The chemical reactions in electrosprays of water do not always correspond to those at the pristine air–water interface

Gallo, Adair; Farinha, Andreia S.F.; Dinis, Miguel; Emwas, Abdul Hamid; Santana, Adriano; Nielsen, Robert J.; Goddard, William A.; Mishra, Himanshu

doi:10.1039/c8sc05538f

Cited by 52 publications

(69 citation statements)

References 105 publications

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“…Numerous versions of SOFAST-HMQC experiments have been proposed for different purposes depending on the experimental conditions [86,87]. As an example, 13 C methyl SOFAST experiment has been developed, allowing the recording of high-quality methyl 1 H-13 C correlation spectra of protein with high Figure 2. Profits of the high-field NMR magnetic fields on spectral resolution and sensitivity.…”

Section: Sofast 2d Nmrmentioning

confidence: 99%

“…Moreover, NMR offers several approaches to studying molecular dynamics and to probing the interactions of inert molecules such as protein-protein, protein-DNA, and proteinligand. The main strength of NMR spectroscopy is its ability to discern or resolve individual resonance frequencies of a wide range of different nuclei (e.g., 1 H, 13 C, Figure 1. Frequency scale ranges and types of spectroscopies that correspond to them, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…Frequency scale ranges and types of spectroscopies that correspond to them, respectively. The natural abundances and chemical shifts of the most common ( 15 N, 13 C, 31 P, 19 F, and 1 H nuclei) nuclei biomolecules studies with respect to the scale of the 600 MHz proton frequency adapted from [1]. New Advances in Fast Methods of 2D NMR Experiments DOI: http://dx.doi.org /10.5772/intechopen.90263 are at 298 K, the most common temperature in which biomolecular NMR measurements are performed.…”

Section: Introductionmentioning

confidence: 99%

“…In earlier days, most NMR experiments only recorded one-dimensional (1D) spectra of which several were of 1 H or 13 C nuclei. For complex biomacromolecules, such as proteins, nucleic acids and their complexes, and complex mixtures, this technique has a particularly low spectral range of 1 H resonance, what leads to the low resolution of the spectra.…”

Section: Introductionmentioning

confidence: 99%

“…More importantly, NMR has the ability to evaluate information about the environment of each atom and their neighbor's nuclei (both through space and through bond), allowing researchers to differentiate the unique magnetic environments of the same nuclei in different positions of a single molecule. Thus, NMR spectroscopy is extensively used for the identification and in the structural elucidation in a wide Nuclear Magnetic Resonance 2 range of applications in gas [2,3], liquid [4][5][6][7][8][9][10][11][12][13][14][15][16], and solid-state samples [17][18][19][20][21][22][23][24][25][26][27][28]. Nowadays, NMR spectroscopy is one of the most important analytical tools that has been used in several fields.…”

mentioning

confidence: 99%

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New Advances in Fast Methods of 2D NMR Experiments

Emwas¹,

Alghrably²,

Al-Harthi³

et al. 2020

Nuclear Magnetic Resonance

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Although nuclear magnetic resonance spectroscopy is a potent analytical tool for identification, quantification, and structural elucidation, it suffers from inherently low sensitivity limitations. This chapter focuses on recently reported methods that enable quick acquisition of NMR spectra, as well as new methods of faster, efficient, and informative two-dimensional (2D) NMR methods. Fast and efficient data acquisition has risen in response to an increasing need to investigate chemical and biological processes in real time. Several new techniques have been successfully introduced. One example of this is band-selective optimized-flip-angle shorttransient (SOFAST) NMR, which has opened the door to studying the kinetics of biological processes such as the phosphorylation of proteins. The fast recording of NMR spectra allows researchers to investigate time sensitive molecules that have limited stability under experimental conditions. The increasing awareness that molecular structures are dynamic, rather than static, has pushed some researchers to find alternatives to standard, time-consuming methods of 15 N relaxation observables acquisition.Keywords: NMR, 2D NMR, ultrafast data processing, SOFAST, relaxation 15 N, 29 Si, 30 Al, 31 P to 235 U). As the resonating frequency is unique for each type of nuclei, one can envision an NMR for each nucleus as a separate spectroscopy such as 1 H NMR spectroscopy, 13 C NMR spectroscopy, 235 U NMR spectroscopy (Figure 1), etc. More importantly, NMR has the ability to evaluate information about the environment of each atom and their neighbor's nuclei (both through space and through bond), allowing researchers to differentiate the unique magnetic environments of the same nuclei in different positions of a single molecule. Thus, NMR spectroscopy is extensively used for the identification and in the structural elucidation in a wide Nuclear Magnetic Resonance 2 range of applications in gas [2,3], liquid [4][5][6][7][8][9][10][11][12][13][14][15][16], and solid-state samples [17][18][19][20][21][22][23][24][25][26][27][28]. Nowadays, NMR spectroscopy is one of the most important analytical tools that has been used in several fields. These fields include structural biology [29][30][31][32][33][34][35][36][37][38], organic chemistry [39][40][41][42][43][44][45][46][47][48][49][50][51][52], polymer characterization [40,46,[53][54][55][56][57][58][59][60][61][62][63][64], inorganic chemistry [65][66][67][68][69][70][71][72][73][74][75], and physics [76][77][78][79][80][81][82][83].Despite its significant advantages, NMR suffers from some limitations, of which the relatively low sensitivity seems to be the most severe. An NMR sample can be treated as a collection of many nuclear spins of magnetically active nuclei that act as small bar magnets. These nuclear spins have two possible orientations with different energy levels that adapt when placed within the strong magnetic field. The number of nuclear spins occupying each energy level is determined by the Boltzmann distribution equation: N ...

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Section: Sofast 2d Nmrmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

See 3 more Smart Citations

New Advances in Fast Methods of 2D NMR Experiments

Emwas¹,

Alghrably²,

Al-Harthi³

et al. 2020

Nuclear Magnetic Resonance

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Water Self‐Dissociation is Insensitive to Nanoscale Environments

Di Pino,

Perez Sirkin,

Morzan

et al. 2023

Angewandte Chemie

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Nanoconfinement effects on water dissociation and reactivity remain controversial, despite their importance to understand the aqueous chemistry at interfaces, pores, or aerosols. The pKw in confined environments has been assessed from experiments and simulations in a few specific cases, leading to dissimilar conclusions. Here, with the use of carefully designed ab initio simulations, we demonstrate that the energetics of bulk water dissociation is conserved intact to unexpectedly small length‐scales, down to aggregates of only a dozen molecules or pores of widths below 2 nm. The reason is that most of the free‐energy involved in water autoionization comes from breaking the O−H covalent bond, which has a comparable barrier in the bulk liquid, in a small droplet of nanometer size, or in a nanopore in the absence of strong interfacial interactions. Thus, dissociation free‐energy profiles in nanoscopic aggregates or in 2D slabs of 1 nm width reproduce the behavior corresponding to the bulk liquid, regardless of whether the corresponding nanophase is delimited by a solid or a gas interface. The present work provides a definite and fundamental description of the mechanism and thermodynamics of water dissociation at different scales with broader implications on reactivity and self‐ionization at the air‐liquid interface.

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