Physicomechanical properties of polyurethane foam filled with pyrolytic chromium coated aluminosilicate ash microspheres

Russian Journal of Applied Chemistry - The possibility of depositing pyrolytic chromium on the surface of aluminosilicate ash microspheres and preparing rigid polyurethane foam filled with...     

Synthesis of metallic copper nanoparticles coated with polypyrrole

This paper describes a method for polypyrrole (PPy) coating of metallic Cu nanoparticles in aqueous solution in atmosphere. Colloid solution of Cu nanoparticles was prepared by reducing Cu ions with the use of hydrazine in an aqueous solution dissolving citric acid and cetyltrimethylammonium bromide as stabilizers. The PPy coating was performed by polymerizing pyrrole with the use of hydrogen peroxide as an initiator in an aqueous colloid solution of the Cu nanoparticles. Ultraviolet–visible extinction measurements, transmission electron microscopy observation, and X-ray diffraction measurements revealed that the metallic Cu nanoparticles with a size of 27.6 ± 11.1 nm were coated with PPy. The obtained PPy-coated Cu particles were chemically stable even in atmosphere.     

Spectrophotometric determination of germanium based on its ternary complex with phenylfluorone and zephiramine

A sensitive Spectrophotometric method for the determination of germanium based on its ternary complex with phenylfluorone and zephiramine was developed. The complex forms in 0.3–1.5 M HCl medium. Maximum absorbance is obtained for the molar ratio of Ge:PF:zeph = 1:16:600. Molar absorptivity (ϵ) is 1.38 × 10⁵ liters mol⁻¹ cm⁻¹ at λ_max = 505 nm. Due to the limited selectivity of the method (Sn, Sb, Nb, Ta, Ti, V, Mo, ClO₄⁻, SO₄²⁻, PO₄³⁻) before determining trace amounts of germanium, it should be separated, e.g., by extraction. Germanium in galman ore was determined with the developed method (about 1 × 10⁻³%). Attempts to achieve satisfactory analytical results failed in the presence of cetyltrimethylammonium ions or cetylpyridinium ions used as cationic surfactants.     

Synthesis and properties of hyperbranched copolymers based on perfluorinated germanium hydrides

Hyperbranched copolymers of various structures and molecular masses in the range 2.0 × 10⁴?4.4 × 10⁵ are prepared via the activated copolycondensation of tris- and bis(pentafluorophenyl)germane in tetrahydrofuran performed in the presence of triethylamine as an activator. The kinetics of copolycondensation is studied via the method of heat-conduction reaction calorimetry. It is found that tris(pentafluorophenyl)germane shows a higher activity in copolycondensation than bis(pentafluorophenyl)germane. Shear moduli, loss factors, and glass-transition temperatures of the copolymers are determined by dynamic mechanical analysis and differential-scanning calorimetry. The copolymers feature glass-transition temperatures up to 250°C. These values are considerably higher than those of perfluorinated polyphenylenegermane (162°C).     

Synthesis of poly(styrene-co-3-trimethoxysilyl propyl methacrylate) microspheres coated with polysiloxane layer

A procedure has been developed to coat micron-sized poly(styrene-co-3-trimethoxysilyl propyl methacrylate) microspheres with a smooth layer of polysiloxane by the hydrolysis and condensation of methyl trimethoxylsilane (MTMS). Firstly, polystyrene microspheres containing silanol groups were prepared by conventional dispersion polymerization using 3-(trimethoxysilyl) propyl methacrylate (MPS) as a functional comonomer in an ethanol/water medium. Secondly, the synthesis of the polysiloxane shell was carried out using a sol–gel process of MTMS. The thickness of the shells can be easily varied with different copolymer seeds and MTMS feed ratio. When we used copolymer particles with 2.00 μm diameter as seeds, the thickness of the polysiloxane shells can be varied from 0.10 to 0.18 μm. The core/shell structure of the composite microspheres was characterized by transmission electron microscope (TEM).     

Interaction between metallic gold and support and its influence on catalysis

The interaction between gold particles and support in Au/TiO₂ and Au/Al₂O₃ catalysts prepared by immobilizing colloidal gold on the support was evidenced by X-ray photoelectron spectroscopy. The reducibility of the support is more responsible than the interaction between the nanogold particles and support for the activity of catalysts.     

Theoretical study on germanium cyanide radical GeCN and its ions

A detailed theoretical study is performed on the hitherto unknown germanium cyanide radical and its ions. The (2)Pi state GeCN lies 5.0 kcal/mol lower than the (2)Pi state GeNC at the coupled-cluster theory including single and double excitations and perturbative inclusion of triple excitations [CCSD(T)]/6-311++G(3df)//quadratic configuration interaction with single and double excitations (QCISD)/6-311G(d)+zero-point vibrational energy (ZPVE) level. For interconversion between them, two electronic state pathways (2)A(') and (2)A(") are located, with the latter being 0.7 kcal/mol more favorable than the former. On the (2)A(") path, the GeCN-->GeNC and GeNC-->GeCN conversion barriers are 14.5 and 9.5 kcal/mol, respectively. The detailed singlet and triplet potential-energy surfaces of both the cationic and anionic GeCN species are also investigated. On the ground-state electronic hypersurface, singlet GeNC(+) is 4.6 kcal/mol more stable than singlet GeCN(+), whereas triplet GeNC(-) is 10.0 kcal/mol less stable than triplet GeCN(-). The relative energy difference between the GeCN(0,+/-) and GeNC(0,+/-) can be well correlated with the number of vacant orbitals on the Ge atom. The stability of the neutral and ionic CGeN and cyclic cGeCN is also discussed. The predicted structures, spectroscopies, ionization, and affinity energies as well as the Renner-Teller properties are expected to provide reliable estimates for future characterization of the potential GeCN and GeNC radicals as well as their ionic counterparts both in the laboratory and in the interstellar space.     

Biodegradation-induced surface change of polymer microspheres and its influence on cell growth

Biodegradable microspheres were fabricated by poly(?-caprolactone) (PCL) homopolymer and poly(?-caprolactone-b-ethylene oxide) (PCL-b-PEO) amphiphilic block copolymer. The regulation of microsphere surface morphology was successfully achieved by controlled enzymatic degradation. The morphological changes induced by biodegradation and their influences on the growth of MG-63 human osteosarcoma cells were studied. Results based on the evaluation of cytotoxicity and the morphological observation of MG-63 cells cultivated on microspheres showed better growth of cells on the surface of degraded microspheres than on the surface of those undegraded microspheres no matter they were fabricated by homopolymers or copolymers. The influences of morphological changes of microsphere surface before and after biodegradation on MG-63 cell growth were discussed. The results of this work indicated that the biodegradation-induced morphological changes of microspheres could be well controlled and were favorable for MG-63 cell attachment and proliferation.     

含环氧基团的聚合物微球固载2,2,6,6-四甲基哌啶氮氧自由基催化剂的制备及其催化分子氧氧化苯甲醇

以甲基丙烯酸缩水甘油酯(GMA)为单体, 以乙二醇二甲基丙烯酸酯(EGDMA)为交联剂, 采用悬浮聚合法制得交联聚甲基丙烯酸缩水甘油酯(CPGMA)微球, 然后以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(4-OH-TEMPO)为试剂, 使CPGMA微球表面的环氧基团发生开环反应, 从而制得了TEMPO固载化微球TEMPO/CPGMA, 考察了制备条件对固载化反应的影响, 并采用多种方法对微球TEMPO/CPGMA进行了表征. 将微球TEMPO/CPGMA与CuCl组成共催化体系, 用于分子氧氧化苯甲醇, 考察了反应条件对催化体系性能的影响. 结果表明, 以含环氧基团的聚合物微球CPGMA为载体, 通过开环反应, 可成功地实现TEMPO的固载化, 开环反应属S_N2亲核取代反应, 适宜采用溶剂N,N''-二甲基甲酰胺和反应温度85℃. 非均相催化剂TEMPO/CPGMA与助催化剂CuCl构成共催化体系, 在室温、常压O₂条件下可高效地将苯甲醇氧化为苯甲醛, 产物选择性和产率分别为100%和90%. 主催化剂TEMPO与助催化剂CuCl适宜的摩尔比为1:1.2; 主催化剂适宜用量为0.90 g. 此外, TEMPO/CPGMA固体催化剂具有良好的循环使用性能.     

空心微珠的疏油改性对泡沫灭火剂发泡性能的影响

用1H,1H,2H,2H-(十三氟代辛烷基)三乙氧基硅烷(F8261)对空心微珠(HGM)进行表面改性处理,测定了不同条件下油滴在改性空心微珠(MHGM)表面的接触角及停留时间,考察了改性剂浓度、反应时间和反应温度等因素对改性效果的影响,对比了HGM和MHGM对蛋白泡沫液发泡倍数、25%析液时间等参数变化,研究了MHGM对泡沫灭火剂发泡性能和泡沫稳定性的影响.结果表明,在F8261浓度为1.0%,温度为60℃时,超声2.0h,油滴与MHGM的接触角可达132.5°,疏油性能明显增强,灭火剂的发泡性能和油面稳定性显著改善.     

Differential scanning calorimetry study of fluoride complexes of germanium,tungsten, uranium,lithium and gallium

The enthalpy and temperature of the sublimation, transition and dissociation of nitrosyl fluoride-germanium, tungsten, uranium, lithium and gallium fluoride adducts were determined from DSC measurements. A closed-cell DSC technique was employed for this purpose and to postulate possible reaction mechanisms of the dissociation.     

Synthesis and properties of a novel plugging agent based on the PAN microspheres with sodium carbonate

A new plugging agent, which derived from the copolymer of polyacrylonitrile, was successfully synthesized by using acrylonitrile as monomer, poly(ethylene glycol) diacrylate as cross-linker, AIBN as initiator, cyclohexane as solvent, and anhydrous sodium carbonate as the alkaline additive, its structure and surface morphology were characterized using FTIR and SEM. As key investigation parameters, in an aqueous environment, the gel viscosity η and distribution of particle size with different dosage of Na₂CO₃, the gel viscosity η with aging time, and the slow release mechanism of Na₂CO₃ in resulting plugging agent were investigated, its gel procedure was also described.     

Application of a new catalyst based on molybdenum for the direct determination of oxygen by pyrolytic gas chromatography

Application of a new catalyst for the direct determination of oxygen by using a pyrolytic gas chromatographic technique is described. Achievement of the optimum experimental conditions depends upon numerous factors which have been examined. The results obtained with such a procedure indicate that the method is applicable for the determination of oxygen in a variety of organic and organometallic compounds.     

Synthesis of butyrate using a heterogeneous catalyst based on polyvinylpolypyrrolidone

A heterogeneous polyvinylpolypyrrolidone supported Brønsted acidic catalyst ([PVPP-BS]HSO₄) was used to synthesize butyrate in this paper. The prepared catalysts were characterized by FT-IR, TG, and FESEM and their catalytic activity in butyric acid esterification with benzyl alcohol was investigated. The influencing factors such as the amount of catalyst, reaction temperature, and reaction time were carefully studied. Under the optimized condition with the butyric acid to benzyl alcohol mole ratio of 1: 1.2 and the reaction temperature of 130°C, the yield of benzyl butyrate reached 96.8 % within 4 h in the presence of 8 mass % of catalyst. Moreover, the catalyst could be reused six times without noticeable drop in activity. This catalyst was also used to synthesize other kinds of butyrates achieving the butyrate yield above 90 %.     

Synthesis and characterization of polyamine‐based cyclophosphazene hybrid microspheres

Starting with hexachlorocyclotriphosphazene (HCCP) and branched polyethylenimine (bPEI) crosslinked cyclomatrix polyphosphazene poly(HCCP‐co‐bPEI) microspheres are prepared by precipitation polymerization in acetonitrile at 50 °C under ultrasound irradiation. The influence of varying reagent ratios on the chemical composition, morphology, and physical and chemical properties of the microspheres is investigated. Furthermore, the microspheres are characterized by Fourier‐transform infrared spectroscopy, dynamic light scattering (DLS), X‐ray photoelectron spectroscopy, elemental analysis, as well as ³¹P MAS NMR. FESEM and DLS analysis show microspheres of smooth and spherical shape which swell both in water and acetonitrile. The particle diameters in the dry state range from 0.4 to 0.9 μm, but due to swelling a size increase between 45 and 140% is observed depending on the chemical composition and the solvent medium. The thermal stability of the microspheres ranges from 262 to 351 °C. The presence of reactive amine groups on the surface is proven by electrophoretic mobility measurements and chemical modification with two model compounds. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 527–536     

Synthesis and characterization of sol–gel derived glass-ceramic and its corrosion protection on 316L SS

Glass-ceramic was prepared by sol–gel method using Ca(NO₃)₂·4H₂O and P₂O₅ as Ca and P precursors, respectively. In order to improve the bioactivity of the implant material, glass-ceramic (β-Ca₂P₂O₇) coating was developed on 316L SS substrate by spin coating method. Coating was annealed at different temperatures and its corrosion resistance was evaluated by electrochemical polarization and impedance analysis using Ringer’s solution as electrolyte. The results from the present study, show excellent corrosion resistance for coated 316L SS, corroborated by the high values of charge transfer resistance from impedance analysis and higher breakdown and repassivation potential with the corresponding lower current density from polarization measurements. Based on the results, the glass-ceramic coating on 316L SS can be considered as a corrosion resistant material.     

Synthesis and characterization of core-shell microspheres with double thermosensitivity

We have synthesized doubly thermosensitive core-shell microspheres composed of chemically cross-linked poly(N-n-propyl acrylamide-co-styrene) (P(nPA-co-S)) with different styrene contents as the core and linear poly(N,N-diethyl acrylamide) (PDEA), poly(N-isopropyl acrylamide) (PiPA), or poly(N-isopropyl methacrylamide) (PiPMA) as the shells. The morphologies and swelling properties of the core and the core-shell microspheres have been studied. The P(nPA-co-S) copolymers have a similar volume phase transition temperature regardless of the styrene content, indicating a two-layer structure in the microspheres with a PS-rich inner core and a PnPA-rich outer layer resulting from soap-free emulsion polymerization in water. Upon the addition of the second shell composed of linear thermosensitive polymers, the core-shell microspheres display a two-step shrinking behavior when heated. The P(nPA-co-S) core exhibits a volume phase transition temperature at 13-15 degrees C, while the shells of PDEA, PiPA, and PiPMA have volume phase transition temperatures at 28, 32, and 42 degrees C, respectively. The core-shell microspheres are composed of three layers and possess two volume phase transition temperatures.     

Synthesis and structural characterization of one- and two-dimensional coordination polymers based on platinum-silver metallic backbones

Seven Pt-Ag coordination polymers [Pt(NH3)2(NHCO(t)Bu)2Ag(H2O)](ClO4) (1), [Pt2(dap)2(NHCO(t)Bu)4Ag2(NO3)(ClO4)] (dap = 1,2-diaminopropane, 2), [Pt2(en)2(NHCO(t)Bu)4Ag2(m-C6H4(CO2)2)].3H2O (en = ethylenediamine, 3), [Pt2(NH3)2(NHCO(t)Bu)2Ag2(p-C6H4(CO2)2)].2H2O (4), [Pt3(en)3(NHCO(t)Bu)6Ag2(p-C6H4(CO2)2)(1.5)].6H2O (5), [Pt(NH3)2(NHCO(t)Bu)4Ag(4-C5H4NCO2)2].10H2O (6), and [Pt2(en)2(NHCO(t)Bu)4Ag2(4-C5H4NCO2)](ClO4) (7) were synthesized from the corresponding [Pt(RNH2)2(NHCO(t)Bu)2] and Ag salts, respectively, and their structures were determined by X-ray crystallography. The Pt and Ag units aggregate into one-dimensional chains based on Pt-Ag backbones. Compounds 1, 2, and 6 possess an extended zigzag Pt-Ag chain motif, and the metallic chains arrange in a parallel fashion into layered structures. Compounds 3-5, and 7 form 2-D brick wall sheets due to the coordination of the bifunctional anions to the Ag+ ions of the neighboring chains. These polymers are constructed based on the Pt-Ag interactions and the coordination of amidate oxygen atoms to Ag ions. There are three kinds of short Pt-Ag bonds observed in the structures of these compounds. The Pt-Ag metallic backbone is formed by the stacking unsupported Pt-Ag bonds, the amidate doubly bridged Pt-Ag bonds, and the amidate singly bridged Pt-Ag bonds. In the chains, the Pt-Ag bond distances are quite short, and appear in the range of 2.78-2.97 A, which are comparable to known Pt-Ag dative bonds.