Enhanced Gas Adsorption on Graphitic Substrates via Defects and Local Curvature: A Density Functional Theory Study

Using van-der-Waals-corrected density functional theory calculations, we explore the possibility of engineering the local structure and morphology of high-surface-area graphene-derived materials to improve the uptake of methane and carbon dioxide for gas storage and sensing. We test the sensitivity of the gas adsorption energy to the introduction of native point defects, curvature, and the application of strain. The binding energy at topological point defect sites is inversely correlated with the number of missing carbon atoms, causing Stone-Wales defects to show the largest enhancement with respect to pristine graphene (similar to 20%). Improvements of similar magnitude are observed at concavely curved surfaces in buckled graphene sheets under compressive strain, whereas tensile strain tends to weaken gas binding. Trends for CO2 and CH4 are, similar, although CO2 binding is generally stronger by similar to 4 to 5 kJ mol(-1). However, the differential between the adsorption of CO2 and CH4 is much higher on folded graphene sheets and at concave curvatures; this could possibly be leveraged for CH4/CO2 flow separation and gasselective sensors.

The Presence of Multiple Cellular Defects Associated with a Novel G50E Iron-Sulfur Cluster Scaffold Protein ( ISCU) Mutation Leads to Development of Mitochondrial Myopathy

Background: Muscle-specific deficiency of iron-sulfur (Fe-S) cluster scaffold protein (ISCU) leads to myopathy. Results: Cells carrying the myopathy-associated G50E ISCU mutation demonstrate impaired Fe-S cluster biogenesis and mitochondrial dysfunction. Conclusion: Reduced mitochondrial respiration as a result of diminished Fe-S cluster synthesis results in muscle weakness in myopathy patients. Significance: The molecular mechanism behind disease progression should provide invaluable information to combat ISCU myopathy. Iron-sulfur (Fe-S) clusters are versatile cofactors involved in regulating multiple physiological activities, including energy generation through cellular respiration. Initially, the Fe-S clusters are assembled on a conserved scaffold protein, iron-sulfur cluster scaffold protein (ISCU), in coordination with iron and sulfur donor proteins in human mitochondria. Loss of ISCU function leads to myopathy, characterized by muscle wasting and cardiac hypertrophy. In addition to the homozygous ISCU mutation (g.7044GC), compound heterozygous patients with severe myopathy have been identified to carry the c.149GA missense mutation converting the glycine 50 residue to glutamate. However, the physiological defects and molecular mechanism associated with G50E mutation have not been elucidated. In this report, we uncover mechanistic insights concerning how the G50E ISCU mutation in humans leads to the development of severe ISCU myopathy, using a human cell line and yeast as the model systems. The biochemical results highlight that the G50E mutation results in compromised interaction with the sulfur donor NFS1 and the J-protein HSCB, thus impairing the rate of Fe-S cluster synthesis. As a result, electron transport chain complexes show significant reduction in their redox properties, leading to loss of cellular respiration. Furthermore, the G50E mutant mitochondria display enhancement in iron level and reactive oxygen species, thereby causing oxidative stress leading to impairment in the mitochondrial functions. Thus, our findings provide compelling evidence that the respiration defect due to impaired biogenesis of Fe-S clusters in myopathy patients leads to manifestation of complex clinical symptoms.

Detailed understanding of the excitation-intensity dependent photoluminescence of ZnO materials: Role of defects

The photoluminescence (PL) of ZnO is shown to be dependent on the excitation intensity (EI) of the laser, and the substantial shift observed in the band to band transition is attributed to the heating effect. In order to understand this phenomenon in detail, we investigate the EI dependent PL of various ZnO samples systematically from liquid nitrogen (LN) to room temperature by varying the laser power. Some of the samples exhibit substantial red shift in the band to band transition with increasing EI even in LN environment, negligible effect is observed for others. Hence, our results strongly suggest that the EI dependent PL is not a characteristic of all ZnO samples. This indicates that laser-induced heating effect is not the dominant factor that governs the shifts in the PL spectra. Rather, the defect level excitation accounts for such observation. (C) 2014 AIP Publishing LLC.

Ontology analysis of global gene expression differences of human bone marrow stromal cells cultured on 3D scaffolds or 2D films

Differences in gene expression of human bone marrow stromal cells (hBMSCs) during culture in three-dimensional (3D) nanofiber scaffolds or on two-dimensional (2D) films were investigated via pathway analysis of microarray mRNA expression profiles. Previous work has shown that hBMSC culture in nanofiber scaffolds can induce osteogenic differentiation in the absence of osteogenic supplements (OS). Analysis using ontology databases revealed that nanofibers and OS regulated similar pathways and that both were enriched for TGF-beta and cell-adhesion/ECM-receptor pathways. The most notable difference between the two was that nanofibers had stronger enrichment for cell-adhesion/ECM-receptor pathways. Comparison of nanofibers scaffolds with flat films yielded stronger differences in gene expression than comparison of nanofibers made from different polymers, suggesting that substrate structure had stronger effects on cell function than substrate polymer composition. These results demonstrate that physical (nanofibers) and biochemical (OS) signals regulate similar ontological pathways, suggesting that these cues use similar molecular mechanisms to control hBMSC differentiation. Published by Elsevier Ltd.

On the Utility of Microscopy and C-Scan Techniques in the Study of Defects Arising From Resin Infusion Process and a Study on the Influence of Voids on the Impact Behavior of CFRP Composites

Carbon Fiber Reinforced Plastic composites were fabricated through vacuum resin infusion technology by adopting two different processing conditions, viz., vacuum only in the first and vacuum plus external pressure in the next, in order to generate two levels of void-bearing samples. They were relatively graded as higher and lower void-bearing ones, respectively. Microscopy and C-scan techniques were utilized to describe the presence of voids arising from the two different processing parameters. Further, to determine the influence of voids on impact behavior, the fabricated +45 degrees/90 degrees/-45 degrees composite samples were subjected to low velocity impacts. The tests show impact properties like peak load and energy to peak load registering higher values for the lower void-bearing case where as the total energy, energy for propagation and ductility indexes were higher for the higher void-bearing ones. Fractographic analysis showed that higher void-bearing samples display lower number of separation of layers in the laminate. These and other results are described and discussed in this report.

Impact of Stone-Wales and lattice vacancy defects on the electro-thermal transport of the free standing structure of metallic ZGNR

We report the effect of topological as well as lattice vacancy defects on the electro-thermal transport properties of the metallic zigzag graphene nano ribbons at their ballistic limit. We employ the density function theory-Non equilibrium green's function combination to calculate the transmission details. We then present an elaborated study considering the variation in the electrical current and the heat current transport with the change in temperature as well as the voltage gradient across the nano ribbons. The comparative analysis shows, that in the case of topological defects, such as the Stone-Wales defect, the electrical current transport is minimum. Besides, for the voltage gradient of 0.5 Volt and the temperature gradient of 300 K, the heat current transport reduces by similar to 62 % and similar to 50% for the cases of Stones-Wales defect and lattice vacancy defect respectively, compared to that of the perfect one.

Perovskite ceramic nanoparticles in polymer composites for augmenting bone tissue regeneration

There is increasing interest in the use of nanoparticles as fillers in polymer matrices to develop biomaterials which mimic the mechanical, chemical and electrical properties of bone tissue for orthopaedic applications. The objective of this study was to prepare poly(epsilon-caprolactone) (PCL) nanocomposites incorporating three different perovskite ceramic nanoparticles, namely, calcium titanate (CT), strontium titanate (ST) and barium titanate (BT). The tensile strength and modulus of the composites increased with the addition of nanoparticles. Scanning electron microscopy indicated that dispersion of the nanoparticles scaled with the density of the ceramics, which in turn played an important role in determining the enhancement in mechanical properties of the composite. Dielectric spectroscopy revealed improved permittivity and reduced losses in the composites when compared to neat PCL. Nanofibrous scaffolds were fabricated via electrospinning. Induction coupled plasma-optical emission spectroscopy indicated the release of small quantities of Ca+2, Sr+2, Ba+2 ions from the scaffolds. Piezo-force microscopy revealed that BT nanoparticles imparted piezoelectric properties to the scaffolds. In vitro studies revealed that all composites support osteoblast proliferation. Expression of osteogenic genes was enhanced on the nanocomposites in the following order: PCL/CT>PCL/ST>PCL/BT>PCL. This study demonstrates that the use of perovskite nanoparticles could be a promising technique to engineer better polymeric scaffolds for bone tissue engineering.

Ductility enhancement in nanoglass: role of interaction stress between flow defects

Using a thermodynamically consistent non-local plasticity model, the mechanistic origin of enhancement in ductility and suppression of dominant shear banding in nanoglasses (NGs) is analysed. It is revealed that the interaction stress between flow defects plays a central role in promoting global plasticity of NGs. Specifically, we find that the intrinsic length associated with this stress provides a scaling for the shear band width and its coupling with grain size governs the level of enhancement in the deformation behaviour of NGs. The present work may provide useful insights in developing highly ductile NGs for practical engineering applications.

Effect of Line Defects on the Electrical Transport Properties of Monolayer MoS2 Sheet

We present a computational study on the impact of line defects on the electronic properties of monolayer MoS2. Four different kinds of line defects with Mo and S as the bridging atoms, consistent with recent theoretical and experimental observations, are considered herein. We employ the density functional tight-binding (DFTB) method with a Slater-Koster-type DFTB-CP2K basis set for evaluating the material properties of perfect and the various defective MoS2 sheets. The transmission spectra are computed with a DFTB-non-equilibrium Green's function formalism. We also perform a detailed analysis of the carrier transmission pathways under a small bias and investigate the phase of the transmission eigenstates of the defective MoS2 sheets. Our simulations show a two to four fold decrease in carrier conductance of MoS2 sheets in the presence of line defects as compared to that for the perfect sheet.

Hydroxyapatite-titanium bulk composites for bone tissue engineering applications

The research work on bulk hydroxyapatite (HA)-based composites are driven by the need to develop biomaterials with better mechanical properties without compromising its bioactivity and biocompatibility properties. Despite several years of research, the mechanical properties of the HA-based composites still need to be enhanced to match the properties of natural cortical bone. In this regard, the scope of this review on the HA-based bulk biomaterials is limited to the processing and the mechanical as well as biocompatibility properties for bone tissue engineering applications of a model system that is hydroxyapatite-titanium (HA-Ti) bulk composites. It will be discussed in this review how HA-Ti based bulk composites can be processed to have better fracture toughness and strength without compromising biocompatibility. The advantages of the functionally gradient materials to integrate the mechanical and biocompatibility properties is a promising approach in hard tissue engineering and has been emphasized here in reference to the limited literature reports. On the biomaterials fabrication aspect, the recent results are discussed to demonstrate that advanced manufacturing techniques, like spark plasma sintering can be adopted as a processing route to restrict the sintering reactions, while enhancing the mechanical properties. Various toughening mechanisms related to careful tailoring of microstructure are discussed. The in vitro cytocompatibilty, cell fate processes as well as in vivo biocompatibility results are also reviewed and the use of flow cytometry to quantify in vitro cell fate processes is being emphasized. (C) 2014 Wiley Periodicals, Inc.

A new approach to depict bone surfaces in finger imaging using photoacoustic tomography

Imaging the vasculature close around the finger joints is of interest in the field of rheumatology. Locally increased vasculature in the synovial membrane of these joints can be a marker for rheumatoid arthritis. In previous work we showed that part of the photoacoustically induced ultrasound from the epidermis reflects on the bone surface within the finger. These reflected signals could be wrongly interpreted as new photoacoustic sources. In this work we show that a conventional ultrasound reconstruction algorithm, that considers the skin as a collection of ultrasound transmitters and the PA tomography probe as the detector array, can be used to delineate bone surfaces of a finger. This can in the future assist in the localization of the joint gaps. This can provide us with a landmark to localize the region of the inflamed synovial membrane. We test the approach on finger mimicking phantoms.

Optoelectronic Properties of Graphene on Silicon Substrate: Effect of Defects in Graphene

Engineering of electronic energy band structure in graphene based nanostructures has several potential applications. Substrate induced bandgap opening in graphene results several optoelectronic properties due to the inter-band transitions. Various defects like structures, including Stone-Walls and higher-order defects are observed when a graphene sheet is exfoliated from graphite and in many other growth conditions. Existence of defect in graphene based nanostructures may cause changes in optoelectronic properties. Defect engineered graphene on silicon system are considered in this paper to study the tunability of optoelectronic properties. Graphene on silicon atomic system is equilibrated using molecular dynamics simulation scheme. Based on this study, we confirm the existence of a stable super-lattice. Density functional calculations are employed to determine the energy band structure for the super-lattice. Increase in the optical energy bandgap is observed with increasing of order of the complexity in the defect structure. Optical conductivity is computed as a function of incident electromagnetic energy which is also increasing with increase in the defect order. Tunability in optoelectronic properties will be useful in understanding graphene based design of photodetectors, photodiodes and tunnelling transistors.

DLTS analysis of amphoteric interface defects in high-TiO2 MOS structures prepared by sol-gel spin-coating

High-kappa TiO2 thin films have been fabricated from a facile, combined sol-gel spin - coating technique on p and n type silicon substrate. XRD and Raman studies headed the existence of anatase phase of TiO2 with a small grain size of 18 nm. The refractive index `n' quantified from ellipsometry is 2.41. AFM studies suggest a high quality, pore free films with a fairly small surface roughness of 6 angstrom. The presence of Ti in its tetravalent state is confirmed by XPS analysis. The defect parameters observed at the interface of Si/TiO2 were studied by capacitance - voltage (C - V) and deep level transient spectroscopy (DLTS). The flat - band voltage (V-FB) and the density of slow interface states estimated are -0.9, -0.44 V and 5.24x10(10), 1.03x10(11) cm(-2); for the NMOS and PMOS capacitors, respectively. The activation energies, interface state densities and capture cross -sections measured by DLTS are E-V + 0.30, E-C - 0.21 eV; 8.73x10(11), 6.41x10(11) eV(-1) cm(-2) and 5.8x10(-23), 8.11x10(-23) cm(2) for the NMOS and PMOS structures, respectively. A low value of interface state density in both P-and N-MOS structures makes it a suitable alternate dielectric layer for CMOS applications. And also very low value of capture cross section for both the carriers due to the amphoteric nature of defect indicates that the traps are not aggressive recombination centers and possibly can not contribute to the device operation to a large extent. (C) 2015 Author(s).

A Method for Delineation of Bone Surfaces in Photoacoustic Computed Tomography of the Finger

Photoacoustic (PA) imaging of interphalangeal peripheral joints is of interest in the context of using the synovial membrane as a surrogate marker of rheumatoid arthritis. Previous work has shown that ultrasound (US) produced by absorption of light at the epidermis reflects on the bone surfaces within the finger. When the reflected signals are backprojected in the region of interest, artifacts are produced, confounding interpretation of the images. In this work, we present an approach where the PA signals known to originate from the epidermis are treated as virtual US transmitters, and a separate reconstruction is performed as in US reflection imaging. This allows us to identify the bone surfaces. Furthermore, the identification of the joint space is important as this provides a landmark to localize a region-of-interest in seeking the inflamed synovial membrane. The ability to delineate bone surfaces allows us to identify not only the artifacts but also the interphalangeal joint space without recourse to new US hardware or a new measurement. We test the approach on phantoms and on a healthy human finger.