Ultra-small-angle X-ray photon correlation spectroscopy using the Eiger detector.

Successful implementation of the single-photon-counting Eiger 500k pixel array detector for sub-millisecond X-ray photon correlation spectroscopy (XPCS) measurements in the ultra-small-angle scattering region is reported. The performance is demonstrated by measuring the dynamics of dilute silica colloids in aqueous solvents when the detector is operated at different counter depths, 4, 8 and 12 bit. In the fastest mode involving 4 bit parallel readout, a stable frame rate of 22 kHz is obtained that enabled measurement of intensity-intensity autocorrelation functions with good statistics down to the 50 µs range for a sample with sufficient scattering power. The high frame rate and spatial resolution together with large number of pixels of the detector facilitate the investigation of sub-millisecond dynamics over a broad length scale by multispeckle XPCS. This is illustrated by an example involving phoretic motion of colloids during the phase separation of the solvent.

Evidence for enhanced optical properties through plasmon resonance energy transfer in silver silica nanocomposites.

Silver nanoparticles were dispersed in the pores of monolithic mesoporous silica prepared by a modified sol-gel method. Structural and microstructural analyses were carried out by Fourier transform infrared spectroscopy and transmission electron microscopy. X-ray photoelectron spectroscopy was employed to determine the chemical states of silver in the silica matrix. Optical absorption studies show the evolution absorption band around 300 nm for silver (Ag) in a silica matrix and it was found to be redshifted to 422 nm on annealing. Photoluminescence studies indicate the presence of various luminescent emitting centers corresponding to silver ions and silver dimers in the SiO2 matrix. The enhancement of absorption and photoluminescence properties is attributed to plasmon resonance energy transfer from Ag nanoparticles to luminescent species in the matrix.

Fractional photo-current dependence of graphene quantum dots prepared from carbon nanotubes.

We report on the photo-conductivity studies of chemically synthesized graphene quantum dots (GQDs) of average size 12 nm obtained by the oxidative acid treatment of MWCNTs. The dependence of photocurrent Iph (Iph = Iill - Idark) on the laser intensity P under a wide range of laser intensities (5 mW ≤ P ≤ 60 mW) shows a fractional power dependence of Iph on light intensity. The temperature dependence (300 K < T < 50 K) of Iph observed in thin films of these GQDs indicates that in the higher temperature region (T > ∼100 K), as the temperature increases, the number of thermally generated carriers increase resulting in increased Iph. At sufficiently low temperatures (T ≤ 100 K), a constant Iph is observed, indicating a constant photo-carrier density. Such a behavior is typically observed in many photoactive disordered semiconductors, which are often used in a variety of applications. We believe that the investigations presented here will enhance our understanding of the photocurrent generation phenomenon in chemically obtained GQDs.

Nanobiocomposite from Collagen Waste Using Iron Oxide Nanoparticles and Its Conversion Into Magnetic Nanocarbon.

Collagenous wastes discarded from leather industry were stabilized using superparamagnetic iron oxide nanoparticles and further converted into a magnetic nanocarbon. Stabilization of collagen using iron oxide nanoparticles treatment (25% offer) was confirmed through differential scanning calorimetric analysis and further evidenced through scanning electron microscopic analysis. A simple high temperature treatment of the collagen-iron oxide nanoparticle composite at 850 degrees C for 2 h under Ar atmosphere yielded a bi-functional, magnetic and conducting, nanocarbon. The X-ray diffraction and Raman spectroscopic analysis reveal the partial graphitation and X-ray photoelectron spectroscopic results show the presence of trace-iron containing carbon, naturally doped with nitrogen and oxygen. Transmission electron microscopic analysis show the presence of larger iron oxide nanocrystals embedded in graphitic carbon layers while superconducting quantum interference device based analysis reveals a perfect ferrimagnetic property with saturation magnetization. Thus, we have stabilized the collagen waste fibers using iron oxide nanoparticles and converted them into a bi-functional nanocarbon, which has potential for various applications including energy, leather making and environmental remediation.

Hybrid multiferroic nanostructure with magnetic-dielectric coupling.

The development of methods to economically synthesize single wire structured multiferroic systems with room temperature spin-charge coupling is expected to be important for building next-generation multifunctional devices with ultralow power consumption. We demonstrate the fabrication of a single nanowire multiferroic system, a new geometry, exhibiting room temperature magnetodielectric coupling. A coaxial nanotube/nanowire heterostructure of barium titanate (BaTiO(3), BTO) and cobalt (Co) has been synthesized using a template-assisted method. Room temperature ferromagnetism and ferroelectricity were exhibited by this coaxial system, indicating the coexistence of more than one ferroic interaction in this composite system.

Artificially stacked atomic layers: toward new van der Waals solids.

Strong in-plane bonding and weak van der Waals interplanar interactions characterize a large number of layered materials, as epitomized by graphite. The advent of graphene (G), individual layers from graphite, and atomic layers isolated from a few other van der Waals bonded layered compounds has enabled the ability to pick, place, and stack atomic layers of arbitrary compositions and build unique layered materials, which would be otherwise impossible to synthesize via other known techniques. Here we demonstrate this concept for solids consisting of randomly stacked layers of graphene and hexagonal boron nitride (h-BN). Dispersions of exfoliated h-BN layers and graphene have been prepared by liquid phase exfoliation methods and mixed, in various concentrations, to create artificially stacked h-BN/G solids. These van der Waals stacked hybrid solid materials show interesting electrical, mechanical, and optical properties distinctly different from their starting parent layers. From extensive first principle calculations we identify (i) a novel approach to control the dipole at the h-BN/G interface by properly sandwiching or sliding layers of h-BN and graphene, and (ii) a way to inject carriers in graphene upon UV excitations of the Frenkell-like excitons of the h-BN layer(s). Our combined approach could be used to create artificial materials, made predominantly from inter planar van der Waals stacking of robust bond saturated atomic layers of different solids with vastly different properties.

Carbon nanotube-nanocup hybrid structures for high power supercapacitor applications.

Here, we design and develop high-power electric double-layer capacitors (EDLCs) using carbon-based three dimensional (3-D) hybrid nanostructured electrodes. 3-D hybrid nanostructured electrodes consisting of vertically aligned carbon nanotubes (CNTs) on highly porous carbon nanocups (CNCs) were synthesized by a combination of anodization and chemical vapor deposition techniques. A 3-D electrode-based supercapacitor showed enhanced areal capacitance by accommodating more charges in a given footprint area than that of a conventional CNC-based device.

Insights into the precipitation kinetics of CaCO3 particles in the presence of polystyrene sulfonate using in situ small-angle X-ray scattering.

The formation of calcium carbonate (CaCO3) nanoparticles (NPs) in the presence of polystyrene sulfonate (PSS) as an additive was examined by time-resolved small-angle X-ray scattering (SAXS) in a flow system that mimics experimental conditions used at home facilities where the precipitation can be achieved in a beaker. The experiments were carried out at low concentrations to remain in the dilute regime. A model-independent analysis was performed using the Porod invariant which defines the scale factor, leaving only the distribution of radii as the adjustable parameter. The presence of the PSS additive strongly retards the precipitation of CaCO3 NPs. The formation of NPs reaches a state of equilibrium after a few minutes. Here, it is shown that the concentration of precursors at a fixed PSS concentration plays a key role in determining the size of the NPs obtained. A full analysis of the SAXS patterns was carried out using the Hurd-Flower model to account for the weaker intensity decay than the classical Porod behaviour. The temporal evolution of the particle radii was determined. Wide-angle X-ray scattering experiments carried out simultaneously show that the particles formed have the structure of vaterite with growth consistent with the evolution of the Porod invariant.

Transition kinetics of mixed lipid:photosurfactant assemblies studied by time-resolved small angle X-ray scattering.

HYPOTHESIS: Photoswitchable surfactants are used in the design of many light-responsive colloids and/or self-assemblies. Photo-isomerization enables to control molecular equilibrium, and triggers transient reorganizations with possibly out-of-equilibrium intermediate states that have been overlooked. Here, we address this question by an in depth structural investigation of intermediate lipid-surfactant assemblies that occur during fast isothermal photo-triggered transition in lipid:surfactant mixtures. EXPERIMENTS: The structural parameters of mixed assemblies of azobenzene-containing cationic surfactant (AzoTMA) and dioleoylphosphatidylcholine (DOPC) lipids were studied by light scattering and time-resolved small angle X-ray scattering. Structural and compositional information about the assemblies and unimers in bulk were determined at the photostationary states, as well as at intermediate kinetic states formed during UV or blue light illumination. FINDINGS: DOPC:AzoTMA systems form mixed assemblies representative of phospholipid:cationic surfactant mixtures, that evolve from spheroid, to rod-like micelles, and vesicles with increasing DOPC fraction. Transient assemblies detected during the photo-triggered kinetics are similar to the ones found in stationary states. But changes of AzoTMA unimers in bulk can be considerably faster than mass reorganizations of the mixed assemblies, suggesting that out-of-equilibrium conditions are transiently reached. Mass reorganization of the surfactant-enriched assemblies is much faster than in the lipid enriched ones, providing insight into the role of lipids in a slow reorganization of the assemblies.

Nonlinear and magneto-optical transmission studies on magnetic nanofluids of non-interacting metallic nickel nanoparticles.

Oxide free stable metallic nanofluids have the potential for various applications such as in thermal management and inkjet printing apart from being a candidate system for fundamental studies. A stable suspension of nickel nanoparticles of ∼ 5 nm size has been realized by a modified two-step synthesis route. Structural characterization by x-ray diffraction and transmission electron microscopy shows that the nanoparticles are metallic and are phase pure. The nanoparticles exhibited superparamagnetic properties. The magneto-optical transmission properties of the nickel nanofluid (Ni-F) were investigated by linear optical dichroism measurements. The magnetic field dependent light transmission studies exhibited a polarization dependent optical absorption, known as optical dichroism, indicating that the nanoparticles suspended in the fluid are non-interacting and superparamagnetic in nature. The nonlinear optical limiting properties of Ni-F under high input optical fluence were then analyzed by an open aperture z-scan technique. The Ni-F exhibits a saturable absorption at moderate laser intensities while effective two-photon absorption is evident at higher intensities. The Ni-F appears to be a unique material for various optical devices such as field modulated gratings and optical switches which can be controlled by an external magnetic field.

Enhanced bio-compatibility of ferrofluids of self-assembled superparamagnetic iron oxide-silica core-shell nanoparticles.

Self-assembled magnetic colloidal suspensions are sought after by material scientists owing to its huge application potential. The biomedical applications of colloidal nanoparticles necessitate that they are biocompatible, non-interacting, monodispersed and hence the synthesis of such nanostructures has great relevance in the realm of nanoscience. Silica-coated superparamagnetic iron oxide nanoparticles based ferrofluids were prepared using polyethylene glycol as carrier fluid by employing a controlled co-precipitation technique followed by a modified sol-gel synthesis. A plausible mechanism for the formation of stable suspension of SiO2-coated Iron Oxide nanoparticles with a size of about 9 nm dispersed in polyethylene glycol (PEG) is proposed. Core-shell nature of the resultant SiO2-Iron Oxide nanocomposite was verified using transmission electron microscopy. Fourier transform-infrared spectroscopy studies were carried out to understand the structure and nature of chemical bonds. The result suggests that Iron Oxide exist in an isolated state inside silica matrix. Moreover, the presence of silanol bonds establishes the hydrophilic nature of silica shell confirming the formation of stable ferrofluid with PEG as carrier fluid. The magnetic characterization reveals the superparamagnetic behavior of the nanoparticles with a rather narrow distribution of blocking temperatures. These properties are not seen in ferrofluids prepared from Iron Oxide nanoparticles without SiO2 coating. The latter suggests the successful tuning of the inter-particle interactions preventing agglomeration of nanoparticles. Cytotoxicity studies on citric acid coated water based ferrofluid and silica-coated PEG-based ferrofluid were evaluated by 3-(4,5-dimethylthiazole-2-yl)-2,5-diphenyltetrazolium chloride assay and it shows an enhanced compatibility for silica modified nanoparticles.

Evaluation of the particle growth of amorphous calcium carbonate in water by means of the Porod invariant from SAXS.

A time-resolved SAXS study has been carried out on the formation of amorphous calcium carbonate from supersaturated aqueous solutions at an initial concentration of 5 mmol/L CaCO(3). Particle formation was induced by mixing equal volumes of equinormal CaCl(2) and Na(2)CO(3) solutions with a stopped-flow device installed at the SAXS beamline. The resulting scattering curves were analyzed without any model assumption with respect to the particle shape. The analysis is based on the intercept of the scattering curve, its initial slope, and the Porod invariant. These parameters give access to the average particle mass, the average particle size, and the mass concentration of the particles, respectively. The evolution of particle mass and concentration with time gives access to the trend in the particle number density. The size and mass values were found to be correlated by characteristic exponents. Two different mass values can be used for this correlation: direct use of the intercept of the scattering curve or alternatively a ratio of this intercept with the corresponding Porod invariant. The resulting exponents depend on the particle growth mechanism. These exponents, together with the evolution of the number density, are capable of discriminating between a monomer-addition mechanism and a particle-particle coagulation mechanism as two alternative building mechanisms for the resulting amorphous CaCO(3) nanoparticles. A detailed description of the data analysis and its merit in establishing a particle growth mechanism is presented.

Structural changes in myosin motors and filaments during relaxation of skeletal muscle.

Structural changes in myosin motors and filaments during relaxation from short tetanic contractions of intact single fibres of frog tibialis anterior muscles at sarcomere length 2.14 mum, 4 degrees C were investigated by X-ray diffraction. Force declined at a steady rate for several hundred milliseconds after the last stimulus, while sarcomere lengths remained almost constant. During this isometric phase of relaxation the intensities of the equatorial and meridional M3 X-ray reflections associated with the radial and axial distributions of myosin motors also recovered at a steady rate towards their resting values, consistent with progressive net detachment of myosin motors from actin filaments. Stiffness measurements confirmed that the fraction of motors attached to actin declined at a constant rate, but also revealed a progressive increase in force per motor. The interference fine structure of the M3 reflection suggested that actin-attached myosin motors are displaced towards the start of their working stroke during isometric relaxation. There was negligible recovery of the intensities of the meridional and layer-line reflections associated with the quasi-helical distribution of myosin motors in resting muscle during isometric relaxation, and the 1.5% increase in the axial periodicity of the myosin filament associated with muscle activation was not reversed. When force had decreased to roughly half its tetanus plateau value, the isometric phase of relaxation abruptly ended, and the ensuing chaotic relaxation had an exponential half-time of ca 60 ms. Recovery of the equatorial X-ray intensities was largely complete during chaotic relaxation, but the other X-ray signals recovered more slowly than force.

Probing the transverse coherence of an undulator x-ray beam using brownian particles.

We present a novel method to map the two-dimensional transverse coherence of an x-ray beam using the dynamical near-field speckles formed by scattering from colloidal particles. Owing to the statistical nature of the method, the coherence properties of synchrotron radiation from an undulator source is obtained with high accuracy. The two-dimensional complex coherence function is determined at the sample position and the imaging optical scheme further allowed us to evaluate the coherence factor at the undulator output despite the aberrations introduced by the focusing optics.

On the synthesis and magnetic properties of multiwall carbon nanotube-superparamagnetic iron oxide nanoparticle nanocomposites.

Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT-SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at approximately 110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT-SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT-SPION composite can be envisaged as a good agent for various biomedical applications.

The synthesis of high coercivity cobalt-in-carbon nanotube hybrid structures and their optical limiting properties.

Magnetic heterostructures with carbon nanotubes having multiple functionalities are fascinating materials which can be manipulated by means of an external magnetic field. In this paper we report our investigations on the synthesis and optical limiting properties of pristine cobalt nanotubes and high coercivity cobalt-in-carbon nanotubes (a new nanosystem where carbon nanotubes are filled with cobalt nanotubes). A general mobility assisted growth mechanism for the formation of one-dimensional nanostructures inside nanopores is verified in the case of carbon nanotubes. The open-aperture z-scan technique is employed for the optical limiting measurements in which nanosecond laser pulses at 532 nm have been used for optical excitation. Compared to the benchmark pristine carbon nanotubes these materials show an enhanced nonlinear optical absorption, and the nonlinear optical parameters calculated from the data show that these materials are efficient optical limiters. To the best of our knowledge this is the first report where the optical limiting properties of metal nanotubes are compared to those of carbon nanotubes.

A Percus-Yevick description of the microstructure of short-range interacting metastable colloidal suspensions.

We present a revised form of the Percus-Yevick approach applicable to dispersions of interacting colloidal particles such as colloid-polymer mixtures and square-well attractive colloids. Our approach is suitable for treating short-range interparticle potentials including excluded volume hard-sphere repulsion, short-range depletion attraction, and square-well attraction. In all these cases, the Ornstein-Zernike equation for the pair correlation function can be satisfied by a trial function, which generalizes the Wertheim [Phys. Rev. Lett. 10, 321 (1963)] and Baxter [J. Chem. Phys. 49, 2770 (1968)] ansatz. Structure factors (or x-ray scattering intensities) calculated by this method are in good agreement with experimental data for colloid-polymer mixtures over a range of parameters pertaining to the stable fluid phase and the metastable state with moderate attraction. On the same footing, we have determined the stability limits and analyzed contributions to the scattered intensity from particle aggregates appearing prior to the phase separation for sufficiently strong short-range attraction. Similar features are observed in the case of square-well attractive colloids when the attraction is turned on.

Correlation between structure and rheology of a model colloidal glass.

The microstructure and rheological properties of a model colloidal system was probed in the vicinity of the glass transition by small-angle and ultra small-angle x-ray scattering, dynamic light scattering (DLS) and bulk rheology. The volume fraction of the particles was deduced by modeling the structure factor and the absolute scattered intensity in a self-consistent way. The glass transition (phi(G)) was identified from the frequency dependence of the shear moduli in the linear regime. The experimentally observed behavior was then compared with the viscoelastic properties derived from mode-coupling theory (MCT) using the experimental structure factor as input to the theory. The ensemble-averaged intermediate scattering functions from DLS measurements were also compared with those calculated from the MCT and reasonable agreement was obtained.

[X-ray interferometry of the axial movement of myosin heads during muscle force generation initiated by T-jump].

The interference fine structure of the M3 reflection on the low-angle x-ray diffraction patterns of muscle fibres is used for the measurements of axial movements of myosin heads with a precision of 0.1-0.2 nm. We have measured changes in the M3 interference profile during tension rise induced by a 5 to 30 degrees C temperature jump in thin bundles of contracting fibers from rabbit skeletal muscle. Interpreting the data with a point diffractor model gives an estimate for the axial movement of the myosin heads during force rise of less than 0.6 nm. Modifications of the point diffractor model are discussed. We show that our experimental data can be explained by a model where myosin heads bind actin in a number of structurally different states.

Corrosion behaviour of Ti-15Mo alloy for dental implant applications.

The corrosion behaviour of Ti-15Mo alloy in 0.15M NaCl solution containing varying concentrations of fluoride ions (190, 570, 1140 and 9500 ppm) is evaluated using potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and chronoamperometric/current-time transient (CTT) studies to ascertain its suitability for dental implant applications. The study reveals that there is a strong dependence of the corrosion resistance of Ti-15Mo alloy on the concentration of fluoride ions in the electrolyte medium. Increase in fluoride ion concentration from 0 to 9500 ppm shifts the corrosion potential (E(corr)) from -275 to -457 mV vs. SCE, increases the corrosion current density (i(corr)) from 0.31 to 2.30 microA/cm(2), the passive current density (i(pass)) from 0.07 to 7.32 mA/cm(2) and the double-layer capacitance (C(dl)) from 9.63 x 10(-5) to 1.79 x 10(-4)F and reduces the charge transfer resistance (R(ct)) from 6.58 x 10(4) to 6.64 x 10(3)Omega cm(2). In spite of the active dissolution, the Ti-15Mo alloy exhibit passivity at anodic potentials at all concentrations of the fluoride ions studied. In dental implants since the exposure of the alloy will be limited only to its 'neck', the amount of Mo ions released from Ti-15Mo alloy is not likely to have an adverse and hence, in terms of biocompatibility this alloy seems to be acceptable for dental implant applications. The results of the study suggest that Ti-15Mo alloy can be a suitable alternative for dental implant applications.