Oxidatively-induced C(sp3)-C(sp3) bond formation at a tucked-in iron(iii) complex.

Carbon-carbon (C-C) bond formation is a cornerstone of synthetic chemistry, relying on routes such as transition-metal mediated cross-coupling for the introduction of new carbon-based functionality. For {[M] n+-C} (M = metal) structural units, studies that offer well-defined relationships between metal oxidation state, hydrocarbon strain, and {[M] n+-C} bond thermochemistry are thus informative, providing a means to reliably access new product classes. Here, we show that one-electron oxidation of the iron tucked-in complex [(η6-C5Me4[double bond, length as m-dash]CH2)Fe(dnppe)] (dnppe = 1,2-bis(di-n-propylphosphino)ethane) results in C(sp3)-C(sp3) bond formation giving unique {Fe2} dimers. Freeze-quenched CW X-band EPR spectroscopy allowed for spectroscopic identification of the reactive [(η6-C5Me4[double bond, length as m-dash]CH2)Fe(dnppe)]+ intermediate. Density functional theory (DFT) calculations reveal a primarily Fe-centered radical and a weak {[Fe]-C} bond (BDE[Fe]-C = 24.5 kcal mol-1, c.f. BDEC-C(ethane) = 90 kcal mol-1). For comparison, a structurally analogous Fe(iii) methyl complex was prepared, [Cp*Fe(dnppe)(CH3)]+ (Cp* = C5Me5 -), where C(sp3)-C(sp3) coupling was not observed, consistent with a larger calculated BDE[Fe]-C value of 47.8 kcal mol-1. These data are analogized to the simple hydrocarbons ethane and cyclopropane, where a strain-induced BDEC-C decrease of 33 kcal mol-1 is witnessed on cyclization.

Giant auxetic behavior in remote-plasma synthesized few-layer tungsten semicarbide.

Auxetic crystals exhibiting highly positive lateral expansivity when stretched are an experimentally elusive class of two-dimensional (2D) materials with tremendous potential, for example in the direct transduction of electric signals and the compensation of thermal expansion at the nanoscale. 2D tungsten semi-carbide (W2C) was theoretically predicted to exhibit giant auxetic behavior, but has yet to be synthesized, as the corresponding full carbide (WC) is energetically favored under thermodynamic equilibrium synthesis processes such as furnace-based chemical vapor deposition. Here, we report on an ad hoc designed dual-zone remote plasma deposition system specially conceived to grow tungsten carbides out of thermodynamic equilibrium with well-tuned ratios of W and C precursors. We report on the specific conditions under which this system allowed for the synthesis of flakes of few-layer tungsten semicarbide (FL-W2C) which are 2D in nature due to retained periodicity at the mesoscopic level in a Stranski-Krastanov growth process. Under applied strain, FL-W2C 2D crystals exhibit the strongest auxetic behavior observed to date. This result suggests that the theoretically predicted high negative Poisson's ratio of single-layer W2C, also extends to thicker FL-W2C flakes that are retaining the periodicity of the 2D crystal at the mesoscopic level.

A methodological primer of extracellular vesicles isolation and characterization via different techniques.

We present four different protocols of varying complexity for the isolation of cell culture-derived extracellular vesicles (EVs)/exosome-enriched fractions with the objective of providing researchers with easily conducted methods that can be adapted for many different uses in various laboratory settings and locations. These protocols are primarily based on polymer precipitation, filtration and/or ultracentrifugation, as well as size-exclusion chromatography (SEC) and include: (i) polyethylene glycol and sodium chloride supplementation of the conditioned medium followed by low-speed centrifugation; (ii) ultracentrifugation of conditioned medium; (iii) filtration of conditioned media through a 100-kDa exclusion filter; and (iv) isolation using a standard commercial kit. These techniques can be followed by further purification by ultracentrifugation, sucrose density gradient centrifugation, or SEC if needed and the equipment is available. HEK293 and SH-SY5Y cell cultures were used to generate conditioned medium containing exosomes. This medium was then depleted of cells and debris, filtered through a 0.2-µM filter, and supplemented with protease and RNAse inhibitors prior to exosomal isolation. The purified EVs can be used immediately or stably stored at 4°C (up to a week for imaging or using intact EVS downstream) or at -80°C for extended periods and then used for biochemical study. Our aim is not to compare these methodologies but to present them with descriptors so that researchers can choose the "best method" for their work under their individual conditions.

Dynamic dielectric function and phonon self-energy from electrons strongly correlated with acoustic phonons in 2D Dirac crystals.

The unique structure of two-dimensional (2D) Dirac crystals, with electronic bands linear in the proximity of the Brillouin-zone boundary and the Fermi energy, creates anomalous situations where small Fermi-energy perturbations critically affect the electron-related lattice properties of the system. The Fermi-surface nesting (FSN) conditions determining such effects via electron-phonon interaction require accurate estimates of the crystal's response function(χ)as a function of the phonon wavevectorqfor any values of temperature, as well as realistic hypotheses on the nature of the phonons involved. Numerous analytical estimates ofχ(q)for 2D Dirac crystals beyond the Thomas-Fermi approximation have been so far carried out only in terms of dielectric response functionχ(q,ω), for photon and optical-phonon perturbations, due to relative ease of incorporating aq-independent oscillation frequency(ω)in calculation. Models accounting for Dirac-electron interaction with acoustic phonons, for whichωis linear toqand is therefore dispersive, are essential to understand many critical crystal properties, including electrical and thermal transport. The lack of such models has often led to the assumption that the dielectric response functionχ(q)in these systems can be understood from free-electron behavior. Here, we show that, different from free-electron systems,χ(q)calculated for acoustic phonons in 2D Dirac crystals using the Lindhard model, exhibits a cuspidal point at the FSN condition. Strong variability of∂χ∂qpersists also at finite temperatures, whileχ(q)tend to infinity in the dynamic case where the speed of sound is small, albeit non negligible, over the Dirac-electron Fermi velocity. The implications of our findings for electron-acoustic phonon interaction and transport properties such as the phonon line width derived from the phonon self-energy will also be discussed.

Universal Transfer Printing of Micelle-Templated Nanoparticles Using Plasma-Functionalized Graphene.

Nanostructure incorporation into devices plays a key role in improving performance, yet processes for preparing two-dimensional (2D) arrays of colloidal nanoparticles tend not to be universally applicable, particularly for soft and oxygen-sensitive substrates for organic and perovskite-based electronics. Here, we show a method of transferring reverse micelle-deposited (RMD) nanoparticles (perovskite and metal oxide) on top of an organic layer, using a functionalized graphene carrier layer for transfer printing. As the technique can be applied universally to RMD nanoparticles, we used magnetic (γ-Fe2O3) and luminescent (methylammonium lead bromide (MAPbBr3)) nanoparticles to validate the transfer-printing methodology. The strong photoluminescence from the MAPbBr3 under UV illumination and high intrinsic field of the γ-Fe2O3 as measured by magnetic force microscopy (MFM), coupled with Raman measurements of the graphene layer, confirm that all components survive the transfer-printing process with little loss of properties. Such an approach to introducing uniform 2D arrays of nanoparticles onto sensitive substrates opens up new avenues to tune the device interfacial properties.

Intrinsic Enzyme-like Activities of Cerium Oxide Nanocomposite and Its Application for Extracellular H2O2 Detection Using an Electrochemical Microfluidic Device.

Artificial enzyme mimics have gained considerable attention for use in sensing applications due to their high stability and outstanding catalytic activity. We show that cerium oxide nanosheets (NSs) exhibit triple-enzyme mimetic activity. The oxidase-, peroxidase-, and catalase-like activities of the proposed nanoparticles are demonstrated using both colorimetric and electron paramagnetic resonance (EPR) spectroscopy. On the basis of the excellent catalytic activity of cerium oxide NSs toward hydrogen peroxide, an electrochemical approach for the high-throughput detection of H2O2 in living cells was established. This report presents an analytical microfluidic chip integrated with a cerium oxide NS mimic enzyme for the fabrication of a simple, sensitive, and low-cost electrochemical sensor. Three Au microelectrodes were fabricated on a glass substrate using photolithography, and the working electrode was functionalized using cerium oxide NSs. The operation of this biosensor is based on cerium oxide NSs and presents a high sensitivity over a wide detection range, between 100 nM and 20 mM, with a low detection limit of 20 nM and a high sensitivity threshold of 226.4 µA·cm-2·µM-1. This microfluidic sensor shows a strong response to H2O2, suggesting potential applications in monitoring H2O2 directly secreted from living cells. This sensor chip provides a promising platform for applications in the field of diagnostics and sensing.

Solid-State Chemiresistors from Two-Dimensional MoS2 Nanosheets Functionalized with l-Cysteine for In-Line Sensing of Part-Per-Billion Cd2+ Ions in Drinking Water.

Sensing of metal contaminants at ultralow concentrations in aqueous environments is vital in today's overpopulated world, with an extremely stringent limit (<5 ppb) for Cd2+ ions in drinking water. Here, we utilize sonochemically exfoliated molybdenum disulfide (MoS2) nanosheets functionalized with l-cysteine (Cys) as highly sensitive and selective two-dimensional (2D) materials for solid-state chemiresistors. We specifically targeted Cd2+ ions due to their high toxicity at low concentrations. MoS2-Cys nanosheets are fabricated using an ad hoc, low-complexity, one-pot synthesis method. Porous MoS2-Cys thin films with a high surface area are assembled from these nanosheets. Two-terminal chemiresistors incorporating MoS2-Cys films are demonstrated to be preferentially sensitive to Cd2+ ions at neutral pH, irrespective of other metal ions present in water flowing through the device. A 5 ppb concentration of the Cd2+ ions in the water stream increases the device resistivity by 20 times. Our devices operate at broad (1-500 ppb) range and fast (∼1 s) response times. Cd2+ is selectively detected because of preferential, size-driven adsorption at the interstitials between l-cysteine functional groups, combined with pH-controlled charge transfer that removes electronic gap states from MoS2. MoS2-Cys-based chemiresistors can be deployed in-line to detect metal ions without any need for additional offline measurements.

Thermal conductivity of thin film-substrate systems from two-side scanning photothermal deflection measurements: Theoretical model and validation.

Photothermal deflection (PTD) has been frequently utilized to measure the thermal properties of thin solid films on a substrate. In the models commonly used to interpret PTD data, the substrate is assumed to be an ideal thermal insulator. This assumption poses important restrictions on the reliability of these thermal measurements and limits the possibility to use PTD for also measuring the specific heat of the samples. Simultaneous knowledge of specific heat and thermal diffusivity is necessary to determine the thermal conductivity of thin solid films. In this work, we calculated the phase and amplitude of the PTD signal at the two opposites sides (film-side and substrate-side) of a thin-film substrate system. We find that, on both sides, the phases of the PTD signal primarily depend on the thermal diffusivity of the thin film, while the amplitudes primarily depend on the specific heat. By using the phases and amplitudes at the two sides, we show that the accuracy of thermal conductivity measurements by PTD can be dramatically improved. We validate our theoretical model by measuring, in a scanning PTD apparatus, the thermal properties of gold thin films, which are in excellent agreement with, and improve on, existing data from the literature.

Contactless near-field scanning thermoreflectance imaging.

Determining and imaging the thermal properties at the nanoscale is a demanding experimental challenge. So far, virtually any techniques used to image nanoscale thermal properties require to position the sample in contact with voluminous probes that act as undesirable thermal sinks and dramatically affect the measurements, in spite of poor interfacial thermal resistivity. Thermoreflectance, a contactless technique in which thermal conductivity is measured by optically probing the heat-induced changes in a sample, is extensively used for measuring the macroscopic and microscopic thermal properties of solids, but, so far, has been limited by diffraction in its applicability at the nanoscale. Here, we present near-field scanning thermoreflectance imaging (NeSTRI), a new scanning probe technique in which an aperture-type near-field optical microscope at sub-wavelength resolution is used to contactlessly determine the thermoreflectance of thin films. As a case study, NeSTRI is here applied to multilayer graphene thin films on glass substrates. Thermal conductivity of micrometre-size multilayer graphene platelets is determined and is consistent with previous macroscopic predictions. We also find that the thermal conductivity is locally higher at specific crystallographic edges of multilayer graphene platelets, which is indicative of the spatial resolution of our method. NeSTRI is uniquely suited to understanding the thermal properties of a large class of nanostructured and nanoscale systems.

Porous graphene-based membranes for water purification from metal ions at low differential pressures.

A new generation of membranes for water purification based on weakly oxidized and nanoporous few-layer graphene is here introduced. These membranes dramatically decrease the high energy requirements of water purification by reverse osmosis. They combine the advantages of porous and non-oxidized single-layer graphene, offering energy-efficient water filtration at relatively low differential pressures, and highly oxidized graphene oxide, exhibiting high performance in terms of impurity adsorption. In the reported fabrication process, leaks between juxtaposed few-layer graphene flakes are sealed by thermally annealed colloidal silica, in a treatment that precedes the opening of (sub)nanometre-size pores in graphene. This process, explored for the first time in this work, results in nanoporous graphene flakes that are water-tight at the edges without occluding the (sub)nanopores. With this method, removal of impurities from water occurs through a combination of size-based pore rejection and pore-edge adsorption. Thinness of graphene flakes allows these membranes to achieve water purification from metal ions in concentrations of few parts-per-million at differential pressures as low as 30 kPa, outperforming existing graphene or graphene oxide purification systems with comparable flow rates.

Tip-enhanced Raman spectroscopy of graphene-like and graphitic platelets on ultraflat gold nanoplates.

In this study, tip-enhanced Raman spectroscopy (TERS) is used to characterize graphene-like and graphitic platelets composed of a few layers of graphene. Specifically, gap-mode TERS geometry provides a larger enhancement of the local electromagnetic field at the junction formed by a gold sharp tip and a gold substrate. Graphene-like platelets are deposited onto ultra-flat thin gold nanoplates using a surfactant-assisted method. Au-coated atomic force microscopy (AFM) tips are used to probe specific substrate regions coated by the platelets. TERS spectra are collected on distinctive points on the graphene-like layers and surrounding substrate using radially or linearly polarized light, with an excitation wavelength of 632.8 nm. The position, width and intensity of G, D, and 2D Raman-active modes of graphene are discussed as a function of the incident light polarization and for distinct positions on the graphene layer. We report here on the nature of the collected TERS spectra focusing in particular on the edges of the graphene platelets.

Three-dimensional scanning near field optical microscopy (3D-SNOM) imaging of random arrays of copper nanoparticles: implications for plasmonic solar cell enhancement.

In order to investigate the suitability of random arrays of nanoparticles for plasmonic enhancement in the visible-near infrared range, we introduced three-dimensional scanning near-field optical microscopy (3D-SNOM) imaging as a useful technique to probe the intensity of near-field radiation scattered by random systems of nanoparticles at heights up to several hundred nm from their surface. We demonstrated our technique using random arrays of copper nanoparticles (Cu-NPs) at different particle diameter and concentration. Bright regions in the 3D-SNOM images, corresponding to constructive interference of forward-scattered plasmonic waves, were obtained at heights Δz ≥ 220 nm from the surface for random arrays of Cu-NPs of ∼ 60-100 nm in diameter. These heights are too large to use Cu-NPs in contact of the active layer for light harvesting in thin organic solar cells, which are typically no thicker than 200 nm. Using a 200 nm transparent spacer between the system of Cu-NPs and the solar cell active layer, we demonstrate that forward-scattered light can be conveyed in 200 nm thin film solar cells. This architecture increases the solar cell photoconversion efficiency by a factor of 3. Our 3D-SNOM technique is general enough to be suitable for a large number of other applications in nanoplasmonics.

Tessellated gold nanostructures from Au144(SCH2CH2Ph)60 molecular precursors and their use in organic solar cell enhancement.

We report for the first time the fabrication of nanocomposite hole-blocking layers consisting of poly-3,4-ethylene-dioxythiophene:poly-styrene-sulfonate (PEDOT:PSS) thin films incorporating networks of gold nanoparticles assembled from Au144(SCH2CH2Ph)60, a molecular gold precursor. These thin films can be prepared reproducibly on indium tin oxide by spinning on it Au144(SCH2CH2Ph)60 solutions in chlorobenzene, annealing the resulting thin film at 400 °C, and subsequently spinning PEDOT:PSS on top. The use of our nanocomposite hole-blocking layers for enhancing the photoconversion efficiency of bulk heterojunction organic solar cells is demonstrated. By varying the concentration of Au144(SCH2CH2Ph)60 in the starting solution and the annealing time, different gold nanostructures were obtained ranging from individual gold nanoparticles (AuNPs) to tessellated networks of gold nanostructures (Tess-AuNPs). Improvement in organic solar cell efficiencies up to 10% relative to a reference cell is demonstrated with Tess-AuNPs embedded in PEDOT:PSS.

Facile nucleation of gold nanoparticles on graphene-based thin films from Au144 molecular precursors.

We demonstrate a facile and cost effective method to obtain gold nanoparticles on graphene by dispersing Au144 molecular nanoclusters by spin coating them in thin layers on graphene-based films and subsequent annealing in a controlled atmosphere. The graphene-based thin films used for these experiments are prepared by solvent-assisted exfoliation of graphite in water in the presence of ribonucleic acid as a surfactant and by subsequent vacuum filtration of the resulting graphene-containing suspensions. Not only is this method easily reproducible, but it leads to gold nanoparticles that are not dependent in size on the number of graphene layers beneath them. This is a distinct advantage over other methods. Plasmonic effects have been detected in our gold nanoparticle-decorated graphene layers, indicating that these thin films may be useful in applications such as plasmonic solar cells and optical memory devices.

Electron paramagnetic resonance in positively charged Au25 molecular nanoclusters.

In this study, we investigated the unpaired electrons and singly occupied molecular orbitals (SOMO) of positively charged Au(25) molecular clusters using solid-state electron paramagnetic resonance (EPR). The EPR powder spectra of the positively charged (Au(25) (+)) and neutral (Au(25) (0)) species of Au(25) are discussed and compared. Our study demonstrates that Au(25) (+) is paramagnetic with a SOMO that is mostly localized about the central gold atom in the core of the molecule and possesses a strong p-type atomic character. The unpaired electron spin is demonstrated to strongly interact with the nuclear spins from other (197)Au nuclei in the core of Au(25) (+) molecules and the hyperfine tensor describing such interaction was extracted from the comparison of the EPR spectra with quantum mechanical simulations assuming an anisotropic structure of the core. Our simulations suggest that the core of Au(25) (+) molecular clusters is more distorted than in the corresponding neutral counterpart. They also confirm previous hypotheses suggesting that the icosahedral core of Au(25) (+) experiences contraction with decreasing temperature.

Transparent and conducting graphene-RNA-based nanocomposites.

Ribonucleic acid (RNA) is proposed as a nonionic surfactant for the efficient exfoliation of graphite in thin flakes of few-layer graphene and the subsequent preparation of transparent and conducting thin films. Parameters such as the type of RNA used and the size of starting graphite flakes are demonstrated to be essential for obtaining RNA-graphene thin films of good quality. A model explaining the exfoliation of graphene by RNA in water is suggested. A number of post- and predeposition treatments (including thermal annealing, functionalization of the films, and the preoxidation of graphite) are critical to improve the performance of graphene-RNA nanocomposites as transparent conductors. The study establishes an ideal link between RNA and graphene, the fundamental building blocks for nanobiology and carbon-based nanotechnology.

Toxicity induced enhanced extracellular matrix production in osteoblastic cells cultured on single-walled carbon nanotube networks.

A central effort in biomedical research concerns the development of materials for sustaining and controlling cell growth. Carbon nanotube based substrates have been shown to support the growth of different kinds of cells (Hu et al 2004 Nano Lett. 4 507-11; Kalbacova et al 2006 Phys. Status Solidi b 13 243; Zanello et al 2006 Nano Lett. 6 562-7); however the underlying molecular mechanisms remain poorly defined. To address the fundamental question of mechanisms by which nanotubes promote bone mitosis and histogenesis, primary calvariae osteoblastic cells were grown on single-walled carbon nanotube thin film (SWNT) substrates. Using a combination of biochemical and optical techniques we demonstrate here that SWNT networks promote cell development through two distinct steps. Initially, SWNTs are absorbed in a process that resembles endocytosis, inducing acute toxicity. Nanotube-mediated cell destruction, however, induces a release of endogenous factors that act to boost the activity of the surviving cells by stimulating the synthesis of extracellular matrix.

Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material.

The integration of novel materials such as single-walled carbon nanotubes and nanowires into devices has been challenging, but developments in transfer printing and solution-based methods now allow these materials to be incorporated into large-area electronics. Similar efforts are now being devoted to making the integration of graphene into devices technologically feasible. Here, we report a solution-based method that allows uniform and controllable deposition of reduced graphene oxide thin films with thicknesses ranging from a single monolayer to several layers over large areas. The opto-electronic properties can thus be tuned over several orders of magnitude, making them potentially useful for flexible and transparent semiconductors or semi-metals. The thinnest films exhibit graphene-like ambipolar transistor characteristics, whereas thicker films behave as graphite-like semi-metals. Collectively, our deposition method could represent a route for translating the interesting fundamental properties of graphene into technologically viable devices.

Optical anisotropy in single-walled carbon nanotube thin films: implications for transparent and conducting electrodes in organic photovoltaics.

Optical anisotropy in single-walled carbon nanotube thin film networks is reported. We obtain the real and imaginary parts of the in-(parallel) and out-of-plane (perpendicular) complex dielectric functions of the single-walled carbon nanotube (SWNT) thin films by combining transmission measurements at several incidence angles with spectroscopic ellipsometry data on different substrates. In sparse networks, the two components of the real part of the complex dielectric constant (epsilon1 parallel and epsilon1 perpendicular) were found to differ by 1.5 at 2.25 eV photon energy. The resulting angular dependence (from 0 to 70 degrees incidence angles) of transmittance is reflected in the conversion efficiency of organic solar cells utilizing SWNT thin films as the hole conducting electrodes. Our results indicate that, in addition to the transparency and sheet resistance, factors such as the optical anisotropy must be considered for optical devices incorporating SWNT networks.

Voltage-induced dependence of Raman-active modes in single-wall carbon nanotube thin films.

We report on electrical Raman measurements in transparent and conducting single-wall carbon nanotube (SWNT) thin films. Application of external voltage results in downshifts of the D and G modes and in reduction of their intensity. The intensities of the radial breathing modes increase with external electric field related to the application of the external voltage in metallic SWNTs, while decreasing in semiconducting SWNTs. A model explaining the phenomenon in terms of both direct and indirect (Joule heating) effects of the field is proposed. Our work rules out the elimination of large amounts of metallic SWNTs in thin film transistors using high field pulses. Our results support the existence of Kohn anomalies in the Raman-active optical branches of metallic graphitic materials.