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151.
A reliable Pd-catalyzed amination protocol is described for the synthesis of N-alkyltacrines and analogs. The Josiphos ligand CyPFtBu was found to provide optimum yields: 16 examples are given. Compared to the typical high-temperature nucleophilic aromatic substitution (NAS) routes, Pd-catalyzed aminations proceed at significantly lower reaction temperatures, and enable the synthesis of otherwise inaccessible products. 相似文献
152.
Avula B Khan SI Tekwani BL Nanayakkara NP McChesney JD Walker LA Khan IA 《Biomedical chromatography : BMC》2011,25(9):1010-1017
The clinical formulation of primaquine (PQ) is a mixture of (−)‐(R)‐ and (+)‐(S)‐ primaquine enantiomers which may show different pharmacokinetic and pharmacodynamic properties. To assess the efficacy and toxicity of primaquine enantiomers, a method using LC‐MSD‐TOF has been developed. The enantiomers were well separated using a Chiralcel OD column (250 × 4.6 mm, 10 µm) with a linear gradient of mobile phase consisting of acetonitrile (0.1% formic acid) and aqueous ammonium formate (20 mm ; 0.1% formic acid) adjusted to pH 5.9 at a flow rate of 0.7 mL/min. The method was validated for linearity, precision, accuracy and limits of detection and quantification. The calibration curves were linear with all correlation coefficients being >0.999. The average recoveries of (−)‐(R)‐ and (+)‐(S)‐primaquine and (−)‐(R)‐ and (+)‐(S)‐carboxyprimaquine were 88 and 92%, respectively, in spiked human plasma and 89 and 93% respectively in spiked mouse plasma samples. The RSD of (−)‐(R)‐ and (+)‐(S)‐primaquine and (−)‐(R)‐ and (+)‐(S)‐carboxyprimaquine were 2.15, 1.74, 1.73 and 2.31, respectively, in spiked human plasma and 2.21, 1.09, 1.95 and 1.17% in spiked mouse plasma, respectively. The intra‐day and inter‐day precisions expressed as RSD were lower than 10% in all analyzed quality control levels. The method as reported is suitable for study of the pharmacokinetic and pharmacodynamic properties of the enantiomers of primaquine. The method was successfully applied to study plasma pharmacokinetic profile of enantiomers of primaquine and carboxyprimaquine in mice administered with primaquine in racemic form. The analytical method was found to be linear, accurate, precise and specific. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
153.
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155.
The extensive use of bisphenol A (BPA) in the manufacture of consumer products results in widespread human exposure to the
chemical. In the body, BPA undergoes first-pass metabolism to form BPA glucuronide, considered to be a major BPA byproduct.
Concentrations of total (free plus conjugated) urinary species of BPA are used to assess human exposure to BPA. However, because
BPA can be present in numerous consumer and household products, potential contamination with parent BPA during collection
and handling may pose a challenge when measuring BPA in such biological samples as blood or urine. In this study we investigated
the in-vitro phase I metabolism of BPA in rat and human liver microsomes by using on-line solid-phase extraction–high-performance
liquid chromatography–tandem mass spectrometry to identify phase I metabolites (e.g., BPA oxidation products) that could be
used as potential alternative biomarkers of BPA exposure. We unambiguously identified 5-hydroxy BPA (BPA catechol) as an in-vitro
oxidative metabolite of BPA, but human microsomes oxidized only about 10% of BPA to BPA catechol. We evaluated the usefulness
of BPA catechol as a potential biomarker of human exposure to BPA by measuring total concentrations of BPA catechol and BPA
in 20 urine samples. We detected BPA catechol at much lower concentrations and frequency than those of BPA. Furthermore, we
found that free BPA catechol was rather unstable in urine, which highlights the importance of sampling techniques to adequate
interpretation of biomonitoring data. Together, these findings suggest that BPA catechol may not be a suitable biomarker of
environmental exposure to BPA, but could be used to confirm BPA exposure in special populations or in situations when urine
specimens were potentially contaminated with BPA. 相似文献
156.
Salandria KJ Arico JW Calhoun AK McLaughlin LW 《Journal of the American Chemical Society》2011,133(6):1766-1768
We describe here the synthesis and properties of A-T rich DNA containing covalently bound water mimics located in the DNA minor groove. 相似文献
157.
Larry Zhao Henny VoldersMikhail Baklanov Zsolt T?keiMarianna Pantouvaki Christopher J. WilsonEls Van Besien Gerald P. BeyerCor Claeys 《Microelectronic Engineering》2011,88(9):3030-3034
A unique test structure based on a metal-insulator-semiconductor planar capacitor (Pcap) design was used to investigate several aspects of metal barrier-induced low-k damage. A special term called Effective Damage Thickness was introduced to describe the degree of damage. Ta(N) barrier was deposited on various dielectric films with porosity up to 32%. It has been found that the Effective Damage Thickness increases as the porosity increases. The damage is influenced more by the porosity of low-k films than the film density. Furthermore, the damage was modulated by Ta(N) deposition conditions. More damage was observed when higher target and/or substrate bias power was used, suggesting that the ion energy of the barrier material plays an important role in the low-k damage mechanism. A same degree of damage was observed for Ta barrier as for Ta(N), suggesting that Ta(N) deposition-induced low-k damage was primarily caused by Ta ions not nitrogen. Impact of Ru(Ta) and Cu(Mn) self forming barrier on low-k damage was also investigated. Among all the barriers studied in this work, the Ta-based barriers caused the most damage while the Cu(Mn) self forming barrier had the least damage to the low-k. The atomic masses for Ta, Ru, and Cu are 181, 101, and 64, respectively, corresponding with the observed degree of damage in the low-k material. 相似文献
158.
A method is proposed for creating a non-equilibrium ensemble with a constant number of molecules, constant temperature and constant pressures with different target values in two reservoirs [referred to as NT(P(1)-P(2)) ensemble] that are connected by a finite length nanopore. This method includes two steps. The first step places a partition between the two reservoirs and then creates a static pressure field and a proper system volume by using two self-adjusting plates on which two external forces/pressures with different target values are exerted. The second step removes the partition and the two self-adjusting plates and the pressure difference between the two reservoirs is maintained by a "pump" designed to simultaneously create a periodic boundary condition between the two reservoirs and supply the necessary force (work) to a subset of molecules for a steady state flow. To examine this method, several cases using liquid argon with a truncated and shift Lennard-Jones potential under different target pressures and pump sizes were studied. Results show that the method proposed in this paper works well. In addition, the method proposed in this paper was compared with the other external force field methods. The results show that as long as the external force is applied to a restricted set of molecules away from the channel a constant pressure difference between two reservoirs is maintained. The advantage of the algorithm proposed here also sets the absolute pressures with different target levels in two reservoirs instead of it being arbitrary. Studies show that the fluid flow rate or permeability through a nanopore depends not only on the pressure difference between two reservoirs, but also on the absolute pressures in two reservoirs. 相似文献
159.
For 0≤k≤n, let be the entries in Euler’s difference table and let . Dumont and Randrianarivony showed equals the number of permutations on [n] whose fixed points are contained in {1,2,…,k}. Rakotondrajao found a combinatorial interpretation of the number in terms of k-fixed-points-permutations of [n]. We show that for any n≥1, the sequence is essentially 2-log-concave and reverse ultra log-concave. 相似文献
160.
Ab initio values for the potential energy functions for ion–neutral interactions can be tested by comparison with gaseous ion transport coefficients, but only if special care is taken to compute the interaction potentials accurately over wide ranges of internuclear separation. This is illustrated here by a reanalysis of the ab initio values for the coinage metal ions interacting with rare gas atoms, precise calculations of the transport cross sections over extremely wide ranges of energy, and similarly precise calculations of the zero-field ion mobilities as functions of gas temperature and the field-dependent ion mobilities at various fixed temperatures. The calculations indicate that the mobilities for Ag+(1S) moving in Ne or Ar can distinguish between the existing, very similar ab initio potentials. They also show that substantial differences exist among the mobilities of the coinage metal anions and the ground and excited states of the cations. The techniques implemented are recommended for future ab initio calculations. 相似文献