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At charged aqueous interfaces, the second-order nonlinear optical response originates from water molecules within the diffuse part of the electrical double layer, which are ordered by the surface field and from water that additionally experiences chemical and physical interactions with the surface in the Stern layer. These two environments can either reinforce or diminish the overall signal and can be disentangled by varying the coherence length of their interaction with external laser fields. Here, we demonstrate a method in which the angle of incidence is varied to afford a significant change in the coherence length. When this technique was applied to the silica-water interface, it was observed that water molecules in the Stern and diffuse layers direct their hydrogen atoms toward the mineral surface at a low ionic strength and neutral pH. A decrease in the signal with increasing ionic strength is attributed to hydrated cation adsorption that competes with free water for deprotonated silanol sites.
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The detection of trace adulterants in opioid samples is an important aspect of drug checking, a harm reduction measure that is required as a result of the variability and unpredictability of the illicit drug supply. While many analytical methods are suitable for such analysis, community-based approaches require techniques that are amenable to point-of-care applications with minimal sample preparation and automated analysis. We demonstrate that surface-enhanced Raman spectroscopy (SERS), combined with a random forest classifier, is able to detect the presence of two common sedatives, bromazolam (0.32-36% w/w) and xylazine (0.15-15% w/w), found in street opioid samples collected as a part of a community drug checking service. The Raman predictions, benchmarked against mass spectrometry results, exhibited high specificity (88% for bromazolam, 96% for xylazine) and sensitivity (88% for bromazolam, 92% for xylazine) for the compounds of interest. We additionally provide evidence that this exceeds the performance of a more conventional approach using infrared spectral data acquired on the same samples. This demonstrates the feasibility of SERS for point-of-care analysis of challenging multicomponent samples containing trace adulterants.
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Vibrational sum frequency generation can provide valuable structural information at surfaces and buried interfaces. Relating the measured spectra to the complex-valued second-order susceptibility χ(2) is at the heart of the technique and a requisite step in nearly all subsequent analyses. The magnitude and phase of χ(2) as a function of frequency reveal important information about molecules and materials in regions where centrosymmetry is broken. In this tutorial-style perspective, the origins of the χ(2) phase are first described, followed by the utility of phase determination. Finally, some practical methods of phase extraction are discussed.
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The nanoscale region immediately adjacent to surfaces, although challenging to probe, is directly responsible for local chemical and physical interactions between a material and its surroundings. Cell-surface contacts are mediated by a combination of electrostatic and acid-base interactions that alter the local environment over time. In this study, a label-free vibrational probe with a nanometer length scale reveals that the electrostatic potential at a silica surface gradually increases in the presence of bacteria in solution. We illustrate that the cells themselves are not responsible for this effect. Rather, they alter the interfacial chemical environment in a manner that is consistent with a reduction of the ionic strength to a level that is roughly four times lower than that of the bulk aqueous phase.
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Dióxido de Silício , Água , Concentração Osmolar , Eletricidade Estática , Propriedades de SuperfícieRESUMO
Resistance to algae contamination is an important characteristic of insulators used in overhead power distribution in coastal environments. It is therefore important to understand the parameters governing algae adhesion onto polymer insulator materials such as silicone. Flow cell-based shear experiments were conducted in order to characterize the adhesion strength of algae onto polydimethylsiloxane surfaces, comparing fresh polymer substrates with those that have been soaked in water and saline solutions for 1 month. Both freshwater algae and seawater species could withstand considerably less drag force and were therefore more easily removed when the polymer was soaked in salt water. The polymer surface was found to be unaltered in terms of its roughness, contact angle, and lack of water uptake; no macroscopic surface characterization was therefore able to account for the differences in cell adhesion strength resulting from the soaking treatment. Surface-specific nonlinear vibrational spectroscopy, however, revealed subtle differences in the orientation of surface methyl groups that resulted from the water and saline exposure.
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Polímeros , Silicones , Adesão Celular , Análise Espectral , Propriedades de SuperfícieRESUMO
A new method is proposed to analyze Doubly Resonant infrared-visible Sum-Frequency Generation (DR-SFG) spectra. Based on the transform technique, this approach is free from assumptions about vibronic modes, energies, or line widths and accurately captures through the overlap spectral function all required aspects of the vibronic structure from simple experimental linear absorption spectra. Details and implementation of the method are provided along with three examples treating rhodamine thin films about one monolayer thick. The technique leads to a perfect agreement between experiment and simulations of the visible DR-SFG line shapes, even in the case of complex intermolecular interactions resulting from J-aggregated chromophores in heterogeneous films. For films with mixed H- and J-aggregates, separation of their responses shows that the J-aggregate DR-SFG response is dominant. Our analysis also accounts for the unexplained results published in the early times of DR-SFG experiments.
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Details of the design and implementation of an open-source platform for studying the adhesion of cells attached to solid substrata are provided. The hardware is based on a laser-cut flow channel connected to a programmable syringe pump. The software automates all aspects of the flow rate profile, data acquisition and image analysis. An example of the pelagic diatom Thalassiosira rotula adhered to poly(dimethyl siloxane) surfaces is provided. The procedure described enables the shear rate to be converted to drag force for arbitrary-shaped objects, of utility to the study of many cell species, especially ones that are obviously non-spherical. It was determined that 90% of cells are removed with the application of drag forces < 3×10-12 N, and that this value is relatively independent of the incubation time on the surface. This result is important to understand how marine species interact with polymer surfaces that are used in electrical insulator applications.
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Diatomáceas , PolímerosRESUMO
BACKGROUND: Drug checking uses chemical analytical technologies to analyze drugs from the unregulated market to reduce substance use-related risks. We aim to examine the frequency of third party use of a community drug checking service to explore the potential for harm reduction to extend beyond the individual into the community, increase service accessibility, and to contribute to upstream interventions in the supply. METHODS: Over 31 months, data were collected from a point-of-care drug checking service operated in Victoria, Canada. Through the implementation of survey questions at the intake of the service, data were collected about whether the drug check was for the individual, to sell, and/or for others. RESULTS: Just over half (52%) of service users were checking for reasons that extended beyond individual use. When checking for others, friends were the most common response, representing 52% of responses, and outreach/support workers checking for others was the second most at 32%. Twelve percent of service users reported checking to sell or for a supplier. CONCLUSIONS: Third party checking is a frequent, and important aspect of drug checking services, which through facilitating community engagement and increasing accessibility, has expanded the reach of interventions beyond individuals to reduce risks within the unregulated market. Therefore, drug checking as an overdose response should be responsive and accessible for those using the service on the behalf of others.
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Overdose de Drogas , Preparações Farmacêuticas , Transtornos Relacionados ao Uso de Substâncias , Canadá , Redução do Dano , Humanos , Transtornos Relacionados ao Uso de Substâncias/prevenção & controleRESUMO
The structure of water adjacent to silica is sensitive to the degree of deprotonation of surface silanol groups. As a result, close inspection of signals originating from these water molecules can be used to reveal the surface charge density. We have used nonlinear vibrational spectroscopy of the water O-H stretching band over a temperature range of 10-75 °C to account for the increase in surface potential from deprotonation. We demonstrate that the behavior at the silica surface is a balance between increasing surface charge and a decreasing contribution of water molecules aligned by the surface charge. Together with a model that accounts for two different types of silanol sites, we use our data to report the changes in enthalpy and entropy for deprotonation at each site. This is the first experimental determination of these thermodynamic parameters for hydrated silanol groups at the silica surface, critical to a wide range of geochemical and technological applications.
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Bacterial adhesion and biofilm formation on abiotic surfaces are important phenomena with industrial, environmental, and biological relevance. Recent findings using vibrational spectroscopy to study Escherichia coli (E. coli) K12 adhesion on silica indicated that interfacial water signals are linked to changes at the surface in the presence of bacteria. Although such techniques provide a unique glimpse into the surface microenvironment, the origin of the features tracked by the water signals remains to be identified. Here, we have used brightfield microscopy with enhanced image processing to study E. coli K12 adhering to silica. Although most of the clusters of cells on the surface are small, with many individual cells adhered throughout the exponential phase, the overall surface coverage was found to be dominated by clusters greater than 100 µm2 in area. However, it is the adhesion profile of the small clusters that most closely matches the interfacial water signals, suggesting that surface-bound water changes immediately upon adhesion.
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Aderência Bacteriana , Escherichia coli , Biofilmes , Dióxido de Silício , Propriedades de SuperfícieRESUMO
We outline a method by which the surface preference of a species in a multicomponent mixture may be obtained using surface-specific visible-infrared sum frequency generation (SFG) spectroscopy combined with bulk infrared absorption and/or Raman data. In general, the problem is complicated by the fact that the SFG signal is a function of both the surface coverage and the structure of the molecules. Two-dimensional correlation analysis can be used to reveal which spectral features are changing synchronously, that is, in phase with each other, and which ones are evolving in a manner that is phase-shifted by 90° (asynchronous correlation) as a function of the bulk composition. We provide a framework for determining the surface preference from the correlations between the vibrational modes in the SFG spectra and between the modes from SFG and bulk infrared and/or Raman spectra. When compared to the equivalent analysis performed using the SFG spectra alone, this method can be used with the data obtained using a single-beam polarization and in congested spectral regions where fitting to isolate the behavior of individual vibrational modes is not robust.
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We illustrate a technique by which heterodyne-detected sum-frequency generation spectroscopy is performed at multiple angles of incidence in order to decompose components of the second-order susceptibility tensor when all beams are polarized parallel to the plane of incidence. As an illustration, we study the non-vibrationally resonant gold response. We benchmark our results by comparing with measurements obtained in a polarization scheme that isolates a single element of the susceptibility tensor. Our technique is particularly valuable in the case of metal substrates, where the surface selection rule often prevents spectra from being acquired in multiple beam polarizations.
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Understanding the adsorption of molecules onto surfaces is integral to a wide variety of fields with scientific, engineering, and industrial applications. The surface-adsorbed structure is governed by the nature of the molecule, surface characteristics, and solution environment. There are therefore three critical interactions that govern adhesion: solvent-analyte, substrate-analyte, and substrate-solvent. The last two interactions require a surface-specific probe restricted to a few nanometers or less. This is particularly true of efforts to probe polymer surface structure without being overwhelmed by bulk polymer signal or interfacial water structure in the presence of bulk water. Second-order nonlinear optical techniques are ideal probes of such interactions, as their reporting depth is determined by the polar arrangement of molecules (a break in the macroscopic inversion symmetry) rather than the penetration of the optical fields. This Account begins with an introduction of surface water structure from the perspective of a nonlinear probe. Details about the unique view of the water orientation distribution are discussed and contrasted with information obtained from conventional vibrational techniques. The salient features of water next to model hydrophobic and hydrophilic surfaces are discussed, in preparation for a discussion of solute interactions that follows. We then present three examples using a combination of linear and nonlinear vibrational spectroscopy and molecular dynamics simulations to illustrate how water is both a mediator and a marker of adhesion. The first is a study of amphipathic peptide adhesion onto hydrophobic and hydrophilic surfaces, characterizing the adsorbed structure in relation to the water surrounding the molecule and trapped near the surface. Water is found to be especially important in mediating adhesion to hydrophilic surfaces, where it aids in solvating the peptide as well as facilitating interactions with the surface. In the second example, we look at adhesion of a multicomponent polymer adhesive using surface-bulk heterospectral correlation analysis, in which surface vibrational spectroscopy is combined with bulk infrared absorption to determine interfacial structure development during the evaporation of water. When acrylic acid is added to the polymer, there is a change in orientation of the polymer before an increase in population. This is opposite to what is observed when no additive is present. In our third example, we show how interfacial water provides a unique window into the surface microenvironment during bacterial adhesion, highlighting the role of solution conditions at the surface in cell attachment and biofilm growth. Changes in the nonlinear vibrational response of interfacial water reflect changes occurring in the pH and ionic strength only at the surface, due to the presence of polymeric adhesives secreted by the bacteria. These studies underline the importance of surface water in governing the structure of adhered molecules and in mediating changes in the interfacial environment as a result of adhesion and provide insight into a nanoscale region that is otherwise difficult to query. They also illustrate the importance of combining surface-sensitive and bulk spectroscopic probes with computer modeling to gain a better understanding of the interplay between water and adsorbate structure.
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Polymer coatings offer a means to modulate the adsorption of molecules onto solid surfaces by offering a surface functionality, charge, roughness, and hydrophobicity that is different from the underlying substrate. One application is to provide anti-fouling functions for metal surfaces. Understanding solvent-surface interactions is an essential component to gaining mechanistic insight into the adsorption process. In this work, we study the adsorption of toluene-heptane binary mixtures onto a perflurorinated polymer surface. We use a combination of IR absorption and Raman scattering spectroscopy to study the mixture in the bulk phase, and surface-specific visible-infrared sum-frequency generation to probe the surface layers. Through the use of homo- and heterospectral two-dimensional correlation spectroscopy, we conclude that the adsorption of the two solvents is reversible and that the surface structure is generally independent of the surface composition, with a small change in toluene orientation as the toluene content increases. We also find that the hydrophobic fluropolymer has very little preference for either solvent, similar to previous studies on hydrophilic surfaces.
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Vibrational sum-frequency generation (SFG) spectroscopy can provide valuable qualitative and quantitative information about molecular species at surface and buried interfaces. For example, the resonance frequency of a particular chemical function group is revealing of the surface environment, especially when compared to what is observed in bulk IR absorption or Raman scattering spectra. Furthermore, the amplitude of the mode can be related to the molecular orientation, providing a detailed quantitative account of the surface structure. Each of these attributes, however, requires fitting the spectra to some vibrationally resonant line shape. This is particularly challenging when the modes of interest co-exist with broad resonance features, such as water O-H stretching. In this perspective, we examine the merits and consequences of different approaches to fitting homodyne SFG data. We illustrate that, while any model can provide a useful description of the data, no model can accurately and consistently provide even the relative phase deeply encoded in homodyne data without the use of additional information.
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Surface-specific nonlinear vibrational spectroscopy, combined with bulk solution measurements and imaging, is used to study the surface conditions during the growth of E. coli. As a result of the silica high surface charge density, the water structure at the silica-aqueous interface is known to be especially sensitive to pH and ionic strength, and surface concentration profiles develop that can be appreciably different from the bulk solution conditions. We illustrate that, in the presence of growing cells, a unique surface micro-environment is established as a result of metabolites accumulating on the silica surface. Even in the subsequent absence of the cells, this surface layer works to reduce the interfacial ionic strength as revealed by the enhanced signal from surface water molecules. In the presence of growing cells, an additional boost in surface water signal is attributed to a local pH that is higher than that of the bulk solution.
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Escherichia coli/crescimento & desenvolvimento , Água/metabolismo , Escherichia coli/citologia , Escherichia coli/metabolismo , Concentração de Íons de Hidrogênio , Íons/química , Íons/metabolismo , Dióxido de Silício/química , Dióxido de Silício/metabolismo , Espectrofotometria Infravermelho , Propriedades de Superfície , Água/químicaRESUMO
The physics and chemistry of mineral-water interfaces are complex, even in idealized systems. Our need to understand this complexity is driven by both pure and applied sciences, that is, by the need for basic understanding of earth systems and for the knowledge to mitigate our influences upon them. The second-order nonlinear optical techniques of second-harmonic generation and sum-frequency generation spectroscopy have proven adept at probing these types of interfaces. This review focuses on the contributions to geochemistry made by nonlinear optical methods. The types of questions probed have included a basic description of the structure adopted by water molecules at the mineral interface, how flow and porosity affect this structure, adsorption of trace metal and organic species, and dissolution mechanisms. We also discuss directions and challenges that lie ahead and the outlook for the continued use of nonlinear optical methods for studies of mineral-water boundaries.
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Total internal reflection infrared (IR) absorption and visible-IR sum-frequency spectroscopies were used to study the role of acrylic acid in the evolution of surface structure in a poly(butyl acrylate)-based pressure-sensitive adhesive during the drying process. By monitoring these spectral responses and calculating the heterospectral correlation coefficients, we established that acrylic acid alters the nature of the molecular interactions at the surface. In the absence of acrylic acid, butyl acrylate orientation is driven by the packing of the polymer as the water evaporates. When acrylic acid is present, a rapid ordering of the copolymer takes place as a result of favorable hydrogen-bonding interactions with the surface.
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Homo- and heterospectral correlation analysis are powerful methods for investigating the effects of external influences on the spectra acquired using distinct and complementary techniques. Nonlinear vibrational spectroscopy is a selective and sensitive probe of surface structure changes, as bulk molecules are excluded on the basis of symmetry. However, as a result of this exquisite specificity, it is blind to changes that may be occurring in the solution. We demonstrate that correlation analysis between surface-specific techniques and bulk probes such as infrared absorption or Raman scattering may be used to reveal additional details of the adsorption process. Using the adsorption of water and ethanol binary mixtures as an example, we illustrate that this provides support for a competitive binding model and adds new insight into a dimer-to-bilayer transition proposed from previous experiments and simulations.