Dynamics of α and α′ relaxation in layered silicate/polystyrene nanocomposites studied by anelastic spectroscopy

The dynamics of polymer chains in layered silicate/polystyrene nanocomposites was studied by anelastic spectroscopy. Two thermal activated peaks (α and α′ peaks) appeared when the specimens were heated to a high temperature and they were related to glass transition and liquid-liquid transition, respectively. The activation energy was calculated based on Arrhenius equation and it showed that the activation energy of glass transition (E _g) is much higher than that of liquid-liquid transition (E _ll). Furthermore, the most interesting result for the activation energy was that there were two contrary trends for E _g and E _ll, E _g decreased and E _ll increased with the addition of clay platelets. The fragile parameter was analyzed and the variation of fragile parameters for the two transitions was also contrary to each other with the addition of clay platelets. All the results indicated that the confinement effect of clay platelets on the dynamics of polymer chain was scale dependent, and perhaps, the two transitions were produced by different mechanisms.     

Evaluation of carbon films on the Japanese smoked roof tile “Ibushi-Kawara” by angle-dependent soft X-ray emission spectroscopy using synchrotron radiation

Surface carbon films on the Japanese smoked roof tile “Ibushi-Kawara” (hereafter “Kawara”) were analyzed by angle-dependent soft X-ray emission spectroscopy using synchrotron radiation. The carbon film microstructure on typical Kawara is 50% carbon-black-like sp² carbon atoms, which form layer-structured clusters parallel to the basal clay plane, and 50% carbon-black-like atoms, which form random-structured clusters that rigidly connect the layer-structured clusters. Weathered Kawara that has been exposed to sea breezes for numerous years was analyzed to understand the weathering effect from a microstructure point of view. The main weathering effect was the removal of the carbon film. It was also determined that the black stripes, which appear on the degraded “Susumaki” Kawara, are made from random-structured carbon black.     

Operando soft x-ray emission spectroscopy of LiMn2O4 thin film involving Li–ion extraction/insertion reaction

We developed an electrochemical in situ cell for soft x-ray emission spectroscopy (XES) to accurately investigate the redox reaction and electronic structure of transition metals in the cathode materials for Li–ion battery. The in situ cell consists of a Li–metal counter electrode, an organic electrolyte solution, and a cathode on a membrane window which separates the liquid electrolyte from high vacuum and can pass the incoming and emitted photons. In this study, the Mn 3d electronic structure of LiMn₂O₄ thin-film electrode was clarified by the operando XES. At the charged state, the XES spectrum changed significantly from the open-circuit-voltage (OCV) state, suggesting oxidation of the Mn^3 + component through Li–ion extraction. Upon discharge up to 3.0 V vs. Li/Li⁺, the XES spectrum almost returned to its profile at the OCV state with small difference, indicating the valence change of Mn: Mn^3.6 + → Mn^4 + → Mn^3.3 + corresponding to the OCV, charged, and discharged states.     

Configurations of anions of β-ketoaldehydes in solutions studied by i.r. spectroscopy

The i.r. spectra of the Li, Na and K salts of β-ketoaldehydes, RCOCH₂CHO (R = Me, Et, i-Pr and t-Bu) in DMSO, methanol and water were investigated. Assignments of bands to stretching modes of particular configurations of the enolate system were given. Influence of the cation radius on the Z,Z ⇌ E,E/Z,E equilibrium and of the substituent R on the E,E ⇌ Z,E equilibrium was observed. Shifts of the enolate bands in protic solvents were observed and hydrogen-bond formation accounted for this phenomenon.     

Local motion in theβ-transition range of partially crystalline polyethylene studied by neutron scattering

We have performed inelastic neutron scattering experiments on protonated and fully deuterated partially crystalline polyethylene. Using a high-resolution, three-axes spectrometer with an energy resolution of 80 eV, it was possible to detect a quasielastic process in the dynamic structure factor with a FWHM of 0.3 meV. This process was shown to be active aboveT ₀=260 K and its FWHM was nearly independent of temperature and scattering vector. The spatial extent of the underlying motional process was displacement increases strongly withT aboveT ₀ up to 4 Ų atT=380 K. Comparison with results from similar work on fully amorphous polymers suggests to relateT ₀ to the glass transition of the amorphous phase in partially crystalline polyethylene. The coherent structure factor showns no evidence for a significant contribution of correlated motion to the process. A speculative explanation of the observed phenomenon as a non-equilibrium soft-mode is proposed.Dedicated to Prof. E. W. Fischer on the occasion of his 65th birthday     

Effect of thickness and monolayer location on thermostability of metal stearate LB films studied by FT-IR reflection—absorption spectroscopy

LB films of Cd and Ca stearates with 1, 3, 9, and 21 monolayers were fabricated on silver-coated glass slides. 9-Monolayer LB films of Cd and Ca salts of deuterated stearic acid, in which the 1st, 5th, or 9th layer was replaced by 1 monolayer of undeuterated analogues, were also prepared on the above substrates. Temperature dependences of Fourier transform infrared (FT-IR) reflection—absorption (RA) spectra were examined for these LB films in the range 31–140°C. At room temperature, the hydrocarbon chains in these LB films were in a well-ordered state with a high degree of perpendicular orientation to the substrate. However, they became disordered at elevated temperatures. These order-disorder phase transition temperatures were dependent on the film thickness, to a small degree in the Cd stearate LB film (102–108°C), but to a large degree in the Ca stearate LB film (103–129°C). In the latter LB film, the effect of dehydration was inferred. The degree of disorder at high temperatures was dependent on the film thickness and the location of monolayer in the 9-monolayer LB films. This result is discussed in terms of the internal pressure within the LB film.     

Triplet excitation dynamics of β-carotene studied in three solvents by ns flash photolysis spectroscopy

Upon anthracene-sensitizing, triplet excitation dynamics of β-carotene(β-Car) were studied in nhexane, in methanol, and in acetonitrile, respectively, by ns flash photolysis spectroscopy. In n-hexane,only the bleaching of the ground state absorption(GSB) and the excitation triplet(~3Car*) absorption were observed, and there were no cationic species detected. In both methanol and acetonitrile, similar excitation dynamics were observed, i.e.,~3Car* having a similar lifetime to that in n-hexane, and the immediate generation of the cation dehydrodimer(~#[Car]2~+) upon excitation following transformation into the radical cation Car*~+, since Car*~+ has much longer lifetime in acetonitrile than in methanol. The results prove that both solvent and carotenoid structure determine the triplet excitation mechanism.     

Hydrogen bonding interactions in α-substituted cinnamic acid ester derivatives studied by FT–IR spectroscopy and calculations

Intermolecular hydrogen bonding interactions in stereoisomeric α-substituted cinnamic acid methyl esters (methyl 2,3-diphenylpropenoate, methyl 2-phenyl-3-(2′-methoxyphenyl)-propenoate, methyl 2-(2′-methoxyphenyl)-3-phenylpropenoate and methyl-2,3-bis(2′-methoxyphenyl)-propenoate) were studied by FT–IR spectroscopy and model calculations at the semi-empirical quantum chemical level of theory. Intermolecular hydrogen bonds of C–H…O types were found to be general in the solid state, but rare in solution. In this hydrogen bond the carbon may be part of either aromatic ring or the olefinic bond. The hydrogen bond acceptor may be the carbonyl oxygen or the oxygen in the methoxy substituent. Modeling helped in determining probable hydrogen bonding sites and their positions and provided with approximate geometric parameters (bond lengths and angles). Pointing out differences between the stereoisomers was also possible.     

Intersystem crossing in jet-cooled naphthalene, α- and β-chloronaphthalene as studied by sensitized phosphorescence excitation spectroscopy

The fluorescence excitation and sensitized phosphorescence excitation spectra of jet-cooled naphthalene-h₈, -d₈, α-chloro naphthalene, β-chloronaphthalene have been measured. It is shown that the intersystem crossing efficiency of naphthalene is large for specific vibronic levels in S₁. This efficiency is due to an accidental resonance with the vibronic level belonging to nearby T₂ state. Cl atom accelerates the intersystem crossing rate of naphthalene by about two orders of magnitude.     

The X2Σ+ state of LiCa studied by Fourier-transform spectroscopy

The paper reports on a successful observation of high resolution Fourier transform spectra of LiCa. The fine structure of the ground state was observed and attributed to effective spin-rotation interaction. The experimental observations are described by two models using potential energy curves. One of them takes into account the fine structure splitting by means of effective constants, the other by means of a R dependent function γ(R), built in the radial Schr?dinger equation. Ab initio calculations were performed for γ(R) which comes close to the experimental function.     

Bremsstrahlung emission in α-decay of210Po

Bremsstrahlung photons associated with the α-decay of²¹⁰Po were measured in α-γ coincidence measurements with Si and Ge detectors. Emission probabilities of the bremsstrahlung deduced for²¹⁰Po were 10⁻¹¹∼10⁻¹²/keV/sr/decay for 100≤E _γ≤600 keV. It was found that the bremsstrahlung yields are much smaller than those predicted by a Coulomb acceleration model. This suggests that α-particles also emit photons inside the barrier. The bremsstrahlung spectrum was compared with a quasi-classical calculation in which the bremsstrahlung emission in tunneling motion of α-particles is taken into account. It is shown that the data can be interpreted as a consequence of destructive interference of radiative amplitudes outside the Coulomb barrier with those in tunneling.     

Degradation of passive layers of iron studied by conversion electron Mössbauer spectroscopy

Integral electron Mössbauer spectroscopy (ICEMS) and additionally some electrochemical methods were used to characterize the passivation process of iron (low carbon steel) in sulfate, sulfate+sulfite (a possible model solution of acid rain) solutions and in phospate buffer. The phase compositions and thicknesses of the passive layers formed due to the electrochemical polarizations were analyzed in dependence on the duration of the anodic passivations and on the pH of the used electrolytes. The passive layer, as determined from the Mössbauer spectra, consists mainly of -FeOOH, however in sulfite containing sulfate aqueous solution at pH 3.5 Fe₃C and despite ex-situ circumstances FeSO₄·H₂O was detected after the shortest polarization time. The film thickness, which was found to grow nearly linearly with polarization time in pure sulfate solution and in phospate buffer, reached a maximum of 60–160 nm (depending on pH) in sulfate+sulfite solution after a passivation time of about 4 hours. It has been proved, that HSO₃ ^–-ion, which is contained by acid rain, initiate pit formation under acid conditions and so enforces the corrosion of iron. The experimental results furthermore suggest, that not the whole oxidic layer is responsible for the passivity but only a very thin intermediate layer formed between an inner oxide layer of a cubic structure and the rhombic oxide (-FeOOH) cover.     

Mechanism of membrane interaction and disruption by α-synuclein

Parkinson's disease is a common progressive neurodegenerative condition, characterized by the deposition of amyloid fibrils as Lewy bodies in the substantia nigra of affected individuals. These insoluble aggregates predominantly consist of the protein α-synuclein. There is increasing evidence suggesting that the aggregation of α-synuclein is influenced by lipid membranes and, vice versa, the membrane integrity is severely affected by the presence of bound aggregates. Here, using the surface-sensitive imaging technique supercritical angle fluorescence microscopy and F?rster resonance energy transfer, we report the direct observation of α-synuclein aggregation on supported lipid bilayers. Both the wild-type and the two mutant forms of α-synuclein studied, namely, the familiar variant A53T and the designed highly toxic variant E57K, were found to follow the same mechanism of polymerization and membrane damage. This mechanism involved the extraction of lipids from the bilayer and their clustering around growing α-synuclein aggregates. Despite all three isoforms following the same pathway, the extent of aggregation and their effect on the bilayers was seen to be variant and concentration dependent. Both A53T and E57K formed cross-β-sheet aggregates and damaged the membrane at submicromolar concentrations. The wild-type also formed aggregates in this range; however, the extent of membrane disruption was greatly reduced. The process of membrane damage could resemble part of the yet poorly understood cellular toxicity phenomenon in vivo.     

Synthesis of symmetrical α-alkyl- and α-arylalkylbenzyl and diarylmethyl ethers by HCl-catalyzed intermolecular dehydration

α-Alkyl-, α-arylalkyl-, and α-aryl-substituted benzyl alcohols were converted into the corresponding symmetrical dibenzyl ethers in the presence of a catalytic amount of 10% aqueous HCl both in methylene chloride and under solvent-free conditions. Analogous reactions in dioxane and on heating afforded mainly the corresponding arylalkenes, whereas symmetrical dibenzyl ethers were formed as minor products.     

Association structures of ionic liquid∕DMSO mixtures studied by high-pressure infrared spectroscopy

Using high-pressure infrared methods, we have investigated close interactions of charge-enhanced C-H-O type in ionic liquid∕dimethyl sulfoxide (DMSO) mixtures. The solvation and association of the 1-butyl-3-methylimidazolium tetrafluoroborate (BMI(+)BF(4)(-)) and 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMM(+)BF(4)(-)) in DMSO-d(6) were examined by analysis of C-H spectral features. Based on our concentration-dependent results, the imidazolium C-H groups are more sensitive sites for C-H-O than the alkyl C-H groups and the dominant imidazolium C-H species in dilute ionic liquid∕DMSO-d(6) should be assigned to the isolated (or dissociated) structures. As the dilute mixtures were compressed by high pressures, the loss in intensity of the bands attributed to the isolated structures was observed. In other words, high pressure can be used to perturb the association-dissociation equilibrium in the polar region. This result is remarkably different from what is revealed for the imidazolium C-H in the BMM(+)BF(4)(-)∕D(2)O mixtures. DFT-calculations are in agreement with our experimental results indicating that C(4)-H-O and C(5)-H-O interactions seem to play non-negligible roles for BMM(+)BF(4)(-)∕DMSO mixtures.     

The pH-dependence of preferential solvation as studied by intermolecular homo- and heteronuclear NOE measurements of adenosine in water–trifluoroethanol mixtures

A study of the state of solvation of the adenine ring in adenosine and adenosine 5-monophosphate disodium salt in water and in a (7.5:2.5) water–TFE mixture has been carried out by measurement of homo- and heteronuclear intermolecular NOE enhancements between water or TFE and the aromatic protons of these compounds. The results give evidence of site specificity in solute–solvent interaction for both solvent systems and preferential solvation of the solute by TFE in the water–TFE mixture. Significant pH dependence of these interactions has been discovered.     

Investigation of hydration of α-amino acids by means of absorption millimeter spectroscopy

The hydration indexes for 19 protein -amino acids are measured by means of absorption millimeter spectroscopy (AMS) at 31.42 GHz. The plot of the hydration indexes on the area of surface of aliphatic amino acid molecules accessible for water is a straight line located above the points corresponding to aromatic or polar amino acids. The contribution of nonpolar groups in the hydration index is greater than that of polar groups provided that their accessible surface areas are equal. The contribution to hydration of -OH and-CONH₂ groups in Ser. Gin, and Asn coincides in sign with that of pure hydrophobic hydration but the value of the contribution is significantly smaller. The change in mobility of water molecules, which is the basis of the AMS method, may serve as the physicochemical foundation for the construction of a new hydrophobicity scale for amino acids comparable with the already existing scales.Deceased September 2, 1995.Translated fromIzvestiya Akodemii Nauk. Seriya Khimicheskaya, No. 3, pp. 618–622, March, 1996.