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631.
Erika Scavetta Lorella Guadagnini Adriana Mignani Domenica Tonelli 《Electroanalysis》2008,20(20):2199-2204
An amperometric biosensor based on Pt electrodes modified with a thin film of a Ni, Al layered double hydroxide (LDH), submitted to a preliminary oxidative treatment in order to have the nickel centers at the oxidation state +4, and glucose oxidase (GOx) is presented. The oxidized LDH acts both as a system to support the enzyme and as a barrier to anions since it acquires an overall negative charge, as demonstrated by electrochemical impedance spectroscopy. Even if the biosensor response is due to the detection of H2O2 at anodic potentials, glucose can be accurately determined in the presence of ascorbic acid or other interferences, commonly present in real matrices in anionic form, since they can not reach the electrode surface. The effectiveness of the developed biosensor has been demonstrated by measuring glucose in samples of fruit juices containing ascorbic acid at high levels. 相似文献
632.
The DOOO radical has been produced by three-body association between OD and O2 in a supersonic free-jet expansion and investigated using action spectroscopy, an IR-UV double-resonance technique. Partially rotationally structured bands observed at 2635.06 and 5182.42 cm(-1) are assigned to the OD stretch fundamental (nu(OD)) and overtone (2nu(OD)), respectively, of the trans-DOOO radical. Unstructured bands observed in both spectral regions are assigned to cis-DOOO. Nascent OD X(2)Pi product state distributions following vibrational predissociation appear to be nearly statistical with respect to the degree of rotational excitation, but display a marked propensity for Pi(A') Lambda-doublets, which is interpreted as a signature of a planar dissociation. The energetically highest open OD X(2)Pi product channel implies an upper limit dissociation energy D0 < or = 1856 cm(-1) or 5.31 kcal mol(-1). This value allows refinement of the upper limit D0 of the atmospherically important HOOO isotopomer, suggesting that it is marginally less stable than previously thought. 相似文献
633.
Bartholomew ER Bertz SH Cope S Dorton DC Murphy M Ogle CA 《Chemical communications (Cambridge, England)》2008,(10):1176-1177
Neutral organocopper(III) complexes have been prepared from organocuprate(I) reagents and alkyl halides in the presence of certain strongly electron donating ligands. 相似文献
634.
Gendron R Kumar MR Paradis H Martin D Ho N Gardiner D Merschrod SE Poduska KM 《Macromolecular bioscience》2012,12(3):360-366
Therapies for corneal disease and injury often rely on artificial implants, but integrating cells into synthetic corneal materials remains a significant challenge. The electrochemically formed collagen-based matrix presented here is non-toxic to cells and controls the proliferation in the corneal fibroblasts seeded onto it. Histology and biomolecular studies show a behavior similar to corneal stromal cells in a native corneal environment. Not only is this result an important first step toward developing a more realistic, multi-component artificial cornea, but it also opens possibilities for using this matrix to control and contain the growth of cells in engineered tissues. 相似文献
635.
A series of new >P(O)‐substituted succinic derivatives was synthesized by the microwave‐assisted phospha‐Michael addition of dialkyl phosphites, ethyl phenyl‐H‐phosphinate, and diphenylphosphine oxide to N‐phenyl and N‐methyl maleimide, as well as to maleic acid anhydride. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:235–240, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21007 相似文献
636.
H Ikeda E Tsuji T Matsubara M Yukawa M Fujisawa E Yukawa H Aki 《Chemical & pharmaceutical bulletin》2012,60(9):1207-1211
Here, we studied the incompatibility between an oral solution of propericiazine (PCZ), an antipsychotic drug, and various commercially available bottled tea-based drinks. When 0.5?mL of the PCZ oral solution (10?mg/mL) was mixed with 16.5?mL of a tea-based drink (such as green tea, oolong tea, and black tea), the residual PCZ content declined to approximately 50% in some mixed solutions. After mixing with other tea-based drinks, the residual PCZ content declined to approximately 30%, while in others, it changed very little. The residual PCZ content declined immediately after mixing with tea-based drinks, but the rate remained almost unchanged for the next 24?h. Furthermore, the pH of the mixture increased to 4.5-5.1 after the oral solution of PCZ (original pH 3.8) was diluted with various tea-based drinks. Afterwards, the pH did not change for 24?h. The mixture became cloudy immediately after diluting PCZ oral solution with tea-based drinks, and the insoluble substance gradually precipitated. In order to elucidate factors responsible for the decline in the content of PCZ, a (-)-epigallocatechin gallate solution, which is a main ingredient of green tea polyphenol, was mixed with the PCZ oral solution. After mixing, the residual PCZ content declined to approximately 60-75%. On the other hand, the content of PCZ did not decline when a (-)-epigallocatechin solution was mixed with the PCZ oral solution. The results from this study demonstrated that PCZ content was reduced after dilution in tea-based drinks because of the interaction between PCZ and polyphenol with a galloyl group in tea-based drinks. 相似文献
637.
Coggins MK Toledo S Shaffer E Kaminsky W Shearer J Kovacs JA 《Inorganic chemistry》2012,51(12):6633-6644
The synthesis, structural, and spectroscopic characterization of four new coordinatively unsaturated mononuclear thiolate-ligated manganese(II) complexes ([Mn(II)(S(Me2)N(4)(6-Me-DPEN))](BF(4)) (1), [Mn(II)(S(Me2)N(4)(6-Me-DPPN))](BPh(4))·MeCN (3), [Mn(II)(S(Me2)N(4)(2-QuinoPN))](PF(6))·MeCN·Et(2)O (4), and [Mn(II)(S(Me2)N(4)(6-H-DPEN)(MeOH)](BPh(4)) (5)) is described, along with their magnetic, redox, and reactivity properties. These complexes are structurally related to recently reported [Mn(II)(S(Me2)N(4)(2-QuinoEN))](PF(6)) (2) (Coggins, M. K.; Kovacs, J. A. J. Am. Chem. Soc.2011, 133, 12470). Dioxygen addition to complexes 1-5 is shown to result in the formation of five new rare examples of Mn(III) dimers containing a single, unsupported oxo bridge: [Mn(III)(S(Me2)N(4)(6-Me-DPEN)](2)-(μ-O)(BF(4))(2)·2MeOH (6), [Mn(III)(S(Me2)N(4)(QuinoEN)](2)-(μ-O)(PF(6))(2)·Et(2)O (7), [Mn(III)(S(Me2)N(4)(6-Me-DPPN)](2)-(μ-O)(BPh(4))(2) (8), [Mn(III)(S(Me2)N(4)(QuinoPN)](2)-(μ-O)(BPh(4))(2) (9), and [Mn(III)(S(Me2)N(4)(6-H-DPEN)](2)-(μ-O)(PF(6))(2)·2MeCN (10). Labeling studies show that the oxo atom is derived from (18)O(2). Ligand modifications, involving either the insertion of a methylene into the backbone or the placement of an ortho substituent on the N-heterocyclic amine, are shown to noticeably modulate the magnetic and reactivity properties. Fits to solid-state magnetic susceptibility data show that the Mn(III) ions of μ-oxo dimers 6-10 are moderately antiferromagnetically coupled, with coupling constants (2J) that fall within the expected range. Metastable intermediates, which ultimately convert to μ-oxo bridged 6 and 7, are observed in low-temperature reactions between 1 and 2 and dioxygen. Complexes 3-5, on the other hand, do not form observable intermediates, thus illustrating the effect that relatively minor ligand modifications have upon the stability of metastable dioxygen-derived species. 相似文献
638.
Herein we report regioselective and mild reactions for the tert-butyldimethylsilyl mono-protection of 5-(2′-hydroxyethyl)cyclopent-2-en-1-ol (2) and 6-(2′-hydroxyethyl)cycohex-2-en-1-ol (5) at the primary hydroxyl group or at the secondary allylic hydroxyl group. The different steric environment surrounding the secondary allylic and saturated primary alcohols is mainly invoked to rationalize the observed regioselectivity. 相似文献
639.
MEKC and linear solvation free energy relationships (LSFERs) have been used to characterize the solute distribution between water and self-assemblies formed from ionic liquid type mono-chain cationic surfactants containing a cyclic pyrrolidinium head group. Several features of the solvation environment afforded by these micellar solutions were found to be quite different from that of CTAB, a structurally analogous cationic surfactant with a conventional, acyclic quaternary ammonium head group. None of the LSFER coefficients were found to vary in any systematic way with increasing alkyl chain length for these unique surfactants. Overall, however, these surfactants display different behavior than do all known cationic detergents such as CTAB. In chemical terms, pseudo-phases formed by these N-alkyl-N-methylpyrrolidinium bromides interact more strongly with polar compounds and less strongly with compounds having nonbonding or pi-electrons and are more cohesive compared to the well-studied CTAB. 相似文献
640.
Díaz-Rojas EI Argüelles-Monal WM Higuera-Ciapara I Hernández J Lizardi-Mendoza J Goycoolea FM 《Macromolecular bioscience》2006,6(5):340-347
Accurate determination of chitin and protein contents in crustacean biomass and the intermediate products during the industrial isolation of chitin cannot be made directly from the total nitrogen content, unless the appropriate corrections are applied. This method, however, is affected by the presence of other nitrogen-containing chemical species that are formed endogenously or by the action of microorganisms during the handling of the sample. Therefore, an alternative rapid method to estimate the contents of these components can be very useful both in research and in various fields of application. An original method has been developed to address this problem. The method consists of the development of a set of equations based on the stoichiometric contents of nitrogen of chitin and protein whereby the amounts of each component can be estimated from the value of the total nitrogen content, provided the rest of the proximate composition of the sample is accurately known. In order to validate the procedure, a set of model mixtures of pure chitin and protein concentrate in the solid state, both extracted from shrimp head waste, are used. Excellent agreement between the predicted and real values of chitin and protein are obtained (R2=0.98, slope=0.90). When the proposed method is tested in the analysis of real samples obtained from five different processing protocols of pretreatment of raw shrimp head, it is found that in general the values of protein and chitin contents throughout the various stages of the process vary as expected. [GRAPH: SEE TEXT] Variation of the measured total nitrogen versus calculated stoichiometric total nitrogen of the chitin-protein mixtures. 相似文献