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31.
The bimetallic complexes [M(CO)(3)](2)(mu:eta(5):eta(5)-Pn) (Pn = pentalene, C(8)H(6); M = Mn, Re) have been synthesized and characterized crystallographically; the Mn compound was isolated as solely the anti-isomer, while the Re analogue was formed as a mixture of anti- and syn-isomers. [Mn(CO)(3)](2)(mu:eta(5):eta(5)-Pn) may be reduced chemically to its mono- and dianions; the mixed-valence Mn(I)/Mn(0) monoanion is shown by ESR, vibrational, and electronic spectroscopies to be a Robin-Day class III system with an exceptionally large electronic coupling between the metal centers.  相似文献   
32.
Summary The relative partial molal thermodynamic functions 1 and have been derived from reported experimental light scattering and calorimetric measurements on micellar solutions ofn-dodecyltrimethylammonium bromide. It is shown that the magnitudes of the thermodynamic functions are considerably larger than can be accounted for by the interaction of the electrical double layers surrounding the micelles. Possible enthalpy changes arising from a change in micelle shape, size and degree of dissociation on dilution are discussed.
Zusammenfassung Die relativen molaren thermodynamischen Partialfunktionen , andS 1wurden abgeleitet aus Literaturwerten von Lichtstreuungsmessungen und kalorimetrischen Untersuchungen an mizellaren Lösungen vonn-Dodecyltrimethylammoniumbromid. Es wird gezeigt, daß die Zahlenwerte der thermodynamischen Funktionen erheblich größer sind als von der Wechselwirkung der elektrischen Doppelschichten zu erwarten ist, die die Mizellen umgeben. Mögliche Enthalpieänderungen, die sich aus Änderungen von Größe, Gestalt und Dissoziationsgrad bei Verdünnung herleiten, werden diskutiert.
  相似文献   
33.
The nonlinear optical properties of self-assembled monolayers obtained from bonding two different alpha-functionalized terthiophenes (alpha-T3) to (111) silver electrode surfaces have been investigated using second harmonic generation (SHG). The two (alpha-T3) compounds used were functionalized with alkane chains of different lengths (C8 and C4), and each was terminated with a thiol anchoring group. A nitrile group was attached to the terminal thiophene ring of the (alpha-T3) compound with the C4 chain. The orientation of the polarization of the incident beam was changed systematically and gradually between "p" and "s" orientation and the SH signal (isotropic and anisotropic contributions) analyzed in both directions ("P" and "S"). The symmetry of the system was reduced by the presence of the adlayers from C3v to C3. The dependence on the applied potential and the incident wavelength has also been studied. The relative magnitudes and phases of the various second-order tensor elements have been estimated and compared with the values for a bare surface. A resonance process in the (alpha-T3) pi moiety has been investigated, and from this, the effective "band-gap" energies of the organic semiconductor SAMs (i.e., the energy difference between the pi-pi bands) have been estimated.  相似文献   
34.
Jones DR 《Talanta》1993,40(1):43-51
Chemical species present in reducing waters have the potential to produce severe negative interferences by consuming the chloramine T (CT) which is used as the oxidising agent in the phenol red-based calorimetric method for trace bromide analysis. Mn(2+) and Fe(2+) were found not to interfere at concentrations up to 200muM. However, hydroxylamine (NH(2)OH), which can be present in both ground-and surface-waters, exerts a strong negative interference. A method involving pre-treatment with permanganate and hydrogen peroxide has been developed for the destruction of NH(2)OH prior to adding the colour reagents. The procedure is not only compatible with the chemistry of the calorimetric method, but is also robust and technically easy to implement.  相似文献   
35.
Carbonyl 2 + 2 photoaddition occurs selectively to the alkene moiety of 3-(4-methyl-3-pentenoxy)pyridine. Photolysis of alkene containing pyridines in acetophenone gives rise to an oxetane which is obtained with extremely high diastereoselectivity as shown by analysis of the major 2 + 2 photoproduct. A second photoproduct, 2,3-dihydroxy-2,3-diphenylbutane, is obtained as a result of acetophenone coupling.  相似文献   
36.
Summary Long-term risk assessment of residual and disposed nuclear fuel reprocessing waste requires good knowledge of component isotopes with long half-lives. For example, the accuracy of the accepted 126Sn half-life of approximately 100,000 years is insufficient for desired risk assessments. From modeling and sampling, 126Sn is known to exist in Hanford nuclear waste. Excess portions of waste characterization samples were used to isolate 126Sn for measurement of its half-life. Isolation was performed with ion-exchange resins. The resulting 126Sn was gamma-assayed with a hyperpure germanium spectrometer for decay photon identification and activity values. An inductively coupled plasma/mass spectrometer was used to measure the atom quantity of the isolated 126Sn. The separation chemistry, observed gamma energies, and calculated half-life are presented. The half-life of 126Sn estimated in this work is (2.33±0.10) . 105 years.  相似文献   
37.
The molecular structure of 1,1,1,2-tetrafluoroethane is studied using gas-phase electron diffraction data collected on the Balzers KDG2 instrument. Effective least-squares refinement of the geometry is achieved with values for vibrational amplitudes transferred from normal coordinate calculations on related molecules. The following values for the main independent geometrical parameters are obtained (ra values with e.s.d. in parentheses): C-C = 1.501(4) Å, C-H = 1.077 (15) Å, C-F(CH2F) = 1.389(6) Å, C-F(CF3) = 1.334 (2) Å, ∠CCH= 106.1(12)°, ∠CCF(CH2F)= 112.3(4) Å, ∠CCF(CF3)= 110.4(2). Other angles are ∠FCF = 108.6 (2)° and ∠FCH = 111.4(15)°, with ∠HCH constrained at 109.4°. The ra bond lengths of all the fluoroethanes are compared.  相似文献   
38.
3-(2S-Heptylcycloprop-1S-yl)propanoic acid 2-phenylethanamide was synthesised from cis-cyclopropan-1,2-dimethanol via enzymatic desymmetrisation of the dibutyrate; it gave identical NMR spectroscopic data to those reported for grenadamide but had an equal and opposite absolute rotation, indicating that the latter is the 2R,1R-enantiomer.  相似文献   
39.
A parallel solution-phase library synthesis of functionalized diaminobenzamides is described. The four-step library synthesis is accomplished using polymer-assisted solution-phase (PASP) synthesis techniques. This high-yielding, multi-step sequence utilizes sequestering resins for the removal of reactants, reactant by-products, and employs a resin capture/release strategy as a key library synthesis step. Step one of the sequence relies on the displacement of an activated fluoro-group from the aromatic ring of 1a, b with a variety of primary amines to introduce the first diversity position. Step two is hydrolysis of the benzoate ester to a benzoic acid which is subsequently captured on a polyamine resin, washed, and released to give 4a, b in pure form. Step three utilizes PASP resins to mediate the amide coupling of a benzoic acid with a variety of primary amines to give the aminonitrobenzamides 5a, b and introduces the second diversity position. Step four is the parallel reduction of the aminonitrobenzamides 5a, b to the functionalized diaminobenzamides 6a, b. This library synthesis proceeds with high overall purities which average 80 % over the 4-step sequence.  相似文献   
40.
Apparent pK values of the wine pigment, 5-carboxypyranomalvidin-3-glucoside (vitisin A), were determined using UV-vis spectroscopy, viz. pKa1=0.98 (±0.10), pKH1=4.51 (±0.03) and pKH2=7.57 (±0.02). An additional ionisation constant at high pH (pKa4=8.84±0.06) was established by high-voltage paper electrophoresis. These data in conjunction with previously published pKa values determined by high-voltage electrophoresis suggest that in wine (pH 3.2-3.8), 5-carboxypyranomalvidin-3-glucoside exists as a complex mixture of hydrated and non-hydrated, partially ionised species with the predominant species being the quinonoidal base (λmax 498 nm).  相似文献   
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