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The intriguing network of antibody–antigen (Ab–Ag) interactions is highly governed by environmental perturbations and the nature of biomolecular interaction. Protein–protein interactions (PPIs) have potential applications in developing protein-adsorption-based sensors and nano-scale materials. Therefore, characterizing PPIs in the presence of a nanomaterial at the molecular level becomes imperative. The present work involves the investigation of antiferritin–ferritin (Ab–Ag) protein interactions under the influence of tungsten disulfide quantum dots (WS2 QDs). Isothermal calorimetry and contact angle measurements validated the strong influence of WS2 QDs on Ab–Ag interactions. The interfacial signatures of nano–bio-interactions were evaluated using sum frequency generation vibration spectroscopy (SFG-VS) at the air–water interface. Our SFG results reveal a variation in the tilt angle of methyl groups by ∼12° ± 2° for the Ab–Ag system in the presence of WS2 QDs. The results illustrated an enhanced ordering of water molecules in the presence of QDs, which underpins the active role of interfacial water molecules during nano–bio-interactions. We have also witnessed a differential impact of QDs on Ab–Ag by raising the concentration of the Ab–Ag combination, which showcased an increased inter-molecular interaction among the Ab and Ag molecules and a minimal influence on the methyl tilt angle. These findings suggest the formation of stronger and ordered Ab–Ag complexes upon introducing WS2 QDs in the aqueous medium and signify the potentiality of WS2 QDs relevant to protein-based sensing assays. [ABSTRACT FROM AUTHOR]

Attenuated total reflectance Fourier transform infrared spectroscopy and sum frequency generation (SFG) vibrational spectroscopy have been employed to probe the molecular structure of N,N-dimethylformamide (DMF) and water mixture by varying the concentration of DMF. From the bulk studies, we observed a gradual decrease in the intensity with a continuous blue shift in the OH-stretch region with the increase in the DMF concentration. In contrast, no significant blue shift in the OH-stretch region is noticed from the SFG spectra collected from the air–aqueous binary mixture interface as a function of DMF concentration. However, the impact of DMF is found to be disruptive in nature toward the existing hydrogen bonding network of the pristine water at the interfacial region. Interestingly, in the CH-stretch region, the vibrational signatures of the DMF molecule show blue shifts, as proposed in earlier studies. We have calculated the molecular tilt angle of the methyl group of the DMF molecule as a function of DMF concentration. For the case of neat DMF, the observed tilt angle is ∼17.7° with respect to the surface normal. The value of tilt angle decreases with the decrease in DMF concentration and reaches a value of ∼1.7° for a mole fraction of 0.5, and it further increases with the decrease in DMF concentration. It achieves a value of ∼20° for the dilute DMF mole fraction of 0.05 in the binary mixture. This indicates that DMF molecules at the air–binary mixture interface are placing their methyl groups more toward the normal for the intermediate DMF concentrations. [ABSTRACT FROM AUTHOR]

The silica (SiO2) nanoparticles of a well-known silica precursor tetraethyl orthosilicate (TEOS) are generally synthesized via a promising solution-gelation inorganic polymerization process. The monodisperse silica nanoparticles have potential applications ranging from the formation of dental nanocomposites to antireflective coatings. In the present study, we have systematically investigated the in situ interfacial molecular structure of TEOS and its impact on the interfacial water structure during the processes of hydrolysis and condensation at the air–aqueous interface using sum-frequency generation (SFG) vibrational spectroscopy. With the presence of water, a gradual decrease in the SFG intensity in the CH-stretch region for each concentration of TEOS with time reflects the elimination of ethoxy groups, which is a signature of the hydrolysis process. Further, the impact of the hydrolysis process is revealed from the significant enhancement in the SFG signal in the OH-stretch region. The hydrolysis of TEOS is then followed by condensation in which the SiO– charged species are replaced by forming the SiOSi bridging network. The signature of the condensation process is reflected with the gradual decrease in the observed enhanced SFG signal in the OH-stretch region. The formation of monodispersed silica nanoparticles as an end product of size variation from 1.75 to 4.67 nm with the increase in TEOS concentration is confirmed with the DLS measurements. We have also probed the pH-dependent SFG studies at three different pH values (2.0, 5.8, and 9.0). The dominant pH-dependent hydrolysis process is revealed from the observed molecular structure of TEOS at the air–aqueous interface. [ABSTRACT FROM AUTHOR]

The use of a liquid microjet as a possible source of interest for Second Harmonic Generation (SHG) and Sum Frequency Generation (SFG) spectroscopy is examined. We measured non-resonant SHG scattering patterns from the air/water interface of a microjet of pure water and observe a strong enhancement of the SHG signal for certain scattering angles. These enhancements can be explained by the optical properties and the shape of the liquid microjet. SFG experiments at the surface of a liquid microjet of ethanol in air show that it is also possible to measure the coherent vibrational SFG spectrum of the ethanol/air interface in this way. Our findings are useful for future far-UV or X-ray based nonlinear optical surface experiments on liquid jets. In addition, combined X-ray photoelectron spectroscopy and SHG/SFG measurements are feasible, which will be very useful in improving our understanding of the molecular foundations of electrostatic and chemical surface properties and phenomena. [ABSTRACT FROM AUTHOR]

The exponential growth in the research field of water pollution control demands the evolution of novel sensing materials for regulation and quantification of metals ions. Within this context, the current work reports a new strategy for the synthesis of carbon dots from the hydrothermal treatment of organic nanoparticles. The organic nanoparticles are found to be selective towards Cs(I) ions with a detection limit of 5.3 nM, whereas the highly fluorescent carbon dots are found to be selective towards Ag(I) ions with a detection limit of 4.8 nM. Both sensing systems illustrate rapid sensing with a working pH range from 4–9. The interfacial molecular restructuring of the sensing systems in the aqueous phase has been investigated in the absence and presence of targeted metal ions using a sum frequency generation vibrational spectroscopic tool. The practical applicability of the sensors was checked in environmental samples. This work opens new avenues for the exploration of temperature‐guided sensing modulation in nanomaterials. [ABSTRACT FROM AUTHOR]

The optimum experimental geometry for visible-infrared sum-frequency generation experiments depends rather sensitively on the molecules adsorbed at the surface, their orientation, and the nature of the adjacent bulk media. We consider the commonly encountered case of methyl groups situated at air-water, air-gold, and polymer-water interfaces. We provide expressions that may be used to determine the optimal visible and IR beam incident angles, considering the symmetric and antisymmetric modes separately and then together. The analysis is carried out for co-propagating (collinear and non-collinear geometries) and counter-propagating configurations. We first consider that one or more vibrational modes are of interest, and the goal is to study them quantitatively under a single polarization scheme; our results enable the user to set the beam angles for such an experiment. In the second case, molecular orientation information is desired, and so the calibrated response is required in all accessible polarization schemes for full characterization of the nonlinear susceptibility tensor. [ABSTRACT FROM AUTHOR]

A detailed model is presented that describes the temporal and spectral interference patterns resulting from phase-recovery infrared-visible sum-frequency spectroscopy. Included in this model are the effects of dispersive elements other than the phase shifting unit placed between the sample and local oscillator signals. This inclusion is critical when considering the interference patterns arising from studies of buried interfaces. Furthermore, in the midinfrared where it is difficult to have high visibility of the fringes, it is demonstrated that local field corrections have a significant effect on the shape of the interference pattern. By collecting and subsequently fitting a two-dimensional interference pattern displaying both temporal and spectral fringes, a complete characterization of all these effects is possible. [ABSTRACT FROM AUTHOR]

Vibrationalsum-frequency generation spectroscopy is valued forits ability to selectively probe molecules at a variety of interfaceswithout the use of extrinsic chromophores. The spectra contain valuableinformation regarding the molecular structure and the interfacialenvironment through the observation of vibrational resonances associatedwith specific moieties. Chemical information is obtained by closeinspection of the frequencies of these bands and the amplitude ofthe response under conditions of different beam polarizations. Suchsensitivity motivates the development of techniques that can providestructural details. We illustrate several approaches by which varioustypes of calculations and molecular simulations may be used to enhancethe sought structural interpretation of experimental data. By applyingthese techniques to the adsorbate molecules, interfacial water, andthe substrate surfaces themselves, we are able to achieve a holisticpicture of the adsorption environment. [ABSTRACT FROM AUTHOR]

The change induced in the physicochemical properties of polymer while hosting ions provides a platform for studying its potential applications in electrochemical devices, water treatment plants, and materials engineering science. The ability to host ions is limited in very few polymers, which lack a detailed molecular-level understanding for showcasing the polymer-ion linkage behavior at the interfacial region. In the present manuscript, we have employed sum frequency generation (SFG) vibrational spectroscopy to investigate the interfacial structure of a new class phosphazene-based methoxyethoxyethoxyphosphazene (MEEP) polymer in the presence of lithium chloride salt at the air-aqueous interface. The interfacial aspects of the molecular system collected through SFG spectral signatures reveal enhanced water ordering and relative hydrogen bonding strength at the air-aqueous interface. The careful observation of the study finds a synchronous contribution of van der Waals and electrostatic forces in facilitating changes in the interfacial water structure that are susceptible to MEEP concentration in the presence of ions. The observation indicates that dilute MEEP concentrations support the role of electrostatic interaction, leading to an ordered water structure in proximity to diffused ions at the interfacial region. Conversely, higher MEEP concentrations promote the dominance of van der Waals interactions at the air-aqueous interface. Our study highlights the establishment of polymer electrolyte (PE) characteristics mediated by intermolecular interactions, as observed through the spectral signatures witnessed at the air-aqueous interface. The investigation illustrates the polymer-ion linkage adsorption effects at the interfacial region, which explains the macroscopic changes observed from the cyclic voltammetry studies. The fundamental findings from our studies can be helpful in the design and fine-tuning of better PE systems that can offer improved hydrophobic membranes and interface stability for use in electrochemical-based power sources., (© 2023 IOP Publishing Ltd.)

Guilty as charged: Water is often modeled as a dielectric continuum, but the molecular structure of water is asymmetric. Two ions that have a virtually identical size, shape, and structure, but an opposite charge sign have been investigated to see whether charge makes a fundamental difference to water structuring. The spectroscopic data for the hydration and interface structures are found to be remarkably different for opposite charges., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Interfacial water commonly distinguishes itself from the bulk phase by adopting a polar, ordered structure. It is well-established that electrolytes can act to perturb this structure; however, the nature of this perturbation remains a topic of interest. In this study, surface- and structure-sensitive nonlinear vibrational spectroscopy is used to monitor electrolyte-induced changes in interfacial water structure. Solution ionic strength was varied over 5 orders of magnitude, and spectra were collected from two mineral surfaces (fused silica and calcium fluoride) and two polymer surfaces (polystyrene and poly(methyl methacrylate)). Analysis of the spectra reveals striking similarities and differences between these four aqueous interfaces; trends in overall intensity do not always follow changes in the spectral shape. Our results reveal the complex interplay between surface charge, ion adsorption, and hydrophobicity in determining interfacial water structure in the presence of dissolved ions.