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.

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.

New core-shell hydroxyapatite/Gum-Acacia nanocomposites for drug delivery and tissue engineering applications.

Core-shell hydroxyapatite (HAP) - gum acacia (GA) nanocomposite, in which the HAP acts as a core while the GA serves as a shell, was synthesized by precipitation techniqueusing Ca(NO3)2.4H2O and NH4H2PO4as precursors for Ca and P, respectively. The crystallite size and morphology of the synthesized core-shell HAP-GA nanocomposite was evaluated by X-ray diffraction measurement and transmission electron microscopy. The crystallite size of GA-HAP nanocomposite is markedly decreased from 89 nm to 63 nm when the concentration of GA in the reaction mixture is increased from 0 to 10%. Transmission electron micrographs confirm encapsulation of GA over the HAP particles, leading to the formation of GA shell-HAP core assembly, which is quite evident for 10% GA-HAP composites. The nature of functional groups present in HAP was identified using FT-IR and Raman spectroscopies while its chemical composition was analyzed by energy dispersive X-ray analysis. The Ca/P ratio of the synthesized HAP's was found to be 1.67. The elemental composition of the HAP samples was evaluated by X-ray photoelectron spectroscopy. The peaks at binding energies 286.5 and 289.3 eV of C 1S and the peaks at 530.6 eV and 532.1 eV of the O 1S spectra further substantiate encapsulation of GA over the HAP particles, resulting in the formation of GA-HAP nanocomposite. Pellet samples of HAP were immersed in simulated body fluid to ascertain their bioactivity using scanning electron micrographs. The drug, naringenin, was loaded within the core of HAP by pellet pressing method. The drug-loaded core-shell HAP composites were subjected to microbial studies, hemolytic studies and MTT assay to assess their biocompatibility.

Dynamic self-assembly of DNA minor groove-binding ligand DB921 into nanotubes triggered by an alkali halide.

We describe a novel self-assembling supramolecular nanotube system formed by a heterocyclic cationic molecule which was originally designed for its potential as an antiparasitic and DNA sequence recognition agent. Our structural characterisation work indicates that the nanotubes form via a hierarchical assembly mechanism that can be triggered and tuned by well-defined concentrations of simple alkali halide salts in water. The nanotubes assembled in NaCl have inner and outer diameters of ca. 22 nm and 26 nm respectively, with lengths that reach into several microns. Our results suggest the tubes consist of DB921 molecules stacked along the direction of the nanotube long axis. The tubes are stabilised by face-to-face π-π stacking and ionic interactions between the charged amidinium groups of the ligand and the negative halide ions. The assembly process of the nanotubes was followed using small-angle X-ray and neutron scattering, transmission electron microscopy and ultraviolet/visible spectroscopy. Our data demonstrate that assembly occurs through the formation of intermediate ribbon-like structures that in turn form helices that tighten and compact to form the final stable filament. This assembly process was tested using different alkali-metal salts, showing a strong preference for chloride or bromide anions and with little dependency on the type of cation. Our data further demonstrates the existence of a critical anion concentration above which the rate of self-assembly is greatly enhanced.

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.

Incorporation of ZrO2 particles in the oxide layer formed on Mg by anodizing: Influence of electrolyte concentration and current modes.

HYPOTHESIS: The objectives of the present study are to ascertain, particle incorporation during the initial stages of microarc oxidation (MAO), feasibility of increasing the level of particle incorporation through manipulation of process variables and, the use of MgO-ZrO2 composite coatings either as a pre-treatment or as a post-treatment for MAO coated Mg. EXPERIMENTS: Anodic oxide coatings were prepared using 0.3M NaOH+15g/l ZrO2 and 3M NaOH+15g/l ZrO2 at 10V under direct current, pulsed current (PC) unipolar and PC bipolar modes. MAO coatings were prepared using 5g/l NaOH+15g/l Na2SiO3 at 250V under direct current mode for 2min. FINDINGS: The study reveals that it is possible to incorporate ZrO2 particles in the anodic oxide layer, suggesting such a possibility during the initial stages of MAO. When the MgO-ZrO2 composite coating is used as a pre-treatment, it helps to reduce the size and density of the pores of the MAO coatings and increased the corrosion resistance. When it is used as a post-treatment, lamellar shaped Mg(OH)2 with a very high surface area is formed on the surface, which would be beneficial to impart a better bioactivity and to facilitate immobilization of biomolecules.

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.

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.

A Facile Method to Modify the Characteristics and Corrosion Behavior of 304 Stainless Steel by Surface Nanostructuring toward Biomedical Applications.

The study addresses how surface nanostructuring of AISI 304 stainless steel (SS) by surface mechanical attrition treatment (SMAT) influences its characteristic properties and corrosion behavior in Ringer's solution. SMAT of 304 SS induced plastic deformation, enabled surface nanocrystallization, refined the grain size, transformed the austenite phase to strain induced α'-martensite phase, increased the surface roughness, induced defects/dislocations, imparted compressive residual stresses at the surface, decreased the contact angle, and increased surface energy. The change in properties of 304 SS following treatment using 5 and 8 mm ⌀ balls for 15, 30, 45, and 60 min has caused a deleterious influence on its corrosion resistance in Ringer's solution, while an improvement in corrosion behavior is observed for those treated using 2 mm ⌀ balls. The increase in surface roughness, transformation of the austenite to α'-martensite phase, a higher extent of deformation, and the presence of larger number of defects/dislocations are main factors responsible for the lower corrosion resistance observed for 304 SS treated using 5 and 8 mm ⌀ balls in Ringer's solution. In spite of having these attributes with a relatively lower extent, 304 SS treated using 2 mm ⌀ balls offered a better corrosion resistance and exhibits a better passivity. For those treated using 2 mm ⌀ balls, the ability of the nanocrystalline surface to promote passivation outweighs the deleterious influences caused by the limited amount of deformation and defects/dislocations. Based on the findings of this study, it is recommend that SMAT of 304 SS using 2 mm ⌀ balls for 15-30 min is the optimum condition to achieve the suitable surface profile, surface characteristics with better corrosion resistance.

Synthesis of N, F and S co-doped graphene quantum dots.

Graphene quantum dots (GQDs) are a promising category of materials with remarkable size dependent properties like tunable bandgap and photoluminescence along with the possibility of effective chemical functionalization. Doping of GQDs with heteroatoms is an interesting way of regulating their properties. Herein, we report a facile and scalable one-step synthesis of luminescent GQDs, substitutionally co-doped with N, F and S, of ∼2 nm average size by a microwave treatment of multi-walled carbon nanotubes in a customized ionic liquid medium. The use of an ionic liquid coupled with the use of a microwave technique enables not only an ultrafast process for the synthesis of co-doped GQDs, but also provides excellent photoluminescence quantum yield (70%), perhaps due to the interaction of defect clusters and dopants.

Tailoring the composition of fluoride conversion coatings to achieve better corrosion protection of magnesium for biomedical applications.

The methodology of deposition of fluoride conversion coatings is modified with the use of galvanic coupling, agitation of the electrolyte solution, and addition of K2CO3, which helps to provide a better understanding of the mechanism and new avenues to tailor the composition of the coating. A very good correlation exists between the F/O ratio of the coatings prepared under varying experimental conditions and their icorr, |Z| and phase angle maximum; the higher the F/O ratio, the better the corrosion protective ability of the coatings in Hank's balanced salt solution. The corrosion behaviour of the coatings of the present study suggests that fluoride conversion coatings show much promise for their use for biomedical applications, as long as their uniformity is improved and the composition is tailored to enrich the MgF2 phase, encompassing a higher F/O ratio.

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.

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.

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.

Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions.

The establishment of covalent junctions between carbon nanotubes (CNTs) and the modification of their straight tubular morphology are two strategies needed to successfully synthesize nanotube-based three-dimensional (3D) frameworks exhibiting superior material properties. Engineering such 3D structures in scalable synthetic processes still remains a challenge. This work pioneers the bulk synthesis of 3D macroscale nanotube elastic solids directly via a boron-doping strategy during chemical vapour deposition, which influences the formation of atomic-scale "elbow" junctions and nanotube covalent interconnections. Detailed elemental analysis revealed that the "elbow" junctions are preferred sites for excess boron atoms, indicating the role of boron and curvature in the junction formation mechanism, in agreement with our first principle theoretical calculations. Exploiting this material's ultra-light weight, super-hydrophobicity, high porosity, thermal stability, and mechanical flexibility, the strongly oleophilic sponge-like solids are demonstrated as unique reusable sorbent scaffolds able to efficiently remove oil from contaminated seawater even after repeated use.

Collagen based magnetic nanocomposites for oil removal applications.

A stable magnetic nanocomposite of collagen and superparamagnetic iron oxide nanoparticles (SPIONs) is prepared by a simple process utilizing protein wastes from leather industry. Molecular interaction between helical collagen fibers and spherical SPIONs is proven through calorimetric, microscopic and spectroscopic techniques. This nanocomposite exhibited selective oil absorption and magnetic tracking ability, allowing it to be used in oil removal applications. The environmental sustainability of the oil adsorbed nanobiocomposite is also demonstrated here through its conversion into a bi-functional graphitic nanocarbon material via heat treatment. The approach highlights new avenues for converting bio-wastes into useful nanomaterials in scalable and inexpensive ways.

Defect induced photoluminescence and ferromagnetic properties of bio-compatible SWCNT/Ni hybrid bundles.

Designing of bio-compatible nanomagnets with multiple functionalities receives immense scientific attention due to their potential applications in bio-labeling, medical diagnosis and treatment. Here we report the synthesis of Nickel (Ni) incorporated single-walled carbon nanotube (SWCNT) hybrid and bio-compatible bundles having interesting magnetic and photoluminescence (PL) properties. The SWCNT exhibits a high-crystallinity and it has an average diameter of ∼1.7 nm. Ni particles of 10-20 nm were incorporated within the SWCNT bundles. These hybrid bundles exhibit PL and it is attributed to the presence of delocalized π electrons and their recombination at the defective sites of SWCNT. Magnetic characterization revealed that the SWCNT/Ni hybrid bundle possesses a high (50 Oe) coercivity compared to bulk Ni and a long range ferromagnetic ordering at room temperature. MTT-assay has been conducted to study the cytotoxicity of these hybrid nanostructures.

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.