Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Solvent effects on Diels-Alder reaction in ionic liquids:A reaction density functional study

Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.

Solvent effects on Pt-Ru/C catalyst for methanol electro-oxidation

Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying degree of the object substance, which lead to a great positive impact on its properties. In this work, three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction （XRD） and Transmission electron microscopy （TEM）. The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry （CV） and Chronoamperometry （CA）. Pt-Ru/C catalyst prepared in H2O or binary solvents of H2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems, Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity, lower onset and peak potentials, compared with the above catalysts. Moreover, the catalyst prepared in ternary solvents of isopropanol, water and tetrahydrofuran had the smallest particle size, and the high alloying degree and the dispersion kept unchanged. Therefore, this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.

Solvent effects on hydrogen bonding between primary alcohols and esters

The interaction by hydrogen bond formation of some primary alcohols （ l-heptanol, l-octanol and l-decanol） with esters （methyl methacrylate, ethyl methacrylate and butyl methacrylate） was investigated in non-polar solvents viz., n-heptane, CC14 and benzene by means of FTIR spectroscopy. Formation constants and free energy changes of complex formation were determined. The dependence of the equilibrium constants and free energy changes of complex formation on the alkyl chain length of both the alcohols and esters are discussed. The solvent interaction between the solute and solvent. effect on the hydrogen bond formation is discussed in terms of specific

Solvent effects on infrared spectra of 2-methyl-4,5-dimethoxy-3-oxo-2H-pyridizine： Part 1. Single solvent systems

Infrared spectroscopy studies of 2 methyl 4,5 dimethoxy 3 oxo 2H pyridizine (MDOP) in 12 pure organic solvents were undertaken to investigate the solvent solute interactions. The frequencies of the carbonyl (C=O) of MDOP were correlated with solvent properties such as solvent acceptor number (AN) and the linear solvation energy relationships (LSER). These frequencies showed a good correlation with the solvent acceptor number (AN) and the LSER.

Growth and Solvent Effects of a Promising Nonlinear Optical Sodium Paranitrophenolate Dihydrate (NO_2-C_H_4-ONa·2H_2O) Single Crystal

Sodium paranitrophenolate dihydrate (NPNa·2H2O) is an excellent semiorganic nonlinear optical (NLO) material, crystallizes both in water and methanol with high degree of transparency. Good optical quality single crystals of dimension upto 18 mm×6 mm×3 mm are obtained by isothermal solvent evaporation technique. The solubility of the crystal in different solvents was measured gravimetrically. The single crystals of NPNa·2H2O show variation in physical properties and growth rate in different solvents. Methanol or ethanol solution yields crystals of bipyramidal shape with clear morphology. However, methanol grown crystal is exhibiting improved hardness parameters and possesses excellent thermal stability as compared to water grown crystals. The effects of solvent on hardness parameter along with thermal and optical properties of NPNa·2H2O was revealed in this paper.

A reaction density functional theory study of solvent effect in the nucleophilic addition reactions in aqueous solution

Whereas the proper choice of reaction solvent constitutes the cornerstone of the green solvent concept,solvent effects on chemical reactions are not mechanistically well understood due to the lack of feasible molecular models.Herein,by taking the case study of nucleophilic addition reaction in aqueous solution,we extend the proposed multiscale reaction density functional theory(RxDFT)method to investigate the intrinsic free energy profile and total free energy profile,and study the solvent effect on the activation and reaction free energy for the nucleophilic addition reactions of hydroxide anion with methanal and carbon dioxide in aqueous solution.The predictions of the free energy profile in aqueous solution for these two nucleophilic addition reactions from RxDFT have a satisfactory agreement with the results from the RISM and MD-FEP simulation.Meanwhile,the solvent effect is successfully addressed by examining the difference of the free energy profile between the gas phase and aqueous phase.In addition,we investigate the solvent effect on the reactions occurred near solid-liquid interfaces.It is shown that the activation free energy is significantly depressed when reaction takes place in the region within 10A distance to the substrate surface owing to the decrease of hydration free energy at the solid-liquid interface.

Responsive mechanism of three novel hypochlorous acid fluorescent probes and solvent effect on their sensing performance

Optical properties and responsive mechanisms of three newly synthesized fluorescent probes for hypochlorous acid （HOC1） are investigated by employing time-dependent density functional theory. The computational results show that the absorption and emission properties of these probes change obviously when they react with hypochlorous acid. It is found that the probe FHZ has the best performance according to the probing behavior. Moreover, the responsive mechanisms of the probes are studied by analyzing the distributions of molecular orbitals and charge transfer, which are shown as the photon- induced electron transfer （PET） for FHZ and the intramolecular charge transfer OCT） for the other two probes. Specially, solvent effect on optical properties of the probe FHZ before and after reaction is studied within the polarizable continuum model （PCM）. It is shown that performance of the probe depends crucially on the solvent polarity. Our computational results agree well with the experimental measurement, and provide information for design of efficient two-photon fluorescent probes.

Solvent effects on structure and optical properties of a D-π-A azobenzene dye

Time-dependent hybrid density functional theory in combination with Onsager reaction field model and super-molecular model has been applied to study solvent effects on the geometrical and electronic structures, as well as one/two-photon absorption properties, of 4-（N-（2-hydroxyethyl）-N-methyl）-amino-4＇-nitroazobenzene. It is found that the short-range interaction has a large effect on the electronic structure of the solute molecule, namely, large red-shift of the maximum one-photon absorption is induced by hydrogen bonding. The solute molecule has a large two-photon absorption cross section, which is enhanced by the solvent effect. The computational results are in good agreement with measurements.

Studies of Solvent Effects on Structure and Low Frequency Vibrational Spectra of 2,4-Dinitrotoluene

Solvent effects on 2,4-dinitrotoluene（2,4-DNT） molecule in different solvents（toluene, ethanol, and water） were studied via DFT PCM method at B3LYP/6-311＋G（d,p） level. The influences of these solvents on the molecular structure, vibrational spectra, charge distribution, and dipole moment were studied as well. The results show that PCM computations are successful in describing the vibrational spectra of 2,4-DNT molecules in these solutions and the solvent effects on the low frequency vibrational spectra are weak.

Solvent effects on optical properties of a newly synthesized two-photon polymerization initiator： BPYPA

Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.

SOLVENT EFFECT ON CONFORMATIONS OF α,ω-BIS(4-NITROPHENOXY)-ALKANES

Solvent effect on the conformations of-bis(4-nitrophenoxy)-alkanes w th different chain Lengths(Nn)was studied by UV spectra.In poor solvents such as EG-H_2O and THF-H_2O,with the water content higher than 50%,the K-bands of N_4. N,N_6 and N_(10)in the UV absorption spectra shifted to longer wavelengths as compared wth 4-nitrophenoxyethane(N_0).It is suggested that in poor solvents the two aromatic gr(?)ps are close to each other in parallel,forming ground state complexes.The K- bead of N_4 showed a blue shift from that of N_0 when the water content was around 5%,probably attributable to a conformation with the nitro group of one benzene ring sit(?)ing on the plane of the other benzene ring.

Solvent effects on the S_0→S_2 absorption spectra of β-carotene

Absorption spectra of β-carotene in 31 solvents are measured in ambient conditions. Solvent effects on the 0-0 band energy, the bandwidth, and the transition moment of the S0 → S2 transition are analysed. The discrepancies between published results of the solvent effects on the 0-0 band energy are explained by taking into account microscopic solutesolvent interactions. The contributions of polarity and polarizability of solvents to 0-0 band energy and bandwidth are quantitatively distinguished. The 0- 0 transition energy of the S2 state at the gas phase is predicted to locate between 23000 and 23600 cm^-1.

Solvent effects and potential of mean force study of the SN2 reaction of CH3F+CN-in water

We used a combined quantum mechanics and molecular mechanics （QM/MM） method to investigate the solvent effects and potential of mean force of the CH3F＋CN- reaction in water. Comparing to gas phase, the water solution substantially affects the structures of the stationary points along the reaction path. We quantitatively obtained the solvent effects＇ contributions to the reaction： 1.7 kcal/mol to the activation barrier and -26.0 kcal/mol to the reaction free energy. The potential mean of force calculated with the density functional theory/MM theory has a barrier height at 19.7 kcal/mol, consistent with the experimental result at 23.0 kcal/mol; the calculated reaction free energy at -43.5 kcal/mol is also consistent with the one estimated based on the gas-phase data at -39.7 kcal/mol.

Studies on the Solvent Effect of N-Carbamoyl-N-(1-Oxyl 2,2,5,5-Tetramethyl-Pyrrolin-3-yl) Ureas

The electron spin resonance spectra of N-carbamoyl-N-(l-oxyl-2,2,5,5-tetramethyl-pyrrolin-3-yl) urea compounds in ten solvents with different polarities were determined. It was found that the hyperfine splitting constant AN and spin density pN. as well as the energy difference between two adjacent energy levels E of different pyrroline nitroxides in the same solvent increase with the increase of electron-withdrawing α-bility of the substituted groups on the aromatic ring. There was a linear correlation between AN and Reichardt ET value, and between AN and Z value as well. Such a linear correlation was also found between solvent viscosity n and ESR rotational correlation time r. On the other hand, the correlation between T and the relative height hr of peak on high field was reverse. The results are discussed in the paper.

A reaction density functional theory study of solvent effects on keto-enol tautomerism and isomerization in pyruvic acid

It is important to study the solvent effect on keto-enol tautomerism that has applications in many areas of chemical engineering.In this work,we use a multiscale reaction density functional theory(Rx DFT)to study the keto-enol tautomerism and isomerization of pyruvic acid.The results show that both effects of solvation and water assistance could reduce the reaction barriers.The water molecule participates the reaction as a catalyst to accept/give the protons with forming a hexagonal ring in the transition state.As a result of this temporary and intermediate hexagonal ring,the solute configuration undergoes a small variation during the reaction,giving a diminished contribution to the intrinsic reaction free energy.The solvent distribution shows a local ordering behavior near the solute that also reduces the contribution of solvation effect to the reaction barrier.Water assistance plays a major role in both pre-reaction and postreaction process.In terms of the driving force for the reaction,the effects of both solvation and water assistance are important.

Solvent Effects on Excited-State Relaxation Dynamics of Paddle-Wheel BODIPY-Hexaoxatriphenylene Conjugates:Insights from Non-adiabatic Dynamics Simulations

Understanding the excited state dynamics of donor-acceptor(D-A)complexes is of fundamental importance both experimentally and theoretically.Herein,we have first explored the photoinduced dynamics of a recently synthesized paddle-wheel BODIPY-hexaoxatriphenylene(BODIPY is the abbreviation for BF_(2)-chelated dipyrromethenes)conjugates D-A complexes with the combination of both electronic structure calculations and nonadiabatic dynamics simulations.On the basis of computational results,we concluded that the BODIPY-hexaoxatriphenylene(BH)conjugates will be promoted to the local excited(LE)states of the BODIPY fragments upon excitation,which is followed by the ultrafast exciton transfer from LE state to charge transfer(CT).Instead of the photoinduced electron transfer process proposed in previous experimental work,such a exciton transfer process is accompanied with the photoinduced hole transfer from BODIPY to hexaoxatriphenylene.Additionally,solvent effects are found to play an important role in the photoinduced dynamics.Specifically,the hole transfer dynamics is accelerated by the acetonitrile solvent,which can be ascribed to significant influences of the solvents on the charge transfer states,i.e.the energy gaps between LE and CT excitons are reduced greatly and the non-adiabatic couplings are increased in the meantime.Our present work not only provides valuable insights into the underlying photoinduced mechanism of BH,but also can be helpful for the future design of novel donor-acceptor conjugates with better optoelectronic performance.

A Quantitative Study of Solvent Effects on Keto-Enol Tautomeric Equilibria

Introduction Organic compounds usually have labile bonds. It is well known that thousands of reactions are carried out in solutions, only a few in the gas-phase. Most chemists are now familiar with the fact that solvent may have a strong influence on reaction rate and equilibrium, so in the last decade, resarching the influence of solvent effects on reaction rate and reaction equilibrium was a very important and

Solvent Effects on Two-Photon Absorption of Alkyne and Alkene π-bridging Chromophores

The present work concerns the study of solvent effects on the geometrical structures, as well as one- and two-photon absorption （TPA） processes, for two series of alkyne and alkene π-bridging molecules, within the framework of the polarization continuum model. Particular emphasis was put on the characterization of solvent effects on the molecular geometrical structures and geometric distortion, which were measured by the bond-length-alternation parameter. The π centres in the compounds are seen to play a decisive role in increasing the TPA cross section and nonlinear optical properties. All studied molecules have relatively strong TPA characteristics, while the alkyne π-bridging ones yield larger TPA cross sections.

Solvent effects on infrared spectra of 2—Methyl—4,5—dimethoxy—3—oxo—2H—Pyridizine：Part 2.Binary Solvent SYstems

This research on the solvent effects of 2 methyl 4,5 dimethoxy 3 oxo 2H pyridizine (MDOP) in binary solvent systems on the infrared spectra for MDOP in n hexane/CHCl 3 mixture solvents showed that there were three forms of carbonyl stretching vibration band [ υ (C=O)] of MPOP as the mole fraction of CHCl 3 in the binary solvents changes. In pure n hexane solvent, the υ (C=O) of MDOP appeared at a relatively high wavenumber. With CHCl 3 added, the υ (C=O) shifted to lower wavenumbers. Two new bands were observed over a certain range of mixture solvent compositions. The origin of the bands was discussed in the terms of two kinds of hydrogen bond together with their individual dependence on mixture composition. Comparisons were drawn for the solvent sensitivities of υ (C=O) for propanone.