Nitrogen-vacancy center magnetic imaging of Fe3O4 nanoparticles inside the gastrointestinal tract of Drosophila melanogaster.

Widefield magnetometry based on nitrogen-vacancy centers enables high spatial resolution imaging of magnetic field distributions without a need for spatial scanning. In this work, we show nitrogen-vacancy center magnetic imaging of Fe3O4 nanoparticles within the gastrointestinal tract of Drosophila melanogaster larvae. Vector magnetic field imaging based on optically detected magnetic resonance is carried out on dissected larvae intestine organs containing accumulations of externally loaded magnetic nanoparticles. The distribution of the magnetic nanoparticles within the tissue can be clearly deduced from the magnetic stray field measurements. Spatially resolved magnetic imaging requires the nitrogen-vacancy centers to be very close to the sample making the technique particularly interesting for thin tissue samples. This study is a proof of principle showing the capability of nitrogen-vacancy center magnetometry as a technique to detect magnetic nanoparticle distributions in Drosophila melanogaster larvae that can be extended to other biological systems.

Imaging local diffusion in microstructures using NV-based pulsed field gradient NMR.

Understanding diffusion in microstructures plays a crucial role in many scientific fields, including neuroscience, medicine, or energy research. While magnetic resonance (MR) methods are the gold standard for diffusion measurements, spatial encoding in MR imaging has limitations. Here, we introduce nitrogen-vacancy (NV) center-based nuclear MR (NMR) spectroscopy as a powerful tool to probe diffusion within microscopic sample volumes. We have developed an experimental scheme that combines pulsed gradient spin echo (PGSE) with optically detected NV-NMR spectroscopy, allowing local quantification of molecular diffusion and flow. We demonstrate correlated optical imaging with spatially resolved PGSE NV-NMR experiments probing anisotropic water diffusion within an individual model microstructure. Our optically detected PGSE NV-NMR technique opens up prospects for extending the current capabilities of investigating diffusion processes with the future potential of probing single cells, tissue microstructures, or ion mobility in thin film materials for battery applications.

Surface-Mediated Charge Transfer of Photogenerated Carriers in Diamond.

Solvated electrons are highly reductive chemical species whose chemical properties remain largely unknown. Diamond materials are proposed as a promising emitter of solvated electrons and visible light excitation would enable solar-driven CO2 or N2 reductions reactions in aqueous medium. But sub-bandgap excitation remains challenging. In this work, the role of surface states on diamond materials for charge separation and emission in both gaseous and aqueous environments from deep UV to visible light excitation is elucidated. Four different X-ray and UV-vis spectroscopy methods are applied to diamond materials with different surface termination, doping and crystallinity. Surface states are found to dominate sub-bandgap charge transfer. However, the surface charge separation is drastically reduced for boron-doped diamond due to a very high density of bulk defects. In a gaseous atmosphere, the oxidized diamond surface maintains a negative electron affinity, allowing charge emission, due to remaining hydrogenated and hydroxylated groups. In an aqueous electrolyte, a photocurrent for illumination down to 3.5 eV is observed for boron-doped nanostructured diamond, independent of the surface termination. This study opens new perspectives on photo-induced interfacial charge transfer processes from metal-free semiconductors such as diamonds.

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.

Diamond Colloidal Probe Force Spectroscopy.

Diamond is a highly attractive coating material as it is characterized by a wide optical transparency window, a high thermal conductivity, and an extraordinary robustness due to its mechanical properties and its chemical inertness. In particular, the latter has aroused a great deal of interest for scanning probe microscopy applications in recent years. In this study, we present a novel method for the fabrication of atomic force microscopy (AFM) probes for force spectroscopy using robust diamond-coated spheres, i.e., colloidal particles. The so-called colloidal probe technique is commonly used to study interactions of single colloidal particles, e.g., on biological samples like living cells, or to measure mechanical properties like the Young's modulus. Under physiological measurement conditions, contamination of the particle often strongly limits the measurement time and often impedes reusability of the probe. Diamond as a chemically inert material allows treatment with harsh chemicals without degradation to refurbish the probe. Apart from that, the large surface area of spherical probes makes sensitive studies on surface interactions possible. This provides detailed insight into the interface of diamond with other materials and/or solvents. To fabricate such probes, silica microspheres were coated with a nanocrystalline diamond film and attached to tipless cantilevers. Measurements on soft polydimethylsiloxane (PDMS) show that the manufactured diamond spheres, even though possessing a rough surface, can be used to determine the Young's modulus from a Derjaguin-Muller-Toporov (DMT) fit. By means of force spectroscopy, they can readily probe force interactions of diamond with different substrate materials under varying conditions. The influence of the surface termination of the diamond was investigated concerning the interaction with flat diamond substrates in air. Additionally, measurements in solution, using varying salt concentrations, were carried out, which provide information on double-layer and van-der-Waals forces at the interface. The developed technique offers detailed insight into surface chemistry and physics of diamond with other materials concerning long and short-range force interactions and may provide a valuable probe for investigations under harsh conditions but also on biological samples, e.g., living cells, due to the robustness, chemical inertness, and biocompatibility of diamond.

High voltage electrochemical exfoliation of graphite for high-yield graphene production.

We demonstrate a highly efficient, single-step, cathodic exfoliation process of graphite to produce single- to few-layer graphene with a yield of over 70% from natural graphite flakes. By employing boron-doped diamond electrodes high potentials up to -60 V can be applied which was found to greatly increase the yield. The produced graphene flakes are partially hydrogenated during the electrochemical treatment likely aiding in their exfoliation. The resulting flakes have a large lateral size with up to 50 µm diameter. Due to the reversibility of the hydrogenation by thermal treatment the graphene flakes possess a low defect density as judged by the Raman D/G ratio yielding highly conductive films with sheet resistances of 100 to 3200 Ω â–¡-1 at 10 to 70% transparency.

Scanning electrochemical microscopy: an analytical perspective.

Scanning electrochemical microscopy (SECM) has evolved from an electrochemical specialist tool to a broadly used electroanalytical surface technique, which has experienced exciting developments for nanoscale electrochemical studies in recent years. Several companies now offer commercial instruments, and SECM has been used in a broad range of applications. SECM research is frequently interdisciplinary, bridging areas ranging from electrochemistry, nanotechnology, and materials science to biomedical research. Although SECM is considered a modern electroanalytical technique, it appears that less attention is paid to so-called analytical figures of merit, which are essential also in electroanalytical chemistry. Besides instrumental developments, this review focuses on aspects such as reliability, repeatability, and reproducibility of SECM data. The review is intended to spark discussion within the community on this topic, but also to raise awareness of the challenges faced during the evaluation of quantitative SECM data.

Silanization of Sapphire Surfaces for Optical Sensing Applications.

Well-characterized silane layers are essential for optimized attachment of (bio)molecules enabling reliable chem/biosensor performance. Herein, binding properties and orientation of 3-mercaptopropyltrimethoxysilane layers at crystalline sapphire (0001) surfaces were determined by water contact angle measurements, infrared reflection absorption spectroscopy, atomic force microscopy, and X-ray photoelectron spectroscopy. Infrared reflection absorption spectroscopy measurements suggest an almost perpendicular arrangement of the MPTMS molecules to the substrate surface. Adhesion force studies between a silicon nitride AFM tip and modified sapphire, gold, and silicon dioxide substrates were investigated by peak force tapping atomic force microscopy and used to define the silane binding properties on these surfaces. As expected, the Al-O-Si bond was determined to be responsible for the layer formation at the sapphire substrate surface.

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.

Focused ion beam-assisted fabrication of soft high-aspect ratio silicon nanowire atomic force microscopy probes.

In this study, high-aspect ratio silicon nanowire (SiNW) - modified atomic force microscopy (AFM) probes are fabricated using focused ion beam (FIB) microfabrication technology and vapor-solid-solid synthesis. Commercially available soft silicon nitride probes are used for localized nanowire growth yielding soft high-aspect ratio AFM probes. The SiNW-modified cantilevers are used here for imaging in PeakForce Tappingۛ (PFT) mode, which offers high force control along with valuable information about tip-sample adhesion. A platinum catalyst, deposited accurately at a truncated AFM tip by ion beam-induced deposition (IBID), was used for localized nanowire synthesis. It could be shown that the deposition of a thin silicon dioxide layer prior to the catalyst deposition resulted in controlled SiNW growth on silicon as well as silicon nitride probes. In addition, a FIB-based method for post-growth alignment of the fabricated SiNW tips is presented, which allows tilt-compensation specifically tailored to the specifications of the used AFM instrumentation. To demonstrate the capability of such soft, high-aspect ratio AFM probes, optical gratings fabricated in GaAs and silver halide fibers were imaged in PFT mode. Additionally, the mechanical stability of these high-aspect AFM probes was evaluated on a sapphire substrate.

Visualization of Diffusion within Nanoarrays.

The direct experimental characterization of diffusion processes at nanoscale remains a challenge that could help elucidate processes in biology, medicine and technology. In this report, two experimental approaches were employed to visualize ion diffusion profiles at the orifices of nanopores (radius (ra) of 86 ± 6 nm) in array format: (1) electrochemically assisted formation of silica deposits based on surfactant ion transfer across nanointerfaces between two immiscible electrolyte solutions (nanoITIES); (2) combined atomic force - scanning electrochemical microscopy (AFM-SECM) imaging of topography and redox species diffusion through the nanopores. The nature of the diffusion zones formed around the pores is directly related to the interpore distance within the array. Nanopore arrays with different ratios of pore center-to-center separation (rc) to pore radius (ra) were fabricated by focused ion beam (FIB) milling of silicon nitride (SiN) membranes, with 100 pores in a hexagonal arrangement. The ion diffusion profiles determined by the two visualization methods indicated the formation of overlapped or independent diffusion profiles at nanopore arrays with rc/ra ratios of 21 ± 2 and 91 ± 7, respectively. In particular, the silica deposition method resulted in formation of a single deposit encompassing the complete array with closer nanopore arrangement, whereas individual silica deposits were formed around each nanopore within the more widely spaced array. The methods reveal direct experimental evidence of diffusion zones at nanopore arrays and provide practical illustration that the pore-pore separation within such arrays has a significant impact on diffusional transport as the pore size is reduced to the nanoscale. These approaches to nanoscale diffusion zone visualization open up possibilities for better understanding of molecular transport processes within miniaturized systems.

Simultaneous Nanomechanical and Electrochemical Mapping: Combining Peak Force Tapping Atomic Force Microscopy with Scanning Electrochemical Microscopy.

Soft electronic devices play a crucial role in, e.g., neural implants as stimulating electrodes, transducers for biosensors, or selective drug-delivery. Because of their elasticity, they can easily adapt to their environment and prevent immunoreactions leading to an overall improved long-term performance. In addition, flexible electronic devices such as stretchable displays will be increasingly used in everyday life, e.g., for so-called electronic wearables. Atomic force microscopy (AFM) is a versatile tool to characterize these micro- and nanostructured devices in terms of their topography. Using advanced imaging techniques such as peak force tapping (PFT), nanomechanical properties including adhesion, deformation, and Young's modulus can be simultaneously mapped along with surface features. However, conventional AFM provides limited laterally resolved information on electrical or electrochemical properties such as the activity of an electrode array. In this study, we present the first combination of AFM with scanning electrochemical microscopy (SECM) in PFT mode, thereby offering spatially correlated electrochemical and nanomechanical information paired with high-resolution topographical data under force control (QNM-AFM-SECM). The versatility of this combined scanning probe approach is demonstrated by mapping topographical, electrochemical, and nanomechanical properties of gold microelectrodes and of gold electrodes patterned onto polydimethylsiloxane.