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Effect of Concentration on Isomerization of Rhodanine Derivatives of Merocyanine Dyes in Polar Solvents 浓度对甲基蓝染料罗丹宁衍生物极性溶剂异构化的影响
Pub Date : 2014-08-27 DOI: 10.1155/2014/468910
O. Dimitriev, K. Grytsenko, O. I. Tolmachev, Y. Slominskii, M. Kudinova, S. Schrader
Rhodanine derivatives of merocyanine dyes with residues of 1,3,3-trimethyl-3H-indole and 3-ethylbenzothiazoline have been found to possess two molecular forms in diluted solutions of polar solvents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidinone. The first molecular form was observed to prevail at low concentrations of the dyes, normally up to 10−5 M. The second one prevails at higher concentrations and is displayed through a new band in the electronic absorption spectrum, which is red-shifted with respect to the absorption band of the first form. No similar effect was found for these dyes by use of nonpolar solvents or upon alkyl-substitution of the molecules at nitrogen atom in the rhodanine moiety. We assign the above two forms to different molecular isomers and the analogous spectral changes were shown to take place by light or heat influence which correspond to a typical isomerization effect for the related merocyanine dyes. It is discussed that the isomer transformation is facilitated by the increased mobility of the proton bonded to the nitrogen atom of the rhodanine moiety in the polar environment and the increased amount of dye-dye collisions.
以1,3,3-三甲基- 3h -吲哚和3-乙基苯并噻唑啉为残基的merocyanine染料的罗丹宁衍生物在极性溶剂如二甲基甲酰胺、二甲基亚砜和n -甲基吡咯烷酮的稀释溶液中具有两种分子形式。第一种分子形式被观察到在低浓度的染料中普遍存在,通常高达10 - 5 M。第二种形式在较高的浓度下普遍存在,并在电子吸收光谱中通过一个新的波段显示,该波段相对于第一种形式的吸收带发生红移。使用非极性溶剂或罗丹宁部分中氮原子分子的烷基取代对这些染料没有类似的效果。我们将上述两种形式分配给不同的分子异构体,并表明类似的光谱变化是在光或热影响下发生的,这对应于相关的merocyanine染料的典型异构化效应。讨论了在极性环境中,与罗丹宁部分的氮原子键合的质子的迁移率增加和染料-染料碰撞量的增加促进了异构体的转变。
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引用次数: 1
Ruthenium(III) Catalysis in Perborate Oxidation of 5-Oxoacids 钌(III)在5-氧酸过硼酸盐氧化中的催化作用
Pub Date : 2014-08-24 DOI: 10.1155/2014/879608
S. Devi, P. Krishnamoorthy, B. Muthukumaran
Ruthenium(III) catalyzes perborate oxidation of substituted 5-oxoacids in acidic solution. The catalyzed oxidation is first order with respect to the oxidant and catalyst. The rate of ruthenium(III) catalyzed oxidation displays the Michaelis-Menten kinetics on the reductant and is independent of [H
钌(III)在酸性溶液中催化取代5-氧酸的过硼酸氧化。对于氧化剂和催化剂来说,催化氧化是一级的。钌(III)催化氧化的速率在还原剂上表现出Michaelis-Menten动力学,与[H]无关
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引用次数: 1
Full Kinetics and a Mechanistic Investigation of the Green Protocol for Synthesis of β-Aminoketone in the Presence of Saccharose as a Catalyst by a One-Pot Three-Component Reaction 一锅三组分催化合成β-氨基酮绿色方案的全动力学和机理研究
Pub Date : 2014-06-16 DOI: 10.1155/2014/426749
S. Habibi‐Khorassani, M. Maghsoodlou, M. Shahraki, Sadegh Talaie Far, M. Mousavi
For the first time, in a green protocol, an investigation of the kinetics and mechanism of the reaction between benzaldehyde 1, 4-chloroanilinne 2, and acetophenone 3 compounds in the presence of saccharose as a catalyst was performed for generating β-aminoketone. For determining the kinetic parameters, the reaction was monitored by using the UV/Vis spectrophotometry technique. The second order rate constant () was automatically calculated by the standard equations contained within the program. In the studied temperature range, the second order rate constant (, ) depended on reciprocal temperature that was in good consistent with Arrhenius and Eyring equations, respectively. These data provided the suitable plots for calculating the activation energy and parameters (Ea, , , and ) of the reaction. Furthermore, useful information was obtained from studying the effects of solvent, concentration, and catalyst on the reaction mechanism. The results showed that the first step of the reaction mechanism is a rate determining step (RDS). The obtained experimental data and also the steady state assumption confirmed the proposed mechanism.
本文首次采用绿色方案研究了苯甲醛1,4 -氯苯胺2与苯乙酮3在蔗糖催化下生成β-氨基酮的反应动力学和反应机理。采用紫外/可见分光光度法测定反应动力学参数。二级速率常数()由程序中包含的标准方程自动计算。在研究温度范围内,二阶速率常数依赖于温度的倒数,与Arrhenius方程和Eyring方程符合较好。这些数据为计算反应的活化能和参数(Ea,,和)提供了合适的图。此外,研究了溶剂、浓度和催化剂对反应机理的影响,得到了有用的信息。结果表明,反应机理的第一步是速率决定步骤(RDS)。得到的实验数据和稳态假设证实了所提出的机理。
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引用次数: 3
A Development of Ethanol/Percarbonate Membraneless Fuel Cell 乙醇/过碳酸酯无膜燃料电池的研究进展
Pub Date : 2014-05-29 DOI: 10.1155/2014/862691
M. Priya, A. Arun, M. Elumalai, S. Kiruthika, B. Muthukumaran
The electrocatalytic oxidation of ethanol on membraneless sodium percarbonate fuel cell using platinum electrodes in alkaline-acidic media is investigated. In this cell, ethanol is used as the fuel and sodium percarbonate is used as an oxidant for the first time in an alkaline-acidic media. Sodium percarbonate generates hydrogen peroxide in aqueous medium. At room temperature, the laminar-flow-based microfluidic membraneless fuel cell can reach a maximum power density of 18.96 mW cm−2 with a fuel mixture flow rate of 0.3 mL min−2. The developed fuel cell features no proton exchange membrane. The simple planar structured membraneless ethanol fuel cell presents with high design flexibility and enables easy integration of the microscale fuel cell into actual microfluidic systems and portable power applications.
研究了在碱性-酸性介质中,铂电极在无膜过碳酸钠燃料电池上电催化氧化乙醇。在这个电池中,乙醇被用作燃料,过碳酸钠被用作氧化剂,这是第一次在碱性-酸性介质中使用。过碳酸钠在水介质中产生过氧化氢。在室温下,当混合燃料流量为0.3 mL min - 2时,基于层流的微流体无膜燃料电池的最大功率密度可达18.96 mW cm - 2。所研制的燃料电池没有质子交换膜。简单的平面结构无膜乙醇燃料电池具有很高的设计灵活性,可以很容易地将微尺度燃料电池集成到实际的微流体系统和便携式电源应用中。
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引用次数: 11
Equilibrium, Kinetics, and Thermodynamics of the Removal of Nickel(II) from Aqueous Solution Using Cow Hooves 用牛蹄从水溶液中去除镍的平衡、动力学和热力学
Pub Date : 2014-05-19 DOI: 10.1155/2014/863173
I. Osasona, O. Ajayi, A. Adebayo
The feasibility of using powdered cow hooves (CH) for removing Ni2+ from aqueous solution was investigated through batch studies. The study was conducted to determine the effect of pH, adsorbent dosage, contact time, adsorbent particle size, and temperature on the adsorption capacity of CH. Equilibrium studies were conducted using initial concentration of Ni2+ ranging from 15 to 100 mgL−1 at 208, 308, and 318 K, respectively. The results of our investigation at room temperature indicated that maximum adsorption of Ni2+ occurred at pH 7 and contact time of 20 minutes. The thermodynamics of the adsorption of Ni2+ onto CH showed that the process was spontaneous and endothermic. Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models were used to quantitatively analysed the equilibrium data. The equilibrium data were best fitted by Freundlich isotherm model, while the adsorption kinetics was well described by pseudo-second-order kinetic equation. The mean adsorption energy obtained from the D-R isotherm revealed that the adsorption process was dominated by physical adsorption. Powdered cow hooves could be utilized as a low-cost adsorbent at room temperature under the conditions of pH 7 and a contact time of 20 minutes for the removal of Ni(II) from aqueous solution.
通过批量试验考察了牛蹄粉(CH)去除水中Ni2+的可行性。研究了pH、吸附剂用量、接触时间、吸附剂粒径和温度对CH吸附能力的影响。在208、308和318 K条件下,Ni2+初始浓度分别为15 ~ 100 mgL−1,进行了平衡研究。在室温下的实验结果表明,在pH为7、接触时间为20分钟时,Ni2+的吸附量最大。甲烷吸附Ni2+的热力学结果表明,吸附过程是自发的、吸热的。采用Langmuir, Freundlich和Dubinin-Radushkevich (D-R)等温线模型对平衡数据进行定量分析。吸附平衡数据用Freundlich等温线模型拟合,吸附动力学用拟二级动力学方程描述。D-R等温线平均吸附能表明吸附过程以物理吸附为主。牛蹄粉可作为一种低成本吸附剂,在室温条件下,pH为7,接触时间为20分钟,可用于去除水溶液中的Ni(II)。
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引用次数: 2
Plasma Formation during Acoustic Cavitation: Toward a New Paradigm for Sonochemistry 声空化过程中的等离子体形成:迈向声化学的新范式
Pub Date : 2014-05-04 DOI: 10.1155/2014/173878
S. Nikitenko
The most recent spectroscopic studies of single bubble (SBSL) and multibubble (MBSL) sonoluminescence reveal that the origin of extreme intrabubble conditions is related to nonequilibrium plasma formed inside the collapsing bubbles. Analysis of the relative populations of OH(A2Σ
最近对单泡(SBSL)和多泡(MBSL)声致发光的光谱研究表明,极端泡内条件的起源与坍缩泡内形成的非平衡等离子体有关。OH相对居群分析(A2Σ)
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引用次数: 24
Sorption of Ammonium Ions onto Natural and Modified Egyptian Kaolinites: Kinetic and Equilibrium Studies 天然和改性埃及高岭石对铵离子的吸附:动力学和平衡研究
Pub Date : 2014-04-24 DOI: 10.1155/2014/935854
O. El-Shafey, N. Fathy, T. El-Nabarawy
Thermally activated, acid-activated, and acid-leached of thermally activated kaolinites were prepared from the Egyptian ore. The physical and chemical properties were studied using N2 sorption at −196°C, FTIR, SEM, and the total surface acidity. The sorption of ions on the investigated sorbents was controlled with the solution pH, sorbent dosage, and initial concentration of solution. Kinetic and equilibrium sorption at 30°C were employed. Four kinetic models were applied to the kinetic sorption data; pseudo-second-order, Elovich, and intraparticle diffusion models fitted well the kinetic data whereas pseudo-first-order model was less applicable. Elovich parameters refer to physical sorption type of on nonuniform sites and the intraparticle diffusion controls the sorption of by kaolinites to a small extent. The equilibrium sorption data followed Langmuir and D-R models; the negative value of indicates a spontaneous sorption and the mean sorption energy obtained shows also physical sorption. The sorption capacities of nonactivated and activated Egyptian kaolinites towards sorption (10.87–45.45 mg·g−1) were good sorbents as compared with those uptaken by other clays reported in the literature and proved to be more active besides being less expensive and highly available.
从埃及矿石中制备了热活化、酸活化和酸浸高岭石。采用- 196°C N2吸附、FTIR、SEM和表面总酸度研究了热活化高岭石的物理化学性质。所研究的吸附剂对离子的吸附受溶液pH、吸附剂用量和溶液初始浓度的控制。采用30℃下的动力学吸附和平衡吸附。对动力学吸附数据采用了四种动力学模型;伪二阶、Elovich和颗粒内扩散模型对动力学数据拟合较好,而伪一阶模型不太适用。Elovich参数是指在非均匀位置上的物理吸附类型,颗粒内扩散对高岭石的吸附有较小的控制作用。平衡吸附数据符合Langmuir和D-R模型;的负值表示自发吸附,平均吸附能也表示物理吸附。与文献报道的其他粘土相比,未活化和活化的埃及高岭土的吸附能力(10.87 ~ 45.45 mg·g−1)都是较好的吸附剂,而且价格便宜,可利用性高。
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引用次数: 15
Dielectric Relaxation Studies of 2-Butoxyethanol with Aniline and Substituted Anilines Using Time Domain Reflectometry 用时域反射法研究2-丁氧基乙醇与苯胺和取代苯胺的介电弛豫
Pub Date : 2014-02-18 DOI: 10.1155/2014/659531
P. Jeevanandham, S. Kumar, P. Periyasamy, A. Kumbharkhane
The complex dielectric spectra of 2-butoxyethanol with aniline and substituted anilines like aniline, o-chloroaniline, m-chloroaniline, o-anisidine and m-anisidine binary mixtures in the composition of different volumes of percent (0%, 25%, 50%, 75%, and 100%) have been measured as a function of frequency between 10 MHz and 30 GHz at 298.15 K. The dielectric parameters like static dielectric constant and relaxation time have been obtained by using least square fit method. By using these parameters , effective Kirkwood correlation factor , corrective Kirkwood correlation factor , Bruggeman factor , excess dielectric constant , and excess inverse relaxation time values are calculated and discussed to yield information on the dipolar alignment and molecular rotation of the binary liquid mixtures. From all the derived dielectric parameters, molecular interactions are interpreted through hydrogen bonding.
在298.15 K下,用不同体积(0%、25%、50%、75%和100%)的苯胺和取代苯胺(如苯胺、邻氯苯胺、间氯苯胺、邻苯胺和间苯胺)组成的2-丁氧基乙醇的复介电光谱作为频率在10 MHz和30 GHz之间的函数进行了测量。采用最小二乘拟合方法得到了介质的静态介电常数和弛豫时间等参数。利用这些参数,计算并讨论了有效Kirkwood相关因子、校正Kirkwood相关因子、Bruggeman因子、多余介电常数和多余逆弛豫时间值,从而得到二元液体混合物的偶极排列和分子旋转的信息。从所有得到的介电参数,分子相互作用解释通过氢键。
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引用次数: 10
Oxidation of Tetracaine Hydrochloride by Chloramine-B in Acid Medium: Kinetic Modeling 氯胺- b在酸性介质中氧化盐酸丁卡因:动力学模拟
Pub Date : 2014-02-10 DOI: 10.1155/2014/238984
J. P. Shubha, Puttaswamy
Tetracaine hydrochloride (TCH) is one of the potent local anaesthetics. A kinetic study of oxidation of tetracaine hydrochloride by sodium N-chlorobenzenesulfonamide (chloramine-B or CAB) has been carried in HClO4 medium at 303 K. The rate shows first-order dependence on , shows fractional–order dependence on , and is self-governing on acid concentration. Decrease of dielectric constant of the medium, by adding methanol, increased the rate. Variation of ionic strength and addition of benzenesulfonamide or NaCl have no significant effect on the rate. The reaction was studied at different temperatures and the activation parameters have been evaluated. The stoichiometry of the reaction was found to be 1 : 5 and the oxidation products were identified by spectral analysis. The conjugate free acid C6H5SO2NHCl of CAB is postulated as the reactive oxidizing species. The observed results have been explained by plausible mechanism and the related rate law has been deduced.
盐酸丁卡因是一种有效的局部麻醉剂。本文研究了n -氯苯磺酰胺钠(chloramine-B或CAB)在HClO4介质中303 K氧化盐酸丁卡因的动力学。反应速率对酸浓度表现为一阶依赖,对酸浓度表现为分数阶依赖,对酸浓度表现为自自治。加入甲醇后,介质介电常数降低,反应速率提高。离子强度的变化和苯磺酰胺或NaCl的加入对反应速率无显著影响。在不同温度下对反应进行了研究,并对活化参数进行了评价。该反应的化学计量比为1:5,并通过光谱分析对氧化产物进行了鉴定。假定CAB的共轭游离酸C6H5SO2NHCl为活性氧化物质。对观测结果进行了合理的机理解释,并推导出相应的速率定律。
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引用次数: 4
Controlled Release Kinetics in Hydroxy Double Salts: Effect of Host Anion Structure 羟基重盐的控释动力学:宿主阴离子结构的影响
Pub Date : 2014-01-15 DOI: 10.1155/2014/710487
Stephen Majoni, J. Hossenlopp
Nanodimensional layered metal hydroxides such as layered double hydroxides (LDHs) and hydroxy double salts (HDSs) can undergo anion exchange reactions releasing intercalated anions. Because of this, these metal hydroxides have found applications in controlled release delivery of bioactive species such as drugs and pesticides. In this work, isomers of hydroxycinnamate were used as model compounds to systematically explore the effects of anion structure on the rate and extent of anion release in HDSs. Following intercalation and subsequent release of the isomers, it has been demonstrated that the nature and position of substituent groups on intercalated anions have profound effects on the rate and extent of release. The extent of release was correlated with the magnitude of dipole moments while the rate of reaction showed strong dependence on the extent of hydrogen bonding within the layers. The orthoisomer showed a more sustained and complete release as compared to the other isomers.
纳米层状金属氢氧化物如层状双氢氧化物(LDHs)和羟基双盐(hds)可以进行阴离子交换反应,释放插层阴离子。正因为如此,这些金属氢氧化物在生物活性物质如药物和农药的控释递送中得到了应用。本研究以羟基肉桂酸同分异构体为模型化合物,系统探讨了阴离子结构对hds阴离子释放速率和程度的影响。在同分异构体的插入和释放之后,已经证明了插入阴离子上取代基的性质和位置对释放的速度和程度有深远的影响。释放的程度与偶极矩的大小有关,而反应速率则与层内氢键的程度密切相关。与其他异构体相比,正位异构体表现出更持久和完全的释放。
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引用次数: 4
期刊
Advances in Physical Chemistry
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