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91.
The mixed ligand coordination compounds containing acesulfamato and N,N -diethylnicotinamide biomolecules of some rare earth metal cations (Eu3+, Tb3+, Ho3+, Er3+ and Yb3+) were synthesized, and their structural properties were investigated. Possible structural formulas have been proposed by determining the chemical composition of molecules (elemental analysis), binding properties (infrared spectroscopy, mass analysis, solid-state UV-vis spectroscopy), thermal degradation properties (TGA / DTA curves). Based on the data collected, it is suggested that rare earth metal cations with a 3+ oxidation state have sextet coordination. The geometries of the structures were thought to be distorted octahedral. The charge balance of the coordination sphere is balanced by a monoanionic acesulfamato located outside the coordination sphere. When the thermal behaviours of the complexes were examined, it was determined that the compounds with Eu3+, Tb3+, and Yb3+ metal cations contained one hydrate water outside the coordination sphere. Hydrate waters do not exist in the Ho3+ and Er3+ metal cation-centred complexes. At the end of the thermal decomposition analysis of all complex structures, it was determined that they leave the relevant metal oxides in the reaction vessels as final decomposition products. 相似文献
92.
John R. Cowles Simon Daily S. L. R. Ellison William A. Hardcastle Carole Williams 《Accreditation and quality assurance》2001,6(8):368-371
It has been suggested that typical ruggedness tests might lead directly to uncertainty estimates. This assertion is tested
using simple experimental studies of uncertainties associated with sample grinding and oven-drying operations. The results
are used to predict the outcome of typical ruggedness tests on the same systems. It is concluded that uncertainty estimation
from ruggedness tests is appropriate only where a strong effect can be observed. Since current practice in ruggedness testing
is predisposed to confirming insignificance, typical ruggedness tests are not likely to lead to reliable uncertainty estimates;
instead, lack of statistical significance in ruggedness tests is better interpreted as reason to leave an effect out of the
uncertainty budget. Only where the ruggedness study is modified in order to achieve statistically significant change is it
useful for uncertainty estimation.
Received: 27 November 2000 Accepted: 13 February 2001 相似文献
93.
Miao S Brombosz SM Schleyer PV Wu JI Barlow S Marder SR Hardcastle KI Bunz UH 《Journal of the American Chemical Society》2008,130(23):7339-7344
The synthesis and X-ray characterization of two new dialkynylated diazatetracenes and the corresponding N, N-dihydrodiazatetracenes are reported. The dialkynylated heteroacenes are packed in a brick-wall motif that enforces significant overlap of their pi-faces. Cyclic voltammetry indicates that the dehydrogenated forms are easily reduced to their radical anions in solution. The planarity of these species validates the discussion of their aromaticity. Nucleus Independent Chemical Shift (NICS) computations demonstrate that both of these 20 pi and 24 pi electron systems are aromatic. Both experimental and computational results suggest that the aromaticity of the dihydroheteroacenes is reduced. 相似文献
94.
Alexander N. Wein Natalie Owens Kenneth I. Hardcastle 《Journal of fluorine chemistry》2009,130(2):197-203
The goal of this study was to establish the relationship between the 19F NMR line broadening and the varying distance between the 19F nucleus and copper(II) ion, with the aim of gathering data that can be used to interpret 19F NMR spectra of subsequent fluorine-labeled, copper-binding proteins. Fluorinated alkyl and aryl copper(II) carboxylates were synthesized from fluorinated carboxylic acids and Cu(OH)2. The copper(II) carboxylates were characterized using 19F NMR, IR, and single crystal X-ray diffraction. In the alkyl carboxylate compounds, the line broadening and chemical shift lessened with increased distance between the fluorine atom and the copper ions; however, in the aryl carboxylate derivatives, increased distance was not a factor in the amount of line broadening or change in chemical shift between the acid and metal salt. The compound, bis(3-(trifluoromethyl)butyrate) copper(II) (5) was found to possess the optimum combination of decreased line broadening and increased chemical shift sensitivity in 19F NMR. The crystal structures obtained for compounds 1, 2, 4, and 6 were analogous to previous copper(II) carboxylate complexes, though it is noted that compound 6, bis(5,5,5-trifluoropentanoate) copper(II) assumes a tetrameric structure lacking apical ligands, and thus enables the formation of an extended network of near-neighbor copper(II) ions. 相似文献
95.
Al-Cu-Fe thin films were prepared by laser induced arc (laser-arc) method from a single source-Al63Cu25Fe12 alloy, which was proved to consist of quasicrystalline phase together with approximant phase. The composition of the deposited films meets the requirement for formation of icosahedral symmetry phase. Quasicrystalline phase was obtained after annealing the amorphous as-deposit film samples. The optical properties of the samples were investigated. Thin film samples of Al, Cu and Fe deposited under the same condition were employed for comparison. The results showed specific reflective properties of Al-Cu-Fe quasicrystal thin film in some wavelength range. The optical conductivity of the films exhibited a negative peak, centered about 440 nm in range of 190to 800 nm. The Al-Cu-Fe quasicrystal thin films could absorb almost all the ray in the wavelength range from 420nm to 450 nm. The ratio of absorption was greater than 99%. 相似文献
96.
Stable suspensions of small metal Au, Ru, PI, Pd, Rh, Co and Nl particles dispersed in n-heptane and n-dodecane have been prepared using a novel two-phase system, Involving the formation of the particles In a methanolic phase and subsequent phase transfer of the panicles to the alkane medium. The dispersions consisted of small particles having diameters In the range of 8-30 nm (the gold sols were very polydlsperse having average diameters of ca.34 nm). The phase transfer of the particles and their subsequent colloid stability were effected by the presence of dissolved dispersant in the hydrocarbon phase (either Oloa 1200 or Hypermer LP 8). In the case of Oloa 1200, a widely-used polylsobutylene succinimide automotive engine dispersant, It Is proposed that the amlne groups adsorb strongly to the acidic surface o1 the particles, and the 70-carbon polyisobutylene chains extend Into the hydrocarbon medium sufficiently to maintain the separation of adjacent particles by steric and possibly also by electrical repulsion. 相似文献
97.
Dissociation constants of some polyprotic acids and bases are determined from spectrophotometric and reversed-phase high performance liquid chromatographic data. A general equation relating additive properties of acids and bases to the pH of the solution is used for this purpose. The method is tested by applying it to the calculation of overlapping pKas without the prerequisite of measuring the limiting values of the property for the individual species that result from the dissociation of the solute. The possibility of applying the same method to hyperpolarizability measurements is pointed out, and a procedure, based on the general equation, for obtaining the activity coefficients of the ionic species as a function of the ionic strength is also suggested. 相似文献
98.
In this paper we study a multidimensional continued fraction algorithm which is related to the Modified Jacobi–Perron algorithm
considered by Podsypanin and Schweiger. We demonstrate that this algorithm has many important properties which are natural
generalisations of properties of one-dimensional continued fractions. For this reason, we call the transformation associated
to the algorithm the d-dimensional Gauss transformation. We construct a coordinate system for the natural extension which reveals its symmetries and allows one to give an explicit
formula for the density of its invariant measure. We also discuss the ergodic properties of this invariant measure.
Received: 4 February 2000 / Accepted: 23 May 2000 相似文献
99.
Michael Day Shariff E. Kabir Erich Wolf Edward Rosenberg Kenneth I. Hardcastle 《Journal of Cluster Science》1990,1(4):355-369
The synthesis of (-H)(-2-RRNCO2)Os3(CO)10 (R=R=CH3
2a; R=R=CH2CH3,2b; R=CH3, R=CH2CH3,2c) and their cyclic analogs (-H)(-2--CO2)Os3(CO)10(n=42d,n=5,2e) from carbon dioxide, secondary amine, and Os3(CO)10(CH3CN)2 (1) are reported. A solid-state structure of2c reveals a bonding mode for the carbamato ligand very similar to that observed for related carboxylato complexes. Compound2c crystallizes in the orthorombic space group Pbca witha=9.136 (3),b=15.310 (4) andc=30.361 (5) Å;V=4247 Å3,Z=8. Least-squares refinement of 2405 observed reflections gave a final agreement factor ofR=0.043 (R
w
=0.043). The reactivity of the complexes2a–2e was examined. Compound2c or2b give good yields of the cluster derivatives (-H)(-X)Os3(CO)10 (X=Cl,3; X=OCH3,4; X=N(CH3)2,7) when reacted with HX. Reaction of2a with P(CH3)3 at 68°C gives good yields of the otherwise difficult to obtain 1,1,2-(P(CH3)3)3Os3(CO)9 (5). Evidence is presented that suggests that2a–2e form by oxidative addition of preformed carbamic acids to1. 相似文献
100.
Treatment of 2-phenylhex-5-enal with benzylamine followed by sequential reaction with ethylthioacetyl chloride and sodium periodate oxidation afforded a E/Z mixture of alpha-sulfinylamides. As anticipated from a 4pi-conrotatory mechanism, cyclization of each olefin afforded fused isoquinoline lactams as single diastereomers epimeric at the ethylthio position without any cross contamination. Some preliminary studies were directed toward the synthesis of mesembrine using a 3,4-dimethoxy aryl group. In this case, the Z-enamide prefers to undergo electrophilic aromatic substitution to give a substituted azepinone as the preferred product in 87% yield. In contrast, the E-enamide isomer provided the desired hydroindolone. The convergency and stereochemical control associated with the tandem Pummerer /Mannich cyclization make it particularly suited for the assembly of jamtine, a tetrahydroisoquinoline alkaloid reputed for its therapeutic properties. The key step in the synthesis involves a domino thionium/N-acyliminium ion cyclization to provide the tricyclic ring skeleton 27a as the major diastereomer. Deprotonation of 27a with NaH gave 28a, which contains the fully assembled skeleton of jamtine. Completion of the synthesis entailed installation of the double bond and reduction of the lactam. Oxidation of a synthetic sample of jamtine with MCPBA afforded the corresponding N-oxide, which does not match the spectral data reported in the literature for this alkaloid. Our synthetic efforts raise the possibility of a revision of the earlier assignment. 相似文献