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31.
A spectrophotometric flow-injection procedure is described for fluoride in aqueous samples. The method is based on the decrease in absorbance of the zirconium/alizarin red S complex at 520 nm; linear response is obtained for the range 0.1–10 mg l?1 fluoride at a sampling rate of 100 h?1. Aluminum(III), iron(III) and phosphate interfere. 相似文献
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Dr. Jacorien Coetzee Dr. Deborah L. Dodds Prof. Jürgen Klankermayer Sandra Brosinski Prof. Walter Leitner Prof. Alexandra M. Z. Slawin Prof. David J. Cole‐Hamilton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):11039-11050
Hydrogenation of amides in the presence of [Ru(acac)3] (acacH=2,4‐pentanedione), triphos [1,1,1‐tris‐ (diphenylphosphinomethyl)ethane] and methanesulfonic acid (MSA) produces secondary and tertiary amines with selectivities as high as 93 % provided that there is at least one aromatic ring on N. The system is also active for the synthesis of primary amines. In an attempt to probe the role of MSA and the mechanism of the reaction, a range of methanesulfonato complexes has been prepared from [Ru(acac)3], triphos and MSA, or from reactions of [RuX(OAc)(triphos)] (X=H or OAc) or [RuH2(CO)(triphos)] with MSA. Crystallographically characterised complexes include: [Ru(OAc‐κ1O)2(H2O)(triphos)], [Ru(OAc‐κ2O,O′)(CH3SO3‐κ1O)(triphos)], [Ru(CH3SO3‐κ1O)2(H2O)(triphos)] and [Ru2(μ‐CH3SO3)3(triphos)2][CH3SO3], whereas other complexes, such as [Ru(OAc‐κ1O)(OAc‐κ2O,O′)(triphos)], [Ru(CH3SO3‐κ1O)(CH3SO3‐κ2O,O′)(triphos)], H[Ru(CH3SO3‐κ1O)3(triphos)], [RuH(CH3SO3‐κ1O)(CO)(triphos)] and [RuH(CH3SO3‐κ2O,O′)(triphos)] have been characterised spectroscopically. The interactions between these various complexes and their relevance to the catalytic reactions are discussed. 相似文献
35.
A novel water-soluble solvatochromic molecule, 7-(dimethylamino)-2-fluorenesulfonate (2,7-DAFS), was prepared by a three-step
reaction from 2-nitrofluorene in good overall yield. The pH and solvent effects on the UV-VIS absorption and fluorescence
spectra of 2,7-DAFS have been studied. Protonation of the dimethylamino group switches the absorption from intramolecular
charge-transfer (ICT) to π → π* transition. The ground state pKa value of 2,7-DAFS was determined as 4.51. The fluorescence spectrum of the excited basic form, *(DAFS), shows a structureless
single band with a large Stokes shift, whereas that of the acidic form, *(+HDAFS), exhibits a structured band with a small Stokes shift. The emission intensities of the basic and acidic forms versus
pH/Ho plots show stretched sigmoidal curves and indicate that (1) the rate of deprotonation of *(+HDAFS) is comparable to the fluorescence decay of the species, and (2) the efficient proton-induced quenching of *(DAFS) fluorescence
occurs. The pKa* was estimated as −1.7 from the fluorescence titration curve. The fluorescence maximum of *(DAFS) is blue-shifted as the
polarity of solvent decreases. However, no clear dependency of the emission intensity and spectral half width, and thus fluorescence
quantum yield, on the solvent polarity was revealed. It appears that the fluorescence sensitivity of 2,7-DAFS is 15 ∼ 25 times
greater than the sensitivity of a widely utilized fluorescent probe, 5-(dimethylamino)-1-naphthalenesulfonate. This higher
sensitivity, together with the ease of derivatization, would provide the fluorene-based fluorescent molecules significant
advantages for a variety of applications. 相似文献
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Perini Nickson Delmonde Marcelo V. F. Ranjan Chinmoy Varela Hamilton 《Journal of Solid State Electrochemistry》2020,24(8):1811-1818
Journal of Solid State Electrochemistry - The characteristics of the electrochemical oscillations that emerge along the catalytic oxidation of small organic molecules critically depend on the... 相似文献
37.
F. J. Martínez Crespo J. A. Palop Y. Sainz S. Narro V. Senador M. Gonzlez A. Lpez De Cerin A. Monge E. Hamilton A. J. Barker 《Journal of heterocyclic chemistry》1996,33(6):1671-1677
Several quinoxaline 1,4-di-N-oxides have been shown to be efficient and selective cytotoxins for hypoxic cells. We present now a series of 4-cyano-2-oxo-1,2,4-oxadiazolo[2,3-a]quinoxaline 5-N-oxides 2a-2k . They were prepared starting from 3-amino-2-quinoxalinecarbonitrile 1,4-di-N-oxides 1a-1k and 2-chloroethyl isocyanate in dry dioxane at 100–110°. A reaction mechanism is proposed. The treatment of 1a with phenyl isocyanate afforded 2a . Reaction of 2c with silica gel yielded 1c . Compounds 2a-2g were heated in the presence of ethanol and 2-propanol giving the corresponding carbamates 3a-3g and 4a-4g . Compound 2d was already obtained by heating a mixture of 1d and ethyl chloroformiate. Compound 2b was prepared when the carbamate 3b was heated at 150°. Quinoxalines were tested as cytotoxic agents both in oxic and hypoxic cells. The most interesting compounds were 3g and 4g . 相似文献
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John de Jersey ZHENG Yuan-zhi FAN Hong-kuan Gary Schenk Luke Guddat Susan Hamilton 《高等学校化学研究》2006,22(2):263-264
Introduction Purpleacidphosphatases(PAPs)compriseofa familyofbinuclearmetal containinghydrolases,some membersofwhichhavebeenisolatedandcharacterized fromanimal,plantandfungalsources[1].PAPsnoton lycatalyzethehydrolysesofawiderangeofphosphate estersandanhy… 相似文献
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Kalin RM Hamilton JT Harper DB Miller LG Lamb C Kennedy JT Downey A McCauley S Goldstein AH 《Rapid communications in mass spectrometry : RCM》2001,15(5):357-363
Gas chromatography/mass spectrometry/isotope ratio mass spectrometry (GC/MS/IRMS) methods for delta(13)C measurement of the halomethanes CH(3)Cl, CH(3)Br, CH(3)I and methanethiol (CH(3)SH) during studies of their biological production, biological degradation, and abiotic reactions are presented. Optimisation of gas chromatographic parameters allowed the identification and quantification of CO(2), O(2), CH(3)Cl, CH(3)Br, CH(3)I and CH(3)SH from a single sample, and also the concurrent measurement of delta(13)C for each of the halomethanes and methanethiol. Precision of delta(13)C measurements for halomethane standards decreased (+/-0.3, +/-0.5 and +/-1.3 per thousand) with increasing mass (CH(3)Cl, CH(3)Br, CH(3)I, respectively). Given that carbon isotope effects during biological production, biological degradation and some chemical (abiotic) reactions can be as much as 100 per thousand, stable isotope analysis offers a precise method to study the global sources and sinks of these halogenated compounds that are of considerable importance to our understanding of stratospheric ozone destruction. 相似文献
40.