共查询到20条相似文献,搜索用时 156 毫秒
1.
研究了N,N-二甲基甲酰胺(DMF)纯溶剂、不同浓度LiCl/DMF和LiNO3/DMF溶液的红外光谱,得到随着温度升高,发生溶剂化作用的DMF分子比例不断降低,阴阳离子对构型比例逐渐增加的规律.采用密度泛函理论计算验证了红外谱图随温度升高变化的实质,得出溶液中存在的团簇构型主要为阴阳离子对构型(LiCl(DMF)n和LiNO3(DMF)n),阳离子构型[Li(DMF)n]+和阴离子构型([Cl(DMF)n]-,[NO3(DMF)n]-)的结论. 相似文献
2.
3.
研究分子的微溶剂化动力学过程是一个热点课题。应用各种光谱、质谱等实验技术并与从头计算和密度泛函等计算方法相结合,通过对生物分子和溶剂分子在气相中形成的分子团簇的研究,可以使我们了解溶剂分子对生物分子的结构和构型的影响。本文首先介绍了一些先进的实验技术及其应用于溶剂化团簇的研究,综述了近年来发展的几种主要理论计算和溶剂化模型方法。文中介绍了氨基酸分子与水、甲醇等发生微溶剂化过程的最新研究进展,然后分别综述了核酸碱基和碱基对、糖类、神经传递分子的溶剂化团簇的最新研究进展。最后,对该领域的研究前景进行了展望。 相似文献
4.
5.
6.
7.
金属纳米团簇(MNCs)作为一种新型的纳米材料,具有合成方法简单、光稳定性强、毒性低、生物相容性好以及发光效率高等优点。在本研究中,使用"一锅法"合成谷胱甘肽保护的铜纳米团簇。在激发波长为370 nm时,GS@CuNCs的荧光发射波长在610 nm左右。铜纳米团簇可以通过有溶剂诱导和阳离子诱导两种方法聚集诱导增强其荧光强度。通过测定在不同溶剂(乙醇、甲醇、N,N-二甲基甲酰胺)中铜纳米团簇的荧光强度,探究了溶剂极性对聚集的影响。研究结果表明:在水溶液中铜纳米团簇只发射弱的荧光,随着乙醇含量从0%到85%,其荧光强度逐渐增强。此外,我们开发了一种新的选择性好、灵敏性高的检测铝离子的荧光探针。线性范围为2-20μmol·L-1,且检测限(LOD)为33 nmol·L-1。进一步探究可得,乙醇和铝离子能使GS@CuNCs荧光强度显著增加的机理为聚集诱导荧光增强。 相似文献
8.
利用13C NMR光谱技术研究了Li+在碳酸丙烯酯(PC)+N,N-二甲基甲酰胺(DMF)混合溶剂中的优先溶剂化现象. 根据溶剂分子中碳原子的化学位移随锂盐浓度的变化关系, 确定了与Li+发生配位的原子. 碳原子的配位位移值随混合溶剂组成的变化关系表明, 在LiClO4+PC+DMF混合物中, DMF分子对Li+的溶剂化作用较PC分子强. 定量计算得到, 在n(PC)∶n(DMF)=1∶1(摩尔比)的混合溶剂中, PC与DMF分子数在Li+第一溶剂化层中的比率为0.12, 说明Li+优先被DMF分子溶剂化. 相似文献
9.
利用分子光谱和基于密度泛函理论的第一性原理,采用改进的TPSSTPSS泛函方法对C、H、O原子用6-31G基组并添加极化和弥散函数,对La原子选用Def2-SV(P)赝势基组,研究La3+/乙醇溶液微团簇构型。优化计算La3+在水溶液中的溶剂化结构,得出气相中的优化结果可以近似代替液相结果的结论;理论优化计算La3+/乙醇溶液可能存在的结构构型的结果表明,溶剂化数n=6时结构最稳定。采用荧光光谱和核磁共振实验对结果进行了验证,表明La3+的加入使荧光强度显著增强,在高浓度时生成的团簇构型比较稳定,且随着溶剂化数目的增加,O—H键长增大,La3+使其附近的质子产生强大的屏蔽效应,化学位移向高场移动,溶剂化数n=6时绝对误差最小,最稳定,与理论计算结论相吻合。 相似文献
10.
激光烧蚀Al+与乙醇团簇的反应研究 总被引:4,自引:0,他引:4
利用激光烧蚀-分子束法对Al等离子体与乙醇团簇的反应进行了研究.飞行时间质谱测得的主要反应产物有Al+(C2H5OH)n (n=3~10)与H+(C2H5OH)n (n=1~14)团簇正离子和(C2H5OH)n(H2O)OH- (n=0~8)团簇负离子.实验发现,烧蚀产生的Al等离子体与脉冲分子束的不同位置反应,对团簇离子的类别、大小及强度分布均产生很大影响.Al等离子体与脉冲分子束的前段反应,主要产生金属-复合物团簇离子Al+(C2H5OH)n,且信号较强;Al等离子体与脉冲分子束的中段及后段反应,主要产生质子化团簇离子H+(C2H5OH)n和团簇负离子(C2H5OH)n(H2O)OH-,同时还出现强度较小的其他水合团簇离子,如H+(H2O)m(C2H5OH)n (m=1~2)等. 相似文献
11.
研究了氧盐在不同溶剂中的光物理性质.结果表明,该化合物在甲苯(或苯)中基态和激发态下均能形成聚集体.浓度效应、温度效应及荧光衰变等为这一结论提供了证据. 相似文献
12.
利用13C NMR光谱技术研究了Li+在碳酸丙烯酯(PC)+N,N-二甲基甲酰胺(DMF)混合溶剂中的优先溶剂化现象. 根据溶剂分子中碳原子的化学位移随锂盐浓度的变化关系, 确定了与Li+发生配位的原子. 碳原子的配位位移值随混合溶剂组成的变化关系表明, 在LiClO4+PC+DMF混合物中, DMF分子对Li+的溶剂化作用较PC分子强. 定量计算得到, 在n(PC)∶n(DMF)=1∶1(摩尔比)的混合溶剂中, PC与DMF分子数在Li+第一溶剂化层中的比率为0.12, 说明Li+优先被DMF分子溶剂化. 相似文献
13.
Maciej Przybyek Anna Miernicka Mateusz Nowak Piotr Cysewski 《Molecules (Basel, Switzerland)》2022,27(10)
New protocol for screening efficient and environmentally friendly solvents was proposed and experimentally verified. The guidance for solvent selection comes from computed solubility via COSMO-RS approach. Furthermore, solute-solvent affinities computed using advanced quantum chemistry level were used as a rationale for observed solvents ranking. The screening protocol pointed out that 4-formylomorpholine (4FM) is an attractive solubilizer compared to commonly used aprotic solvents such as DMSO and DMF. This was tested experimentally by measuring the solubility of the title compounds in aqueous binary mixtures in the temperature range between 298.15 K and 313.15 K. Additional measurements were also performed for aqueous binary mixtures of DMSO and DMF. It has been found that the solubility of studied aromatic amides is very high and quite similar in all three aprotic solvents. For most aqueous binary mixtures, a significant decrease in solubility with a decrease in the organic fraction is observed, indicating that all systems can be regarded as efficient solvent-anti-solvent pairs. In the case of salicylamide dissolved in aqueous-4FM binary mixtures, a strong synergistic effect has been found leading to the highest solubility for 0.6 mole fraction of 4-FM. 相似文献
14.
Sasirekha V Ramakrishnan V 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,70(3):626-633
The role of solute-solvent and solvent-solvent interaction on the preferential solvation characteristics of 2,6-diaminoanthraquinone (DAAQ) has been analysed by monitoring the optical absorption and fluorescence emission spectra. Binary mixtures consist of dimethylformamide (DMF)-ethanol (EtOH), DMF-dimelthylsulfoxide (DMSO), benzene (BZ)-DMF and acetonitrile (ACN)-DMF. The optical absorption spectra maximum and emission spectra maximum of DAAQ show the changes with varying the solvents and change in the composition in the case of binary mixtures. Non-ideal solvation characteristics are observed in all binary mixtures. It is found that at certain concentrations two mixed solvents interact to form a common structure with a nu(12) (wave number in cm(-1)) value not always intermediate (nu(1) and nu(2)) between the values of the solvents mixed. Synergistic effect is observed in the case of DMF-EtOH mixtures. The preferential solvation parameters local mole fraction X(2)(L), solvation index delta(S2), exchange constant K(12) are calculated in all binary mixtures expect in the case of DMF-BZ mixture and DMF-EtOH mixture in the ground state. We have also monitored excitation wavelength effect on the probe molecule in aprotic polar and protic polar solvents. 相似文献
15.
系列羟基苯基卟啉化合物荧光性质的研究 总被引:13,自引:0,他引:13
对照紫外光谱的变化分析了5种卟啉周边羟基的数目、位置及其在不同溶剂条件下的荧光光谱的变化情况.研究表明,利用控制卟啉周边取代基的数目、对称性及选择溶剂可获得不同强度的荧光物质. 相似文献
16.
The complexation reaction between a macrocyclic polyether, 18-crown-6 (18C6), and potassium ion was studied in methanol (MeOH)-acetonitrile (AN), dimethylformamide (DMF)-AN and propylecarbonate (PC)-DMF binary solvent systems at different temperatures using a conductometric method. It was found that the stability of the 1:1 complex formed between K(+) ion and this ligand increases with decreasing temperature. Standard enthalpies and standard entropies of the complex formation were obtained from the temperature dependence of the stability constant. In all cases negative DeltaH(o)(c) and DeltaS(o)(c) values characterize the formation of 18C6-K(+) complex. The results obtained show that the stability of the complex is governed by the solvent medium and the thermodynamic parameters DeltaH(o)(c), DeltaS(o)(c) and DeltaG(o)(c) are sensitive to the composition of the mixed solvents. In addition, it was found that the stability constant of the resulting 1:1 complex among various neat solvents used varies in the order PC > MeOH > AN > DMF. 相似文献
17.
This review delineates on molecular interactions of N,N-dimethylformamide (DMF) with some solvents reported by various thermodynamic and thermophysical measurements. Several topics and examples of thermodynamic studies are depicted on the basis of the present author's experience focusing on the structural behavior for binary and ternary mixtures of DMF with different non-electrolytes. Valuable information on the behavior and factors governing of the liquid structure of the strongly associated solvents are also reviewed. A discussion is presented and deviations are interpreted in terms of size, shape, the position of ketone group, the chain length of alkanol and hydrogen bond effects in the liquid mixtures to explain about chemical and thermophysical behavior. Our goal in this review is to provide the structural and thermophysical contribution of the literature related to DMF with other solvents. Eventually, we reviewed what has been learned about the excess volumes and ultrasonic studies of ternary mixtures containing DMF with other solvents from experimental studies and also summarized the important contributions of DMF in the molecular interactions with other solvents. 相似文献
18.
Ravibhai Bhola Haresh Modi Chirag Patel Hasit Vaghani Keyur Bhatt Rizwan Ghumara 《印度化学会志》2022,99(5):100427
Solubility of 2, 6-bis (4-hydroxybenzylidene) cyclohexanone (BHBC) in pure solvents such as 1,4-dioxane, methanol, 1-butanol, 1-propanol, ethyl acetate, acetone, tetrahydrofuran (THF), glacial acetic acid, dimethyl sulphoxide (DMSO) and binary solvents dimethyl formamide (DMF) and (1-Propanol + Tetrahydrofuran) were investigated by gravimetric method at different temperature range. The experiment solubility increases with increase in temperature in both pure and binary solvents. The Maximum solubility is found in DMF at 328.15 K and for binary solvent mixture i.e. 1-propanol and THF (0.9 mol fraction) it was maximum at 318.15 K. Further modified Apelblate and Buchowski-Ksiazczak models were used for the theoretical calculation of solubility of BHBC in pure as well binary solvents. A satisfactory correlation of these models with experimental data was observed. The solution thermodynamics parameters like enthalpies, Gibb's free energy of dissolution and entropy of solutions were calculated using Van't Hoff and Gibb's equation, which reveals the solvation mechanism is non-spontaneous and entropy driven. 相似文献
19.
The fluorescence properties of 1-naphthol, 2-naphthol and 1,2,3,4-tetrahydronaphthol were obtained in binary aqueous-alcohol solvents with and without beta-cyclodextrin. The fluorescence of both the molecular and anionic forms of 1-naphthol and 2-naphthol were observed in the binary solvents without beta-cyclodextrin. Only the fluorescence of the molecular form of 2-naphthol appeared in the binary solvents with beta-cyclodextrin present, and its fluorescence was quenched with increasing amounts of beta-cyclodextrin. However, the fluorescence intensity of the molecular form of 1-naphthol increased with an increasing amount of beta-cyclodextrin in the binary solvents. The fluorescence intensity of 1,2,3,4-tetrahydronaphthol decreased with an increase in the amount of beta-cyclodextrin. The fluorescence results were interpreted with the Stern-Volmer equation and a modified Stern-Volmer equation. 相似文献
20.
Hassina Fisli Nadjia Bensouilah Nabila Dhaoui Mohamed Abdaoui 《Journal of inclusion phenomena and macrocyclic chemistry》2012,73(1-4):369-376
Fluorescent behaviour of lomustine, a DNA cross-linking agent, was investigated in different solvents, pH and in the presence of β-cyclodextrin (β-CD). The solvents in which fluorescence spectra were observed play a major role in determining the spectral intensity of fluorophore, since it was found to exhibit new fluorescent properties essentially influenced by intermolecular interactions, particularly by intermolecular H-bonding formed with solvents. The pH-dependence profile was typically U-shape with a maximum at pH between 3.51 and 6.58. It was corroborated that the fluorescence emission band of lomustine is significantly intensified in the presence of β-CD. From the changes in the fluorescence spectra, it was concluded that β-CD forms a 1:1 inclusion complex with lomustine and its association constant was calculated. 相似文献