Drying dissipative structures of aqueous solution of poly(ethylene glycol) on a cover glass, a watch glass, and a glass dish

Drying dissipative structures of aqueous solution of poly(ethylene glycol) (PEG) of molecular weights ranging from 200 to 3,500,000 were studied on a cover glass, a watch glass, and a glass dish on macroscopic and microscopic scales. Any convectional and sedimentation patterns did not appear during the course of drying the PEG solutions. Several important findings on the drying patterns are reported. Firstly, the crystalline structures of the dried film changed from hedrites to spherulites as the molecular weight and/or concentration of PEG increased. Secondly, lamellae were formed along the ring patterns especially at high concentrations and high molecular weights. The coupled crystalline patterns of the spherulites and the lamellae were observed in a watch glass along the ring structures, supporting the important role of the convection by the gravity during the course of dryness. The coupled patterns were difficult to be formed on a cover glass and a glass dish, except at the outside edge of the dried film. Thirdly, the size of the broad ring at the outside edge of the dried film especially on a cover glass and a watch glass increased sharply as the molecular weight increased and also as the polymer concentration increased. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Impedance investigations on heat-stressed,pH-sensitive glass membranes

The behaviour of pH glass sensors is determined strongly by the kind and composition of glasses. For the heat stability, the kind and concentration of the alkaline oxide as modifier play an important role. It could be shown by potentiometric and impedimetric measurements that lithium oxide-containing glass membranes are much more stable than those with sodium oxide concerning the emf of the electrochemical cell. They tolerate several 5-h heat treatments at temperatures of 100°C. The impedance plots show differences in electrochemical kinetics between both glass membranes, which can be caused by different leaching due to differences in ionic radii of Li⁺ and Na⁺, respectively.     

Proline zwitterion dynamics in solution, glass, and crystalline state

Raman and Raman optical activity spectra of L- and D-proline zwitterionic (PROZW) forms were recorded for H(2)O and D(2)O solutions in a wide frequency range and analyzed with respect to the motion of the proline ring and rotation of the carbonyl group. The solution spectra were additionally compared to Raman scattering of glass and crystalline powder proline. Solution and glass spectral band broadenings are similar and reveal information about the extent of internal molecular motion. Two distinct but equally populated flexible forms were found in the glass and the solution. The equal population is consistent with NMR data, temperature, and concentration dependencies. The molecular flexibility is reduced significantly in the crystal, however, where only one conformer is present. Consequently, the crystal bands are narrow and exhibit minor frequency shifts. The spectra were interpreted with the aid of density functional theory computations involving both continuum and explicit solvent. A two-dimensional potential energy surface pertaining to the five-member ring puckering coordinates was constructed and used for dynamical averaging of spectral properties. Comparison of the computed and experimental bandwidths suggests that the puckering is strongly correlated with the carbonyl rotation. An averaging over these two motions produces similar results. The interpretation of the Raman experiments with the aid of the simulation techniques also indicates that the environment modulates properties of the hydrophobic part of the molecule indirectly by interacting with the ionic group. Such behavior may be important for the reactivity and biological activity of proline-containing peptides and proteins.     

Affinity chromatography of beta-galactosidase on controlled-pore glass derivatives.

Several controlled-pore glass (CPG) derivatives were examined as supports for the affinity chromatographic purification of the enzyme beta-galactosidase. The competitive inhibitor p-aminophenyl-beta-D-thiogalactopyranoside was coupled to an azelaic acid and a malonic acid derivative of 750-A alkylamine CPG of 80-120 mesh and to an azelaic acid derivative of 550-A alkylamine CPG of 40-80 mesh. The latter derivative exhibited particularly good load capacity and separation efficiency; however, both arm lengths were effective. Hydrophobic interactions between the arm and the enzyme contribute to the separation.     

Molecular modeling of polymers. IV. Estimation of glass transition temperatures

A method is described which allows molecular modeling to be combined with a group additive property model to estimate glass transition temperatures of linear polymers. T_g is assumed to be a function of conformational entropy and mass moments of the polymer. These two molecular properties are estimated in terms of the torsion angle units composing the polymer using conformational energy calculations. A “universal” T_g equation is derived using 30 structurally diverse polymers and multidimensional linear regression analysis. “Designer” T_g equations are also derived specifically for acrylate and methacrylate polymers. The work described here demonstrates how molecular modeling can be combined with group additivity theory to yield open-ended models that are not restricted by lack of requisite group additive parameters and take advantage of three-dimensional molecular information.     

High-selectivity,high-flexibility glass hollow-fiber membrane for gas separation

A high gas selectivity, high flexibility glass hollow-fiber membrane based on spinodal phase separation has been prepared by direct winding from glass melt, followed by acid leaching processing.     

Theoretical study of glass systems using molecular electronic structure theory. 2. Structure and spectroscopy of the B2O3 glass

The structure and spectroscopic properties of B 2O 3 glass are examined from a theoretical point of view by using a model of 20 B 2O 3 molecules at the DFT/6-31G* level of theory and no predetermined constraints. Useful results are deduced regarding the structure, the fraction of boroxol rings, and the infrared and Raman spectra.     

Towards environmentally friendly, dry deposited, water developable molecular glass photoresists

Photoresists based on molecular glasses are gaining more and more importance as resist material to replace polymer based photoresist. In addition environmental issues have to be considered in the long-term. Therefore the paper describes novel negative photoresists containing a ternary mixture of a glassy low molecular functional polyphenol where the film preparation is possible by solvent-free physical vapor deposition. After UV light exposure and a thermal annealing process to enable acid catalyzed crosslinking between the molecular glass and the crosslinker, the photoresist was developed using only water to give well-defined patterns. In order to experimentally study efficiently the multiple parameters such as composition, exposure dose, and development times combinatorial PVD techniques were utilized.     

Surface characterizations of mono-, di-, and tri-aminosilane treated glass substrates

The surface properties and structure of mono-, di-, and tri-aminosilane treated glass surfaces were investigated using surface analytical techniques including X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, atomic force microscopy (AFM), and streaming potential. An optimized dip-coating process was demonstrated to produce roughly silane monolayer coverage on the glass surface. The surface charge measurements indicated that aminosilanization converts the glass surface from negative to positive potentials at neutral pH values. Higher positive streaming potential was observed for tri-compared with mono- and di-aminosilane treated glass surfaces. For all aminosilane treated glass samples, the high-resolution N 1s XPS spectra indicated a preferential orientation of the protonated amino-groups towards the glass surface whereas the free amino groups were protruding outward. This study aimed to obtain uniform, reproducibly thin, strongly adhering, internally cross-linked, and high positively charged aminosilane-coated glass surfaces for the attachment of DNA fragments used in microarraying experiments.     

Controlled pore glass chromatography of protein-sodium dodecyl sulphate complexes.

The inclusion of urea has been found to eliminate adsorption of protein-sodium dodecyl sulphate (SDS) complexes to controlled pore glass. Using buffer containing 6 M urea, 0.5% SDS and glass with pore diameter 12.3 nm, it is possible to determine protein molecular weights in the range 3500-12,000. Results with glass of larger pore diameter (25.5 nm) are similar to those reported in the absence of urea in the molecular-weight range 12,000-140,000. Controlled pore glass chromatography also permits the study of the relative importance of conformation free of charge effects for those proteins which deviate from the normal calibration curve for SDS-polyacrylamide gels.     

Analysis of glass and glass melts during the vitrification of fly and bottom ashes by laser-induced plasma spectroscopy. Part II. Process analysis

Laser-induced plasma spectroscopy (LIPS) is employed for in situ and on-line process analysis of major glass constituents during a vitrification process for fly and bottom ashes from waste incineration. The system is based on an Nd:YAG laser for plasma ignition, while the elemental emissions from the plasma are detected time-resolved by an intensified multichannel analyzer. The perpendicular, single axis, imaging optics allow a remote sensing of the composition of the hot glass melt. Taking into account the plasma characteristics for calibration, good agreement between the LIPS analysis and the established reference analysis is achieved for the concentration ratios of SiO₂, Al₂O₃, and CaO. In addition, LIPS is applied to the analysis of aerosols generated by homogeneous nucleation during the heating-up of the investigated fly ashes. A distinctive temperature dependence of the heavy metal concentration of the aerosols is observed.     

A glass capillary ultramicroelectrode with an electrokinetic sampling ability.

A glass capillary ultramicroelectrode (tip diameter approximately 1.2 microm) having an electrokinetic sampling ability is described. It is composed of a pulled glass capillary filled with an inner solution and three internal electrodes (Pt working and counter electrodes and an Ag/AgCl reference electrode). The voltammetric response of the capillary electrode is based on electrokinetic transport of analyte ions from the sample solution into the inner solution across the conical tip. It was found that the electrophoretic migration of analytes at the conical tip is faster than electroosmotic flow, enabling electrokinetic transport of analyte ions into the inner solution of the electrode. By using [Fe(CN)6]4- and (ferrocenylmethyl)trimethylammonium (FcTMA+) ions as model analytes, differential pulse voltammetric responses of the capillary electrode were investigated in terms of tip diameter of the capillary, sampling voltage, sampling time, detection limit and selectivity. The magnitude of the response depends on the size and charge of analyte ions. With a capillary electrode having a approximately 1.2-microm tip diameter, which minimizes non-selective diffusional entry of analytes, the response after 1 h sampling at +1.7 V is linearly related to [Fe(CN)6]4- concentration in the range of 0.50-5.0 mM with the detection limit of 30 microM. Application of a potential of the same sign as that of the analyte ion forces the analyte to move out from the electrode to the solution, enabling reuse of the same capillary electrode. The charge-selective detection of analytes with the capillary electrode is demonstrated for [Fe(CN)6]4- in the presence of FcTMA+.     

Processing,microstructure and properties of bulk metallic glass composites

A Zr-Nb-Cu-Ni-Al bulk metallic glass was reinforced with up to 80 volume-percent (% V_f) continuous fibers, short fibers or particles. Characterization based on X-ray diffraction, differential scanning calorimetry, electron microprobe and scanning electron microscopy is presented. The metallic glass matrix remains amorphous after adding reinforcements. Reactions at the matrix/reinforcement interfaces were examined using transmission electron microscopy. A narrow band of crystalline particles typically forms adjacent to the reinforcement. The composites were tested in compression. Compressive strain-to-failure increased by up to factor of 12 compared to the unreinforced bulk metallic glass. The increase in compressive strain-to-failure is due to the particles restricting shear band propagation, promoting the generation of multiple shear bands and additional fracture surface area.