Configuration-dependent diffusion can shift the kinetic transition state and barrier height of protein folding

We show that diffusion can play an important role in protein-folding kinetics. We explicitly calculate the diffusion coefficient of protein folding in a lattice model. We found that diffusion typically is configuration- or reaction coordinate-dependent. The diffusion coefficient is found to be decreasing with respect to the progression of folding toward the native state, which is caused by the collapse to a compact state constraining the configurational space for exploration. The configuration- or position-dependent diffusion coefficient has a significant contribution to the kinetics in addition to the thermodynamic free-energy barrier. It effectively changes (increases in this case) the kinetic barrier height as well as the position of the corresponding transition state and therefore modifies the folding kinetic rates as well as the kinetic routes. The resulting folding time, by considering both kinetic diffusion and the thermodynamic folding free-energy profile, thus is slower than the estimation from the thermodynamic free-energy barrier with constant diffusion but is consistent with the results from kinetic simulations. The configuration- or coordinate-dependent diffusion is especially important with respect to fast folding, when there is a small or no free-energy barrier and kinetics is controlled by diffusion.Including the configurational dependence will challenge the transition state theory of protein folding.

Application of rare earths in thermal barrier coating materials

Rare earths are a series of minerals with special properties that make them essential for applications including miniaturized electronics, computer hard disks, display panels, missile guidance, pollution controlling catalysts, H-2-storage and other advanced materials. The use of thermal barrier coatings (TBCs) has the potential to extend the working temperature and the life of a gas turbine by providing a layer of thermal insulation between the metallic substrate and the hot gas. Yttria (Y2O3), as one of the most important rare earth oxides, has already been used in the typical TBC material YSZ (yttria stabilized zirconia). In the development of the TBC materials, especially in the latest ten years, rare earths have been found to be more and more important. All the new candidates of TBC materials contain a large quantity of rare earths, such as R2Zr2O7 (R=La, Ce, Nd, Gd), CeO2-YSZ, RMeAl11O19 (R=La, Nd; Me=Mg, Ca, Sr) and LaPO4. The concept of double-ceramic-layer coatings based on the rare earth materials and YSZ is effective for the improvement of the thermal shock life of TBCs at high temperature.

Ceramic materials for thermal barrier coatings

This paper summarizes the basic properties of ceramic materials for thermal barrier coatings. Ceramics, in contrast to metals, are often more resistant to oxidation, corrosion and wear, as well as being better thermal insulators. Except yttria stabilized zirconia, other materials such as lanthanum zirconate and rare earth oxides are also promising materials for thermal barrier coatings.

Micellization and reversible pH-sensitive phase transfer of the hyperbranched multiarm PEI-PBLG copolymer

A novel, hyperbranched, amphiphilic multiarm biodegradable polyethylenimine-poly(gamma-benZyl-L-gluta- mate) (PEI-PBLG) copolymer was prepared by the ring-opening polymerization of gamma-benzyl-L-glutamate-N-car-boxyanhydride (BLG-NCA) with hyperbranched PEI as a macroinitiator. The copolymer could self-assemble into core-shell micelles in aqueous solution with highly hydrophobic micelle cores. As the PBLG content was increased, the size of the micelles increased and the critical micelle concentration (CMC) decreased. The surface of the micelles had a positive potential. The cationic micelles were capable of complexing with plasmid DNA (pDNA), which could be released subsequently by treatment with polyanions. The PEI-PBLG copolymer formed unimolecular micelles in chloroform solution. ne pH-sensitive phase-transfer behavior exhibited two critical pH points for triggering the encapsulation and release of guest molecules. Both the encapsulation and release processes were rapid and reversible. Under strong acidic or alkaline conditions, the release process became partially or completely irreversible.

Synthesis of PtNPs/AQ/Ru(bpy)(3)(2+) colloid and its application as a sensitive solid-state electrochemiluminescence sensor material

The facile synthesis of the novel platinum nanoparticles/Eastman AQ55D/ruthenium(II) tris( bipyridine) (PtNPs/ AQ/Ru(bpy)(3)(2+)) colloidal material for ultrasensitive ECL solid-state sensors was reported for the first time. The cation ion-exchanger AQ was used not only to immobilize ECL active species Ru(bpy)(3)(2+) but also as the dispersant of PtNPs. Colloidal characterization was accomplished by transmission electron microscopy (TEM), X-ray photoelectron spectrum (XPS), and UV-vis spectroscopy. Directly coating the as-prepared colloid on the surface of a glassy carbon electrode produces an electrochemiluminescence (ECL) sensor. The electronic conductivity and electroactivity of PtNPs in composite film made the sensor exhibit faster electron transfer, higher ECL intensity of Ru(bpy)(3)(2+), and a shorter equilibration time than Ru(bpy)(3)(2+) immobilized in pure AQ film. Furthermore, it was demonstrated that the combination of PtNPs and permselective cation exchanger made the sensor exhibite excellent ECL behavior and stability and a very low limit of detection (1 x 10(-15) M) of tripropylamine with application prospects in bioanalysis. This method was very simple, effective, and low cost.

Highly sensitive electrogenerated chemiluminescence produced at Ru(bpy)(3)(2+) in Eastman-AQ55D-carbon nanotube composite film electrode

The electrochemistry and electrogenerated chemilurninescence (ECL) of tris(2,2-bipyridyl)ruthenium(II) ion-exchanged in Eastman-AQ-carbon nanotube (CNT) composite films were investigated at a glassy carbon (GC) electrode. Eastman-AQ55D is a poly (ester sulfonic acid) cation exchanger available in a commercial dissolved form. It is much more hydrophilic than Nafion due to its unique structure, so Ru(bpy)(3)(2+) does not diffuse into the hydrophobic region where it may lose its electroactivity as that in Nafion. The interfused CNT could act as electronic wires that connect the electrode with Ru(bpy)(3)(2+), which made the composite film much more electronically which finally led to the increasing of Ru(bpy)(3)(2+) conductive. Besides, the negatively charged CNT could also absorb some Ru(bpy)(3)(2+). Moreover, the strong electrostatic interaction between AQ and Ru(bpy)(3)(2+) made the composite films much more stable. The combination of AQ and CNT brings excellent sensitivity with the detection limit as low as 3 x 10(-11) M for TPA.

The thermal cycling behavior of Lanthanum-Cerium Oxide thermal barrier coating prepared by EB-PVD

Bulk material and coatings of Lanthanum-Cerium Oxide (La2Ce2O7) with a fluorite structure were studied as a candidate material for thermal barrier coating (TBC). It has been showed that such material has the properties of low thermal conductivity about four times lower than YSZ, the difference in the thermal expansion coefficient between La2Ce2O7 and bond coat is smaller than that of YSZ in TBC systems, high phase stability between room temperature and 1673 K, about 300 K higher than that of the YSZ. The coating prepared by electron beam physical vapor deposition (EB-PVD) showed that it has good thermal cycling behavior, implying that Such material can be a promising thermal barrier coating material. The deviation of coating composition from ingot can be overcome by the addition of excess La2O3 during ingot preparation and/or by adjusting the process parameters.

Neodymium-cerium oxide as new thermal barrier coating material

Neodymium-cerium oxide (Nd2Ce2O7) was proposed as a new thermal barrier coating material in this work. Monolithic Nd2Ce2O7 powder was prepared by the solid-state reaction at 1400 degrees C. The phase composition, thermal stability and thermophysical properties of Nd2Ce2O7 were investigated. Nd2Ce2O7 with fluorite structure was thermally stable in the temperature range of interest for TBC applications. The results indicated that the thermal expansion coefficient (TEC) of Nd2Ce2O7 was higher than that of YSZ (6-8 Wt-% Y2O3 + ZrO2) and even more interesting was the TEC change as a function of temperature paralleling that of the superalloy bond coat. Moreover, the thermal conductivity of Nd2Ce2O7 is 30% lower than that of YSZ, which was discussed based on the theory of heat conduction. Thermal barrier coating of Nd2Ce2O7 was produced by atmospheric plasma spraying (APS) using the spray-dried powder. The thermal cycling was performed with a gas burner test facility to examine the thermal stability of the as-prepared coating.

New double-ceramic-layer thermal barrier coatings based on zirconia-rare earth composite oxides

A series of La2O3-ZrO2-CeO2 composite oxides were synthesized by solid-state reaction. The final product keeps fluorite structure when the molar ratio Ce/Zr >= 0.7/0.3, and below this ratio only mixtures of La2Zr2O7 (pyrochlore) and La2O3-CeO2 (fluorite) exist. Averagely speaking, the increase of CeO2 content gives rise to the increase of thermal expansion coefficient and the reduction of thermal conductivity, but La-2(Zr0.7Ce0.3)(2)O-7 has the lowest sintering ability and the lowest thermal conductivity which could be explained by the theory of phonon scattering. Based on the large thermal expansion coefficient of La2Ce3.25O9.5, the low thermal conductivities and low sintering abilities of La2Zr2O7 and La-2(Zr0.7Ce0.3)(2)O-7, double-ceramic-layer thermal barrier coatings were prepared. The thermal cycling tests indicate that such a design can largely improve the thermal cycling lives of the coatings. Since no single material that has been studied so far satisfies all the requirements for high temperature thermal barrier coatings, double-ceramic-layer coating may be an important development direction of thermal barrier coatings.

Thermal stability of double-ceramic-layer thermal barrier coatings with various coating thickness

Double-ceramic-layer (DCL) coatings with various thickness ratios composed of YSZ (6-8 wt.% Y2O3 + ZrO2) and lanthanum zirconate (LZ, La2Zr2O7) were produced by the atmospheric plasma spraying. Chemical stability of LZ in contact with YSZ in DCL coatings was investigated by calcining powder blends at different temperatures. No obvious reaction was observed when the calcination temperature was lower than 1250 degrees C, implying that LZ and YSZ had good chemical applicability for producing DCL coating. The thermal cycling test indicate that the cycling lives of the DCL coatings are strongly dependent on the thickness ratio of LZ and YSZ, and the coatings with YSZ thickness between 150 and 200 mu m have even longer lives than the single-layer YSZ coating. When the YSZ layer is thinner than 100 mu m, the DCL coatings failed in the LZ layer close to the interface of YSZ layer and LZ layer. For the coatings with the YSZ thickness above 150 mu m, the failure mainly occurs at the interface of the YSZ layer and the bond coat.

Conformational and orientational analyses of 2,2 '-bithiophene under interaction of external electric field constructed by point charges

The fully relaxed single-bond torsional potentials and orientation-related rotational potentials of 2,2'-bithiophene (BT) under the interaction of an external electric field (EF) constructed by point charges have been evaluated with semi-empirical AMI and PM3 calculations. The torsional potentials are sensitive to both EF strength and direction. While the EF is parallel to the molecular long axis, the torsional barrier around C-x-C-x' bond obviously rises with increasing the EF strength, whereas the relative energies of syn and anti minima show a slight change. The interaction between the EF and the induced dipole moment has been proposed to elucidate this observation. On the other hand, the relative energy difference between the syn and anti minima shows an obvious change, while the EF is perpendicular to the molecular long axis. This feature has been ascribed to the interaction between the EF and the permanent dipole moment of BT. Furthermore, conformational and orientational analyses in two dimensions have been carried out by changing the torsional and rotational angles in the different EF. The conformation and orientation of a gas-phase BT in the EF are governed by both the above factors.

Excimer-laser irradiated polyimide films as temperature-sensitive materials

The temperature dependence of the resistivity of KrF laser irradiated polyimide films was studied. In all cases, the resistivity decreased with increasing temperature. The irradiated polyimide film exhibited a typical semiconducting property. This result indicated that the irradiated polyimide films can be used as temperature-sensitive materials. We demonstrated that both the sensitivity and the sensitive temperature range of the irradiated polyimide films can be altered by adjusting laser irradiation parameters. The intrinsic relationship between the temperature coefficient of the resistivity and irradiation condition was interpreted in terms of the microstructural change. The result provided a new insight into the fundamental aspects of laser irradiated polyimide film structure and a method of preparing temperature-sensitive materials. (C) 2000 Elsevier Science B.V. All rights reserved.

Barrier properties of vinylidene chloride methyl acrylate copolymer

A series of vinylidene dichloride (VDC) copolymers with methyl acrylate (MA) as comonomer (3-12wt%), was prepared by free-radical suspension copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor were measured at 30 degrees C and 100% relative humidity. All the VDC/MA copolymers studied are semicrystalline. As the MA content increases, the permeability coefficients of the copolymers to oxygen, carbon dioxide, and water vapor are progressively increased, caused by decrease in crystalline fraction and increase in free volume of VDC/MA copolymers.

Barrier property and structure of acrylonitrile/acrylic copolymers

A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerisation. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 degrees C, and those to water vapor also measured at 100% relative humidity and at 30 degrees C. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.