Mg-based nanocomposites with high capacity and fast kinetics for hydrogen storage

Magnesium and its alloys have shown a great potential in effective hydrogen storage due to their advantages of high volumetric/ gravimetric hydrogen storage capacity and low cost. However, the use of these materials in fuel cells for automotive applications at the present time is limited by high hydrogenation temperature and sluggish sorption kinetics. This paper presents the recent results of design and development of magnesium-based nanocomposites demonstrating the catalytic effects of carbon nanotubes and transition metals on hydrogen adsorption in these materials. The results are promising for the application of magnesium materials for hydrogen storage, with significantly reduced absorption temperatures and enhanced ab/desorption kinetics. High level Density Functional Theory calculations support the analysis of the hydrogenation mechanisms by revealing the detailed atomic and molecular interactions that underpin the catalytic roles of incorporated carbon and titanium, providing clear guidance for further design and development of such materials with better hydrogen storage properties.

Optimum conditions for adsorptive storage

The storage of gases in porous adsorbents, such as activated carbon and carbon nanotubes, is examined here thermodynamically from a systems viewpoint, considering the entire adsorption-desorption cycle. The results provide concrete objective criteria to guide the search for the Holy Grail adsorbent, for which the adsorptive delivery is maximized. It is shown that, for ambient temperature storage of hydrogen and delivery between 30 and 1.5 bar pressure, for the optimum adsorbent the adsorption enthalpy change is 15.1 kJ/mol. For carbons, for which the average enthalpy change is typically 5.8 kJ/mol, an optimum operating temperature of about 115 K is predicted. For methane, an optimum enthalpy change of 18.8 kJ/mol is found, with the optimum temperature for carbons being 254 K. It is also demonstrated that for maximum delivery of the gas the optimum adsorbent must be homogeneous, and that introduction of heterogeneity, such as by ball milling, irradiation, and other means, can only provide small increases in physisorption-related delivery for hydrogen. For methane, heterogeneity is always detrimental, at any value of average adsorption enthalpy change. These results are confirmed with the help of experimental data from the literature, as well as extensive Monte Carlo simulations conducted here using slit pore models of activated carbons as well as atomistic models of carbon nanotubes. The simulations also demonstrate that carbon nanotubes offer little or no advantage over activated carbons in terms of enhanced delivery, when used as storage media for either hydrogen or methane.

Inorganic nanoparticles as carriers for efficient cellular delivery

Cellular delivery involving the transfer of various drugs and bio-active molecules (peptides, proteins and DNAs, etc.) through the cell membrane into cells has attracted increasing attention because of its importance in medicine and drug delivery. This topic has been extensively reviewed. The direct delivery of drugs and biomolecules, however, is generally inefficient and suffering from problems such as enzymic degradation of DNAs. Therefore, searching for efficient and safe transport vehicles (carriers) to delivery genes or drugs into cells has been challenging yet exciting area of research. In past decades, many carriers have been developed and investigated extensively which can be generally classified into four major groups: viral carriers, organic cationic compounds, recombinant protiens and inorganic nanoparticles. Many inorganic materials, such as calcium phosphate, gold, carbon materials, silicon oxide, iron oxide and layered double hydroxide (LDH), have been studied. Inorganic nanoparticles show low toxicity and promise for controlled delivery properties, thus presenting a new alternative to viral carriers and cationic carriers. Inorganic nanoparticles generally possess versatile properties suitable for cellular delivery, including wide availability, rich functionality, good biocompatibility, potential capability of targeted delivery (e.g. selectively destroying cancer cells but sparing normal tissues) and controlled release of carried drugs. This paper reviews the latest advances in inorganic nanoparticle applications as cellular delivery carriers and highlights some key issues in efficient cellular delivery using inorganic nanoparticles. Critical proper-ties of inorganic nanoparticles, surface functionalisation (modification), uptake of biomolecules, the driving forces for delivery, and release of biomolecules will be reviewed systematically. Selected examples of promising inorganic nanoparticle delivery systems, including gold, fullerences and carbon nanotubes, LDH and various oxide nanoparticles in particular their applications for gene delivery will be discussed. The fundamental understanding of properties of inorganic nanoparticles in relation to cellular delivery efficiency as the most paramount issue will be highlighted. (c) 2005 Elsevier Ltd. All rights reserved.

First-principle study of adsorption of hydrogen on Ti-doped Mg(0001) surface

Ab initio density functional theory (DFT) calculations are performed to study the adsorption of H-2 molecules on a Ti-doped Mg(0001) surface. We find that two hydrogen molecules are able to dissociate on top of the Ti atom with very small activation barriers (0.103 and 0.145 eV for the first and second H-2 molecules, respectively). Additionally, a molecular adsorption state of H-2 above the Ti atom is observed for the first time and is attributed to the polarization of the H-2 molecule by the Ti cation. Our results parallel recent findings for H-2 adsorption on Ti-doped carbon nanotubes or fullerenes. They provide new insight into the preliminary stages of hydrogen adsorption onto Ti-incorporated Mg surfaces.

Determinants of biological activity of nanomaterials in innate immunity cells: the role of aspect ratio, environmental contaminants and protein corona

As defined by the European Union, “ ’Nanomaterial’ (NM) means a natural, incidental or manufactured material containing particles, in an unbound state or as an aggregate or agglomerate, where, for 50 % or more of the particles in the number size distribution, one or more external dimensions is in the size range 1 nm-100 nm ” (2011/696/UE). Given their peculiar physico-chemical features, nanostructured materials are largely used in many industrial fields (e.g. cosmetics, electronics, agriculture, biomedical) and their applications have astonishingly increased in the last fifteen years. Nanostructured materials are endowed with very large specific surface area that, besides making them very useful in many industrial processes, renders them very reactive towards the biological systems and, hence, potentially endowed with significant hazard for human health. For these reasons, in recent years, many studies have been focused on the identification of toxic properties of nanostructured materials, investigating, in particular, the mechanisms behind their toxic effects as well as their determinants of toxicity. This thesis investigates two types of nanostructured TiO2 materials, TiO2 nanoparticles (NP), which are yearly produced in tonnage quantities, and TiO2 nanofibres (NF), a relatively novel nanomaterial. Moreover, several preparations of MultiWalled Carbon Nanotubes (MWCNT), another nanomaterial widely present in many products, are also investigated.- Although many in vitro and in vivo studies have characterized the toxic properties of these materials, the identification of their determinants of toxicity is still incomplete. The aim of this thesis is to identify the structural determinants of toxicity, using several in vitro models. Specific fields of investigation have been a) the role of shape and the aspect ratio in the determination of biological effects of TiO2 nanofibres of different length; b) the synergistic effect of LPS and TiO2 NP on the expression of inflammatory markers and the role played therein by TLR-4; c) the role of functionalization and agglomeration in the biological effects of MWCNT. As far as biological effects elicited by TiO2 NF are concerned, the first part of the thesis demonstrates that long TiO2 nanofibres caused frustrated phagocytosis, cytotoxicity, hemolysis, oxidative stress and epithelial barrier perturbation. All these effects were mitigated by fibre shortening through ball-milling. However, short TiO2 NF exhibited enhanced ability to activate acute pro-inflammatory effects in macrophages, an effect dependent on phagocytosis. Therefore, aspect ratio reduction mitigated toxic effects, while enhanced macrophage activation, likely rendering the NF more prone to phagocytosis. These results suggest that, under in vivo conditions, short NF will be associated with acute inflammatory reaction, but will undergo a relatively rapid clearance, while long NF, although associated with a relatively smaller acute activation of innate immunity cells, are not expected to be removed efficiently and, therefore, may be associated to chronic inflammatory responses. As far as the relationship between the effects of TiO2 NP and LPS, investigated in the second part of the thesis, are concerned, TiO2 NP markedly enhanced macrophage activation by LPS through a TLR-4-dependent intracellular pathway. The adsorption of LPS onto the surface of TiO2 NP led to the formation of a specific bio-corona, suggesting that, when bound to TiO2 NP, LPS exerts a much more powerful pro-inflammatory effect. These data suggest that the inflammatory changes observed upon exposure to TiO2 NP may be due, at least in part, to their capability to bind LPS and, possibly, other TLR agonists, thus enhancing their biological activities. Finally, the last part of the thesis demonstrates that surface functionalization of MWCNT with amino or carboxylic groups mitigates the toxic effects of MWCNT in terms of macrophage activation and capability to perturb epithelial barriers. Interestingly, surface chemistry (in particular surface charge) influenced the protein adsorption onto the MWCNT surface, allowing to the formation of different protein coronae and the tendency to form agglomerates of different size. In particular functionalization a) changed the amount and the type of proteins adsorbed to MWCNT and b) enhanced the tendency of MWCNT to form large agglomerates. These data suggest that the different biological behavior of functionalized and pristine MWCNT may be due, at least in part, to the different tendency to form large agglomerates, which is significantly influenced by their different capability to interact with proteins contained in biological fluids. All together, these data demonstrate that the interaction between physico-chemical properties of nanostructured materials and the environment (cells + biological fluids) in which these materials are present is of pivotal importance for the understanding of the biological effects of NM. In particular, bio-persistence and the capability to elicit an effective inflammatory response are attributable to the interaction between NM and macrophages. However, the interaction NM-cells is heavily influenced by the formation at the nano-bio interface of specific bio-coronae that confer a novel biological identity to the nanostructured materials, setting the basis for their specific biological activities.

Nanotube-polymer composites for ultrafast photonics

Polymer composites are one of the most attractive near-term means to exploit the unique properties of carbon nanotubes and graphene. This is particularly true for composites aimed at electronics and photonics, where a number of promising applications have already been demonstrated. One such example is nanotube-based saturable absorbers. These can be used as all-optical switches, optical amplifier noise suppressors, or mode-lockers to generate ultrashort laser pulses. Here, we review various aspects of fabrication, characterization, device implementation and operation of nanotube-polymer composites to be used in photonic applications. We also summarize recent results on graphene-based saturable absorbers for ultrafast lasers.

Polarization attractors in harmonic mode-locked fiber laser

We report on a polarimetry of harmonic mode-locked erbium-doped fiber laser with carbon nanotubes saturable absorber. We find new types of vector solitons with locked, switching and precessing states of polarization. The underlying physics presents interplay between birefringence of a laser cavity created by polarization controller along with light induced anisotropy caused by polarization hole burning. © 2014 Optical Society of America.

Spiral attractor created by vector solitons

Mode-locked lasers emitting a train of femtosecond pulses called dissipative solitons are an enabling technology for metrology, high-resolution spectroscopy, fibre optic communications, nano-optics and many other fields of science and applications. Recently, the vector nature of dissipative solitons has been exploited to demonstrate mode locked lasing with both locked and rapidly evolving states of polarisation. Here, for an erbium-doped fibre laser mode locked with carbon nanotubes, we demonstrate the first experimental and theoretical evidence of a new class of slowly evolving vector solitons characterized by a double-scroll chaotic polarisation attractor substantially different from Lorenz, Rössler and Ikeda strange attractors. The underlying physics comprises a long time scale coherent coupling of two polarisation modes. The observed phenomena, apart from the fundamental interest, provide a base for advances in secure communications, trapping and manipulation of atoms and nanoparticles, control of magnetisation in data storage devices and many other areas. © 2014 CIOMP. All rights reserved.

Analytical model for active metamaterials with quantum ingredients

We present an analytical model for describing complex dynamics of a hybrid system consisting of resonantly coupled classical resonator and quantum structures. Classical resonators in our model correspond to plasmonic metamaterials of various geometries, as well as other types of nano- and microstructure, the optical responses of which can be described classically. Quantum resonators are represented by atoms or molecules, or their aggregates (for example, quantum dots, carbon nanotubes, dye molecules, polymer or bio-molecules etc), which can be accurately modelled only with the use of the quantum mechanical approach. Our model is based on the set of equations that combines well established density matrix formalism appropriate for quantum systems, coupled with harmonic-oscillator equations ideal for modelling sub-wavelength plasmonic and optical resonators. As a particular example of application of our model, we show that the saturation nonlinearity of carbon nanotubes increases multifold in the resonantly enhanced near field of a metamaterial. In the framework of our model, we discuss the effect of inhomogeneity of the carbon-nanotube layer (bandgap value distribution) on the nonlinearity enhancement. © 2012 IOP Publishing Ltd.

Fast and slowly evolving vector solitons in mode-locked fibre lasers

We report on a new vector model of an erbium-doped fibre laser mode locked with carbon nanotubes. This model goes beyond the limitations of the previously used models based on either coupled nonlinear Schrödinger or Ginzburg-Landau equations. Unlike the previous models, it accounts for the vector nature of the interaction between an optical field and an erbium-doped active medium, slow relaxation dynamics of erbium ions, linear birefringence in a fibre, linear and circular birefringence of a laser cavity caused by in-cavity polarization controller and light-induced anisotropy caused by elliptically polarized pump field. Interplay of aforementioned factors changes coherent coupling of two polarization modes at a long time scale and so results in a new family of vector solitons (VSs) with fast and slowly evolving states of polarization. The observed VSs can be of interest in secure communications, trapping and manipulation of atoms and nanoparticles, control of magnetization in data storage devices and many other areas.

Dissipative vector solitons with fast evolving states of polarization

We report on a new vector model of an erbium doped fiber laser mode locked with carbon nanotubes. This model goes beyond the limitations of the previously used models based on either coupled nonlinear Schrödinger or Ginzburg-Landau equations. It results in a new family of vector solitons with fast evolving states of polarization experimentally observed in our previous papers.

Vector solitons in harmonic mode-locked erbium-doped fiber lasers

We report experimental study of vector solitons for the fundamental and harmonic mode-locked operation in erbiumdoper fiber lasers with carbon nanotubes based saturable absorbers and anomalous dispersion cavities. We measure evolution of the output pulses polarization and demonstrate vector solitons with various polarization attractors, including locked polarization, periodic polarization switching, and polarization precession.

Vector solitons in mode locked fibre lasers

We overview our recent results on polarisation dynamics of vector solitons in erbium doped fibre laser mode locked with carbon nanotubes. Our experimental and theoretical study revealed new families of vector solitons for fundamental and bound-state soliton operations. The observed scenario of the evolution of the states of polarisation (SOPs) on the Poincare sphere includes fast polarisation switching between two and three SOPs along with slow SOP evolution on a double scroll chaotic attractor. The underlying physics presents an interplay between effects of birefringence of the laser cavity and light induced anisotropy caused by polarisation hole burning. © 2014 IEEE.

Slow deterministic vector rogue waves

For an erbium-doped fiber laser mode-locked by carbon nanotubes, we demonstrate experimentally and theoretically a new type of the vector rogue waves emerging as a result of the chaotic evolution of the trajectories between two orthogonal states of polarization on the Poincare sphere. In terms of fluctuation induced phenomena, by tuning polarization controller for the pump wave and in-cavity polarization controller, we are able to control the Kramers time, i.e. the residence time of the trajectory in vicinity of each orthogonal state of polarization, and so can cause the rare events satisfying rogue wave criteria and having the form of transitions from the state with the long residence time to the state with a short residence time.

C-MEMS Based Micro Enzymatic Biofuel Cells

Miniaturized, self-sufficient bioelectronics powered by unconventional micropower may lead to a new generation of implantable, wireless, minimally invasive medical devices, such as pacemakers, defibrillators, drug-delivering pumps, sensor transmitters, and neurostimulators. Studies have shown that micro-enzymatic biofuel cells (EBFCs) are among the most intuitive candidates for in vivo micropower. In the fisrt part of this thesis, the prototype design of an EBFC chip, having 3D intedigitated microelectrode arrays was proposed to obtain an optimum design of 3D microelectrode arrays for carbon microelectromechanical systems (C-MEMS) based EBFCs. A detailed modeling solving partial differential equations (PDEs) by finite element techniques has been developed on the effect of 1) dimensions of microelectrodes, 2) spatial arrangement of 3D microelectrode arrays, 3) geometry of microelectrode on the EBFC performance based on COMSOL Multiphysics. In the second part of this thesis, in order to investigate the performance of an EBFC, behavior of an EBFC chip performance inside an artery has been studied. COMSOL Multiphysics software has also been applied to analyze mass transport for different orientations of an EBFC chip inside a blood artery. Two orientations: horizontal position (HP) and vertical position (VP) have been analyzed. The third part of this thesis has been focused on experimental work towards high performance EBFC. This work has integrated graphene/enzyme onto three-dimensional (3D) micropillar arrays in order to obtain efficient enzyme immobilization, enhanced enzyme loading and facilitate direct electron transfer. The developed 3D graphene/enzyme network based EBFC generated a maximum power density of 136.3 μWcm-2 at 0.59 V, which is almost 7 times of the maximum power density of the bare 3D carbon micropillar arrays based EBFC. To further improve the EBFC performance, reduced graphene oxide (rGO)/carbon nanotubes (CNTs) has been integrated onto 3D mciropillar arrays to further increase EBFC performance in the fourth part of this thesisThe developed rGO/CNTs based EBFC generated twice the maximum power density of rGO based EBFC. Through a comparison of experimental and theoretical results, the cell performance efficiency is noted to be 67%.