Developing a methodology for XPS profiling of biofilms and biological materials

Films of cells on solid substrates are encountered in a variety of biological and biomedical environments, including cells in biofilms that spontaneously colonize medical devices and multilayers of cells filtered from suspensions for analysis. Understanding the chemical properties of cells in such films is important for providing clues about the behavior of the cells or about the effects of treatments that had been applied to the cells. X-ray Photoelectron Spectroscopy (XPS), with its combination of chemical selectivity and surface specificity, is an ideal technique for analysing these biofilms and multilayers, but it needs to be combined with profiling to more fully characterise the samples. It is well known that profiling with traditionally used argon monomers results in a high degree of chemical modification for most organic materials. Recent studies have shown, however, that argon cluster beams may be used for depth profiling of organic materials while preserving the chemical information. This poster will present data from cluster profiling studies of biofilms and biomaterials. The methodology required for optimum profiling of these samples will be discussed, including an evaluation of XPS data acquisition protocols, as well as sputtering conditions

Disintegration of microcrystalline Zn2SiO4:Mn phosphor powder

Zn2SiO4:Mn (willemite) nanoparticles ∼30 nm in size have been prepared by disintegrating microcrystalline willemite powder in a planetary ball mill. X-ray diffraction and scanning electron micros-copy characterization showed that ball milling of the Zn2SiO 4:Mn powder for 60 min or a longer time ensured complete disintegration of the microcrystalline material and that the crystal structure of the resultant nanoparticles was identical to that of the parent powder. © 2013 Pleiades Publishing, Ltd

pH-Induced Modulation of Vibrio fischeri Population Life Cycle

Commonly used as biological chemosensors in toxicity assays, Vibrio fischeri bacteria were systematically characterized using complementary physicochemical and biological techniques to elucidate the evolution of their properties under varying environmental conditions. Changing the pH above or below the optimal pH 7 was used to model the long-term stress that would be experienced by V. fischeri in environmental toxicology assays. The spectral shape of bioluminescence and cell-surface charge during the exponential growth phase were largely unaffected by pH changes. The pH-induced modulation of V. fischeri growth, monitored via the optical density (OD), was moderate. In contrast, the concomitant changes in the time-profiles of their bioluminescence, which is used as the readout in assays, were more significant. Imaging at discrete timepoints by scanning electron microscopy (SEM) and helium-ion microscopy (HIM) revealed that mature V. fischeri cells maintained a rod-shaped morphology with the average length of 2.2 ± 1 µm and diameter of 0.6 ± 0.1 µm. Detailed morphological analysis revealed subpopulations of rods having aspect ratios significantly larger than those of average individuals, suggesting the use of such elongated rods as an indicator of the multigenerational environmental stress. The observed modulation of bioluminescence and morphology supports the suitability of V. fischeri as biological chemosensors for both rapid and long-term assays, including under environmental conditions that can modify the physicochemical properties of novel anthropogenic pollutants, such as nanomaterials and especially stimulus-responsive nanomaterial

Attomolar label-free detection of DNA hybridization with electrolyte-gated Graphene field-effect transistors

In this work, we develop a field-effect transistor with a two-dimensional channel made of a single graphene layer to achieve label-free detection of DNA hybridization down to attomolar concentration, while being able to discriminate a single nucleotide polymorphism (SNP). The SNP-level target specificity is achieved by immobilization of probe DNA on the graphene surface through a pyrene-derivative heterobifunctional linker. Biorecognition events result in a positive gate voltage shift of the graphene charge neutrality point. The graphene transistor biosensor displays a sensitivity of 24 mV/dec with a detection limit of 25 aM: the lowest target DNA concentration for which the sensor can discriminate between a perfect-match target sequence and SNP-containing one.Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013 and project POCI01-0145-FEDER-031069 (PORTGRAPHE). G. Machado Jr. acknowledges a PhD grant (no. 237630/2012–5) from CNPq– Brazil. J.B. acknowledges European funding from NBFS project under contract NORTE-01-0145-FEDER-00001

Atomic Scale Memory at a Silicon Surface

The limits of pushing storage density to the atomic scale are explored with a memory that stores a bit by the presence or absence of one silicon atom. These atoms are positioned at lattice sites along self-assembled tracks with a pitch of 5 atom rows. The writing process involves removal of Si atoms with the tip of a scanning tunneling microscope. The memory can be reformatted by controlled deposition of silicon. The constraints on speed and reliability are compared with data storage in magnetic hard disks and DNA.Comment: 13 pages, 5 figures, accepted by Nanotechnolog

pH-induced modulation of Vibrio fischeri population life cycle

Commonly used as biological chemosensors in toxicity assays, Vibrio fischeri bacteria were systematically characterized using complementary physicochemical and biological techniques to elucidate the evolution of their properties under varying environmental conditions. Changing the pH above or below the optimal pH 7 was used to model the long-term stress that would be experienced by V. fischeri in environmental toxicology assays. The spectral shape of bioluminescence and cell-surface charge during the exponential growth phase were largely unaffected by pH changes. The pH-induced modulation of V. fischeri growth, monitored via the optical density (OD), was moderate. In contrast, the concomitant changes in the time-profiles of their bioluminescence, which is used as the readout in assays, were more significant. Imaging at discrete timepoints by scanning electron microscopy (SEM) and helium-ion microscopy (HIM) revealed that mature V. fischeri cells maintained a rod-shaped morphology with the average length of 2.2 ± 1 µm and diameter of 0.6 ± 0.1 µm. Detailed morphological analysis revealed subpopulations of rods having aspect ratios significantly larger than those of average individuals, suggesting the use of such elongated rods as an indicator of the multigenerational environmental stress. The observed modulation of bioluminescence and morphology supports the suitability of V. fischeri as biological chemosensors for both rapid and long-term assays, including under environmental conditions that can modify the physicochemical properties of novel anthropogenic pollutants, such as nanomaterials and especially stimulus-responsive nanomaterials.Portuguese Foundation for Science and Technology (FCT) under the scope of the strategic funding of UIDB/04469/2020 unit and COMPETE 2020 (POCI‐ 01‐0145‐FEDER‐006684) and BioTecNorte operation (NORTE‐01‐0145‐FEDER‐000004) funded by European Regional Development Fund under the scope of Norte2020 Programa Operacional Re‐ gional do Norte. A.R.S. holds an FCT fellowship SFRH/BD/131905/2017. Measurements using the helium‐ion microscope were supported by the Karlsruhe Nano Micro Facility (KNMF) of the Karls‐ ruhe Institute of Technology (KIT) under projects 2016‐015‐010689 and 2018‐019‐021475info:eu-repo/semantics/publishedVersio

Crystallographic Facet Selective HER Catalysis: Exemplified in FeP and NiP2 Single Crystals

How the crystal structures of ordered transition-metal phosphide catalysts affect the hydrogen-evolution reaction (HER) is investigated by measuring the anisotropic catalytic activities of selected crystallographic facets on large (mm-sized) single crystals of iron-phosphide (FeP) and monoclinic nickel-diphosphide (m-NiP2). We find that different crystallographic facets exhibit distinct HER activities, in contrast to a commonly held assumption of severe surface restructuring during catalytic activity. Moreover, density-functional-theory-based computational studies show that the observed facet activity correlates well with the H-binding energy to P atoms on specific surface terminations. Direction dependent catalytic properties of two different phosphides with different transition metals, crystal structures, and electronic properties (FeP is a metal, while m-NiP2 is a semiconductor) suggests that the anisotropy of catalytic properties is a common trend for HER phosphide catalysts. This realization opens an additional rational design for highly efficient HER phosphide catalysts, through the growth of nanocrystals with specific exposed facets. Furthermore, the agreement between theory and experimental trends indicates that screening using DFT methods can accelerate the identification of desirable facets, especially for ternary or multinary compounds. The large single-crystal nature of the phosphide electrodes with well-defined surfaces allows for determination of the catalytically important double-layer capacitance of a flat surface, Cdl = 39(2) μF cm−2 for FeP, useful for an accurate calculation of the turnover frequency (TOF). X-ray photoelectron spectroscopy (XPS) studies of the catalytic crystals that were used show the formation of a thin oxide/phosphate overlayer, presumably ex situ due to air-exposure. This layer is easily removed for FeP, revealing a surface of pristine metal phosphide

Transport spin polarization of Ni_xFe_{1-x}: electronic kinematics and band structure

We present measurements of the transport spin polarization of Ni_xFe_{1-x} (0<x<1) using the recently-developed Point Contact Andreev Reflection technique, and compare them with our first principles calculations of the spin polarization for this system. Surpisingly, the measured spin polarization is almost composition-independent. The results clearly demonstrate that the sign of the transport spin polarization does not coincide with that of the difference of the densities of states at the Fermi level. Calculations indicate that the independence of the spin polarization of the composition is due to compensation of density of states and Fermi velocity in the s- and d- bands