Quantifying the fraction of glycine and alanine in beta-sheet and helical conformations in spider dragline silk using solid-state NMR

Solid-state two-dimensional refocused INADEQUATE MAS NMR experiments resolve distinct helical and beta-sheet conformational environments for both alanine and glycine in Nephila clavipes dragline silk fibers; the fraction of alanine and glycine in beta-sheet structures is determined to be 82% +/- 4% and 28% +/- 5%, respectively.     

Poly(amidoamine) dendrimers on lipid bilayers I: Free energy and conformation of binding

Third-generation (G3) poly(amidoamine) (PAMAM) dendrimers are simulated approaching 1,2-dimyristoyl- sn-glycero-3-phosphocholine (DMPC) bilayers with fully atomistic molecular dynamics, which enables the calculation of a free energy profile along the approach coordinate. Three different dendrimer terminations are examined: protonated primary amine, uncharged acetamide, and deprotonated carboxylic acid. As the dendrimer and lipids become closer, their attractive force increases (up to 240 pN) and the dendrimer becomes deformed as it interacts with the lipids. The total energy release upon binding of a G3-NH3+, G3-Ac, or G3-COO- dendrimer to a DMPC bilayer is, respectively, 36, 26, or 47 kcal/mol or, equivalently, 5.2, 3.2, or 4.7x10(-3) kcal/g. These results are analyzed in terms of the dendrimers' size, shape, and atomic distributions as well as proximity of individual lipid molecules and particular lipid atoms to the dendrimer. For example, an area of 9.6, 8.2, or 7.9 nm2 is covered on the bilayer for the G3-NH3+, G3-Ac, or G3-COO- dendrimers, respectively, while interacting strongly with 18-13 individual lipid molecules.     

Collective and noncollective models of NMR relaxation in lipid vesicles and multilayers

NMR (13)C spin lattice relaxation (1/T(1)) rates of dipalmitoylphosphatidylcholine (DPPC) bilayers obtained from molecular dynamics simulations of 72 and 288 lipids are compared with each other, with experimental values from large liposomes obtained by magic angle spinning, and with previously published experimental data from small vesicles. The experimental results for multilayers and vesicles at the same frequencies differ only slightly. The simulation results indicate that T(1) relaxation in the 15.1 to 201.2 MHz carbon frequency range and up to 100 A length scale is dominated by fast isomerizations and slower lipid wobble (D perpendicular approximately 2.5 x 10(8) s(-1)). Rotational diffusion about the lipid long axis (described by D(parallel)) does not make a substantial contribution to the T(1). Modifications to the acyl chain torsional potential energy function used for the simulations substantially improve agreement with experiment.     

Characterization and utilization of a novel triflate ionic liquid stationary phase for use in comprehensive two-dimensional gas chromatography

A novel triflate (trifluoromethylsulfonate) ionic liquid (IL) thin film (0.08 microm) stationary phase was implemented for use within the second column of a comprehensive GC x GC configuration. The first column in the configuration had a 5% phenyl/95% dimethyl polysiloxane (DMPS) stationary phase with a 0.4 microm film. The DMPS x IL column configuration was used to separate a mixture of 32 compounds of various chemical functional classes. The GC x GC results for the IL column were compared with a commercially available polar column (with a 0.1 microm PEG stationary phase film) used as the second column instead. Additional studies focused on the rapid and selective separation of four phosphorous-oxygen (P-O) containing compounds from the 32-compound matrix: dimethyl methylphosphonate (DMMP), diethyl methylphosphonate (DEMP), diisopropyl methylphosphonate (DIMP), and triethyl phosphate (TEP). van't Hoff plots (plots of ln k vs. 1/T) demonstrated the difference in retention between the P-O containing compounds (with DMMP reported in detail) and other classes of compounds (i. e., 2-pentanol and n-dodecane as representative) using either the IL column or the commercial PEG column. The selectivity (alpha) of the triflate IL column and the commercially available PEG column were also compared. The IL column provided significantly larger selectivities between DMMP and the other two compounds (2-pentanol and n-dodecane) than the commercial PEG column. The alpha for DMMP relative to n-dodecane was 3.0-fold greater for the triflate IL column, and the alpha for DMMP relative to 2-pentanol was 1.7-fold greater for the triflate IL column than for the PEG column.     

Influence of the apical ligand in the thermotropic mesomorphism of cationic copper-based surfactants

A new pyridine-based bidentate ligand L (PyC18) was used to develop copper-containing surfactants that exhibit mesomorphism. Complexes [(L (PyC18)) 2Cu (II)Y]Y were synthesized, where Y is an anionic ligand bromo ( 1), nitrato ( 2), or perchlorato ( 3). The nature of these apical ligands determines the mesogenic behavior of 1- 3: The smallest bromo-substituted species 1 shows a metastable liquid crystalline phase at 110 degrees C, the nitrato-substituted 2 increases the transition temperature to 136 degrees C, and the bulky perchlorato-substituted 3 shows reversible mesophases at 153 degrees C. The behavior of these complexes shows similarities and suggests that at low temperatures the crystals of these compounds are bilayered structures with interdigitated alkyl tails. At higher temperatures the tails undergo rapid conformational changes that force these layers to swell until the opposing alkyl chains are separated from each other, and the mesophase is a monolayer smectic A. Small changes in the geometry of cationic mesogens can be imposed by the presence of apically coordinated anions, allowing for tuning in the properties of the resulting mesophases.     

Vibrational dynamics of amorphous beryllium hydride and lithium beryllium hydrides

The vibrational density of states of amorphous beryllium hydride (a-BeH2) and lithium beryllium hydrides have been studied using inelastic neutron scattering, infrared, and Raman spectroscopies. The positions of the symmetrical (120-180 meV) and antisymmetrical (200-260 meV) Be-H stretching modes and those of the H-Be-H bending mode (50-120 meV) have been determined and the results discussed and compared with recent theoretical calculations. With the addition of lithium to the beryllium hydride network, the vibrational bands are shifted to lower energies, indicating a less rigid network.     

A general statistical test for correlations in a finite-length time series

The statistical properties of the autocorrelation function from a time series composed of independently and identically distributed stochastic variables has been studied. Analytical expressions for the autocorrelation function's variance have been derived. It has been found that two common ways of calculating the autocorrelation, moving-average and Fourier transform, exhibit different uncertainty characteristics. For periodic time series, the Fourier transform method is preferred because it gives smaller uncertainties that are uniform through all time lags. Based on these analytical results, a statistically robust method has been proposed to test the existence of correlations in a time series. The statistical test is verified by computer simulations and an application to single-molecule fluorescence spectroscopy is discussed.     

Molecular dynamics of hydrogen dissociation on an oxygen covered Pt(111) surface

The dissociation of hydrogen on a Pt(111) surface covered with a p(2 x 2) oxygen phase was investigated using quasiclassical, six-dimensional molecular dynamics. The potential energy surface (PES) used in these simulations was obtained by an iterative novelty sampling algorithm. Compared to molecular beam experiments performed under similar conditions, the simulations give an accurate prediction of the reaction probability via a direct dissociation pathway. When compared to previously reported reaction probability curves for the clean Pt(111) surface, we find that the presence of an oxygen overlayer inhibits the direct pathway to hydrogen dissociation. This inhibition is a function of incident energy and cannot be described by a simple site blocking model. An indirect pathway to dissociation, which was observed in experiments, is not properly captured by the PES. Spatially resolved "reaction maps" indicate that the preferred site for hydrogen dissociation on an oxygen covered Pt surface is the top site of the Pt atom farthest from the adsorbed oxygen atom.     

On-the-fly green generation and dispersion of AgI nanoparticles for cloud seeding nuclei

This study reports on an on-the-fly green synthesis/dispersion of silver iodide (AgI) nanoparticles from the combustion of AgIO₃/carbon black (CB)/nitrocellulose (NC) composites, which could be used as a candidate for a cloud-seeding pyrotechnic. Films were formed by direct electrospray deposition of a mixture of synthesized silver iodate with CB and NC. The decomposition pathways of AgIO₃/CB and AgIO₃/CB/NC were evaluated by temperature jump time of flight mass spectrometry (T-jump TOFMS) and XRD, showing that AgI particles and CO₂ are released from the reaction between AgIO₃ and CB without other toxic residuals. The flame propagation velocity of AgIO₃/CB/NC films increases with the increasing of particle mass loading of AgIO₃ and CB and peaks at 40 wt%, which is much higher than that of an AgI/AP/NC film. The mean diameter of the resultant AgI nanoparticles is from 51 to 97 nm. The mass loading of AgIO₃ and CB was found to play a major role in size control of the AgI nanoparticles.     

Synthesis and structures of 11,11,12,12‐tetracyano‐2,6‐diiodo‐9,10‐anthraquinodimethane and its 2:1 cocrystals with anthracene,pyrene and tetrathiafulvalene

Radical salts and charge‐transfer complexes (CTCs) containing tetracyanoquinodimethane (TCNQ) display electrical conductivity, which has led to the development of many TCNQ derivatives with enhanced electron‐accepting properties that are applicable toward organic electronics. To expand the family of TCNQ derivatives, we report the synthesis and structures of 11,11,12,12‐tetracyano‐2,6‐diiodo‐9,10‐anthraquinodimethane (abbreviated as DITCAQ), C₂₀H₆I₂N₄, and its charge‐transfer complexes with various electron donors, namely DITCAQ–anthracene (2/1), C₂₀H₆I₂N₄·0.5C₁₄H₁₀, (I), DITCAQ–pyrene (2/1), C₂₀H₆I₂N₄·0.5C₁₆H₁₀, (II), and DITCAQ–tetrathiafulvalene (2/1), C₂₀H₆I₂N₄·0.5C₆H₄S₄, (III). The molecular structure of DITCAQ consists of a 2,6‐diiodo‐9,10‐dihydroanthracene moiety with two malononitrile substituents. DITCAQ possesses a saddle shape, since the malononitrile groups bend significantly up out of the plane of the central ring and the two benzene rings bend down out of the same plane. π–π interactions between DITCAQ and the electron‐donor molecules control the degree of charge transfer in cocrystals (I), (II), and (III), which is reflected in both the dihedral angles between the terminal benzene ring and the central ring on the DITCAQ motifs, and their corresponding IR spectra.