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81.
82.
The keto-enol tautomerization of p-hydroxyphenylpyruvic acid (pHPP) in aqueous solutions and the complexation reaction between enolic pHPP and boric acid have been studied by electrochemical techniques including linear sweep voltammetry (LSV), pulse voltammetry, and cyclic voltammetry (CV), combining with UV spectrometry. Electrochemical techniques reveal that in aqueous solution, there are two tautomers of pHPP: enolic form and ketonic form; the former exists mainly in freshly prepared pHPP solution, and the latter exists mainly in equilibrium solution. Both enolic and ketonic pHPP are electroactive. The electrochemical oxidation of enolic pHPP gives rise to two anodic waves, I(a) and II(a), while the electrochemical oxidation of ketonic pHPP only results in the observation of the second wave II(a). The oxidation process I(a) is revealed to be associated with the quasi-reversible, two-electron two-proton oxidation of "C=C"group at the side chain of enolic pHPP, and the oxidation process II(a) is proposed to result from the irreversible oxidation of phenolic hydroxyl group. It is observed that in aqueous solution, enolic pHPP can quickly complex with boric acid to yield enol-borate complex that can also oxidize at a glassy carbon electrode to yield an anodic wave. 相似文献
83.
The complexes between R3Tr (Tr = B, Al, and Ga; R = H, F, Cl, and Br) and H2X (X = O, S, and Se) were theoretically studied. The interaction energies of R3Al⋯H2X and R3Ga⋯H2X are consistent with the electronegativity of the halogen atom R (R ≠ H), but an opposite dependence is found for R3B⋯H2X. The triel bond of R3Tr⋯H2X is weaker for the heavier chalcogen donor. The dependence of triel bonding strength on the triel atom is complicated, depending on the nature of R and X. The methyl substitution of H2X causes a substantial increase in the interaction energy from −5.74 kcal/mol to −22.88 kcal/mol, and its effect is relevant to the nature of Tr, X, and R groups. For the S and Se donors, the increased percentage of interaction energy is almost the same due to the methyl substitution, which is larger than that of the O analogue. In most triel-bonded complexes, electrostatic dominates and polarization has comparable contribution. However, polarization plays a dominant role in R3B⋯ and R3B⋯ (R = Cl and Br; R′ = H and Me). 相似文献
84.
The design of a supramolecular allosteric catalyst system for catalytic signal amplification and detection is presented. The catalyst was switched "on" by the introduction of an analyte that also behaves as an allosteric activator. Concentrations of Cl- ions as low as 800 nM were catalytically amplified and detected. The signal was transduced via a pH-sensitive fluorescent probe and observed visually using a laboratory, handheld UV lamp and by spectrophotometry. Furthermore, the allosteric effect was quantified using gas chromatography for a range of Cl- concentrations. This three-part detection scheme involving analyte binding, allosteric catalyst activation, and signal transduction represents a new approach to small-molecule detection. 相似文献
85.
86.
A series of chemoselective polymers had been designed and synthesized to enhance the sorption properties of polymer coated chemical sensors for polynitroaromatic analytes. To evaluate the effectiveness of the chemoselective coatings, a polynitroaromatic vapor test bed was utilized to challenge polymer coated surface acoustic wave (SAW) devices with different explosive vapors. Dinitrotoluene detection limits were determined to be in the <100 parts per trillion ranges. ATR-FTIR studies were used to determine the nature of the polymer-polynitroaromatic analyte interactions, and confirm the presence of hydrogen-bonding between polymer pendant groups and the nitro functional groups of polynitroaromatic explosive materials. 相似文献
87.
Synthesis, structure and magnetic properties of the S=1/2, one-dimensional antiferromagnet, Y5Re2O12
Lisheng Chi 《Journal of solid state chemistry》2003,172(2):451-457
Single crystals of Y5Re2O12 have been grown, and the crystal structure has been determined by X-ray diffraction. This compound crystallizes in space group C2/m with cell dimensions of a=12.4081(10) Å b=5.6604(5)Å, c=7.4951(6) Å, β=107.837(3)°, Z=2. The final refinement led to R1=0.0238, WR2=0.0459 for 1053 observed reflections with F>4σ(F0). Edge-sharing ReO6 octahedra form infinite linear [ReO2O4/2]n chains along the b direction with alternating short and long Re-Re distances. Three crystallographically independent yttrium atoms surround O2 to form OY4 tetrahedra, which share edges and corners in the ab plane to form a two-dimensional Y5O4 network which separates the [ReO2O4/2]n magnetic chains. This compound is therefore isostructural with the series Ln5Re2O12Ln=Gd-Lu, which have been known since 1969. The average Re oxidation state is +4.5 in the chains and a reasonable, if qualitative MO scheme results in one unpaired electron per Re dimer. Consistent with this, magnetic susceptibility data can be fitted to the one-dimensional antiferromagnetic Heisenberg model with S=1/2 and parameters Jintra/k=−89(1)K, g=2.15(4) and χ(TIP)=5(1)×10−4 emu/mol. There is no sign of long-range magnetic order down to 2 K. These results are contrasted with those for the isostructural Y5Mo2O12. 相似文献
88.
Bar G Bennati M Nguyen HH Ge J Stubbe JA Griffin RG 《Journal of the American Chemical Society》2001,123(15):3569-3576
High-frequency pulsed EPR and ENDOR have been employed to characterize the tyrosyl radical (Y*)-diiron cofactor in the Y2-containing R2 subunit of ribonucleotide reductase (RNR) from yeast. The present work represents the first use of 140-GHz time domain EPR and ENDOR to examine this system and demonstrates the capabilities of the method to elucidate the electronic structure and the chemical environment of protein radicals. Low-temperature spin-echo-detected EPR spectra of yeast Y* reveal an EPR line shape typical of a tyrosyl radical; however, when compared with the EPR spectra of Y* from E. coli RNR, a substantial upfield shift of the g(1)-value is observed. The origin of the shift in g(1) was investigated by 140-GHz (1)H and (2)H pulsed ENDOR experiments of the Y2-containing subunit in protonated and D(2)O-exchanged buffer. (2)H ENDOR spectra and simulations provide unambiguous evidence for one strongly coupled (2)H arising from a bond between the radical and an exchangeable proton of an adjacent residue or a water molecule. Orientation-selective 140-GHz ENDOR spectra indicate the direction of the hydrogen bond with respect to the molecular symmetry axes and the bond length (1.81 A). Finally, we have performed saturation recovery experiments and observed enhanced spin lattice relaxation rates of the Y* above 10 K. At temperatures higher than 20 K, the relaxation rates are isotropic across the EPR line, a phenomenon that we attribute to isotropic exchange interaction between Y* and the first excited paramagnetic state of the diiron cluster adjacent to it. From the activation energy of the rates, we determine the exchange interaction between the two irons of the cluster, J(exc) = -85 cm(-)(1). The relaxation mechanism and the presence of the hydrogen bond are discussed in terms of the differences in the structure of the Y*-diiron cofactor in yeast Y2 and other class I R2s. 相似文献
89.
Whereas the thermospray mass spectra of most compounds consist of only the pseudo-molecular ion with little fragmentation, the thermospray mass spectra of arteether (a cyclic endoperoxide) and its metabolites are relatively complex. Assignments of structures to individual fragments from normal spectra was particularly ambiguous because of uncertainties as to which fragments arose from ammonium ion or methanol adducts. In this study, these assignments could be resolved through the comparison of the regular spectrum with the deuterium-exchange spectrum (in an ND4O2CCH3–CD3OD–D2O mobile phase) achieved using ‘sandwiched slug’ injection technique. The mass spectra of arteether and four of its metabolites all showed [M + ND4]+ pseudo-molecular ions with greater than 91% H/D exchange, indicating a high efficiency with a minimal use of deuterated mobile phase. Most fragments showed H/D exchange rates in the 70–90% range and the isotope shift of individual spectral lines (ΔM) was found to be extremely useful in determining the structure of the fragment. 相似文献
90.
Qijin Chi Wolfgang Göpel Tautgirdas Ruzgas Lo Gorton Peter Heiduschka 《Electroanalysis》1997,9(5):357-365
The electrochemical properties of carbon paste electrodes (CPEs), including unmodified and modified with protein and polycations, were investigated by impedance spectroscopy (IS) using ferricyanide and ferrocene monocarboxylic acid (FcMA) as redox probes. Various electrochemical pretreatments were applied to the unmodified CPE. The heterogeneous charge transfer rate constant of ferro/ferricyanide couple is enhanced by 2 to 10 times compared with that obtained at untreated electrodes. It was found that for ferricyanide the more suitable pretreatments are successive cyclic voltammetric scans, cathodization and a square wave-like stepping rather than high-potential anodization. However, the pretreatment only exhibits a slight effect on the kinetics of FcMA. At the CPEs containing modifier, the electron transfer rate of the redox couple depends more on the pH of electrolyte solution if ferro/ferricyanide is used. The results can be explained by the differently charged states of the CPEs that were caused by the protonation or deprotonation of the modifiers in various pH solutions and demonstrate the importance of the electrostatic interaction on the kinetics of the highly polar species such as ferricyanide. The different adsorptive behavior of ferricyanide and FcMA is also discussed. 相似文献