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Eranda Harinath Puwakkatiya‐Kankanamage Salvador García‐Muoz Lorenz T. Biegler 《Journal of Chemometrics》2014,28(7):575-584
Advances in sensory systems have led to many industrial applications with large amounts of highly correlated data, particularly in chemical and pharmaceutical processes. With these correlated data sets, it becomes important to consider advanced modeling approaches built to deal with correlated inputs in order to understand the underlying sources of variability and how this variability will affect the final quality of the product. Additional to the correlated nature of the data sets, it is also common to find missing elements and noise in these data matrices. Latent variable regression methods such as partial least squares or projection to latent structures (PLS) have gained much attention in industry for their ability to handle ill‐conditioned matrices with missing elements. This feature of the PLS method is accomplished through the nonlinear iterative PLS (NIPALS) algorithm, with a simple modification to consider the missing data. Moreover, in expectation maximization PLS (EM‐PLS), imputed values are provided for missing data elements as initial estimates, conventional PLS is then applied to update these elements, and the process iterates to convergence. This study is the extension of previous work for principal component analysis (PCA), where we introduced nonlinear programming (NLP) as a means to estimate the parameters of the PCA model. Here, we focus on the parameters of a PLS model. As an alternative to modified NIPALS and EM‐PLS, this paper presents an efficient NLP‐based technique to find model parameters for PLS, where the desired properties of the parameters can be explicitly posed as constraints in the optimization problem of the proposed algorithm. We also present a number of simulation studies, where we compare effectiveness of the proposed algorithm with competing algorithms. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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The presence of sulfide/polysulfide redox couple is crucial in achieving stability of metal chalcogenide (e.g., CdS and CdSe)-based quantum dot-sensitized solar cells (QDSC). However, the interfacial charge transfer processes play a pivotal role in dictating the net photoconversion efficiency. We present here kinetics of hole transfer, characterization of the intermediates involved in the hole oxidation of sulfide ion, and the back electron transfer between sulfide radical and electrons injected into TiO(2) nanoparticles. The kinetic rate constant (10(7)-10(9) s(-1)) for the hole transfer obtained from the emission lifetime measurements suggests slow hole scavenging from CdSe by S(2-) is one of the limiting factors in attaining high overall efficiency. The presence of the oxidized couple, by addition of S or Se to the electrolyte, increases the photocurrent, but it also enhances the rate of back electron transfer. 相似文献
4.
M. Lakshmi Kantam Kalluri V.S. Ranganath Lakkoju Chakrapani 《Tetrahedron letters》2007,48(43):7646-7649
Highly enantioselective Michael addition of malonates to cyclic and acyclic enones has been achieved by using nanocrystalline magnesium oxide at −20 °C. 相似文献
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M. Lakshmi Kantam Thekkathu Ramani Lakkoju Chakrapani K.Vijay Kumar 《Tetrahedron letters》2008,49(9):1498-1501
The direct asymmetric aldol reactions of aromatic and heteroaromatic aldehydes with acetone to afford chiral β-hydroxy carbonyl compounds in good yields and good to moderate enantioselectivities are realized using nanocrystalline copper(II) oxide in the presence of (1S,2S)-(−)-1,2-diphenylethylenediamine at −30 °C. The catalyst can be reused for four cycles with consistent activity and enantioselectivity. 相似文献
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Gupta Abhishek Verma Shikhar Dwivedi Harinath Rawat Ajay Kumar Singh 《平面色谱法杂志一现代薄层色谱法》2016,29(6):423-428
JPC – Journal of Planar Chromatography – Modern TLC - A high-performance thin-layer chromatography (HPTLC) method for the simultaneous quantitative determination of lupeol and ursolic... 相似文献
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Prerona Bora Suman Manna Mrutyunjay A. Nair Rupali R. M. Sathe Shubham Singh Venkata Sai Sreyas Adury Kavya Gupta Arnab Mukherjee Deepak K. Saini Siddhesh S. Kamat Amrita B. Hazra Harinath Chakrapani 《Chemical science》2021,12(39):12939
Persulfides and polysulfides, collectively known as the sulfane sulfur pool along with hydrogen sulfide (H2S), play a central role in cellular physiology and disease. Exogenously enhancing these species in cells is an emerging therapeutic paradigm for mitigating oxidative stress and inflammation that are associated with several diseases. In this study, we present a unique approach of using the cell''s own enzyme machinery coupled with an array of artificial substrates to enhance the cellular sulfane sulfur pool. We report the synthesis and validation of artificial/unnatural substrates specific for 3-mercaptopyruvate sulfurtransferase (3-MST), an important enzyme that contributes to sulfur trafficking in cells. We demonstrate that these artificial substrates generate persulfides in vitro as well as mediate sulfur transfer to low molecular weight thiols and to cysteine-containing proteins. A nearly 100-fold difference in the rates of H2S production for the various substrates is observed supporting the tunability of persulfide generation by the 3-MST enzyme/artificial substrate system. Next, we show that the substrate 1a permeates cells and is selectively turned over by 3-MST to generate 3-MST-persulfide, which protects against reactive oxygen species-induced lethality. Lastly, in a mouse model, 1a is found to significantly mitigate neuroinflammation in the brain tissue. Together, the approach that we have developed allows for the on-demand generation of persulfides in vitro and in vivo using a range of shelf-stable, artificial substrates of 3-MST, while opening up possibilities of harnessing these molecules for therapeutic applications.A persulfide/hydrogen sulfide generation strategy through artificial substrates for 3-mercaptopyruvate sulfurtransferase (3-MST) is reported, which enhances cellular persulfides, attenuates reactive oxygen species (ROS), and alleviates inflammation. 相似文献
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P. Chandrasekhar Reddy Chakrapani B. Rangamannar 《Journal of Radioanalytical and Nuclear Chemistry》1992,165(1):57-60
A radiochemical displacement method has been developed for the determination of 10 g amounts of iron and antimony. The effect of pH and various foreign ions on the displacement of tracer60Co from labeled Co-o-Hydroxybenzaldehyde isonicotinoyl hydrazone (BIH) complex in isoamyl alcohol by iron and antimony was studied. 相似文献