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Recording VCD spectra of aqueous solution poses a particular challenge as water is a strong infrared absorber. Likewise, the computational analysis of VCD spectra by means of DFT-based spectral calculations requires the consideration of explicit solvent molecules, thus posing an even greater challenge. Several studies suggested that by modeling the solvent environment with a few water molecules in a micro-solvation approach would be sufficient to describe experimental spectra. For example, using proline at different pH values, we herein show that a change in the relative spatial orientation of a single water molecule in five-fold solvated structures strongly affects the computed VCD spectral signatures and that Boltzmann-weighted spectra do not correctly reproduce the experiment. We thus explored an approach based on molecular dynamics and subsequent DFT-calculations, in which we considered 30 water molecules (about 1.5 solvation shells). Once again, it was found that the Boltzmann-weighted spectra obtained on the basis of several hundred structures did not correctly reproduce experimental signatures, and a simple averaging scheme resulted in well-matching spectra with comparable bandwidths. The rationale behind the procedure was that sampling the configurational space of the solvent molecules is as equally important as the conformational sampling of the solute. For conformationally more flexible molecules, it is assumed that a much larger set of structures will have to be computed in order to properly sample the conformational space of both solute and solvent.
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http://dx.doi.org/10.1039/d4cp01768d | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, United States.
We report a stereo-differentiating dynamic kinetic asymmetric Rh(I)-catalyzed Pauson-Khand reaction, which provides access to an array of thapsigargin stereoisomers. Using catalyst-control, a consistent stereochemical outcome is achieved at C2─for both matched and mismatched cases─regardless of the allene-yne C8 stereochemistry. The stereochemical configuration for all stereoisomers was assigned by comparing experimental vibrational circular dichroism (VCD) and C NMR to DFT-computed spectra.
View Article and Find Full Text PDFPhytochemistry
February 2025
Natural Product Research Institute and Research Institute of Pharmaceutical Sciences, College of Pharmacy, Seoul National University, Seoul, 08826, Republic of Korea. Electronic address:
Nine previously undescribed (1-9) and seven known (10-16) cycloartane-type triterpenoids were isolated and characterized from Combretum quadrangulare Kurz using physicochemical and spectroscopic methods. The absolute configurations of these compounds were determined through modified Mosher's method and quantum chemical calculation of electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) spectra. Their inhibitory activities against PCSK9 secretion were assessed, and a plausible structure-activity relationship was delineated.
View Article and Find Full Text PDFPharmaceuticals (Basel)
September 2024
Laboratory for Chiral Technologies, Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Bijenička Cesta 54, 10000 Zagreb, Croatia.
Hydantoins, a class of five-membered heterocyclic compounds, exhibit diverse biological activities. The aim of this study was to synthesize and characterize a series of novel 3,5-disubstituted hydantoins and to investigate their antiproliferative activity against human cancer cell lines. The new hydantoin derivatives - were prepared as racemic mixtures of - and -isomers via a base-assisted intramolecular amidolysis of C-3 functionalized β-lactams.
View Article and Find Full Text PDFNanoscale
November 2024
Faculty of Science, Ehime University, 2-5 Bunkyo-cho, Matsuyama, Ehime, 790-8577, Japan.
Layered zinc(II) hydroxides (LZH) intercalating the deprotonated forms of -(-) or -(+)-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (denoted as - or -BNDHPH, respectively) were prepared from Zn(NO) at pH 5 and 60 °C by the mixing method. The obtained hybrid compounds (denoted as - or -BNDHP/LZH, respectively) were heated from room temperature up to 800 °C under nitrogen atmosphere. According to the thermal gravimetric/differential thermal analysis measurements, hydroxyl groups were dehydrated at 270-400 °C, followed by the decomposition of organic components at 420-600 °C.
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.
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