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41.
Homogeneous sets of data from strong acid-strong base potentiometric titrations in aqueous solution at various constant ionic strengths have been analysed by statistical criteria. The aim is to see whether the error distribution matches that for the equilibrium constants determined by competitive potentiometric methods using the glass electrode. The titration curve can be defined when the estimated equivalence volume VEM, with standard deviation (s.d.) sigma (VEM), the standard potential E(0), with s.d. sigma(E(0)), and the operational ionic product of water K(*)(w) (or E(*)(w) in mV), with s.d. sigma(K(*)(w)) [or sigma(E(*)(w))] are known. A special computer program, BEATRIX, has been written which optimizes the values of VEM, E(0) and K(*)(w) by linearization of the titration curve as a Gran plot. Analysis of variance applied to a set of 11 titrations in 1.0M sodium chloride medium at 298 K has demonstrated that the values of VEM belong to a normal population of points corresponding to individual potential/volume data-pairs (E(i); v(i)) of any titration, whereas the values of pK(*)(w) (or of E(*)(w)) belong to a normal population with members corresponding to individual titrations, which is also the case for the equilibrium constants. The intertitration variation is attributable to the electrochemical component of the system and appears as signal noise distributed over the titrations. The correction for junction-potentials, introduced in a further stage of the program by optimization in a Nernst equation, increases the noise, i.e., sigma(pK(*)(w)). This correction should therefore be avoided whenever it causes an increase of sigma(pK(*)(w)). The influence of the ionic medium has been examined by processing data from acid-base titrations in 0.1M potassium chloride and 0.5M potassium nitrate media. The titrations in potassium chloride medium showed the same behaviour as those in sodium chloride medium, but with an s.d. for pK(*)(w) that was smaller and close to the expected instrumental noise, whereas the titrations in nitrate medium had a high noise level and even the determination of VEM was less certain. Procedures are also proposed for obtaining reference sets of data and checking the conformity of the solutions and apparatus to the chosen reference. 相似文献
42.
Fortunelli A Leoni P Marchetti L Pasquali M Sbrana F Selmi M 《Inorganic chemistry》2001,40(13):3055-3060
The reaction of the Pt(I)Pt(I)Pt(II) triangulo cluster Pt(3)(micro-PBu(t)()(2))(3)(H)(CO)(2) (1) with TfOH (Tf = CF(3)SO(2)) affords the hydride-bridged cationic derivative [Pt(3)(mu-PBu(t)()(2))(2)(mu-H)(PBu(t)()(2)H)(CO)(2)]OTf (2). With TfOD the reaction gives selectively [Pt(3)(mu-PBu(t)(2))(2)(mu-D)(PBu(t)(2)H)(CO)(2)]OTf (2-D(1)), implying that the proton is transferred to a metal center while a P-H bond is formed by the reductive coupling of one of the bridging phosphides and the terminal hydride ligand of the reagent. The reaction proceeds through the formation of a thermally unstable kinetic intermediate which was characterized at low temperatures, and was suggested to be the CO-hydrogen-bonded (or protonated) [Pt(3)(mu-PBu(t)(2))(3)(H)(CO)(2)].HOTf (3). An ab initio theoretical study predicts a hydrogen-bonded complex or a proton-transfer tight ion pair as a possible candidate for the structure of the kinetic intermediate. 相似文献
43.
Stefano De Benedetti Camilla Leogrande Francesco Castagna Giuditta C. Heinzl Matias Pasquali Alessandro L. Heinzl Daniela Lupi Alessio Scarafoni 《Molecules (Basel, Switzerland)》2022,27(1)
The present work aimed to characterize the molecular relationships between structure and function of the seed storage protein β-vignin, the vicilin storage protein of cowpea (Vigna unguiculata, l. Walp) seeds. The molecular characterization of β-vignin was carried out firstly by assessing its thermal stability, under different conditions of pH and ionic strength, by thermal shift assay (TSA) using SYPRO Orange fluorescent dye. Secondly, its aggregation propensity was evaluated using a combination of chromatographic and electrophoretic techniques. Two forms of β-vignin were considered: the native form purified from mature quiescent seeds, and a stable breakdown intermediate of 27 kDa produced while seeds germinate. TSA is a useful tool for determining and following over time the structural changes that occur to the protein during germination. The main result was the molecular characterization of the 27 kDa intermediate breakdown polypeptide, which, to the best of our knowledge, has never been described before. β-vignin seems to retain its trimeric conformation despite the evident degradation of its polypeptides. 相似文献
44.
G. Casini M. Bini S. Calamai R. Laforest P.R. Maurenzig A. Olmi G. Pasquali S. Piantelli G. Poggi F. Saint-Laurent J.C. Steckmeyer A.A. Stefanini N. Taccetti 《The European Physical Journal A - Hadrons and Nuclei》2000,9(4):491-513
Primary and secondary masses of heavy reaction products have been deduced from kinematics and E-ToF measurements, respectively,
for the direct and reverse collisions of 93Nb and 116Sn at 25 AMeV. Light charged particles have also been measured in coincidence with the heavy fragments. Direct experimental
evidence of the correlation of energy-sharing with net mass transfer has been found using information from both the heavy
fragments and the light charged particles. The ratio of hydrogen and helium multiplicities points to a further correlation
of angular momentum sharing with net mass transfer.
Received: 18 September 2000 / Accepted: 2 December 2000 相似文献
45.
M. Girasole A. Cricenti R. Generosi A. Congiu-Castellano D. Pozzi E. Pasquali A. Lisi N. Santoro S. Grimaldi 《Applied Physics A: Materials Science & Processing》1998,67(2):219-223
Received: 18 December 1997/Accepted: 5 January 1998 相似文献
46.
Vavro J Llaguno MC Fischer JE Ramesh S Saini RK Ericson LM Davis VA Hauge RH Pasquali M Smalley RE 《Physical review letters》2003,90(6):065503
We measured thermoelectric power S of bulk single-wall carbon nanotube materials p doped with acids. In contrast to oxygen-exposed or degassed samples, S is very small at the lowest temperatures, increases superlinearly above a characteristic and sample-dependent T, and then levels off. We attribute this unusual behavior to 1D phonon drag, in which the depression of the Fermi energy cuts off electron-phonon scattering at temperatures below a characteristic T0. This idea is supported by a model calculation in which the low temperature behavior of phonon drag is specifically related to the one-dimensional character of the electronic spectrum. 相似文献
47.
Francesco P. Colonna Giuseppe Distefano Vinicio Galasso 《Journal of Electron Spectroscopy and Related Phenomena》1980,18(1):75-83
The photoelectron (He(I)) spectra of 1,4-dithiin (1), 1,4-thiaselenin (2), 1,4-thiatellurin (3) and 4H-thiopyran (4) were assigned by comparison with published spectra of similar compounds and with the help of ab initio and semi-empirical calculations. The proposed orbital sequences for the outermost orbitals are π4, π3, π2, σ for 1, 2 and 3, and π4, π2, σ, π3 for 4. π4 and π3 correspond to the symmetric and antisymmetric combinations, respectively, of the heteroatom lone pairs, while π2 is the antisymmetric combination of the πeth orbitals. 相似文献
48.
Summary A simple, fast, fully automated method for plasma serotonin determination is described. Full automation is obtained by coupling two devices: a sample processing station and a solid-phase autosampler. The sample processing station dilutes the plasma sample and is then connected, on-stream, with the solid-phase autosampler. It firstly fills a loop with all the solvents necessary for the sample clean-up, then, inverting the flow, pumps these solvents through the silica-bonded cation-exchange disposable extraction cartridge positioned on the autosampler. For the elution, the cartridge is switched on-stream with the HPLC analytical column and serotonin is eluted by the HPLC mobile-phase. The HPLC separation is performed by ion-pairing reversed-phase liquid chromatography. The column effluent is completely reduced by an electrochemical reactor and serotonin is detected in an oxidation-mode by a dual-cell electrochemical detector. The plasma sample is 50 l, the plasma sensitivity is 40 ng/l, the retention time is 6 min and the recovery is 95%. The repeatibility, the normal ranges for platelet-poor and for platelet-rich plasma have been established and correlation with manual HPLC calculated.Presented at the 17th International Symposium on Chromatography, September 25–30, 1988, Vienna, Austria. 相似文献
49.
Vinicio Galasso Giorgio Pellizer Giuseppe C. Pappalardo 《Magnetic resonance in chemistry : MRC》1977,9(7):401-403
13C n.m.r. spectra are reported for 1,2-indandione, coumarandione and thionaphthenequinone in CDCl3 solution and for isatin in dimethyl sulphoxide solution. The chemical shifts are assigned and discussed in connection with the influence of the heteroatom on the dicarbonyl group and the aromatic ring. The 13C shieldings have also been calculated by means of Pople's perturbation theory using CNDO/S wave functions. 相似文献
50.
This paper reports on a method of numerical solution of sensitive nonlinear two-point boundary-value problems. The method consists of a modification of the continuation technique in quasilinearization obtained by combination with an orthogonalization procedure for linear boundary-value problems.This work was supported by CNR, Rome, Italy, within the framework of GNAFA. 相似文献