Surface charge density and distribution play an important role in almost all interfacial processes, influencing, for example, adsorption, colloidal stability, functional material activity, electrochemical processes, corrosion, nanoparticle toxicity, and cellular processes such as signaling, absorption, and adhesion. Understanding the heterogeneity in, and distribution of, surface and interfacial charge is key to elucidating the mechanisms underlying reactivity, the stability of materials, and biophysical processes. Atomic force microscopy (AFM) and scanning ion conductance microscopy (SICM) are highly suitable for probing the material/electrolyte interface at the nanoscale through recent advances in probe design, significant instrumental (hardware and software) developments, and the evolution of multifunctional imaging protocols. Here, we assess the capability of AFM and SICM for surface charge mapping, covering the basic underpinning principles alongside experimental considerations. We illustrate and compare the use of AFM and SICM for visualizing surface and interfacial charge with examples from materials science, geochemistry, and the life sciences. Expected final online publication date for the Annual Review of Analytical Chemistry Volume 15 is June 2022. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

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Biofilms are known to be well-organized microbial communities embedded in an extracellular polymeric matrix, which supplies bacterial protection against external stressors. Biofilms are widespread and diverse, and despite the considerable large number of publications and efforts reported regarding composition, structure and cell-to-cell communication within biofilms in the last decades, the mechanisms of biofilm formation, the interaction and communication between bacteria are still not fully understood. This knowledge is required to understand why biofilms form and how we can combat them or how we can take advantage of these sessile communities, e.g. in biofuel cells. Therefore, in situ and real-time monitoring of nutrients, metabolites and quorum sensing molecules is of high importance, which may help to fill that knowledge gap. This review focuses on the potential of scanning electrochemical microscopy (SECM) as a versatile method for in situ studies providing temporal and lateral resolution in order to elucidate cell-to-cell communication, microbial metabolism and antimicrobial impact, e.g. of antimicrobial coatings through the study of electrochemical active molecules. Given the complexity and diversity of biofilms, challenges and limitations will be also discussed.

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Diamond thin-film waveguides with a nanocrystalline diamond layer of approximately 20 μm thickness were used in the mid-infrared regime in combination with quantum cascade lasers to detect the IR signature of caffeine. The diamond thin-film waveguides were fundamentally characterized with respect to their morphological properties via AFM and SEM. Theoretical simulations confirmed the feasibility of using a larger sensing area of approximately 50 mm2 compared to conventionally used strip waveguides. A comprehensive and comparative analysis confirmed the performance of the diamond thin-film-waveguide-based sensing system vs data obtained via conventional attenuated total reflection Fourier transform infrared spectroscopy using a single-bounce diamond internal reflection element. Hence, the utility of innovative diamond thin-film-waveguide-based sensors coupled with quantum cascade laser light sources has been confirmed as an innovative analytical tool, which may be used in a wide range of application scenarios, ranging from environmental to medical sensing, taking advantage of the robustness and inertness of nanocrystalline diamond.

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Antibacterial polymer materials have gained interest due to their capability to inhibit or eradicate biofilms with greater efficiency in comparison with their monomeric counterparts. Among the antimicrobial and anti-biofouling polymers, catecholamine-based polymers — and in particular polydopamine — have been studied due to their favorable adhesion properties, which can be tuned by controlling the pH value. In this study, we used atomic force microscopy (AFM)–based spectroscopy to investigate the relation between the adhesion properties and surface charge density and the pH of electrochemically deposited polydopamine films presenting a dissociation constant of polydopamine of 6.3 ± 0.2 and a point of zero charge of 5.37 ± 0.06. Furthermore, using AFM and attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR), the influence of the surface charge density of polydopamine on bacterial adhesion and biofilm formation was investigated. It was shown that the adhesion of Escherichia coli at positively charged polydopamine is three times higher compared to a negatively charged polymer, and that the formation of biofilms is favored at positively charged polymers. Graphical abstract

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