Carbon-13 NMR evidence for cocrystallization of cellulose as a mechanism for hornification of bleached kraft pulp

Solid-state ¹³C NMR spectroscopy was used to characterize a bleached softwood kraft pulp in the never-dried state and after cycles of drying and remoistening. Changes in NMR signal strengths indicated that growth of crystalline domains involved cocrystallization rather than accretion of cellulose from noncrystalline domains. A cluster of C-4 signals at 89.4 ppm, assigned to the interiors of crystalline domains, grew at the expense of C-4 signals at 84.0 and 84.9 ppm, assigned to the well-ordered surfaces of crystalline domains. Irreversible changes were not detected until the moisture content dropped below 18%. They were enhanced by a second drying/remoistening cycle, but showed little further change on subsequent cycles. The necessary conditions resembled those reported for hornification, suggesting that cocrystallization might provide a mechanism for hornification.     

La5Al3Ni2 – an Intermetallic Phase Observed upon Crystallization of La50Al25Ni25 Metallic Glass

The yet unknown intermetallic phase La₅Al₃Ni₂ was obtained by partially crystallizing amorphous La₅₀Al₂₅Ni₂₅ at 550 K (further heating above 600 K leads to irreversible disappearance of this phase), and its crystal structure was determined from X‐ray powder diffraction data. The crystal structure of the La₅Al₃Ni₂ phase constitutes a new structure type (Cmcm, a = 14.231Å, b = 6.914Å, c = 10.460Å, oC40) and is built from [Al₃Ni₂] chains surrounded by La atoms. In the ternary system La‐Al‐Ni La₅Al₃Ni₂ is located on the section La₅₀Al_50−nNi_n (0 ≤ n ≤ 50) with the binary compounds LaAl and LaNi as end members. Strikingly, also the crystal structures of the end members can be conceived as chain structures with Al and Ni chains surrounded by La, respectively.     

Photoluminescence activity of Yang and Secco etched multicrystalline silicon material

Ultraviolet and blue-green photoluminescence (PL) was investigated on multicrystalline silicon (mc-Si) samples chemically etched by Secco and Yang solutions. The samples were characterized by dislocation density (10⁵-10⁶ cm⁻²). The form of etched pits is triangular with Yang etch and like a honeycomb with Secco etch as observed with a scanning electron microscope (SEM). These textures of mc-Si wafers give a PL activity similar to that obtained with nanostructures of porous silicon (PS) as reported in the literature. The ultraviolet PL spectra observed with Yang etch shift to the blue-green spectrum range when applying Secco etch. In our experiments we have observed 3-5 μm diameter macro pores separated by a high density of nanowalls. These observations suggest that the origin of the PL activity are quantum dots resulting from the silicon nanocrystallites obtained after few minutes of chemical etching.     

New HPLC-chiral stationary phases for enantiomeric resolution of sulfoxides and selenoxides

Summary Enantiomers of several sulfoxides and some selenoxides can be easily separated by using a new chiral stationary phase (CSP-DACH-DNB) containing the 3,5-dinitrobenzoyl derivative of R,R-(-)1,2-diamino-cyclohexane as selector, covalently bonded to the siliceous matrix. The easy operative conditions and the high enantioselectivity values (α) allow a direct transfer of the analytical separations to a semi-preparative and preparative scale.     

Liquid phase oxidation of p-chlorotoluene to p-chlorobenzaldehyde over cobalt-doped mesoporous titania with a crystalline framework

Cobalt-doped mesoporous titania with a crystalline framework synthesized by surfactant templating method presented highly selective (99%) and reasonable conversion rate (49%) of catalytic oxidation of para-chlorotoluene to para-chlorobenzaldehyde in acetic acid using aqueous hydrogen peroxide as oxidant for the first time. Recycling of the catalyst indicates that the catalyst can be used a number of times without losing its activity to a greater extent. By contrast, cobalt-doped mesoporous titania without a crystalline structure and cobalt doped the commercial titania, Degussa P25 prepared by impregnation method with the similar concentration of cobalt were found inactive. The effects of catalyst concentration, reaction time, reaction temperature, and solvents on the performance of the catalyst were also investigated.     

Insights on some chiral smectic phases

Combining layered positional order as smectic order and chirality can generate complex architectures since twist parallel to the layers is not allowed. This paper will review some new experimental results on different phases resulting from the competition between smectic positional order and twist orientational order. It concerns the TGB_A and the NL^*, that is the liquid line phase as well as the SmQ phase. Chiral effects in the isotropic phase will also be discussed.     

Towards the synthesis of MAX-phase functional coatings by pulsed laser deposition

Pulsed laser deposition with a Nd:YAG laser was used to grow thin films from a pre-synthesized Ti₃SiC₂ MAX-phase formulated ablation target on oxidized Si(1 0 0) and MgO(1 0 0) substrates. The depositions were carried out in a substrate temperature range from 300 to 900 K, and the pressure in the deposition chamber ranged from vacuum (10⁻⁵ Pa) to 0.05 Pa Argon background pressure. The properties of the films have been investigated by Rutherford backscattering spectrometry for film thickness and stoichiometric composition and X-ray diffraction for the crystallinity of the films. The silicon content of the films varied with the energy density of the laser beam. To suppress especially the silicon re-sputtering from the substrate, the energy of the incoming particles must be below a threshold of 20 eV. Therefore, the energy density of the laser beam must not be too high. At constant deposition energy density the film thickness depends strongly on the background pressure. The X-ray diffraction measurements show patterns that are typical of amorphous films, i.e. no Ti₃SiC₂ related reflections were found. Only a very weak TiC(2 0 0) reflection was seen, indicating the presence of a small amount of crystalline TiC.     

正丁基苝四羧酸二酰亚胺的晶型和性能研究

文章合成了N,N'-二正丁基苝四羧酸二酰亚胺,并纯化、调晶,进行了IR、元素分析、X射线等测定.分析该化合物在DMF中的紫外光谱(最大吸收波长524.80 nm)、荧光光谱(最大发射波长539.0 nm)、Stokes位移(数值15 nm)等光谱性质.在400～700 nm范围内,α晶型薄膜紫外-可见吸收出现很强的吸收峰,且由β型变为α型,最大吸收波长有明显的红移(545 nm变为580 nm).X射线粉末衍射也反映出α晶型的2θ在26.0°处衍射峰CPS为2 508,β型在25.2°为1 891.α,β晶型作为电荷产生材料制得的功能分离型有机光导体,在光源滤波波长λ=532 nm曝光下,测得含α,β感光体达到饱和电位的时间分别为46,93.98 s,光衰电位(5.3千伏电压负充电电晕,1～2 s后的表面电位)分别为727和525 V,半衰曝光量分别为4.32,4.34μJ·cm-2,残余电位分别为30和45 V等光导性能数值.     

Structural and lithium intercalation studies of Mn(0.5−x)CaxTi2(PO4)3 phases (0≤x≤0.50)

Materials from the Mn_(0.5−x)Ca_xTi₂(PO₄)₃ (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, ³¹P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R space group. Mn²⁺/Ca²⁺ ions occupy only the M1 sites in the Ti₂(PO₄)₃ framework. The divalent cations are ordered in one of two M1 sites, except for the Mn_0.50Ti₂(PO₄)₃ phase, where a small departure from the ideal order is observed by XRD and ³¹P MAS NMR. The electrochemical behaviour of Mn_0.50Ti₂(PO₄)₃ and Mn_(0.5−x)Ca_xTi₂(PO₄)₃ phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti₂(PO₄)₃ framework. In the 0≤y≤2 range, the OCV curves of Li//Li_yMn_0.50Ti₂(PO₄)₃ cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li_(1+y)Ti₂(PO₄)₃ and Li//Li_yMn_0.50Ti₂(PO₄)₃ shows that the intercalation occurs first in the unoccupied M1 site of Mn_0.50Ti₂(PO₄)₃ at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn_0.50Ti₂(PO₄)₃ on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn_0.50Ti₂(PO₄)₃, the stability of Mn²⁺ either in an octahedral or tetrahedral environment facilitates cationic migration.