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101.
Tatiana M. Birshtein Alexey A. Polotsky Volker Abetz 《Macromolecular theory and simulations》2004,13(6):512-519
Summary: The theory of lamellar superstructures of an ABC 3‐miktoarm star terpolymer in the conditions corresponding to the strong segregation limit for linear ABC triblock terpolymer has been developed. According to the particular molecular topology (namely, the common junction point for all three blocks), the system cannot avoid volume interactions between monomers of different blocks even in this limit. Hence, in the lamellar superstructure, there exists the so‐called “mixed” domain containing monomers of all three blocks but formed mainly of the block with the lowest degree of incompatibility. It is shown that unfavorable volume interactions in this domain are minimized by the increase of the interfacial area per ABC molecule which makes the mixed domain narrow. This leads to an unusual behavior of the period of the superstructure which decreases with an increase in the length of the block with the lowest incompatibility. However, in the case of a “synchronous” increase in the size of the branches of the ABC 3‐miktoarm star terpolymer, the period of the superstructure increases similarly to that for a linear ABC triblock terpolymer.
102.
Conducting polymer (CP) films, used as ion-sensing membranes under open circuit potentiometric conditions, are usually characterised with rather high detection limit, in the range of 10−4-10−5 mol dm−3. This effect is unfavourable, not only from the point of view of CP applications in potentiometry as ion sensitive membranes, but also when these materials are used as ion-to-electron transducers (solid contacts) for ion-selective electrodes. The theoretical considerations presented underline the crucial role of spontaneous processes of polymer charging/discharging—the source of observed high detection limit of sensors comprising CP layer under zero current conditions. Although the mechanism of occurring process is different from that observed for plastic, solvent polymeric based ion-selective electrodes, the ultimate result—alteration of activity of electrolyte at the membrane/solution interface leading to elevation of the detection limit—is the same.The method of estimation of parameters characterising spontaneous charge transfer processes is presented. The values obtained can be used to calculate the resulting polymer/solution interface activity of electrolyte ions, thus the detection limit of CP membrane can be theoretically predicted.A method of lowering of the detection limit of conducting polymer membranes, applying galvanostatic polarisation to compensate the spontaneous process of polymer charging/discharging, is presented.The experimental results obtained for poly(pyrrole), poly(N-methylpyrrole) and poly(3,4-ethylenedioxythiophene) are in good accordance with predictions of the presented model. 相似文献
103.
The extrapolation scheme of correlation energy is revisited to evaluate the complete basis set limit from double‐zeta (DZ) and triple‐zeta levels of calculations. The DZ level results are adjusted to the standard asymptotic behavior with respect to the cardinal number, observed at the higher levels of basis sets. Two types of adjusting schemes with effective scaling factors, which recover errors in extrapolations with the DZ level basis set, are examined. The first scheme scales the cardinal number for the DZ level energy, while the second scheme scales the prefactor of the extrapolation function. Systematic assessments on the Gaussian‐3X and Gaussian‐2 test sets reveal that these calibration schemes successfully and drastically reduce errors without additional computational efforts. © 2015 Wiley Periodicals, Inc. 相似文献
104.
105.
《Arabian Journal of Chemistry》2022,15(10):104116
The misuses of veterinary drugs can result in the accumulation of residues in food of animal origin that can make its way to the final consumer. Herein we describe a simple method for the accurate determination of beta-lactams, quinolones, sulphonamides, and tetracyclines in fish, poultry, and red meat. No extraction cartridges were used; instead, the extraction process consisted of the addition of an organic solvents, shaking, centrifugation, and dilution. An extensive validation process demonstrated an excellent linearity (R2 ≥ 0.99) for 23-drug residues. The recovery of drugs in different matrices at two concentration levels (n = 6) was in the range of 82–119%. The method was proved to be repeatable and reproducible with intra/inter-day measurements (RSDs lower than 20%). The quantification limits of drug residues were in the range of 0.8 to 45.3 ug/kg, which is well below the maximum residue limits set by most regulatory authorities. This method was successfully applied to the routine analysis of 20 fish, poultry, and red meat samples (n = 60). 相似文献
106.
Wei Zheng Prof. XuPing Li Dr. Glib V. Baryshnikov Xueru Shan Dr. Farhan Siddique Dr. Cheng Qian Prof. Shengyin Zhao Prof. Hongwei Wu 《Angewandte Chemie (International ed. in English)》2023,62(32):e202305925
It is challenging to achieve stable and efficient radical emissions under ambient conditions. Herein, we present a rational design strategy to protect photoinduced carbonyl free radical emission through electrostatic interaction and spin delocalization effects. The host-guest system is constructed from tricarbonyl-substituted benzene molecules and a series of imidazolium ionic liquids as the guest and host, respectively, whereby the carbonyl anion radical emission can be in situ generated under the light irradiation and further stabilized by electrostatic interaction. More importantly, the anion species and the alkyl chain length of imidazolium ionic liquids show a noticeable effect on luminescence efficiency, with the highest radical emission efficiency is as high as 53.3 % after optimizing the imidazole ionic liquid's structure, which is about four times higher than the polymer-protected radical system. Theoretical calculations confirm the synergistic effect of strong electrostatic interactions and that the spin delocalization effect significantly stabilizes the radical emission. Moreover, such a radical emission system also could be integrated with a fluorescent dye to induce multi-color or even white light emission with reversible temperature-responsive characteristics. The radical emission system can also be used to detect different amine compounds on the basis of the emission changes and photoactivation time. 相似文献
107.
108.
分析方法标准验证实验得到的分析方法基本性能参数重复性限和再现性限是日常检测工作质控规范重要依据。以环境监测领域土壤、沉积物及固废样品中无机元素分析为例,考察了已颁布执行的标准文本和在生态环境部官网公开征求意见的分析方法标准中重复性限。将重复性限转化为相对偏差后,与日常检测工作中质控限值进行了比较。根据目前现行有效的平行双样测定结果相对偏差限值,方法验证数据有多大比例符合质控要求?根据方法验证结果,平行双样测定结果相对偏差限值有无改进可能?从上述两个角度进行了研究。研究结果表明:土壤、沉积物、固体废弃物中无机元素的测定,不同文献来源相同分析方法标准和不同分析方法标准,其重复性限转化得到的平行测定相对偏差合格率存在明显区别;用平行测定相对偏差限值可以快速判断标准文本中的重复性限是否合理,审核方法验证数据质量是否满足要求。基于已有标准文本方法验证数据,探讨了修改平行测定结果相对偏差限值可行性。 相似文献
109.
A label-free DNA-based electrochemical biosensor owning high sensitivity and selectivity has been established for detecting bisphenol A in a wide range of applications. Coupling the high electrochemical performance of graphene oxide-thionine-Au nanomaterial with the specific binding capacity of the aptamers to BPA, the monitoring of trace amount of BPA was realized, the detection limit was 3.3 pg ⋅ mL−1 with strong anti-interference. Besides, using molecular docking, it was found that BPA binds to the bases DC-49, DC-51, DG-52, DG-53 and DA-63 on the aptamer via hydrogen bonding and π-π stacking interactions. Finally, the biosensor had been successfully applied in different real samples. 相似文献
110.
《Journal of Saudi Chemical Society》2022,26(5):101531
We used SERS with silver nanoparticles (AgNPs) as the active substrate to develop a, simple, quick, and accurate method for the detection and characterization SARS-CoV-2 without the need for RNA isolation and purification. Inactivated SARS-CoV-2 was used. The SERS signals were more than 105 times enhanced than the normal Raman (NR) spectra. The SERS spectra of SARS-CoV-2 fingerprint revealed pronounced intensity signals of nucleic acids; aromatic amino acid side chains: 1007 cm?1 (Phe marker), 1095 cm?1 (CN and PO2? markers), 1580 cm?1 (Tyr, Trp markers). Vibrations of the protein main chain: 1144 cm?1 (CN and NH2 markers), 1221 cm?1 (CN and NH markers), 1270 cm?1 (NH2 marker), 1453 cm?1 (CHCH2 marker). All of these biomolecules could be adsorbed on the AgNPs surface's dense hot patches. The intensity of the SERS band varied with the concentration of SARS-CoV-2, with a virus detection limit of less than 103 vp/mL and RSDs of 20 %. 相似文献