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71.
Chiral separability of boron cluster species studied by screening approaches utilizing polysaccharide‐based chiral stationary phases 下载免费PDF全文
In this study, the screening steps of chiral separation strategies with polysaccharide‐based chiral stationary phases were applied on boron cluster compounds in normal‐phase liquid chromatography (NPLC) and polar organic solvents chromatography (POSC). Since the screening steps were initially developed to analyze organic compounds, their applicability for boron clusters was investigated. Overall, the screening steps in NPLC were applicable for the separation of zwitterions, while for anions mostly no elution was observed. A hypothesis for the latter behavior is precipitation of anions in the nonpolar mobile phases. Ten out of 11 compounds could be partially or baseline separated on the NPLC screening systems. In POSC, all zwitterions were separated on at least one of the screening systems, with an overall lower retention as in NPLC. Anions were detected but not separated in the majority of the experiments. Also their retention on the chiral stationary phases was very limited. This study showed that the chiral discrimination potential of chemically modified polysaccharides is meaningful for chiral separations of structurally chiral boron cluster species, but needs further systematic research, in which recognition mechanisms should be further explored. In addition, some unusual peaks also indicated that conditions with a high separation efficiency must first be searched for some of the tested systems. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
72.
This paper considers the problem of change point in single index models. In order to obtain asymptotically valid confidence intervals for the estimation of the change point, the convergence rate and asymptotic distribution of the change point estimate is studied. Some simulation results are presented which show that the numerical performance of our estimator is satisfactory. 相似文献
73.
Computational Insights into the Charge Relaying Properties of β‐Turn Peptides in Protein Charge Transfers 下载免费PDF全文
Ru Zhang Dr. Jinxiang Liu Dr. Hongfang Yang Shoushan Wang Meng Zhang Prof. Dr. Yuxiang Bu 《Chemphyschem》2015,16(2):436-446
Density functional theory calculations suggest that β‐turn peptide segments can act as a novel dual‐relay elements to facilitate long‐range charge hopping transport in proteins, with the N terminus relaying electron hopping transfer and the C terminus relaying hole hopping migration. The electron‐ or hole‐binding ability of such a β‐turn is subject to the conformations of oligopeptides and lengths of its linking strands. On the one hand, strand extension at the C‐terminal end of a β‐turn considerably enhances the electron‐binding of the β‐turn N terminus, due to its unique electropositivity in the macro‐dipole, but does not enhance hole‐forming of the β‐turn C terminus because of competition from other sites within the β‐strand. On the other hand, strand extension at the N terminal end of the β‐turn greatly enhances hole‐binding of the β‐turn C terminus, due to its distinct electronegativity in the macro‐dipole, but does not considerably enhance electron‐binding ability of the N terminus because of the shared responsibility of other sites in the β‐strand. Thus, in the β‐hairpin structures, electron‐ or hole‐binding abilities of both termini of the β‐turn motif degenerate compared with those of the two hook structures, due to the decreased macro‐dipole polarity caused by the extending the two terminal strands. In general, the high polarity of a macro‐dipole always plays a principal role in determining charge‐relay properties through modifying the components and energies of the highest occupied and lowest unoccupied molecular orbitals of the β‐turn motif, whereas local dipoles with low polarity only play a cooperative assisting role. Further exploration is needed to identify other factors that influence relay properties in these protein motifs. 相似文献
74.
Experimental Charge Density Evidence for Pnicogen Bonding in a Crystal of Ammonium Chloride 下载免费PDF全文
Dr. Yulia V. Nelyubina Prof. Alexander A. Korlyukov Prof. Konstantin A. Lyssenko 《Chemphyschem》2015,16(3):676-681
Chemical binding in crystalline ammonium chloride, a simple inorganic salt with an unexpectedly complex bonding pattern, was studied by using a topological analysis of electron density function derived from high‐resolution X‐ray diffraction. Supported by periodic quantum chemical calculations, it provided experimental evidence for weak σ‐hole bonds (1.5 kcal mol?1) that involve ammonium cations in a crystal. Our results show this type of supramolecular interaction to be more numerous than has been found to date by using gas‐phase calculations or statistical analysis of CSD. 相似文献
75.
Development of a liquid chromatography with mass spectrometry method for the determination of gelsemine in rat plasma and tissue: Application to a pharmacokinetic and tissue distribution study 下载免费PDF全文
Shuangshuang Zhang Shuping Hu Xiangxiang Yang Jiaqi Shen Xiaoyong Zheng Kexin Huang Zheng Xiang 《Journal of separation science》2015,38(6):936-942
Gelsemine from Gelsemium elegans Benth is a potential anesthetic and analgesic agent with no physical dependence and opiate addiction. This study was aimed at developing an ultrafast liquid chromatography coupled to tandem mass spectrometry method to quantify gelsemine in rat plasma and tissues. Plasma and tissues were processed with acetonitrile precipitation, and dendrobine was chosen as the internal standard. Sample separation was performed on an ACQUITY HSS T3 column. The mobile phase consisted of acetonitrile and 0.1% formic acid aqueous solution. Multiple reactions monitoring mode was utilized to detect the compounds of interest. The mass spectrometer was operated in the positive ion mode for detection. The MS/MS ion transitions monitored were m/z 323.2→70.5 for gelsemine and 264.2→108.05 for dendrobine, respectively. The calibration curves were linear over the range of 1–500 ng/mL in all biological matrices. The lower limit of quantification for rats plasma and tissues was 1.0 ng/mL. The values for inter‐ and intraday precision and accuracy were well within the ranges acceptable (< 15%). It was successfully applied to the pharmacokinetic and tissue distribution studies of gelsemine after intravenous doses of 5, 2, and 0.5 mg/kg in rats. These data of gelsemine would be useful for clinical application and further development. 相似文献
76.
Jairo Z. Goncalves 《代数通讯》2017,45(12):5193-5201
Let k(t) be the field of rational functions over the field k, let σ be a k-automorphism of K = k(t), let D = K(X;σ) be the ring of fractions of the skew polynomial ring K[X;σ], and let D? be the multiplicative group of D. We show that if N is a noncentral normal subgroup of D?, then N contains a free subgroup. We also prove that when k is algebraically closed and σ has infinite order, there exists a specialization from D to a quaternion algebra. This allows us to explicitly present free subgroups in D?. 相似文献
77.
Stability,periodicity, and symmetries of certain second‐order fractional difference equation with quadratic terms via KAM theory 下载免费PDF全文
Mirela Garić‐Demirović M. Nurkanović Z. Nurkanović 《Mathematical Methods in the Applied Sciences》2017,40(1):306-318
By using the Kolmogorov–Arnold–Moser theory, we investigate the stability of the equilibrium solution of the difference equation where A ,B ,D > 0,u ?1,u 0>0. We also use the symmetries to find effectively the periodic solutions with feasible periods. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
78.
Liming Zhang Tao Qian Weixiong Mai Pei Dang 《Mathematical Methods in the Applied Sciences》2017,40(8):2815-2833
The Dirac‐type time‐frequency distribution (TFD), regarded as ideal TFD, has long been desired. It, until the present time, cannot be implemented, due to the fact that there has been no appropriate representation of signals leading to such TFD. Instead, people have been developing other types of TFD, including the Wigner and the windowed Fourier transform types. This paper promotes a practical passage leading to a Dirac‐type TFD. Based on the proposed function decomposition method, viz., adaptive Fourier decomposition, we establish a rigorous and practical Dirac‐type TFD theory. We do follow the route of analytic signal representation of signals founded and developed by Garbo, Ville, Cohen, Boashash, Picinbono, and others. The difference, however, is that our treatment is theoretically throughout and rigorous. To well illustrate the new theory and the related TFD, we include several examples and experiments of which some are in comparison with the most commonly used TFDs. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
79.
Yongqiao Wang Donghe Pei Xiupeng Cui 《Mathematical Methods in the Applied Sciences》2017,40(18):7151-7161
We introduce the notions of the pseudospherical normal Darboux images for the curve on a lightlike surface in Minkowski 3‐space and study these Darboux images by using technics of the singularity theory. Furthermore, we give a relation between these Darboux images and Darboux frame from the viewpoint of Legendrian dualities. 相似文献
80.
Gerardo Cáceres Montenegro Carolina G. Gutierrez Santiago E. Vaillard Roque J. Minari Jorge R. Vega Luis M. Gugliotta 《大分子反应工程》2017,11(3)
The synthesis of poly(acrylic acid) (PAA) of low molar mass under safe conditions is difficult due to the high polymerization rate of acrylic acid (AA) and the fast heat generation. The aqueous‐solution “semibatch” polymerization of non‐ionized AA in almost starved conditions involves high initiator loads when low molar masses are required. This article proposes the simultaneous feeding of AA and nonconventional chain transfer agents (CTA) as a strategy aimed at controlling both the molar masses and the generated heat rate. Three CTAs are investigated: 2‐mercaptoethanol, thioglycolic acid, and isopropyl alcohol. Even when PAA of relatively low molar mass can be produced by adequately selecting the flow rates and concentrations of both AA and CTA, it is found that the nature of CTA can have a significant effect on the polymerizations kinetics. The mechanisms responsible for these effects are discussed with the help of a representative mathematical model.