A new optical parametric amplifier based on lithium thioindate used for sum frequency generation vibrational spectroscopic studies of the amide I mode of an interfacial model peptide

We describe a new optical parametric amplifier (OPA) that employs lithium thioindate, LiInS2 (LIS), to create tunable infrared light between 1500 cm(-1) and 2000 cm(-1). The OPA based on LIS described within provides intense infrared light with a good beam profile relative to similar OPAs built on silver gallium sulfide, AgGaS2 (AGS), or silver gallium selenide, AgGaSe2 (AGSe). We have used the new LIS OPA to perform surface-specific sum frequency generation (SFG) vibrational spectroscopy of the amide I vibrational mode of a model peptide at the hydrophobic deuterated polystyrene (d8-PS)-phosphate buffered saline interface. This model polypeptide (which is known to be an alpha-helix in the bulk solution under the high ionic strength conditions employed here) contains hydrophobic leucyl (L) residues and hydrophilic lysyl (K) residues, with sequence Ac-LKKLLKLLKKLLKL-NH2. The amide I mode at the d8-PS-buffer interface was found to be centered around 1655 cm(-1). This can be interpreted as the peptide having maintained its alpha-helical structure when adsorbed on the hydrophobic surface, although other interpretations are discussed.     

Graphene-based ultracapacitors

The surface area of a single graphene sheet is 2630 m(2)/g, substantially higher than values derived from BET surface area measurements of activated carbons used in current electrochemical double layer capacitors. Our group has pioneered a new carbon material that we call chemically modified graphene (CMG). CMG materials are made from 1-atom thick sheets of carbon, functionalized as needed, and here we demonstrate in an ultracapacitor cell their performance. Specific capacitances of 135 and 99 F/g in aqueous and organic electrolytes, respectively, have been measured. In addition, high electrical conductivity gives these materials consistently good performance over a wide range of voltage scan rates. These encouraging results illustrate the exciting potential for high performance, electrical energy storage devices based on this new class of carbon material.     

The graphene-gold interface and its implications for nanoelectronics

We combine optical microspectroscopy and electronic measurements to study how gold deposition affects the physical properties of graphene. We find that the electronic structure, the electron-phonon coupling, and the doping level in gold-plated graphene are largely preserved. The transfer lengths for electrons and holes at the graphene-gold contact have values as high as 1.6 μm. However, the interfacial coupling of graphene and gold causes local temperature drops of up to 500 K in operating electronic devices.     

Single-ensemble-based eigen-processing methods for color flow imaging--Part II. The matrix pencil estimator

Parametric spectral estimators can potentially be used to obtain flow estimates directly from raw slow-time ensembles whose clutter has not been suppressed. We present a new eigen-based parametric flow estimation method called the matrix pencil, whose principles are based on a matrix form under the same name. The presented method models the slow-time signal as a sum of dominant complex sinusoids in the slow-time ensemble, and it computes the principal Doppler frequencies by using a generalized eigen-value problem-formulation and matrix rank reduction principles. Both fixed rank (rank-one, rank-two) and adaptive-rank matrix pencil flow estimators are proposed, and their potential applicability to color flow signal processing is discussed. For the adaptive-rank estimator, the nominal rank was defined as the minimum eigen-structure rank that yields principal frequency estimates with a spread greater than a prescribed bandwidth. In our initial performance evaluation, the fixed-rank matrix pencil estimators were applied to raw color flow data (transmit frequency: 5 MHz; pulse repetition period: 0.175 ms; ensemble size: 14) acquired from a steady flow phantom (70 cm/s at centerline) that was surrounded by rigid-tissue-mimicking material. These fixed-rank estimators produced velocity maps that are well correlated with the theoretical flow profile (correlation coefficient: 0.964 to 0.975). To facilitate further evaluation, the matrix pencil estimators were applied to synthetic slow-time data (transmit frequency: 5 MHz; pulse repetition period: 1.0 ms; ensemble size: 10) modeling flow scenarios without and with tissue motion (up to 1 cm/s). The bias and root-mean-squared error of the estimators were computed as a function of blood-signal-to-noise ratio and blood velocity. The matrix pencil flow estimators showed that they are comparatively less biased than most of the existing frequency-based flow estimators like the lagone autocorrelator.     

N-terminal isotope tagging strategy for quantitative proteomics: results-driven analysis of protein abundance changes

Comparing the relative abundance of each protein present in two or more complex samples can be accomplished using isotope-coded tags incorporated at the peptide level. Here we describe a chemical labeling strategy for the incorporation of a single isotope label per peptide, which is completely sequence-independent so that it potentially labels every peptide from a protein including those containing posttranslational modifications. It is based on a gentle chemical labeling strategy that specifically labels the N-terminus of all peptides in a digested sample with either a d5- or d0-propionyl group. Lysine side chains are blocked by guanidination prior to N-terminal labeling to prevent the incorporation of multiple labels. In this paper, we describe the optimization of this N-terminal isotopic tagging strategy and validate its use for peptide-based protein abundance measurements with a 10-protein standard mixture. Using a results-driven strategy, which targets proteins for identification based on MALDI TOF-MS analysis of isotopically labeled peptide pairs, we also show that this labeling strategy can detect a small number of differentially expressed proteins in a mixture as complex as a yeast cell lysate. Only peptides that show a difference in relative abundance are targeted for identification by tandem MS. Despite the fact that many peptides are quantitated, only those few showing a difference in abundance are targeted for protein identification. Proteins are identified by either targeted LC-ES MS/MS or MALDI TOF/TOF. Identifications can be accomplished equally well by either technique on the basis of multiple peptides. This increases the confidence level for both identification and quantitation. The merits of ES MS/MS or MALDI MS/MS for protein identification in a results-driven strategy are discussed.     

Adsorptive, thermodynamic and kinetic performances of Al/Ti and Al/Zr-pillared clays from the Brazilian Amazon region for zinc cation removal

Smectite clay samples from the Amazon region, Brazil, were pillarized by intercalating the species obtained from the chemical reactions: (i) AlCl₃·6H₂O/NaOH, (ii) titanium ethoxide in hydrochloric acid and (iii) direct use of ZrOCl₂·8H₂O solution. The natural matrices and the pillaring solutions were maintained under vigorous stirring at 298 K for 3 h and then subjected to calcination at temperatures of 723 and 873 K. Natural and pillared matrices were characterized by XRD, FTIR, TG–DTG and nitrogen adsorption–desorption isotherms. The resulting materials were used for zinc adsorption from aqueous solution at room temperature. The Langmuir, Freundlich and Temkin adsorption isotherm models have been applied to fit the experimental data and the Freundlich model is limited for higher concentrations. The pillaring process increases the thermal stability, the basal spacing of the natural clay sample (A₁) from 1.55 to 2.06 nm and the surface area from 44.30 to 223.73 m² g⁻¹. Kinetic studies demonstrated an equilibrium time of 180 min for zinc adsorption on the pillared matrices. Pseudo-first-order, Lagergren pseudo-second-order and Elovich equations demonstrated a better agreement with second-order kinetics was obtained with K₂ = 4.17–10.43 × 10⁻³ g mg⁻¹ min⁻¹ for the A₁ sample.     

Adaptive helical mirror for generation of optical phase singularity

We report a specially designed adaptive mirror that can be bent into a helical shape for generation of an optical phase singularity. The adaptive helical mirror (AHM) reported here is a reflective device that can provide a continuous phase variation of the optical field in the azimuthal direction. The construction details and evaluation of the AHM are presented. A Michelson interferometer is used for the detection of the phase singularity. The AHM can be used for generation of a singular beam having multiple topological charges, positive or negative, just by controlling the excitation voltage of the AHM.     

Effects on spermatogenesis in swiss mice of a protein isolated from the roots of Ricinus communis (Linn.) (Euphorbiaceae)

This study was aimed to evaluate the effect on spermatogenesis of a 62 kDa protein (Rp) isolated from 50% ethanolic extract of the root of Ricinus communis in mice. A dose response study in mice revealed that 25mg/kg body weight/day was the most effective dose. Swiss strain mature male mice of 30 days old were divided into two group namely control and Rp treated (25mg/kg body weight/day). The study showed that sperm motility and count were decreased significantly in the treated group as compared to the control. The fertility index of the treated groups was reduced by 100%. The activity of HMG Co A reductase and cholesterol were increased significantly in the treated group. The testicular activities of 3βHSD, 17βHSD, glucose 6-phosphate dehydrogenase and malic enzyme and the level of serum testosterone were decreased significantly in the treated group. The expression of 3βHSD and 17βHSD were decreased and the expression of StAR increased significantly in the treated group as compared to the control. Proteolytic digestion of the native protein with trypsin and chymotrypsin showed that the proteolytic cleavage did not affect the spermicidal action of Rp. Hence this study can be concluded that Rp impaired spermatogenesis in vivo by suppressing the production of testosterone.     

The effect of substrate material on silver nanoparticle antimicrobial efficacy

With the advent of nanotechnology, silver nanoparticles increasingly are being used in coatings, especially in medical device applications, to capitalize on their antimicrobial properties. The attractiveness of nanoparticulate silver systems is the expected increased antimicrobial efficacy relative to their bulk counterparts, which may be attributed to an increased silver ion (Ag+) solubility, and hence availability, that arises from capillarity effects in small, nanometer-sized particles. However, a change of the material upon which the antimicrobial nanoparticulate silver is deposited (herein called "substrate") may affect the availability of Ag+ ions and the intended efficacy of the device. We utilize both theory and experiment to determine the effect of substrate on ion release from silver particles in electrochemical environments and find that substrate surface charge, chemical reactivity or affinity of the surface for Ag+ ions, and wettability of the surface all affect availability of Ag+ ions, and hence antimicrobial efficacy. It is also observed that with time of exposure to deionized water, Ag+ ion release increases to a maximum value at 5 min before decreasing to undetectable levels, which is attributed to coarsening of the nanoparticles, and which subsequently reduces the solubility and availability of Ag+ ions. This coarsening phenomenon is also predicted by the theoretical considerations and has been confirmed experimentally by transmission electron microscopy.