Two-dimensional Spectroscopy Research Articles

Lipid Landscapes: Vibrational Spectroscopy for Decoding Membrane Complexity.

Cell membranes are incredibly complex environments containing hundreds of components. Despite substantial advances in the past decade, fundamental questions related to lipid-lipid interactions and heterogeneity persist. This review explores the complexity of lipid membranes, showcasing recent advances in vibrational spectroscopy to characterize the structure, dynamics, and interactions at the membrane interface. We include an overview of modern techniques such as surface-enhanced infrared spectroscopy as a steady-state technique with single-bilayer sensitivity, two-dimensional sum-frequency generation spectroscopy, and two-dimensional infrared spectroscopy to measure time-evolving structures and dynamics with femtosecond time resolution. Furthermore, we discuss the potential of multiscale molecular dynamics (MD) simulations, focusing on recently developed simulation algorithms, which have emerged as a powerful approach to interpret complex spectra. We highlight the ongoing challenges in studying heterogeneous environments in multicomponent membranes via current vibrational spectroscopic techniques and MD simulations. Overall, this review provides an up-to-date comprehensive overview of the powerful combination of vibrational spectroscopy and simulations, which has great potential to illuminate lipid-lipid, lipid-protein, and lipid-water interactions in the intricate conformational landscape of cell membranes.

Strategy for the Enzymatic Acylation of the Apple Flavonoid Phloretin Based on Prior α-Glucosylation.

The acylation of flavonoids serves as a means to alter their physicochemical properties, enhance their stability, and improve their bioactivity. Compared with natural flavonoid glycosides, the acylation of nonglycosylated flavonoids presents greater challenges since they contain fewer reactive sites. In this work, we propose an efficient strategy to solve this problem based on a first α-glucosylation step catalyzed by a sucrose phosphorylase, followed by acylation using a lipase. The method was applied to phloretin, a bioactive dihydrochalcone mainly present in apples. Phloretin underwent initial glucosylation at the 4'-OH position, followed by subsequent (and quantitative) acylation with C8, C12, and C16 acyl chains employing an immobilized lipase from Thermomyces lanuginosus. Electrospray ionization-mass spectrometry (ESI-MS) and two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) confirmed that the acylation took place at 6-OH of glucose. The water solubility of C8 acyl glucoside closely resembled that of aglycone, but for C12 and C16 derivatives, it was approximately 3 times lower. Compared with phloretin, the radical scavenging capacity of the new derivatives slightly decreased with 2,2-diphenyl-1-picrylhydrazyl (DPPH) and was similar to 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+). Interestingly, C12 acyl-α-glucoside displayed an enhanced (3-fold) transdermal absorption (using pig skin biopsies) compared to phloretin and its α-glucoside.

Exciton-carrier coupling in a metal halide perovskite nanocrystal assembly probed by two-dimensional coherent spectroscopy

The surface chemistry and inter-connectivity within perovskite nanocrystals play a critical role in determining the electronic interactions. They manifest in the Coulomb screening of electron–hole correlations and the carrier relaxation dynamics, among other many-body processes. Here, we characterize the coupling between the exciton and free carrier states close to the band-edge in a ligand-free formamidinium lead bromide nanocrystal assembly via two-dimensional coherent spectroscopy. The optical signatures observed in this work show: (i) a nonlinear spectral lineshape reminiscent of Fano-like interference that evidences the coupling between discrete electronic states and a continuum, (ii) symmetric excited state absorption cross-peaks that suggest the existence of a coupled exciton-carrier excited state, and (iii) ultrafast carrier thermalization and exciton formation. Our results highlight the presence of coherent coupling between exciton and free carriers, particularly in the sub-100 femtosecond timescales.

Structural analysis of pharmaceutical tablets using two-dimensional X-ray absorption fine-structure spectroscopy and its combination with X-ray computed tomography

The pharmaceutical properties of a solid formulations depend on their structure. To obtain structural information, such as the density, porosity, crystal forms of drugs, and the three-dimensional distribution of the drug and excipient particles within the formulations, is useful for formulation design and development. In this research, two-dimensional X-ray absorption fine-structure spectroscopy (2D-XAFS) and its combination with X-ray computed tomography (CT) were used for internal-structure analysis of tablets. Tablets containing form-II crystals and/or an amorphous solid dispersion (ASD) of bromhexine hydrochloride (BRH) were prepared and measured at a synchrotron radiation facility. The XAFS spectra of form-II crystals and the ASD of BRH were obtained after properly calibrating the irradiated X-ray energies. Their XAFS spectra showed small but marked differences. Form-II crystals and the ASD could be distinguished and visualized in the 2D-XAFS transmission and CT-XAFS slice images. Both 2D-XAFS and CT-XAFS provided detailed structural information and may be a useful alternative method in the development stage of solid dosage formulations.

Helical sulfonyl-γ-AApeptides modulating Aβ oligomerization and cytotoxicity by recognizing Aβ helix

In contrast to prevalent strategies which make use of β-sheet mimetics to block Aβ fibrillar growth, in this study, we designed a series of sulfonyl-γ-AApeptide helices that targeted the crucial α-helix domain of Aβ13-26 and stabilized Aβ conformation to avoid forming the neurotoxic Aβ oligomeric β-sheets. Biophysical assays such as amyloid kinetics and TEM demonstrated that the Aβ oligomerization and fibrillation could be greatly prevented and even reversed in the presence of sulfonyl-γ-AApeptides in a sequence-specific and dose-dependent manner. The studies based on circular dichroism, Two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR) spectra unambiguously suggested that the sulfonyl-γ-AApeptide Ab-6 could bind to the central region of Aβ42 and induce α-helix conformation in Aβ. Additionally, Electrospray ionisation-ion mobility spectrometry-mass spectrometry (ESI-IMS-MS) was employed to rule out a colloidal mechanism of inhibitor and clearly supported the capability of Ab-6 for inhibiting the formation of Aβ aggregated forms. Furthermore, Ab-6 could rescue neuroblastoma cells by eradicating Aβ-mediated cytotoxicity even in the presence of pre-formed Aβ aggregates. The confocal microscopy demonstrated that Ab-6 could still specifically bind Aβ42 and colocalize into mitochondria in the cellular environment, suggesting the rescue of cell viability might be due to the protection of mitochondrial function otherwise impaired by Aβ42 aggregation. Taken together, our studies indicated that sulfonyl-γ-AApeptides as helical peptidomimetics could direct Aβ into the off-pathway helical secondary structure, thereby preventing the formation of Aβ oligomerization, fibrillation and rescuing Aβ induced cell cytotoxicity.

Two-Dimensional Spectroscopy Isolates Infrared Rovibrational Patterns.

The rovibrational spectra of freely rotating gas phase molecules are often plagued by spectral congestion due to the high density of rotational peaks. The congestion is especially severe at higher infrared frequencies due to the large numbers of overlapping overtones and combination bands that form polyads. As a result, rovibrational peaks in the near-infrared region of the spectrum are seldom assigned. This work describes how two-dimensional (2D) rovibrational spectroscopy can use the coupling between vibrational modes to isolate rovibrational bands that would otherwise remain overlapped and congested. Multidimensional spectroscopic techniques that make use of the large number of cross-peaks that form rich 2D rovibrational patterns are explored. Propyne is used to demonstrate 2D methods for identifying the frequencies and symmetries of coupled vibrations and for assigning rotational quantum numbers, even in regions that are heavily congested.

Characterization of the nonlinear THz focus for 2D THz spectroscopy

We present a sensitive imaging method capable of the selective characterization of the nonlinear THz beam profile, providing a direct handle to optimize χ(3) light-matter interactions that are critical to two-dimensional (2D) THz spectroscopies. In particular, this method facilitates the development of experimentally challenging 2D THz spectroscopies with multiple THz emitters, which enables direct investigations of fast picosecond dynamics in liquids and solids that are challenging in single-emitter 2D THz spectroscopic setups.

New indole derivatives from endophytic fungus Colletotruchum sp. HK-08 originated from leaves of Nerium indicum

ObjectiveTo study secondary metabolites from endophytic fungus Colletotruchum sp. HK-08 originated from the leaves of Nerium indicum. MethodsThe compounds were isolated by various column chromatographic techniques, and their structures were elucidated by spectroscopic techniques [high resolution electrospray ionization mass spectroscopy (HRESIMS), one-dimensional (1D) and two-dimensional (2D) nuclear magnetic resonance spectroscopy (NMR)], as well as comparison with literature data. The Ellman method was used to determine the acetylcholinesterase (AChE) inhibitory activity. ResultsFour indole derivatives were identified from Colletotruchum sp. HK-08, including 6′-hydroxymonaspiloindole (1), 2-(2-oxoindolin-3-yl)ethyl 2-(4-hydroxyphenyl) acetate (2), 2-(2-oxoindolin-3-yl)ethyl 2-(2-hydroxyphenyl)acetate (3), and monaspiloindole (4). Compound 4 presented weak AChE inhibitory activity with IC50 value of (69.30 ± 6.27) μmol/L [tacrine as the positive control, with IC50 value of (0.61 ± 0.07) μmol/L]. ConclusionCompounds 1–3 were new compounds, and compound 4 had weak AChE inhibitory activity.

Cross-phase modulation in two-dimensional spectroscopy.

Developing from transient absorption (TA) spectroscopy, two-dimensional (2D) spectroscopy with pump-probe geometry has emerged as a versatile approach for alleviating the difficulty in implementing 2D spectroscopy with other geometries. However, the presence of cross-phase modulation (XPM) in TA spectroscopy introduces significant spectral distortions, particularly when the pump and probe pulses overlap. We demonstrate that this phenomenon is extended to the 2D spectroscopy with pump-probe geometry and the XPM is induced by the interference of the two pump pulses. We present the oscillatory behavior of XPM in the 2D spectrum and its displacement with respect to the waiting time delay through both experimental measurements and numerical simulations. Additionally, we explore the influence of probe pulse chirp on XPM and discover that by compressing the chirp, the impact of XPM on the desired signal can be reduced.

Microscopic many-body theory of two-dimensional coherent spectroscopy of excitons and trions in atomically thin transition metal dichalcogenides

Microscopic many-body theory of two-dimensional coherent spectroscopy of excitons and trions in atomically thin transition metal dichalcogenides

The development and applications of multidimensional biomolecular spectroscopy illustrated by photosynthetic light harvesting.

The parallel and synergistic developments of atomic resolution structural information, new spectroscopic methods, their underpinning formalism, and the application of sophisticated theoretical methods have led to a step function change in our understanding of photosynthetic light harvesting, the process by which photosynthetic organisms collect solar energy and supply it to their reaction centers to initiate the chemistry of photosynthesis. The new spectroscopic methods, in particular multidimensional spectroscopies, have enabled a transition from recording rates of processes to focusing on mechanism. We discuss two ultrafast spectroscopies - two-dimensional electronic spectroscopy and two-dimensional electronic-vibrational spectroscopy - and illustrate their development through the lens of photosynthetic light harvesting. Both spectroscopies provide enhanced spectral resolution and, in different ways, reveal pathways of energy flow and coherent oscillations which relate to the quantum mechanical mixing of, for example, electronic excitations (excitons) and nuclear motions. The new types of information present in these spectra provoked the application of sophisticated quantum dynamical theories to describe the temporal evolution of the spectra and provide new questions for experimental investigation. While multidimensional spectroscopies have applications in many other areas of science, we feel that the investigation of photosynthetic light harvesting has had the largest influence on the development of spectroscopic and theoretical methods for the study of quantum dynamics in biology, hence the focus of this review. We conclude with key questions for the next decade of this review.

Targeted synthesis of gold nanorods and characterization of their tailored surface properties using optical and X-ray spectroscopy.

In recent years, nanophotonics have had a transformative impact on harnessing energy, directing chemical reactions, and enabling novel molecular dynamics for thermodynamically intensive applications. Plasmonic nanoparticles have emerged as a tool for confining light on nanometer-length scales where regions of intense electromagnetic fields can be precisely tuned for controlled surface chemistry. We demonstrate a precision pH-driven synthesis of gold nanorods with optical resonance properties widely tunable across the near-infrared spectrum. Through controlled electrostatic interactions, we can perform selective adsorbate molecule attachment and monitor the surface transitions through spectroscopic techniques that include ground-state absorption spectrophotometry, two-dimensional X-ray absorption near-edge spectroscopy, Fourier-transform infrared spectroscopy, and surface-enhanced Raman spectroscopy. We elucidate the electronic, structural, and chemical factors that contribute to plasmon-molecule dynamics at the nanoscale with broad implications for the fields of energy, photonics, and bio-inspired materials.

Two-dimensional total absorption spectroscopy with conditional generative adversarial networks

We explore the use of machine learning techniques to remove the response of large volume γ-ray detectors from experimental spectra. Segmented γ-ray total absorption spectrometers (TAS) allow for the simultaneous measurement of individual γ-ray energy (Eγ) and total excitation energy (Ex). Analysis of TAS detector data is complicated by the fact that the Ex and Eγ quantities are correlated, and therefore, techniques that simply unfold using Ex and Eγ response functions independently are not as accurate. In this work, we investigate the use of conditional generative adversarial networks (cGANs) to simultaneously unfold Ex and Eγ data in TAS detectors. Specifically, we employ a Pix2Pix cGAN, a generative modeling technique based on recent advances in deep learning, to treat (Ex,Eγ) matrix unfolding as an image-to-image translation problem. We present results for simulated and experimental matrices of single-γ and double-γ decay cascades. Our model demonstrates characterization capabilities within detector resolution limits for upwards of 93% of simulated test cases.

Molecular photothermal effects, diffusion, and sample flow in time-resolved spectroscopy and microscopy

Time-resolved pump–probe and two-dimensional spectroscopy are widely used to study ultrafast chemical and biological processes in solutions. However, the corresponding signals at long times can be contaminated by molecular photothermal effects, which are caused by the nonradiative heat dissipation of photoexcited molecules to the surroundings. Additionally, molecular diffusion affects the transient spectroscopic signals because photoexcited molecules can diffuse away from the pump and probe beam focuses. Recently, a theoretical description of molecular photothermal effects on time-resolved IR spectroscopy was reported. In this work, I consider the molecular photothermal process, molecular diffusion, and sample flow to develop a generalized theoretical description of time-resolved spectroscopy. The present work can be used to interpret time-resolved spectroscopic signals of electronic or vibrational chromophores and understand the rate and mechanisms of the conversion of high-frequency molecular electronic and vibrational energy to solvent kinetic energy in condensed phases.

Theoretical Study of the Two-Dimensional Vibrational Sum Frequency Generation Spectroscopy of the Air-Water Interface at Varying Temperature and Its Connections to the Interfacial Structure and Dynamics.

We performed a theoretical study of the temperature variation of two-dimensional vibrational sum frequency generation (2D-VSFG) spectra of the OH stretch modes at air-water interfaces in the mid-IR region. The calculations are performed at four different temperatures from 250 to 325 K by using a combination of techniques involving response function formalism of nonlinear spectroscopy, electronic structure calculations, and molecular dynamics simulations. Also, the calculations are performed for isotopically dilute solutions so that the intra- and intermolecular coupling between the vibrational modes of interest can be ignored. We have established the connections of temperature variation of various frequency- and time-dependent features of the calculated spectra to the changes in the underlying structure and dynamics of the interfaces. The results reveal that interfacial water is dynamically more heterogeneous than bulk water, with three dominant dynamical processes exhibiting their corresponding time-dependent features in the 2D-VSFG spectrum. These are the spectral diffusion of hydrogen-bonded OH groups at the interface, conversion of an initially hydrogen-bonded OH group to a dangling OH which is a stable state for surface water, unlike the bulk water, and the third one, which involves the conversion of an initially free or dangling OH group to its hydrogen-bonded state at the interface. The temporal appearance of the cross peaks corresponding to interconversion of the hydrogen-bonded state to the dangling state or vice versa of an interfacial OH group is found to take place at a slower rate than the dynamics of spectral diffusion of hydrogen-bonded molecules at the interface, which, in turn, is slower than the corresponding spectral diffusion of bulk water molecules. The temperature variation of these dynamic processes can be linked to the decay of appropriate hydrogen-bond and non-hydrogen-bond time correlation functions of interfacial water molecules for the different air-water systems studied in this work.

Synthesis and spectroscopic characterization of 13 C4 -labeled 4-cyano-2-oxobutyraldehyde semicarbazone: A metabolite of nitrofurazone.

Nitrofurazone usage in food-producing animals is prohibited in most countries, including the United States. Regulatory agencies regularly monitor its use in domestic, export/import animals' food products by measuring the semicarbazide (SEM) metabolite as a biomarker of nitrofurazone exposure. However, the use of SEM is controversial because it is also produced in food naturally and thus gives false positive results. A cyano-metabolite, 4-cyano-2-oxobutyraldehyde semicarbazone (COBS), is proposed as an alternate specific marker of nitrofurazone to distinguish nitrofurazone from treated or untreated animals. A synthetic method was developed to produce COBS via metallic hydrogenation of nitrofurazone. The product was isolated and characterized by one- and two-dimensional nuclear magnetic spectroscopy (NMR) experiments, Fourier-transform infrared spectroscopy (FT-IR), and mass spectrometry. The developed synthetic procedure was further extended to synthesize isotopically labeled 4-[13 C]-cyano-2-oxo- [2, 3, 4-13 C3 ]-butyraldehyde semicarbazone. Labeled COBS is useful as an internal standard for its quantification in food-producing animals. Thus, the developed method provides a possibility for its commercial synthesis to procure COBS. This is the first synthesis of the alternate specific marker metabolite of nitrofurazone for possible usage in regulatory analysis to solve a real-world problem.

Deep learning based on the Vis-NIR two-dimensional spectroscopy for adulteration identification of beef and mutton

Rapid and accurate identification of contaminated meat products represents a global challenge, particularly with regard to minced meat products. This study reports on two methods for analyzing the adulteration of beef and mutton: the deep learning combined with two-dimensional correlation spectroscopy (2DCOS) method, and the PLS-DA method. The 2DCOS method employed in this research substantially improves the resolution of one-dimensional Vis-NIR spectra, allowing for the visualization of spectral information changes within the samples. By analyzing the impact of various proportions of chicken, duck, and pork mixed with beef or mutton, the synchronous 2DCOS images unveil distinct patterns of chemical information alteration within the spectra under different adulteration scenarios. Notably, the auto peaks and cross peaks observed within the 400–1400 nm range serve as key indicators of these changing patterns. The ResNet deep learning method possesses the advantageous capability to effectively extract 2DCOS feature information, resulting in the achievement of high accuracy models (100%). In contrast, the accuracy of the PLS-DA model test set, based on either raw or pre-processed spectral data matrices, ranged from 32.97% to 50.64%. These results substantiate the effectiveness of utilizing 2DCOS in combination with deep learning as a powerful tool for discerning beef and mutton adulteration.

Absolute electron density fluctuation reconstruction for two-dimensional hydrogen beam emission spectroscopy.

Scrape-off layer (SOL) and edge plasma turbulence significantly contribute to the radial particle and heat transport, lowering the plasma confinement and increasing the heat load on the plasma facing components. SOL turbulence is predominantly intermittent, which manifests in the occurrence of isolated density filaments or blobs. Filaments propagate radially outward toward plasma facing components, limiting their lifetime by erosion and sputtering. To characterize this phenomenon in detail, few diagnostic techniques are available. Beam emission spectroscopy is a diagnostic capable of measuring plasma turbulence in both SOL and edge plasmas. Due to the finite lifetime of the excitation states during the beam-plasma interaction and the misalignment between the optics and the magnetic field, spatial smearing is introduced in the measurement. In this paper, a novel method is introduced to overcome this hindering effect by inverting the fluctuation response matrix on an optimally smoothed signal. We show that this method is fast and provides significantly more accurate absolute density fluctuation reconstruction than the direct inversion technique. The presented method is usable for all types of beam emission diagnostics where the spatial resolution is higher than the combined smearing of the atomic physics and the observation.

Enantiodetection via two-dimensional spectroscopy: Extending the methodology to general experimental conditions

Enantiodetection via two-dimensional spectroscopy: Extending the methodology to general experimental conditions

Frontiers of NIR Imaging

After a brief introduction to the technique, this review will discuss the state-of-the-art NIR imaging instrumentation and its applications, including applications of an ordinary NIR imaging system to solvent diffusion into a polymer. Other imaging applications discussed include the use of a portable NIR imaging system in the pharmaceutical industry, high-speed and wide-area monitoring of polymers, and imaging for fish embryos development research. Also discussed is an imaging-type two-dimensional Fourier spectroscopy (ITFS) system and its application to medaka (Japanese rice fish, Oryzias latipes) egg development. Finally, general perspectives on NIR imaging will be provided.