Recent advances in linear and nonlinear Raman spectroscopy. Part VII

Nafie, Laurence A.

doi:10.1002/jrs.4417

Cited by 20 publications

(33 citation statements)

References 303 publications

(303 reference statements)

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Section: Nih-pa Author Manuscriptmentioning

confidence: 99%

“…Because the C=O stretching vibration of esters is also Raman active, [20] we expect that the frequency-field relationships devised here can also be used to study relevant biochemical and biophysical problems in conjunction with Raman based techniques. [21] …”

Section: Nih-pa Author Manuscriptmentioning

confidence: 99%

“…In addition, we show that, when situated in a non-hydrogen bonding environment, this probe can also be used to measure the local dielectric constant (ε). For example, applying it to amyloid fibrils formed by Aβ [16][17][18][19][20][21][22] reveals that the interior of such β-sheet assemblies has a ε of ~5.6. …”

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confidence: 99%

“…As indicated (Figure 3), the non-hydrogen-bonded peaks of these peptides obtained in methanol also corroborate this picture. Thus, these results demonstrate the ability of the ester carbonyl stretching vibration to sense minimal changes in its local electrostatic environment.In the second study, we used D M to quantify the electrostatic environment in amyloid fibrils formed by a short segment of the Alzheimer's β-amyloid peptide, KLVFFAE (i.e., Aβ [16][17][18][19][20][21][22] ).While it is generally assumed that the interior of amyloid has a low dielectric constant, to the best of our knowledge, no experiments have been attempted to directly measure the electrostatic properties of such β-sheet assemblies. Here, we mutated the leucine residue of Aβ [16][17][18][19][20][21][22] to D M (the resultant peptide is referred to as Aβ-D M ) since the sidechains are similar in size.…”

mentioning

confidence: 99%

“…In the second study, we used D M to quantify the electrostatic environment in amyloid fibrils formed by a short segment of the Alzheimer's β-amyloid peptide, KLVFFAE (i.e., Aβ [16][17][18][19][20][21][22] ). While it is generally assumed that the interior of amyloid has a low dielectric constant, to the best of our knowledge, no experiments have been attempted to directly measure the electrostatic properties of such β-sheet assemblies.…”

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Ester Carbonyl Vibration as a Sensitive Probe of Protein Local Electric Field

et al. 2014

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The ability to quantify the local electrostatic environment of proteins and protein/peptide assemblies is key to yielding a microscopic understanding of many biological interactions and processes. Herein, we show that the ester carbonyl stretching vibration of two non-natural amino acids, L-aspartic acid 4-methyl ester and L-glutamic acid 5-methyl ester, is a convenient and sensitive probe in this regard since its frequency correlates linearly with the local electrostatic field for both hydrogen-bonding and non-hydrogen-bonding environments. We expect that the resultant frequency-electric field map will find use in various applications. In addition, we show that, when situated in a non-hydrogen bonding environment, this probe can also be used to measure the local dielectric constant (ε). For example, applying it to amyloid fibrils formed by Aβ [16][17][18][19][20][21][22] reveals that the interior of such β-sheet assemblies has a ε of ~5.6. Keywords IR Probe; Protein Electrostatics; Hydrogen BondingElectrostatic interactions are ubiquitous in biological molecules and, in many cases, play a key role in molecular association and enzymatic reactions. [1] However, quantifying the local electric field or how it changes inside a protein, especially in a site-specific manner and/or as a function of time, still remains a challenging task. One promising method in this regard is vibrational Stark spectroscopy, [2] which capitalizes on the fact that vibrational transitions have an intrinsic dependence on local electrostatic environment and uses an infrared (IR) probe that has a well-defined, localized vibrational mode to sense local electric field amplitude through the response of the frequency. [3] For example, the vibrational Stark effect has been used to determine the local electric field at protein interfaces and to monitor protein conformational transitions and dynamics. [4] While the theoretical underpinning of this methodology is straightforward, in practice the application of vibrational Stark spectroscopy to biological systems is currently limited by the availability of suitable vibrational probes. Herein, we show, using linear and nonlinear IR measurements and molecular dynamics (MD) simulations, that the ester carbonyl vibration in two non-natural amino acids can be used to quantitatively and site-specifically probe the electric fields of proteins, including those arising from hydrogen-bond (H-bond) interactions.The utility of a vibrational probe to reliably and conveniently measure local electric fields in proteins is evaluated by how well it meets several criteria. First and foremost, its frequency must show a sensitive and quantifiable dependence on the local electric field. Also, a chemical or biological method must exist to incorporate the probe into a protein.Furthermore, it must minimally perturb the native chemical and structural environment of interest. Finally, its vibration must be a localized mode having a large cross-section and, ideally, be located in an uncongested region of the IR spectru...

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Section: Nih-pa Author Manuscriptmentioning

confidence: 99%

Section: Nih-pa Author Manuscriptmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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confidence: 99%

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Ester Carbonyl Vibration as a Sensitive Probe of Protein Local Electric Field

et al. 2014

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Vibrational Spectroscopy as a Tool to Investigate Carotenoids

Dobrowolski

2016

Carotenoids

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Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

Wang,

Li,

Xie

et al. 2024

Angewandte Chemie

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Electrolytes that can keep liquid state are one of the most important physical metrics to ensure the ions transfer with stable operation of rechargeable lithium‐based batteries at a wide temperature window. It is generally accepted that strong polar solvents with high melting points favor the safe operation of batteries above room temperatures but are susceptible to crystallization at low temperatures (≤−40 °C). Here, a crystallization limitation strategy was proposed to handle this issue. We demonstrate that, although the high melting points of ethylene sulfite (ES, −17 °C) and fluoroethylene carbonate (FEC, ≈23 °C), their mixtures can avoid crystallization at low temperatures, which can be attributed to low intermolecular interactions and altered molecular motion dynamics. A suitable ES/FEC ratio (10 % FEC) can balance the bulk and interface transport of ions, enabling LiNi0.8Mn0.1Co0.1O2||lithium (NCM811||Li) full cells to deliver excellent temperature resilience and cycling stability over a wide temperature range from −50 °C to +70 °C. More than 66 % of the capacity retention was achieved at −50 °C compared to room temperature. The NCM811||Li pouch cells exhibit high cycling stability under realistic conditions (electrolyte weight to cathode capacity ratio (E/C)≤3.5 g Ah−1, negative to positive electrode capacity ratio (N/P)≤1.09) at different temperatures.

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Recent advances in linear and nonlinear Raman spectroscopy. Part VII

Abstract: are highlighted in this review and reflect topics and advances at the frontier of Raman spectroscopy, a field that is expanding rapidly as a sensitive photonic probe of matter at the molecular level in an ever widening sphere of novel applications.

Cited by 20 publications

References 303 publications

Ester Carbonyl Vibration as a Sensitive Probe of Protein Local Electric Field

Ester Carbonyl Vibration as a Sensitive Probe of Protein Local Electric Field

Vibrational Spectroscopy as a Tool to Investigate Carotenoids

Asymmetric Solvents Regulated Crystallization‐Limited Electrolytes for All‐Climate Lithium Metal Batteries

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