We report the first mid-infrared observation of vibrational circular birefringence (VCB) arising from individual chiral molecules. VCB can also be called vibrational optical rotatory dispersion (VORD) and is the Kramers-Kronig transform of vibrational circular dichroism (VCD). The method of measurement involves a simple change in the optical set-up and electronic processing of a VCD spectrometer such that the VCB spectrum appears at twice the polarization modulation frequency as a pseudo vibrational linear dichroism (VLD) spectrum. VCB spectra are also calculated with density function theory (DFT) for the first time using a commercially available program for rotational strengths where the calculated intensities are convolved with the real, dispersive part of a normalized complex Lorentzian lineshape rather than the imaginary, absorptive part, normally used for IR and VCD intensity calculations. Comparison of the measured and calculated VCB, VCD, and IR spectra of (+)-R-limonene and (-)-S-alpha-pinene show close agreement and confirm the validity of the new VCB measurements.
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http://dx.doi.org/10.1002/chir.20816 | DOI Listing |
Chemphyschem
December 2024
Freie Universität Berlin: Freie Universitat Berlin, Dahlem Center of Complex Quantum Systems and Fachbereich Physik, Arnimallee 14, 14195, Berlin, GERMANY.
Quantum chemical calculations of one-photon absorption, electronic circular dichroism and anisotropy factor spectra for the A-band transition of fenchone, camphor and 3-methylcyclopentanone (3MCP) are reported. While the only weakly allowed nature of the transition leads to comparatively large anisotropies, a proper theoretical description of the absorption for such a transition requires to account for non-Condon effects. We present experimental data for the anisotropy of 3MCP in the liquid phase and show that corresponding Herzberg-Teller corrections are critical to reproduce the main experimental features.
View Article and Find Full Text PDFJ Phys Chem B
December 2024
Department of Chemistry, Drexel University, Philadelphia, Pennsylvania 19104, United States.
The ultrashort peptide -fluorenylmethoxycarbonyl-phenylalanyl-phenylalanine (FmocFF) has been largely investigated due to its ability to self-assemble into fibrils (100 nm-μm scale) that can form a sample-spanning gel network. The initiation of the gelation process requires either a solvent switch (water added to dimethyl sulfoxide) or a pH-switch (alkaline to neutral) protocol, both of which ensure the solubility of the peptide as a necessary step preceding gelation. While the respective gel phases are well understood in structural and material characteristics terms the pregelation conditions are known to a lesser extent.
View Article and Find Full Text PDFJ 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 PDFLab Chip
December 2024
College of Engineering and Applied Sciences, Nanjing University, Jiangsu 210093, China.
Acoustic waves provide an effective method for object manipulation in microfluidics, often requiring high-frequency ultrasound in the megahertz range when directly handling microsized objects, which can be costly. Micro-air-bubbles in water offer a solution toward low-cost technologies using low-frequency acoustic waves. Owing to their high compressibility and low elastic modulus, these bubbles can exhibit significant expansion and contraction in response to even kilohertz acoustic waves, leading to resonances with frequencies determined and tuned by air-bubble size.
View Article and Find Full Text PDFSensors (Basel)
November 2024
Faculty of Mechanical Engineering, Lublin University of Technology, 36, 20-618 Lublin, Poland.
This paper experimentally examines the influence of hybrid excitation on the performance of vibrational piezoelectric energy harvesting systems on a bluff body with a variable cross section along its generatrix. A combination of vibrational excitation from a shaker and airflow is considered the source from which energy is harvested. Varied excitation frequencies and airflow velocities across five different masses were considered, each defining the natural frequency of the system.
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