Enhanced hydrophobicity of fluorinated lipid bilayer: a molecular dynamics study

A molecular dynamics simulation of a partially fluorinated phospholipid bilayer has been carried out to understand the effects of fluorination of the hydrophobic chains on the structure and water permeability across the membrane. Fluorocarbon chains typically have an all-trans conformation, showing a highly ordered structure in the membrane core compared to ordinary hydrocarbon chains. The free energy profiles of water across the bilayers were successfully estimated by a revised cavity insertion Widom method. The fluorinated bilayer showed a higher free energy barrier than an ordinary nonfluorinated lipid bilayer by about 1.2 kcal/mol, suggesting a lower water permeability of the fluorinated bilayer membrane. A cavity distribution analysis elucidated the reduced free volume in the fluorinated membrane due to the neatly packed chains, which should account for the higher free energy barrier.     

Oligopyridine ligands derived from amino acid precursors: their Zn2+ complexation and effects on hepatic stellate cell functions

A series of oligopyridine ligands were derived from amino acid amides in which amide oxygen and ternary nitrogen atoms were combined with pyridine moieties. 1H NMR and circular dichroism spectroscopic characterizations revealed that they formed stable Zn2+ complexes in neutral aqueous solutions and caused Zn2+ deficiency in the hepatic stellate cell systems. Since collagen synthesis was effectively promoted in the cells, the present oligopyridine derivatives worked as biocompatible ligands for Zn2+ complexation and cell activation.     

Liquid Structures and Ion Dynamics of Ionic Liquids Viewed from Intermolecular Interactions

The elucidation of the factors determining liquid structures and transport properties of ionic liquids is important for the design and development of ionic liquid electrolytes. This personal account introduces the importance of computational methods for studying ionic liquids. Molecular dynamics simulations provide detailed information on liquid structures of ionic liquid such as the structures of solvated cation complexes in equimolar mixtures of glymes and Li[TFSA] and the effects of the charges of electrode on liquid structure near the electrode. Ab initio calculations reveal that the magnitude of the attraction between ions and conformational flexibility ions play important roles in determining transport properties of ionic liquids. First principle molecular dynamics simulations elucidate why solvated cation complex is stable in the equimolar mixtures, although the Li⁺-[TFSA]⁻ interaction is greater than Li⁺-glyme interaction.     

A Cl- anion-responsive luminescent Eu3+ complex with a chiral tripod: ligand substituent effects on ternary complex stoichiometry and anion sensing selectivity

A new series of N3,O-mixed donor tripods was prepared for luminescent Eu3+ complexes, in which the soft quinoline nitrogen, tertiary amine nitrogen, and hard amide oxygen donors were cooperatively involved. The mixed donor tripods formed more stable 1 : 1 complexes with Eu(NO3)3, La(NO3)3 and Tb(NO3)3 than the corresponding N4 donor tripods, and their Eu3+ complexes particularly exhibited anion-responsive luminescence properties. NMR, UV, and luminescence spectroscopic characterizations revealed that -CH3 substitution on the tripod skeleton remarkably altered the preferred stoichiometry of the "tripod-Eu3+-anion" ternary complex and gave anion-dependent europium luminescence. Although the disubstituted tripod preferred to form non-luminescent 2 : 1 (tripod : Eu3+) complexes with Eu(NO3)3 and other salts, it formed a luminescent 1 : 1 complex with EuCl3. Thus, this type of tripod offered Cl- anion-selective luminescence enhancement that was easily observed by the naked eye.     

Nuclear reactions of C on a liquid hydrogen target measured with the superconducting TOF spectrometer

Reaction cross sections with various kinds of breakup channels for neutron-rich carbon isotopes ^18-20C and for ⁹Be impinging on a liquid hydrogen target were investigated at 40 MeV/nucleon. The nuclides of interest were produced via projectile fragmentation from a 63 MeV/nucleon ⁴⁰Ar beam and were separated in flight at the RIKEN projectile fragment separator (RIPS). The combination of the large-acceptance superconducting TOF spectrometer, TOMBEE (TOF Mass analyzer for exotic BEam Experiment), with a liquid hydrogen target, CRYPTA (CRYogenic ProTon and Alpha target system), enables simultaneous measurements of several reaction channels: the reaction cross sections (σR), individual elemental fragmentation cross sections (σΔZ), charge-changing cross sections (σcc), neutron-removal cross sections (σ−xn), and charge-pickup cross sections (σΔZ+1) for ^19,20C; σΔZ, σ−xn, and σΔZ+1 for ¹⁸C; and σR for ⁹Be. The present σR of ⁹Be on proton, σR=397±23 mb, measured in the inverse kinematics, was consistent with the previous measurements using proton beams at different laboratories. The σR of ¹⁹C and ²⁰C on proton were determined to be σR=754±22 mb and σR=791±34 mb, respectively. Taking into account the beam energy and target dependence of σR, the present σR are found to be considerably enhanced compared with those measured at around 1 GeV/nucleon. The σΔZ+1 appears to increase with the mass number of the projectiles, and it significantly contributes to σR in the present energy range. The finite-range optical-limit and few-body Glauber model analyses were performed for σR to study the nuclear matter density distributions and to derive the relative strength of the s-wave components of the valence neutrons in ¹⁹C and ²⁰C. A neutron halo structure of ¹⁹C is confirmed with an s-wave dominance of the valence neutron when the effect of the charge-pickup reaction is taken into account. The large σ−n of ¹⁹C and σ−2n of ²⁰C also support the decoupled structures of ¹⁸C +n and ¹⁸C+2n, respectively. The σcc of ¹⁹C and ²⁰C agree with each other within their experimental uncertainties, which might indicate a similar proton density distribution in ¹⁹C and ²⁰C. The σΔZ decreases monotonically without the even-odd effect as the number of removed protons increases.     

Focused terahertz radiation formed by coherently scattered surface plasmon polaritons from partially uncorrugated metal surfaces

We present that a focus of terahertz radiation can be tailored based on coherent scattering of surface plasmon polaritons (SPPs) from a partially defected metal corrugation based on numerical simulations. The introduction of teeth defects in the corrugation allows coupling of the guided SPPs with the radiation and the far-field behavior is tailored by the spatial arrangement of such defects. The proposed structures serve as a kind of planar lenses which are quite thin and inexpensive. Promising applications include interfacing lens antennas between terahertz plasmonic integrated circuits and the external free space, which make terahertz systems very compact and low-cost.     

Mixed-metal complexes incorporating platinum and lanthanide centers for selective binding and chirality sensing of succinates

A chromophoric platinum complex was combined with a nonacoordinated cyclen-lanthanide complex to give a new series of mixed-metal receptors. They specifically formed 1:1 complexes with dicarboxylates and offered selective chirality sensing of succinates.     

Effects of conformational flexibility of alkyl chains of cations on diffusion of ions in ionic liquids

Molecular dynamics simulations of ionic liquids [1-alkyl-3-methylimidazolium (alkyl = ethyl, butyl and hexyl), N-butylpyridinium, N-butyl-N,N,N-trimethylammonium and N-butyl-N-methylpyrrolidinium cations combined with the (CF(3)SO(2))(2)N(-) (TFSA) anion] show that the conformational flexibility of the alkyl chains in the cations is one of the important factors determining the diffusion of ions. Artificial constraint imposed on the internal rotation of alkyl chains significantly decreases the self-diffusion coefficients of cations and anions. The internal rotation of the C-N bond connecting the alkyl chain and the aromatic ring has large effects on the diffusion of ions in imidazolium and pyridinium based ionic liquids. The calculated self-diffusion coefficients of cations and anions decrease 20-40% by imposing the torsional constraint of the C-N bond. On the other hand the torsional constraint of the C-N bond does not largely change the diffusion of ions in the quaternary alkyl ammonium based ionic liquids. The conformational flexibility of the terminal C-C-C-C bond of the alkyl chains has large effects on the diffusion of ions in the quaternary alkyl ammonium based ionic liquids. The influence of the electrostatic interactions and the high density of ionic liquids on the diffusion of ions were studied. The electrostatic interactions have the paramount importance on the slow diffusion of ions in ionic liquids, while the high density of ionic liquids is also responsible for the slow diffusion. The electrostatic interactions and the high density of ionic liquids enhance the effects of the torsional constraint on the diffusion of ions, which suggests that the charge-ordering structure and small free volume originated in the strong electrostatic interactions are the causes of the significant effects of the conformational flexibility on the diffusion of ions in ionic liquids.     

Reevaluation of donor number using titration calorimetry

Many empirical parameters have been suggested to measure solvent effects in chemical reactions. Gutmann's donor number has been a successful parameter to quantify the electron-donating property of the solvent molecule; it is defined as the enthalpy change of the addition reaction of solvent molecule to SbCl(5) in 1,2-dichloroethane. Calorimetric measurements can be applied to determine the quantity. Because the existence of water is critical for reactions in organic solvents, we have analyzed the enthalpy change using the titration calorimetry while considering the complexation with water. The determined donor numbers of formamide, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and 1,1,3,3-tetramethylurea (TMU) are 22.4, 26.5, 30.0, and 40.4, respectively. The values of DMF and DMSO are in perfect agreement with those of Gutmann. A reliable value for TMU is obtained for the first time on the basis of the enthalpy change for the addition reaction.     

Temperature Dependence of Raman Spectrum in Solid Carbon Tetrabromide

Laser Raman spectra of carbon tetrabromide have been observed for the lattice and intramolecular vibrational regions over a temperature range of 80–370 K. Many bands were observed in the lattice region and the spectrum at the lower temperature in the monoclinic phase is similar to that of γ-Si(CH₃)₄. The temperature dependence of each band has been studied. The v₃ fundamental indicates a distinct variation corresponding to the phase transition.