首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 0 毫秒
1.
The phase diagrams of the ternary systems NaCl–NaBO2–KCl, NaCl–KCl–Na2CO3, and KCl–NaBO2–Na2CO3 and the quaternary system NaCl–NaBO2–Na2CO3–KCl were studied by the calculation–experimental method and differential thermal analysis. Analytical models of phase equilibria were obtained, and the coordinates of ternary eutectics and a quaternary eutectic. It was shown that low-melting eutectic melts can be used as media for synthesizing oxide tungsten bronzes.  相似文献   

2.
Enzymes that act on substrates R–O–PO3H2 often work on substrate analogues R–O–AsO3H2; such substrates are unstable, since esters of H3AsO4 hydrolyse easily. They also form easily, so that an enzyme that acts on R–O–PO3H2 often acts on a mixture of R–OH and arsenate via an ester that forms at the active site. Similarly coenzyme analogues may be formed; for example, a stable and active aspartate aminotransferase forms from the apoenzyme with free pyridoxal and arsenate. Enzymes that convert R–O–PO3H2 into a diester often act on R–CH2–AsO3H2, a stable substrate analogue; then the product is unstable and hydrolyses to re-form the analogue, giving a futile cycle. For example, RNA polymerase acquires exonuclease activity in the presence of H2O3P–CH2–AsO3H2; adenylate kinase acquires ATPase activity in the presence of the arsonomethyl analogue of AMP. A recent observation is that HO–CH2–CHOH–CH2–CH2–AsO3H2 is a good substrate for glycerol-3-phosphate dehydrogenase. The product is unstable and eliminates arsenite, sharing this ability with other 3-oxoalkylarsonates. Thus this enzyme–catalysed oxidation is a lethal synthesis, in view of the toxicity of arsenite. Another unusual biochemical reaction of an arsonic acid is seen in the ability of a bacterium to use arsonoacetate as its sole source of carbon and energy. In contrast with the elimination of arsenite by 3-oxoalylarsonic acids, 3-oxoalkylphosphonic acids, R–CO–CH2–CH2–PO3H2, are stable. 2-Oxoalkylphosphonic acids, R–CO–CH2–PO3H2, however, are moderately unstable to hydrolysis, yielding phosphate and R–CO–CH3. 2-Oxoalkylarsonic acids, R–CO–CH2–AsO3H2, decompose in the same way, but much more readily, yielding arsenate. © 1997 by John Wiley & Sons, Ltd.  相似文献   

3.
Investigations on the Insertion of Carbenes into Al–Al, Ga–Ga, and In–In Bonds Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 reacts with methylthiomethyl lithium LiCH2SMe by the formation of lithium thiomethanolate LiSMe and the insertion of the remaining carbene CH2 into its Al–Al single bond. A chelating Lewis acid is formed exhibiting a central R2Al–CH2–AlR2 group with two coordinatively unsaturated Al atoms, which coordinate the thiomethanolate anion by Al–S bonds. The product (μ-methylene)(μ-thiomethanolato)bis{bis[bis(trimethylsilyl)methyl]aluminate} ( 4 ) was characterized by a crystal structure determination and has a strongly folded Al2CS heterocycle in the molecular core. In contrast, the corresponding compounds with Ga–Ga or In–In bonds show on treatment with methylthiomethyl lithium a fragmentation, and the carbene intermediate could not be detected in both isolated products, which were identified as [R2E(CH2SMe)2][Li(TMEDA)] (E = Ga: 5 ; E = In: 6 ) and LiCH(SiMe3)2 probably formed by a metal exchange reaction.  相似文献   

4.
New Alkali Metal Coordinations by Chelating Siloxazane Units within Molecules of the General Formula [X–N–SiMe2–O–SiMe2–N–X]2M4 New solvent free alkali metal amides with Si–O–Si bridges of the general formula [X–N–SiMe2–O–SiMe2–N–X]2M4 (X = tBu ( 1 ), SiMe3 ( 2 ), SiMe2tBu ( 3 ) with M = Li; X = tBu ( 4 ), SiMe3 ( 5 ) with M = Na; X = tBu mit M = K, Li ( 6 )) have been synthesised and characterised by spectroscopic means. X‐ray structure analyses of the six metal derivatives reveal a common structural principle: the four metal atoms within the molecules are incorporated between two molecular halfs and form the bonding links between the two parts. The central molecular skeleton of the molecular halfs consists of a zig‐zag chain N–Si–O–Si–N. This chain is connected to the second one either ideally or approximately by S4 (4) symmetry. The point symmetries within the crystal are either S4 (4) (compounds 2 and 4 ), C2 (2) (compound 6 ), and C1 (1) (compounds 3 and 5 ). Compound 1 is special in different aspects: the molecule has the high crystallographic point symmetry D2d (4m2) and the lithium atoms occupy split atom positions (in a similar way as in compound 2 ). The high symmetry of 1 as well as the split atom positions of the lithium atoms are a consequence of dynamics within the crystal.  相似文献   

5.
Visible light active Ag doped SnO2 nanoparticles modified with curcumin (Cur–Ag–SnO2) have been prepared by a combined precipitation and chemical impregnation route. The optical properties, phase structures and morphologies of the as-prepared nanoparticles were characterized using UV–visible diffuse reflectance spectra (UV–vis-DRS), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The surface area was measured by Brunauer. Emmett. Teller (B.E.T) analysis. Compared to bare SnO2, the surface modified photocatalysts (Ag–SnO2 and Cur–Ag–SnO2) showed a red shift in the visible region. The photocatalytic activity was monitored via the degradation of rose bengal (RB) dye and the results revealed that Cur–Ag–SnO2 shows better photocatalytic activity than that of Ag–SnO2 and SnO2. The superior photocatalytic activity of Cur–Ag–SnO2 could be attributed to the effective electron-hole separation by surface modification. The effect of photocatalyst concentration, initial dye concentration and electron scavenger on the photocatalytic activity was examined in detail. Furthermore, the antifungal activity of the photocatalysts and the reusability of Cur–Ag–SnO2 were tested.  相似文献   

6.
The azadiboriridine [–BR–NR–BR–] ( 1 ; R = tBu) is bromoborated at the B–B bond by alkyldibromoboranes R′BBr2 to give the products Br–BR–NR=BR–BR′–Br ( 8 a – g : R′ = Me, Bu, iBu, Bzl, CH2CHEt2, CH2Cy, CH2(4‐C6H4tBu)). Two isomers of each of the products 8 a – g are formed and attributed to a cis/trans isomerism at the BN double bond; the isomerization is followed thermodynamically and kinetically by NMR methods with 8 a – d . The analogous chloroboration of 1 with BCl3 yields Cl–BR–NR=BR–BCl2 ( 8 h ), which at ambient temperature undergoes a degenerate exchange of the ligands Cl and BCl2 along the B–N–B skeleton. At room temperature, the isomer Cl–BR–NR=BCl–BR–Cl ( 8 h ′) is slowly formed by an irreversible exchange of R and Cl along the B–B bond of 8 h . Different from BCl3, the chloroborane BH2Cl is simply added to the B–B bond of 1 under formation of the aza‐nido‐tetraborane NB3R3H2Cl ( 2 b ). The chloroborane BHCl2 gives a mixture of 8 h ′ and 2 b upon addition to 1 , apparently according to a preceding dismutation into BCl3 and BH2Cl. The configuration at the B3 atom of the nido‐clusters NB3R3H2X (X = H, Cl) is discussed on the basis of the corresponding model molecules NB3Me3H2X, whose structure and NMR signals are computed by the B3LYP method. The boranes 8 b – g can be debrominated with Li in the presence of tmen on applying ultrasound. The products are found to be the B‐borylated azadiboriridines [–BR–NR–B(BRR′)–] ( 9 b – g ). The 2‐borylazadiboriridines NB3H4 ( 9 h ) and NB3Me4 ( 9 i ) were found as local minima on the energy hyperface by the B3LYP method, but minima for structural isomers with lower energy were also found; the tetrahedral clusters NB3R4 give high‐energy minima with triplet ground states. Computations of the 11B NMR shifts of 9 h and 9 i support the proposed structures of 9 b – g .  相似文献   

7.
The partial substitution of CaF2 for CaO in the Na2O–CaO–SiO2–P2O5 system was conducted by the sol–gel method and a comparison of the glass–ceramic properties was reported. Based on thermogravimetric and differential thermal analysis, the gels were sintered with a suitable heat treatment procedure. The glass–ceramic properties were characterized by X-ray diffraction, fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectrometer and so on, and the bioactivity of the glass–ceramic was evaluated by in vitro assays in simulated body fluid. Results indicate that with the partial substitution of CaF2 for CaO in glass composition, the volume density, apparent porosity, bending strength and microhardness of the glass–ceramics have been significantly improved. Furthermore, CaF2 promotes glass crystallization which does not inhibit the glass–ceramic bioactivity.  相似文献   

8.
The idea of repulsion in random copolymers was applied to the miscibility modification between polystyrene (PS) and polyarylate (PAr) segments of PS–PAr block copolymer (PAr–PS–PAr). Acrylonitrile (AN), which has a large positive interaction parameter against styrene, was used as a miscibility modifier toward PAr segments. AN was introduced into the carboxyl terminated telechelic‐PS at AN wt % ranging from 12 to 37 wt %. Based on these telechelic acrylonitrile–styrene random copolymers (SANx's where x represents AN wt %), SANx and PAr block copolymers (PAr–SANx–PAr's) were synthesized. The miscibility of SANx and PAr segments was estimated from the results of DSC with Fox's equation and spin–spin relaxation time measured by pulsed NMR. These results evidenced that the miscibility between PS and PAr segments can be modified by introducing AN into PS segments. The estimated volume fraction of the interfacial layer between SANx and PAr segments was increased as x was increased toward 24 wt %, around which the predicted miscibility reaches a maximum. Above that AN wt %, it began to decrease. The flexural strength increased as the miscibility between SANx and PAr segments increased. In particular, when x was between 20 and 30 wt %, PAr–SANx–PAr exhibited three times larger flexural strength than PAr–PS–PAr. The fracture behavior changed from brittle to ductile, even though the telechelic SANx by themselves exhibited almost the same fracture strength as the telechelic PS. The results of dynamic mechanical measurements and the percolation model suggested that around these AN wt % the continuum matrices in PAr–SANx–PAr changed from SANx phase to a cocontinuous phase of SANx and PAr. From these results, PAr–SANx–PAr was explained to perform such a high flexural strength by this phase change in the continuum matrices. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 127–137, 2000  相似文献   

9.
Crystalline cesium nitratometalates(II), Cs2[M(NO3)4] (M = Mn ( I ), Co ( II ), Ni ( III ), and Zn ( IV )) were synthesized from M(NO3)2 · n H2O and CsNO3 by heating at 80–120 °C over 10–12 h. According to X-ray crystal structure analysis, the compounds are built from Cs+ cations and [M(NO3)4]2– anions. The latter differ by the type of metal coordination: a dodecahedron for Mn in I (CN = 8, rMn–O 2.24–2.37 Å), a seven coordination for Co in II (CN = 4 + 3, rCo–O 2.03–2.16 Å and 2.21–2.35 Å) and a tetrahedral distorted dodecahedron for Zn in IV (CN = 4 + 4, rZn–O 1.98–2.15 Å and 2.38–2.72 Å). Ni atom in III has a distorted octahedral NiO6 environment provided by two unidentate and two bidentate NO3 groups with Ni–O distances of 2.01–2.14 Å. The differences in metal coordination are discussed in terms of valence electron configurations, ionic radii, and the packing effects.  相似文献   

10.
The catalytic behavior of binary systems derived from AIR3 and alkali metal hydroxide in a molar ratio of 1 to 0.5 in situ for stereospecific polymerization of acetaldehyde was studied for the purpose of preparation of isotactic polyacetal. The polymer obtained can be readily stretched to a film. The polymerization proceeds slowly (in ~20 hr). The polymer yield and stereospecificity of the polymerization by AlEt3–LiOH (1:0.5) catalyst were not significantly changed by the nature of solvent or dilution as far as studied. AlEt3–NaOH, AlEt3–KOH, AlEt3–CsOH, AliBu3–LiOH and AlMe3–LiOH in molar ratios of 1 to 0.5 behaved similarly. AlMe3–NaOH, AlMe3–KOH and AliBu3–NaOH also gave isotactic polymer of high stereoregularity but in lower yields.  相似文献   

11.
《Tetrahedron: Asymmetry》1998,9(15):2701-2713
l-Phenylalanine cyclohexylamide has been used as a chiral auxiliary for the medium-scale resolution of 2′,1′:1,2;1″,2″:3,4-dinaphthcyclohepta-1,3-diene-6-amino-6-carboxylic acid (Bin), an α,α-disubstituted glycine with only axial dissymmetry. Coupling of X–Bin–OH (X=Ac; Bz) with H–(l)-Phe–NH–C6H11 by the EDC/HOBt method gave the dipeptide diastereoisomers X–(R)-Bin–(l)-Phe–NH–C6H11 and X–(S)-Bin–(l)-Phe–NH–C6H11, which were separated by crystallization (X=Bz) and/or chromatography. Extensive acidic hydrolysis, followed by esterification of the resulting free amino acid enantiomers, led to enantiomerically pure (−)-(R)-H–Bin–OMe and (+)-(S)-H–Bin–OMe with high yields.  相似文献   

12.
The quaternary reciprocal system comprising fluorides, chlorides, and tungstates of lithium and potassium was partitioned into simplexes using graph theory, and a phase tree of the system was constructed. In the cutting triangles LiF–KCl–Li2WO4 and LiF–KCl–LiKWO4 by differential thermal analysis, the melting points and compositions of ternary eutectics were determined, and the crystallization fields of phases are delineated. For each element of the state diagram, phase reactions were described. The compositions of crystallizing phases in the cutting triangles LiF–KCl–Li2WO4 and LiF–KCl–LiKWO4 were confirmed by X-ray powder diffraction analysis.  相似文献   

13.
The System Ammonium Nitrate–Monoammonium Phosphate–Urea Nitrate–Urea Phosphate–Water The 20 and 40°C isotherms of the quaternary system ammonium nitrate– monoammonium phosphate–urea nitrate–urea phosphate–water have been determined by an analytical method. NH4H2PO4 and CO(NH2)2·HNO3 form a stable ternary system at both temperatures.  相似文献   

14.
An ion chromatography method was developed for the simultaneous detection of three soluble herbicides (glyphosate, bentazone and picloram), three chlorine disinfection byproducts (monochloroacetic acid, dichloroacetic acid and trichloroacetic acid) and 12 anions in water (Cl, Br, SO42–, CO32–, ClO3, ClO4, BrO3, PO43–, NO2, NO3, CH3COO and COO). High linearity (r2 > 0.996) was observed for all target analytes for each respective concentration range. The limit of detection and limit of quantitation were between 0.21–0.85 and 0.06–25.46 μg/L, respectively. However, the interference effect of Cl, NO3, SO42– and CO32– on some target analytes must be considered during the analysis. Sample pre‐treatment by a hydrogen column (H‐column) required to reduce the negative effect of CO32–. Additionally, sample pre‐treatment by a sliver–hydrogen column (Ag–H‐column) is required when Cl > 100 mg/L and SO42– < 50 mg/L, and pre‐treatment by both a barium column (Ba‐column) and an H‐column is required when Cl > 100 mg/L and SO42– > 50 mg/L. When Cl > 100 mg/L, SO42– > 50 mg/L and CO32– > 20 mg/L, the sample pre‐treatment by either an Ag–H–Ba‐column or an Ag–H‐column and Ba‐column is required to minimize interference.  相似文献   

15.
This review paper reports the recent progress concerning the application of nickel–alumina–zirconia based catalysts to the ethanol steam reforming for hydrogen production. Several series of mesoporous nickel–alumina–zirconia based catalysts were prepared by an epoxide-initiated sol–gel method. The first series comprised Ni–Al2O3–ZrO2 xerogel catalysts with diverse Zr/Al molar ratios. Chemical species maintained a well-dispersed state, while catalyst acidity decreased with increasing Zr/Al molar ratio. An optimal amount of Zr (Zr/Al molar ratio of 0.2) was required to achieve the highest hydrogen yield. In the second series, Ni–Al2O3–ZrO2 xerogel catalysts with different Ni content were examined. Reducibility and nickel surface area of the catalysts could be modulated by changing nickel content. Ni–Al2O3–ZrO2 catalyst with 15 wt% of nickel content showed the highest nickel surface area and the best catalytic performance. In the catalysts where copper was introduced as an additive (Cu–Ni–Al2O3–ZrO2), it was found that nickel dispersion, nickel surface area, and ethanol adsorption capacity were enhanced at an appropriate amount of copper introduction, leading to a promising catalytic activity. Ni–Sr–Al2O3–ZrO2 catalysts prepared by changing drying method were tested as well. Textural properties of Ni–Sr–Al2O3–ZrO2 aerogel catalyst produced from supercritical drying were enhanced when compared to those of xerogel catalyst produced from conventional drying. Nickel dispersion and nickel surface area were higher on Ni–Sr–Al2O3–ZrO2 aerogel catalyst, which led to higher hydrogen yield and catalyst stability over Ni–Sr–Al2O3–ZrO2 aerogel catalyst.  相似文献   

16.
An organoruthenium complex (–[biphRuCp]PF6–; biph = –(C6H4)2–, Cp = C5H5), constructed within a biphenylene-bridged inorganic–organic hybrid mesoporous material (HMM–biph) by use of a simple ligand-exchange reaction, has been used as a heterogeneous catalyst. UV–visible and X-ray absorption fine structure (XAFS) studies furnished evidence that the structure of the complex is closely similar to that of [(C6H6)RuCp]PF6, suggesting that the biphenylene moiety within HMM–biph directly coordinates the metal center of the organoruthenium complex. The –[biphRuCp]PF6– complex constructed within the HMM–biph (HMM–biphRuCp) catalyzes hydrosilylation of 1-hexyne with triethylsilane in a solid–gas heterogeneous system and gives α-vinylsilane as a main product. Moreover, HMM–biphRuCp has higher catalytic activity than the –[phRuCp]PF6– (ph = –C6H4–) complex constructed within phenylene-bridged HMM (HMM–phRuCp). The high catalytic performance of HMM–biphRuCp can be attributed to the high loading of the HMM–biph with the Ru complex, because of the electron-donating ability of the biphenylene moieties.  相似文献   

17.
Internalization of nano- and microparticles into live cells correlates closely with their potential applications, functions, cytotoxicity and intracellular drug delivery. Particularly, delivery of a large variety of cargoes such as proteins, peptides, nucleic acids and small particles into cells could be enhanced by some ligands such as Tat peptide. In this work, the ability of Tat mediated cellular uptake was assessed. The Tat peptide was covalently immobilized to fluorescein tagged SiO2 particles (FITC–SiO2–NH2 particles) with a diameter of 200 nm. BCA protein assay determined that the grafting amount of the Tat peptide could be controlled within a range of 0–3.5 μg/mg SiO2 particles by the Tat feeding amount. Surface immobilization of the Tat peptide did not bring apparent changes on the surface morphology and charge property of the SiO2–NH2 particles. By contrast, the surface charge of both the FITC–SiO2–NH2 particles and the FITC–SiO2–Tat particles was reversed from slight positive in Dulbecco's Modified Eagles Medium (DMEM) to slight negative in DMEM/fetal bovine serum, conveying adsorption of plasma proteins on the particles. Flow cytometry measurement showed that the FITC–SiO2–Tat particles were internalized by HepG2 cells with a significant faster rate and a higher number of particles than that of the FITC–SiO2–NH2 particles. Moreover, internalization of the Tat peptide decorated particles was less influenced by the low temperature at 4 °C. The Tat decoration affected the subcellular distribution of the particles as well, resulting in localization of the particles in the cell nucleus. No obvious cytotoxicity was detected for both the FITC–SiO2–NH2 particles and the FITC–SiO2–Tat particles.  相似文献   

18.
Ionic mobility and electrical conductivity of solid solutions with fluorite structure, obtained with solid-state approach in PbF2–SbF3 and PbF2–SnF2–SbF3 systems, are studied by 19F NMR and electrochemical impedance spectroscopy methods. The 19F NMR spectra parameters, types of ion motions in the fluoride sublattice, and the ionic conductivity magnitude are shown to be determined by the temperature and fluoride concentration in the solid solutions. The solid solution specific conductivity in the PbF2–SbF3 and PbF2–SnF2–SbF3 systems at 420–450 K is as high as ~10–2 S/cm, which allows accounting the solid solutions as a base for preparation of functional materials.  相似文献   

19.
ZnO–SnO2 nanoparticles were prepared by coprecipitation method; then Mg, with different molar ratios and calcination temperatures, was loaded on the coupled nanoparticles by impregnation method. The synthesized nanoparticles were characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X‐ray spectroscopy (EDX), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), and Brunauer–Emmett–Teller (BET) techniques. Based on XRD results, the ZnO–SnO2 and Mg/ZnO–SnO2 nanoparticles were made of ZnO and SnO2 nanocrystallites. According to DRS spectra, the band gap energy value of 3.13 and 3.18 eV were obtained for ZnO–SnO2 and Mg/ZnO–SnO2 nanoparticles, respectively. BET analysis revealed a Type III isotherm with a microporous structure and surface area of 32.051 and 49.065 m2 g?1 for ZnO–SnO2 and Mg/ZnO–SnO2, respectively. Also, the spherical shape of nanocrystallites was deduced from TEM and FESEM images. The photocatalytic performance of pure ZnO–SnO2 and Mg/ZnO–SnO2 was analyzed in the photocatalytic removal of methyl orange (MO). The results indicated that Mg/ZnO–SnO2 exhibited superior photocatalytic activity to bare ZnO–SnO2 photocatalyst due to high surface area, increased MO adsorption and larger band gap energy. Maximum photocatalytic activity of Mg/ZnO–SnO2 nanoparticles was obtained with 0.8 mol% Mg and calcination temperature of 350°C.  相似文献   

20.
Fe3O4–graphene composites with three‐dimensional laminated structures have been synthesised by a simple in situ hydrothermal method. From field‐emission and transmission electron microscopy results, the Fe3O4 nanoparticles, around 3–15 nm in size, are highly encapsulated in a graphene nanosheet matrix. The reversible Li‐cycling properties of Fe3O4–graphene have been evaluated by galvanostatic discharge–charge cycling, cyclic voltammetry and impedance spectroscopy. Results show that the Fe3O4–graphene nanocomposite with a graphene content of 38.0 wt % exhibits a stable capacity of about 650 mAh g?1 with no noticeable fading for up to 100 cycles in the voltage range of 0.0–3.0 V. The superior performance of Fe3O4–graphene is clearly established by comparison of the results with those from bare Fe3O4. The graphene nanosheets in the composite materials could act not only as lithium storage active materials, but also as an electronically conductive matrix to improve the electrochemical performance of Fe3O4.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号