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.

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.

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.

Mechanistic, Energetic and Structural Aspects of the Adsorption of Carmustine on the Functionalized Carbon Nanotubes

Using density functional theory, noncovalent interactions and two mechanisms of covalent functionalization of drug carmustine with functionalized carbon nanotube（CNT） have been investigated. Quantum molecular descriptors of noncovalent configurations were studied. It was specified that binding of drug carmustine with functionalized CNT is thermodynamically suitable. NTCOOH and NTCOCl can bond to the NH group of carmustine through OH（COOH mechanism） and Cl（COCl mechanism） groups, respectively. The activation energies, activation enthalpies and activation Gibbs free energies of two pathways were calculated and compared with each other. The activation parameters related to COOH mechanism are higher than those related to COCl mechanism, and therefore COCl mechanism is suitable for covalent functionalization. COOH functionalized CNT（NTCOOH） has more binding energy than COCl functionalized CNT（NTCOCl） and can act as a favorable system for carmustine drug delivery within biological and chemical systems（noncovalent）. These results could be generalized to other similar drugs.

SYNTHESIS OF CATALYSIS BY THE FUNCTIONALIZATION OF SILICA AND ITS APPLICATIONS

Hybrid organic-inorganic silica materials containing organic functional groups have been preparedby the reaction of activated silica with a silane coupling reagent such as N-(2-aminoethyl)3-aminopropyltrimethoxysilane. The hybrid silica was further modified by organic compounds having abifunctional group. These modified hybrid silicas were used as catalysts for various nucleophilic reactions.And also, these were complexed with metallic ions for use as catalysts for oxygen oxidation of hydrocarbons.

Effect of electroacupuncture on the mRNA and protein expression of Rho-A and Rho-associated kinase Ⅱ in spinal cord injury rats

Electroacupuncture is beneficial for the recovery of spinal cord injury, but the underlying mechanism is unclear. The Rho/Rho-associated kinase（ROCK） signaling pathway regulates the actin cytoskeleton by controlling the adhesive and migratory behaviors of cells that could inhibit neurite regrowth after neural injury and consequently hinder the recovery from spinal cord injury. Therefore, we hypothesized electroacupuncture could affect the Rho/ROCK signaling pathway to promote the recovery of spinal cord injury. In our experiments, the spinal cord injury in adult Sprague-Dawley rats was caused by an impact device. Those rats were subjected to electroacupuncture at Yaoyangguan（GV3）, Dazhui（GV14）, Zusanli（ST36） and Ciliao（BL32） and/or monosialoganglioside treatment. Behavioral scores revealed that the hindlimb motor functions improved with those treatments. Real-time quantitative polymerase chain reaction, fluorescence in situ hybridization and western blot assay showed that electroacupuncture suppressed the m RNA and protein expression of Rho-A and Rho-associated kinase Ⅱ（ROCKⅡ） of injured spinal cord. Although monosialoganglioside promoted the recovery of hindlimb motor function, monosialoganglioside did not affect the expression of Rho-A and ROCKⅡ. However, electroacupuncture combined with monosialoganglioside did not further improve the motor function or suppress the expression of Rho-A and ROCKⅡ. Our data suggested that the electroacupuncture could specifically inhibit the activation of the Rho/ROCK signaling pathway thus partially contributing to the repair of injured spinal cord. Monosialoganglioside could promote the motor function but did not suppress expression of Rho A and ROCKⅡ. There was no synergistic effect of electroacupuncture combined with monosialoganglioside.

Ozone-Mediated Functionalization of Multi-Walled Carbon Nanotubes and Their Activities for Oxygen Reduction Reaction

The functionalization of multi-walled carbon nanotubes （MWCNTs） by ozone treatment has been sys- tematically investigated by using Raman spectroscopy, transmission electron microscopy （TEM）, Fourier transform inhared spectroscopy （FTIR）, X-ray photoelectron spectroscopy （XPS）, organic elemental anal- ysis （OEA） and Boehm titration. The results showed that the functionalization process occurred at defective sites （opened mouths, tube caps, debris, etc.） before opening caps and truncating walls, and finally the graphitic structure was deteriorated. The surface oxygen content first increased with the treatment time but kept at around 8.0 wt% after 5 h. The analysis of the distribution of oxygen-containing groups re- vealed that phenolic hydroxyl was gradually converted to carboxyl and lactone, The carboxyl was found to play a pivotal role to reduce the over-potentials when we used the functionalized MWCNTs as the cat- alyst for oxygen reduction reaction （ORR）.

A convenient,highly-efficient method for preparation of hydroxyl-terminated isotactic poly(propylene) and functional di-block copolymer

Both terminated functional isotactic polypropylene （iPP） and block copolymers containing iPP segment are desirable for commercial applications. This paper provides a convenient, highly-efficient method to prepare hydroxyl-terminated isotactic polypropylene （iPP-t-OH） and functional di-block copolymer containing the iPP segment through a combination of coordination polymerization and coupling reaction. The coordination polymerization was catalyzed by TiCI4/MgCI2/AIEt3 catalyst system using ZnEt2 as chain transfer agent. Further, the Zn-terminated iPP was oxidized and subsequently hydrolyzed to provide iPP-t-OH. Soxhlet extraction and 13C NMR were used to calculate the isotacticity of iPP-t-OH. The degree of polymerization and the number of hydroxyl groups at the chain end of iPP-t-OH were measured by GPC and 1H NMR. Despite the high molecular weight and heterogeneous reaction, iPP-t-OH is effectively linked with PEG-t-NCO to produce di-block copolymers. DSC analysis of the di-block copolymer shows an obvious decrease in Tm and To, which indicated that PEG was successfully linked to the terminal end of iPP.

Hydrogenation of graphene nanoflakes and C-H bond dissociation of hydrogenated graphene nanoflakes： a density functional theory study

The Gibbs free energy change for the hydro- genation of graphene nanoflakes Cn （n = 24, 28, 30 and 32） and the C-H bond dissociation energy of hydrogenated graphene nanoflakes CnHm （n = 24, 28, 30 and 32; and m = 1, 2 and 3） are evaluated using density functional theory calculations. It is concluded that the graphene nanoflakes and hydrogenated graphene nanoflakes accept the orth- aryne structure with peripheral carbon atoms bonded via the most triple bonds and leaving the least unpaired dan- gling electrons. Five-membered rings are formed at the deep bay sites attributing to the stabilization effect from the pairing of dangling electrons. The hydrogenation reactions which eliminate one unpaired dangling electron and thus decrease the overall multiplicity of the graphene nanoflakes or hydrogenated graphene nanoflakes are spontaneous with negative or near zero Gibbs free energy change. And the resulting C-H bonds are stable with bond dissociation energy in the same range as those of aromatic compounds. The other C-H bonds are not as stable attributing to the excessive unpaired dangling electrons being filled into the C-H anti-bond orbital.

Linearity relationship between solvatochromic shifts of stilbazolium-like dyes and modified reaction field function

We analyzed statistically the linear correlation of the solvatochromic shifts of the stilbazolium-like dyes in the nonselected solvents with the reaction field function, L(?T) — bL(n2), and the solvent polarity parameter, ENT respectively, and observed that there were not perfectly linearity relationships between them, so we introduced ENT into L(?T) — bL( n2) to form a new reaction field function, L(?T) — bL(n2) + g ENT called as me modified reaction field function, which can be perfectly linearly correlated with the solvatochromic shifts of the stilbazolium-like dyes in the nonselected solvents.