Analysis of cold denaturation mechanism of β‐lactoglobulin and comparison with thermal denaturation from Raman spectroscopy investigations

Cold‐ and heat‐induced β‐lactoglobulin (BLG) transformations have been analyzed in the presence of 4 M urea, from Raman spectroscopy investigations carried out simultaneously in the low wavenumber range (10–400 cm⁻¹) and in the amide I region (1500–1800 cm⁻¹). These investigations show common features between the denaturation processes at low and high temperatures. The denatured states are reached via an intermediate state characterized by a soft tertiary structure without detectable conformational changes. This intermediate is intimately connected with a tetrahedral hydrogen‐bond structure of water which extends over a limited range. It is shown that the disruption of the hydrogen‐bond network of D₂O has an important consequence on the solvent dynamics, which controls protein dynamics and is characterized by an anharmonic behavior. By monitoring the amide I mode, conformational changes are detected at low temperature (below 5 °C) and determined to be similar to those detected at high temperature in the presence of urea near 65 °C, and in the absence of urea near 80 °C. The conformational changes are described as a loss of α‐helix structures and a concomitant formation of β‐sheets. The temperature dependence of the amide I wavenumber in BLG dissolved in the 4 M urea aqueous solution was interpreted on the basis of a two‐state model, leading to the protein stability curve related to its molecular conformation. Copyright © 2011 John Wiley & Sons, Ltd.     

Lattice disorder in germanium by boron ion bombardment

Abstract

The lattice disorder produced in germanium by 56keV boron-ion bombardment has been measured using the channeling-effect technique. The dependence on dose (10¹⁴-10¹⁶ ions/cm²) and implantation temperature (?90 °C to +130°C) has been studied. It is found that at room-temperature, each incident boron ion creates ?10 times more disorder in germanium than in silicon. It is remarked that, contrary to the present results, previously established anneal stages generally occur at significantly lower temperatures in germanium than in silicon.     

Formation of defects in the oxide layer of ion-irradiated Si/SiO2 structures

Electroluminescence and high-frequency voltage-capacitance methods are used to study Si/SiO₂ structures obtained by thermal oxidation of KéF-5 (100)Si wafers at 950°C in wet oxygen (oxide thickness 250 nm). The structures are irradiated by 130-keV argon ions with doses in the range of 10¹³−3.2×10¹⁷ cm⁻². A correlation between the origin, properties, and formation mechanism of implantation-induced defects in the oxide layer is established, and a model of defect formation is proposed.     

p-type conduction in nitrogen-doped SnO2 films grown by thermal processing of tin nitride films

p-type nitrogen-doped SnO₂ (SnO₂:N) films were grown by thermal processing of amorphous tin nitride films at temperatures between 350 and 500?^°C in flowing O₂?CAr gas mixture. From high-resolution X-ray photoelectron spectroscopy (XPS) and X-ray diffraction patterns, it is deduced that the N atoms replace the O atoms in the SnO₂ lattice. The N dopant is more tightly bound in SnO₂:N at higher thermal oxidation temperatures deduced from the XPS results. The hole concentration obtained at an oxidation temperature of 400?^°C is 1.87×10¹⁹?cm^?3, which is dramatically enhanced compared to previous reports. Our results indicate that the high-temperature thermal oxidation of tin nitride is a facile and effective route to alleviate the self-compensation effect, reduce the content of ??-N₂ double donors, and reinforce the stability of N dopant in the SnO₂:N films.     

Recrystallization of hexagonal silicon carbide after gold ion irradiation and thermal annealing

Silicon carbide (SiC) single crystals with the 6H polytype structure were irradiated with 4.0-MeV Au ions at room temperature (RT) for increasing fluences ranging from 1?×?10¹² to 2?×?10¹⁵ cm^?2, corresponding to irradiation doses from ~0.03 to 5.3 displacements per atom (dpa). The damage build-up was studied by micro-Raman spectroscopy that shows a progressive amorphization by the decrease and broadening of 6H-SiC lattice phonon peaks and the related growth of bands assigned to Si–Si and C–C homonuclear bonds. A saturation of the lattice damage fraction deduced from Raman spectra is found for ~0.8?dpa (i.e. ion fluence of 3?×?10¹⁴ cm^?2). This process is accompanied by an increase and saturation of the out-of-plane expansion (also for ~0.8?dpa), deduced from the step height at the sample surface, as measured by phase-shift interferometry. Isochronal thermal annealing experiments were then performed on partially amorphous (from 30 to 90%) and fully amorphous samples for temperatures from 200 °C up to 1500 °C under vacuum. Damage recovery and densification take place at the same annealing stage with an onset temperature of ~200 °C. Almost complete 6H polytype regrowth is found for partially amorphous samples (for doses lower than 0.8 dpa) at 1000 °C, whereas a residual damage and swelling remain for larger doses. In the latter case, these unrelaxed internal stresses give rise to an exfoliation process for higher annealing temperatures.     

Gelatin-HCl biomembranes with ionic-conducting properties

Gelatin-HCl protonic gel polymer electrolytes were obtained by crosslinking with formaldehyde in the presence of hydrochloric acid and glycerol as plasticizer and characterized in present study. The ionic conductivity measurements revealed the best value of 5.35?×?10^?5 S cm^?1 at room temperature. Factorial design analysis showed that influence of glycerol is more pronounced than influence of acid on ionic conductivity values. Moreover, the 90 % transparent membranes evidenced a linear increase of ionic conductivity values of 5.35?×?10^?5 S cm^?1 at 26.5 °C to 5.77?×?10^?4 S cm^?1 at 82.8 °C following Arrhenius type mechanism of charge mobility.     

Hydrogen-plasma etching of hydrogenated amorphous silicon: a study by a combination of spectroscopic ellipsometry and trap-limited diffusion model

The kinetics of etching hydrogenated amorphous silicon by a hydrogen plasma has been studied by in-situ spectroscopic ellipsometry measurements. The formation of a hydrogen-rich sublayer is clearly emphasized. Its thickness increases from 7 to 27?nm when the temperature during the hydrogen-plasma treatment is raised from 100 to 250°C. This effect is interpreted by solving the differential equation for trap-limited hydrogen diffusion through a mobile surface. By assigning the thickness of this sublayer to the mean diffusion distance of hydrogen we determined values of the effective diffusion coefficient of hydrogen higher than 10^?14?cm²s^?1 with an activation energy of 0.22?eV. The density of hydrogen traps is found to decrease from 7.3 × 10¹⁸ to 4.5 × 10¹⁷?cm^?3 as the temperature of the hydrogen treatment increases from 100 to 250°C with an activation energy of 0.43?eV. This effect is interpreted by a thermal equilibrium involving hydrogen transitions between shallow states and hydrogen-trapping sites.     

Autoassociation du cyclohexanol. II - caracteristiques spectroscopiques des vibrateurs ν(OH) dans les complexes d'autoassociation.

From a thermodynamic model of associated solution, the molar extinction coefficients for the spectroscopically discernable ν(OH) vibrations of associated species of cyclohexanol in isooctane solutions at 25°C and 45°C are obtained. It is found that the molar extinction coefficients for the end hydroxyl group of open species and for the monomer band are very near (57 M^?1 cm^?1 at 25°C). For the hydrogen bonded hydroxyl groups, molar extinction coefficients at 25°C are found to be, in M^?1 cm^?1 units : 93 for the open dimer ($\text{ν}$ = 3515 cm^?1), 90 for the open trimer ($\text{ν}$ = 3440 cm^?1), 126 for the other i-mers ($\text{ν}$ = 3340 cm^?1).     

Bound Energy of Water in Hard Dental Tissues

Abstract

Enamel and dentin are composed, respectively, of 3 wt% and 10 wt% of water, which exhibits different features in the tissues: loosely and tightly bound water. The objective of this study is to clarify by infrared spectroscopy, the different features of the water in heated (100–1000°C) hard dental tissues (enamel and dentin). The water band between 3800 cm^?1 and 2500 cm^?1 was analyzed by infrared spectroscopy. The area dependence of the water band with temperature was compared with the Arrhenius equation in two regions (100–400°C and 700–1000°C). The activation energy was determined for these two regions, and similar values were observed for both tissues. For enamel we obtain ?4.1±0.2 kJ/mol at 100–400 °C and ?63±9 kJ/mol at 700–1000°C; for dentin ?4.1±0.2 kJ/mol at 100–400°C and ?60±11 kJ/mol at 700–1000°C. The water loss changes the color of the tissues, hydroxyapatite crystallographic parameters, and produce ESR signals. These changes were discussed and compared with the results observed in this work and after laser irradiation. We conclude that these two activation energies could be assigned to the adsorbed (loosely bound) and trapped (tightly bound) water.     

Thermo‐Raman spectroscopy of synthetic nesquehonite — implication for the geosequestration of greenhouse gases

Pure nesquehonite (MgCO₃·3H₂O)/Mg(HCO₃)(OH)·2H₂O was synthesised and characterised by a combination of thermo‐Raman spectroscopy and thermogravimetry with evolved gas analysis. Thermo‐Raman spectroscopy shows an intense band at 1098 cm⁻¹, which shifts to 1105 cm⁻¹ at 450 °C, assigned to the ν₁CO₃²⁻ symmetric stretching mode. Two bands at 1419 and 1509 cm⁻¹ assigned to the ν₃ antisymmetric stretching mode shift to 1434 and 1504 cm⁻¹ at 175 °C. Two new peaks at 1385 and 1405 cm⁻¹ observed at temperatures higher than 175 °C are assigned to the antisymmetric stretching modes of the (HCO₃)⁻ units. Throughout all the thermo‐Raman spectra, a band at 3550 cm⁻¹ is attributed to the stretching vibration of OH units. Raman bands at 3124, 3295 and 3423 cm⁻¹ are assigned to water stretching vibrations. The intensity of these bands is lost by 175 °C. The Raman spectra were in harmony with the thermal analysis data. This research has defined the thermal stability of one of the hydrous carbonates, namely nesquehonite. Thermo‐Raman spectroscopy enables the thermal stability of the mineral nesquehonite to be defined, and, further, the changes in the formula of nesquehonite with temperature change can be defined. Indeed, Raman spectroscopy enables the formula of nesquehonite to be better defined as Mg(OH)(HCO₃)·2H₂O. Copyright © 2008 John Wiley & Sons, Ltd.     

Phase evolution and effect of pre-heating temperature on the characteristics of PZT thin films grown by using a triol sol--gel route

Lead zirconate titanate (PZT) films were fabricated on Pt(111)/Ti/SiO₂/Si(100) using the triol sol--gel method. The effect of the pre-heating temperature on the phase transformations, microstructures, electrical properties and ferroelectric properties of the PZT thin films was investigated. Randomly-oriented PZT thin films pre-heated at 400°C for 10?min and annealed at 600°C for 30?min showed well-defined ferroelectric hysteresis loops with a remanent polarization of 26.57?µC?cm^?2 and a coercive field of 115.42?kV?cm^?1. The dielectric constant and dielectric loss of the PZT films were 621 and 0.0395, respectively. The microstructures of the thin films are dense, crack-free and homogeneous with fine grains about 15–20?nm in size.     

Gettering of implanted Au in MeV?C implanted Si

The gettering behavior of 1 MeV?C implantation induced defects for Au (1.5 MeV, 2.2×10¹⁵ cm^-2), implanted into FZ Si(111), has been investigated using Rutherford backscattering spectrometry and cross-sectional transmission electron microscopy. The gettering efficiency of the C implanted layer has been studied as a function of C dose, annealing temperature and time. For a C dose of 2×10¹⁶ cm^-2, a 2 h anneal at 950 °C has been found to result in a gettering efficiency going beyond ?90%. Thermal stability of the gettered Au in the C implanted layer has subsequently been investigated over a temperature range of 950–1150 °C using isochronal annealing. The gettered amount has been found to be stable up to 1050 °C beyond which there is a release. We have observed nanovoids in the C implanted layer surrounded by ?-SiC precipitates along with patches of a-SiC. Up to about 1050 °C, these nanovoids act as efficient gettering centers beyond which they seem to release the trapped Au. Four distinct regimes in annealing temperature with different mechanisms for Au gettering have been observed.     

Features of infralow-frequency polarization relaxation processes in LiNbO3 single crystals

The dielectric response of lithium niobate single crystal in ac fields with amplitudes E of 3.74 to 13.1 kV cm^?1 is investigated at frequencies of 1 and 10 Hz in the temperature range of 70 to 200°C. The increase in effective dielectric permittivity ?_eff′ and the effective dielectric losses ?_eff″ is found to be associated with the formation of short-radius Nb _Li ⁴⁺ polarons at temperatures T > 130°C and their contribution to polarization relaxation in a LiNbO₃ crystal.     

Investigation of silicon doped by zinc ions with a large dose

The formation of nanoparticles in СZn-Si(100) implanted with ⁶⁴Zn⁺ ions using a dose of 5 × 10¹⁶ cm^–2 and an energy of 50 keV at room temperature with subsequent thermal processing in oxygen at temperatures ranging from 400 to 900°C is studied. The surface topology is investigated with scanning electron (in the secondary emission mode) and atomic force microscopes. The structure and composition of the near-surface silicon layer are examined using a high-resolution transmission electronic microscope fitted with a device for energy dispersive microanalysis. An amorphized near-surface Si layer up to 130 nm thick forms when zinc is implanted. Amorphous zinc nanoparticles with an average size of 4 nm are observed in this layer. A damaged silicon layer 50 nm thick also forms due to radiation defects. The metallic zinc phase is found in the sample after low-temperature annealing in the range of 400–600°C. When the annealing temperature is raised to 700°C, zinc oxide ZnO phase can form in the near-surface layer. The complex ZnO · Zn₂SiO₄ phase presumably emerges at temperatures of 800°C or higher, and zinc-containing nanoparticles with lateral sizes of 20–50 nm form on the sample’s surface.     

Correlation of dielectric properties,Raman spectra and calorimetric measurements of β-cyclodextrin-polyiodide complexes (β-cyclodextrin)2 ·BaI7 ·11H2O and (β-cyclodextrin)2 ·CdI7·15H2O

The frequency and temperature dependence of real and imaginary parts of the dielectric constant (ε′,?ε″), the phase shift (?) and the ac-conductivity (σ) of polycrystalline complexes (β-CD)₂·BaI₇·11H₂O and (β-CD)₂·CdI₇·15H₂O (β-CD?=?β-cyclodextrin) has been investigated over the frequency and temperature ranges 0–100?kHz and 140–420?K in combination with their Raman spectra, DSC traces and XRD patterns. The ε′(T), ε″(T) and ?(T) values at frequency 300?Hz in the range T<330?K show two sigmoids, two bell-shaped curves and two minima respectively revealing the existence of two kinds of water molecule, the tightly bound and the easily movable. Both complexes show the transition of normal hydrogen bonds to flip-flop type at 201?K. In the β-Ba complex most of the eleven water molecules remain tightly bound and only a small number of them are easily movable. On the contrary, in the β-Cd case the tightly bound water molecules are transformed gradually to easily movable. Their DSC traces show endothermic peaks with onset temperatures 118°C, 128°C for β-Ba and 106°C, 123°C, 131°C for β-Cd. The peaks 118°C, 106°C, 123°C are related to the easily movable and the tightly bound water molecules, while the peaks at 128°C, 131°C are caused by the sublimation of iodine. The activation energy of Ba²⁺ ions is 0.52?eV when all the water molecules exist in the sample and 0.99?eV when the easily movable water molecules have been removed. In the case of β-Cd the corresponding activation energies are 0.57?eV and 0.33?eV. The Raman peaks at 179?cm^?1, 170?cm^?1 and 165–166?cm^?1 are due to the charge transfer interactions in the polyiodide chains.     

Generation of dangling bonds by high temperature annealing and hopping conduction in amorphous silicon films

By annealing evaporated a-Si films between 450°C and 620°C, it is found that new dangling bonds are generated. These dangling bonds can act as hopping centres. Quantitative analysis of experimental results on electrical resistivity and ESR measurements favours a conduction mechanism of hopping to nearest neighbours between room temperature and ?100°C. Films annealed just before crystallisation temperature have a density of states near Fermi level of about 3 × 10¹⁸ cm^?3 eV^?1.     

A two-fraction model for the calculation of the resonance spectra of the complex permittivity of ice in the far infrared

A two-fraction model that makes it possible to calculate analytically the complex dielectric permittivity of ice in the far infrared and submillimeter wavelength ranges is proposed. The librational and vibrational fractions are considered. The first fraction, consisting of rigid dipoles executing anharmonic reorientations in defects of the structure, gives rise to the librational band of ice at 800 cm^?1. The second fraction consists of elastically vibrating oppositely charged H-bonded molecules. This fraction describes two bands of ice in the range 100–300 cm^?1, and the nonresonant background of dielectric losses in the submillimeter wavelength range. The dielectric permittivity spectra of ice calculated for the temperature of ?7°C are consistent with the experimental spectra. The spectra of ice at the temperature ?30°C are predicted.     

The surface of ice near 0°C studied by 100 keV proton channeling

The basal plane of ice in thermodynamic equilibrium with the vapor is studied by means of 100 keV proton channeling between ?130°C and ?2°C. The minimum yield increase rapidly above 35°C, indicating the existence of a 90 nm thick disordered layer at ?2°C.     

Structural and crystallization behavior of (Ba,Sr)TiO3 borosilicate glasses

Various glass samples were prepared by melt quench technique in the glass system [(Ba_{1? x} Sr _x ) TiO₃]–[2SiO₂–B₂O₃]–[K₂O] doped with 1?mole% of La₂O₃. Infrared spectra show the number of absorption peaks with different spliting in the wave number range from 450 to 4000?cm^?1. Absorption peaks occurs due to asymetric vibrational streching of borate by relaxation of the bond B–O of trigonal BO₃. Raman spectra show the Raman bands due to ring-type metaborate anions, symmetric breathing vibrations BO₃ triangles replaced by BO₄ tetrahedra, and symmetric breathing vibrations of six-member rings. The differential thermal analysis of a glass sample corresponding to composition x?=?0.0 shows crystallization temperature at 847°C and glass transition temperature at 688°C. X-ray diffraction (XRD) pattern of glass ceramic samples shows the major crystalline phase of BaTiO₃ whereas pyrochlore phases of barium titanium silicate. Scanning electron micrographs confirm the results of XRD as barium titanate is major crystalline phase along with pyrochlore phase of barium titanium silicate.     

Synthesis and Characterization of A Novel Macromolecular Hindered Phenol Antioxidant and Its Thermo-Oxidative Aging Resistance for Natural Rubber

A novel macromolecular hindered phenol antioxidant with high antioxidative efficiency, polyhydroxylated polybutadiene (PHPB)-bound 2, 2′-thiobis (4-methyl-6-tert-butylphenol) (PHPB-b-TPH), was prepared by binding 2, 2′-thiobis (4-methyl-6-tert-butylphenol) (TPH) onto PHPB with isophorone diisocyanate (IPDI), using dibutyltin dilaurate (DBTDL) as catalyst, via a two-step nucleophilic addition reaction. The PHPB was first synthesized from hydroxyl-terminated polybutadiene (HTPB) and 2-mercaptoethanol via a thiol-ene click reaction. The PHPB-b-TPH was characterized by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance (¹H-NMR), gel permeation chromatography (GPC), and thermal gravimetric analysis (TGA). The thermo-oxidative aging resistance of natural rubber (NR) with PHPB-b-TPH was evaluated by an accelerated thermal aging test and the oxidation induction time (OIT). The results showed that the ?OH groups of PHPB first reacted with highly active secondary ?NCO groups of IPDI at 35°C to form the adduct PHPB-NCO, and the PHPB-b-TPH was successfully obtained by one of the phenolic ?OH in TPH reacting with the primary ?NCO groups of PHPB-NCO at 70°C. The PHPB-b-TPH had better thermal stability and thermo-oxidative aging resistance for NR than TPH.