Pt-Black-Modified (Hemi)spherical AFM Sensors: In Situ Imaging of Light-Driven Hydrogen Peroxide Evolution.

In this work, we present (hemi)spherical atomic force microscopy (AFM) sensors for the detection of hydrogen peroxide. Platinum-black (Pt-B) was electrodeposited onto conductive colloidal AFM probes or directly at recessed microelectrodes located at the end of a tipless cantilever, resulting in electrocatalytically active cantilever-based sensors that have a small geometric area but, due to the porosity of the films, exhibit a large electroactive surface area. Focused ion beam-scanning electron microscopy tomography revealed the porous 3D structure of the deposited Pt-B. Given the accurate positioning capability of AFM, these probes are suitable for local in situ sensing of hydrogen peroxide and at the same time can be used for (electrochemical) force spectroscopy measurements. Detection limits for hydrogen peroxide in the nanomolar range (LOD = 68 ± 7 nM) were obtained. Stability test and first in situ proof-of-principle experiments to achieve the electrochemical imaging of hydrogen peroxide generated at a microelectrode and at photocatalytically active structured poly(heptazine imide) films are demonstrated. Force spectroscopic data of the photocatalyst films were recorded in ambient conditions, in solution, and by applying a potential, which demonstrates the versatility of these novel Pt-B-modified spherical AFM probes.

Redox Switchable Polydopamine-Modified AFM-SECM Probes: A Probe for Electrochemical Force Spectroscopy.

Polydopamine (PDA) has high potential in biorelevant applications as a versatile thin film material, e.g., as adhesive coating for cell immobilization or for sensing applications due to the plethora of functional groups. In this study we present the modification of conductive colloidal atomic force-scanning electrochemical microscopy (AFM-SECM) probes with electrochemically deposited PDA resulting in functional probes for quantitative electrochemical adhesion studies. Surface functionality of PDA can be altered by oxidation or reduction of functional groups applying an appropriate potential to the PDA-modified AFM-SECM probe, thereby enabling adhesion measurements under potential control. This facilitates probing specific interactions of surface groups present in PDA with various surfaces of different wettabilities. The versatility of such switchable AFM-SECM probes is demonstrated for electrochemical force spectroscopic studies at model samples such as plasma-treated gold substrates, hydrophobic or hydrophilic self-assembled monolayers, and for adhesion measurements of bacteria in dependence of altered surface charges of the colloidal probe. The maximum obtained adhesion force of a positively polarized PDA-modified AFM-SECM probe was 6.2 ± 2.2 nN, and it was about 50% less (i.e., 2.6 ± 1.1 nN) for a negatively polarized probe at a hydrophilic OH-terminated gold surface. In situ control of the active surface groups enabled investigations on the influence of surface charges on adhesion. Furthermore, plateaus of constant force were observed, which are a characteristic of polymer structures. Finally, electrochemical force measurements with switchable probes were used for the first time during adhesion studies of bacterial cells (i.e., Pseudomonas fluorescens). Positively biased PDA-coated colloidal probes revealed adhesion forces of 6.0 ± 1.1 nN, whereas significantly reduced adhesion forces 1.1 ± 0.7 nN were observed for negatively biased PDA-modified colloidal probes.

Direct infrared spectroscopy for the size-independent identification and quantification of respirable particles relative mass in mine dusts.

Due to the global need for energy and resources, many workers are involved in underground and surface mining operations where they can be exposed to potentially hazardous crystalline dust particles. Besides commonly known alpha quartz, a variety of other materials may be inhaled when a worker is exposed to airborne dust. To date, the challenge of rapid in-field monitoring, identification, differentiation, and quantification of those particles has not been solved satisfactorily, in part because conventional analytical techniques require laboratory environments, complex method handling, and tedious sample preparation procedures and are in part limited by the effects of particle size. Using a set of the three most abundant minerals in limestone mine dust (i.e., calcite, dolomite, and quartz) and real-world dust samples, we demonstrate that Fourier transform infrared (FTIR) spectroscopy in combination with appropriate multivariate data analysis strategies provides a versatile tool for the identification and quantification of the mineral composition in relative complex matrices. An innovative analytical method with the potential of in-field application for quantifying the relative mass of crystalline particles in mine dust has been developed using transmission and diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) within a unified multivariate model. This proof-of-principle study shows how direct on-site quantification of crystalline particles in ambient air may be accomplished based on a direct-on-filter measurement, after mine dust particles are collected directly onto PVC filters by the worker using body-mounted devices. Without any further sample preparation, these loaded filters may be analyzed via transmission infrared (IR) spectroscopy and/or DRIFTS, and the mineral content is immediately quantified via a partial least squares regression (PLSR) algorithm that enables the combining of the spectral data of both methods into a single robust model. Furthermore, it was also demonstrated that the size regime of dust particles may be classified into groups of hazardous and less hazardous size regimes. Thus, this technique may provide additional essential information for controlling air quality in surface and underground mining operations. Graphical Abstract.

Multifunctional Boron-Doped Diamond Colloidal AFM Probes.

Scanning probe microscopy techniques providing information on conductivity, chemical fluxes, and interfacial reactivity synchronized with topographical information have gained importance within the last decades. Herein, a novel colloidal atomic force microscopy (AFM) probe is presented using a spherical boron-doped diamond (BDD) electrode attached and electrically connected to a modified silicon nitride cantilever. These conductive spherical BDD-AFM probes allow for electrochemical force spectroscopy. The physical robustness of these bifunctional probes, and the excellent electrochemical properties of BDD renders this concept a unique multifunctional tool for a wide variety of scanning probe studies including conductive AFM, hybrid atomic force-scanning electrochemical microscopy, and tip-integrated chem/bio sensing.

Physicochemical and Electrochemical Characterization of Electropolymerized Polydopamine Films: Influence of the Deposition Process.

Polydopamine (PDA) is a synthetic eumelanin polymer which is, to date, mostly obtained by dip coating processes. In this contribution, we evaluate the physical and electrochemical properties of electrochemically deposited PDA films obtained by cyclic voltammetry or pulsed deposition. The obtained PDA thin films are investigated with respect to their electrochemical properties, i.e., electron transfer (ET) kinetics and charge transfer resistance using scanning electrochemical microscopy and electrochemical impedance spectroscopy, and their nanomechanical properties, i.e., Young's modulus and adhesion forces at varying experimental conditions, such as applied potential or pH value of the medium using atomic force microscopy. In particular, the ET behavior at different pH values has not to date been investigated in detail for electrodeposited PDA thin films, which is of particular interest for a multitude of applications. Adhesion forces strongly depend on applied potential and surrounding pH value. Moreover, force spectroscopic measurements reveal a significantly higher percentage of polymeric character compared to films obtained by dip coating. Additionally, distinct differences between the two depositions methods are observed, which indicate that the pulse deposition process leads to denser, more cross-linked films.

Micro-Structured Polydopamine Films via Pulsed Electrochemical Deposition.

Polydopamine (PDA) films are interesting as smart functional materials, and their controlled structured formation plays a significant role in a wide range of applications ranging from cell adhesion to sensing and catalysis. A pulsed deposition technique is reported for micro-structuring polydopamine films using scanning electrochemical microscopy (SECM) in direct mode. Thereby, precise and reproducible film thicknesses of the deposited spots could be achieved ranging from 5.9 +/- 0.48 nm (1 pulse cycle) to 75.4 nm +/- 2.5 nm for 90 pulse cycles. The obtained morphology is different in comparison to films deposited via cyclic voltammetry or films formed by autooxidation showing a cracked blister-like structure for high pulse cycle numbers. The obtained polydopamine spots were investigated in respect to their electrochemical properties using SECM approach curves. Quantitative kinetic data in dependence of the film thickness, the substrate potential, and the used redox species were obtained.

Time-resolved ATP measurements during vesicle respiration.

In vitro synthesis of ATP catalyzed by the ATP-synthase requires membrane vesicles, in which the ATP-synthase is present within the bilayer membrane. Inverted vesicle prepared from Gram negative cells (e.g., Escherichia coli or Pseudomonas putida) can be readily obtained and used for in vitro ATP-synthesis. Up to now, quantification of ATP synthesized by membrane vesicles has been mostly analyzed via bioluminescence-based assays. Alternatively, vesicle respiration and the associated ATP level can be determined using biosensors, which not only provide high selectivity, but allow ATP measurements without the sample being illuminated. Here, we present a microbiosensor for ATP in combination with scanning electrochemical microscopy (SECM) using an innovative two-compartment electrochemical cell for the determination of ATP levels at E.coli or P. putida inverted vesicles. For a protein concentration of 22 mg/ml, a total amount of 0.29 ±â€¯0.03 µM/µl ATP per vesicle was determined in case of E.coli; in turn, P. putida derived vesicles yielded 0.48 ±â€¯0.02 µM/µl ATP per vesicle at a total protein concentration of 25.2 mg/ml. Inhibition experiments with Venturicidin A clearly revealed that the respiratory chain enzyme complex responsible for ATP generation is effectively involved.

polyHWG: 3D Printed Substrate-Integrated Hollow Waveguides for Mid-Infrared Gas Sensing.

Gas analysis via mid-infrared (MIR) spectroscopic techniques has gained significance due to its inherent molecular selectivity and sensitivity probing pronounced vibrational, rotational, and roto-vibrational modes. In addition, MIR gas sensors are suitable for real-time monitoring in a wide variety of sensing scenarios. Our research team has recently introduced so-called substrate-integrated hollow waveguides (iHWGs) fabricated by precision milling, which have been demonstrated to be useful in online process monitoring, environmental sensing, and exhaled breath analysis especially if low sample volumes (i.e., few hundreds of microliters) are probed with rapid signal transients. A logical next step is to establish ultralightweight, potentially disposable, and low-cost substrate-integrated hollow waveguides, which may be readily customized and tailored to specific applications using 3D printing techniques. 3D printing provides access to an unprecedented variety of thermoplastic materials including biocompatible polylactides, readily etchable styrene copolymers, and magnetic or conductive materials. Thus, the properties of the waveguide may be adapted to suit its designated application, e.g., drone-mounted ultralightweight waveguides for environmental monitoring or biocompatible disposable sensor interfaces in medical/clinical applications.

Template- and Additive-free Electrosynthesis and Characterization of Spherical Gold Nanoparticles on Hydrophobic Conducting Polydimethylsiloxane.

Carbon-doped poly(dimethylsiloxane) (C-PDMS) modified with gold nanoparticles (AuNPs) is a highly promising material for the development of flexible lab-on-chip biosensors. Here, we present an electrochemical method to prepare stabilizer-free AuNPs directly on hydrophobic conducting substrates like C-PDMS without physical or chemical pre-treatment of the C-PDMS substrate. Using a potentiostatic triple pulse strategy, spherical, non-stabilized AuNPs of diameter 76±5 nm could be deposited within 5 s with narrow size-dispersion on the hydrophobic C-PDMS substrate in the absence of any structure directing or stabilizing agent. The detailed investigation of the mechanism of electrochemical formation of gold seeds and their three-dimensional growth on the hydrophobic surface along with nanomechanical atomic force-scanning electrochemical microscopy (QNM-AFM-SECM) characterization as well as conductive AFM allowed developing this fast electrochemical strategy with control in the desired size and size-dispersion of AuNPs. A detailed electrochemical investigation using cyclic voltammetry, anodic differential pulse voltammetry, and electrochemical impedance spectroscopy was conducted to characterize the electrochemical behavior of uncapped AuNPs deposited on C-PDMS. The Fc+ (MeOH)2 /Fc(MeOH)2 redox reaction at AuNPs-C-PDMS showed an improved charge transfer coefficient and heterogeneous charge transfer rate constant compared to the bare C-PDMS substrate.

From molecular to colloidal manganese vanadium oxides for water oxidation catalysis.

The spontaneous, sonication-driven conversion of a molecular manganese vanadium oxide water oxidation catalyst, (n-Bu4N)3[Mn4V4O17(OAc)3] × 3H2O, into colloidal manganese vanadium oxide particles (average particle size ca. 70 nm) together with their stability and chemical water oxidation activity is reported. The nanoparticulate metal oxide colloid (approximate composition: VMn5O10·ca. 6H2O·ca. 0.2nBu4N+) is formed spontaneously when the molecular precursor is sonicated in water. The particles show water oxidation activity when combined with CeIV as the oxidant, are stable even under highly acidic reaction conditions and can be recovered and reused.