Ab initio calculation of vibrational frequencies of GexSe1−x glass

We have used the density functional theory to make the models of Ge_xSe_1?x glass for which the energy is a minimum. The clusters, Ge₂Se₂, Ge₂Se₃, Ge₃Se, Ge₃Se₂, Ge₄Se, GeSe₃, GeSe₄, chain mode zig-zag Ge₄Se₃, corner sharing GeSe₄, and edge sharing Ge₂Se₆, have been made successfully and their vibrational spectra have been calculated from the first principles. We are able to optimize the bond distances as well as the bond angles. The calculated values of the frequencies of vibrations of the various clusters have been compared with those obtained from the experimental Raman spectra of actual glasses, Ge_xSe_1?x(0 < x < 0.3). The local concentration, x within 0.25 nm is nonuniform in the amorphous material. When the same cluster occurs in two stable configurations, low frequency vibrations of frequency, ν < 100 cm^?1, are found. The corner sharing GeSe₄ has low frequency modes at 54 cm^?1 and 93 cm^?1 whereas these modes disappear in the pyramidal configuration. The low frequency modes are therefore associated with the breaking of C₄ symmetry of the pyramidal configuration. The computed vibrational frequencies of clusters Ge₃, Ge₄Se₃, Ge₂Se₃, GeSe₃ and Ge₃Se₂ are actually present in the Raman spectra of the glass, Ge_xSe_1?x(0 < x < 0.3).     

Extraction of molybdenum(VI) from hydrochloric acid solution by N,N’-carbonyl difatty amides

Hydrofluoric acid has been used as a stripping agent for molybdenum(VI) using a mixture of N,N’-carbonyl difatty amides (CDFAs) synthesized from palm oil as a extractant. The CDFAs was characterized by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance technique. In the extraction step, the effects of parameters, such as type of diluent, hydrochloric acid, metal concentration, and temperature, have been studied. The effects of various stripping agents on stripping efficiency have also been investigated. This work presents the development of a low-cost and environmentally friendly extractant to recover molybdenum.     

Enhanced physical and chemical adsorption of carbon dioxide using bimetallic copper–magnesium oxide/carbon nanocomposite

Mixed Cu and Mg oxides on nitrogen-rich activated carbon (AC) from Nypha fruticans biomass were characterized and their CO₂ adsorption performance was measured. Highly dispersed CuO and MgO nanoparticles on AC was obtained using an ultrasonic-assisted impregnation method. The optimum adsorbent is 5%CuO–25%MgO/AC having good surface properties of high surface area, pores volume and low particles agglomeration. The higher content of MgO of 5%CuO–25%MgO/AC adsorbent contributes to less metal carbide formation which increases their porosity, surface area and surface basicity. XPS analysis showed some amount of nitrogen content on the surface of the adsorbent which increased their surface basicity towards selective CO₂ adsorption. The presence of moisture accelerated the CO₂ chemisorption to form a hydroxyl layer on the surfaces. The 5%CuO–25%MgO/AC adsorbent successfully adsorbed CO₂ via physisorption and chemisorption of 14.8 and 36.2 wt%, respectively. It was significantly higher than fresh AC with better selectivity to CO₂.     

Adsorption of alpha amino acids at the water/goethite interface

The adsorption of amino acids onto mineral surfaces plays an important role in a wide range of areas, e.g., low-temperature aqueous geochemistry, bone formation and protein-bone interactions. In this work, the adsorption of three alpha aminoacids (sarcosine, MIDA and EDDA) onto goethite (alpha-FeOOH) was studied as a function of pH and background electrolyte concentration at 25.0 degrees C, and the molecular structures of the surface complexes formed were analyzed by means of ATR-FTIR spectroscopy. The results showed that adsorption of alpha amino acids were strongly dependent on the functionality and structure of the ligands. No adsorption was detected for the zwitterionic sarcosine indicating that simple alpha amino acids without other ionizable and/or functional groups display insignificant affinity for mineral surfaces such as goethite. With respect to the more complex amino acids, which are surface reactive, the number and relative positions of carboxylate and amine groups determine the types of surface interactions. These interactions range from non-specific outer-sphere to specific inner-sphere interactions as shown by the MIDA and EDDA results, respectively. The results presented herein suggest that isomerically-selective adsorption might only occur for amino acids that are capable of specific surface interactions, either through site-specific hydrogen bonding or inner-sphere complexation.     

Surface properties of semiconductor analogs of CdB<Superscript>VI</Superscript> and their solid substitution solutions

The physicochemical (acidic-basic, adsorption, and electrophysical) surface properties of binary semiconductor analogs of CdB^VI (CdTe, CdSe, and CdS), and (CdTe)_x(CdSe)_1–x, and (CdTe)_x(CdS)_1–x solid substitution solutions were studied using modern methods and equipment. The nature of the active centers and the mechanisms of acidic-basic, adsorption (involving СО), and electronic interactions, interrelated tendencies in variation of the surface properties under study, and their correlations with the known bulk physicochemical properties were elucidated; the property–composition diagrams were constructed, which were used to reveal the most active adsorbents suggested for use as materials for СО (carbon monoxide) microimpurity sensors.     

Gold nanoparticle mediated method for spatially resolved deposition of DNA on nano-gapped interdigitated electrodes,and its application to the detection of the human <Emphasis Type="Italic">Papillomavirus</Emphasis>

The authors introduce a method for spatially arranged DNA immobilization on 10-nm gold nanoparticles (GNP) deposited on a silicon substrate carrying nanogapped interdigitated electrodes. The GNPs are covalently bound to the surface via silane chemistry, and the single steps of fabrication are monitored by FTIR spectroscopy and atomic force microscopy. This GNP deposition technique is shown to reduce the size of the nanogaps to 130 nm. FTIR also was used to monitor the immobilization of DNA on the surface of the interdigitated electrodes. This method allows DNA to be immobilized in a uniform and homogenous way. The utility of the method is demonstrated by immobilizing probe DNA on the surface and detecting target DNA specific for the human papilloma virus via fluorescence with a detection limit as low as 1 pM. In our perception, this method for GNP-mediated DNA immobilization enables high-performance sensing of a wide range of target (analyte) DNA.

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Graphical abstract Schematic presentation of gold nanoparticle-mediated and spatially resolved deposition of DNA on nano-gapped interdigitated electrodes. The method was applied to the chemiluminescent determination of the human papillomavirus

     

Synthesis of libraries of thiazole, oxazole and imidazole-based cyclic peptides from azole-based amino acids. A new synthetic approach to bistratamides and didmolamides

Treatment of a 1 : 1 mixture of the thiazole-based amino acids 8a and 8b with FDPP-i-Pr(2)NEt in CH(3)CN gave a mixture of the cyclic trimers 14, 15, 16 and 17 and the cyclic tetramers 19 and 23 in the ratio 2 : 7 : 5 : 8 : 1 : 1 and in a combined yield of 70%. Separate coupling reactions between the bisimidazole amino acid 45 and the thiazole/oxazole amino acids 43a and 42a in the presence of FDPP-i-Pr(2)NEt led to the bisimidazole based cyclic trimers 55 and 57 respectively (54-57%) and to the cyclic tetramer 56 (8-11%). Similar coupling reactions involving the bisthiazole and bisoxazole amino acids 49 and 47 with the imidazole/oxazole/thiazole amino acids 41a, 42a and 43a gave rise to the library of oxazole, thiazole and imidazole-based cyclic peptides 58, 59, 60, 61, 62, 63, 64 and 65. A coupling reaction between the bisthiazole amino acid 49 and the oxazole amino acid 73 led to an efficient (36% overall) synthesis of bistratamide H (67) found in the ascidian Lissoclinum bistratum. Coupling reactions involving oxazolines with thiazole amino acids were less successful. Thus, a coupling reaction between the phenylalanine-based oxazoline amino acid 71a and either the thiazole amino acid 8a or the bisthiazole amino acid 74 gave only a 2% yield of the cyclic hexapeptide didmolamide A (4) found in the ascidian Didemnum molle. Didmolamide B (68) was obtained in 9% yield from a coupling reaction between 74 and the phenylalanine threonine amino acid 72, using either FDPP or DPPA.     

MHD Stagnation Point on Nanofluid Flow and Heat Transfer of Carbon Nanotube over a Shrinking Surface with Heat Sink Effect

This study is to investigate the magnetohydrodynamic (MHD) stagnation point flow and heat transfer characteristic nanofluid of carbon nanotube (CNTs) over the shrinking surface with heat sink effects. Similarity equations deduced from momentum and energy equation of partial differential equations are solved numerically. This study looks at the different parameters of the flow and heat transfer using first phase model which is Tiwari-Das. The parameter discussed were volume fraction nanoparticle, magnetic parameter, heat sink/source parameters, and a different type of nanofluid and based fluids. Present results revealed that the rate of nanofluid (SWCNT/kerosene) in terms of flow and heat transfer is better than (MWCNT/kerosene) and (CNT/water) and regular fluid (water). Graphically, the variation results of dual solution exist for shrinking parameter in range λc<λ≤−1 for different values of volume fraction nanoparticle, magnetic, heat sink parameters, and a different type of nanofluid. However, a unique solution exists at −1<λ<1, and no solutions exist at λ<λc which is a critical value. In addition, the local Nusselt number decreases with increasing volume fraction nanoparticle when there exists a heat sink effect. The values of the skin friction coefficient and local Nusselt number increase for both solutions with the increase in magnetic parameter. In this study, the investigation on the flow and heat transfer of MHD stagnation point nanofluid through a shrinking surface with heat sink effect shows how important the application to industrial applications.     

Utilization of saffron (<Emphasis Type="Italic">Crocus sativus L.</Emphasis>) as sensitizer in dye-sensitized solar cells (DSSCs)

Photoelectrodes of dye-sensitized solar cells (DSSCs) have been prepared using nanosized titanium dioxide that have soaked in a solution of different saffron (Crocus sativus L.) spice content in ethanol. The optimized polyacrylonitrile (PAN)-based gel polymer electrolyte with 40.93 wt.% ethylene carbonate, 37.97 wt.% propylene carbonate, 4.37 wt.% tetrapropylammonium iodide, 9.86 wt.% PAN, 1.24 wt.% 1-butyl-3-methylimidazolium iodide, 4.35 wt.% lithium iodide and 1.28 wt.% iodine has been used as the electrolyte for DSSC. The electrolyte has conductivity of 2.91 mS cm^?1 at room temperature (298 K). DSSCs were also sensitized with saffron solution that has been added with 30 wt.% chenodeoxycholic acid (CDCA) co-adsorbent and designated as DSSC P4. The solar cell converts light-to-electricity at an efficiency of 0.31%. This is 29% enhancement in efficiency for the DSSC without addition of CDCA in the saffron-ethanol solution. The DSSC exhibits current density at short-circuit (J _sc ) of 1.26 mA cm^?2, voltage at open circuit (V _oc ) of 0.48 V and 51% fill factor. DSSC P4 also exhibits the highest incident photon-to-current density of more than 40% at 340 nm wavelength.