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1.
Violetta Patroniak Wanda Radecka‐Paryzek Maciej Kubicki 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(9):o511-o513
The structure of a trifluoromethanesulfonate salt of a nontypical triply protonated linear tetramine, C7H23N43+·3CF3SO3−, with a layered crystal structure is presented. One N atom remains unprotonated. The conformation of the cation is enforced by intra‐ and intermolecular hydrogen bonds. The crystal structure is built of ca 10 Å deep layers, within which cations and anions are hydrogen bonded. Each layer is only weakly bound to its neighbours. This study shows a rare example of an unsymmetrically protonated polyamine and the relation between the lack of protonation, intramolecular hydrogen bonding and the conformation of the cation. 相似文献
2.
The selenenylation of racemic and optically active α-phosphoryl sulfoxides is a key step leading efficiently to α-phosphorylvinyl sulfoxides or α-phosphorylvinyl selenides depending on the reaction conditions. Oxidation of α-phosphorylvinyl selenides and subsequent thermolysis of selenoxides afford alkynylphosphonates. Studies of the stereochemical course of nucleophilic addition to α-phosphoryl sulfoxides show high facial stereoselectivity of the reaction, however, epimerisation at the α-carbon atom leads to mixtures of diastereomers. 相似文献
3.
Large-scale classical and quantum simulations are used to generate a-Si:H structures. The bond-resolved density of the occupied electron states discloses the nature of microscopic defects responsible for levels in the gap. Highly strained bonds give rise to band tails and midgap states. The latter originate mainly from stretched bonds, in addition to dangling bonds, and can act as hole traps. This study provides strong evidence for photoinduced degradation (Staebler-Wronski effect) driven by strain, thus supporting recent work on a-Si, and sheds light on the role of hydrogen. 相似文献
4.
The paper is focused on the phenomena of various steady-state oscillations exhibited by the twin-well potential system. Regions of existence of different attractors in the system parameter domain are examined and a picture book of different steady states for fixed damping and forcing is presented: 20 different combinations of single or coexisting, small orbit or large orbit, periodic and chaotic attractors are displayed. Computer simulations are followed by an approximate analytical analysis: A study of various forms of instability of periodic solutions gives close form approximate criteria for occurrence of T-periodic small orbit and large orbit oscillations, and for cross-well chaos. 相似文献
5.
Janusz Malarz Anna Stojakowska Wanda Kisiel 《Applied biochemistry and biotechnology》2013,170(7):1589-1601
Foam fractionation is a promising method for separation and concentration of biochemicals. It is simple, easily scalable, inexpensive, and environment friendly. Foam fractionation thus represents an alternative to the traditional methods used for immunoglobulin enrichment. However, little, if any, literature exists documenting the utilization of foam fractionation in the enrichment of immunoglobulins. Milk were utilized as an immunoglobulin source to serve as examples of a real system in this study. The investigation examined the effects of varying five different process parameters: the initial pH value, the initial concentration of immunoglobulin, the nitrogen flow rate, the column height, and the foaming time. Experimental results demonstrated that immunoglobulin could effectively be enriched from milk by foam fractionation. The maximum enrichment ratio with pretreatment (using pH 4.6 precipitation) was 6.30 along with a more than 92 % recovery for IgG and an enrichment ratio of 5.1 with 85 % recovery for IgM. 相似文献
6.
By using calculations based on density functional theory, we investigate the physical factors determining the elemental charge transfer in Alq3, taken as a prototype of molecular systems in condensed phase. The effect of the environment on the hopping of the charge carrier is evaluated self-consistently in a model in which an Alq3 dimer is embedded in an ensemble of permanent and polarizable dipoles, including orientational disorder and the presence of impurities. The results indicate that the origin of the activation barrier is mainly extrinsic and that the local orientation of the dipole moments plays a major role. The influence of nonadiabaticity is also studied and found to be more important for a hole than for an electron. 相似文献
7.
Electrospray ionization mass spectrometry (MS) has been widely used to detect noncovalent interactions in supramolecular compounds, especially in biological systems. In our work, we present the application of the electrospray ionization MS technique to characterize the metallamacrocycles, known as metallacrowns. This project involves investigations of the aminohydroxamic acids structure and chirality influence on formation of ternary 12‐metallacrown‐4 complexes. For our experiments, we used a series of β‐aminohydroxamic acids and derivatives of histidinehydroxamic acid. A high stability of the studied supramolecular systems in the gas phase was confirmed by MS/MS experiments. We also proposed the fragmentation pathways for the studied compounds. Obtained results reveal that the ternary 12‐metallacrown‐4 formation process is not selective, and ligands of various structures and chiralities can be incorporated into these systems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
8.
Bodnar WM Blackburn RK Krise JM Moseley MA 《Journal of the American Society for Mass Spectrometry》2003,14(9):971-979
The goal of this work was to evaluate the improvement in proteome coverage of complex protein mixtures gained by analyzing samples using both LC/ESI/MS/MS and LC/MALDI/MS/MS. Parallel analyses of a single sample were accomplished by interfacing a Probot fractionation system with a nanoscale LC system. The Probot was configured to perform a post-column split such that a fraction (20%) of the column effluent was sent for on-line LC/ESI/MS/MS data acquisition, and the majority of the sample (80%) was mixed with a matrix solution and deposited onto the MALDI target plate. The split-flow approach takes advantage of the concentration sensitive nature of ESI and provides sufficient quantity of sample for MALDI/MS/MS. Hybrid quadrupole time-of-flight mass spectrometers were used to acquire LC/ESI/MS/MS data and LC/MALDI/MS/MS data from a tryptic digest of a preparation of mammalian mitochondrial ribosomes. The mass spectrometers were configured to operate in a data dependent acquisition mode in which precursor ions observed in MS survey scans are automatically selected for interrogation by MS/MS. This type of acquisition scheme maximizes the number of peptide fragmentation spectra obtained and is commonly referred to as shotgun analysis. While a significant degree of overlap (63%) was observed between the proteins identified in the LC/ESI/MS/MS and LC/MALDI/MS/MS data sets, both unique peptides and unique proteins were observed by each method. These results demonstrate that improved proteome coverage can be obtained using a combination of these ionization techniques. 相似文献
9.
Mirosław Giurg Katarzyna Piekielska Magdalena Gębala Bartosz Ditkowski Marcin Wolański Wanda Peczyńska‐Czoch 《合成通讯》2013,43(11):1779-1789
The catalytic oxidative cyclocondensation of the o‐aminophenols 1a–f was investigated. The oxidants used were air/laccase, H2O2/horseradish peroxidase, H2O2/ebselen (3), and TBHP/diphenyl diselenide 4. The products obtained were 2‐amino‐3H‐phenoxazin‐3‐one—questiomycin A, its derivative 2b, and cinnabarinic acid and actinocin (2c,d). Substrates with methyl groups at 4 and 5 positions of benzene ring were converted to different dihydrophenoxazinones 2g,h. Compounds having chlorine atoms at the same positions underwent oxidation to planar phenoxa-zinones 2e,f with elimination of one hydrochloride molecule. 相似文献
10.
In this communication we report a stereoselective total synthesis of N-Boc-dolaproine (Dap), an amino acid residue of the antineoplastic pentapeptide Dolastatin 10. Our strategy is based on a Baylis-Hillman reaction between N-Boc-prolinal and methyl acrylate, followed by a diastereoselective double bond hydrogenation and hydrolysis of the ester function. 相似文献