A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure,Redox Properties,and Oxidation Reactions Investigated by DFT Calculations

The electronic structure and redox properties of the highly oxidizing, isolable Ru^V?O complex [Ru^V(N₄O)(O)]²⁺, its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol^?1, respectively. The overall free energy activation barrier (ΔG^≠=25.5 kcal mol^?1) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru^III(N₄O)(HOCl)]²⁺ (ΔG=15.0 kcal mol^?1) and the substitution of HOCl by a water molecule (ΔG^≠=10.5 kcal mol^?1). For water oxidation, nucleophilic attack on Ru^V?O by water, leading to O? O bond formation, has a free energy barrier of 24.0 kcal mol^?1, the major component of which comes from the cleavage of the H? OH bond of water. Intermolecular self‐coupling of two molecules of [Ru^V(N₄O)(O)]²⁺ leads to the [(N₄O)Ru^IV? O₂? Ru^III(N₄O)]⁴⁺ complex with a calculated free energy barrier of 12.0 kcal mol^?1.     

A Facile and Universal Top‐Down Method for Preparation of Monodisperse Transition‐Metal Dichalcogenide Nanodots

Despite unique properties of layered transition‐metal dichalcogenide (TMD) nanosheets, there is still lack of a facile and general strategy for the preparation of TMD nanodots (NDs). Reported herein is the preparation of a series of TMD NDs, including TMD quantum dots (e.g. MoS₂, WS₂, ReS₂, TaS₂, MoSe₂ and WSe₂) and NbSe₂ NDs, from their bulk crystals by using a combination of grinding and sonication techniques. These NDs could be easily separated from the N‐methyl‐2‐pyrrolidone when post‐treated with n‐hexane and then chloroform. All the TMD NDs with sizes of less than 10 nm show a narrow size distribution with high dispersity in solution. As a proof‐of‐concept application, memory devices using TMD NDs, for example, MoSe₂, WS₂, or NbSe₂, mixed with polyvinylpyrrolidone as active layers, have been fabricated, which exhibit a nonvolatile write‐once‐read‐many behavior. These high‐quality TMD NDs should have various applications in optoelectronics, solar cells, catalysis, and biomedicine.     

Specific heat and Lindemann-like parameter of metallic clusters: mono- and polyvalent metals

The Brownian-type molecular dynamics simulation is revisited and applied to study the thermal and geometric properties of four mono- and two polyvalent metallic clusters. For the thermal property, we report the specific heat at constant volume CV and study the solid-liquid-like transition by scrutinizing its characteristic. For the geometric property, we calculate the root mean square relative bond-length fluctuation delta as a function of increasing temperature. The thermal change in delta reflects the movement of atoms and hence is a relevant parameter in understanding the phase transition in clusters. The simulated results for the CV of alkali and aluminum clusters whose ground state structures exhibit icosahedral symmetry generally show one phase transition. In contrast, the tetravalent lead is quite often seen to exhibit two phase transitions, a premelting process followed by a progressive melting. In connection with the premelting scenario, it is found here that those (magic number) clusters identified to be of lesser stability (among other stable ones) according to the second energy difference are clusters showing a greater possibility of undergoing premelting process. This energy criterion applies to aluminum clusters nAl=28 and 38. To delve further into the thermal behavior of clusters, we have analyzed also the thermal variation of deltaT and attempted to correlate it with CV(T). It turns out that the premelting (if exist) and melting temperatures of the smaller size clusters (n less, similar 50) extracted from CV do not always agree quantitatively with that deduced from delta.     

Convenient synthesis of mono(6-N-allylamino-6-deoxy)permethylated β-cyclodextrin: a promising chiral selector for an HPLC chiral stationary phase

Mono(6-(p-toluenesulfonyl))permethylated β-cyclodextrin, a versatile precursor for a wide variety of mono-functionalized permethyl β-cyclodextrins, has been generated successfully by the direct methylation of monotosylated cyclodextrin. This afforded a convenient synthesis of mono(6^A-N-allylamino-6^A-deoxy)permethylated β-cyclodextrin. Hydrosilylation of the chiral selector with (EtO)₃SiH and reaction of the resultant reactive siloxane with pristine silica gel afforded a facile entry into a structurally well-defined chiral HPLC stationary phase.     

Modeling of oxygen transport and cell killing in type-II photodynamic therapy

Photodynamic therapy (PDT) provides an effective option for treatment of tumors and other diseases in superficial tissues and attracts attention for in vitro study with cells. In this study, we present a significantly improved model of in vitro cell killing through Type-II PDT for simulation of the molecular interactions and cell killing in time domain in the presence of oxygen transport within a spherical cell. The self-consistency of the approach is examined by determination of conditions for obtaining positive definitive solutions of molecular concentrations. Decay constants of photosensitizers and unoxidized receptors are extracted as the key indices of molecular kinetics with different oxygen diffusion constants and permeability at the cell membrane. By coupling the molecular kinetics to cell killing, we develop a modeling method of PDT cytotoxicity caused by singlet oxygen and obtain the cell survival ratio as a function of light fluence or initial photosensitizer concentration with different photon density or irradiance of incident light and other parameters of oxygen transport. The results show that the present model of Type-II PDT yields a powerful tool to quantitate various events underlying PDT at the molecular and cellular levels and to interpret experimental results of in vitro cell studies.     

Static ultrasonic oscillations induced degradation and its effect on the linear rheological behavior of novel propylene based plastomer melts

The ultrasonic degradation of novel propylene based plastomer (DP) melts with different melt viscosities was conducted in a “static” ultrasonic device where the samples were taken from various distances from the tip of an ultrasonic probe. The effects of ultrasonic time, oscillation temperature, ultrasonic intensity and the distance from the ultrasonic probe tip on the degradation behavior of DP melts as well as the ultrasonic degradation effect on the linear rheological behavior of DP melts were studied. The results show that the increase of initial melt viscosity of DP (higher molecular weight) has greater impact on the ultrasonic degradation of DP melt. The molecular weight and intrinsic viscosity of DP decrease with the increase of ultrasonic oscillation time and they approach to a limiting value. The molecular weight distribution of DP increases after ultrasonic degradation. Decreasing oscillation temperature and distance from probe tip and increasing ultrasonic intensity lead to an increase in the degradation of DP melt. The linear rheological behavior measurements of the samples obtained near the ultrasonic probe tip show that ultrasonic oscillations decrease the complex viscosity, zero shear viscosity, viscoelastic moduli, cross modulus, relaxation time and the slope of log G′ − log G″ for DP melts.     

Novel diastereoselective synthesis of (E)- and (Z)-allylsilanes via organoboranes

A simple, novel diastereoselective synthesis of both (E)- and (Z)-allylsilanes via organoboranes is developed. (E)-1-Alkenylboronate esters easily prepared from the corresponding terminal alkynes via hydroboration with dibromoborane-methyl sulfide complex followed by treatment with 1,3-propane diol readily react with trimethylsilylmethyllithium at −78 °C in methanol followed by reaction with iodine in methanol to produce the corresponding (Z)-allylsilanes in high yields (72-80%) and in high stereochemical purities (98% as evidenced by CMR spectral data). Similarly, the (Z)-1-alkenylboronate esters react with trimethylsilylmethyllithium at −78 °C in methanol followed by treatment with iodine in methanol to produce the corresponding (E)-allylsilanes in moderate yields (57-65%) in high stereochemical purities (>98% as revealed by CMR spectral data).     

Free energy perturbation study of water dimer dissociation kinetics

An efficient approach is described for using accurate ab initio calculations to determine the rates of elementary condensation and evaporation processes that lead to nucleation of aqueous aerosols. The feasibility of the method is demonstrated in an application to evaporation rates of water dimer at 230 K. The method, known as ABC-FEP (ab initio/classical free energy perturbation), begins with a calculation of the potential of mean force for the dissociation (evaporation) of small water clusters using a molecular dynamics (MD) simulation with a model potential. The free energy perturbation is used to calculate how changing from the model potential to a potential calculated from ab initio methods would alter the potential of mean force. The difference in free energy is the Boltzmann-weighted average of the difference between the ab initio and classical potential energies, with the average taken over a sample of configurations from the MD simulation. In principle, the method does not require a highly accurate model potential, though more accurate potentials require fewer configurations to achieve a small sampling error in the free energy perturbation step. To test the feasibility of obtaining accurate potentials of mean force from ab initio calculations at a modest number of configurations, the free energy perturbation method has been used to correct the errors when some standard models for bulk water (SPC, TIP4P, and TIP4PFQ) are applied to water dimer. To allow a thorough exploration of sampling issues, a highly accurate fit to results of accurate ab initio calculations, known as SAPT-5s, as been used a proxy for the ab initio calculations. It is shown that accurate values for a point on the potential of mean force can be obtained from any of the water models using ab initio calculations at only 50 configurations. Thus, this method allows accurate simulations of small clusters without the need to develop water models specifically for clusters.     

Poly(l-glutamic acid)-based star-block copolymers as pH-responsive nanocarriers for cationic drugs

Star-block copolymers PEI-g-(PLG-b-PEG), which consist of a hyperbranched polyethylenimine (PEI) core, a poly(l-glutamic acid) (PLG) inner shell, and a poly(ethylene glycol) (PEG) outer shell, were synthesised and evaluated as nanocarriers for cationic drugs. The synthesised star-block copolymers were characterised by ¹H NMR, gel permeation chromatography (GPC), dynamic light scattering (DLS), and transmission electron microscopy (TEM). Crystal violet (CV), as a model cationic dye, and doxorubicin hydrochloride (DOX), as a model anticancer drug, could be efficiently entrapped by the synthesised star-block copolymers at physiological pH as a result of electrostatic interactions between the cationic guest molecules and the negatively charged PLG segments in the PEI-g-(PLG-b-PEG) host. The drug–polymer complexes showed relatively high temporal stability at physiological pH and sustained release of the encapsulated drugs was observed. The entrapped model compounds demonstrated accelerated release as the pH was gradually decreased.     

Structures,vibrational spectra,and relative energies of HXSiS (X = H,F, and Cl) isomers

The potential energy surface for the decomposition of HXSiS (X = H, F, and Cl) on the singlet state has been explored by B3LYP and CCSD(T) calculations. Five different types of reaction are proposed: (A) 1,1‐HX elimination, (B) 1,2‐H shift, (C) 1,2‐X shift, (D) H · and XSiS · radical formation, and (E) X · and HSiS · radical formation. These results show interesting trends for the HXSiS isomers. Our theoretical investigations suggest that the doubly bonded species HXSiS should be the lowest energy structure among the isomers from both kinetic and thermodynamic viewpoints. We also report theoretical predictions of molecular parameters and vibrational infrared (IR) spectra of the monohalogen‐substituted silanethione, which should be useful for future experimental observations. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 14–25, 2001