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      Nanoparticle-based Chemiluminescence for Chiral Discrimination of Thiol-Containing Amino Acids

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      1 , 1 , 1 , 2 ,
      Scientific Reports
      Nature Publishing Group UK

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          Abstract

          The ability to recognize the molecular chirality of enantiomers is extremely important owing to their critical role in drug development and biochemistry. Convenient discrimination of enantiomers has remained a challenge due to lack of unsophisticated methods. In this work, we have reported a simple strategy for chiral recognition of thiol-containing amino acids including penicillamine (PA), and cysteine (Cys). We have successfully designed a nanoparticle-based chemiluminescence (CL) system based on the reaction between cadmium telluride quantum dots (CdTe QDs) and the enantiomers. The different interactions of CdTe QDs with PA enantiomers or Cys enantiomers led to different CL intensities, resulting in the chiral recognition of these enantiomers. The developed method showed the ability for determination of enantiomeric excess of PA and Cys. It has also obtained an enantioselective concentration range from 1.15 to 9.2 mM for PA. To demonstrate the potential application of this method, the designed platform was applied for the quantification of PA in urine and tablet samples. For the first time, we presented a novel practical application of nanoparticle-based CL system for chiral discrimination.

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          Similar topological origin of chiral centers in organic and nanoscale inorganic structures: effect of stabilizer chirality on optical isomerism and growth of CdTe nanocrystals.

          It is observed in this study that the chirality of cysteine stabilizers has a distinct effect on both the growth kinetics and the optical properties of CdTe nanocrystals synthesized in aqueous solution. The effect was studied by circular dichroism spectroscopy, temporal UV-vis spectroscopy, photoluminescence spectroscopy, and several other microscopy and spectroscopic techniques including atomic modeling. Detailed analysis of the entirety of experimental and theoretical data led to the hypothesis that the atomic origin of chiral sites in nanocrystals is topologically similar to that in organic compounds. Since atoms in CdTe nanocrystals are arranged as tetrahedrons, chirality can occur when all four atomic positions have chemical differences. This can happen in apexes of nanocrystals, which are the most susceptible to chemical modification and substitution. Quantum mechanical calculations reveal that the thermodynamically preferred configuration of CdTe nanocrystals is S type when the stabilizer is D-cysteine and R type when L-cysteine is used as a stabilizer, which correlates well with the experimental kinetics of particle growth. These findings help clarify the nature of chirality in inorganic nanomaterials, the methods of selective production of optical isomers of nanocrystals, the influence of chiral biomolecules on the nanoscale crystallization, and practical perspectives of chiral nanomaterials for optics and medicine.
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            Gold nanoparticle-catalyzed luminol chemiluminescence and its analytical applications.

            Gold colloids with nanoparticles of different sizes were found to enhance the chemiluminescence (CL) of the luminol-H2O2 system, and the most intensive CL signals were obtained with 38-nm-diameter gold nanoparticles. UV-visible spectra, X-ray photoelectron spectra, and transmission electron microscopy studies were carried out before and after the CL reaction to investigate the CL enhancement mechanism. The CL enhancement by gold nanoparticles of the luminol-H2O2 system was supposed to originate from the catalysis of gold nanoparticles, which facilitated the radical generation and electron-transfer processes taking place on the surface of the gold nanoparticles. The effects of the reactant concentrations, the size of the gold nanoparticles. and some organic compounds were also investigated. Organic compounds containing OH, NH2, and SH groups were observed to inhibit the CL signal of the luminol-H2O2-gold colloids system, which made it applicable for the determination of such compounds.
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              Intrinsic Chirality of CdSe/ZnS Quantum Dots and Quantum Rods.

              A new class of chiral nanoparticles is of great interest not only for nanotechnology, but also for many other fields of scientific endeavor. Normally the chirality in semiconductor nanocrystals is induced by the initial presence of chiral ligands/stabilizer molecules. Here we report intrinsic chirality of ZnS coated CdSe quantum dots (QDs) and quantum rods (QRs) stabilized by achiral ligands. As-prepared ensembles of these nanocrystals have been found to be a racemic mixture of d- and l-nanocrystals which also includes a portion of nonchiral nanocrystals and so in total the solution does not show a circular dichroism (CD) signal. We have developed a new enantioselective phase transfer technique to separate chiral nanocrystals using an appropriate chiral ligand and obtain optically active ensembles of CdSe/ZnS QDs and QRs. After enantioselective phase transfer, the nanocrystals isolated in organic phase, still capped with achiral ligands, now display circular dichroism (CD). We propose that the intrinsic chirality of CdSe/ZnS nanocrystals is caused by the presence of naturally occurring chiral defects.
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                Author and article information

                Contributors
                hormozi@sharif.edu
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                18 September 2018
                18 September 2018
                2018
                : 8
                : 14011
                Affiliations
                [1 ]ISNI 0000 0001 0740 9747, GRID grid.412553.4, Department of Chemistry, , Sharif University of Technology, ; Tehran, 11155-9516 Iran
                [2 ]ISNI 0000 0001 0740 9747, GRID grid.412553.4, Institute for Nanoscience and Nanotechnology, , Sharif University of Technology, ; Tehran, Iran
                Article
                32416
                10.1038/s41598-018-32416-z
                6143635
                30228291
                48d2b60f-1dd9-442f-915b-e9f67a961875
                © The Author(s) 2018

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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                : 18 May 2018
                : 4 September 2018
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