Neutral and Charged 1-Butyl-3-methylimidazolium Triflate Clusters: Equilibrium Concentration in the Vapor Phase and Thermal Properties of Nanometric Droplets

Ground state energy, structure, and harmonic vibrational modes of 1-butyl-3-methylimidazolium triflate ([bmim][Tf]) clusters have been computed using an all-atom empirical potential model. Neutral and charged species have been considered up to a size (30 [bmim][Tf] pairs) well into the nanometric range. Free energy computations and thermodynamic modeling have been used to predict the equilibrium composition of the vapor phase as a function of temperature and density. The results point to a nonnegligible concentration of very small charged species at pressures (P ~ 0.01 Pa) and temperatures (T 600 K) at the boundary of the stability range of [bmim][Tf]. Thermal properties of nanometric neutral droplets have been investigated in the 0 T 700 K range. A near-continuous transition between a liquidlike phase at high T and a solidlike phase at low T takes place at T ~ 190 K in close correspondence with the bulk glass point Tg ~ 200 K. Solidification is accompanied by a transition in the dielectric properties of the droplet, giving rise to a small permanent dipole embedded into the solid cluster. The simulation results highlight the molecular precursors of several macroscopic properties and phenomena and point to the close competition of Coulomb and dispersion forces as their common origin.

Structure-activity studies on position 14 of human alpha-calcitonin gene-related peptide

A structure-activity study was performed to examine the role of position 14 of human alpha-calcitonin gene-related peptide (h-alpha-CGRP) in activating the CGRP receptor. Interestingly, position 14 of h-alpha-CGRP contains a glycyl residue and is part of an alpha-helix spanning residues 8-18. Analogues [Ala(14)]-h-alpha-CGRP, [Aib(14)]-h-alpha-CGRP, [Asp(14)]-h-alpha-CGRP, [Asn(14)]-h-alpha-CGRP, and [Pro(14)]-h-alpha-CGRP were synthesized by solid phase peptide methodology and purified by RP-HPLC. Secondary structure was measured by circular dichroism spectroscopy. Agonist activities were determined as the analogues' ability to stimulate amylase secretion from guinea pig pancreatic acini and to relax precontracted porcine coronary arteries. Analogues [Ala(1)4]-h-alpha-CGRP, [Aib(14)]-h-alpha-CGRP, [Asp(14)]-h-alpha-CGRP, and [Asn(14)]-h-alpha-CGRP, all containing residues with a high helical propensity in position 14, were potent full agonists compared to h-alpha-CGRP in both tissues. Interestingly, replacement of Gly(14) of h-alpha-CGRP with these residues did not substantially increase the helical content of these analogues. [Pro(14)]-h-alpha-CGRP, predictably, has significantly lower helical content and is a 20-fold less potent agonist on coronary artery, known to contain CGRP-1 receptor subtypes, and an antagonist on pancreatic acini, known to contain CGRP-2 receptor subtypes. In conclusion, the residue in position 14 plays a structural role in stabilizing the alpha-helix spanning residues 8-18. The alpha-helix is crucial for maintaining highly potent agonist effects of h-alpha-CGRP at CGRP receptors. The wide variety of functional groups that can be tolerated in position 14 with no substantial modification of agonist effects suggests the residue in this position is not in contact with the CGRP receptor. [Pro(14)]-h-alpha-CGRP may be a useful pharmacological tool to distinguish between CGRP-1 and CGRP-2 receptor subtypes.

Thermodynamics, structure, and dynamics in room temperature ionic liquids: The case of 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF6])

A detailed investigation of the phase diagram of 1-butyl-3-methyl imidazolium hexafluorophosphate ([bmim][PF6]) is presented on the basis of a wide set of experimental data accessing thermodynamic, structural, and dynamical properties of this important room temperature ionic liquid (RTIL). The combination of quasi adiabatic, continuous calorimetry, wide angle neutron and X-ray diffraction, and quasi elastic neutron scattering allows the exploration of many novel features of this material. Thermodynamic and microscopic structural information is derived on both glassy and crystalline states and compared with results that recently appeared in the literature allowing direct information to be obtained on the existence of two crystalline phases that were not previously characterized and confirming the view that RTILs show a substantial degree of order (even in their amorphous states), which resembles the crystalline order. We highlight a strong connection between structure and dynamics, showing the existence of three temperature ranges in the glassy state across which both the spatial correlation and the dynamics change. The complex crystalline polymorphism in [bmim][PF6] also is investigated; we compare our findings with the corresponding findings for similar RTILs. These results provide a strong experimental basis for the exploration of the features of the phase diagram of RTILs and for the further study of longer alkyl chain salts.

Liquid structure of the ionic liquid 1,3-dimethylimidazolium bis{(trifluoromethyl)sulfonyl}amide

Neutron diffraction has been used to determine the liquid structure of 1,3-dimethylimidazolium bis{( trifluoromethyl) sulfonyl} amide ([dmim][NTf2]). Significantly smaller charge ordering is found in this liquid compared with analogous chloride and hexafluorophosphate salts due to the diffuse charge density and size of the [NTf2](-) anion. This is manifested in a much larger cation-cation and cation-anion separation and an overlap of the cation-cation and cation-anion shells. Comparison of the liquid structure with the crystal structure reported by Holbrey et al. ( Dalton Trans. 2004, 2267) indicates little correlation, for example, the [NTf2](-) anion adopts a trans orientation predominantly in the liquid whereas a cis orientation is found in the solid phase.

Effects of Accretion Flow on the Chemical Structure in the Inner Regions of Protoplanetary Disks

Aims. We study the dependence of the profiles of molecular abundances and line emission on the accretion flow in the hot (100 K) inner region of protoplanetary disks.
Methods. The gas-phase reactions initiated by evaporation of the ice mantle on dust grains are calculated along the accretion flow. We focus on methanol, a molecule that is formed predominantly by the evaporation of warm ice mantles, to demonstrate how its abundance profile and line emission depend on the accretion flow.
Results. Our results indicate that some evaporated molecules retain high abundances only when the accretion velocity is sufficiently high, and that methanol could be useful as a diagnostic of the accretion flow by means of ALMA observations at the disk radius of 10 AU.

Space and phase resolved optical emission in mode transitions of radio-frequency inductively coupled plasmas

Inductively coupled radio-frequency plasmas can be operated in two distinct modes. At low power and comparatively low plasma densities the plasma is sustained in capacitive mode (E-mode). As the plasma density increases a transition to inductive mode (H-mode) is observed. This transition region is of particular interest and governed by non-linear dynamics, which under certain conditions results in structure formation with strong spatial gradients in light emission. These modes show pronounced differences is various measureable quantities e.g. electron densities, electron energy distribution functions, ion energy distribution functions, dynamics of optical light emission. Here the transition from E- to H- mode in an oxygen containing inductively coupled plasma (ICP) is investigated using space and phase resolved optical emission spectroscopy (PROES). The emission, measured phase resolved, allows investigation of the electron dynamics within the rf cycle, important for understanding the power coupling and ionization mechanisms in the discharge. The temporal variation of the emission reflects the dynamics of relatively high-energy electrons. It is possible to distinguish between E- and H-mode from the intensity and temporal behaviour of the emission.

Kinetics of Aqueous Phase Dehydration of Xylose into Furfural Catalyzed by ZSM-5 Zeolite

ZSM-5 zeolite in H+ form with an average pore size of 1.2 nm was used for aqueous phase dehydration of xylose to furfural at low temperatures;, that is, from 413 to 493 K. The selectivity in furfural increased with the temperature to a value of 473 K. Beyond this temperature, condensation reactions were significant and facilitated by the intrinsic structure of ZSM-5. A reaction mechanism that included isomerization of xylose to lyxose, dehydration of lyxose and xylose to furfural, fragmentation of furfural to organic acids, oligomerization of furfural to bi- and tridimensional furilic species, and complete dehydration of organic acids to carbonaceous deposits was developed, and the associated kinetic parameters were estimated. The rate of furfural production was found to be more sensitive to temperature than the rates of side reactions, with an estimated activation energy of 32.1 kcal/mol. This value correlated well with data in the literature obtained by homogeneous catalytic dehydration.

Characterisation of microwave phase conjugate signal generation using nonlinearly loaded wire frequency selective surface (FSS)

Both experimental and theoretical information regarding the scattering and phase conjugate mixing properties of a 2D double-periodic array of wires loaded with nonlinear/linear lumped elements have been provided. An experimental means for assessing the phase conjugate energy production capability for the array is given. These investigations enable identification of the fundamental operational characteristics and underlying mechanisms associated with the production of phase conjugate energy by this type of artificial electromagnetic media. Means for enhancing the phase conjugate energy production capability of the structure by using additional linear lumped loads is examined theoretically and limits on the production of phase conjugate energy established. Theoretical far-field prediction of the behaviour of the structure indicates that retro-directive reflector action as well as negative refraction should be possible.

Prediction of the formation and stabilities of energetic salts and ionic liquids based on ab initio electronic structure calculations

A computational approach to predict the thermodynamics for forming a variety of imidazolium-based salts and ionic liquids from typical starting materials is described. The gas-phase proton and methyl cation acidities of several protonating and methylating agents, as well as the proton and methyl cation affinities of many important methyl-, nitro-, and cyano- substituted imidazoles, have been calculated reliably by using the computationally feasible DFT (B3LYP) and MP2 (extrapolated to the complete basis set limit) methods. These accurately calculated proton and methyl cation affinities of neutrals and anions are used in conjunction with an empirical approach based on molecular volumes to estimate the lattice enthalpies and entropies of ionic liquids, organic solids, and organic liquids. These quantities were used to construct a thermodynamic cycle for salt formation to reliably predict the ability to synthesize a variety of salts including ones with potentially high energetic densities. An adjustment of the gas phase thermodynamic cycle to account for solid- and liquid-phase chemistries provides the best overall assessment of salt formation and stability. This has been applied to imidazoles (the cation to be formed) with alkyl, nitro, and cyano substituents. The proton and methyl cation donors studied were as follows: HCl, HBr, HI, (HO)(2)SO2, HSO3CF3 (TfOH), and HSO3(C6H4)CH3 (TsOH); CH3Cl, CH3Br, CH3I, (CH3O)(2)SO2, CH3SO3CF3 (TfOCH3) and CH3SO3(C6H4)CH3 (TsOCH3). As substitution of the cation with electron-withdrawing groups increases, the triflate reagents appear to be the best overall choice as protonating and methylating agents. Even stronger alkylating agents should be considered to enhance the chances of synthetic success. When using the enthalpies of reaction for the gas-phase reactants (eq 6) to form a salt, a cutoff value of - 13 kcal mol(-1) or lower (more negative) should be used as the minimum value for predicting whether a salt can be synthesized.

Observation and characterization of laser-driven Phase Space Electron Holes

The direct observation and full characterization of a phase space electron hole (EH) generated during laser-matter interaction is presented. This structure, propagating in a tenuous, nonmagnetized plasma, has been detected via proton radiography during the irradiation with a ns laser pulse (I?2 ˜ 1014 W/cm2) of a gold hohlraum. This technique has allowed the simultaneous detection of propagation velocity, potential, and electron density spatial profile across the EH with fine spatial and temporal resolution allowing a detailed comparison with theoretical and numerical models.

[Ag(NH3)(2)]ClO4: Crystal structures, phase transition, and vibrational spectra

[Ag(NH3)(2)](ClO4) is obtained from a solution of AgClO4 in cone. ammonia as colourless single crystals (orthorhombic, Pnmn, Z = 4, a = 795.2(1) pm, b 617.7(1) pm, c = 1298.2(2) pm, R-all = 0.0494). The structure consists of linearly coordinated cations, [Ag(NH3)(2)](+), stacked in a staggered conformation and of tetrahedral (ClO4)(-) anions. A first order phase transition was observed between 210 and 200 K and the crystal structure of the low-temperature modification (monoclinic. P2/m, Z = 4, a = 789.9(5) pm, b = 604.1(5) pm, c = 1290.4(5) pm, beta = 97.436(5)degrees, at 170 K, R-all = 0.0636) has also been solved. Spectroscopic investigations (IR/Raman) have been carried out and the assignment of the spectra is discussed.

The structure of helokinestatin-5 and its biosynthetic precursor from Gila monster (Heloderma suspectum) venom: Evidence for helokinestatin antagonism of bradykinin-induced relaxation of rat tail artery smooth muscle

Here we report the primary structure of a novel peptide, named helokinestatin-5 (VPPPLQMPLIPR), from the venom of the Gila monster (Heloderma suspectum). Helokinestatin-5 differs in structure from helokinestatin-3 by deletion of a single prolyl residue in the N-terminally located polyproline region. Two different biosynthetic precursors were consistently cloned from a venom-derived cDNA library. The first encoded helokinestatins 1–4 and a single copy of C-type natriuretic peptide, as previously described, whereas the second was virtually identical, lacking only a single prolyl codon as found in the mature attenuated helokinestatin-5 peptide. Helokinestatins 1–3 and 5 were synthesized by solid-phase fmoc chemistry and each synthetic replicate was found to antagonize the relaxation effect induced by bradykinin on rat tail artery smooth muscle. Helokinestatins thus represent a novel family of vasoactive peptides from the venom of helodermatid lizards

Observation of stable phase jump lines in convection of a twisted nematic liquid crystal

We report observations of stable, localized, linelike structures in the spatially periodic pattern formed by nematic electroconvection, along which the phase of the pattern jumps by pi. With increasing electric voltage, these lines form a gridlike structure that goes over into a structure indistinguishable from the well-known grid pattern. We present theoretical arguments that suggest that the twisted cell geometry we are using is indirectly stabilizing the phase jump lines, and that the phase jump lines lattice is caused by an interaction of phase jump lines and a zig-zag instability of the surrounding pattern.

Thermodynamic properties and atomistic structure of the dry amorphous silica surface from a reactive force field model

A force field model of the Keating type supplemented by rules to break, form, and interchange bonds is applied to investigate thermodynamic and structural properties of the amorphous SiO2 surface. A simulated quench from the liquid phase has been carried out for a silica sample made of 3888 silicon and 7776 oxygen atoms arranged on a slab similar to 40 angstrom thick, periodically repeated along two directions. The quench results into an amorphous sample, exposing two parallel square surfaces of similar to 42 nm(2) area each. Thermal averages computed during the quench allow us to determine the surface thermodynamic properties as a function of temperature. The surface tension turns out to be gamma=310 +/- 20 erg/cm(2) at room temperature and gamma=270 +/- 30 at T=2000 K, in fair agreement with available experimental estimates. The entropy contribution Ts-s to the surface tension is relatively low at all temperatures, representing at most similar to 20% of the surface energy. Almost without exceptions, Si atoms are fourfold coordinated and oxygen atoms are twofold coordinated. Twofold and threefold rings appear only at low concentration and are preferentially found in proximity of the surface. Above the glass temperature T-g=1660 +/- 50 K, the mobility of surface atoms is, as expected, slightly higher than that of bulk atoms. The computation of the height-height correlation function shows that the silica surface is rough in the equilibrium and undercooled liquid phase, becoming smooth below the glass temperature T-g.

Attosecond phase locking of harmonics emitted from laser-produced plasmas

Laser-driven coherent extreme-ultraviolet (XUV) sources provide pulses lasting a few hundred attoseconds(1,2), enabling real-time access to dynamic changes of the electronic structure of matter(3,4), the fastest processes outside the atomic nucleus. These pulses, however, are typically rather weak. Exploiting the ultrahigh brilliance of accelerator-based XUV sources(5) and the unique time structure of their laser-based counterparts would open intriguing opportunities in ultrafast X-ray and high-field science, extending powerful nonlinear optical and pump-probe techniques towards X-ray frequencies, and paving the way towards unequalled radiation intensities. Relativistic laser-plasma interactions have been identified as a promising approach to achieve this goal(6-13). Recent experiments confirmed that relativistically driven overdense plasmas are able to convert infrared laser light into harmonic XUV radiation with unparalleled efficiency, and demonstrated the scalability of the generation technique towards hard X-rays(14-19). Here we show that the phases of the XUV harmonics emanating from the interaction processes are synchronized, and therefore enable attosecond temporal bunching. Along with the previous findings concerning energy conversion and recent advances in high-power laser technology, our experiment demonstrates the feasibility of confining unprecedented amounts of light energy to within less than one femtosecond.