In acetone, only the e‐w effect of the substituents increase the reactivity of the substrates, and the change of the structure of the TSs with the substituents is small. In water, polar and very loose TSs are formed in the reactions of benzoyl chlorides bearing e‐d substituents, and the rate enhancing effect of both e‐d and e‐w groups can be computed at higher level of theory. Calculated reactivities and the changes of the structure of the TSs with substituents and solvent are in accordance with the results of kinetic studies. In S_N2 nucleophilic substitutions late/early TSs are formed if the attacking reagent is poorer/better nucleophile than the leaving group, and loose/tight TSs are formed for substrates bearing e‐d/e‐w substituents and in protic/aprotic solvents. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of the solvent on the segmental dynamics and structure in mixed compositions of polyurethane and styrene-acrylonitrile copolymer

The effect of the tetrahydrofuran (THF), methyl ethyl ketone (MEK), ethyl acetate (EA), and acetone (A) solvents on the structure and segmental dynamics of polyurethane (PU)-(styrene-acrylonitrile) (SAN) mixed compositions are studied by spin-probe EPR spectroscopy, differential scanning calorimetry, and infrared spectroscopy. The molecular mobility τ, the degree of crystallinity χ, the modulus of elasticity E alter only slightly in passing from 100% PU to a 50% PU-50% SAN, but the structural and dynamic properties change abruptly at a high SAN content in the composition, regardless of the type of solvent. The values of τ, χ, and elastic modulus for the mixed compositions increases depending on the type of solvent in the following sequence: THF, MEK, EA, A, which can be explained by the thermodynamic affinity between the solvent and solute. It is also shown that, with growing content of SAN in the composition, the number of intermolecular hydrogen bonds between nitrile and urethane groups (3344-cm^?1 band) increases.     

Surface modification of copper with 2-dodecylpropane-1,3-dithiol: The key effect of the solvent

Self-assembly of alkanethiol on gold in various solvents (alkane, alcohol, etc) leads to monolayers with similar properties. However when the self-assembly is performed on copper substrates, the nature of the solvent has an effect on the properties of the monolayer. This phenomenon arises from the chemical interaction of copper with the solvent, which is not the case of gold.Ethanol is a solvent widely used for self-assembly, however some studies pointed out its negative effect due to its significant chemical reactivity towards copper and its ability to chemisorb on the surface.The aim of this work consists in a comparative investigation of 2-dodecylpropane-1,3-dithiol (or R(SH)₂) in various solvents and its ability to form stable SAMs, densely packed and well ordered. Characterizations of the SAMs are carried out using X-ray photoelectron spectroscopy (XPS), polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and cyclic voltammetry (CV).     

基于溶剂化效应的BDE-15分子振动光谱增强特征振动研究

利用密度泛函与自洽反应场理论在B3LYP/6-31+G(d)水平下分别计算气态及24种不同极性溶剂中4,4’-二溴二苯醚(4,4’-dibrominated diphenyl ethers, BDE-15)的分子振动光谱(红外光谱、拉曼光谱),以气态分子振动光谱为基准,筛选出对溶剂极性敏感的特征振动作为指标构建溶剂对BDE-15振动光谱溶剂化效应指标体系,探究溶剂对BDE-15分子振动频率、红外/拉曼峰强溶剂化效应及综合效应,并寻求显著增强BDE-15分子特征振动频移/强度的溶剂。研究表明：从分子振动频率角度,溶剂极性敏感的(频移>1 cm-1)分子特征振动均为伸缩振和面外弯曲振,但24种溶剂对BDE-15分子振动频率溶剂化效应并不显著;从分子振动峰强角度,24种溶剂对BDE-15分子振动光谱峰强的增强效应主要发生在红外光谱的中低频区及拉曼光谱的高频区,其中起显著增强(红外/拉曼效应指标值分别大于6与5)的溶剂为醇类、乙腈、二甲亚砜、硝基苯;不同极性溶剂对BDE-15拉曼峰强溶剂化效应及综合效应指标值均表现出随溶剂介电常数增长由线性到对数的增长趋势,而红外峰强只保留低介电常数溶剂时的线性关系。利用上述BDE-15分子振动光谱峰强增强方法对BDE-153,BDE-154和BDE-209进行验证,醇类、乙腈、二甲亚砜、硝基苯对三者的振动光谱红外/拉曼峰强的效应指标值分别大于6与5,且最大峰强增倍数皆大于33,说明所建BDE-15分子振动光谱增强特征振动方法有助于进一步开展基于分子振动光谱的PBDEs同系物间辨识研究。     

Correlation between charge decay and solvent effect for melt-blown polypropylene electret filter fabrics

Melt-blown polypropylene electret fabrics are widely used as air filter media. However, its filtration efficiency gradually decays in application process. This paper is to investigate the correlation between filtration efficiency decay and solvent effect. Experimental results show that filtration efficiency displays a regular decrease when polypropylene electret fabrics are exposed to solvents in the sequence of water, ethanol, isopropanol and acetone. The results can be correlated to solubility parameter difference between polypropylene and solvent according to the Flory–Huggins swelling theory. Smaller solubility parameter difference leads to greater decay of filtration efficiency owing to greater affinity between polypropylene and solvent.     

Multivariate optimization and comparison between conventional extraction (CE) and ultrasonic-assisted extraction (UAE) of carotenoid extraction from cashew apple

Carotenoids are an essential component of cashew and can be used in pharmaceuticals, cosmetics, natural pigment, food additives, among other applications. The present work focuses on optimizing and comparing conventional and ultrasound-assisted extraction methods. Every optimization step took place with a 1:1 (w:w) mixture of yellow and red cashew apples lyophilized and ground in a cryogenic mill. A Simplex-centroid design was applied for both methods, and the solvents acetone, methanol, ethanol, and petroleum ether were evaluated. After choosing the extractor solvent, a central composite design was applied to optimize the sample mass (59–201 mg) and extraction time (6–34 min). The optimum conditions for the extractor solvent were 38% acetone, 30% ethanol, and 32% petroleum ether for CE and a mixture of 44% acetone and 56% methanol for UAE. The best experimental conditions for UAE were a sonication time of 19 min and a sample mass of 153 mg, while the CE was 23 min and 136 mg. Comparing red and yellow cashews, red cashews showed a higher carotenoid content in both methodologies. The UAE methodology was ca. 21% faster, presented a more straightforward composition of extracting solution, showed an average yield of superior carotenoid content in all samples compared to CE. Therefore, UAE has demonstrated a simple, efficient, fast, low-cost adjustment methodology and a reliable alternative for other applications involving these bioactive compounds in the studied or similar matrix.     

Comparison Between the Induced Changes in the Intensities of Mid and Near Infrared Absorption Bands of Poly[Vinyl Alcohol] Due to Temperature and Solvents

The temperature induced changes in the intensities of the infrared absorption bands of PVA in both MID and NIR regions are presented. The absorption band at 1141cm^-1 is the only band among the bands in the mid region which is markedly affected by temperature. This band is taken as a measure of crystallinity of PVA. PVA shows two phase transitions at 80c⁰ and 120c⁰. The absorbances of the 1940nm in the near region is also temperature sensititve. The temperature dependence of the other bands in either mid or near regions is very weak. The effect of non polar and polar solvents such as n-hexane, carbon tetrachloride, toluene, chloroform, methanol and acetone is discussed. Comparison between the solvent induced changes in the intensities of the bands in mid and near regions is carried out. The data demonstrate that the bands in the near region ( overtone and combinations) are more sensitive to solvents than the bands in the mid regions. The combined effect of temperature and solvents on the intensities of absorption bands of PVA is also studied.     

Interference effect in scattering loss of high-index-contrast planar waveguides caused by boundary reflections

We present theoretical and experimental results on an interference effect caused by boundary reflections on the optical scattering loss in high-index-contrast planar waveguides. Analytical expressions for the polarization-dependent scattering loss are derived using a surface Green's function. For high-index-contrast waveguides of submicrometer dimensions a significant deviation from accepted theory arises, including scattering loss suppression owing to a thin-film interference effect. Our theoretical predictions are confirmed by loss measurements on silicon-on-insulator channel waveguides.     

溶剂对辐射变色膜吸收剂量的影响

本实验室分别选用无水乙醇和丙酮溶液为溶剂制成两种类型的辐射变色膜, 并对这两种辐射变色膜进行了60Co γ射线与紫外线辐照, 研究不同溶剂对辐射变色膜吸收剂量的影响。实验发现, 60Co γ射线与紫外线辐照后, 使用丙酮作溶剂的辐射变色膜变色效果比无水乙醇的更加明显。在相同的辐照剂量下, 使用丙酮作为溶剂的变色膜比用无水乙醇的光谱吸收峰(680 nm)值平均高65.5%。γ射线辐照时, 用丙酮作为溶剂的辐射变色膜变色的辐照剂量下限为0.5 Gy, 而用无水乙醇做为溶剂的为1 Gy; 紫外辐照时, 用丙酮为溶剂的辐射变色膜吸收峰处吸收剂量的线性响应区间为0～6×100 μJ/cm2, 而用无水乙醇做为溶剂的为0～36×100 μJ/cm2。     

Synthesis of a fluorinated photoresist for optical waveguide devices

A linear fluorinated bis-phenol-A novolac resin (LFAR) for optical waveguide was synthesized based on 4,4′-(hexafluoro-isopropylidene)diphenol, epoxy chloropropane and formaldehyde. Negative fluorinated photoresist (FP) was made by composing the LFAR, diphenyl iodonium salt and solvent. The film, which was made by spin-coating FP, had good UV light lithograph sensitivity, large hardness and high glass transition temperature (T _g >170°C, after crosslinking). Low-loss optical waveguides with very smooth top surface were fabricated from the resulting FP by direct UV exposure and chemical development. For waveguides without upper cladding, the propagation loss of the channel waveguides was measured to be 0.21 dB/cm at 1550 nm.     

Kinetics of the thermal decomposition reaction of diethylketone cyclic triperoxide in acetone–toluene and acetone–1‐propanol binary solvent mixtures

The thermal decomposition reaction of diethylketone triperoxide (DEKT) ca. 0.02 M was studied in binary mixtures of acetone–toluene and acetone–1‐propanol at 150 °C. Products of DEKT thermolysis in solution, detected by GC analysis, were diethylketone, bibenzyl and butane. The reactions were explored by GC at different solvent compositions and in each case the reactions followed a pseudo first order kinetic law, up to at least 90% peroxide conversion. The rate coefficient value of the reaction is affected by the solvent properties, showing an increase in the k_obs values with increases in the polarity of the solvent mixture in acetone–toluene systems. Changes in the rate coefficient values are probably caused by the presence of the apolar toluene solvent, which dominates the preferential solvation around the DEKT molecule through non‐specific interactions. In acetone–1‐propanol mixtures the solvation effect is slightly dominated by the specific interactions between the 1‐propanol and a polar intermediate specie represented by the biradical, initially formed. The rate coefficient value increases ca. 6% in the mixture with 0.1 mole fraction of 1‐propanol in comparison with the value in pure acetone; but no more changes in rate coefficient values are observed when the amount of the alcohol increases. The critical state of the reaction (intermediate biradical) is preferentially solvated by the 1‐propanol instead of acetone, but in mixtures of different composition, it is not possible to detect any effect on the reactivity for homolytic rupture of the O? O bond. Copyright © 2008 John Wiley & Sons, Ltd.