Study of the structure of poly(methyl methacrylate) obtained in the presence of potassium hydride

Electrospray ionization mass spectrometry (ESI-MS) in positive- and negative-ion mode and multi-step tandem mass spectrometry (ESI-MS ( n) ) were selected for the determination of the structure of poly(methyl methacrylate) obtained using potassium hydride as initiator. Macromolecules with methoxy and methyl starting groups, i. e. those situated at the beginning of the polymer backbone, were observed in this case. No other differences in the chain structure were found in the polymer.     

Water in carbon nanotubes: adsorption isotherms and thermodynamic properties from molecular simulation

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled (6:6), (8:8), (10:10), (12:12), and (20:20) carbon nanotubes in the 248-548 K temperature range. At room temperature the resulting adsorption isotherms in (10:10) and wider single-walled carbon nanotubes (SWCNs) are characterized by negligible water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of the hysteresis loops decreases as pore diameter narrows and it becomes negligible for water adsorption in (8:8) and (6:6) SWCNs. Results for the isosteric heat of adsorption, density profiles along the pore axis and across the pore radii, order parameter across the pore radii, and x-ray diffraction patterns are presented. Layered structures are observed when the internal diameter of the nanotubes is commensurate to the establishment of a hydrogen-bonded network. The structure of water in (8:8) and (10:10) SWCNs is ordered when the temperature is 298 and 248 K, respectively. By simulating adsorption isotherms at various temperatures, the hysteresis critical temperature, e.g., the lowest temperature at which no hysteresis can be detected, is determined for water adsorbed in (20:20), (12:12), and (10:10) SWCNs. The hysteresis critical temperature is lower than the vapor-liquid critical temperature for bulk Simple Point Charge-Extended (SPCE) water model.     

Cell-permeable GPNA with appropriate backbone stereochemistry and spacing binds sequence-specifically to RNA

Guanidine-based peptide nucleic acid (GPNA) with a d-backbone configuration and alternate spacing binds sequence-specifically to RNA and is readily taken up by both human somatic and embryonic stem (ES) cells.     

PFGSE-NMR study of the self-diffusion of sucrose fatty acid monoesters in water

The micellization of pure monosubstituted sucrose fatty acid esters in water, namely sucrose octanoate, sucrose decanoate, sucrose laurate, sucrose dodec-5-cis-enoate, sucrose myristate, and sucrose palmitate, has been investigated by means of two NMR methods, pulsed field gradient spin-echo NMR (PFGSE-NMR), giving access to the self-diffusion coefficients of free molecules and micelles in solution, and the ERETIC method (electronic reference to access in vivo concentrations) for the measurement of concentrations by external calibration of a synthetic NMR signal. The early micellar regions and, when possible, the premicellar regions were investigated. By this method, we obtained the hydrodynamic radii of micelles, displaying a linear progression in relation to the chain length and an accurate determination of critical micellar concentration (CMC) for each sucrose ester. The effect of the regiochemistry of fatty chain grafting has been investigated, showing special behavior for 1'-O-sucrose palmitate.     

Numerical treatment discussion and ab initio computational reinvestigation of physisorption of molecular hydrogen on graphene

A numerical treatment suitable for the computational investigation of physisorption of molecular hydrogen on carbon nanostructures has not been sufficiently discussed. In this paper it is shown that results used as a reference are actually a product of poorly solved interactions and contaminated estimates with errors which would be of the order of 60%. Moreover, using ab initio molecular orbital theory, under the rigid monomer supermolecular approach, the physisorption energy of molecular hydrogen on graphene was reinvestigated. The graphene surface was modeled as a coronenelike (C(24)H(12)) graphene sheet. The basis set superposition error was corrected by means of the counterpoise method. The H(2)-H(2) and H(2)-benzene interactions were examined, under systematic combinations of basis sets and correlation methods, including the aug-cc-pVQZ basis set and the coupled cluster correlation method with single, double, and noniterative triple excitations, searching for a numerical treatment with a reasonable trade-off between efficiency and accuracy. Asymmetrical modeling strategies, using diffusion augmented basis sets with preference for the adsorbate, were found to be effective. Also local modeling strategies, using more complete basis sets for the nearest atoms to the adsorbate than for the rest of the substrate, were considered. The aug-cc-pVTZ basis set for the adsorbate and for the nearest atoms to the adsorbate and the cc-pVTZ basis set for the rest of the cluster-modeled graphene, at the second-order Moller-Plesset perturbation theory correlation level, was selected as reference treatment. It was found that the physisorption energy of molecular hydrogen on graphene would be of the order of 0.06 eV, which would be 25% less than what has been previously published, though it would be sufficient to permit the storage of hydrogen physisorbed on carbon. To our knowledge this would be the most realistic theoretical estimate of the mentioned energy to date.     

Five-component food-grade microemulsions: structural characterization by SANS

In this paper we present the structural characterization of a five-component food-grade microemulsion containing Tween 80, R(+)-limonene, ethanol, glycerol, and water. Our main approach to investigating the microstructure of dense microemulsions, and how it can be influenced by the various components, was to employ small-angle neutron scattering and the new evaluation technique for dense, interacting systems, the Generalized Indirect Fourier Transformation. We started our investigation with the impact of glycerol and ethanol on Tween 80 micelles in water. We found that glycerol increases the aggregation number and withdraws the hydrating agents from the headgroup region of the surfactant, resulting in a higher packing density of molecules in a micelle at slightly increasing size. The same trend holds when the micelles are oil swollen and/or ethanol is present. Ethanol, on the other hand, redistributes mainly between water and the interface-headgroup region of the surfactant. Part of it replaces surfactant molecules in the micelles, which increases the available interface and results in a higher number of micelles with shrinking size. The same trend holds when the micelles are oil swollen and/or glycerol is present in the aqueous phase. We also investigated samples along the dilution of a mixture of surfactant and oil phase (R(+)-limonene and ethanol), which can be diluted with aqueous phase (mixture of water and glycerol) without the occurrence of phase separation. In some samples of this dilution most probably bicontinuous structures are present. To elucidate this point, we also employed dynamic light scattering, viscosity, and conductivity measurements.     

Identifying acetylated lignin units in non-wood fibers using pyrolysis-gas chromatography/mass spectrometry

A series of non-wood plant fibers, namely kenaf, jute, sisal and abaca, have been analyzed upon pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of the whole material. The pyrolysis products mainly arise from the carbohydrate and lignin moieties of the fibers. The lignin-derived phenols belonged to the p-hydroxyphenylpropanoid (H), guaiacylpropanoid (G) and syringylpropanoid (S) structures, and showed a high S/G ratio of between 2.0 and 5.4, the highest corresponding to kenaf. Among the lignin-derived phenols released, small amounts of sinapyl and coniferyl acetates (in both cis- and trans-forms) were identified for the first time upon Py-GC/MS of lignocellulosic materials. Acetylation of the sinapyl and coniferyl alcohols was at the gamma-position of the side chain. The release of these alcohols derived from intact acetylated lignin units upon pyrolysis seems to indicate that the native lignin in the fibers selected for this study is at least partially acetylated. Sinapyl (and coniferyl) acetates have recently been suggested to be authentic lignin precursors involved in the polymerization of lignin along with the normal sinapyl and coniferyl alcohols. Py-GC/MS will offer a convenient and rapid tool for analyzing naturally acetylated lignins, as well as to screen plant materials for the presence of acetylated units in lignin.     

Theoretical study of the He-HF+ complex. II. Rovibronic states from coupled diabatic potential energy surfaces

The bound rovibronic levels of the He-HF+ complex were calculated for total angular momentum J=1/2, 3/2, 5/2, 7/2, and 9/2 with the use of ab initio diabatic intermolecular potentials presented in Paper I and the inclusion of spin-orbit coupling. The character of the rovibronic states was interpreted by a series of calculations with the intermolecular distance R fixed at values ranging from 1.5 to 8.5 A and by analysis of the wave functions. In this analysis we used approximate angular momentum quantum numbers defined with respect to a dimer body-fixed (BF) frame with its z axis parallel to the intermolecular vector R and with respect to a molecule-fixed (MF) frame with its z axis parallel to the HF+ bond. The linear equilibrium geometry makes the He-HF+ complex a Renner-Teller system. We found both sets of quantum numbers, BF and MF, useful to understand the characteristics of the Renner-Teller effect in this system. In addition to the properties of a "normal" semirigid molecule Renner-Teller system it shows typical features caused by large-amplitude internal (bending) motion. We also present spectroscopic data: stretch and bend frequencies, spin-orbit splittings, parity splittings, and rotational constants.     

Rationally functionalized deltahedral zintl ions: synthesis and characterization of [Ge9-ER3]3-, [R3E-Ge9-ER3]2-, and [R3E-Ge9-Ge9-ER3]4- (E=Ge, Sn; R=Me, Ph)

Six new derivatized deltahedral Zintl ions have been synthesized by reactions between the known Zintl ions Ge(9) (n-) with the halides R(3)EX and/or the corresponding anions R(3)E(-) for E=Ge or Sn. This rational approach is based on our previous discovery that these derivatization reactions are based on nucleophilic addition to the clusters. All species were structurally characterized as their salts with potassium countercations sequestered in 2,2,2-crypt or [18]crown-6 ether. The tin-containing anions were characterized also in solutions by (119)Sn NMR spectroscopy. The reaction types for such substitutions and the structures of the new anions are discussed.     

Estimating entropies from molecular dynamics simulations

While the determination of free-energy differences by MD simulation has become a standard procedure for which many techniques have been developed, total entropies and entropy differences are still hardly ever computed. An overview of techniques to determine entropy differences is given, and the accuracy and convergence behavior of five methods based on thermodynamic integration and perturbation techniques was evaluated using liquid water as a test system. Reasonably accurate entropy differences are obtained through thermodynamic integration in which many copies of a solute are desolvated. When only one solute molecule is involved, only two methods seem to yield useful results, the calculation of solute-solvent entropy through thermodynamic integration, and the calculation of solvation entropy through the temperature derivative of the corresponding free-energy difference. One-step perturbation methods seem unsuitable to obtain entropy estimates.