Synthesis, thermal, spectroscopic and magnetic studies of the Mn(SeO3).2H2O and Fe2(SeO3)3.3H2O selenites

Mn(SeO(3)).2H(2)O (1) and Fe(2)(SeO(3))(3).3H(2)O (2) have been synthesized by slow evaporation from an aqueous solution in the case of (1) and using mild hydrothermal conditions for (2). The crystal structures of both phases have been refined by the Rietveld method. The compounds crystallize in different spatial groups, the P2(1)/n monoclinic one with parameters a=6.649(1)A, b=6.542(1)A, c=10.890(1)A and beta=103.85(1) degrees being Z=4 for (1) and the R3c trigonal space group with parameters a=9.361(1)A, c=20.276(1)A and Z=6 for (2). The crystal structure of compound (1) consists of a three-dimensional framework formed by MnO(6) octahedra and (SeO(3))(2-) oxoanions with trigonal pyramidal geometry, which gives rise to Mn(2)O(10) dimers of edge-sharing octahedra. The crystal structure of phase (2) can be described as a three-dimensional framework formed by MnO(6) octahedra and (SeO(3))(2-) oxoanions with trigonal pyramidal geometry. In this phase the octahedral entities are linked along the three crystallographic axes through the selenite anions. Diffuse reflectance spectrum and luminescent measurements for (1) indicate the existence of Mn(2+) cations in a slightly distorted octahedral environment. Diffuse reflectance spectrum and M?ssbauer spectroscopy, in the paramagnetic region, for (2) show the existence of Fe(3+) cations in slightly distorted octahedral symmetry. ESR spectra of both compounds are isotropic with a g-value of 1.99(1) and 2.00(1), respectively. Magnetic measurements of both phases indicate an antiferromagnetic behavior. For phase (2), both, the ESR and magnetic measurements suggest a spin change from Fe(3+) (S=5/2) to Fe(2+) (S=2) at low temperatures.     

Novel method for measurement of glutathione kinetics in neonates using liquid chromatography coupled to isotope ratio mass spectrometry

A novel analytical method using liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS) was developed for measuring the fractional synthesis rate (FSR) of glutathione (GSH) in neonates after infusion of [1-(13)C]-glycine as a tracer. After transformation of GSH into GSSG, its dimeric form, the intra-erythrocytic concentration and (13)C-isotopic enrichment of GSH were determined using 200 microL of blood. The results showed that, using LC/IRMS, the concentration (range of micromol/mL) was reliably measured using norvaline as internal standard with precision better than 0.1 micromol/mL. In addition, the (13)C-isotopic enrichment measured in the same run gave reliable values with excellent precision (with standard deviation (sd) lower than 0.3 per thousand) and accuracy (measured between 0 and 2 Atom % Excess (APE)). The inter-assay repeatability of delta(13)C of norvaline used as internal standard with in vivo samples was assessed at -26.07 +/- 0.28 per thousand with coefficient of variance (CV) at 1.1%. The FSR calculated either with GSH or GSSG showed similar results with slightly higher values for GSSG (41.6 +/- 4.7 and 46.5 +/- 4.4, respectively). The slightly lower FSR of GSH is probably due to interfering compounds in the biological matrix. Successfully used in a clinical study, this rapid and reliable method opens up a variety of kinetic studies with relatively low administration of tracer infusates, reducing the total cost of the study design. The small volume of blood needed enables studies even in extremely small subjects, such as premature infants, as reported in this study.     

Effect of Surface‐Hydroxylated CdS Nanoparticles on the Morphological Transformation of Polystyrene‐block‐Poly(ethylene oxide) Thin Films

Summary: Polystyrene‐block‐poly(ethylene oxide) (SEO) block copolymer thin films, in which CdS clusters have been sequestered into the PEO domains of the SEO block copolymers, are found to induce the morphological transformation of PEO from cylinders to spheres, as shown by using atomic force microscopy (AFM), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). This transformation is caused by the presence of hydrogen‐bonding interactions between surface‐hydroxylated CdS and PEO, as confirmed by nuclear magnetic resonance (NMR) studies.

Morphological transformation of PEO cylinders into CdS/PEO spheres by hydrogen‐bonding interactions between surface‐hydroxylated CdS and PEO.     

Molecular dynamics simulations of fluid methane properties using ab initio intermolecular interaction potentials

Intermolecular interaction energy data for the methane dimer have been calculated at a spectroscopic accuracy and employed to construct an ab initio potential energy surface (PES) for molecular dynamics (MD) simulations of fluid methane properties. The full potential curves of the methane dimer at 12 symmetric conformations were calculated by the supermolecule counterpoise‐corrected second‐order Møller‐Plesset (MP2) perturbation theory. Single‐point coupled cluster with single and double and perturbative triple excitations [CCSD(T)] calculations were also carried out to calibrate the MP2 potentials. We employed Pople's medium size basis sets [up to 6‐311++G(3df, 3pd)] and Dunning's correlation consistent basis sets (cc‐pVXZ and aug‐cc‐pVXZ, X = D, T, Q). For each conformer, the intermolecular carbon–carbon separation was sampled in a step 0.1 Å for a range of 3–9 Å, resulting in a total of 732 configuration points calculated. The MP2 binding curves display significant anisotropy with respect to the relative orientations of the dimer. The potential curves at the complete basis set (CBS) limit were estimated using well‐established analytical extrapolation schemes. A 4‐site potential model with sites located at the hydrogen atoms was used to fit the ab initio potential data. This model stems from a hydrogen–hydrogen repulsion mechanism to explain the stability of the dimer structure. MD simulations using the ab initio PES show quantitative agreements on both the atom‐wise radial distribution functions and the self‐diffusion coefficients over a wide range of experimental conditions. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009     

Structural, thermal, spectroscopic, specific-heat, and magnetic studies of (C5H18N3)[Fe3(HPO3)6].3H2O: a new organically templated iron(III) phosphite with a pillared structure formed by the interpenetration of two subnets

A new open framework iron(III) phosphite with formula (C5H18N3)[Fe3(HPO3)6].3H2O has been prepared by hydrothermal synthesis with N-(2-aminoethyl)-1,3-propanediamine as a templating agent. The crystal structure was solved from single-crystal X-ray diffraction data in the trigonal space group R. The unit cell parameters are a= 8.803(1) A and c= 25.292(2) A with Z = 3. The complex pillared structure can be described as two interpenetrating subnets, one organic, [(C5H18N3).3H2O]3+, and one inorganic, [Fe3(HPO3)6]3-. In the inorganic subnet, the pillars are formed by FeO6 trimers linked by vertex sharing phosphite groups, while in the cationic subnet the organic molecules act like pillars. With increasing temperature, the flexibility of the structure allows contraction due to dehydration followed by thermal expansion before reaching the thermal stability limit. The Dq and Racah parameters calculated for (C5H18N3)[Fe3(HPO3)6].3H2O are Dq = 965, B = 1080, and C = 2472 cm(-1). M?ssbauer spectroscopy confirms the trivalent oxidation state of iron cations and the crystallographic multiplicities of their sites. The ESR spectra show isotropic signals with a g-value of 2.00(1). Specific-heat measurements show a three-dimensional (lambda-type) peak at a critical temperature Tc = 32 K. The value of the entropy at saturation is 46 J/mol K, very near the expected value of 44.7 J/mol K for the iron(III) cations with S = 5/2. Magnetic measurements indicate a three-dimensional antiferromagnetic ordering below 32 K and a reorientation of spins below 15 K with an incomplete cancellation of spins due to triangular interactions inherent to the structure.     

Parametrization of the magnetic behavior of the triangular spin ladder chains organically templated: (C2N2H10)[M(HPO3)F3] (M(III) = Fe, Cr, and V). Crystal structure and thermal and spectroscopic properties of the iron(III) phase

A new iron(III) phosphite templated by ethylenediamine has been synthesized using solvothermal conditions under autogenous pressure. The (C2N2H10)[Fe(HPO3)F3] compound has been characterized by single-crystal X-ray diffraction data and spectroscopic and magnetic techniques. The crystal structure is formed by chains extended along the c axis and surrounded by ethylenediammonium cations. A study by diffuse-reflectance spectroscopy has been performed, and the calculated Dq, B, and C parameters for the Fe(III) cations are 1030, 720, and 3080 cm(-1), respectively. The M?ssbauer spectrum at room temperature is characteristic of Fe(III) ions. The electron spin resonance (ESR) spectra carried out at different temperatures show isotropic signals with a g value of 2.00(1). The thermal evolution of the intensity of the ESR signals indicates the existence of antiferromagnetic interactions for the Fe(III) phase. The magnetic susceptibility data of the Cr(III) and V(III) compounds show antiferromagnetic couplings. The J-exchange parameters of the Fe(III) and Cr(III) compounds have been calculated by using a model for a triangular spin ladder chain. The values are J1 = -1.63(1) K and J2 = -0.87(2) K with g = 2.02 for the Fe(III) phase and J(1) = -0.56(2) K and J2 = -0.40(2) K with g = 1.99 for the Cr(III) compound. In the case of the V(III) phase, the fit has been performed considering a linear chain with the magnetic parameters D = 2.5 cm(-1) and J = -1.15(1) K.     

Helium irradiation-induced defects in deformed 316L stainless steel

Well-annealed 316L stainless steel was first cold rolled to 10% and 20% reductions in thickness and then irradiated by 50 keV He⁺ to a dose of 1 × 10²⁰ He⁺/m² at room temperature. Thermal desorption spectroscopy was used to investigate the helium desorption behaviour at different helium trapping states. The results showed that high-density dislocations had stronger inhibitory effect for helium desorption at temperatures from 800 to 1200 K. Positron annihilation Doppler broadening spectroscopy measurements were used to investigate the distribution of helium irradiation-induced defects. The S–E and ΔS–E plots clearly demonstrated that the helium irradiation-induced defects were trapped and restricted in motion by dislocations. The interaction between dislocations and helium irradiation-induced defects in deformed 316L stainless steel was investigated.     

不同结构碳黑填充的复合体系的太赫兹时域光谱研究

利用熔融共混、压片的方法制备了两种不同结构的碳黑(乙炔碳黑和高结构碳黑)填充的高密度聚乙烯复合材料,并利用太赫兹时域光谱研究了复合体系在太赫兹波段的介电性质.研究发现,随着频率的增加,体系的吸收系数逐渐增大而折射率则逐渐降低;在相同的频率下,吸收系数和折射率均随颗粒浓度的增加而增大;与乙炔碳黑相比,相同浓度的高结构碳熙填充的复合体系具有较大的吸收系数和较低的折射率,这与碳黑的颗粒结构以及颗粒间的团聚状态是紧密相关的.假定复合体系的介电损耗是由碳黑颗粒内部载流子的极化和聚乙烯基体的界面极化所导致的,利用双德拜模型对实验结果进行了解释,分别得到了两种极化模式所对应的弛豫时间和弛豫强度等信息.     

In situ investigation of synchrotron radiation damage effect of ancient paintings by time-resolved ED-XAS and IR combined techniques

Advanced synchrotron radiation light is a powerful tool for archaeometry research. However, its applications to precious cultural relics, especially for color painting, have been hindered to some degree due to potential X-ray radiation damage. Compared to inorganic mineral pigments, organic binders in the painting are easier to be damaged by synchrotron radiation X-ray beam. The radiation damage effect of two typical painting samples, pure rabbit skin glue and the mixed sample of rabbit skin glue and zinc white, has been investigated by in situ time-resolved ED-XAS and IR combined techniques. The results show that the radiation damage effect of pure rabbit skin glue is more serious at low X-ray energy (7775 eV). The radiation damage effect of the mixed sample increases significantly due to more X-ray absorption by inorganic pigments. Furthermore, the radiation damage is more serious at the energy near Zn K-edge and is somewhat slight at higher energy (13,054 eV). These damages are more obvious from the point of view of protein secondary structures. The irradiation damage effects increase more rapidly at the beginning and are not linear with the irradiating time. The results indicate that synchrotron radiation damage can be reduced effectively by using X-ray energy far away from the X-ray absorption edge of the major element in the pigments during XRF, XRD and CT experiments, or by using time-resolved techniques such as QXAFS and ED-XAS during XAFS experiments.