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131.
Maier CS Yan X Harder ME Schimerlik MI Deinzer ML Pasa-Tolić L Smith RD 《Journal of the American Society for Mass Spectrometry》2000,11(3):237-243
The potential of electrospray ionization (ESI) Fourier transform ion cyclotron mass spectrometry (FTICR-MS) to assist in the structural characterization of monomeric and dimeric derivatives of the macrophage colony stimulating factor beta (rhM-CSF beta) was assessed. Mass spectrometric analysis of the 49 kDa protein required the use of sustained off-resonance irradiation (SORI) in-trap cleanup to reduce adduction. High resolution mass spectra were acquired for a fully reduced and a fully S-cyanylated monomeric derivative (approximately 25 kDa). Mass accuracy for monomeric derivatives was better than 5 ppm, after applying a new calibration method (i.e., DeCAL) which eliminates space charge effects upon high accuracy mass measurements. This high mass accuracy allowed the direct determination of the exact number of incorporated cyanyl groups. Collisionally induced dissociation using SORI yielded b- and y-fragment ions within the N- and C-terminal regions for the monomeric derivatives, but obtaining information on other regions required proteolytic digestion, or potentially the use of alternative dissociation methods. 相似文献
132.
Najat Aburas Aleksandar Loli? Nikola Stevanovi? Tatjana Tripkovi? Sne?ana Nikoli?-Mandi? Rada Bao?i? 《Journal of the Iranian Chemical Society》2012,9(6):859-864
This study describes the effects of the substituents on electrochemical behavior and antioxidant activity of the six tetradentate Schiff bases, containing ethane-1,2-diamine or propane-1,2-diamine as the amine part and pentane-2,4-dione and/or 1-phenylbutane-1,3-dione as ??-diketone, and corresponding copper(II) complexes. Cyclic voltammograms of these compounds were recorded in dimethylsulfoxide and 0.1?M sodium perchlorate as supporting electrolyte with glassy carbon as working electrode at different scan rates. The voltammograms of Schiff bases alone showed only one irreversible peak. Voltammograms recorded for complexes showed the presence of quasi-reversible processes taking place at the metal center and reversible process at the ligand part. Both steric and inductive effects of substituents and structure of imine bridge of Schiff base ligands as well as complexes were discussed. These effects appear relevant for the antioxidant activity. Antioxidant activity of the investigated compounds expressed as Trolox equivalent antioxidant capacity is also discussed. The electrochemical behavior showed a high correlation with the antioxidant activity for investigated compounds. 相似文献
133.
A Giuliani AR Milosavljević K Hinsen F Canon C Nicolas M Réfrégiers L Nahon 《Angewandte Chemie (International ed. in English)》2012,51(38):9552-9556
Photoionization of protein ions: The ionization energy of polyprotonated protein cations in the gas phase measured using VUV synchrotron radiation appears to be correlated with the charge state z of the protein and its tertiary structure. A simple electrostatic model accounts for the results and also shows predictive capabilities to derive a mean radius R(m) of the protein ion from the ionization energy, and vice versa. 相似文献
134.
135.
Pašalić H Tunega D Aquino AJ Haberhauer G Gerzabek MH Lischka H 《Physical chemistry chemical physics : PCCP》2012,14(12):4162-4170
The thermodynamic stability of the acetic acid dimer conformers in microhydrated environments and in aqueous solution was studied by means of molecular dynamics simulations using the density functional based tight binding (DFTB) method. To confirm the reliability of this method for the system studied, density functional theory (DFT) and second order M?ller-Plesset perturbation theory (MP2) calculations were performed for comparison. Classical optimized potentials for liquid simulations (OPLS) force field dynamics was used as well. One focus of this work was laid on the study of the capabilities of water molecules to break the hydrogen bonds of the acetic acid dimer. The barrier for insertion of one water molecule into the most stable cyclic dimer is found to lie between 3.25 and 4.8 kcal mol(-1) for the quantum mechanical methods, but only at 1.2 kcal mol(-1) for OPLS. Starting from different acetic acid dimer structures optimized in gas phase, DFTB dynamics simulations give a different picture of the stability in the microhydrated environment (4 to 12 water molecules) as compared to aqueous solution. In the former case all conformers are converted to the hydrated cyclic dimer, which remains stable over the entire simulation time of 1 ns. These results demonstrate that the considered microhydrated environment is not sufficient to dissociate the acetic acid dimer. In aqueous solution, however, the DFTB dynamics shows dissociation of all dimer structures (or processes leading thereto) starting after about 50 ps, demonstrating the capability of the water environment to break up the relatively strong hydrogen bridges. The OPLS dynamics in the aqueous environment shows--in contrast to the DFTB results--immediate dissociation, but a similar long-term behavior. 相似文献
136.
Chen R Trieu V Zeradjanin AR Natter H Teschner D Kintrup J Bulan A Schuhmann W Hempelmann R 《Physical chemistry chemical physics : PCCP》2012,14(20):7392-7399
Sol-gel Ru(0.3)Sn(0.7)O(2) electrode coatings with crack-free and mud-crack surface morphology deposited onto a Ti-substrate are prepared for a comparative investigation of the microstructural effect on the electrochemical activity for Cl(2) production and the Cl(2) bubble evolution behaviour. For comparison, a state-of-the-art mud-crack commercial Ru(0.3)Ti(0.7)O(2) coating is used. The compact coating is potentially durable over a long term compared to the mud-crack coating due to the reduced penetration of the electrolyte. Ti L-edge X-ray absorption spectroscopy confirms that a TiO(x) interlayer is formed between the mud-crack Ru(0.3)Sn(0.7)O(2) coating and the underlying Ti-substrate due to the attack of the electrolyte. Meanwhile, the compact coating shows enhanced activity in comparison to the commercial coating, benefiting from the nanoparticle-nanoporosity architecture. The dependence of the overall electrode polarization behaviour on the local activity and the bubble evolution behaviour for the Ru(0.3)Sn(0.7)O(2) coatings with different surface microstructure are evaluated by means of scanning electrochemical microscopy and microscopic bubble imaging. 相似文献
137.
Hyejeong Yun Yeonkuk Jung Kyung Haeng Lee Hyun Pa Song Keehyuk Kim Cheorun Jo 《Radiation Physics and Chemistry》2012,81(8):1163-1165
Irradiation is an excellent method for improving the safety and functional properties of egg. However, the internal quality of egg can be deteriorated due to a rapid decrease in Haugh units. In this study, the optimal conditions for maintaining the quality and maximizing the safety and functional properties of egg were determined when combination of irradiation and chitosan coating was treated using response surface methodology (RSM). Independent degradation parameters—irradiation dose (0–2 kGy) and concentration of chitosan coating (0–2%) were assigned (?2,–1, 0, 1, 2), and 10 intervals were set on the basis of central composite design for the degradation experiment. The dependant variables within a confidence level less than 5% were Haugh units, foaming ability, foam stability, and number of Salmonella typhimurium. The predicted maximum values of Haugh units and foaming ability were 82.7 (irradiation dose 0.0006 kGy and concentration of chitosan solution 1.03%) and 62.2 mm (1.99 kGy and 0.86%), respectively. S. typhimurium inoculated on the egg surface was not detected after 1.86 kGy and 0.48%. Based on superimposing four-dimensional RSM with respect to freshness (Haugh units), functional property (foaming capacity and foam stability), and reduction of S. typhimurium, the predicted optimum ranges for irradiation dose and chitosan solution concentration were 0.35–0.65 kGy and 0.25–0.85%, respectively. The predicted optimum values were obtained from 0.45 kGy and 0.525%. This methodology can be used to predict egg quality and safety when different combination treatments were applied. 相似文献
138.
In this paper we introduce a simple bivariate integer-valued time series model with positively correlated geometric marginals based on the negative binomial thinning mechanism. Some properties of the model are considered. The unknown parameters of the model are estimated using the modified conditional least squares method. 相似文献
139.
P Dolashka F Zal A Dolashki L Molin P Traldi B Salvato 《Journal of mass spectrometry : JMS》2012,47(7):940-947
The understanding of the function of macromolecular complexes is mainly related to a precise knowledge of their structure. Recently, the development of suitable mass spectrometric techniques (electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI)) and multi-angle laser light scattering has enabled mass determination of native complexes and of their subunits. By these techniques, the structure and association/dissociation behavior of huge molecules of molluscan Octopus vulgaris, Sepia officinalis and Rapana venosa have been characterized. Molecular masses of the native and dissociated molecule of cephalopodan Hcs O. vulgaris (3545 and 359.3?kDa, respectively) and S. officinalis (4134 and 443.8?kDa, respectively) revealed that only one type subunit organizes their molecules, while the presence of two isoforms with different masses (422.8 and 400.0?kDa) has been determined for gastropodan R. venosa Hc, aggregated into didecamers. The difference of their structural subunits was also established after limited proteolysis with TPCK-trypsin. Eight functional units (FUs) with masses of?~?50?kDa were isolated from both subunits of RvH and isoform of Sepia officinalis, while seven FUs were purified from OvH. Further characterization of proteins by ESI-mass spectrometry (MS) and MALDI-MS, methods gave insights into post-translational modifications such as glycosylation. Glycosylation of O. vulgaris and S. officinalis Hcs was suggested based on the differences (11.6 and 40.0?kDa, respectively) between the masses measured by ESI-MS and those calculated by their gene sequences. 相似文献
140.
We obtain a new upper bound for the sum Σ
h≤H
Δ
k
(N, h) when 1 ≤ H ≤ N, k ∈ ℕ, k ≥ 3, where Δ
k
(N, h) is the (expected) error term in the asymptotic formula for Σ
N<n≤2N
d
k
(n)d
k
(n + h), and d
k
(n) is the divisor function generated by ζ(s)
k
. When k = 3, the result improves, for H ≥ N
1/2, the bound given in a recent work of Baier, Browning, Marasingha and Zhao, who dealt with the case k = 3. 相似文献