Strength reliability and in vitro degradation of three-dimensional powder printed strontium-substituted magnesium phosphate scaffolds

Strontium ions (Sr2+) are known to prevent osteoporosis and also encourage bone formation. Such twin requirements have motivated researchers to develop Sr-substituted biomaterials for orthopaedic applications. The present study demonstrates a new concept of developing Sr-substituted Mg-3(PO4)(2) - based biodegradable scaffolds. In particular, this work reports the fabrication, mechanical properties with an emphasis on strength reliability as well as in vitro degradation of highly biodegradable strontium-incorporated magnesium phosphate cements. These implantable scaffolds were fabricated using three-dimensional powder printing, followed by high temperature sintering and/or chemical conversion, a technique adaptable to develop patient-specific implants. A moderate combination of strength properties of 36.7 MPa (compression), 242 MPa (bending) and 10.7 MPa (tension) were measured. A reasonably modest Weibull modulus of up to 8.8 was recorded after uniaxial compression or diametral tensile tests on 3D printed scaffolds. A comparison among scaffolds with varying compositions or among sintered or chemically hardened scaffolds reveals that the strength reliability is not compromised in Sr-substituted scaffolds compared to baseline Mg-3(PO4)(2). The micro-computed tomography analysis reveals the presence of highly interconnected porous architecture in three-dimension with lognormal pore size distribution having median in the range of 17.74-26.29 mu m for the investigated scaffolds. The results of extensive in vitro ion release study revealed passive degradation with a reduced Mg2+ release and slow but sustained release of Sr2+ from strontium-substituted magnesium phosphate scaffolds. Taken together, the present study unequivocally illustrates that the newly designed Sr-substituted magnesium phosphate scaffolds with good strength reliability could be used for biomedical applications requiring consistent Sr2+-release, while the scaffold degrades in physiological medium. Statement of significance The study investigates the additive manufacturing of scaffolds based on different strontium-substituted magnesium phosphate bone cements by means of three-dimensional powder printing technique (3DPP). Magnesium phosphates were chosen due to their higher biodegradability compared to calcium phosphates, which is due to both a higher solubility as well as the absence of phase changes (to low soluble hydroxyapatite) in vivo. Since strontium ions are known to promote bone formation by stimulating osteoblast growth, we aimed to establish such a highly degradable magnesium phosphate ceramic with an enhanced bioactivity for new bone ingrowth. After post-processing, mechanical strengths of up to 36.7 MPa (compression), 24.2 MPa (bending) and 10.7 MPa (tension) could be achieved. Simultaneously, the failure reliability of those bioceramic implant materials, measured by Weibull modulus calculations, were in the range of 4.3-8.8. Passive dissolution studies in vitro proved an ion release of Mg2+ and PO43- as well as Sr2+, which is fundamental for in vivo degradation and a bone growth promoting effect. In our opinion, this work broadens the range of bioceramic bone replacement materials suitable for additive manufacturing processing. The high biodegradability of MPC ceramics together with the anticipated promoting effect on osseointegration opens up the way for a patient-specific treatment with the prospect of a fast and complete healing of bone fractures. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Tunability of 1/f Noise at Multiple Dirac Cones in hBN Encapsulated Graphene Devices

The emergence of multiple Dirac cones in hexagonal boron nitride (hBN)-graphene heterostructures is particularly attractive because it offers potentially better landscape for higher and versatile transport properties than the primary Dirac cone. However, the transport coefficients of the cloned Dirac cones is yet not fully characterized and many open questions, including the evolution of charge dynamics and impurity scattering responsible for them, have remained unexplored. Noise measurements, having the potential to address these questions, have not been performed to date in dual-gated hBN graphene hBN devices. Here, we present the low frequency 1/f noise measurements at multiple Dirac cones in hBN encapsulated single and bilayer graphene in dual-gated geometry. Our results reveal that the low-frequency noise in graphene can be tuned by more than two-orders of magnitude by changing carrier concentration as well as by modifying the band structure in bilayer graphene. We find that the noise is surprisingly suppressed at the cloned Dirac cone compared to the primary Dirac cone in single layer graphene device, while it is strongly enhanced for the bilayer graphene with band gap opening. The results are explained with the calculation of dielectric function using tight-binding model. Our results also indicate that the 1/f noise indeed follows the Hooge's empirical formula in hBN-protected devices in dual-gated geometry. We also present for the first time the noise data in bipolar regime of a graphene device.

Evidence for 3D isotropic long range spin-spin interaction near the ferromagnetic transition in bulk and thin film SrRuO3

In the case of metallic ferromagnets there has always been a controversy, i.e. whether the magnetic interaction is itinerant or localized. For example SrRuO3 is known to be an itinerant ferromagnet where the spin-spin interaction is expected to be mean field in nature. However, it is reported to behave like Ising, Heisenberg or mean field by different groups. Despite several theoretical and experimental studies and the importance of strongly correlated systems, the experimental conclusion regarding the type of spin-spin interaction in SrRuO3 is lacking. To resolve this issue, we have investigated the critical behaviour in the vicinity of the paramagnetic-ferromagnetic phase transition using various techniques on polycrystalline as well as (001) oriented SrRuO3 films. Our analysis reveals that the application of a scaling law in the field-cooled magnetization data extracts the value of the critical exponent only when it is measured at H -> 0. To substantiate the actual nature without any ambiguity, the critical behavior is studied across the phase transition using the modified Arrott plot, Kouvel-Fisher plot and M-H isotherms. The critical analysis yields self-consistent beta, gamma and delta values and the spin interaction follows the long-range mean field model. Further the directional dependence of the critical exponent is studied in thin films and it reveals the isotropic nature. It is elucidated that the different experimental protocols followed by different groups are the reason for the ambiguity in determining the critical exponents in SrRuO3.

Accelerating method of moments based package-board 3D parasitic extraction using FPGA

In this article, a Field Programmable Gate Array (FPGA)-based hardware accelerator for 3D electromagnetic extraction, using Method of Moments (MoM) is presented. As the number of nets or ports in a system increases, leading to a corresponding increase in the number of right-hand-side (RHS) vectors, the computational cost for multiple matrix-vector products presents a time bottleneck in a linear-complexity fast solver framework. In this work, an FPGA-based hardware implementation is proposed toward a two-level parallelization scheme: (i) matrix level parallelization for single RHS and (ii) pipelining for multiple-RHS. The method is applied to accelerate electrostatic parasitic capacitance extraction of multiple nets in a Ball Grid Array (BGA) package. The acceleration is shown to be linearly scalable with FPGA resources and speed-ups over 10x against equivalent software implementation on a 2.4GHz Intel Core i5 processor is achieved using a Virtex-6 XC6VLX240T FPGA on Xilinx's ML605 board with the implemented design operating at 200MHz clock frequency. (c) 2016 Wiley Periodicals, Inc. Microwave Opt Technol Lett 58:776-783, 2016

Ultrafine graphene oxide-CoFe2O4 nanoparticle composite as T-1 and T-2 contrast agent for magnetic resonance imaging

Graphene oxide-CoFe2O4 nanoparticle composites were synthesized using a two step synthesis method in which graphene oxide was initially synthesized followed by precipitation of CoFe2O4 nanoparticles in a reaction mixture containing graphene oxide. Samples were extracted from the reaction mixture at different times at 80 degrees C. All the extracted samples contained CoFe2O4 nanoparticles formed over the graphene oxide. It was observed that the increase in the reflux time significantly increased the saturation magnetization value for the superparamagnetic nanoparticles in the composite. It was also noticed that the size of the nanoparticles increased with increase in the reflux time. Transverse relaxivity of the water protons increased monotonically with increase in the reflux time. Whereas, the longitudinal relaxivity value initially increased and then decreased with the reflux time. Graphene oxide-CoFe2O4 nanoparticle composites also exhibit biocompatibility towards the MCF-7 cell line.

Chitosan Immobilized Porous Polyolefin As Sustainable and Efficient Antibacterial Membranes

Polyolefinic membranes have attracted a great deal of interest owing to their ease of processing and chemical inertness. In this study, porous polyolefin membranes were derived by selectively etching PEO from PE/PEO (polyethylene/poly(ethylene oxide)) blends. The hydrophobic polyolefin (low density polyethylene) was treated with UV-ozone followed by dip coating in chitosan acetate solution to obtain a hydrophilic-antibacterial surface. The chitosan immobilized PE membranes were further characterized by Fourier transform infrared spectroscope (FTIR) and X-ray photoelectron spectroscope (XPS). It was found that surface grafting of chitosan onto PE membranes enhanced the surface roughness and the concentration of nitrogen (or amine) scaled with increasing concentration of chitosan (0.25 to 2% wt/vol), as inferred from Kjeldahl nitrogen analysis. The pure water flux was almost similar for chitosan immobilized PE membranes as compared to membranes without chitosan. The bacterial population, substantially reduced for membranes with higher concentration of chitosan. For instance, 90 and 94% reduction in Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) colony forming unit respectively was observed with 2% wt/vol of chitosan. This study opens new avenues in designing polyolefinic based antibacterial membranes for water purification.

Hierarchically porous Li1.2Mn0.6Ni0.2O2 as a high capacity and high rate capability positive electrode material

Layered composite samples of lithium-rich manganese oxide (Li1.2Mn0.6Ni0.2O2) are prepared by a reverse microemutsion route employing a soft polymer template and studied as a positive electrode material. The product samples possess dual porosity with distribution of pores at 3.5 and 60 nm. Pore volume and surface area decrease on increasing the temperature of preparation. Nevertheless, the electrochemical activity of the composite increases with an increase in temperature. The discharge capacity value of the samples prepared at 800 and 900 degrees C is about 240 mA h g(-1) at a specific current of 25 mA g(-1) with a good cycling stability. The composite sample heated at 900 degrees C possesses a high rate capability with a discharge capacity of 100 mA h g(-1) at a specific current of 500 mA g(-1). The high rate capability is attributed to porous nature of the composite sample.

Tailored electrical conductivity, electromagnetic shielding and thermal transport in polymeric blends with graphene sheets decorated with nickel nanoparticles

Electromagnetic interference shielding (EMI) materials were designed using PC (polycarbonate)/SAN poly(styrene-co-acrylonitrile)] blends containing few-layered graphene nanosheets decorated with nickel nanoparticles (G-Ni). The graphene nanosheets were decorated with nickel nanoparticles via the uniform nucleation of the metal salt precursor on graphene sheets as the substrate. In order to localize the nanoparticles in the PC phase of the PC/SAN blends, a two-step mixing protocol was adopted. In the first step, graphene sheets were mixed with PC in solution and casted into a film, followed by dilution of these PC master batch films with SAN in the subsequent melt extrusion step. The dynamic mechanical properties, ac electrical conductivity, EMI shielding effectiveness and thermal conductivity of the composites were evaluated. The G-Ni nanoparticles significantly improved the electrical and thermal conductivity in the blends. In addition, a total shielding effectiveness (SET) of -29.4 dB at 18 GHz was achieved with G-Ni nanoparticles. Moreover, the blends with G-Ni exhibited an impressive 276% higher thermal conductivity and 29.2% higher elastic modulus with respect to the neat blends.

Facile synthesis of Graphene Oxide/Double-stranded DNA composite liquid crystals and Hydrogels

Investigation of the interactions between graphene oxide (GO) and biomolecules is very crucial for the development of biomedical applications based on GO. This study reports the first observation of the spontaneous formation of self-assembled liquid crystals and three-dimensional hydrogels of graphene oxide with double-stranded DNA by simple mixing in an aqueous buffer media without unwinding double-stranded DNA to single-stranded DNA. The GO/dsDNA hydrogels have shown controlled porosity by changing the concentration of the components. The strong binding between dsDNA and graphene is proved by Raman spectroscopy.

Enhancing photoresponsivity using MoTe2-graphene vertical heterostructures

MoTe2 with a narrow band-gap of similar to 1.1 eV is a promising candidate for optoelectronic applications, especially for the near-infrared photo detection. However, the photo responsivity of few layers MoTe2 is very small (<1mAW(-1)). In this work, we show that a few layer MoTe2-graphene vertical heterostructures have a much larger photo responsivity of similar to 20mAW(-1). The trans-conductance measurements with back gate voltage show on-off ratio of the vertical transistor to be similar to(0.5-1) x 10(5). The rectification nature of the source-drain current with the back gate voltage reveals the presence of a stronger Schottky barrier at the MoTe2-metal contact as compared to the MoTe2-graphene interface. In order to quantify the barrier height, it is essential to measure the work function of a few layers MoTe2, not known so far. We demonstrate a method to determine the work function by measuring the photo-response of the vertical transistor as a function of the Schottky barrier height at the MoTe2-graphene interface tuned by electrolytic top gating. (C) 2016 AIP Publishing LLC.

Nitrogen-assisted electroless assembling of 3D nanodendrites consisting of Pd and N-doped carbon nanoparticles as bifunctional catalysts

We report a facile synthesis of three-dimensional (3D) nanodendrites of Pd nanoparticles (NPs) and nitrogen-doped carbon NPs (N-CNPs) by electroless deposition of Pd2+ ions. N-CNPs being an electron-enriched material act as a reducing agent. Moreover, the availability of a variety of nitrogen species in N-CNPs promotes the open arm structure as well as stabilizes the oriented 3D assembly of primary Pd NPs. The dendrites exhibit superior catalytic activity for methanol (0.5 M) oxidation in alkaline media (1 M NaOH) which is ascribed to the large electrochemical active surface area and the enhanced mass activity with repeated use. Further mass activity improvement has been realized after acid-treatment of dendrites which is attributed to the increment in the -OH group. The dendrites show higher mass activity (J(f) similar to 653 A g(-1)) in comparison with a commercial Pt-carbon/Pd-carbon (Pt-C/Pd-C) catalyst (J(f) similar to 46 and 163 A g(-1), respectively), better operational stability, superior CO tolerance with I-f/I-b (similar to 3.7) over a commercial Pt-C/Pd-C catalyst (I-f/I-b similar to 1.6 and 1.75, respectively) and may serve as a promising alternative to commercial Pt-C catalysts for anode application in alkaline fuel cells. To ensure the adaptability of our 3D-nanodendrites for other catalytic activities, we studied 4-nitrophenol reduction at room temperature. The 3D-nanodendrites show excellent catalytic activity toward 4-nitrophenol reduction, as well.

Engineering a multi-biofunctional composite using poly(ethylenimine) decorated graphene oxide for bone tissue regeneration

Toward preparing strong multi-biofunctional materials, poly(ethylenimine) (PEI) conjugated graphene oxide (GO_PEI) was synthesized using poly(acrylic acid) (PAA) as a spacer and incorporated in poly( e-caprolactone) (PCL) at different fractions. GO_PEI significantly promoted the proliferation and formation of focal adhesions in human mesenchymal stem cells (hMSCs) on PCL. GO_PEI was highly potent in inducing stem cell osteogenesis leading to near doubling of alkaline phosphatase expression and mineralization over neat PCL with 5% filler content and was approximate to 50% better than GO. Remarkably, 5% GO_ PEI was as potent as soluble osteoinductive factors. Increased adsorption of osteogenic factors due to the amine and oxygen containing functional groups on GO_ PEI augment stem cell differentiation. GO_ PEI was also highly efficient in imparting bactericidal activity with 85% reduction in counts of E. coli colonies compared to neat PCL at 5% filler content and was more than twice as efficient as GO. This may be attributed to the synergistic effect of the sharp edges of the particles along with the presence of the different chemical moieties. Thus, GO_ PEI based polymer composites can be utilized to prepare bioactive resorbable biomaterials as an alternative to using labile biomolecules for fabricating orthopedic devices for fracture fixation and tissue engineering.

Electrochemical deposition of manganese oxide-phosphate-reduced graphene oxide composite and electrocatalysis of the oxygen evolution reaction

A composite of manganese oxide and reduced graphene oxide (rGO) is prepared in a single step electrochemical reduction process in a phosphate buffer solution for studying as an electrocatalyst for the oxygen evolution reaction (OER). The novel composite catalyst, namely, MnOx-Pi-rGO, is electrodeposited from a suspension of graphene oxide (GO) in a neutral phosphate buffer solution containing KMnO4. The manganese oxide incorporates phosphate ions and deposits on the rGO sheet, which in turn is formed on the substrate electrode by electrochemical reduction of GO in the suspension. The OER is studied with the MnOx-Pi-rGO catalyst in a neutral phosphate electrolyte by linear sweep voltammetry. The results indicate a positive influence of rGO in the catalyst. By varying the ratio of KMnO4 and GO in the deposition medium and performing linear sweep voltammetry for the OER, the optimum composition of the deposition medium is obtained as 20 mM KMnO4 + 6.5% GO in 0.1 M phosphate buffer solution of pH 7. Under identical conditions, the MnOx-Pi-rGO catalyst exhibits 6.2 mA cm(-2) OER current against 2.9 mA cm(-2) by MnOx-Pi catalyst at 2.05 V in neutral phosphate solution. The Tafel slopes measured for OER at MnOx-Pi and MnOx-Pi-rGO are similar in magnitude at about 0.180 V decade(-1). The high Tafel slopes are attributed to partial dissolution of the catalyst during oxygen evolution. The O-2 evolved at the catalyst is measured by the water displacement method and the positive role of rGO on catalytic activity of MnOx-Pi is demonstrated.

Making consistent contacts to graphene: effect of architecture and growth induced defects

The effects of contact architecture, graphene defect density and metal-semiconductor work function difference on the resistivity of metal-graphene contacts have been investigated. An architecture with metal on the bottom of graphene is found to yield resistivities that are lower, by a factor of four, and most consistent as compared to metal on top of graphene. Growth defects in graphene film were found to further reduce resistivity by a factor of two. Using a combination of method and metal used, the contact resistivity of graphene has been decreased by a factor of 10 to 1200. +/-. 250 Omega mu m using palladium as the contact metal. While the improved consistency is due to the metal being able to contact uncontaminated graphene in the metal on the bottom architecture, lower contact resistivities observed on defective graphene with the same metal are attributed to the increased number of modes of quantum transport in the channel.

Minuscule weight percent of graphene oxide and reduced graphene oxide modified Ag3PO4: new insight into improved photocatalytic activity

Designing and fabricating hybrid systems with a visible light active semiconductor as one of its components is an important research area for the development of highly efficient photocatalysts. Herein, we report visible-light driven photocatalytic activity of graphene oxide (GO) and controllably reduced GO (rGO) modified Ag3PO4 composites fabricated by an in situ method. Concentration of graphene derivatives in GO/rGO-Ag3PO4 composites was in the range of 0.13-0.52 wt% which is very minute compared to those reported previously. The optimal concentration of GO in Ag3PO4 with a kinetics (k = 1.23 +/- 0.04 min(-1)) for the degradation of rhodamine B is 0.26 wt%. GO-Ag3PO4 photocatalysts display an improved catalytic activity compared with pristine and rGOs modified Ag3PO4. In line with this, GO/rGO-Ag3PO4 composites show improved photocatalytic activity for the degradation of 2-chlorophenol compared with Degussa P-25. Our experiments with GO reduced to different extents show that, rGO with more polar functional groups exhibits a higher photocatalytic efficiency. The photocatalytic activity in the presence of different scavengers reveals that holes and O-2(-center dot) reactive species play major roles in the degradation phenomenon. In view of our experimental results and reported theoretical studies, a change in conduction band energy level and variation in the contribution of different charge orbitals (C 2p and O 2p) to the conduction band in the composite favours electron flow from graphene derivatives to the semiconductor, enhancing its photocatalytic response.