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911.
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
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912.
Mohammad Hayatifar Luca Bernazzani Anna Maria Raspolli Galletti 《Journal of Thermal Analysis and Calorimetry》2014,115(2):1711-1718
Random ethylene/1-hexene copolymers with the 1-hexene content in the range from 2 to 28 mol% were produced with a novel post-metallocene catalyst and analyzed by three techniques, FTIR, 13C NMR, and DSC. The 1-hexene content and the sequence distribution in the copolymers were determined by means of FTIR-M and 13C NMR. The crystallization behavior of the copolymers was studied by DSC under dynamic and isothermal conditions; the Avrami model was used to analyze the crystallization kinetics. It was found that both the 1-hexene content and the crystallization temperature affect the relative crystallinity. The bulk crystallization rate decreases with the 1-hexene content and reduces exponentially with an increase of T c. The melting behavior of isothermally crystallized samples was also investigated and it was found that the melting temperatures of the copolymers under equilibrium conditions were related to the composition. 相似文献
913.
Nataliia Yu. Strutynska Marina A. Bondarenko Ivan V. Ogorodnyk Igor V. Zatovsky Nikolay S. Slobodyanik Vyacheslav N. Baumer Anna N. Puzan 《Crystal Research and Technology》2015,50(7):549-555
The interaction in the molten system Rb2O‐P2O5‐TiO2‐NiO was investigated at different molar ratios Rb/P = 0.5‐1.3, fixed Ti/P = 0.15, Ti/Ni = 1.0 at temperature range 1073–953 K. The conditions of formation of complex phosphates RbTi2(PO4)3, Rb2Ni0.5Ti1.5(PO4)3 and RbNiPO4 have been determined. The new phosphate Rb2Ni0.5Ti1.5(PO4)3 (space group P213, a = 9.9386(2) Å) has been obtained and investigated by the single crystal X‐ray diffraction and FTIR‐spectroscopy. It has langbeinite‐like structure, that is built up from mixed (Ni/Ti)O6‐octahedra and РО4‐tetrahedra. Rubidium atoms are located in closed cavities of 3D‐framework. 相似文献
914.
Structure‐Based Design of Inhibitors of the Aspartic Protease Endothiapepsin by Exploiting Dynamic Combinatorial Chemistry 下载免费PDF全文
Milon Mondal Nedyalka Radeva Dr. Helene Köster Dr. Ahyoung Park Dr. Constantinos Potamitis Dr. Maria Zervou Prof. Dr. Gerhard Klebe Dr. Anna K. H. Hirsch 《Angewandte Chemie (International ed. in English)》2014,53(12):3259-3263
Structure‐based design (SBD) can be used for the design and/or optimization of new inhibitors for a biological target. Whereas de novo SBD is rarely used, most reports on SBD are dealing with the optimization of an initial hit. Dynamic combinatorial chemistry (DCC) has emerged as a powerful strategy to identify bioactive ligands given that it enables the target to direct the synthesis of its strongest binder. We have designed a library of potential inhibitors (acylhydrazones) generated from five aldehydes and five hydrazides and used DCC to identify the best binder(s). After addition of the aspartic protease endothiapepsin, we characterized the protein‐bound library member(s) by saturation‐transfer difference NMR spectroscopy. Cocrystallization experiments validated the predicted binding mode of the two most potent inhibitors, thus demonstrating that the combination of de novo SBD and DCC constitutes an efficient starting point for hit identification and optimization. 相似文献
915.
916.
A Deadly Organometallic Luminescent Probe: Anticancer Activity of a ReI Bisquinoline Complex 下载免费PDF全文
Dr. Igor Kitanovic Suzan Can Dr. Hamed Alborzinia Dr. Ana Kitanovic Vanessa Pierroz Anna Leonidova Dr. Antonio Pinto Priv. Doz. Dr. Bernhard Spingler Priv. Doz. Dr. Stefano Ferrari Roberto Molteni Dr. Andreas Steffen Prof. Dr. Nils Metzler‐Nolte Prof. Dr. Stefan Wölfl Prof. Dr. Gilles Gasser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(9):2496-2507
The photophysical properties of [Re(CO)3(L ‐N3)]Br (L ‐N3=2‐azido‐N,N‐bis[(quinolin‐2‐yl)methyl]ethanamine), which could not be localized in cancer cells by fluorescence microscopy, have been revisited in order to evaluate its use as a luminescent probe in a biological environment. The ReI complex displays concentration‐dependent residual fluorescence besides the expected phosphorescence, and the nature of the emitting excited states have been evaluated by DFT and time‐dependent (TD) DFT methods. The results show that fluorescence occurs from a 1LC/MLCT state, whereas phosphorescence mainly stems from a 3LC state, in contrast to previous assignments. We found that our luminescent probe, [Re(CO)3(L ‐N3)]Br, exhibits an interesting cytotoxic activity in the low micromolar range in various cancer cell lines. Several biochemical assays were performed to unveil the cytotoxic mechanism of the organometallic ReI bisquinoline complex. [Re(CO)3(L ‐N3)]Br was found to be stable in human plasma indicating that [Re(CO)3(L ‐N3)]Br itself and not a decomposition product is responsible for the observed cytotoxicity. Addition of [Re(CO)3(L ‐N3)]Br to MCF‐7 breast cancer cells grown on a biosensor chip micro‐bioreactor immediately led to reduced cellular respiration and increased glycolysis, indicating a large shift in cellular metabolism and inhibition of mitochondrial activity. Further analysis of respiration of isolated mitochondria clearly showed that mitochondrial respiratory activity was a direct target of [Re(CO)3(L ‐N3)]Br and involved two modes of action, namely increased respiration at lower concentrations, potentially through increased proton transport through the inner mitochondrial membrane, and efficient blocking of respiration at higher concentrations. Thus, we believe that the direct targeting of mitochondria in cells by [Re(CO)3(L ‐N3)]Br is responsible for the anticancer activity. 相似文献
917.
Back Cover: Chemical Preparation of Graphene Materials Results in Extensive Unintentional Doping with Heteroatoms and Metals (Chem. Eur. J. 48/2014) 下载免费PDF全文
918.
919.
920.
HUA Wei-Bo ZHENG Zhuo LI Long-Yan GUO Xiao-Dong LIU Heng SHEN Chong-Heng WU Zhen-Guo ZHONG Ben-He HUANG Ling 《物理化学学报》2014,30(8):1481-1486
采用氨蒸发诱导法成功制备出纳米结构LiNi1/3Co1/3Mn1/3O2正极材料,借助X射线衍射(XRD)分析、扫描电镜(SEM)、透射电镜(TEM)、高分辨率透射电镜(HRTEM)、能量分散谱(EDS)和比表面测试等表征手段及恒电流充放电测试研究了其晶体结构、微观形貌和电化学性能.研究表明该方法制备出的材料具有良好的α-NaFeO2层状结构,阳离子混排程度低.纳米片交错堆积而成核桃仁状形貌,片与片之间形成许多纳米孔,而且纳米片的侧面属于{010}活性面,能够提供较多的锂离子的脱嵌通道.在室温下及3.0-4.6 V充放电范围内,该材料在电流密度为0.5C、1C、3C、5C和10C时放电比容量分别为172.90、153.95、147.09、142.16和131.23mAh?g-1.说明其具有优异的电化学性能,非常有潜力用于动力汽车等高功率密度锂离子电池中. 相似文献