On the role of liquid phase stability and GFA parameters

Role of liquid phase stability on the glass forming ability (GFA) has been reviewed and the alloy systems have been analyzed by introducing a contribution factor (w_g) to the characteristic temperature T_g, in the γ parameter. The kinetics of glass formation for various alloy systems has been found to vary with liquid phase stability in metastable state. The GFA of a fragile liquid is found to be more responsive to the contribution of metastable stability compared to strong liquid.     

Fullerene derived molecularly imprinted polymer for chemosensing of adenosine-5′-triphosphate (ATP)

For molecular imprinting of oxidatively electroactive analytes by electropolymerization, we used herein reductively electroactive functional monomers. As a proof of concept, we applied C₆₀ fullerene adducts as such for the first time. For that, we derivatized C₆₀ to bear either an uracil or an amide, or a carboxy addend for recognition of the adenosine-5′-triphosphate (ATP) oxidizable analyte with the ATP-templated molecularly imprinted polymer (MIP-ATP). Accordingly, the ATP complex with all of the functional monomers formed in solution was potentiodynamically electropolymerized to deposit an MIP-ATP film either on an Au electrode of the quartz crystal resonator or on a Pt disk electrode for the piezoelectric microgravimetry (PM) or capacitive impedimetry (CI) determination of ATP, respectively, under the flow-injection analysis (FIA) conditions. The apparent imprinting factor for ATP was ∼4.0. After extraction of the ATP template, analytical performance of the resulting chemosensors, including detectability, sensitivity, and selectivity, was characterized. The limit of detection was 0.3 and 0.03 mM ATP for the PM and CI chemosensor, respectively. The MIP-ATP film discriminated structural analogues of ATP quite well. The Langmuir, Freundlich, and Langmuir–Freundlich isotherms were fitted to the experimental data of the ATP sorption and sorption stability constants appeared to be nearly independent of the adopted sorption model.     

Evaluation of Thermal Behavior of Microwave Induced Graft Copolymerization of Ethylmethacrylate onto Soy Protein Concentrate

Graft copolymerization of ethylmethacrylate (EMA) onto soy protein concentrate (SPC) was carried-out using ascorbic acid/potassium persulphate as redox initiator under microwave radiations. Different reaction parameters like reaction time, solvent amount, initiator ratio, pH and monomer concentration were optimized to get maximum graft yield (78.8%). The graft copolymer formed was characterized by FTIR, XRD, SEM, TGA, DTA and DTG techniques. Graft copolymer showed higher moisture resistance along with increased chemical and thermal stability. TGA, DTA and DTG studies could reveal the distinctive features of graft copolymerization of EMA onto S-S linkages of soy protein concentrate under the influence of microwave irradiations in addition to grafting at peptide linkages, which were further supported by FT-IR studies.     

Determination of electrochemical kinetic parameters by square-wave polarography: Polarographic reduction of Zn(II) in concentrated nitrate and perchlorate supporting electrolyte solutions

The electrochemical kinetic parameters for the polarographic reduction of Zn(II) at a dropping mercury electrode in concentrated supporting electrolytes consisting of sodium, ammonium, lithium, magnesium and calcium nitrates and sodium perchlorate have been determined at 25.0±0.1°C by the square-wave polarographic method. The rate parameter decreased with increase of radius of the alkali-metal cations present in the electrolyte and with increase of charge of the cation of the electrolyte in solution of the same ionic strength. It also decreases, passes through a minimum and then increases with the increase in the concentration of any of the supporting electrolytes. The initial decrease is ascribed to the Frumkin double-layer effect but the latter increase has been explained in terms of the change in the activity of water around the electrode.     

Solvothermally synthesized europium-doped CdS nanorods: applications as phosphors

To exploit the photoluminescent behavior of CdS at nanoscale with different doping concentration of europium—a rare earth element, we report the synthesis of Eu-doped CdS nanorods by using low temperature solvothermal process by using ethylenediamine. The outcomes can have future applications as phosphors, photovoltaic cells, lasers, light emitting diodes, bio-imaging, and sensors. The doping was confirmed by electron dispersive spectroscopy supported by X-ray diffraction. From scanning electron microscopy and transmission electron microscopy analysis it was observed that the average diameter of the Cd_1−x Eu _x S nanorods is about 10–12 nm having lengths in the range of 50–100 nm. UV–Visible spectroscopy study was carried out to determine the band gap of the nanorods and the absorbance peaks showed blue shift with respect to the bulk CdS. The blue shift was also observed as the doping concentration of Eu increases. From photoluminescence (PL) studies at λ_ex = 450 nm, peaks at 528 and 540 nm were observed due to CdS, peak at 570 nm is due to defects related transitions, while the peak at 613 nm is due to Eu. As the doping concentration of Eu is increased the intensity of the luminescent peak at 613 nm is increased. Thermogravimetric analysis showed the nanorods are thermally stable up to 300 °C. The traces of impurities adsorbed on the nanorods were confirmed by Fourier transform infrared spectroscopy.     

DNP by thermal mixing under optimized conditions yields >60,000-fold enhancement of 89Y NMR signal

Hyperpolarized (89)Y complexes are attractive NMR spectroscopy and MR imaging probes due to the exceptionally long spin-lattice relaxation time (T(1) ≈ 10 min) of the (89)Y nucleus. However, in vivo imaging of (89)Y has not yet been realized because of the low NMR signal enhancement levels previously achieved for this ultra low-γ(n) nucleus. Here, we report liquid-state (89)Y NMR signal enhancements over 60,000 times the thermal signal at 298 K in a 9.4 T magnet, achieved after the dynamic nuclear polarization (DNP) of Y(III) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) samples at 3.35 T and 1.4 K. The (89)Y DNP was shown to proceed by thermal mixing and the liquid state (89)Y NMR signal enhancement was maximized by (i) establishing the optimal microwave irradiation frequency, (ii) optimizing the glassing matrix, (iii) choosing a radical with negligible inhomogeneous line broadening contribution to the ESR linewidth, and (iv) addition of an electron T(1e) relaxation agent. The highest enhancements were achieved using a trityl OX063 radical combined with a gadolinium relaxation agent in water-glycerol matrix. Co-polarization of (89)YDOTA and sodium [1-(13)C]pyruvate showed that both (89)Y and (13)C nuclear species acquired the same spin temperature, consistent with thermal mixing theory of DNP. This methodology may be applicable for the optimization of DNP of other low-γ(n) nuclei.