IR and Raman frequency shifts have been reported for numerous probes of enzyme transition states, leading to diverse interpretations. In the case model ketosteroid isomerase (KSI), we argued that spectral a carbonyl probe at active site can provide connection between electric field activation free energy (Fried et al. Science 2014, 346, 1510–1514). Here generalize this approach much broader set (e.g., oxoesters, thioesters, amides), first establishing sensitivity each an using vibrational...

The physical origins of vibrational frequency shifts have been extensively studied in order to understand noncovalent intermolecular interactions the condensed phase. In case carbonyls, solvatochromism, MD simulations, and Stark spectroscopy suggest that observed simple solvents arise predominately from environment's electric field due effect. This is contrary many previously invoked descriptions shifts, such as bond polarization, whereby bond's force constant and/or partial nuclear charges...

The interplay of enzyme active site electrostatics and chemical positioning is important for understanding the origin(s) catalysis design novel catalysts. We reconstruct evolutionary trajectory TEM-1 β-lactamase to TEM-52 toward extended-spectrum activity better understand emergence antibiotic resistance provide insights into structure-function paradigm noncovalent interactions involved in catalysis. Utilizing a detailed kinetic analysis vibrational Stark effect, we quantify changes rates...

To understand the consequences of macromolecular crowding, studies have largely employed in vitro experiments with synthetic polymers assumed to be both pure and "inert". These alter enzyme kinetics by excluding volume that would otherwise available enzymes, substrates, products. Presented here is evidence other factors, addition excluded volume, must considered interpretation crowding polymers. Dextran has a weaker effect on Michaelis-Menten kinetic parameters yeast alcohol dehydrogenase...

Noncovalent interactions underlie nearly all molecular processes in the condensed phase from solvation to catalysis. Their quantification within a physically consistent framework remains challenging. Experimental vibrational Stark effect (VSE)-based solvatochromism can be combined with dynamics (MD) simulations quantify electrostatic forces solute–solvent for small rigid molecules and, by extension, when these solutes bind enzyme active sites. While generalizing this approach toward more...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTProtonated cyclopropane intermediates in the reactions of cyclopropanecarboxylic acidsNorman C. Deno, Wilbur E. Billups, Daniel LaVietes, Philip Scholl, and Samuel SchneiderCite this: J. Am. Chem. Soc. 1970, 92, 12, 3700–3703Publication Date (Print):June 1, 1970Publication History Published online1 May 2002Published inissue 1 June 1970https://pubs.acs.org/doi/10.1021/ja00715a027https://doi.org/10.1021/ja00715a027research-articleACS...

Lithium ion batteries frequently employ carbonate-based electrolyte solvents to support reversible lithium storage in response electric fields applied the electrode/electrolyte junction. Although these are critical for controlling beneficial and deleterious electrochemical reactions alike, quantifying their magnitude is a persistent challenge that inhibits our fundamental understanding of high-voltage energy devices. In this study, we utilize complementary experimental techniques vibrational...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTAlkylation of acetic anhydride by triphenylmethyl cationNorman C. Deno, W. Edward. Billups, Ronald E. DiStefano, Kathryn M. McDonald, and Samuel. SchneiderCite this: J. Org. Chem. 1970, 35, 1, 278–279Publication Date (Print):January 1970Publication History Published online1 May 2002Published inissue 1 January 1970https://pubs.acs.org/doi/10.1021/jo00826a071https://doi.org/10.1021/jo00826a071research-articleACS PublicationsRequest reuse...

We demonstrate the performance of a dual frequency comb quantum cascade laser (QCL) spectrometer for application vibrational Stark spectroscopy. Measurements performed on fluorobenzene with dual-comb (DCS) were compared to results obtained using conventional Fourier transform infrared (FT-IR) instrument in terms spectral response, parameter estimation, and signal-to-noise ratio (S/N). The provided similar qualitative quantitative data as FT-IR setup 250 times shorter acquisition time. For...

A biophysical understanding of the mechanistic, chemical, and physical origins underlying antibiotic action resistance is vital to discovery novel therapeutics development strategies combat growing emergence resistance. The site-specific introduction stable-isotope labels into chemically complex natural products particularly important for techniques such as NMR, IR, mass spectrometry, imaging, kinetic isotope effects. Toward this goal, we developed a biosynthetic strategy incorporation 13C...

This work deals with the mathematical modeling and control of semi-active suspension an MAN off-road truck a payload 5 tons which comprises electrorheological dampers. Thereby, cascaded structure four controllers for quarter-car in inner loop superimposed strategy overall vehicle is used. The main goal to reduce motion chassis (especially roll, pitch vertical movement) while increasing driving stability. capability demonstrated by means simulation studies measurement results.

Non-covalent interactions underlie nearly all molecular processes in the condensed phase from solvation tocatalysis. Their quantification within a physically consistent framework remains challenging. Experimental vibrational Stark effect (VSE)-based solvatochromism can be combined with dynamics (MD) simulations to quantify electrostatic forces solute-solvent for small rigid molecules and, by extension, when these solutes bind enzyme active sites. While generalizing this approach towards more...

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to "Stark Tuning Rates of Organic Carbonates Used in Electrochemical Energy Storage Devices"Jarred Z. OlsonJarred OlsonMore by Jarred Olsonhttp://orcid.org/0000-0001-7560-8668, Samuel H. SchneiderSamuel SchneiderMore Schneiderhttp://orcid.org/0000-0002-5792-4015, Patrik K. JohanssonPatrik JohanssonMore Johansson, Ting S. LukTing LukMore Luk, and Cody W. Schlenker*Cody SchlenkerMore...

A biophysical understanding of the mechanistic, chemical, and physical origins underlying antibiotic action resistance is vital to discovery novel therapeutics development strategies combat growing emergence resistance. The site-specific introduction stable-isotope labels into chemically complex natural products particularly important for techniques such as NMR, IR, mass spectrometry, imaging, kinetic isotope effects. Towards this goal, we developed a biosynthetic strategy incorporation 13...

A biophysical understanding of the mechanistic, chemical, and physical origins underlying antibiotic action resistance is vital to discovery novel therapeutics development strategies combat growing emergence resistance. The site-specific introduction stable-isotope labels into chemically complex natural products particularly important for techniques such as NMR, IR, mass spectrometry, imaging, kinetic isotope effects. Towards this goal, we developed a biosynthetic strategy incorporation...

We demonstrate the performance of a dual frequency comb QCL spectrometer for application vibrational Stark spectroscopy. Measurements performed on fluorobenzene with dual-comb (DCS) were compared to results obtained using conventional Fourier transform infrared (FTIR) instrument in terms spectral response, parameter estimation, and signal-to-noise ratio. The provided similar qualitative quantitative data as FTIR setup 250 times shorter acquisition time. For fluorobenzene, DCS measurement...

Abstract The interplay of enzyme active site electrostatics and chemical positioning are important for understanding the origin(s) catalysis design novel catalysts. We reconstruct evolutionary trajectory TEM-1 β-lactamase to TEM-52 towards extended-spectrum activity better understand emergence antibiotic resistance provide insights into structure-function paradigm non-covalent interactions involved in catalysis. Utilizing a detailed kinetic analysis vibrational Stark effect, we quantify...

<div>Non-covalent interactions underlie nearly all molecular processes in the condensed phase from solvation to</div><div>catalysis. Their quantification within a physically consistent framework remains challenging. Experimental vibrational Stark effect (VSE)-based solvatochromism can be combined with dynamics (MD) simulations to quantify electrostatic forces solute-solvent for small rigid molecules and, by extension, when these solutes bind enzyme active sites. While...