Chirality () is a fundamental property of objects, in terms of symmetry. It is extremely important to sense and distinguish chiral molecules in the fields of biochemistry, science, and medicine. Vibrational circular dichroism (VCD) spectroscopy, obtained from the differential absorption of left- and right- circularly polarized light (CPL) in the infrared range, is a promising technique for enantiomeric detection and separation. However, VCD signals are typically very weak for most small molecules. Dielectric metasurfaces are an emerging platform to enhance the sensitivity of VCD spectroscopy of chiral molecules via superchiral field manipulation. Here, we demonstrate a dielectric metasurface consisting of achiral germanium (Ge) tetramer nanoresonators that provide a proper and accessible high enhancement (). We realize a maximum enhancement () with respect to the incident CPL ( = ) of more than 750. The volume-averaged enhancement ( = ) is 148 in the 50 nm thick region above the sample surface and 215 in the central region of the structure. Especially, the corresponding values are more than 89 and 183 even when a 50 nm thick chiral lossy molecular layer is coated on the metasurface. The metasurface benefits from geometrically achiral nanostructure design to eliminate intrinsic background chiral-optical signal from the substrate, which is useful in chiral sensing, enantioselectivity, and VCD spectroscopy applications in the mid-infrared range.
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http://dx.doi.org/10.1021/acsphotonics.3c01186 | DOI Listing |
Chirality
November 2024
Instituto de Ciência e Tecnologia, Universidade Federal de São Paulo, São José do Campos, São Paulo, Brazil.
Fargesin is an important bioactive furofuran lignan isolated from different plant species. Despite presenting potent biological activities, its stereochemical characterization has relied mostly on empirical correlations of optical rotation, an approach considered risky that commonly leads to misassignments and error propagation. Additionally, the enantiomeric purity of fargesin isolates used for biological assays has not been previously investigated.
View Article and Find Full Text PDFJ Nat Prod
November 2024
Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Tongji Medical College, Huazhong University of Science and Technology, Wuhan 430030, People's Republic of China.
A chemical investigation of the coral-derived fungus sp. TJ403-AL05 led to the isolation of 18 duclauxin analogues (-), 14 of which, taladuxins A-N (-), are new and consist of the first example of duclauxin fused with one 1,6-dioxaspiro[4.5]decan-2-one moiety (), as well as its biosynthetic product (), and 12 6/6/6/5/6/6/6 heptacyclic derivatives (-).
View Article and Find Full Text PDFJ Biotechnol
November 2024
Nanoscale Biophotonics Laboratory, University of Galway, Galway H91TK33, Ireland. Electronic address:
Biopharmaceutical process development often involves the use of small-scale bioreactors (SSBR) for optimizing media formulations and process conditions during scale up to commercial scale production. Two key process parameters (CPP) used in SSBR studies are protein titre and viable cell density (VCD). Here, we explore the efficacy of parallel polarized total synchronous fluorescence spectroscopy (TSFS) and Synchronous Light Scattering (SyLS) to qualitatively monitor these CPPs and quantitatively predict titre and VCD for a large-scale cell culture media optimization SSBR study.
View Article and Find Full Text PDFInt J Mol Sci
September 2024
Department of Organic Chemistry, University of Debrecen, P. O. Box 400, 4002 Debrecen, Hungary.
Optically active heterodimeric 5,5'-linked -isochromans, containing a stereogenic -trisubstituted biaryl axis and up to four chirality centers, were synthesized stereoselectively by using a Suzuki-Miyaura biaryl coupling reaction of optically active isochroman and 1-arylpropan-2-ol derivatives, providing the first access to synthetic biaryl-type isochroman dimers. Enantiomeric pairs and stereoisomers up to seven derivatives were prepared with four different substitution patterns, which enabled us to test how OR, ECD, and VCD measurements and DFT calculations can be used to determine parallel central and axial chirality elements in three isolated blocks of chirality. In contrast to natural penicisteckins A-D and related biaryls, the ECD spectra and OR data of (a) and (a) atropodiastereomers did not reflect the opposite axial chirality, but they were characteristic of the central chirality.
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