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71.
In this study, a soft method is proposed to calculate concentration and spectral profiles for the two‐way spectral data from dissociation equilibria of polyprotic acids (HnA). This method has four main distinct steps: (i) a fixed size moving window evolving factor analysis (FSMWEFA) was used to identify the local rank map, (ii) WFA was applied to calculate the concentration profiles of HnA and An− (selection of the window for application of WFA was performed using EFA), (iii) PVA was used to calculate Hn − 1A to HA spectral profiles, and (iv) a symmetry constraint, in addition to the non‐negativity constraint, was utilized to obtain the unique concentration and spectral profiles from different acceptable sets of profiles. In the absence of any selective region in the spectral data, the proposed soft method resulted in unique solution without rotational ambiguity. This study is the first application of symmetry constraint on concentration profiles. The rotational ambiguity drastically decreased on considering the constraint of symmetry of the Hn − 1A and HA concentration profiles, in addition to non‐negativity of profiles. Simulated examples were used to confirm these approaches. Effect of closeness of dissociation constants on the estimated values of constants was investigated. The results showed that when the difference between pKa values is more than 1.2, the obtained errors in the estimation of pKa values are less than about 6.5%. The considered real data were from pH‐metric titration of fluorescein. The obtained spectral and concentration profiles and the estimated pKa values for fluorescein were in good agreement with the previously reported data. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
72.
73.
Zhuomin Gu Shu Tian Qun Zhou Wenjuan Wei Lili Zhao Xiaowei Li Junwei Zheng 《Journal of Raman spectroscopy : JRS》2013,44(12):1682-1688
We presented a controlled particles‐in‐cavity (PIC) pattern for surface‐enhanced Raman scattering (SERS) detection. The periodic gold cavity array was fabricated by electrodeposition using highly ordered polystyrene spheres as a template. The as‐prepared gold cavities can be used as a SERS active substrate with significant spectral enhancement and reproducibility, which was evaluated by SERS signals using 4‐mercaptobenzoic acid (4‐MBA) as probe molecules. The surface of these gold cavities was further functionalized with cetyltrimethylammonium bromide molecules, which may immobilize the 4‐MBA‐modified silver nanoparticles in the gold cavity to form a PIC structure via the electrostatic interaction. We have demonstrated that there exists a pH window for the immobilization of the nanoparticles inside cavities. Therefore, the silver nanoparticles can be selectively immobilized into the functionalized gold cavities under the optimized pH value of the media. Further enhancement of the Raman scattering of the labeled molecules can be achieved due to the interconnection between the silver nanoparticles and gold cavity. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
74.
An updated main coupler has been designed for the superconducting accelerator of Free Electron Laser (FEL) project under construction in Peking University. A capacitive structure is chosen for the main coupler. Numerical investigation using CST Microwave Studio demonstrates the cold window part. The other nonstandard structures such as holding rods and antenna are also optimized. The coupler uses a 95% purity Al2O3 ceramic cold window. The VSWR (Vottage Standing Wave Ratio) is 1.02 at 1.3GHz and the frequency bandwidth is 45MHz with VSWR<1.1. The electric field intensity is 8.5×10-2kV/mm around the window with 20kW Continuous Wave (CW) transmitted power. The Qext is designed variable from 5×106 to 1×107. 相似文献
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76.
Dr. Celina Sikorska 《Chemphyschem》2019,20(17):2236-2246
Superhalogens, owing to their large electron affinity (EA, exceeding those of any halogen atom), play an essential role in physical chemistry as well as new material design. They have applications in hydrogen storage and lithium-ion batteries. Owing to the unique geometries and electronic features of magnesium-based clusters, their potential to form a new class of lithium salts has been investigated here theoretically. The idea is assessed by conducting ab initio computations on Li+/MgnF2n+1-2mOm− compounds (n=2, 3; m=0-3) and analyzing their performance as potential Li-ion battery electrolytes. The Mg3F7− cluster, with large electron binding energy (EA of 7.93 eV), has been proven to serve as a building block for lithium salts. It is shown that, apart from high electronic stability, the new superhalogen-based electrolytes exhibit a set of desirable properties, including a large band gap, high electrolyte stability window, easy mobility of the Li+, and favorable insensitivity to water. 相似文献
77.
《Electrophoresis》2018,39(14):1794-1801
In our previous work, it was found that the vesicles were formed spontaneously by mixing octyltriethylammonium bromide (C8NE3Br) with sodium dodecyl benzene sulfonate (SDBS), and the vesicles have been developed as a pseudostationary phase (PSP) in EKC. In the present work, the effects of the concentration and the molar ratio of cationic to anionic surfactant on the vesicle properties and the performances of vesicle PSP in EKC have been investigated. The aggregates at all mixing ratio were negatively charged regardless of which surfactant surplus. As C8NE3Br proportion increased, the microviscosity of the vesicle became larger. With the increase in the total surfactant concentration, the migration time window broadened at the molar ratio of C8NE3Br to SDBS of 3:7. Unexpectedly, the window became narrowed at molar ratio of 5:5 and 6:4. However, the methylene selectivity of vesicle PSP at all above‐mentioned molar ratios enhanced as the total surfactant concentration increased, no matter whether the migration time window enlarged or narrowed. It implied that the vesicle PSP at molar ratio of 5:5 and 6:4 made it possible to obtain a better separation in a shorter time. When the total surfactant concentration was fixed at 20 mM, the methylene selectivity of the vesicle PSP of molar ratio of 5:5 was comparable to that of 3:7, but the migration time shortened by a half. 相似文献
78.
Imaging of Colorectal Cancers Using Activatable Nanoprobes with Second Near‐Infrared Window Emission 下载免费PDF全文
Ge Xu Qinglong Yan Xiaoguang Lv Prof. Ying Zhu Kai Xin Ben Shi Rongchen Wang Jian Chen Wei Gao Prof. Ping Shi Prof. Chunhai Fan Prof. Chunchang Zhao Prof. He Tian 《Angewandte Chemie (International ed. in English)》2018,57(14):3626-3630
Fluorescent probes in the second near‐infrared window (NIR‐II) allow high‐resolution bioimaging with deep‐tissue penetration. However, existing NIR‐II materials often have poor signal‐to‐background ratios because of the lack of target specificity. Herein, an activatable NIR‐II nanoprobe for visualizing colorectal cancers was devised. This designed probe displays H2S‐activated ratiometric fluorescence and light‐up NIR‐II emission at 900–1300 nm. By using this activatable and target specific probe for deep‐tissue imaging of H2S‐rich colon cancer cells, accurate identification of colorectal tumors in animal models were performed. It is anticipated that the development of activatable NIR‐II probes will find widespread applications in biological and clinical systems. 相似文献
79.
The components (H3PO4, HNO3, CH3COOH and water) in an etchant solution have been accurately measured in an on-line manner using near-infrared (NIR) spectroscopy by directly illuminating NIR radiation through a Teflon line. In particular, the spectral features according to the change of H3PO4 or HNO3 concentrations were not mainly from NIR absorption themselves, but from the perturbation (or displacement) of water bands; therefore, the resulting spectral variations were quite similar to each other. Consequently partial least squares (PLS) prediction selectivity among the components should be the most critical issue for continuous on-line compositional monitoring by NIR spectroscopy. To improve selectivity of the calibration model, we have optimized the calibration models by finding selective spectral ranges with the use of moving window PLS. Using the optimized PLS models for each component, the resulting prediction accuracies were substantially improved. Furthermore, on-line prediction selectivity was evaluated by spiking individual pure components step by step and examining the resulting prediction trends. When optimized PLS models were used, each concentration was selectively and sensitively varied at each spike; meanwhile, when whole or non-optimized ranges were used for PLS, the prediction selectivity was greatly degraded. This study verifies that the selection of an optimal spectral range for PLS is the most important factor to make Teflon-based NIR measurements successful for on-line and real-time monitoring of etching solutions. 相似文献
80.
ABSTRACTThis article describes an experimental investigation on the behavior of transmission control protocol in throughput measurements to be used in the verification of the service-level agreement between the Internet service provider and user in terms of line capacity for ultra-broadband access networks typical of fiber-to-the-x architectures. It is experimentally shown different conditions in high bandwidth-delay product links where the estimation of the line capacity based on a single transmission control protocol session results are unreliable. Simple equations reported in this work, and experimentally verified, point out the conditions in terms of packet loss, time delay, and line capacity, that allow consideration of the reliability of the measurement carried out with a single transmission control protocol session test by adopting a suitable measurement time duration. 相似文献