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131.
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Laurence E. Strong Danny J. Blubaugh Christopher R. Cavalli 《Journal of solution chemistry》1981,10(11):811-830
Precise conductance measurements are reported for four xylic acids, 2,3-2,5-2,6 and 3,5-dimethylbenzoics. Limiting molar conductances ΛO and pK a obtained from a Fuoss type analysis, are reported for each of these acids at five degree intervals covering the range from 0° to 100°C. The ΛO values for each acid are described by a polynomial in the Celsius temperature. The pK a were smoothed as a function of the Kelvin temperature T with an equation of the form: $$pK_{\text{a}} = A{\text{ }} + {\text{ }}B/T{\text{ }} + {\text{ }}C{\text{ }}logT{\text{ }} + {\text{ }}DT$$ where the term linear in T was required only for the 2,3-acid. Standard enthalpy, entropy, and heat capacity changes were calculated by suitable differentiation of this equation. Walden products were calculated for the four anions at each of the temperatures and are compared with earlier data for the toluate and the benzoate ions. Those acids with ortho groups undergo a large decrease in enthalpy on ionization and are substantially more acidic than benzoic acid. These effects are especially large for 2,6-dimethylbenzoic acid. A methyl group in the meta position lowers acidity slightly both in m-toluic and in 2,5-dimethylbenzoic acid. However, 2,3-dimethylbenzoic acid is more acidic than o-toluic. 相似文献
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Botta M Quici S Pozzi G Marzanni G Pagliarin R Barra S Geninatti Crich S 《Organic & biomolecular chemistry》2004,2(4):570-577
Five novel Gd(iii) complexes based on the structure of the heptadentate macrocyclic 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) ligand have been synthesized and their (1)H and (17)O NMR relaxometric properties investigated in detail. The complexes have been functionalised on the secondary nitrogen atom of the macrocyclic ring with different pendant groups for promoting their ability to interact non-covalently with human serum albumin (HSA). The analysis of the proton relaxivity, measured as a function of pH and magnetic field strength, have revealed that the three complexes bearing a poly(ethylene glycol)(PEG) chain possess a single coordinated water molecule, whereas the complexes functionalised with 1-[3-(2-hydroxyphenyl)]-propyl and 1-[3-(2-carboxyphenyloxy)]-propyl pendant groups have two inner sphere water molecules. The water exchange rates, measured by variable temperature (17)O NMR, cover a broad range of values (from 18 to 770 ns) as a function of their charge, the chemical nature of the substituent and its ability to organize a second sphere of hydration near the water(s) binding site. All the complexes have shown some degree of interaction with HSA, with a stronger binding affinity measured for those bearing an aromatic moiety on the pendant group. However, upon binding the expected relaxation enhancement has not been observed and this has been explained with the displacement of the coordinated water molecules by the protein and formation of ternary adducts. 相似文献
136.
[reaction: see text] A new cellulose-supported reagent for the synthesis of guanidine in aqueous medium is reported starting from commercially available functionalized cellulose beads. Primary and secondary amines, anilines, and amino acids were transformed to the corresponding guanidines in high yields and under very mild conditions. 相似文献
137.
We correct a Feynman diagram presented in the paper ‘Heavy neutral gauge bosons at the LHC in an extended MSSM’, published in Nuclear Physics B 866 (2013) 293. 相似文献
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Amino Acid Oxidation: A Combined Study of Cysteine Oxo Forms by IRMPD Spectroscopy and Simulations
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Dr. Debora Scuderi Prof. Enrico Bodo Dr. Barbara Chiavarino Prof. Simonetta Fornarini Prof. Maria Elisa Crestoni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17239-17250
The redox activity of cysteine sulfur allows numerous post‐translational protein modifications involved in the oxidative regulation of metabolism, in metal binding, and in signal transduction. A combined approach based on infrared multiple photon dissociation spectroscopy at the Centre Laser Infrarouge d'Orsay (CLIO) free electron laser facility, calculations of IR frequencies, and finite temperature ab initio molecular dynamics simulations has been employed to characterize the gas‐phase structures of deprotonated cysteine sulfenic, sulfinic, and sulfonic acids, [cysSOx]? (x=1, 2, 3, representing the number of S‐bound oxygen atoms), which are key intermediates in the redox‐switching chemistry of proteins. The ions show different structural motifs owing to preferential binding of the proton to either the carboxylate or sulfur‐containing group. Due to the decreasing basicity of the sulfenic, sulfinic, and sulfonic terminals, the proton bound to SO? in [cysSO]? migrates to the carboxylate in [cysSO3]?, whereas it turns out to be shared in [cysSO2]?. Evidence is gathered that a mixture of close‐lying low‐energy conformers is sampled for each cysteine oxo form in a Paul ion trap at room temperature. 相似文献
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