Intelligent Chiral Sensing Based on Supramolecular and Interfacial Concepts

Of the known intelligently-operating systems, the majority can undoubtedly be classed as being of biological origin. One of the notable differences between biological and artificial systems is the important fact that biological materials consist mostly of chiral molecules. While most biochemical processes routinely discriminate chiral molecules, differentiation between chiral molecules in artificial systems is currently one of the challenging subjects in the field of molecular recognition. Therefore, one of the important challenges for intelligent man-made sensors is to prepare a sensing system that can discriminate chiral molecules. Because intermolecular interactions and detection at surfaces are respectively parts of supramolecular chemistry and interfacial science, chiral sensing based on supramolecular and interfacial concepts is a significant topic. In this review, we briefly summarize recent advances in these fields, including supramolecular hosts for color detection on chiral sensing, indicator-displacement assays, kinetic resolution in supramolecular reactions with analyses by mass spectrometry, use of chiral shape-defined polymers, such as dynamic helical polymers, molecular imprinting, thin films on surfaces of devices such as QCM, functional electrodes, FET, and SPR, the combined technique of magnetic resonance imaging and immunoassay, and chiral detection using scanning tunneling microscopy and cantilever technology. In addition, we will discuss novel concepts in recent research including the use of achiral reagents for chiral sensing with NMR, and mechanical control of chiral sensing. The importance of integration of chiral sensing systems with rapidly developing nanotechnology and nanomaterials is also emphasized

Changes in protein expression in mussels Mytilus galloprovincialis dietarily exposed to PVP/PEI coated silver nanoparticles at different seasons

Potential toxic effects of Ag NPs ingested through the food web and depending on the season have not been addressed in marine bivalves. This work aimed to assess differences in protein expression in the digestive gland of female mussels after dietary exposure to Ag NPs in autumn and spring. Mussels were fed daily with microalgae previously exposed for 24 hours to 10 µg/L of PVP/PEI coated 5 nm Ag NPs. After 21 days, mussels significantly accumulated Ag in both seasons and Ag NPs were found within digestive gland cells and gills. Two-dimensional electrophoresis distinguished 104 differentially expressed protein spots in autumn and 142 in spring. Among them, chitinase like protein-3, partial and glyceraldehyde-3-phosphate dehydrogenase, that are involved in amino sugar and nucleotide sugar metabolism, carbon metabolism, glycolysis/gluconeogenesis and the biosynthesis of amino acids KEGG pathways, were overexpressed in autumn but underexpressed in spring. In autumn, pyruvate metabolism, citrate cycle, cysteine and methionine metabolism and glyoxylate and dicarboxylate metabolism were altered, while in spring, proteins related to the formation of phagosomes and hydrogen peroxide metabolism were differentially expressed. Overall, protein expression signatures depended on season and Ag NPs exposure, suggesting that season significantly influences responses of mussels to NP exposure.This work has been funded by the Spanish Ministry of Economy and Competitiveness (NanoSilverOmics project MAT2012-39372), Basque Government (SAIOTEK project S-PE13UN142 and Consolidated Research Group GIC IT810-13) and the University of the Basque Country UPV/EHU (UFI 11/37 and PhD fellowship to N.D.). This study had also the support of Fundação para a Ciência e Tecnologia (FCT) from Portugal through the Strategic Project UID/MAH00350/2013 granted to CIMA. The contribution of K. Mehennaoui was possible within the project NanoGAM (AFR-PhD-9229040) and M. Mikolaczyk was supported by a PhD fellowship from the French Ministry of Higher Education and Research.info:eu-repo/semantics/acceptedVersio

Understanding the catalyst-free transformation of amorphous carbon into graphene by current-induced annealing

We shed light on the catalyst-free growth of graphene from amorphous carbon (a–C) by current induced annealing by witnessing the mechanism both with in-situ transmission electron microscopy and with molecular dynamics simulations. Both in experiment and in simulation, we observe that small a–C clusters on top of a graphene substrate rearrange and crystallize into graphene patches. The process is aided by the high temperatures involved and by the van der Waals interactions with the substrate. Furthermore, in the presence of a–C, graphene can grow from the borders of holes and form a seamless graphene sheet, a novel finding that has not been reported before and that is reproduced by the simulations as well. These findings open up new avenues for bottom-up engineering of graphene-based devices.QN/Quantum NanoscienceApplied Science