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991.
Paulo J. Amorim Madeira Ana Raquel Fernandes Sitoe Daniel Gonçalves Tiago Rodrigues Rita C. Guedes Francisca Lopes Rui Moreira M. Rosário Bronze 《Journal of the American Society for Mass Spectrometry》2014,25(9):1650-1661
The gas-phase behavior of 12 quinolon-4(1H)-imine derivatives with antiplasmodial activity was investigated using electrospray ionization tandem mass spectrometry together with collision induced dissociation and density functional theory (DFT) calculations. The most probable protonation site was predicted by calculating the proton affinity (PA) values for each possible protonation site and it was found to be the imine nitrogen for all compounds under study. Fragmentation pathways of the protonated molecules were proposed and the assignment of product ion structures was performed taking into account theoretical calculations. The nature of the quinoline substituent was found to influence the gas-phase behavior of the compounds under study. The data acquired allowed to bracket the proton affinity of the quinolin-4-imine scaffold, which can be a useful starting point to choose appropriate references for determining PA values of this scaffold. Figure
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992.
Effects of Cations on Protein and Peptide Charging in Electrospray Ionization from Aqueous Solutions
Anna C. Susa Daniel N. Mortensen Evan R. Williams 《Journal of the American Society for Mass Spectrometry》2014,25(6):918-927
The effects of eight different cations with ionic radii between 69 and 337 pm on the charging of peptides and proteins with electrospray ionization from aqueous acetate salt solutions are reported. Significant adduction occurs for all cations except NH4 +, and the average protein charge is lower when formed from solutions containing salts compared with solutions without salts added. Circular dichroism and ion mobility results show the protein conformations are different in pure water compared with salt solutions, which likely affects the extent of charging. The average charge of protein and peptide ions formed from solutions with Li+ and Cs+, which have Gibbs solvation free energies (GSFEs) that differ by 225 kJ/mol, is similar. Lower charge states are typically formed from solutions with tetramethylammonium and tetraethylammonium that have lower GSFE values. Loss of the larger cations that have the lowest GSFEs is facile when adducted protein ions are collisionally activated, resulting in the formation of lower analyte charge states. This reaction pathway provides a route to produce abundant singly protonated protein ions under native mass spectrometry conditions. The average protein and peptide charge with NH4 + is nearly the same as that with Rb+ and K+, cations with similar GSFE and ionic radii. This indicates that proton transfer from NH4 + to proteins plays an insignificant role in the extent of protein charging in native mass spectrometry. Figure
? 相似文献
993.
Cătălin Tănase Lucia Odochian Tiberius Balaeş Gabriela Lisă Daniel Gherca Aurel Pui 《Journal of Thermal Analysis and Calorimetry》2014,115(1):947-953
This paper is aimed to analyse the thermal behaviour in air of edible mushrooms through nonisothermal (TG, DTG, DTA) and calorimetric (Berthelot calorimeter) methods. The studied mushrooms were Pleurotus ostreatus spontaneously grown and from culture and Agaricus bisporus from culture, currently used in alimentation but insufficiently investigated from this point of view. The analysis of TG–DTG–DTA curves has indicated that the degradation mechanism is complex and characteristic to every species and major differences between the cap and the stipe of investigated mushrooms have not been recorded. These species are thermally stable in the range of 30–160 °C. The thermal stability in terms of initial degradation temperature (T i °C) and the temperature corresponding to the conversion grade (T α=0.03 °C) indicate that the stipe has a thermal stability close to the cap one and that the cultivated mushrooms are more thermally stable than those spontaneously grown. The obtained results concerning the combustion of the sample using Berthelot calorimeter are in accordance with the TG–DTG–DTA analysis. The residue obtained is a measure of the mineral content and is quantitatively close. 相似文献
994.
Meng Li Hong‐Ye Bai Zu‐Lin Da Xu Yan Chao Chen Jin‐Hui Jiang Wei‐Qiang Fan Wei‐Dong Shi 《Crystal Research and Technology》2015,50(3):244-249
CaFe2O4/MgFe2O4 nanowires with heterostructure had been successfully synthesized by electrospinning method. The obtained samples were systematically characterized by scanning electron microscopy (SEM), X‐Ray diffraction (XRD), UV–Vis diffuse reflectance spectra (UV‐Vis DR) and Environment scanning electron microscopy (ESEM). The novel CaFe2O4/MgFe2O4 nanowires exhibit an enhanced photocatalytic activity for degrading of tetracycline (TC) under visible light. Compared with bare CaFe2O4 or MgFe2O4 samples, the prepared CaFe2O4/MgFe2O4 (Ca:Mg:Fe = 3:2:10) composited nanowires show the best photocatalytic performance with a degradation efficiency of 40% after 150 min reaction time. This enhancement is attributed to the heterostructure of CaFe2O4/MgFe2O4 nanowires, which effectively repress the recombination of photo‐generated electrons and holes. Based on heterostructure and energy band positions, the enhancement of mechanism under visible‐light enhances the photocatalytic activity. 相似文献
995.
Isabela P. Veronez Josiane S. P. Daniel Jerusa S. Garcia Marcello G. Trevisan 《Journal of Thermal Analysis and Calorimetry》2014,115(3):2407-2414
Desloratadine (DL) is a selective antagonist of the histamine H1 receptor, which has been widely used to treat allergic symptoms, and stands out from other drugs in this therapeutic class because it does not cause sedative effects. In the present study, the physico-chemical properties of DL were fully characterized using six analytical techniques such as Differential Scanning Calorimetry (DSC), Thermogravimetric analysis (TG/DTG), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, Powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). The DSC curve shows a sharp endothermic event at 158.4 °C, and the TG/DTG curve presents two decomposition events between 178.4 and 451.9 °C. A compatibility study involving DL and nine pharmaceutical excipients generally used in pharmaceutical formulations was performed. Physical binary mixtures of DL with each excipient were prepared in a 1:1 (w/w) ratio. After preparation, the samples were analyzed immediately and the results reveal solid-state interaction with anhydrous lactose, microcrystalline cellulose, magnesium stearate, and stearic acid. 相似文献
996.
Petr Brázda Eva Večerníková Eva Pližingrová Adriana Lančok Daniel Nižňanský 《Journal of Thermal Analysis and Calorimetry》2014,117(1):85-91
Thermal behavior of highly crystalline ε-Fe2O3 nanoparticles of different apparent crystallite sizes was characterized using thermogravimetry, differential thermal analysis, and analysis of evolved gas by mass spectrometry. Phase composition of the samples was monitored ex situ by X-ray powder diffraction. The results show that the thermal stability of this metastable iron oxide polymorph decreases with increasing particle size. For the particle diameter of 19(2) nm, the transformation temperature was equal to 794(5) °C, while for 28(2) nm only 755(10) °C. Surface of the nanoparticles contained adsorbed water and carbon dioxide. Elimination of these species proceeds in two steps. Water is removed at temperatures below 200 °C and CO2 in the temperature range between 200 and 450 °C. 相似文献
997.
Dr. Steve Y. Rhieu Dr. Aaron A. Urbas Dr. Daniel W. Bearden Dr. John P. Marino Dr. Katrice A. Lippa Dr. Vytas Reipa 《Angewandte Chemie (International ed. in English)》2014,53(2):447-450
Non‐invasive and real‐time analysis of cellular redox processes has been greatly hampered by lack of suitable measurement techniques. Here we describe an in‐cell nuclear magnetic resonance (NMR) based method for measuring the intracellular glutathione redox potential by direct and quantitative measurement of isotopically labeled glutathione introduced exogenously into living yeast. By using this approach, perturbations in the cellular glutathione redox homeostasis were also monitored as yeast cells were subjected to oxidative stress. 相似文献
998.
Acylsilanes in Rhodium(III)‐Catalyzed Directed Aromatic C–H Alkenylations and Siloxycarbene Reactions with CC Double Bonds 下载免费PDF全文
Peter Becker Dr. Daniel L. Priebbenow Ramona Pirwerdjan Prof. Dr. Carsten Bolm 《Angewandte Chemie (International ed. in English)》2014,53(1):269-271
Acylsilanes are known to undergo a 1,2‐silicon‐to‐oxygen migration under thermal or photochemical conditions to form siloxycarbenes. However, there are few reports regarding the application of siloxycarbenes in organic synthesis and surprisingly, their reaction with C? C double or triple bonds remains virtually unexplored. To facilitate such a study, previously inaccessible aromatic acylsilanes containing an ortho‐tethered C? C double bond were identified as suitable substrates. To access these key intermediates, we developed a new synthetic method utilizing a rhodium‐catalyzed oxidative Heck‐type olefination involving the application of an acylsilane moiety as a directing group. When exposed to visible‐light irradiation, the ortho‐olefinated acylsilanes underwent a smooth intramolecular cyclization process to afford valuable indanone derivatives in quantitative yields. This result paves the way for the development of new transformations involving siloxycarbene intermediates. 相似文献
999.
Dehydrogenative Meyer–Schuster‐Like Rearrangement: A Gold‐Catalyzed Reaction Generating an Alkyne 下载免费PDF全文
M. Sc. Yang Yu M. Sc. Weibo Yang M. Sc. Daniel Pflästerer Prof. Dr. A. Stephen K. Hashmi 《Angewandte Chemie (International ed. in English)》2014,53(4):1144-1147
Easily accessible propargylic esters are converted to the inverted alkynyl ketones in an oxidative gold‐catalyzed reaction. Gagosz’s catalyst in combination with PhI(OAc)2 is the best system for this conversion and 18 examples with yields up to 80 % are reported. The results indicate that the triple bond in the product is formed by elimination from a vinylgold intermediate. In a formal sense the new conversion overall is a dehydrogenative Meyer–Schuster rearrangement. 相似文献
1000.
Ortal Haik Francis Susai Amalraj Daniel Hirshberg Luba Burlaka Michael Talianker Boris Markovsky Ella Zinigrad Doron Aurbach Jordan K. Lampert Ji-Yong Shin Martin Schulz-Dobrick Arnd Garsuch 《Journal of Solid State Electrochemistry》2014,18(8):2333-2342
Thermodynamic instability of positive electrodes (cathodes) in Li-ion batteries in humid air and battery solutions results in capacity fading and batteries degradation, especially at elevated temperatures. In this work, we studied thermal interactions between cathode materials Li2MnO3, xLi2MnO3 .(1???x)Li(MnNiCo)O2,LiNi0.33Mn0.33Co0.33O2, LiNi0.4Mn0.4Co0.2O2, LiNi0.8Co0.15Al0.05O2 LiMn1.5Ni0.5O4, LiMn(or Fe)PO4, and battery solutions containing ethylene carbonate (EC) or propylene carbonate (PC), dimethyl carbonate (DMC) or ethylmethyl carbonate (EMC) and LiPF6 salt in the temperature range of 40–400 °C. It was found that these materials are stable chemically and well performing in LiPF6-based solutions up to 60 °C. The thermal decomposition of the electrolyte solutions starts >180 °C. The macro-structural transformations of cathode materials upon exothermic reactions were studied by transmission electron microscopy (TEM), X-ray difraction (XRD) and Raman spectroscopy. Differential scanning calorimetry (DSC) studies have shown that the exothermic reactions in the temperature range of 60–140 °C lead to partial decomposition of both the cathode material and electrolyte solution. The systems thus formed consisted of partially decomposed solutions and partially chemically delithiated cathode materials covered by reactions products. Thermal reactions terminate and this system reaches equilibrium at about 120 °C. It remains stable up to the beginning of the solution decomposition at about 180 °C. The increased content of surface Li2CO3 is found to significantly affect the thermal processes at high temperature range due to extensive exothermic decomposition at low temperatures. 相似文献