ABSTRACT
Research investigating the interface between biological organisms and nanomaterials nowadays requires multi-faceted microscopic methods to elucidate the interaction mechanisms and effects. Here we describe a novel approach and methodology correlating data from an atomic force microscope inside a scanning electron microscope (AFM-in-SEM). This approach is demonstrated on bacteria-diamond-metal nanocomposite samples relevant in current life science research. We describe a procedure for preparing such multi-component test samples containing E. coli bacteria and chitosan-coated hydrogenated nanodiamonds decorated with silver nanoparticles on a carbon-coated gold grid. Microscopic topography information (AFM) is combined with chemical, material, and morphological information (SEM using SE and BSE at varied acceleration voltages) from the same region of interest and processed to create 3D correlative probe-electron microscopy (CPEM) images. We also establish a novel 3D RGB color image algorithm for merging multiple SE/BSE data from SEM with the AFM surface topography data which provides additional information about microscopic interaction of the diamond-metal nanocomposite with bacteria, not achievable by individual analyses. The methodology of CPEM data interpretation is independently corroborated by further in-situ (EDS) and ex-situ (micro-Raman) chemical characterization as well as by force volume AFM analysis. We also discuss the broader applicability and benefits of the methodology for life science research.
ABSTRACT
Nanodiamonds (NDs) are versatile, broadly available nanomaterials with a set of features highly attractive for applications from biology over energy harvesting to quantum technologies. Via synthesis and surface chemistry, NDs can be tuned from the sub-micron to the single-digit size, from conductive to insulating, from hydrophobic to hydrophilic, and from positively to negatively charged surface by simple annealing processes. Such ND diversity makes it difficult to understand and take advantage of their electronic properties. Here we present a systematic correlated study of structural and electronic properties of NDs with different origins and surface terminations. The absolute energy level diagrams are obtained by the combination of optical (UV-vis) and photoelectron (UPS) spectroscopies, Kelvin probe measurements, and energy-resolved electrochemical impedance spectroscopy (ER-EIS). The energy levels and density of states in the bandgap of NDs are correlated with the surface chemistry and structure characterized by FTIR and Raman spectroscopy. We show profound differences in energy band shifts (by up to 3 eV), Fermi level position (from p-type to n-type), electron affinity (from +0.5 eV to -2.2 eV), optical band gap (5.2 eV to 5.5 eV), band gap states (tail or mid-gap), and electrical conductivity depending on the high-pressure, high-temperature and detonation origin of NDs as well as on the effects of NDs' oxidation, hydrogenation, sp2/sp3 carbon phases and surface adsorbates. These data are fundamental for understanding and designing NDs' optoelectrochemical functional mechanisms in diverse application areas.
ABSTRACT
Solely light-induced water splitting represents a promising avenue for a carbon-free energy future, based on reliable energy sources. Such processes can be performed using coupled semiconductor materials (the so-called direct Z-scheme design) that facilitate spatial separation of (photo)excited electrons and holes, prevent their recombination, and allow water-splitting half-reactions proceeding at each corresponding semiconductor side. In this work, we proposed and prepared a specific structure, based on WO3g-x/CdWO4/CdS coupled semiconductors, created by annealing of a common WO3/CdS direct Z-scheme. WO3-x/CdWO4/CdS flakes were further combined with a plasmon-active grating for the creation of the so-called artificial leaf design, making possible complete utilization of the sunlight spectrum. The proposed structure enables water splitting with high production of stoichiometric amounts of oxygen and hydrogen without undesirable catalyst photodegradation. Several control experiments confirm the creation of electrons and holes participating in the water splitting half-reaction in a spatially selective manner.
ABSTRACT
The electrospinning of an ethylene vinyl acetate (EVA) copolymer with a vinyl acetate content of 28 wt.% is limited due to the solubility of the copolymer in standard laboratory conditions. Poly(lactic acid) (PLA) is a biodegradable polymer that can be electrospun easily. However, PLA has limited applicability because it is brittle. Blends of these polymers are of interest in order to obtain new types of materials with counterbalanced properties originating from both polymeric compounds. The fibers were electrospun on a water surface from a solution mixture containing various weight ratios of both polymers using a dichloromethane and acetone (70:30 v/v) mixture as solvent. The morphologies of the prepared non-woven mats were examined by scanning electron microscopy (SEM), and the chemical composition was investigated by X-ray photoelectron spectroscopy (XPS) and by Fourier Transform Infrared Spectroscopy (FTIR). The fibers' thermal properties and stability were examined, and the mechanical properties were tested. The results showed that the strength and flexibility of the blend samples were enhanced by the presence of PLA.
ABSTRACT
We report on the design of an amperometric tyrosinase-based biosensor using a self-assembled monolayer of ω-mercaptopropyl naphthoquinone on gold electrode as an electron mediator. Under optimal conditions (i.e. pH=7.4 and E=-0.35V vs. KCl), the chronoamperometric response of the naphthoquinone-modified bioelectrode to successive additions of phenol was evaluated. The biosensor exhibits sensitive bioelectrocatalytic response at a working potential of -0.35V vs. Ag/AgCl (sat.KCl), reaching the steady-state current within 40s after each addition of phenol solution with a range of 0-135µM and a limit of detection and quantification which are 0.019µM and 0.0633µM, respectively. The bioelectrode was used to determine the content in polyphenol in a local virgin olive oil.
