Andrei Kolmakov

Interactions between engineered nanoparticles (ENPs) and plants: Phytotoxicity, uptake and accumulation

The rapid development and potential release of engineered nanoparticles (ENPs) have raised considerable concerns due to the unique properties of nanomaterials. An important aspect of the risk assessment of ENPs is to understand the interactions of ENPs with plants, an essential base component of all ecosystems. The impact of ENPs on plant varies, depending on the composition, concentration, size and other important physical chemical properties of ENPs and plant species. Both enhancive and inhibitive effects of ENPs on plant growth at different developmental stages have been documented. ENPs could be potentially taken up by plant roots and transported to shoots through vascular systems depending upon the composition, shape, size of ENPs and plant anatomy. Despite the insights gained through many previous studies, many questions remain concerning the fate and behavior of ENPs in plant systems such as the role of surface area or surface activity of ENPs on phytotoxicity, the potential route of entrance to plant vascular tissues and the role of plant cell walls in internalization of ENPs. This article reviewed the current knowledge on the phytotoxicity and interactions of ENPs with plants at seedling and cellular levels and discussed the information gap and some immediate research needs to further our knowledge on this topic.

Gas Sensor Based on Metal−Insulator Transition in VO2 Nanowire Thermistor

Using temperature driven sharp metal-insulator phase transition in single crystal VO(2) nanowires, the realization of a novel gas sensing concept has been tested. Varying the temperature of the nanowire close to the transition edge, the conductance of the nanowire becomes extremely responsive to the tiny changes in molecular composition, pressure, and temperature of the ambient gas environment. This gas sensing analog of the transition edge sensor radiometry used in astrophysics opens new opportunities in gas sensorics.

Graphene oxide windows for in situ environmental cell photoelectron spectroscopy

The performance of new materials and devices often depends on processes taking place at the interface between an active solid element and the environment (such as air, water or other fluids). Understanding and controlling such interfacial processes require surface-specific spectroscopic information acquired under real-world operating conditions, which can be challenging because standard approaches such as X-ray photoelectron spectroscopy generally require high-vacuum conditions. The state-of-the-art approach to this problem relies on unique and expensive apparatus including electron analysers coupled with sophisticated differentially pumped lenses. Here, we develop a simple environmental cell with graphene oxide windows that are transparent to low-energy electrons (down to 400 eV), and demonstrate the feasibility of X-ray photoelectron spectroscopy measurements on model samples such as gold nanoparticles and aqueous salt solution placed on the back side of a window. These proof-of-principle results show the potential of using graphene oxide, graphene and other emerging ultrathin membrane windows for the fabrication of low-cost, single-use environmental cells compatible with commercial X-ray and Auger microprobes as well as scanning or transmission electron microscopes.

Highly selective gas sensor arrays based on thermally reduced graphene oxide

The electrical properties of reduced graphene oxide (rGO) have been previously shown to be very sensitive to surface adsorbates, thus making rGO a very promising platform for highly sensitive gas sensors. However, poor selectivity of rGO-based gas sensors remains a major problem for their practical use. In this paper, we address the selectivity problem by employing an array of rGO-based integrated sensors instead of focusing on the performance of a single sensing element. Each rGO-based device in such an array has a unique sensor response due to the irregular structure of rGO films at different levels of organization, ranging from nanoscale to macroscale. The resulting rGO-based gas sensing system could reliably recognize analytes of nearly the same chemical nature. In our experiments rGO-based sensor arrays demonstrated a high selectivity that was sufficient to discriminate between different alcohols, such as methanol, ethanol and isopropanol, at a 100% success rate. We also discuss a possible sensing mechanism that provides the basis for analyte differentiation.

Phytotoxicity, accumulation and transport of silver nanoparticles by Arabidopsis thaliana

Abstract The widespread availability of nano-enabled products in the global market may lead to the release of a substantial amount of engineered nanoparticles in the environment, which frequently display drastically different physiochemical properties than their bulk counterparts. The purpose of the study was to evaluate the impact of citrate-stabilised silver nanoparticles (AgNPs) on the plant Arabidopsis thaliana at three levels, physiological phytotoxicity, cellular accumulation and subcellular transport of AgNPs. The monodisperse AgNPs of three different sizes (20, 40 and 80 nm) aggregated into much larger sizes after mixing with quarter-strength Hoagland solution and became polydisperse. Immersion in AgNP suspension inhibited seedling root elongation and demonstrated a linear dose–response relationship within the tested concentration range. The phytotoxic effect of AgNPs could not be fully explained by the released silver ions. Plants exposed to AgNP suspensions bioaccumulated higher silver content than plants exposed to AgNO3 solutions (Ag+ representative), indicating AgNP uptake by plants. AgNP toxicity was size and concentration dependent. AgNPs accumulated progressively in this sequence: border cells, root cap, columella and columella initials. AgNPs were apoplastically transported in the cell wall and found aggregated at plasmodesmata. In all the three levels studied, AgNP impacts differed from equivalent dosages of AgNO3.

ESCA Microscopy at ELETTRA: what it is like to perform spectromicroscopy experiments on a third generation synchrotron radiation source

Abstract We present ESCA Microscopy, the first X-ray microscopy beamline operating on ELETTRA, the third generation synchrotron radiation source in Trieste, Italy. ESCA Microscopy is an advanced user facility open to the international scientific community; its operation is based on the use of a Fresnel zone plate to demagnify to submicrometre dimensions the photon beam emitted by an undulator in the 200–1000 eV energy range. ESCA Microscopy was designed as a scanning photoemission microscope especially suited for surface analysis; it also operates in transmission mode and should find many applications in materials science, chemistry and physics. We describe here the beamline experimental setup and present some recent results obtained during the first months of operation. While so doing, we will outline certain spectroscopic aspects and point out some operational problems that are typical of scanning photoemission microscopy, a technique which should find in advanced sources such as ELETTRA the right conditions to achieve maturity.

Current rectification in a single GaN nanowire with a well-defined p-n junction

This letter discusses Mg incorporation in GaN nanowires with diameters ∼35 nm, fabricated by vapor–liquid–solid synthesis in p-type nanowires. Turning on the Mg doping halfway through the synthesis produced nanowires with p–n junctions that showed excellent rectification properties down to 2.6 K. The nanowires are shown to possess good-quality, crystalline, hexagonal GaN inner cores surrounded by an amorphous GaN outer layer. Most wires grow such that the crystalline c axis is normal to the long axis of the nanowire. The temperature dependence of the current–voltage characteristics is consistent with electron tunneling through a voltage-dependent barrier.

Symmetry relationship and strain-induced transitions between insulating M1 and M2 and metallic R phases of vanadium dioxide.

The ability to synthesize VO2 in the form of single-crystalline nanobeams and nano- and microcrystals uncovered a number of previously unknown aspects of the metal-insulator transition (MIT) in this oxide. In particular, several reports demonstrated that the MIT can proceed through competition between two monoclinic (insulating) phases M1 and M2 and the tetragonal (metallic) R phase under influence of strain. The nature of such phase behavior has been not identified. Here we show that the competition between M1 and M2 phases is purely lattice-symmetry-driven. Within the framework of the Ginzburg-Landau formalism, both M phases correspond to different directions of the same four-component structural order parameter, and as a consequence, the M2 phase can appear under a small perturbation of the M1 structure such as doping or stress. We analyze the strain-controlled phase diagram of VO2 in the vicinity of the R-M2-M1 triple point using the Ginzburg-Landau formalism and identify and experimentally verify the pathways for strain-control of the transition. These insights open the door toward more systematic approaches to synthesis of VO2 nanostructures in desired phase states and to use of external fields in the control of the VO2 phase states. Additionally, we report observation of the triclinic T phase at the heterophase domain boundaries in strained quasi-two-dimensional VO2 nanoplatelets, and theoretically predict phases that have not been previously observed.

Highly sensitive gas sensor based on integrated titania nanosponge arrays

Highly sensitive gas sensors were fabricated using nanostructured titania pad arrays. Nanostructured titania (NST) formed is sponge-like consisting of interconnected nanoscale wires and walls, which are made up of anatase nanocrystals. Electrical characterization indicates that contacts were ohmic and NST was highly sensitive to O2. Variations of hundreds of oxygen molecules over a 20μm NST square pad sensing element were detected at 250°C. The NST-based sensor operates at lower temperatures, has fast response time, and superior sensitivity relative to oxygen sensors based on porous undoped titania reported in the literature.

Interplay between Ferroelastic and Metal−Insulator Phase Transitions in Strained Quasi-Two-Dimensional VO2 Nanoplatelets

Formation of ferroelastic twin domains in vanadium dioxide (VO(2)) nanosystems can strongly affect local strain distributions, and hence couple to the strain-controlled metal-insulator transition. Here we report polarized-light optical and scanning microwave microscopy studies of interrelated ferroelastic and metal-insulator transitions in single-crystalline VO(2) quasi-two-dimensional (quasi-2D) nanoplatelets (NPls). In contrast to quasi-1D single-crystalline nanobeams, the 2D geometric frustration results in emergence of several possible families of ferroelastic domains in NPls, thus allowing systematic studies of strain-controlled transitions in the presence of geometrical frustration. We demonstrate the possibility of controlling the ferroelastic domain population by the strength of the NPl-substrate interaction, mechanical stress, and by the NPl lateral size. Ferroelastic domain species and domain walls are identified based on standard group-theoretical considerations. Using variable temperature microscopy, we imaged the development of domains of metallic and semiconducting phases during the metal-insulator phase transition and nontrivial strain-driven reentrant domain formation. A long-range reconstruction of ferroelastic structures accommodating metal-insulator domain formation has been observed. These studies illustrate that a complete picture of the phase transitions in single-crystalline and disordered VO(2) structures can be drawn only if both ferroelastic and metal-insulator strain effects are taken into consideration and understood.