Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present.     

A new maritime lifesaving multiple-effect solar still design

This paper presents a new maritime lifesaving multiple-effect solar still design where several extended wicks feed seawater to their evaporating areas by capillary force, and the resulting water vapor diffuses and condenses on facing wicks with the condensate flowing through the wicks into storage bags. A theoretical analysis showed that a temperature drop through diffusion layers between evaporating and condensing wicks slowly increases in the main evaporating areas and rapidly near salt depositions whereas the evaporation rate decreases slowly in the main area and rapidly near salt depositions. These changes are caused by increases in salt concentrations and resulting boiling point elevation. With steady-state transfer analysis, the proposed still is predicted to produce about 15 kg m ⁻²d⁻¹ fresh water on a sunny day of 22 MJm⁻²d⁻¹ solar radiation, showing a potential to be a maritime lifesaving desalinator.     

Diffusion/adsorption model of cellulose dyeing. II. Ordinary cellulose–direct dye system

The diffusion and adsorption of C.I. Direct Yellow 12 and Blue 15 in water-swollen ordinary cellophane sheets were examined at various ionic strengths. The concentration dependence of apparent diffusion coefficients, D_c, for these dyes was obtained from the diffusion profiles in the substrate, which were measured by the use of the cylindrical film roll method. The decrease of apparent porosity with an increase in the amounts of adsorption was observed. To explain the diffusion/adsorption behaviors of these systems, a variable porosity model was proposed and was applied to analyze the concentration dependence of D_c's. The diffusion/adsorption behaviors of these dyes could be quantitatively described by this model at relatively low ionic strengths. At higher ionic strengths and/or lower values of C, i.e., at the large values of C_im/C_m, where the C's are the concentrations of immobilized (suffix im) and mobile (suffix m) species, it needed to introduce the concept of dynamic equilibria which occurred simultaneously with diffusion but deviated from the true equiliblia measured by the adsorption experiments.     

Mechanisms of CO2 separation by microporous crystals estimated by computational chemistry

The diffusion and adsorption of CO₂ inside the pores of Li, Na, and K ion-exchanged X-type zeolites were simulated by molecular dynamics and Monte Carlo calculations. Carbon dioxide diffused inside the zeolites pores while it was colliding with pore walls. Then it stayed in a super cage of zeolites. Inside the pore of Li ⁺ ion-exchanged X-type zeolite (Li-X), the electrostatic potential term was −570 kcal/mol, this value was considerably smaller than those of CO₂ inside the pores of Na-X and K-X. On the other hand, from Monte Carlo calculations, CO₂ was found to strongly absorb near the 3B site for Li ⁺ ions. When CO₂ passed through the pores of alkali ion-exchanged X-type zeolites, the interaction between the CO₂ molecule and the 3B site for Li cation was fairly large.     

Glass transition behavior of emulsion-polymerized polymer films containing a surface-active agent

The glass transition behavior of emulsion-polymerized poly(methyl methacrylate) and polystyrene films containing sodium laurylsulfate as emulsifier was studied by measurements of dynamic mechanical properties and thermal depolarization current. The film specimens of the emulsion-polymerized polymers were prepared by casting from their benzene solutions. The glass transition temperatures of the emulsion-polymerized films are higher than those of the bulk-polymerized films. The higher glass transition temperature of the emulsion-polymerized films is attributed to the colloidal properties of sodium laurylsulfate in the process of the film formation. The restriction of the molecular chains in the emulsion-polymerized films is attributed to the interaction between the hydrophobic groups of sodium laurylsulfate and the polymer molecules.     

Hydrophobic effects on protein/nucleic acid interaction: enhancement of substrate binding by mutating tyrosine 45 to tryptophan in ribonuclease Tl

Hydrophobic effects on binding of ribonuclease Tl to guaninebases of several ribonucleotides have been proved by mutatinga hydrophobic residue at the recognition site and by measuringthe effect on binding. Mutation of a hydrophobic surface residueto a more hydrophobic residue (Tyr45 – Trp) enhances thebinding to ribonucleotides, including mononucleotide inhibitorand product, and a synthetic substrate-analog trinudeotide aswell as the binding to dinucleotide substrates and RNA. Enhancementson binding to non-substrate ribonucleotides by the mutationhave been observed with free energy changes ranging from –2.2 to – 3 .9 kJ/mol. These changes are in good agreementwith that of substrate binding, –2.3 kJ/mol, which iscalculated from Michaelis constants obtained from kinetic studies.It is shown, by comparing the observed and calculated changesin binding free energy with differences in the observed transferfree energy changes of the amino acid side chains from organicsolvents to water, that the enhancement observed on guaninebinding comes from the difference in the hydrophobic effectsof the side chains of tyrosine and tryptophan. Furthermore,a linear relationship between nucleolytic activities and hydrophobicityof the residues (Ala, Phe, Tyr, Trp) at position 45 is observed.The mutation could not change substantially the base specificityof RNase Tl, which exhibits a prime requirement for guaninebases of substrates.     

Characterization of alicyclic polyimides based on cyclobutane ring dianhydride and aromatic diamine

Films of alicyclic polyamic acid and polyimide containing cyclobutane ring in dianhydride moiety and aromatic ring with p- or m-linkages in diamine moiety were characterized by infrared (IR) spectroscopy, dynamic viscoelasticity, differential-scanning calorimetry (DSC), density, and wide-angle X-ray diffraction analyses. Partially and fully imidized polyimides were obtained by varying the imidization temperature, e.g., 150°C, 250°C, and 350°C. It was found from the results of IR spectra, dynamic viscoelasticity, and DSC measurements that the imidization of alicyclic polyamic acid was reduced at about 150°C and needed a higher imidization temperature than aromatic polyamic acid. Alicyclic polyimide with m-linkage in the diamine moiety had a higher density and a much more ordered structure than with p-linkage. © 1994 John Wiley & Sons, Inc.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Preparation of plasma-polymerized membranes from I-(trimethylsilyl)-I-propyne and gas permeability through the membranes

Summary Plasma-polymerized membranes for gas separation were prepared from 1-(trimethylsilyl)-1-propyne. The permeation data of He, H₂ 0₂, N₂, CO₂, and CH₄ through the membranes showed plasma-polymerized 1-(trimethylsilyl)-1-propyne had high permselectivity but low permeability compared with poly[l-(trimethylsilyl)-1-propyne]. This behavior is considered to be due to the crosslinking structure of the plasma-polymerized membrane. The correlation between plasma polymerization conditions and the membrane performance was studied. The optimum condition at which the deposition rate of the plasma polymer is maximized agreed with the optimum value to yield maximum separation factor of gases through the membrane.     

ARCOR,a new photolithography technique with antireflective coating on resist

The multiple interference effect is one of the major causes of the fluctuation in critical dimension control (CD) and in mark detection for alignment. Suppressing this effect is critical for future photolithography. We propose a new photolithography technique called anti reflective coating on resist (ARCOR), which improves linewidth accuracy and overlay accuracy by suppressing multiple interference. ARCOR consists of relatively simple processes: A clear antireflective film is spun onto the resist prior to the mark detecting for alignment and exposure. The film is subsequently removed and the resist developed in the conventional way. ARCOR differs from ARC, which suppresses the reflection at the resist/substrate interface. ARCOR suppresses the reflection at the air/resist interface. ARCOR allows mark detection and exposure without light intensity-loss and multiple interference. The experiments mainly examine polysiloxane and perfluoroalkylpolyether as ARCOR materials. It is shown that linewidth accuracy can be improved from 0.3 to 0.03 μm. The signal-to-noise ratio of the alignment signal is drastically improved, and the overlay error is about half that of the conventional method. ARCOR is also effective for directly measuring the reflectivity at the resist/substrate interface, which is a key parameter of the multiple interference effect and the halation. Using ARCOR and a thin resist film, the measured ratio of reflected light to incident light indicates the reflectivity at the resist/substrate interface. Because, the probe light does not reflect off the resist surface and the intensity-loss at the resist surface is suppressed. With perfluoroalkylpolyether film, the measurement error is ～ 1.5%.