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61.
Grace‐Ann M. Lobo Sneha A. Chitre Spandan M. Rathod Robert B. Smith Ray Leslie Callum Livingstone James Davis 《Electroanalysis》2007,19(24):2523-2528
The exploitation of 2‐bromo‐1,4‐naphthoquinone (NQBr) as a selective redox label for the determination of reduced thiol functionalities (RSH) has been investigated. The system is selective for RSH functionality, giving distinct voltammetric signals for glutathione and cysteine but can also be adapted for broad spectrum thiol detection. Ion chromatographic protocols based on conductimetric detection enable total RSH analysis (protein and monomolecular moieties) within human plasma. Bromide released through the reaction can be easily quantified and integrated within normal IC measurements. The efficacy of the approach has been assessed and the response validated through comparison with the standard colorimetric technique. 相似文献
62.
[structure: see text] The synthesis and characterization of a series of low-valent organoselenium compounds derived from 1-bromo-4-tert-butyl-2,6-di(formyl)benzene (22) is described. The synthesis of diselenide 25 was achieved by the lithiation route whereas bis(4-tert-butyl-2,6-di(formyl)phenyl) diselenide (26) was synthesized by treating 22 with disodium diselenide. A series of monoselenides (27, 28, and 29) was obtained by facile nucleophilic substitution of bromine in 22, using the corresponding selenolates as nucleophiles. The halogenation reactions of bis(4-tert-butyl-2,6-di(formyl)phenyl) diselenide (26) did not afford the corresponding selenenyl halides but resulted in the isolation of an unexpected cyclic selenenate ester 34 as a product. The selenide 32 was synthesized by the treatment of dimethoxymethyl diselenide with trilithiated 2-bromo-5-tert-butyl-N,N'-di(phenyl)isophthalamide. The existence of potential Se...O intramolecular nonbonding interactions was examined by IR, (1)H, and (77)Se NMR spectroscopy, X-ray crystallography, and computational studies. The X-ray crystal structures of 26 and 27, having two ortho formyl groups, reveal the absence of any Se...O interactions. However, the Se...O interactions were observed in the selenenate ester 34 where one of the formyl groups has been utilized for the selenenate ring formation. The crystal structures of 26 and 27 exhibited intermolecular short-range C-H...Se interactions (hydrogen bonding). Although there are four heteroatoms in carbamoyl moieties ortho to selenium capable of forming a five-membered ring on intramolecular coordination, no such intramolecular Se...X (X = N, O) interaction was observed in the crystal structure of 32. The density functional theory calculations at the B3LYP/6-31G* level predicted that for all the diformyl systems (47a-c, 48a-c), the anti,anti conformer (when both formyl oxygen atoms point away from the selenium) is more stable. This preference was found to be reversed in the monoformyl-substituted systems (50a,b, 51a,b), where the syn conformer (when formyl oxygen is near the selenium) is energetically more favorable than the anti conformer. 相似文献
63.
Frost RL Kristof J Horvath E Martens WN Kloprogge JT 《Journal of colloid and interface science》2002,251(2):350-359
Controlled rate thermal analysis (CRTA) allows the separation of adsorbed and intercalated hydrazine. CRTA displays the presence of three different types of hydrogen-bonded hydrazine in the intercalation complex: (a) The first is adsorbed loosely bonded on the kaolinite structure fully expanded by hydrazine-hydrate and liberated between approx 50 and 70 degrees C (b) The second intercalated hydrazine is lost between approx 70 and 85 degrees C. (c) The third type of intercalated-hydrazine molecule is lost in the 85-130 degrees C range. CRTA at 70 degrees C enables the removal of hydrazine-water and results in the partial collapse of the hydrazine-intercalated kaolinite structure to form a hydrazine-intercalated kaolinite. Removal of the adsorbed hydrazine enables the DRIFT spectra of the hydrazine-intercalated complex without any adsorbed hydrazine to be obtained. A band at 3626 cm(-1) attributed to the inner surface hydroxyls of kaolinite hydrogen bonded to hydrazine is observed. The intercalation of hydrazine-hydrate into kaolinite is complex and results from the different types of surface interactions of the hydrazine with the kaolinite surfaces. 相似文献
64.
J. Lawry A. Ray D. Klimesch P. Thomas J.-P. Guerbois J. Harrison 《Journal of Thermal Analysis and Calorimetry》2005,80(3):637-641
Summary Due to growing environmental concerns and the need to use less energy-intensive building products, alternatives and improvements to Portland cement (PC) are being actively researched worldwide. Use of supplementary materials is now a common practice where PC is the predominant component of inorganic building products. This study aims to investigate the potential of magnesia (MgO), derived from a naturally occurring raw material magnesite, as a supplementary material. Results from mortar samples prepared with 10 and 20% replacements of ordinary Portland cement (OPC) by MgO are presented. DTA-TG was used to study and characterise the hydration behaviour of MgO in OPC environment after 3, 7, 14, 28, 56 and 90 days of moist curing. Microstructural and compressive strength determinations providing additional information on the influence of hydrated phases are also reported. 相似文献
65.
Reaction of Hg(S7N)2 with cis- PtCl2(PR3)2 (PR3 = PPh3, PPh2Me, PPHMe2, PEt3) in the presence of Na[PF6] gives [Pt(S3N)(PR3)2][PF6] in 32–46% yield. The complexes have been characterized by IR, NMR and microanalyses. The X-ray crystal structures of two examples (PR3 = PPh2Me and PEt3) show that the S3N− ligand coordinates in a bidentate fashion via two sulphur atoms. 相似文献
66.
Frost RL Erickson KL 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(1-2):51-56
The hydrotalcite minerals stitchtite, iowaite and desautelsite together with the arsenate exchanged takovite and arsenate exchanged hydrotalcite have been studied using near-IR reflectance spectroscopy. Each mineral has its own characteristic NIR spectrum enabling recognition of the particular hydrotalcite. As such the technique has application in the field for the analysis and identification of hydrotalcites. Hydrotalcites have proven useful as an anion exchange material. Takovite and hydrotalcite were used to exchange carbonate anions by arsenate. Three Near-IR spectral regions are identified: (a) the high wavenumber region between 6400 and 7400 cm(-1) attributed to the first overtone of the fundamental hydroxyl stretching mode, (b) the 4800-5400 cm(-1) region attributed to water combination modes of the hydroxyl fundamentals of water, and (c) the 4000-4800 cm(-1) region attributed to the combination of the stretching and deformation modes of the MOH units of the hydrotalcites. NIR spectroscopy enables the separation of the hydroxyl bands of the water and M-OH units for the hydrotalcites. Compared with the NIR spectroscopy of the structural units of the hydrotalcites namely gibbsite and brucite, the bands are broad. 相似文献
67.
Preparation and characterization of individual peptide-wrapped single-walled carbon nanotubes 总被引:3,自引:0,他引:3
Zorbas V Ortiz-Acevedo A Dalton AB Yoshida MM Dieckmann GR Draper RK Baughman RH Jose-Yacaman M Musselman IH 《Journal of the American Chemical Society》2004,126(23):7222-7227
Two challenges for effectively exploiting the remarkable properties of single-walled carbon nanotubes (SWNTs) are the isolation of intact individual nanotubes from the raw material and the assembly of these isolated SWNTs into useful structures. In this study, we present atomic force microscopy (AFM) evidence that we can isolate individual peptide-wrapped SWNTs, possibly connected end-to-end into long fibrillar structures, using an amphiphilic alpha-helical peptide, termed nano-1. Transmission electron microscopy (TEM) and well-resolved absorption spectral features further corroborate nano-1's ability to debundle SWNTs in aqueous solution. Peptide-assisted assembly of SWNT structures, specifically in the form of Y-, X-, and intraloop junctions, was observed in the AFM and TEM images. 相似文献
68.
Frost RL Duong L Weier M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(8-9):1853-1859
A series of tungstate bearing minerals including scheelite, stolzite, ferberite, hübnerite, wolframite, russellite, tungstenian wulfenite and cuprotungstite have been analyzed by Raman microscopy. The results of the Raman spectroscopic analysis are compared with published data. These minerals are closely related and often have related paragenesis. Raman microscopy enables the selection of individual crystals of these minerals for spectroscopic analysis even though several of the minerals can be found in the same matrix because of the pargenetic relationships between the minerals. The Raman spectra are assigned according to factor group analysis and related to the structure of the minerals. These minerals have characteristically different Raman spectra. The nu1(Ag) band is observed at 909 cm(-1) and although the corresponding nu1(Bu) vibration should be inactive a minor band is observed around 894 cm(-1). The bands at 790 and 881 cm(-1) are associated with the antisymmetric and symmetric Ag modes of terminal WO2. The band at 695 cm(-1) is interpreted as an antisymmetric bridging mode associated with the tungstate chain. The nu4(Eg) band was absent for scheelite. The bands at 353 and 401 cm(-1) are assigned as either deformation modes or as r(Bg) and delta(Ag) modes of terminal WO2. The band at 462 cm(-1) has an equivalent band in the infrared at 455 cm(-1) assigned as delta(as)(Au) of the (W2O4)n chain. The band at 508 cm(-1) is assigned as nu(sym)(Bg) of the (W2O4)n chain. 相似文献
69.
Chekmenev EY Xu RZ Mashuta MS Wittebort RJ 《Journal of the American Chemical Society》2002,124(40):11894-11899
We report here (13)C(alpha) chemical shielding parameters for central Gly residues in tripeptides adopting alpha-helix, beta-strand, polyglycine II, and fully extended 2 degrees structures. To assess experimental uncertainties in the shielding parameters and the effects of (14)N-(13)C(alpha) or (15)N-(13)C(alpha) dipolar coupling, stationary and magic angle spinning (MAS) spectra with and without (15)N decoupling were obtained from natural abundance and double-labeled samples containing [2-(13)C, (15)N]Gly. We find that accurate (<1 ppm uncertainty) shielding parameters are measured with good sensitivity and resolution in (15)N decoupled 1D or 2D MAS spectra of double-labeled samples. Compared to variations of isotropic shifts with peptide angles, those of (13)C(alpha) shielding anisotropy and asymmetry are greater. Trends relating shielding parameters to the 2 degrees structure are apparent, and the correlation of the experimental values with unscaled ab initio shielding calculations has an rms error of 3 ppm. Using the experimental data and the ab initio shielding values, the empirical trends relating the 2 degrees structure to shielding are extended to the larger range of torsion angles found in proteins. 相似文献
70.
The feasibility of remote sensing by means of two-photon excited molecular fluorescence was investigated by using a single 115-m multimode optical fibr.Because of modal dispersion and reflecton of Rayleigh scatter, time-resolved detection ws required to resolve the weak fluorescence from the relatively intense laser background. The bare-ended probe, which both delivered the excitation and collected the fluorescence emission, was employed to detect an analyte in an optically dense environment. For a fixed amount of fluorophore, the solvent was continuously changed from 90% (w/w) ethanol (non-absorbing) to 100% acetone (absorbing). The result was a flurorescence signal constant to within 5%. Quantitation via one-photon excitatation using a 50-cm optical fiber demonstrated the characteristic inner filter roll-off of optically dense systems. Because of th elarge attenuation of the waveguide in the ultraviolet range, remote sensing via one-photon excited fluorescence proved impossible. However, linear calibration plots for the nonlinear excitation process were obtained from micromolar to near saturation levels. Sources of interference were isolated, and the extension to a single-mode fiber was made. 相似文献