Detection of surface structural changes during adsorption events using two-trace two-dimensional (2T2D) correlation spectroscopy

Gozdzialski, Lea; Hore, Dennis K.

doi:10.1016/j.molstruc.2020.128246

Cited by 8 publications

(3 citation statements)

References 28 publications

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“…In such cases, it has recently been demonstrated that 2T‐2D analysis can qualitatively reveal whether changes in the orientation distribution occur, thereby interfering with interpretation based on population alone. [ 131 ] Heterospectral 2T‐2D is on the horizon, and we anticipate that powerful variants merging Raman and surface sensitive probes such as SFG will greatly facilitate the understanding of structure at aqueous interfaces.…”

Section: Combined Use Of Raman and Sfg Datamentioning

confidence: 99%

The utility of Raman spectra in aiding the interpretation of surface structure at aqueous interfaces

Azam

Hore

2022

J Raman Spectroscopy

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In this perspective, we review how Raman spectroscopy of bulk aqueous phases can assist in the interpretation of surface-selective vibrational spectra obtained from visible-infrared sum-frequency generation experiments. This overcomes the limitations associated with a reliance on spectral fitting to study characteristic vibrational modes of all species and thereby provides an allexperimental route for analysis of spectral features, including cases where spectra are available in only a single set of beam polarizations. The basic principle is based on two-dimensional correlation analysis, a generalized method with broad applicability, but most well-known in its application to vibrational spectra. We provide an example of the type of information that can be obtained when using heterospectral correlation that includes both sum-frequency and Raman data. The combination of these methods can help to unravel characteristic features of aqueous interfaces such as the surface preference of adsorbed species relative to their bulk concentration.

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Section: Combined Use Of Raman and Sfg Datamentioning

confidence: 99%

The utility of Raman spectra in aiding the interpretation of surface structure at aqueous interfaces

Azam

Hore

2022

J Raman Spectroscopy

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“…In 2D-COS, a group of spectra, obtained under some form of perturbation on the sample, are converted into a correlation intensity plot defined by two independent spectral variable axes. During the past three decades, 2D-COS has attracted extensive interest and numerous publications have been accumulated. − Many subtle spectral variations, not readily observed in original spectra, can be revealed via the characteristic cross-peaks in the corresponding 2D correlation spectra. Especially, 2D-COS provides a promising chance to investigate intermolecular interactions.…”

Section: Introductionmentioning

confidence: 99%

Novel Method for Extracting the Spectrum of a Supramolecular Complex via a Comprehensive Approach Involving Two-Dimensional Correlation Spectroscopy, Genetic Algorithm, and Grid Searching

Song

et al. 2022

Anal. Chem.

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A supramolecular complex may be formed by two solutes via a weak intermolecular interaction in a solution. The spectrum of the complex is often inundated by the spectra of the solutes that are not involved in the intermolecular interaction. Herein, a novel spectral analysis approach is proposed to retrieve the spectrum of the supramolecular complex. First, a two-dimensional (2D) asynchronous spectrum is constructed. Then, a genetic algorithm is used to obtain a heuristic spectrum of the supramolecular complex. The heuristic spectrum is a linear combination of the spectrum of the complex and the spectrum of a solute. The coefficients of the linear combination are then obtained, according to which the equilibrium constants are invariant among the sample solutions used to construct the 2D asynchronous spectrum. We have applied the approach to a supramolecular system formed by benzene and I2. In the analysis, several binding models are evaluated, and a benzene molecule interacting with two iodine molecules via halogen bonding turns out to be the only possible model. Hence, the characteristic band of the benzene/I2 supramolecular complex around 1819 cm–1 in the Fourier transform infrared (FTIR) spectrum and the corresponding equilibrium constant are obtained. The above results indicate that the novel approach provides a chance to get new insight into various intermolecular interactions studied by spectroscopy.

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“…2D-COS , (a brief description of 2D-COS is present in Part 1 in the Supporting Information) may provide an alternative way to obtain the spectra of pure components from the DOSY-NMR experiment. During the past three decades, numerous papers relevant to 2D-COS have been published − since many subtle spectral variations that are not observable in conventional spectra can be revealed by 2D-COS. There is a considerable amount of work relevant to the application of 2D-COS in the analysis of NMR spectra. − Among these works, Eads and Noda showed that 2D-COS is a promising way to discriminate NMR peaks from different components based on their distinct decay behaviors in a DOSY–NMR experiment .…”

Section: Introductionmentioning

confidence: 99%

Retrieving Spectra of Pure Components from the DOSY-NMR Experiment via a Comprehensive Approach Involving the 2D Asynchronous Spectrum, 2D Quotient Spectrum, and Genetic Algorithm Refinement

et al. 2022

Anal. Chem.

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When diffusion coefficients of different components in a mixture are similar, NMR spectra of pure individual components are difficult to be obtained via a diffusion-ordered spectroscopy (DOSY) experiment. Two-dimensional correlation spectroscopy (2D-COS) is used to analyze the data from the DOSY experiment. Through the properties of the systematic absence of cross-peak (SACP) in the 2D asynchronous spectra, spectra of pure components can be obtained even if their diffusion coefficients are similar. However, fluctuations in peak-position and peak-width are often unavoidable in NMR spectra, which makes SACPs unrecognizable. To address the problem, a 2D quotient spectrum is used to identify the masked SACPs. However, undesirable interference peaks due to the fluctuations in peak-position and peak-width are still present when we extract a spectrum of a component by slicing the 2D asynchronous spectrum across the SACP. A genetic algorithm (GA) is used to select a suitable subset of spectra where the diversities of peak-position and peak-width are significantly reduced. Then, we used the selected spectra to construct a refined 2D asynchronous spectrum so that the spectra of pure components with significant attenuated interference can be obtained. The above approach has been proven to be effective on a model system and a real-world example, demonstrating that 2D-COS possesses a bright perspective in the analysis of the bilinear data from DOSY experiments.

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Detection of surface structural changes during adsorption events using two-trace two-dimensional (2T2D) correlation spectroscopy

Cited by 8 publications

References 28 publications

The utility of Raman spectra in aiding the interpretation of surface structure at aqueous interfaces

The utility of Raman spectra in aiding the interpretation of surface structure at aqueous interfaces

Novel Method for Extracting the Spectrum of a Supramolecular Complex via a Comprehensive Approach Involving Two-Dimensional Correlation Spectroscopy, Genetic Algorithm, and Grid Searching

Retrieving Spectra of Pure Components from the DOSY-NMR Experiment via a Comprehensive Approach Involving the 2D Asynchronous Spectrum, 2D Quotient Spectrum, and Genetic Algorithm Refinement

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