Conformational analysis of ethylene oxide and ethylene imine oligomers by quantum chemical calculations: solvent effects

Summary  Conformational analyses using quantum chemical calculations were carried out for 1- to 4-mers of ethylene oxide (EO) and ethylene imine (EI) oligomer models (EO-x and EI-x, x = 1 - 4) in the liquid phase using four solvents (permittivity: ε = 2.0 ~80.1). The results were compared against those obtained in the gaseous phase. The calculations involved either RHF/6-31+G(d,p) or B3LYP/6-31G(d) // SCRF/IPCM, based on the observed and calculated results for the energy difference between trans- and cis-dichloroethane. The conformations repeated for a unit of X-C, C-C and C-X bonds (X: O or N) were examined. For both oligomers, the energies of every conformer decreased with increasing ε values, and were linear against the Kirkwood function (K_f = (ε-1)/(2ε+1)). For the EO oligomers, the (ttt)_x conformer was most stable in the gaseous phase. In liquid phases, however, the preference for the gauche-conformation (gauche preference) of the C-C bonds increased with higher values of ε. In the case of EO-3, the (tg⁺t)_x conformer was most stable above an ε value of 8.9, which were in good agreement with those observed for triglyme solutions using NMR analysis. For the EI oligomers, the (tg⁺t)_x conformer was most stable in either gaseous or liquid phase, and the gauche preference of the C-C bonds in both phases were comparable. These results were in good agreement with those observed for di-MEDA solutions using NMR analysis. It was estimated that such small solvent effects on gauche preferences of the EI oligomers result in weakening for hydrogen bonds (NH-N) of neighboring imino groups by solvents.     

Kinetic parameters for anodic oxidation of hypochlorite ion on Pt and Pt oxide electrodes in alkaline solution

Kinetic parameters for the anodic oxidation of hypochlorite ion have been determined by means of normal pulse voltammetry by using a platinum disk as the working electrode. By using the working electrode that formed an oxide film by electrochemical pretreatment, the effect of the lattice oxygen of the surface oxide on the reaction was also examined. The measurement results were analyzed by the classical method, and then the analytical results were evaluated by digital simulation. The normal pulse voltammogram of the hypochlorite ion showed quasi-reversible oxidation waves. The apparent rate constant was calculated to be 5.0-8.1 × 10⁻⁴ cm s⁻¹, depending on the electrode surface state. At the low-concentration range of <4.0 mg Cl dm⁻³, the oxidation current was concentration dependent at the cathodically polarized electrode, while it became independent after the anodic polarization.     

Preparation and properties of biodegradable network poly(ester-carbonate) elastomers

Biodegradable elastomeric network poly(ester-carbonate)s were prepared from multifunctional aliphatic carboxylic acids such as tricarballylic acid (Y_t) or trimesic acid (Y) and polycarbonate diols (PCD) with molecular weights of 1000 and 2000 g/mol. Prepolymers prepared by a melt polycondensation were cast from dimethylformamide solution and postpolymerized at 270 °C for 40-80 min to form a network. The resultant films were transparent, flexible and insoluble in organic solvents. WAXS exhibited the crystalline peaks due to polycarbonate segments for the network films from PCD₂₀₀₀, while those from PCD₁₀₀₀ were amorphous. The tensile properties were determined for these network films at the temperatures 22, 30, 40 and 50 °C. These films showed elastomeric properties at all temperatures measured. The elongation at break was much higher for the films from PCD₂₀₀₀ (208-434%) than those from PCD₁₀₀₀ (40-120%), and decreased with increasing temperatures. The weight losses of the network films degraded in the buffer solution of Rhizopus delemar lipase at 37 °C increased with time, suggesting that these network films are biodegradable. The degradation rate of the network films from Y_t is faster than that from Y. The GPC curves showed that the lipase hydrolyzed both the ester linkages between Y or Y_t and PCD as well as polycarbonate moiety in the network polymer.     

Electrooxidation of C1 to C3 alcohols with Pt and Pt–Ru sputter deposited interdigitated array electrodes

The electrooxidation of methanol, ethanol, and 2-propanol was investigated with interdigitated array electrodes (IDAEs). The IDAE oxidizes alcohol at the generator and reduces the reaction intermediates produced by the oxidation process at the collector. Thus, the reaction intermediates can be estimated with the IDAE. The IDAE in the present work was made of sputter deposited Pt and Pt–Ru. The use of Ru free and added electrodes provides information on the effect of Ru addition on the alcohol oxidation. Cyclic voltammetric analyses revealed that Ru addition enhances the oxidation currents and reduces the E_onset of the alcohols. The detectable reaction intermediate at the methanol and ethanol oxidation was proton, while the intermediate species was acetone in 2-propnaol oxidation.     

Smart sunglasses based on electrochromic polymers

Smart sunglasses based on electrochromic polymers are proposed and developed in this study. This article discusses the design, processing, and the optical and electrical performance of a prototype smart sunglasses based on cathodic electrochromic (EC) polymers, which show several merits compared with traditional materials for sunglasses lens as well as other smart window materials. It is a multilayer design of device. The conjugated polymer, poly[3,3‐dimethyl‐3,4‐dihydro‐2H‐thieno [3,4‐b] [1,4]dioxepine] (PProDOT‐Me₂), is utilized as the electrochromic working layer. The counter layer of the device is vanadium oxide (V₂O₅) film, which serves as an ion storage layer. There is also a polymer gel electrolyte acting as the ionic transport layer, sandwiched between the working and counter layers. The characteristics of the prototype device are reported, including transmittance (%T), driving power, response time, open circuit memory, and lifetime. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Molecular dynamics model structures for the molten globule state of {alpha}-lactalbumin: aromatic residue clusters I and II

To model the molten globule structure of -lactalbumin, moleculardynamics (MD) simulations were carried out for the protein inexplicit water at high temperature. In these simulations, long-rangeCoulomb interactions were evaluated explicitly with an originalmethod (particle–particle and particle–cell: PPPC)to avoid artifacts caused by the cut-off. The MD simulationswere started from two initial conditions to verify that similarresults would be obtained. From the last 150 ps trajectoriesof the two MD simulations, two partially unfolded average structureswere obtained. These structures had the following common structuralfeatures which are characteristic of the molten globule state.The radii of gyration for these conformations were 7.4 and 9.6%larger than that of the native state. These values were almostthe same as the experimental value (9.6%) observed recentlyby small-angle X-ray scattering (Kataoka,M., Kuwajima,K., Tokunaga,F.and Goto,Y., 1997, Protein Sci., 6, 422–430). Furthermore,aromatic residues of clusters I and II in these structures werefar apart from each other except for Try103–Trp104. Thisresult is in good agreement with NMR experimental results forthe acid-denatured molten globule state (Alexandrescu et al.,1992, 1993); that is, NOE signals between the aromatic residueswere not observed, except for that of Try103–Trp104 inthe molten globule state. Other structural features of thesemodels for the molten globule state are discussed with referenceto native state structures.     

In situ observation of initial rust formation process on carbon steel under Na2SO4 and NaCl solution films with wet/dry cycles using synchrotron radiation X-rays

Atmospheric corrosion of steel proceeds under thin electrolyte film formed by rain and dew condensation followed by wet and dry cycles. It is said that rust layer formed on steel as a result of atmospheric corrosion strongly affects the corrosion behavior of steel. The effect of environmental corrosiveness on the formation process and structure of the rust layer is, however, not clear to date. In this study, in situ observation of the rusting process of a carbon steel covered with a thin film of Na₂SO₄ or NaCl solution was performed under a wet/dry repeating condition by X-ray diffraction spectroscopy with white X-rays obtained from synchrotron radiation. The present in situ experiments successfully detected initial process of the rust formation. In the early cycles, the rust constituents were not well crystallized yet, but the presence of Fe(OH)₂ and Fe(OH)₃ was confirmed. In the subsequent cycles, two different solutions resulted in difference in preferential phase of the rust constituents. α-FeOOH was preferentially formed in the case of the Na₂SO₄ solution film, whereas β-FeOOH appeared only under the NaCl solution film.     

Precise analysis of H, C, N, and O as dominant impurities in Cu films: complementary use of SIMS and GDMS

Secondary ion mass spectrometry (SIMS) and glow discharge mass spectrometry (GDMS) were used to determine the impurity concentrations of hydrogen, carbon, nitrogen, and oxygen elements in Cu films, and the results of SIMS and GDMS were carefully interpreted. The Cu films were deposited on Si (100) substrates at substrate bias voltages ranging from 0 V to −150 V using a non-mass separated ion beam deposition method. From the results of SIMS using a Cs⁻ ion beam, as a whole, many high intensity peaks were observed in the Cu films deposited without substrate bias voltage. From the quantitative GDMS results, these peaks were determined to be signals detected as a cluster state such as C_xH_x, O_xH_x, C_xO_xH_x. Therefore, using a combination of these dominant impurities, all the unknown peaks observed in the SIMS results could be interpreted. Moreover, it was found that the dominant impurities having a great influence on the film purity were hydrogen, carbon, nitrogen, and oxygen.     

Precipitation Characteristics and Mechanism of Vanadium Carbides in a V-Microalloyed Medium-Carbon Steel

The precipitation characteristics and mechanism of vanadium carbides during isothermal transformation at 650 ℃ in a V-microalloyed medium-carbon steel were investigated through scanning electron microscopy and transmission electron microscopy as well as dilatometry test. Five morphologies of vanadium carbides were found to precipitate at different nucleation sites during the transformation. Two kinds of interphase precipitation form simultaneously in both pro-eutectoid and pearlitic ferrites. The linear arrays of fine interphase precipitates are parallel to the c/a interface, and the fine needles of interphase precipitates are perpendicular to the c/a interface. The vanadium carbides of long or short fibers, coarse particles and fine particles form in both pro-eutectoid and pearlitic ferrites, displaying different precipitation distributions and orientation relationships with ferrite. The precipitation mechanisms of vanadium carbide precipitates with different modes were proposed, and the precipitation sequence of various vanadium carbide precipitates was finally ascertained.     

Electropolymerization kinetic study of 3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine and its optical optimization for electrochromic window applications

Poly (3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine), PProDOT-Me₂, is one of the most promising conducting polymers in the alkylenedioxythiophene based family for electrochromic window applications. In the electropolymerization kinetic study of 3,3-dimethyl-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (ProDOT-Me₂), microgravimetry and chronoamperometry were used to determine the reaction orders with respect to the electrolyte and monomer, and the corresponding general kinetic equation of electropolymerization. This study presents that monomer concentration has a strong impact on electropolymerization mechanism. The relationship between film thickness and polymerization time was analyzed indicating that saturation of polymerization reduced the increase rate of film thickness with polymerization time. Also, the electropolymerization conditions were optimized to reach high contrast (Δ%T > 70%) with the minimum of transmittance (%T_min < 1) for electrochromic window applications.