Self-assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small-angle x-ray scattering

The aggregation behaviour of styrene-vinyl benzoic acid (PSm-b-PVBAn) amphiphilic diblock copolymers in selective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We have carried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymers of narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found that the aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms fiat disc objects with the ratio of radius ω=0.4. The average radius gyration Rg of the copolymer decreases as solvents change from isopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with the addition of COCl2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h) ∝ h^-α in different selective solutions, suggesting that the PSm-b-PVBAn coils have self-similar structure behaviour or a fractal structure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changes dramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (Dm) from 2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course of changing solvents, decreasing surface fractal dimension (Ds) from 2.98 to 2.58 indicates that the copolymer micelle change from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasing Dm and Ds from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rather compact and rough disc form by adding COCl2 in ethanol solvents.     

Elastic constants and softening of acoustic mode in K_2SnCl_6 crystal studied by Brillouin scattering

In this paper we present the Brillouin Scattering measurementsof the longitudinal and transverse sound velocities for the hexahalome-atllate K_2SnCl_6 at room temperature.The elastic constants,refractiveindex,volume compressibility are determined from the Brillouinline shifts.Furthermore,the sound velocity in the [111] direction is inves-tigated as a function of temperature 252K相似文献   

Self—assembly behaviour of amphiphilic diblock copolymer in selective solvents studied by synchrotron small—angle x—ray scattering

The aggregation behaviour of styrene-vinyl benzoic acid (PS_m-b-PVBA_n) amphiphilic diblock copolymers in selective solvents with different m and n was investigated by synchrotron small-angle x-ray scattering (SAXS). We have carried out a detailed analysis of scattering intensity, dimension, shape and microstructure of the diblock copolymers of narrow distribution in water, methanol, ethanol and isopropanol selective solvents, respectively. We have found that the aggregation behaviour of the copolymer depends on the nature of the solvent and the micelle forms flat disc objects with the ratio of radius ω=0.4. The average radius gyration R_g of the copolymer decreases as solvents change from isopropanol to ethanol and to methanol, and increases with increasing pH in aqueous solution, but decreases with the addition of CoCl_2 in ethanol solvent. The scattering intensity of diblock copolymer micelle follows I(h)∝h^{-α} in different selective solutions, suggesting that the PS_m-b-PVBA_n coils have self-similar structure behaviour or a fractal structure in the selective solvents. All of these revealed that the aggregation behaviour of the diblock copolymer changes dramatically with experimental condition in the selective solvent. The increase of mass fractal dimension (D_m) from 2.12 to 2.47 indicates that the copolymer chain changes from a swollen coil to a rather compact disc in the course of changing solvents, decreasing surface fractal dimension (D_s) from 2.98 to 2.58 indicates that the copolymer micelle change from a rather rough surface to a smooth form in the course of increasing pH in aqueous solutions, and increasing D_m and D_s from 2.29 to 2.35 and 2.70 to 2.90, respectively, indicates the shrinkage of copolymer micelle to a rather compact and rough disc form by adding CoCl_2 in ethanol solvents.     

Oxidation state characterization in Cr oxides by means of Cr-Kβ emission spectroscopy

High-resolution Kβ spectra of Cr oxide were measured using a non-conventional spectrometer. Theoretical spectra were obtained using the DV-Xα method in order to interpret the Kβ spectrum structures. Kβ spectrum structures were analyzed and spectral parameters show a great sensitivity to the oxidation state and to the Cr-O distance. High-purity samples of CrO₂ were obtained by means of thermal treatment at 513 °C under oxygen pressure of 200 bar. X-ray diffraction patterns show a typical rutile structure, without spurious phases. The CrO₂ data allowed to confirm the linear dependency of the Kβ_1,3 and Kβ_2,5 energy positions with the oxidation state. The energy of the Kβ_2,5 line relative to the Kβ_1,3 line seems to be a suitable parameter for characterization of the oxidation state. The relative Kβ″ transition probability per Cr-O falls exponentially with Cr-O increasing distance. This behaviour was not found in the literature for Cr oxides.     

Structural evolution of glutathionate-protected gold clusters studied by means of 197 Au Mössbauer spectroscopy

¹⁹⁷Au Mössbauer spectra of a series of glutathionate-protected gold clusters, Au _n (SG) _m , with n = 10 ? ~55, were re-analyzed to understand the structure evolution behavior. The numbers of gold atoms coordinated by different numbers (0, 1, and 2) of the GS ligands were successfully determined by assuming individual isomer shifts and quadrupole splittings for the three sites in Au₂₅(SG)₁₈ (Tsukuda et al., Chem Lett 40:1292, 2011). The analysis revealed the drastic structural evolution of Au _n (SG) _m in the range of n = 10 ? ~55. In Au₁₀(SG)₁₀, all the gold atoms are bonded to GS ligands, indicating –Au–S(G)– cyclic structures. A catenane structure was proposed for Au₁₀(SG)₁₀. At n = 25, a single Au atom without the GS ligation appeared, consistent with the formation of an icosahedral Au₁₃ core protected by six staples, –S(G)–[Au–S(G)–]₂. At n = 39, it is considered that Au₃₉(SG)₂₄ has a similar structure to that of Au₃₈(SC₂H₄Ph)₂₄ with face-fused bi-icosahedral Au₂₃ core.     

Study of the structure and electronic state of thiolate-protected gold clusters by means of 197Au Mössbauer spectroscopy

We have investigated the structures and electronic states of a series of glutathionate-protected Au clusters, Au _n (SG) _m with n = 10 ? ～55, using ¹⁹⁷Au Mössbauer spectroscopy, which allows us to probe the local environment of the constituent Au atoms via isomer shift (IS) and quadrupole splitting (QS). The spectral profile abruptly changes on going from Au₂₂(SG)₁₇ to Au₂₅(SG)₁₈, then it smoothly changes to that of Au～₅₅(SG)_m. However, the spectral profile dramatically changes on going from Au～₅₅(SG)_m to the dodecanethiolate-protected Au cluster with average diameter of 2 nm. The ¹⁹⁷Au Mössbauer spectra of glutathionate-protected Au clusters and dodecanethiolate-protected Au clusters were successfully analyzed on the basis of the structure and electronic state of Au₂₅(SG)₁₈.     

Weathering of Martian and Earth surface studied by Mössbauer spectroscopy

Martian regolith and Earth’s basaltoid samples have been investigated by means of Mössbauer spectroscopy. The identification of the same minerals: olivine, pyroxene, magnetite, hematite and confrontation of the Fe^3?+?/Fe^2?+?, Fe^3?+?/Fe_tot, Fe^2?+?/Fe_tot ratios are presented. Co-existence of olivine and hematite in Martian regolith, absent in presented by authors terrestrial samples has been tentatively explained.     

Hydrogenation of FeCoZr–Al2O3 nanocomposites studied by Mössbauer spectroscopy and magnetometry

Hydrogenation effects on crystalline and magnetic structure of nanocomposites (FeCoZr) _x (Al₂O₃)_100???x , 38?≤?x?≤?63 at.% are studied by ⁵⁷Fe Mössbauer spectroscopy and magnetometry. Variations of local structure, blocking temperature and mean FeCoZr nanoparticles’ volume are discussed with respect to (i) composition and (ii) two competing processes—H₂ incorporation and annealing—occurred during treatment in H₂ plasma.     

Autler–Townes spectroscopy of high-lying state by phase conjugate six-wave mixing

An Autler-Townes(AT) spectroscopy based on phase conjugate six-wave mixing(SWM) is proposed to detect AT doublet of high-lying state in a Doppler-broadened cascade four-level system.It is found that the SWM spectrum is dependent strongly on the ratios between the magnitudes of the wave vectors.We discuss how the Doppler broadening affects the SWM spectrum from a time-domain viewpoint and find that,due the atomic motion,the atomic polarizations acquire different phases for atoms with different velocities as time evolves.The Doppler free SWM spectrum can be obtained only when the atomic polarization can be rephasing again at certain time after the interactions of all the incident fields.     

Lactate quantification by means of press spectroscopy—Influence of refocusing pulses and timing scheme

The quantitative assessment of lactic acid in tissue is an important goal for in vivo volume-selective NMR spectroscopy to aid in the noninvasive diagnosis of oxygen deficiency or other metabolic disorders. PRESS localized ¹H spectra provide comparatively high signal-to-noise ratio from small volume elements in a single acquisition mode. The quantification of lactate after multipulse excitation is not trivial due to the J-coupling characteristics which do not occur for the substances serving as references. The influence of the timing scheme and of the quality of the refocusing pulses was systematically evaluated for the lactate resonances by volume-selective measurements. Gaussian pulses, Hanning-filtered sinc pulses, and numerically optimized RE-BURP-pulses were applied for refocusing the magnetization in the PRESS sequence and the effects on the lactate AX₃ spin system were compared. For these pulses, sequence parameters are presented providing high sensitivity to lactate signals. Timing schemes are shown which provide good quantification of lactate, even in cases with B₁-inhomogeneities or slight misadjustment of the transmitter amplitude. The combination of both echo times in the double-echo sequences clearly influences the signal characteristics of lactate at overall echo times near TE = 145 and 290 ms, which may result in pure in-phase magnetization for this weakly coupled homonuclear system. Numerically optimized refocusing pulses (RE-BURP) provided up to 50% higher signal ratio of the methyl protons of lactate to uncoupled nuclei than the often used Hanning-filtered sinc pulses.     

Adsorption of nitrogen and ammonia by polycrystalline iron surfaces in the temperature range 80–290 K studied by electron spectroscopy

X-ray and uv induced photoelectron spectroscopy have provided information on the various molecular states of nitrogen formed on polycrystalline iron surfaces from dinitrogen and ammonia. At 85 K two distinct states are observed with N₂(g) which have N(1s) binding energy values of 405.3 and 400.2 eV. These are in equilibrium with N₂(g), are weakly held, and are desorbed on warming to 290 K leaving a nitrogen free surface. The two states are assigned to a molecularly adsorbed

and linear

species the former characterised by an N(1s) value of 400.2 eV and the latter by 405.3 eV. At 290 K nitrogen is adsorbed with a very low sticking probability (?10^?6) giving rise to an N(1s) value of 397.2 eV. This is undoubtedly the dissociatively chemisorbed

species. At a nitrogen pressure of l Torr adsorption is “instantaneous” and the N(1s) value is 397 eV. No evidence for the unstable bridged and linear forms of nitrogen is obtained at 290 K although they may well be precursors to the formation of the strongly chemisorbed nitrogen species. Shifts in the N(1s) binding energy induced by subsequent oxygen adsorption are discussed briefly. At 85 K ammonia adsorbs largely in the molecular form with a broad N(1s) peak centred at about 400 eV but on warming to 290 K this splits to give two peaks one at 397 eV and the other at 400 eV. Interaction at 290 K leads to a dominant peak at 397.2 eV and a subidiary one at 400 eV. Helium (1) spectra support the assignment of the 397.2 eV peak to dissociated species (N, NH) and the 400 eV peak to molecular adsorption. The conclusions with N₂ and NH₃ are substantiated further by comparing the data with results for nitric oxide. The concentration of nitrogen adatom species formed from NO at 290 K and 10^?6 Torr is some ten times that formed from N₂ at 1 Torr and three times that from NH₃ at 10^?6 Torr and the same temperature.     

Pressure induced structural change in PbPc studied by infrared and UV–visible spectroscopy and theoretical calculation

Lead phthalocyanine (PbPc) has a non-planar ‘shuttle-cock’ structure with a C_4v molecular symmetry and forms a one-dimensional column in the crystal. We measured infrared and UV–visible spectra for the PbPc crystal under high hydrostatic pressure by using a diamond anvil cell. The IR spectrum of PbPc shows three strong peaks in the 1000–1200 cm⁻¹ region. With increasing pressure, the intensity ratio of the middle peak to the other two peaks increased. This result suggests a structural transformation of the PbPc molecule from the shuttle-cock structure toward the planar structure with increasing pressure. In the UV–visible spectra, two remarkable changes were observed under high pressure: the peak intensity of the band at 2.7 eV was decreased, and the band at 1.5 eV was shifted to lower energy and broadened. The former feature suggests that the highest occupied molecular orbital (HOMO) band is not filled perfectly in the solid-state of PbPc under ambient pressure, and that the filling of the HOMO band occurs with increasing pressure. The change on the low energy band at 1.5 eV due to increasing pressure can be attributed to an increase in the intermolecular interaction.     

Influence of γ-irradiation on properties of amorphous Fe78B13Si9 alloy studied by Mössbauer spectroscopy and positron annihilation technique

The influence of γ-irradiation on properties of METGLAS 2605S2 and FC3-1 Fe₇₈B₁₃Si₉ has been investigated by Mössbauer spectroscopy, positron annihilation technique as well as bending test. The ductility and orientation of magnetization were changed by γ-irradiation. They probably correlate with the change of microscopic free volume and release of stress in the ribbon, respectively.     

Corrosion studies of iron and its alloys by means of57Fe Mössbauer spectroscopy

Some of the advantages and limitations of Mössbauer spectroscopy when used in corrosion research are shown by using three examples taken from the work of the authors on (i) the passive layer of iron, (ii) the corrosion of weathering steels by SO₂-polluted atmospheres and (iii) the performance of rust converters.     

Precise measurement of Brillouin scattering spectrum in the ocean using F–P etalon and ICCD

A new method for analyzing the signal of the spectrum of Brillouin scattering in the ocean using F–P etalon and ICCD is proposed. It is based on the principle of interference of the F–P etalon. The capability of the method is confirmed by processing experimental data from stimulated Brillouin scattering spectrum in the water at different temperatures. The experimental results show very good agreement with theoretical values. This method provides a feasible way to measure Brillouin frequency shift and line width with high precision.     

Dynamics of iron in Fe-porphyrin aggregates studied by X-ray absorption and Mössbauer spectroscopy

The iron-porphyrin aggregates were studied by optical absorption and fluorescence method, infrared spectroscopy, X-ray absorption and Mössbauer spectroscopy. The aggregation of porphyrin molecules strengthens the Fe-ligands bonds and accelerates the spin-spin relaxations. A significant speeding-up of relaxation was observed with lowering the temperature down to 25 K. The comparison of the EXAFS (Extended X-ray Absorption Fine Structure) and Mössbauer spectroscopy results enabled some separation of the individual Fe vibration from its collective movement with ligands.     

Structure of the proton emitter La studied by proton and γ-ray spectroscopy

Proton radioactivity from ¹¹⁷La was re-investigated with much improved statistics and precision. Only the ground-state proton decay (Ep=813(3) keV, T1/2=20.1(25) ms) was observed, no evidence for a previously reported isomeric proton decay was found. Prompt γ rays in ¹¹⁷La were identified using the Recoil-Decay Tagging method. Overall the data indicate that the proton-emitting state is associated with a Kπ=3/²⁺ configuration, in agreement with all the published proton-decay calculations and predictions for the ground-state configuration of ¹¹⁷La calculated in the framework of either adiabatic or non-adiabatic particle models. However, this is not in agreement with the most recent state-of-the-art quasi-particle non-adiabatic model calculations which predict a Kπ=7/²⁻ configuration.     

Perturbation approach for equation of state for hard-sphere and Lennard–Jones pure fluids

In this paper we have established the equation of state (EOS) for liquids. The EOS was established for hard-sphere (HS) fluid along with Lennard–Jones (LJ) fluid incorporating perturbation techniques. The calculations are based on suitable axiomatic functional forms for surface tension S _m (r), r ≥ d/2 with intermolecular separation r, as a variable, and m is an arbitrary real number (pole). The results for βP/ρ from the present EOS thus obtained are compared with Percus-Yevick (PY), scaled particle theory (SPT), and Carnahan–Starling (CS). In addition, we have found a simple EOS for the HS fluid in the region which represents the simulation data accurately.