石质文物表面生物矿化保护材料的仿生制备

许多濒危石质文物急需进行保护处理. 但是, 调查表明已经使用过的表面防护材料很难令人满意, 探索新的石质文物保护材料已是当务之急. 本工作以石质文物表面天然生成的生物矿化膜为仿生合成目标, 依据生物矿化的原理, 以硫酸软骨素作为有机模板, 草酸钙的亚稳过饱和溶液作为无机前驱物, 室温下在石材表面仿生合成了主要成分为一水草酸钙的无机表面保护材料. 其制备工艺用正交试验进行了优化; 结构和形貌用X射线衍射分析仪和原子力显微镜进行了表征; 通过憎水性、耐污性和耐酸性试验进行了合成膜的保护性能测试, 效果良好. 本方法为开拓新的石质文物保护材料提供了思路.     

Evaluation of barium hydroxide treatment efficacy on a dolomitic marble

The Arch of Peace, by Luigi Cagnola, is one of the most famous neoclassical monuments in Milan. It has been subjected to conservative intervention in 1998. In the present paper the efficacy of the consolidation by means of barium hydroxide has been evaluated. The stone material showed severe degradation phenomena as: erosion, pulverisation, exfoliation. The analytical data acquired through X-ray diffraction (XRD), infrared spectrophotometry (FTIR) and scanning electron microscopy (SEM-EDX), allowed to compare the conditions of stone before and after the treatment with barium hydroxide. The presence of barium has been put in evidence mainly on the surface as barium sulphate, whereas barium is only sporadically present within the thickness of the decayed material. The treatment was judged not satisfying and its inefficacy is, most probably, due to a not suitable cleaning procedure carried out before the consolidation.     

Fe3O4 nanocrystals with novel fractal

Fe3O4 novel fractal nanocrystals have been synthesized by a surfactant-assisted solvothermal process for the first time. X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), M?ssbauer spectroscopy (MS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) have been used to investigate the novel fractal nanocrystals. The lengths of the fractals are about 2-3 microm, and the trunks and branches of Fe3O4 fractals have almost the same diameters of ca. 30-50 nm. The roles of surfactant PEG-20000 and N2H4 have been discussed in detail. One key fact has been found that the ferrocene concentration has a vital effect on the morphologies of the products. The side-branching process and the oscillation of the concentration have been proposed to illustrate the formation mechanisms of the fractal nanocrystals. In addition, magnetic properties of Fe3O4 fractal nanocrystals have also been detected by a vibrating sample magnetometer, showing relatively high saturation magnetization (Ms) of ca. 78.75 emu/g.     

DSC investigations of amalgam formation in Bi-Sn-Hg system doped with indium

Differential scanning calorimetric (DSC) measurements have been carried out on Bi-Sn based amalgam precursors to be used in compact fluorescent lamps (CFLs) to study the changes in melting and solidifying behaviour caused by In dopant. The phase and elemental compositions of the samples have been characterized by using X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), respectively. One of the endothermic peaks of the liquid amalgam formation shifted from 121°C to 112 and 105°C, with increasing content of 2.5 and 4.8 mass% In of samples, respectively.     

Analysis of urinary stone constituents using powder X-ray diffraction and FT-IR

Constituents of urinary stones obtained from various patients from western part of India, which is a highly urinary stone disease-prone area, have been analysed. Eight stones from four patients were collected through urologists and have been analysed using powder X-ray diffraction and FT-IR. Thermogravimetric analysis (TGA) and scanning electron microscopic (SEM) image of selected samples were also carried out. The analysis revealed that calcium oxalate monohydrate, which is also known as whewellite, is the common constituent of all of the stones, particularly at the initial stage of stone formation. However, multi phases viz. whewellite phase, and hydroxyl and carbonate apatite phases are also detected in the case of third and fourth patients, from where multiple stones were obtained. Interestingly, in these mixed phase stones the concentration of whewellite decreases with increasing the concentration of apatite phases. Thermal behaviour of the whewellite phase was studied by TGA and variable temperature XRD analysis. Morphology of the whewellite and apatite phases, examined by SEM image, has also been reported.     

Ca(11)N(6)(CN(2))(2) and Ca(4)N(2)(CN(2)): The True Nature of an "Unusual Binary Nitride" Is Finally Revealed

One calcium nitride less! Several different binary nitrides of calcium have been reported: Ca(3)N(2), Ca(2)N, Ca(3)N(4), and Ca(11)N(8). X-ray structural analysis and spectroscopy revealed the latter is actually calcium nitride cyanamide and one of, so far, two examples of a new class of ternary phases (see boxes in the phase diagram).     

Two new norsesquiterpenes from Ligularia lapathifolia

Two new norsesquiterpenes were isolated from the extracts of the roots and rhizomes of Ligularia lapathifolia (Franch.) Hand.-Mazz. Their structures were identified as 2-acetyl-3a-methyl-5-(2-methyl-but-2-enoyloxy)-3a,4,5,6,7,7a-hexahydro-H-indene-4-carboxylic acid (1) and 2-acetyl-8a-methyl-2-(2-methyl-but-2-enoyloxy)-6-oxo-1,2,3,4,4a,5,6,8a-octahydro-naphthalene-1-carboxylic acid (2), respectively, on the basis of spectral data and for 1 by single-crystal X-ray analysis.     

Characterization of 16th and 18th century building materials from Veracruz City, Mexico

A study was made of samples of building materials of the Fortress of San Juan de Ulua (16th century) and of the Portal de Miranda (18th century) in Veracruz City, Mexico. One of these materials, known as ‘mucara’ stone, analyzed by means of stereoscopic and scanning electron microscopy, X-ray diffraction, neutron activation, atomic absorption spectrometry, X-ray fluorescence and thermogravimetry, was identified as the skeleton of the coral Diploria strigosa, whose main component is aragonite. The Vickers microhardness number, real and apparent densities and the porosity of coral skeleton were determined and real density value agrees with aragonite values. The building mortar used in the Portal de Miranda was also analyzed.     

Twelve new compounds from Ligularia melanothyrsa; isolation of melanothyrsins A–E,normelanothyrsin A,and other eremophilane sesquiterpenoids

Twelve new compounds, namely, five melanothyrsins A–E (1α-angeloyloxyeremophilenolides), normelanothyrsin A (1α-angeloyloxynoreremophilenone), and six other eremophilane-type compounds, have been isolated from Ligularia melanothyrsa Hand.-Mazz. (Asteraceae), collected in the Sichuan Province of China. Six of the compounds have a 1α-angeloyloxy moiety, while the other six have no functional group at the C-1 position. The absolute configuration was also determined using CD spectra. This is the first chemical study of compounds isolated from this species.     

NMR assignments and single-crystal X-ray diffraction analysis of deoxyloganic acid

7-Deoxyloganic acid (1), citrusin C (2), 3,4-dihydroxyl benzoic acid (3) and (E)-caffeic acid (4) were isolated from the water-soluble fraction of ethanol extracts of Morina nepalensis var. alba Hand.-Mazz. and their structures were determined on the basis of spectroscopic evidence. The total assignments of 1H and 13C NMR spectra of 1 in solvents CD3OD, D2O and CDCl3 were reported, in addition to the single-crystal X-ray diffraction analysis of its tetraacetate 1a. All compounds were obtained from Morina genus for the first time.     

X-ray fluorescence analysis of obsidian objects from Catamarca,Argentina

The concentrations of five trace elements (Rb, Zr, Sr, Ti and Mn) and one major (Fe) element have been determined in groups of obsidian samples by wavelength dispersive X-ray fluorescence spectrometry. Two methods were used for different elements on the basis of different excitation conditions and sample preparation procedures. Synthetic standards with compositions similar to those of the igneous stone were prepared into which the analytes were incorporated in solution. The method was used to establish the provenance of a number of prehistoric obsidian artifacts. The results ascertained in these analyses are discussed in this paper.     

Mesomorphic properties of a homologous series of chiral liquid crystals containing the α-chloroester group

The mesomorphic properties of the N*, S*_c and higher ordered smectic phases have been investigated for a homologous series of 4-[(S)-2-chlor-3-methylbutanoyloxy]-4'-(4-n-alkyloxy-benzoyloxy)biphenyls. They have been characterized by optical texture observation, differential scanning calorimetry (DSC), small angle X-ray scattering and electro-optic measurements. The compounds exhibit a strongly twisted cholesteric phase and smectic phases with large spontaneous polarization and tilt angle values. One or two higher ordered, monotropic smectic phases were found which significantly differ in their rotational viscosity.     

Studies of kidney stones using INAA,EDXRF and XRD techniques

Four kidney stones collected from patients being treated in the Advance Urology Centre of PGIMR, Chandigarh were characterized using instrumental neutron activation analysis (INAA), energy dispersive X-ray fluorescence (EDXRF) and X-ray diffraction (XRD) techniques. For INAA, samples were irradiated in tray rod facility of Dhruva reactor, Mumbai and pneumatic fast transfer system of KAMINI reactor, IGCAR, Kalpakkam. Radioactive assay was carried out using HPGe detector coupled to 8k channel analyzer. Elements determined in the samples by INAA are Zn, Sr, Co, Fe, Cr, Sc, Se, Na and Mn. EDXRF was used for the quantification of Ca. XRD patterns showed that three of the kidney stones are calcium oxalate stone and the other one is uric acid stone. The concentrations of trace elements in general were found to be higher in calcium oxalate stones and positive correlation was observed in the concentrations of Ca with Sr and Zn.     

Crystallization of a Keplerate-type polyoxometalate into a superposed kagome-lattice with huge channels

Crystal structures of two Sr(2+) salts of the Keplerate-type polyoxometalate, [Mo(VI)(72)Mo(V)(60)O(372)(CH(3)COO)(30)(H(2)O)(72)](42-), have been determined by single crystal X-ray diffraction. One compound exhibits a superposed kagome-lattice with huge channels whose diameters measure approximately 3.0 nm, while the arrangement of the Keplerate anions in the other compound approximates to a distorted cubic close packing.     

Copper complexes of thiosemicarbazone-pyridylhydrazine (THYNIC) hybrid ligands: a new versatile potential bifunctional chelator for copper radiopharmaceuticals

Two new thiosemicarbazone-pyridylhydrazine (THYNIC) hybrid ligands have been synthesized. Copper(II) and copper(I) complexes of the ligands have been prepared and characterized by X-ray crystallography. Cyclic voltammetry measurements show that the copper(II) complexes undergo quasi-reversible reductions at biologically accessible potentials. One of the ligands, bearing a pendant carboxylate arm, has been conjugated to N-alpha-(tert-butoxycarbonyl)-L-lysine.     

EDXRF as an analytical tool in art: Case studies from pigment identification and treatment assessment

Energy dispersive X-ray fluorescence (EDXRF) was employed for the identification of pigments decorating Hellenistic figurines, and the assessment of the efficiency of a treatment with barium hydroxide applied to stone. Elements present in the colored areas of the figurines, as well as the treated stone was identified by EDXRF. These data together with complementary information obtained by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD) led to the identification of several precious pigments. As far as the treatment efficiency is concerned, EDXRF analysis revealed that barium is unevenly distributed on the treated surface and reaches a maximum depth of 2.5 mm.     

EDXRF as an analytical tool in art: Case studies from pigment identification and treatment assessment

Energy dispersive X-ray fluorescence (EDXRF) was employed for the identification of pigments decorating Hellenistic figurines, and the assessment of the efficiency of a treatment with barium hydroxide applied to stone. Elements present in the colored areas of the figurines, as well as the treated stone was identified by EDXRF. These data together with complementary information obtained by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD) led to the identification of several precious pigments. As far as the treatment efficiency is concerned, EDXRF analysis revealed that barium is unevenly distributed on the treated surface and reaches a maximum depth of 2.5 mm.     

Photocatalytic TiO2 coatings on limestone

The application of photocatalytic coatings on stone has been investigated for providing surface protection and self-cleaning properties. Sol–Gel and hydrothermal processes were used to synthesise TiO₂ colloidal suspensions and coatings with enhanced photocatalytic activity without any thermal curing of the coated stone. The stone was a porous limestone (apulian sedimentary carbonatic, calcite stone). Films and powders prepared from TiO₂ sols were studied using X-ray diffraction to evaluate the microstructure and identify rutile and anatase phases. A morphological and physical characterisation was carried out on coated and uncoated stone to establish the changes of appearance, colour, water absorption by capillarity and water vapour permeability. The photocatalytic activity of the coated surface was evaluated under UV irradiation through NO _x and organics degradation tests. The performances of the synthesised TiO₂ sols were compared with commercial TiO₂ suspension. Since the coating doesn’t need temperature treatments for activating the photocatalytic properties, the nano-crystalline hydrothermal TiO₂ sols seem good candidate for coating applications on stone that cannot be annealed after the coating application.     

Determination of nanocrystal sizes: a comparison of TEM, SAXS, and XRD studies of highly monodisperse CoPt3 particles

One of the most fundamental tasks in nanoscience is the accurate determination of particle sizes. Various methods have been developed to elucidate the mean particle diameter and the standard deviation for an ensemble of nanocrystals. However, good agreement between the results from different methods is not always encountered in the literature. In this study, we investigate colloidally prepared, highly monodisperse CoPt3 nanoparticles by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and powder X-ray diffraction (XRD). The results are compared in order to examine to which extent agreement is obtained by the different techniques when applied to small nanocrystals in the size range below 10 nm. In particular, the applicability of the simple Scherrer formula for size determination from the broadening of XRD reflections is checked. When the different techniques are correctly applied, the results from all methods are in good agreement.     

Synthesis of functionalized cage propellanes and D3-Trishomocubanes via the ring-closing metathesis and acid-promoted rearrangement

Several functionalized cage propellanes and D₃-trishomocubanes containing spiro linkage have been reported starting with commercially available materials such as 1,4-hydroquinone and dicyclopentadiene. In this regard, Claisen rearrangement, Diels–Alder reaction (DA), ring-closing metathesis (RCM) and acid-promoted rearrangement have been used as key steps. The strategies described here, opens up new opportunities to assemble intricate cage systems that are difficult to construct by conventional methods. Carbocation intermediates generated during the rearrangement process play a prominent role in designing unusual cage systems. One of the rearranged cage compound's structure was unambiguously established by single crystal X-ray diffraction studies.