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31.
Some new N‐glycosides of 4‐(2‐phenylethyl)‐5‐pyridyl‐1,2,4‐triazole‐3‐thiones were synthesised by the coupling reaction of halo sugar with 4,5‐disubstituted 3H‐1,2,4‐triazole‐3‐thiones in the presence of mercuric cyanide and dry nitromethane as solvent, followed by deprotection using dry ammonia in methanol. All of the above compounds were fully characterized by means of infrared, 1H NMR spectroscopy, mass spectroscopy and elemental analysis. 相似文献
32.
A novel membrane sensor for selective monitoring of iodide, consisting of a triiodide‐ketoconazole ion pair complex dispersed in a PVC matrix, plasticized with a mixture of 2‐nitrophenyl octyl ether and dioctylphtalate with unique selectivity toward iodide ions, is described. The influence of membrane composition, pH of test solution and foreign ions on the electrode performance were investigated. The optimized membrane demonstrates a near‐Nernstian response for iodide ions over a wide linear range from 1.0 × 10?2 to 1.0 × 10?5 M, at 25 ± 1 °C. The electrode could be used over a wide pH range 3–10 and has the advantages of high selectivity, fast response time and good lifetime (over 4 months). It was successfully used as indicator electrode in potentiometric titrations and direct potentiometric assay of iodide ions. 相似文献
33.
Xu Q Tanaka K Mori M Helaleh MI Hu W Hasebe K Toada H 《Journal of chromatography. A》2003,997(1-2):183-190
A monolithic ODS-silica gel column modified by saturating it with lithium dodecylsulfate (Li-DS) was used to demonstrate the high-speed separation of H+ from other mono- and divalent cations, such as Na+, NH4+, K+, Mg2+ and Ca2+ using ion chromatography (IC). Using a 5 mM EDTA-2K solution containing 0.10 mM Li-DS (pH 4.80) as eluent, H+ was eluted with a sharp and symmetrical peak within 1.0 min before other cations at a flow-rate of 1.5 ml min(-1). The rapid elution of H+ and its conductimetric detection could be attributed to the presence of EDTA (HY2-), which can convert H+ ions as anions. i.e. H(+) + H2Y(2-) --> H3Y(-). The acidity of rainwater and deionized water samples was determined using this IC system with satisfactory results. 相似文献
34.
The possibility of using the NMR chemical shift to evaluate and develop intermolecular potentials for cross-interactions between polar and nonpolar molecules has been examined using the method of molecular dynamics. Such interaction potential models are known to be notoriously difficult to develop. Our work has shown that chemical shift can be obtained quite efficiently in simulations and converges much faster than other properties traditionally used for such evaluations (for example, the infinite dilution activity coefficients, Henry’s constants or the solubility of solutes in solvents). We have also found chemical shift to be quite sensitive to the intermolecular potentials which makes it a rather promising property to investigate polar–nonpolar interactions in fluids. 相似文献
35.
An unprecedented one-pot reductive trimerization of aromatic aldehydes to 1,2,3-triaryl-2-propen-1-ones as well as tandem reductive coupling-rearrangements of aryl ketones to pinacolone analogues was efficiently achieved using tetrachlorosilane-zinc at room temperature. 相似文献
36.
A new synthetic procedure has been developed in Mn cluster chemistry involving reductive aggregation of permanganate (MnO4-) ions in MeOH in the presence of benzoic acid, and the first products from its use are described. The reductive aggregation of NBu(n)4MnO4 in MeOH/benzoic acid gave the new 4Mn(IV), 8Mn(III) anion [Mn12O12(OMe)2(O2CPh)16(H2O)2]2-, which was isolated as a mixture of two crystal forms (NBu(n)4)2[Mn12O12(OMe)2(O2CPh)16(H2O)2].2H2O.4CH2Cl2 (1a) and (NBu(n)4)2[Mn12O12(OMe)2(O2CPh)16(H2O)2].2H2O.CH2Cl2 (1b). The anion of 1 contains a central [Mn(IV)4(mu3-O)2(mu-O)2(mu-OMe)2]6+ unit surrounded by a nonplanar ring of eight Mn(III) atoms that are connected to the central Mn4 unit by eight bridging mu3-O2- ions. This compound is very similar to the well-known [Mn12O12(O2CR)16(H2O)4] complexes (hereafter called "normal Mn12"), with the main difference being the structure of the central cores. Longer reaction times (approximately 2 weeks) led to isolation of polymeric [Mn(OMe)(O2CPh)2]n2, which contains a linear chain of repeating [Mn(III)(mu-O2CPh)2(mu-OMe)Mn(III)] units. The chains are parallel to each other and interact weakly through pi-stacking between the benzoate rings. When KMnO4 was used instead of NBu(n)4MnO4, two types of compounds were obtained, [Mn12O12(O2CPh)16(H2O)4] (3), a normal Mn12 complex, and [Mn4O2(O2CPh)8(MeOH)4].2MeOH (4.2MeOH), a new member of the Mn4 butterfly family. The cyclic voltammogram of 1 exhibits three irreversible processes, two reductions and one oxidation. One-electron reduction of 1 by treatment with 1 equiv of I- in CH2Cl2 gave (NBu(n)4[Mn12O12(O2CPh)16(H2O)3].6CH2Cl2 (5.6CH2Cl2), a normal Mn12 complex in a one-electron reduced state. The variable-temperature magnetic properties of 1, 2, and 5 were studied by both direct current (dc) and alternating current (ac) magnetic susceptibility measurements. Variable-temperature dc magnetic susceptibility studies revealed that (i) complex 1 possesses an S = 6 ground state, (ii) complex 2 contains antiferromagnetically coupled chains, and (iii) complex 5 is a typical [Mn12]- cluster with an S = 19/2 ground state. Variable-temperature ac susceptibility measurements suggested that 5 and both isomeric forms of 1 (1a,b) are single-molecule magnets (SMMs). This was confirmed by the observation of hysteresis loops in magnetization vs dc field scans. In addition, 1a,b, like normal Mn12 clusters, display both faster and slower relaxing magnetization dynamics that are assigned to the presence of Jahn-Teller isomerism. 相似文献
37.
Ab initio multireference configuration interaction potential energy surfaces are computed for the eight lowest singlet surfaces of C(3). These reveal several important features, including several conical intersections in linear, nonlinear, and equilateral triangle geometries. These intersections are important because, particularly for the excited A (1)Pi(u) state, reasonable ab initio results could only be obtained by including nearby, near degenerate, (1)Sigma(u) (-) and (1)Delta(u) states that cross the A (1)Pi(u) state around 4500 cm(-1) above the equilibrium geometry, and a (1)Pi(g) state whose potential in turn crosses the other states about 2000 cm(-1) further up. These states are probably responsible for the complexity of the shorter wavelength UV absorption spectrum of C(3). The computed potential energy surface for the ground, X (1)Sigma(g) (+), state and for the lowest two excited singlet surfaces (which both correlate with the A (1)Pi(u) state in a collinear geometry) are fitted to analytic functional forms. Vibrational energy levels are calculated for both states, taking account of the Renner-Teller coupling in the excited A (1)Pi(u) state. The potential parameters for both states are then least-squares fitted to experimental data. The ground-state fit covers a range of approximately 8500 cm(-1) above the lowest level, and reproduces 100 observed vibrational levels with an average error of 2.8 cm(-1). The A (1)Pi(u) state surfaces cover a range of 3250 cm(-1) above the zero-point level, and reproduce the 44 observed levels in this range with an average error of 2.8 cm(-1). 相似文献
38.
Flow injection analysis with on-line preconcentration using a minicolumn loaded with dialkyldithiocarbamate immobilized on controlled pore glass is described for the determination of Rh(III), Co2+, Cu2+, Hg2+, and Hg22+. The detection limits range from 0.05 ng ml−1 for Cu2+ to 50 ng ml−1 for Hg2+ for 5- or 10-ml samples, improvement of 2–3 orders of magnitude compared with direct injection. The operating conditions are optimized and the effects of interferents are studied. The capacity of the collector varied from 0.9 mmol g−1 for Rh(III) to ca 4 mmol g−1 (Co2+, Cu2+, Hg2+). 相似文献
39.
The dissolution of zinc in 0.48–1.49M HNO3 was studied at 15–25°C, by following simultaneously the concentration changes of the reactants (Zn and HNO3), intermediate (HNO2) and product (Zn2+) with time. Explicit mechanisms were suggested for the dissolution of zinc in nitric acid. The kinetics of the dissolution process show that it is of the first-order with respect to [Zn] and [HNO2]. The data obtained show that the dissolution process is diffusion-controlled. The mechanism of zinc dissolution is compared with the mechanism of copper dissolution.
Die Kinetik der Auflösung von Zink in Salpetersäure
Zusammenfassung Die Auflösung von Zink in 0.48–1.49M HNO3 wurde bei 15–25°C mittels gleichzeitiger Verfolgung der Konzentrationsänderungen der Reaktanden (Zn und HNO3), des intermediären HNO2 und des Produkts Zn2+ untersucht. Es wird ein Mechanismus vorgeschlagen. Die Kinetik der Auflösung ist erster Ordnung bezüglich [Zn] und [HNO2]. Die Daten zeigen, daß der Auflösungsvorgang diffusionskontrolliert ist. Der Mechanismus der Auflösung von Zink wird mit dem der Kupferauflösung verglichen.相似文献
40.
Poly(trimethylene carbonate)/Poly(malic acid) Amphiphilic Diblock Copolymers as Biocompatible Nanoparticles
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Ghislaine Barouti Ali Khalil Clement Orione Kathleen Jarnouen Dr. Sandrine Cammas‐Marion Dr. Pascal Loyer Prof. Sophie M. Guillaume 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(8):2819-2830
Amphiphilic polycarbonate–poly(hydroxyalkanoate) diblock copolymers, namely, poly(trimethylene carbonate) (PTMC)‐b‐poly(β‐malic acid) (PMLA), are reported for the first time. The synthetic strategy relies on commercially available catalysts and initiator. The controlled ring‐opening polymerization (ROP) of trimethylene carbonate (TMC) catalyzed by the organic guanidine base 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), associated with iPrOH as an initiator, provided iPrO?PTMC?OH, which served as a macroinitiator in the controlled ROP of benzyl β‐malolactonate (MLABe) catalyzed by the neodymium triflate salt (Nd(OTf)3). The resulting hydrophobic iPrO?PTMC‐b‐PMLABe?OH copolymers were then hydrogenolyzed into the parent iPrO?PTMC‐b‐PMLA?OH copolymers. A range of well‐defined copolymers, featuring different sizes of segments (Mn,NMR up to 9300 g mol?1; ÐM=1.28–1.40), were thus isolated in gram quantities, as evidenced by NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, and contact angle analyses. Subsequently, PTMC‐b‐PMLA copolymers with different hydrophilic weight fractions (11–75 %) self‐assembled in phosphate‐buffered saline upon nanoprecipitation into well‐defined nano‐objects with Dh=61–176 nm, a polydispersity index <0.25, and a negative surface charge, as characterized by dynamic light scattering and zeta‐potential analyses. In addition, these nanoparticles demonstrated no significant effect on cell viability at low concentrations, and a very low cytotoxicity at high concentrations only for PTMC‐b‐PMLA copolymers exhibiting hydrophilic fractions over 47 %, thus illustrating the potential of these copolymers as promising nanoparticles. 相似文献