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121.
《Electroanalysis》2017,29(2):635-642
An electrochemical sensor for paracetamol (PC) based on the hexacyanoferate(III) intercalated Ni−Al layered double hydroxide (Ni−Al−HCF) was presented. The as‐prepared LDH structurally and morphologically was characterized by scanning electron microscopy, X‐ray diffraction, and Fourier transform IR. Electrochemical studies revealed that Ni−Al−HCF film modified glassy carbon (GC) electrode exhibited remarkable electrocatalytic activity toward the oxidation of paracetamol. The electrochemical behavior of PC on the Ni−Al−HCF film was investigated in detail. Under optimum experimental conditions, the electrocatalytic response of the modified GC electrode was linear in the PC concentration range 3×10−6−–1.5×10−3 mol L−1, with a detection limit of 8×10−7 mol L−1 (S/N=3), using hydrodynamic amperometry. In addition, the modified electrode exhibited good reproducibility, long‐term stability and anti‐interference property. The fabricated sensor was successfully applied to determination of PC in various pharmaceutical preparations such as tablets, oral solution, and oral drops. Finally, the method was validated by the analysis of paracetamol spiked human serum samples, and good recoveries were obtained in the range of 99.2–103 %. 相似文献
122.
《Journal of computational chemistry》2017,38(22):1921-1929
Structural dissimilarity sampling (SDS) has been proposed as an enhanced conformational sampling method for reproducing the structural transitions of a given protein. SDS consists of cycles of two steps: (1) Selections of initial structures with structural dissimilarities by referring to a measure. (2) Conformational resampling by restarting short‐time molecular dynamics (MD) simulations from the initial structures. In the present study, an efficient measure is proposed as a dynamically self‐guiding selection to accelerate the structural transitions from a reactant state to a product state as an extension to the original SDS. In the extended SDS, the inner product (IP ) between the reactant and the snapshots generated by short‐time MD simulations are evaluated and ranked according to the IP s at every cycle. Then, the snapshots with low IP s are selected as initial structures for the short‐time MD simulations. This scheme enables one to choose dissimilar and distant initial structures from the reactant, and thus the initial structures dynamically head towards the product, promoting structural transitions from the reactant. To confirm the conformational sampling efficiency, the extended SDS was applied to maltodextrin binding protein (MBP), and we successfully reproduced the structural transition from the open to closed states with submicrosecond‐order simulation times. However, a conventional long‐time MD simulation failed to reproduce the same structural transition. We also compared the performance with that obtained by the ordinary SDS and other sampling techniques that have been developed by us to characterize the possible utility of the extended SDS for actual applications. © 2017 Wiley Periodicals, Inc. 相似文献
123.
《Journal of computational chemistry》2017,38(31):2721-2729
A metadynamics scheme is presented in which the free energy surface is filled with progressively adding adaptive biasing potentials, obtained from the accumulated probability distribution of the collective variables. Instead of adding Gaussians with assigned height and width in conventional metadynamics method, here we add a more realistic adaptive biasing potential to the Hamiltonian of the system. The shape of the adaptive biasing potential is adjusted on the fly by sampling over the visited states. As the top of the barrier is approached, the biasing potentials become wider. This decreases the problem of trapping the system in the niches, introduced by the addition of Gaussians of fixed height in metadynamics. Our results for the free energy profiles of three test systems show that this method is more accurate and converges more quickly than the conventional metadynamics, and is quite comparable (in accuracy and convergence rate) with the well‐tempered metadynamics method. © 2017 Wiley Periodicals, Inc. 相似文献
124.
125.
Detection of ethanol in human body fluids by headspace solid-phase micro extraction (SPME)/capillary gas chromatography 总被引:1,自引:0,他引:1
Summary Ethanol has been found extractable from human whole blood and urine samples by headspace solid-phase micro extraction (SPME) with a Carbowax/divinylbenzene-coated fiber. After heating a vial containing the body fluid sample with ethanol, and isobutanol as internal standard (IS) at 70°C in the presence of (NH4)2SO4, a Carbowax/divinylbenzene-coated SPME fiber was exposed in the headspace of the vial to allow adsorption of the compounds. The fiber needle was then injected into a middle-bore capillary gas chromatography (GC) port. The headspace SPME-GC gave intense peaks for both compounds; a small amount of background noises appeared, but did not interfere with the detection of the compounds. Recoveries of ethanol and IS were 0.049 and 0.026% for whole blood, respectively, and 0.054 and 0.085% for urine, respectively. The calibration curves for ethanol showed excellent linearity in the range of 80–5000 mg L–1 for whole blood and 40–5000 mg L–1 for urine; the detection limits for both samples were 20 and 10 mg L–1, respectively. The data on actual determination of ethanol after the drinking of beer are also presented for two subjects. 相似文献
126.
悬浮液进样流动注射在线微波消解-冷蒸气原子荧光光谱法测定生物和环境样品中的汞 总被引:12,自引:0,他引:12
建立了悬浮液进样流动注射在线微波消解-冷蒸气原子荧光光谱法测定生物和环境样品中Hg的方法。样品分散在50%(V/V)王水中,通过磁力搅拌保证样品溶液的均一性与稳定性。方法的检出限为O.06μ/L。方法简单快速,灵敏度高,样品损失少,而且没有样品交叉污染。应用此方法测定了5种标准参考物质以及5个实际样品中的Hg含量,并与传统的高压焖罐强酸消解方法进行了比较,两种方法所得结果一致,标准参考物质的测定值与标准值很好地吻合。 相似文献
127.
Summary The effects of electron beam irradiation on cork volatile compounds was studied at different doses (25, 100, 1000 kGy). Volatiles
were isolated from cork using the dynamic headspace-sampling technique, then identified by gas chromatography-mass spectrometry
(GC-MS). Similar gas chromatographic profiles were obtained for non-irradiated and irradiated corks. Quantitative differences
induced by the three doses were evaluated by calculating peak areas for each compound identified. The quantitative differences
between non-irradiated corks and those irradiated at 25 kGy were significant for only a few substances, whereas significant
quantitative differences were found in samples irradiated at 100 and 1000 kGy. For these doses, the content of volatile compounds
generally increased, especially that of aliphatic hydrocarbons and carbonyl compounds. The behaviour of radiolytic hydrocarbons
indicates that the mechanisms proposed for their formation in irradiated foods could take place even in cork. 相似文献
128.
Christian Bartels Michael Schaefer Martin Karplus 《Theoretical chemistry accounts》1999,101(1-3):62-66
Adaptive umbrella sampling of the potential energy is used as a search method to determine the structures and thermodynamics
of peptides in solution. It leads to uniform sampling of the potential energy, so as to combine sampling of low-energy conformations
that dominate the properties of the system at room temperature with sampling of high-energy conformations that are important
for transitions between different minima. A modification of the procedure for updating the umbrella potential is introduced
to increase the number of transitions between folded and unfolded conformations. The method does not depend on assumptions
about the geometry of the native state. Two peptides with 12 and 13 residues, respectively, are studied using the CHARMM polar-hydrogen
energy function and the analytical continuum solvent potential for treatment of solvation. In the original adaptive umbrella
sampling simulations of the two peptides, two and six transitions occur between folded and unfolded conformations, respectively,
over a simulation time of 10 ns. The modification increases the number of transitions to 6 and 12, respectively, in the same
simulation time. The precision of estimates of the average effective energy of the system as a function of temperature and
of the contributions to the average effective energy of folded conformations obtained with the adaptive methods is discussed.
Received: 11 July 1998 / Accepted: 22 September 1998 / Published online: 17 December 1998 相似文献
129.
Multielemental trace analysis of biological materials using double focusing inductively coupled plasma mass spectrometry detection 总被引:4,自引:0,他引:4
Juan Manuel Marchante-Gay n Cristina Sariego Mu iz Jos Ignacio Garcí a Alonso Alfredo Sanz-Medel 《Analytica chimica acta》1999,400(1-3):307-320
The analytical potential of double focusing-inductively coupled plasma-mass spectrometry (DF-ICP-MS) for total elemental analysis in clinical samples (serum, blood, urine and other biological fluids), tissues and food products is illustrated by reviewing typical applications recently published. Also, the use of DF-ICP-MS as specific detector for trace element speciation in biological samples is discussed. After adequate separation of interferences in the chromatographic column, low resolution measurements (R = 300) can be used to provide enhanced sensitivities of more than 100 times compared with quadrupole-inductively coupled plasma-mass spectrometry (Q-ICP-MS). This capability is extremely valuable in speciation studies. Also, the use of DF-ICP-MS at low resolution could provide very precise isotope ratio measurements for isotope dilution analysis due to the ‘flat topped’ peaks obtained at this resolution. Unfortunately, the literature on these last two issues is rather scarce so far, in spite of their extremely high analytical possibilities for biological research. Moreover, the bright future of DF-ICP-MS as a most powerful multielemental detector for trace element applications in biological systems will be highlighted. Apart from applications detailed above other important application fields can be envisaged. In particular, we will speculate on its possible use to confirm/establish ‘reference values’ of trace element content in ‘normal’ populations and so to help to diagnose health and disease status, related with trace element total content or their speciation in clinical specimens. 相似文献
130.
固体分层取样方案的最优化设计 总被引:1,自引:0,他引:1
本文首次从理论上探讨了取得量对分层取样误差的影响,提出了总取样量一定时各层的最佳取样量和最小取样方差的计算公式,从而为分层取样的最佳取样方案设计提供了理论依据。 相似文献