Design and synthesis of optically transparent calcium‐incorporated polymer complexes

Transparent thin films of calcium‐ion‐incorporated polymer composites were synthesized with calcium carbonate (CaCO₃) and polymers such as poly(acrylic acid) (PAA), poly(ethylene glycol) (PEG), and methylcellulose. The homogeneous distribution of Ca²⁺ in the composite films was observed because of the high concentration of COO^? groups along the PAA backbone for the complexation of Ca²⁺ ions. The optical transparency of the composites depends on the weight percentages of the three polymers and the molar concentration of CaCO₃ in the composites. Maximum transparency was obtained for a composite film with a PAA/CaCO₃ ratio of 9:1. The results indicated that methylcellulose improved the film‐forming capabilities and that PEG improved the transparency of the composites. All polymer complexes were characterized with X‐ray diffraction, fourier transfer infrared spectroscopy, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, dynamic mechanical analysis, and optical transparency measurements. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4459–4465, 2004     

磷矿及磷肥中氧化钙测定方法改进

为了解决磷矿及磷肥中氧化钙酸溶不完全和消除测定过程中磷酸根、镁、铁等的干扰,对磷矿和磷肥中氧化钙的测定方法进行改进.对不同酸溶解体系选择、酸用量、加热时间、干扰掩蔽实验、pH值等条件进行实验,确定采用10 mL王水、3 mL氢氟酸分解试样,加入2 mL盐酸溶解盐类,加入10 mL糊精和5 mL三乙醇胺溶液掩蔽Mg2+、...     

Spectrophotometric determination of silicon in silicates by flow-injection analysis

A flow-injection spectrophotometric method has been developed for the accurate, continuous determination of silicon in silicate rocks. A rock sample solution is prepared by fusion with a 1:1 mixture of lithium carbonate and boric acid and subsequent dissolution of the cake in 1 M hydrochloric acid. The preparation technique is the same as that used for the determination of total iron, aluminium, calcium, titanium, and phosphorus in silicate rocks by flow-injection spectrophotometry. Because of the marked polymerization of silicic acid in acid solution, silicic acid is depolymerized in alkaline medium after a simple cation-exchange column filtration of the rock sample solution and then determined by a static or an FIA spectrophotometric method. The FIA system consists of two channels which carry the carrier solution and molybdate reagent, and allows the colour reaction to proceed under controlled conditions. The FIA system permits high throughput of 70 samples per hour. The procedure has been applied to a variety of standard silicate rocks of the U.S. Geological Survey and the Geological Survey of Japan, and gave satisfactory agreement with the recommended values.     

Preparation of porous ultrafine polyacrylonitrile (PAN) fibers by electrospinning

A facile method for the preparation of porous ultrafine nanofibers was demonstrated. The PAN/NaHCO₃ composite nanofibers were electrospun, and then NaHCO₃ was removed by a selective dissolution and reaction with the solution of hydrochloric acid (10 wt%). The obtained PAN fibers showed highly porous surfaces after the extraction of NaHCO₃. The structure and properties of ultrafine PAN nanofibers were characterized by Fourier transform infrared (FT‐IR), X‐ray diffraction (XRD), and thermogravimetry (TG). The results indicated that NaHCO₃ could be introduced into the PAN solution and successfully electrospun. CO₂ is released and pores are formed on the fibers. The morphology image of the fibers was detected by scanning electron microscope (SEM) and showed that many pores aligned the nanofibers. Copyright © 2008 John Wiley & Sons, Ltd.     

碳酸盐岩钙同位素化学分离方法改进及其在青藏高原地质样品中的应用前景

本文报导了在前人基础上改进的碳酸盐岩(白云石－方解石)地质样品钙同位素化学分离方案。通过对比云南永善桧溪剖面白云岩－灰岩过渡岩性在不同浓度盐酸下淋洗结果,确定了4N浓度盐酸能有效富集白云石－方解石体系中的钙元素,且热电离质谱(TIMS)测试结果显示4N盐酸与1.6N盐酸淋洗方案处理后钙同位素测试结果一致,表明在相同测试精度的情况下,针对白云石－方解石体系下碳酸盐岩地质样品化学分离方案能提高化学分离效率。本文进一步结合青藏高原研究热点问题,对钙同位素在青藏高原地质样品的应用前景进行了分析,分析表明,钙同位素在青藏高原隆升前古海洋环境重建、隆升期构造活动恢复及隆升后火成岩来源示踪上具有广泛应用前景。     

Changes in the characteristics of acid‐treated clay after the inclusion of proteins

The aim of this work is to study the difference in the characteristics of commercial clay after the inclusion of two proteins. Bovine serum albumin and egg white lysozyme were immobilized on the structure of commercial montmorillonite, which was previously treated with a hydrochloric acid solution. Studies were carried out at two different concentrations, fixing the pH to ensure the charge of biomolecules and clay surface. Acid‐treated clay containing proteins was characterized by X‐ray diffraction, Fourier transformed infrared spectroscopy, thermogravimetric analysis, and nitrogen adsorption at 77 K. The powders showed similar thermal behavior after the inclusion of proteins but with variations in the amount of mass loss in each sample. Moreover, changes in the surface characteristics of the final solid were observed, depending on both the concentration and the nature of the incorporated protein. The differences observed in the acid‐treated clay characteristics after the inclusion of each type of protein are discussed. The characterization of materials after the inclusion of protein molecules can be useful to understand the adsorption mechanism of biomolecules on solid surfaces. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and orientation study of a magnetically aligned liquid‐crystalline chitin/poly(acrylic acid) composite

A high magnetic field of 5 T was used to fabricate a magnetically aligned, optically anisotropic, liquid‐crystalline chitin/poly(acrylic acid) composite. The aligned mesophase was fixed by photoinitiated free‐radical polymerization. From an examination of polarized optical micrographs and an X‐ray diffraction study, a high degree of orientation of 0.70 was observed for the composite with a higher liquid‐crystalline chitin concentration (10.70 wt %); the orientation was reduced with a decreased chitin concentration at a given acrylic acid concentration. The X‐ray data for the developed composite showed a uniplanar orientation for the chitin crystallites, with its molecular long axes perpendicular to the direction of the magnetic field. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 711–714, 2003     

Properties of bacterial cellulose transparent film regenerated from dimethylacetamide–LiCl solution

Excellent transparent films were prepared from bacterial cellulose (BC) sheets by solubilization of its defibrillated freeze‐dried specimens in a solvent of dimethylacetamide (DMAc) containing 8.0% (w/w) lithium chloride (LiCl), and their properties were compared with those of the native BC. Fibrillar structure of the native BC disappeared after dissolution, and the film formed after dissolution also loose this structure. Occurence of structural transformation from crystalline to amorphous state was also evidenced by X‐ray diffraction, solid state cross polarization/magic angle spinning ¹³C‐NMR and attenuated total reflectance–Fourier transform infrared spectroscopic analyses. In addition, excellent 3D uniform structure of the transparent BC film was further evidenced by X‐ray micro computed tomography. Plastic‐like characteristic was enhanced by film formation after dissolving the BC specimens in the DMAc–LiCl solution as shown by changing mechanical properties, a slight decrease in tensile strength (67.2 to 59.6 MPa) and breaking stress (67.2 to 58.4 MPa) but significant increase in elongation at break from 3.4 to 10.5%, and improvement of work of fracture from 5.8 to 21.2 kJ/m². Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and Photoluminescent Properties of New Aza‐Indenofluorene Derivatives

The carbazole derivatives 5a – h were synthesized by four steps involving Suzuki coupling of boronic acid 1 with 1‐bromo‐2‐nitrobenzene, followed with the Cadogan ring closure reaction. Their UV and photoluminescence properties are also reported, and the compounds showed medium‐to‐strong photoluminescence between 370 and 446 nm at the concentration of 1 × 10⁻⁵ M CH₂Cl₂. Also, the X‐ray structure of the carbazole derivative 6 was elucidated by an X‐ray diffractometer. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 24:18–24, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21058     

A Study on the Dissolution of Ferric Oxide in Aqueous Hydrochloric Acid Solutions

The effect of hydrochloric acid concentration and the effect of temperature on the rate of dissolution of Fe₂O³ have been investigated. Being heterogeneous, the dissolution reaction has been characterized to have an apparent activation energy of 21.5 Kcal/mol for a 7.11 m aqueous hydrochloric acid solution at temperatures between 273 and 373°K. The rate is linearly correlated to the mean activity of hydrochloric acid in the range from 1.3 to 10.8 m at 300°K.     

Shape-controlled Synthesis of Nanostructure Ramsdellite-type Manganese Oxide at Atmospheric Pressure

Ramsdellite (R‐MnO₂) was prepared by oxidizing bivalent manganese salts, such as MnCl₂, MnSO₄ and Mn(NO₃)₂, with NaClO solution using a refluxing process at atmospheric pressure. The products were characterized by X‐ray diffraction, fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy and flame photometry. R‐MnO₂ microstructure and morphology were controlled by adjusting reaction temperature, the amount of hydrochloric acid (HCl) and anions of bivalent manganese salts. Ramsdellite grain was formed with three different bivalent manganese salts oxidized by NaClO solution at 60°C, and increased with the increase of reflux temperature. R‐MnO₂ nanorod and nanowire crystals were obtained when MnCl₂ and MnSO₄ were used as bivalent manganese salts at 100°C respectively. Nanosized flake of R‐MnO₂ came into being when Mn(NO₃)₂ was applied at 80°C. When 30 mmol MnCl₂ was oxidized by 60 mmol NaClO solution with adding 20 mmol HCl in refluxing solution, specific surface area of R‐MnO₂ grain obtained at 60°C was greater than 140 m²/g, and the self‐assembly of nanorod bundles into interesting flowerlike architectures was achieved at 100°C. The process of dissolution‐precipitation equilibrium might be the primary cause for the morphology transformation.     

Synthesis and Characterization of 3,5‐Diamino‐1,2,4‐triazolium Dinitramide

3,5‐Diamino‐1,2,4‐triazole ( 1 , guanozol) was protonated with diluted hydrochloric acid, nitric acid, as well as perchloric acid forming 3,5‐diamino‐1,2,4‐triazolium chloride hemihydrate ( 2 ), 3,5‐diamino‐1,2,4‐triazolium nitrate ( 3 ) and 3,5‐diamino‐1,2,4‐triazolium perchlorate ( 4 ), respectively. In a second step 4 reacted with potassium dinitramide forming 3,5‐diamino‐1,2,4‐triazolium dinitramide ( 5 ) and low soluble potassium perchlorate. Compounds 2 – 5 were characterized by low temperature single X‐ray diffraction, IR and Raman as well as multinuclear NMR spectroscopy, mass spectrometry and differential scanning calorimetry. The heats of formation of 1 – 5 were calculated by the CBS‐4M method to be 81.1 ( 1 ), 124.7 ( 2 ), –76.1 ( 3 ), –25.2 ( 4 ) and 138.7 ( 5 ) kJ·mol^–1. With these values as well as the X‐ray densities several detonation parameters were calculated using both computer codes EXPLO5.03 and EXPLO5.04. In addition, the sensitivities of 1 – 5 were determined by the BAM drophammer and friction tester as well as a small scale electrical discharge device.     

Sonochemical synthetic methods to produce functionalized conducting copolymers

Polyaniline (PANI) is one of the most investigated intrinsically conducting polymers. Copolymerization of aniline with aniline derivatives was considered one of the most effective and promising ways of improving the properties of PANI. In this work, firstly ethyl 3‐aminobenzoate and butyl 3‐aminobenzoate were synthesized from 3‐aminobenzoic acid by direct esterification. Then the copolymerization of 3‐amino benzoic acid, ethyl 3‐aminobenzoate, and butyl 3‐aminobenzoate with aniline was carried out by sonochemical polymerization in aqueous hydrochloric acid using ammonium persulfate (APS) as an initiator. The effects of variation in the molar ratio of the two monomers on chain structure, conductivity, and the redox properties of the copolymer are discussed. The prepared polymers are characterized by ¹H NMR spectroscopy, X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT‐IR). Thermal behavior of the prepared copolymers was studied by differential scanning calorimetry. The copolymers were doped with HCl and their conductivity was measured. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of polyamidoamine dendrimer (PAMAM/CuS/AA) nanocomposite and its application in the removal of Isma acid fast yellow G Dye

The adsorption of Isma acid fast yellow G dye was studied using polyamidoamine (PAMAM)/Copper sulfide (CuS)/AA nanocomposite containing different amounts of CuS by batch technique. PAMAM dendrimer/CuS/AA nanocomposites were synthesized via gamma irradiation cross‐linking method with the aid of sonication. The nanocomposites were characterized by Fourier‐transform infrared, X‐ray diffraction, transmission electron microscope, energy dispersive spectroscopy X‐ray, thermal gravimetric analysis, ultraviolet‐visible, and fluorescence spectroscopy. The size of the CuS nanoparticles was formed in the range of 12–19 nm. The adsorption capacity of the nanocomposites was evaluated as a function of initial dye concentration, pH, adsorbent dosage, and time. It was verified that the adsorption rate fits a pseudo‐second‐order kinetics for initial Isma acid fast yellow G dye concentrations. Results indicated that the adsorption of Isma acid fast yellow G dye fitted well to the Langmuir model. Our results demonstrate that the PAMAM dendrimer/CuS/AA nanocomposite is very promising for removing organic dyes from wastewater. Copyright © 2015 John Wiley & Sons, Ltd.     

Crystal Engineering of Stable Temozolomide Cocrystals

The antitumor prodrug temozolomide (TMZ) decomposes in aqueous medium of pH≥7 but is relatively stable under acidic conditions. Pure TMZ is obtained as a white powder but turns pink and then brown, which is indicative of chemical degradation. Pharmaceutical cocrystals of TMZ were engineered with safe coformers such as oxalic acid, succinic acid, salicylic acid, d,l ‐malic acid, and d,l ‐tartaric acid, to stabilize the drug as a cocrystal. All cocrystals were characterized by powder X‐ray diffraction (PXRD), single crystal X‐ray diffraction, and FT‐IR as well as FT‐Raman spectroscopy. Temozolomide cocrystals with organic acids (pK_a 2–6) were found to be more stable than the reference drug under physiological conditions. The half‐life (T_1/2) of TMZ–oxalic and TMZ–salicylic acid measured by UV/Vis spectroscopy in pH 7 buffer is two times longer than that of TMZ (3.5 h and 3.6 h vs. 1.7 h); TMZ–succinic acid, TMZ–tartaric acid, and TMZ–malic acid also exhibited a longer half‐life (2.3, 2.5, and 2.8 h, respectively). Stability studies at 40 °C and 75 % relative humidity (ICH conditions) showed that hydrolytic degradation of temozolomide in the solid state started after one week, as determined by PXRD, whereas its cocrystals with succinic acid and oxalic acid were intact at 28 weeks, thus confirming the greater stability of cocrystals compared to the reference drug. The intrinsic dissolution rate (IDR) profile of TMZ–oxalic acid and TMZ–succinic acid cocrystals in buffer of pH 7 is comparable to that of temozolomide. Among the temozolomide cocrystals examined, those with succinic acid and oxalic acid exhibited both an improved stability and a comparable dissolution rate to the reference drug.     

Treatment of phosphate rocks with hydrochloric acid

Phosphate rocks were leached with hydrochloric acid; and radium was removed by co-precipitation with BaSO₄. Uranium and lanthanides were extracted by di(2-ethyl hexyl) phosphoric acid and tributyl phosphate. Phosphoric acid was then separated from calcium chloride solution and other impurities by extraction using undiluted iso-amyl alcohol. Gypsum was precipitated by sulfuric acid to regenerate hydrochloric acid for recycling. Fluorine was precipitated from the initial leach solution as Na₂SiF₆.     

Preparation and structure elucidation of 1,6,9,13‐tetraoxadispiro(4.2.4.2)tetradecane

The tricyclic title compound, a symmetrical dispiro oxygen heterocycle, was isolated as a byproduct in the hydrogenation of furfuryl alcohol in the presence of hydrochloric acid. NMR studies and single crystal X‐ray analysis have established the relative stereochemistry of the two ketal carbons. Formation of the observed trans stereoisomer under equilibrating conditions is attributed to the anomeric effect.     

Monte Carlo simulation of spatial distribution of X rays in multifilm targets. III: optimum design as applied to W/Al‐film targets

The brightness of the X‐ray source in a W/Al‐film target used for X‐ray projection microscopy was studied by an approach using the Monte Carlo simulation. Since continuous X rays generated in a thin film have a specific angular distribution of emission, the brightness of the continuous X‐ray source cannot simply be estimated on the assumption that the angular distribution is homogeneous. The newly developed approach using the Monte Carlo simulation enables the evaluation of the effective source size, angular distribution, and brightness of a continuous X‐ray source with sufficient accuracy that it leads to the optimum design of a high‐brightness X‐ray source for uses such as X‐ray projection microscopy. The Monte Carlo calculations were performed for W(Δz)/Al (200 µm)‐film targets with different thicknesses of W film, Δz, under bombardment of 60 kV electrons. The results have suggested an optimum design consisting of a W (2 µm)/Al (200 µm)‐film target as most promising for providing an X‐ray source of higher brightness than the W (5 µm)/Al (200 µm)‐film target, which has already been in practice for X‐ray projection microscopy. Copyright © 2006 John Wiley & Sons, Ltd.     

Analytical characterization of corrosion products of copper and its alloys on stained stone surfaces

Monuments, where stone and metals or metallic alloys are used together, are very frequently met in all historical periods and in all countries. In the case of bronze and other copper alloys, their corrosion products can be dissolved by the action of acid rain and thus reach the porous building materials in contact with (or near to) the metallic structures. Once absorbed by the stone, they precipitate on the external stone surface and inside its porous space. As the majority of these products are coloured, their precipitates may produce stains, which are perceived as unpleasant alterations of the original ‘values’ of the stone monuments. The removal of stains is therefore required on the occasion of conservation treatments. The paper reports on the characterisation of copper corrosion products found on two, very different, monuments in Rome: ‘Fontana delle Tartarughe’ (by T. Landini, last quarter of the 16th century) and ‘Statua dello Studente’ (by A. Cataldi, 1920). To identify the speciation of copper compounds in their carbonate matrices, different techniques [X‐ray diffraction, X‐ray fluorescence, SEM/energy‐dispersive X‐ray spectroscopy (EDS), micro‐Raman and XPS] had to be employed. To further confirm the identification of the chemical species, SEM/EDS data were also processed by principal component analysis. Copyright © 2013 John Wiley & Sons, Ltd.     

Nitrogen‐Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction

The catalytic activity of manganese oxynitrides in the oxygen reduction reaction (ORR) was investigated in alkaline solutions to clarify the effect of the incorporated nitrogen atoms on the ORR activity. These oxynitrides, with rock‐salt‐like structures with different nitrogen contents, were synthesized by reacting MnO, Mn₂O₃, or MnO₂ with molten NaNH₂ at 240–280 °C. The anion contents and the Mn valence states were determined by combustion analysis, powder X‐ray diffraction, and X‐ray absorption near‐edge structure analysis. An increase in the nitrogen content of rock‐salt‐based manganese oxynitrides increases the valence of the manganese ions and reinforces the catalytic activity for the ORR in 1 m KOH solution. Nearly single‐electron occupancy of the antibonding e_g states and highly covalent Mn?N bonding thus enhance the ORR activity of nitrogen‐rich manganese oxynitrides.