HF in clusters of molecular hydrogen. I. Size evolution of quantum solvation by parahydrogen molecules

We present a theoretical study of the quantum solvation of the HF molecule by a small number of parahydrogen molecules, having n = 1-13 solvent particles. The minimum-energy cluster structures determined for n = 1-12 have all of the H(2) molecules in the first solvent shell. The first solvent shell closes at n = 12 and its geometry is icosahedral, with the HF molecule at the center. The quantum-mechanical ground-state properties of the clusters are calculated exactly using the diffusion Monte Carlo method. The zero-point energy of (p-H(2))(n)HF clusters is unusually large, amounting to 86% of the potential well depth for n > 7. The radial probability distribution functions (PDFs) confirm that the first solvent shell is complete for n = 12, and that the 13th p-H(2) molecule begins to fill the second solvent shell. The p-H(2) molecules execute large-amplitude motions and are highly mobile, making the solvent cage exceptionally fluxional. The anisotropy of the solvent, very pronounced for small clusters, decreases rapidly with increasing n, so that for n approximately 8-9 the solvent environment is practically isotropic. The analysis of the pair angular PDF reveals that for a given n, the parahydrogen solvent density around the HF is modulated in a pattern which clearly reflects the lowest-energy cluster configuration. The rigidity of the solvent clusters displays an interesting size dependence, increasing from n = 6 to 9, becoming floppier for n = 10, and increasing again up to n = 12, as the solvent shell is filled. The rigidity of the solvent cage appears to reach its maximum for n = 12, the point at which the first solvent shell is closed.     

Broadening of peaks eluted before the solvent in capillary GC Part II: The role of phase soaking

Summary Phase soaking is a solvent effect which tends to reconcentrate peaks eluted after and to broaden peaks eluted before the solvent. The principles of the phase soaking effect on peaks eluted before the solvent are discussed. The broadening effect is distinguished from the broadening effect occurring in the flooded column inlet by partial solvent trapping. It was found that in most cases broadening by partial solvent trapping strongly predominated over broadening by phase soaking. Phase soaking was noticeable only in the neighbourhood of the solvent peak.Phase soaking does not broaden peaks eluted before the solvent as much as it re-concentrates those eluted after it. The two phase soaking effects on the front and the rear of the solvent band (that is, of the soaked zone) differ strongly from each other.Peak broadening by phase soaking is negligible for non-trapped components, because such solutes start their chromatography before a significant quantity of solvent enters the column. Phase soaking only broadens solute bands which were retained by the solvent in the column inlet, that is, bands already broadened by partial solvent trapping.     

用气相色谱法研究乙酸乙烯酯不对称氢甲酰化反应中溶剂的影响

用毛细管气相色谱、色－质谱和旋光色散及圆二色性谱仪等方法对乙酸乙烯酯在非极性和极性溶剂中的不对称氢甲酰化反应产物进行分离和鉴定。实验结果表明,在非极性溶剂中反应的收率、选择性、光学收率ｅ．ｅ．值（ｅｎａｎｔｉｏｍｅｒｉｃｅｘｃｅｓｓ）均比极性溶剂中的结果为好。由此探讨了不对称氢甲酰化反应中溶剂的影响。     

Chemical reaction in binary mixtures near the critical region: thermal decomposition of 2,2'-azobis(isobutyronitrile) in CO2/ethanol

The effects of pressure and of the composition of the CO2/ethanol mixed solvent in the critical region on the kinetics of the decomposition of 2,2'-azobis(isobutyronitrile) (AIBN) were studied at 333.15 K. The rate constants (kd) in the mixed solvent far from the critical point and in liquid n-hexane and ethanol were also determined for comparison. It was found that kd is very sensitive to pressure in the mixed solvent near the critical point. However, in the mixed solvent outside the critical region kd is nearly independent of pressure. Interestingly, kd in the mixed solvent in the critical region can be higher than that in ethanol at the same temperature, suggesting that no significant enhancement in the reaction rate by a small pressure change in the critical region of the mixed solvent can be achieved by changing the composition of the liquid solvent in the traditional way. Transition-state theory can predict kd in the mixed solvent far from the critical point and in the liquid solvents well. However, it cannot predict kd in the mixed solvent in the critical region. The special intermolecular interaction between the solvent and the reaction species may contribute to this interesting phenomenon. This work also shows that if pure CO2 or ethanol are used as solvents, the reaction cannot be carried out in the critical region of the solvents at the desired temperature, while it can be conducted in the critical region of the mixed solvent of suitable composition, where the solvent is highly compressible.     

Mechanism of decoloration by solvent of thermally degraded poly(vinyl chloride)

The mechanism of decoloration of thermally degraded poly(vinyl chloride (PVC)) by solvents has been investigated systematically. The main results obtained are as follows. Good solvents for PVC, especially tetrahydrofuran, methyl ethyl ketone, and dioxane are effective for decoloration. The solvent peroxide which is formed by autoxidation of solvent contributes to decoloration. The number of double bonds in degraded PVC decreases as the decoloration proceeds and at the same time the solvent peroxide existing in solvent is consumed. Moreover, the existence of solvent fragments in decolored PVC is recognized. From these results, it is most reasonable to conclude that the decoloration mechanism is as follows: the solvent partially is changed to a solvent peroxide by autoxidation, and the solvent peroxide reacts with polyene double bonds of degraded PVC and breaks down conjugated double bonds, and consequently degraded PVC is decolored.     

Ab initio QM/MM study of excited state electron transfer between pyrene and 4,4′‐bis(dimethylamino)‐diphenylmethane with different solvent systems: Role of hydrogen bonding within solvent molecules

The exciplex is a charge transfer species formed in the process of electron transfer between an electron donor and an electron acceptor and hence is very sensitive to solvent polarity. In order to understand the role of solvent in exciplex formation between pyrene (PY) and 4,4′‐bis(dimethylamino)diphenylmethane (DMDPM), we used two types of solvent approximations: an implicit solvent model and an explicit solvent model. The difference in energies between the excited and the meta‐stable Frank–Condon state (ΔE) of the structures were assumed to correspond to the emission maximum of the exciplex in different solvents. The ΔE values show the trend of stabilization of the exciplex with an increase in solvent polarity. This trend in stabilization is substantially more prominent in the explicit solvent model than that with the implicit solvent model. The ΔE value obtained in methanol reflects equal stabilization compared to that in a more polar solvent, N,N‐dimethylformamide. This extra stabilization of the exciplex may be explained on the basis of the H‐bonding capability of the protic solvent, methanol. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Solvent effects on the electrochemical p-doping of PEDOT

EQCM experiments were carried out on PEDOT films exposed to TEABF(4)/CH(3)CN and TEABF(4)/CH(2)Cl(2) under permselective conditions and subjected to cyclic voltammetry in the potential range corresponding to p-doping. Current and frequency responses were used to obtain time-resolved ion and solvent flux data as functions of potential. Normalization of these fluxes with potential scan rate distinguishes thermodynamically (ir)reversible elementary steps in the overall redox process. The specific mechanisms are different in the two solvents, although both show mechanistic switches at partial redox conversion during both p-doping and undoping. These different mechanistic signatures are characterized according to the solvent identity, by different patterns of deviation from scan rate normalization for the experimentally measured ion and solvent fluxes. Comparison of these ion and solvent fluxes demonstrates that the rates of solvent expulsion (during doping) and entry (during undoping) are key determinants of mechanism. In both switching directions there are changes between kinetically limiting and rapid solvent transfer that depend upon solvent identity, i.e. the mechanism depends substantially upon charge state, switching direction and solvent. These mechanistic pathways and shifts can be visualized by a scheme-of-cubes representation.     

极性敏感的BDP分子溶剂化效应的光谱性质

合成了具有分子内电荷转移(ICT)性质的三重态光敏剂分子BDP, 研究了其稳态吸收光谱、 荧光光谱、 荧光寿命、 飞秒/纳秒瞬态吸收光谱及诱导产生单线态氧的能力等性质, 发现强极性溶剂对BDP分子的溶剂化效应降低了其ICT态和第一激发三重态(T₁态)的能量, 从而降低了BDP分子单线态氧的产量.     

Solvent dependence of electronic transition intensities

Most of the research on solvent effects on the electronic spectra of organic molecules has been concerned with frequency shifts. Solvent induced intensity changes, however, have not received much attention. At present there is no simple, general theory that relates: (a) the solvent induced changes in electronic transition intensities to (b) the macroscopic properties of the solvent. In this article we derive an equation that provides a quantitative interpretation for the changes in the absorption intensities. We show that solvent induced intensity changes are related to van der Waals constants for solvent and solute. Absorption data, some from previous investigations, are presented to show the usefulness and limitations of the theory.     

To gel or not to gel: A prior prediction of gelation in solvent mixtures

The gelation behaviours of low molecular weight gelators 1,3:2,5:4,6-tris(3,4-dichlorobenzylidene)-D-mannitol(G1)and 2,4-(3,4-dichlorobenzylidene)-N-(3-aminopropyl)-D-gluconamide(G2)in 34 solvents have been studied.We found that sample dissolved at low concentrations may become a gel or precipitate at higher concentrations.The Hansen solubility parameters(HSPs)and a Teas plot were employed to correlate the gelation behaviours with solvent properties,but with no success if the concentration of the tests was not maintained constant.Instead,on the basis of the gelation results obtained for the G1 and G2 in single solvents,we studied the gelation behaviours of G1 and G2 in 23 solvent mixtures and found that the tendency of a gelator to form a gel in mixed solvents is strongly correlated with its gelation behaviours in good solvents.If the gelation occurs in a good solvent at higher concentrations,it will take place as well in a mixed solvent(the good solvent plus a poor solvent)at a certain volume ratio.In contrast,if the gelator forms a precipitate in a good solvent at higher concentrations,no gelation is to be observed in the mixed solvents.A gelation rule for mixed solvents is thus proposed,which may facilitate decision making with regard to solvent selection for gel formation in the solvent mixtures in practical applications.     

Effect of Solvent Polarity on Excited-State Double Proton Transfer Process of 1, 5-Dihydroxyanthraquinone

The excited-state double proton transfer (ESDPT) properties of 1, 5-dihydroxyanthraquinone (1, 5-DHAQ) in various solvents were investigated using femtosecond transient absorption spectroscopy and the DFT/TDDFT method. The steady-state fluorescence spectra in toluene, tetrahydrofuran (THF) and acetonitrile (ACN) solvents presented that the solvent polarity has an effect on the position of the ESDPT fluorescence emission peak for the 1, 5-DHAQ system. Transient absorption spectra show that the increasing polarity of the solvent accelerates the rate of excited state dynamics. Calculated potential energy curves analysis further verified the experimental results. The ESDPT barrier decreases gradually with the increase of solvent polarity from toluene, THF to ACN solvent. It is convinced that the increase of solvent polarity can promote the occurrence of the ESDPT dynamic processes for the 1, 5-DHAQ system. This work clarifies the mechanism of the influence of solvent polarity on the ESDPT process of 1, 5-DHAQ, which provides novel ideas for design and synthesis of new hydroxyanthraquinone derivatives.     

Role of entropy and autosolvation in dimerization and complexation of C60 by Zn7 metallocavitands

The supramolecular chemistry of bowl-shaped heptazinc metallocavitands templated by Schiff base macrocycles has been investigated. Dimerization thermodynamics were probed by (1)H NMR spectroscopy in benzene-d(6), toluene-d(8), and p-xylene-d(10) and revealed the process to be entropy-driven and enthalpy-opposed in each solvent. Trends in the experimentally determined enthalpy and entropy values are related to the thermodynamics of solvent autosolvation, solvent molecules being released from the monomeric metallocavitand cavity into the bulk solvent upon dimerization. The relationship established between experimentally measured dimerization thermodynamics and autosolvation data successfully predicts the absence of dimerization in CH(2)Cl(2) and CHCl(3) and was used to estimate the number of solvent molecules interacting with the monomeric metallocavitand in solution. Host-guest interactions between heptazinc metallocavitands and fullerene C(60) have also been investigated. Interestingly, metallocavitand-C(60) interactions are only observed in solvents that facilitate entropy-driven dimerization suggesting entropy and solvent autosolvation may be important in explaining concave-convex interactions.     

反相液相色谱中溶剂强度规律的研究

 以溶质计量置换保留模型 (SDM R)为依据 ,通过研究 3种正链醇同系物溶剂置换剂对 14种正链醇同系物溶质色谱保留行为的影响 ,发现计量置换参数Z(对应 1mol溶质被吸附时从溶质与固定相接触处释放出的溶剂的总摩尔数 )、lgI(与 1mol溶质对固定相亲和势有关的常数 )和 j(与 1mol溶剂对固定相亲和势有关的常数 )均随着同系物置换剂相对分子质量的增大而减小 ,并呈现出线性变化 ,表明溶剂强度与溶剂分子的大小有关 ,分子愈大 ,溶剂洗脱能力愈强 ,并遵循同系物规律。     

Solvent vapor annealing of block copolymer thin films: removal of processing history

The ordering processes of PS-b-P2VP block copolymer thin films with different processing histories were studied during solvent vapor annealing by in situ grazing incidence small-angle X-ray scattering (GISAXS). We compared cylinder-forming PS-b-P2VP thin films with 34 kg/mol molecular weight that were prepared in three different ways: spin coating, spin coating and subsequent solvent vapor annealing where the solvent vapor was removed instantaneously, and spin coating and subsequent solvent vapor annealing where the solvent vapor was removed slowly. Block copolymer thin films retained the morphology resulting from the different “processing histories” at smaller swelling ratios. This processing history was erased when the samples reached a higher swelling ratio (~1.4). After the solvent was slowly removed from the swollen film, the surface morphology was characterized by ex situ AFM. All samples showed the same morphology after solvent annealing regardless of the initial morphology, indicating the morphology of solvent annealed samples is determined by the polymer concentration in the swollen film and the solvent vapor removal rate, but not the processing history.     

Loop-type interface for concurrent solvent evaporation in coupled HPLC-GC. Analysis of raspberry ketone in a raspberry sauce as an example

Presently, two coupling techniques are used for directly introducing HPLC fractions into capillary GC: The retention gap technique (involving negligible or partially concurrent solvent evaporation) and fully concurrent solvent evaporation. While the former involves use of a conventional on-column injector, it is now proposed that concurrent solvent evaporation technique be carried out using a switching valve with a built-in sample loop. The technique is based on the concept that the carrier gas pushes the HPLC eluent into the GC capillary against its own vapor pressure, generated by a column temperature slightly exceeding the solvent boiling point at the carrier gas inlet pressure. Further improvement of the technique is achieved by flow regulation of the carrier gas (accelerated solvent evaporation) and backflushing of the sample valve (improved solvent peak shape). Concurrent solvent evaporation using the loop-type interface is easy to handle, allows transfer of very large volumes of HPLC eluent (exceeding 1 ml), and renders solvent evaporation very efficient, allowing discharge of the vapors of 1 ml of solvent through the column within 5–10 min.     

Conformation of a flexible chain in explicit solvent: exact solvation potentials for short Lennard-Jones chains

The average conformation of a flexible chain molecule in solution is coupled to the local solvent structure. In a dense solvent, local chain structure often mirrors the pure solvent structure, whereas, in a dilute solvent, the chain can strongly perturb the solvent structure which, in turn, can lead to either chain expansion or compression. Here we use Monte Carlo (MC) simulation to study such solvent effects for a short Lennard-Lones (LJ) chain in monomeric LJ solvent. For an n-site chain molecule in solution these many-body solvent effects can be formally mapped to an n-body solvation potential. We have previously shown that for hard-sphere and square-well chain-in-solvent systems this n-body potential can be decomposed into a set of two-body potentials. Here, we show that this decomposition is also valid for the LJ system. Starting from high precision MC results for the n = 5 LJ chain-in-solvent system, we use a Boltzmann inversion technique to compute numerically exact sets of two-body solvation potentials which map the many-body chain-in-solvent problem to a few-body single-chain problem. We have carried out this mapping across the full solvent phase diagram including the dilute vapor, dense liquid, and supercritical regions and find that these sets of solvation potentials are able to encode the complete range of solvent effects found in the LJ chain-in-solvent system. We also show that these two-site solvation potentials can be used to obtain accurate multi-site intramolecular distribution functions and we discuss the application of these exact short chain potentials to the study of longer chains in solvent.     

Dissolution of cellulose in ethylene diamine/salt solvent systems

Investigation of the dissolution of cellulose in Ethylene Diamine (EDA)/Potassium thiocyanate (KSCN) solutions by infrared spectroscopy (FTIR) and thermal analysis (DSC) indicated that changes to the solvent during freeze thaw cycling of mixtures was consistent with increased interaction between cellulose and solvent. Thermal transitions in the system, however, occurred at temperatures outside the range used in thermal cycling to promote dissolution. Further exploration of the dissolution and mixing process indicated that mixing was the limiting step in solution formation. The dissolution of two types of cellulose with different molecular weights (Degree of Polymerization (DP)=210 and >1000) was studied using EDA/KSCN solution as the solvent. The solubility and the dissolution rate of cellulose depended on both the solvent composition and cellulose molecular weight. Cellulose could dissolve faster in the solvent with lower salt concentration but the highest cellulose concentration was obtained in the solvent with 30~35% KSCN. Rheological measurements showed that cellulose solutions exhibited viscous solution behavior at low KSCN concentration but primarily elastic behavior at high salt concentration.     

Phase Separation of Polyethylene Glycol/Salt Aqueous Two-Phase Systems

Abstract

Salt in polyethylene glycol (PEG)/salt aqueous two-phase systems was excluded by PEG and concentrated in the solvent volume available for dissolution of salt (PEG-free solvent). The concentration of salt in the PEG-free solvent of the PEG-rich phase was the same as that at the critical point regardless of the compositions of the PEG/salt two-phase systems. This explained that the phase separation of PEG/salt two-phase systems occurs when the concentration of salt in the PEG-free solvent reaches its solubility limit. The concentration of salt required in the PEG-free solvent for the phase separation was lower with higher molecular weight of PEG. The solubility of salt in the PEG-free solvent decreased with increases in the molal surface tension increment of salt. The solubility limit of salt in the PEG-free solvent was 0.93 M for ammonium sulfate, 0.77 M for potassium phosphate, 0.75 M for sodium tartrate, 0.67 M for sodium phosphate, and 0.53 M for potassium citrate.     

高效液相色谱梯度洗脱中弱溶剂的在线净化

利用一个在线净化预柱减少了高压梯度洗脱中由于试剂纯度不够造成的基线噪音。预柱的位置在溶剂泵Ａ和流动相混合器之间,由一个六通阀来控制。在线净化结果良好,有效地除去了空白梯度色谱图中的杂质峰,提高了梯度洗脱的分离重现性。该方法对开展梯度洗脱有实用价值。