Directing chondrogenesis of stem cells with specific blends of cellulose and silk.

Biomaterials that can stimulate stem cell differentiation without growth factor supplementation provide potent and cost-effective scaffolds for regenerative medicine. We hypothesize that a scaffold prepared from cellulose and silk blends can direct stem cell chondrogenic fate. We systematically prepared cellulose blends with silk at different compositions using an environmentally benign processing method based on ionic liquids as a common solvent. We tested the effect of blend compositions on the physical properties of the materials as well as on their ability to support mesenchymal stem cell (MSC) growth and chondrogenic differentiation. The stiffness and tensile strength of cellulose was significantly reduced by blending with silk. The characterized materials were tested using MSCs derived from four different patients. Growing MSCs on a specific blend combination of cellulose and silk in a 75:25 ratio significantly upregulated the chondrogenic marker genes SOX9, aggrecan, and type II collagen in the absence of specific growth factors. This chondrogenic effect was neither found with neat cellulose nor the cellulose/silk 50:50 blend composition. No adipogenic or osteogenic differentiation was detected on the blends, suggesting that the cellulose/silk 75:25 blend induced specific stem cell differentiation into the chondrogenic lineage without addition of the soluble growth factor TGF-ß. The cellulose/silk blend we identified can be used both for in vitro tissue engineering and as an implantable device for stimulating endogenous stem cells to initiate cartilage repair.

A comparative study based on performance and techno-economic analysis of different strategies for PV-Electrolyzer (green) hydrogen fueling incinerator system.

The integration of hydrogen in the primary energy mix requires a major technological shift in virtually every energy-related application. This study has attempted to investigate the techno-economic solar photovoltaic (PV) integrated water electrolysis and waste incineration system. Three different strategies, i.e., (i) PV + Battery(Hybrid mode with required batteries); (ii) auto-ignition (Direct coupling); and (iii) PV + Secondary-Electrolyzer(Direct coupling assisted with secondary electrolyzer), have been envisioned. The 'PV + Battery' consume 42.42 % and 15.07 % less energy than the auto-ignition and 'PV + Secondary-Electrolyzer' methods. However, the capital cost of 'PV + Battery' has been calculated to be 15.4 % and 11.8 % more than auto-ignition and 'PV + Secondary-Electrolyzer, respectively.The energy consumption relative to waste input, the 'PV + Battery' method used 80 % less energy, while auto-ignition and 'PV + Secondary-Electrolyzer' showed 70.5 % and 77.5 % less energy, respectively. Furthermore, these approaches showed a vast difference in cost-benefit for the longer run. 'PV + Battery' was forecasted to be 73.3 % and 23.3 % more expensive than auto-ignition and 'PV + Secondary-Electrolyzer' methods, respectively, for 30 years. Overall, this study can benefit from using either of these methods depending on the application, usage scale, and climatic conditions.

Symmetrical and unsymmetrical alpha,omega-nucleobase amide-conjugated systems.

We present the synthesis and selected physicochemical properties of several novel symmetrical and unsymmetrical alpha,omega-nucleobase mono- and bis-amide conjugated systems containing aliphatic, aromatic or saccharidic linkages. The final stage of the synthesis involves condensation of a subunit bearing carboxylic group with an amine subunit. 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM) was found to be a particularly effective condensing agent. The subunits containing carboxylic groups were obtained by acidic hydrolysis of N-1 Michael adducts of uracils or N-9 Michael adducts of 6-chloropurine with methyl acrylate. The amines used were aliphatic/aromatic diamines, adenine, 5-substituted 1-(ω-aminoalkyl)uracils and 5'-amino-2',5'-dideoxythymidine. The title compounds may find application as antiprotozoal agents. Moreover, preliminary microscopy TEM studies of supramolecular behaviour showed that target molecules with bolaamphiphilic structures were capable of forming highly ordered assemblies, mainly nanofibres.

Macroscopic fibers of well-aligned carbon nanotubes by wet spinning.

A simple process to spin fibers consisting of multi-walled carbon nanotubes (CNTs) directly from their lyotropic liquid-crystalline phase is reported. Ethylene glycol is used as the lyotropic solvent, enabling a wider range of CNT types to be spun than previously. Fibers spun with CNTs and nitrogen-doped CNTs are compared. X-ray analysis reveals that nitrogen-doped CNTs have a misalignment of only +/-7.8 degrees to the fiber axis. The tensile strength of the CNT and nitrogen-doped CNT fibers is comparable but the modulus and electrical conductivity of the are lower. The electrical conductivity of both types of CNT fibers is found to be highly anisotropic. The results are discussed in context of the microstructure of the CNTs and fibers.

Carbon nanotube functionalization as a route to enhancing the electrical and mechanical properties of Cu-CNT composites.

Copper-CNT (carbon nanotube) composite materials are promising alternatives to conventional conductors in applications ranging from interconnects in microelectronics to electrical cabling in aircraft and vehicles. Unfortunately, exploiting the full potential of these composites is difficult due to the poor Cu-CNT electro-mechanical interface. We demonstrate through large-scale ab initio calculations and sonication experiments that this problem can be addressed by CNT surface modification. Our calculations show that covalent functionalization of CNTs below 6.7 at% significantly improves Cu-CNT wetting and the mechanical properties of the composite. Oxidative pre-treatment of CNTs enhances the Young's modulus of the composite by nearly a factor 3 above that of pure Cu, whereas amination slightly improves the electrical current density with respect to the unmodified Cu-CNT system in the high bias regime. However, only nitrogen doping can effectively improve both the mechanical and electrical properties of the composite. As the experiments show, consistent with the calculations, substitutional doping with nitrogen effectively improves adhesion of the CNT to the Cu matrix. We also predict an improvement in the mechanical properties for the composite containing doped double-wall CNTs. Moreover, the calculations indicate that the presence of nitrogen dopants almost doubles locally the transmission through the nanotube and reduces the back scattering in the Cu matrix around the CNT. The computed electrical conductance of N-doped Cu-CNT "carpets" exceeds that of an undoped system by ∼160%.

Advancing the Use of High-Performance Graphene-Based Multimodal Polymer Nanocomposite at Scale.

The production of an innovative, high-performance graphene-based polymer nanocomposite using cost-effective techniques was pursued in this study. Well-dispersed and uniformly distributed graphene platelets within a polymer matrix, with strong interfacial bonding between the platelets and the matrix, provided an optimal nanocomposite system for industrial interest. This study reports on the reinforcement of high molecular weight multimodal-high-density polyethylene reinforced by a microwave-induced plasma graphene, using melt intercalation. The tailored process included designing a suitable screw configuration, paired with coordinating extruder conditions and blending techniques. This enabled the polymer to sufficiently degrade, predominantly through thermomechanical-degradation, as well as thermo-oxidative degradation, which subsequently created a suitable medium for the graphene sheets to disperse readily and distribute evenly within the polymer matrix. Different microscopy techniques were employed to prove the effectiveness. This was then qualitatively assessed by Raman spectroscopy, X-ray diffraction, rheology, mechanical testing, density measurements, thermal expansion, and thermogravimetric analysis, confirming both the originality as well as the effectiveness of the process.

Improving the electrical properties of carbon nanotubes with interhalogen compounds.

The electronic properties of carbon nanostructures such as carbon nanotubes (CNTs) or graphene can easily be tuned by the action of various doping agents. We present an experimental study and numerical analysis of how and why metallic and semiconductive CNTs can be p-doped by exposing them to two interhalogens: iodine monochloride and iodine monobromide. Simple application of these compounds was found to reduce the electrical resistance by as much as 2/3 without causing any unfavorable chemical modification, which could disrupt the highly conductive network of sp2 carbon atoms. To gain better insight into the underlying mechanism of the observed experimental results, we provide a first principles indication of how interhalogens interact with model metallic (5,5) and semiconductive (10,0) CNTs.

Breaking the electrical barrier between copper and carbon nanotubes.

Improving the interface between copper and carbon nanotubes (CNTs) offers a straightforward strategy for the effective manufacturing and utilisation of Cu-CNT composite material that could be used in various industries including microelectronics, aerospace and transportation. Motivated by a combination of structural and electrical measurements on Cu-M-CNT bimetal systems (M = Ni, Cr) we show, using first principles calculations, that the conductance of this composite can exceed that of a pure Cu-CNT system and that the current density can even reach 1011 A cm-2. The results show that the proper choice of alloying element (M) and type of contact facilitate the fabrication of ultra-conductive Cu-M-CNT systems by creating a favourable interface geometry, increasing the interface electronic density of states and reducing the contact resistance. In particular, a small concentration of Ni between the Cu matrix and the CNT using either an "end contact" and or a "dot contact" can significantly improve the electrical performance of the composite. Furthermore the predicted conductance of Ni-doped Cu-CNT "carpets" exceeds that of an undoped system by ∼200%. Cr is shown to improve CNT integration and composite conductance over a wide temperature range while Al, at low voltages, can enhance the conductance beyond that of Cr.

Soldering of Carbon Materials Using Transition Metal Rich Alloys.

Joining of carbon materials via soldering has not been possible up to now due to lack of wetting of carbons by metals at standard soldering temperatures. This issue has been a severely restricting factor for many potential electrical/electronic and mechanical applications of nanostructured and conventional carbon materials. Here we demonstrate the formation of alloys that enable soldering of these structures. By addition of several percent (2.5-5%) of transition metal such as chromium or nickel to a standard lead-free soldering tin based alloy we obtained a solder that can be applied using a commercial soldering iron at typical soldering temperatures of approximately 350 °C and at ambient conditions. The use of this solder enables the formation of mechanically strong and electrically conductive joints between carbon materials and, when supported by a simple two-step technique, can successfully bond carbon structures to any metal terminal. It has been shown using optical and scanning electron microscope images as well as X-ray diffraction patterns and energy dispersive X-ray mapping that the successful formation of carbon-solder bonds is possible, first, thanks to the uniform nonreactive dispersion of transition metals in the tin-based matrix. Further, during the soldering process, these free elements diffuse into the carbon-alloy border with no formation of brazing-like carbides, which would damage the surface of the carbon materials.

Ultra-pure single wall carbon nanotube fibres continuously spun without promoter.

We report a new strategy towards the control of carbon nanotube (CNT) structure and continuous fibre formation using a floating catalyst direct spinning CVD process. In the procedures used to date, a sulphur promoter precursor is added to significantly enhance the rate of CNT formation in the floating catalyst synthesis. Within the reaction zone, the rapidly grown nanotubes self-assemble into bundles, followed by their continuous spinning into fibres, yarns, films or tapes. In this paper we demonstrate a catalyst control strategy in the floating catalyst system, where the CNT formation process is independent of the presence of a promoter but leads to successful spinning of the macroscopic carbon nanotube assemblies with specific morphology, high purity (Raman D/G 0.03) and very narrow diameter range (0.8-2.5 nm). This can be achieved by the control of catalyst precursor decomposition and subsequent formation of homogeneous nano-sized catalyst particles.

Piezoresistive effect in carbon nanotube fibers.

The complex structure of the macroscopic assemblies of carbon nanotubes and variable intrinsic piezoresistivity of nanotubes themselves lead to highly interesting piezoresistive performance of this new type of conductive material. Here, we present an in-depth study of the piezoresistive effect in carbon nanotube fibers, i.e., yarnlike assemblies made purely of aligned carbon nanotubes, which are expected to find applications as electrical and electronic materials. The resistivity changes of carbon nanotube fibers were measured on initial loading, through the elastic/plastic transition, on cyclic loading and on stress relaxation. The various regimes of stress/strain behavior were modeled using a standard linear solid model, which was modified with an additional element in series to account for the observed creep behavior. On the basis of the experimental and modeling results, the origin of piezoresistivity is discussed. An additional effect on the resistivity was found as the fiber was held under load which led to observations of the effect of humidity and the associated water adsorption level on the resistivity. We show that the equilibrium uptake of moisture leads to the decrease in gauge factor of the fiber decrease, i.e., the reduction in the sensitivity of fiber resistivity to loading.

En route to controlled catalytic CVD synthesis of densely packed and vertically aligned nitrogen-doped carbon nanotube arrays.

The catalytic chemical vapour deposition (c-CVD) technique was applied in the synthesis of vertically aligned arrays of nitrogen-doped carbon nanotubes (N-CNTs). A mixture of toluene (main carbon source), pyrazine (1,4-diazine, nitrogen source) and ferrocene (catalyst precursor) was used as the injection feedstock. To optimize conditions for growing the most dense and aligned N-CNT arrays, we investigated the influence of key parameters, i.e., growth temperature (660, 760 and 860 °C), composition of the feedstock and time of growth, on morphology and properties of N-CNTs. The presence of nitrogen species in the hot zone of the quartz reactor decreased the growth rate of N-CNTs down to about one twentieth compared to the growth rate of multi-wall CNTs (MWCNTs). As revealed by electron microscopy studies (SEM, TEM), the individual N-CNTs (half as thick as MWCNTs) grown under the optimal conditions were characterized by a superior straightness of the outer walls, which translated into a high alignment of dense nanotube arrays, i.e., 5 × 10(8) nanotubes per mm(2) (100 times more than for MWCNTs grown in the absence of nitrogen precursor). In turn, the internal crystallographic order of the N-CNTs was found to be of a 'bamboo'-like or 'membrane'-like (multi-compartmental structure) morphology. The nitrogen content in the nanotube products, which ranged from 0.0 to 3.0 wt %, was controlled through the concentration of pyrazine in the feedstock. Moreover, as revealed by Raman/FT-IR spectroscopy, the incorporation of nitrogen atoms into the nanotube walls was found to be proportional to the number of deviations from the sp(2)-hybridisation of graphene C-atoms. As studied by XRD, the temperature and the [pyrazine]/[ferrocene] ratio in the feedstock affected the composition of the catalyst particles, and hence changed the growth mechanism of individual N-CNTs into a 'mixed base-and-tip' (primarily of the base-type) type as compared to the purely 'base'-type for undoped MWCNTs.

Microwave conductivity of sorted CNT assemblies.

Recent progress with tailored growth and post-process sorting enables carbon nanotube (CNT) assemblies with predominantly metallic or semi-conducting concentrations. Cryogenic and microwave measurements performed here show transport dimensionality and overall order increasing with increasing metallic concentration, even in atmospheric doping conditions. By 120 GHz, the conductivity of predominantly semi-conducting assemblies grew to 400% its DC value at an increasing growth rate, while other concentrations a growth rate that tapered off. A generalized Drude model fits to the different frequency dependent behaviors and yields useful quality control parameters such as plasma frequency, mean free path, and degree of localization. As one of the first demonstrations of waveguides fabricated from this material, sorted CNTs from both as-made and post-process sources were inserted into sections of practical micro-strip. With both sources, sorted CNT micro-strip increasingly outperformed the unsorted with increasing frequency-- illustrating that sorted CNT assemblies will be important for high frequency applications.

Lipid nanoscaffolds in carbon nanotube arrays.

We present the fabrication of lipid nanoscaffolds inside carbon nanotube arrays by employing the nanostructural self-assembly of lipid molecules. The nanoscaffolds are finely tunable into model biomembrane-like architectures (planar), soft nanochannels (cylindrical) or 3-dimensionally ordered continuous bilayer structures (cubic). Carbon nanotube arrays hosting the above nanoscaffolds are formed by packing of highly oriented multiwalled carbon nanotubes which facilitate the alignment of lipid nanostructures without requiring an external force. Furthermore, the lipid nanoscaffolds can be created under both dry and hydrated conditions. We show their direct application in reconstitution of egg proteins. Such nanoscaffolds find enormous potential in bio- and nano-technological fields.

Liberation of drugs from multi-wall carbon nanotube carriers.

MWCNTs in the 'nanotube-drug' hybrids can play a role of carriers or additives (enhancers) in the more complex formulations. This work reviews qualitative and quantitative analyses of Drug Delivery Systems (DDSs) based on multi-wall carbon nanotubes (MWCNTs) and their chemically modified analogues (mainly oxidised MWCNTs). A special emphasis was placed on the chemical interactions between drug molecules and the nanotube carrier critical both in the stage of preparation/synthesis of the hybrids and liberation of the drug.

Nitrogen-induced catalyst restructuring for epitaxial growth of multiwalled carbon nanotubes.

The ability to simply and economically produce carbon nanotubes (CNTs) with a defined chiral angle is crucial for the exploitation of nanotubes for their electrical properties. We investigate a diverse range of nitrogen sources for their ability to control CNT chiral angle via epitaxial growth from highly ordered catalyst particles. Through the use of in situ mass and infrared spectrometry, we elucidate the mechanism by which these ordered catalyst particles are formed, showing that ammonia is a key intermediate in the process. Subsequently, the direct addition of a small amount of ammonia to an otherwise standard CNT synthesis is shown to be able to form catalyst particles that grow single chiral angle multiwalled carbon nanotubes. Variation in the ammonia concentration clarifies the catalyst restructuring necessary for the epitaxial growth of carbon nanotubes and subsequent chiral angle control. The simple addition of a nitrogen source is an attractive route for chiral angle control; however, the model also suggests further ways to optimize CNT chiral angle distributions as well as to improve CNT and graphene yield and crystallinity. This understanding also explains the action of ammonia in its widely used role in activating catalyst prior to CNT growth. Finally, this work highlights the uses of novel surface geometries that are achievable through multiphase catalysts.

Dynamics of capillary infiltration of liquids into a highly aligned multi-walled carbon nanotube film.

The physical compatibility of a highly aligned carbon nanotube (HACNT) film with liquids was established using a fast and convenient experimental protocol. Two parameters were found to be decisive for the infiltration process. For a given density of nanotube packing, the thermodynamics of the infiltration process (wettability) were described by the contact angle between the nanotube wall and a liquid meniscus (θ). Once the wettability criterion (θ < 90°) was met, the HACNT film (of free volume equal to 91%) was penetrated gradually by the liquid in a rate that can be linearly correlated to dynamic viscosity of the liquid (η). The experimental results follow the classical theory of capillarity for a steady process (Lucas-Washburn law), where the nanoscale capillary force, here supported by gravity, is compensated by viscous drag. This most general theory of capillarity can be applied in a prediction of both wettability of HACNT films and the dynamics of capillary rise in the intertube space in various technological applications.

Enhancement of the mechanical properties of directly spun CNT fibers by chemical treatment.

Translating the remarkable mechanical properties of individual carbon nanotubes to macroscopic assemblies presents a unique challenge in maximizing the potential of these remarkable entities for new materials. Infinitely long individual nanotubes would represent the ideal molecular building blocks; however, in the case of length-limited nanotubes, typically in the range of micro- and millimeters, an alternative strategy could be based on the improvement of the mechanical coherency between bundles assembling the macroscopic materials, like fibers or films. Here, we present a method to enhance the mechanical performance of fibers continuously spun from a CVD reactor, by a postproduction processing methodology utilizing a chemical agent aided by UV irradiation. The treatment results in an increase of 100% in specific strength and 300% in toughness of the fibers with strength values rocketing to as high as 3.5 GPa SG(-1). An attempt has been made to explore the nature of the chemical modifications introduced in the fiber and the consequential effects on its properties.

Tunable chemistry and morphology of multi-wall carbon nanotubes as a route to non-toxic, theranostic systems.

Nanomedicine is one of the most promising areas of exploitation for multi-walled carbon nanotubes (MWNTs). These 'needle-like' nanovehicles are capable of carrying drug molecules via exo- and endohedral functionalisation and are steerable by an external magnetic field due to the presence of ferromagnetic nanoparticles in the nanotube core (up to 7.3wt.%). These properties make them promising candidates for drug targeting or MRI contrast agents. Particularly, oxidised and nitrogen-doped MWNTs exhibiting enhanced chemical reactivity compared to their unmodified precursors/analogues could be exploited in this field. Here, we assessed the toxicity and intracellular localisation of two different, chemically modified and unmodified nanotubes towards human macrophage cells using a range of toxicity and imaging techniques. Oxidised and N-doped MWNTs were not significantly toxic to HMMs in contrast to unmodified MWNTs. All types of MWNTs entered the cell via active phagocytosis/endocytosis, but also passively by 'self-injection' through the plasma membrane, and were ultimately found in the cytoplasm and possibly also the nucleus. The attained results carry hope to utilise functionalised nanotube vectors as non-cytotoxic controllable drug delivery systems.

Toxicity and imaging of multi-walled carbon nanotubes in human macrophage cells.

Multi-walled carbon nanotubes (MWNTs) have been proposed for use in many applications and concerns about their potential effect on human health have led to the interest in understanding the interactions between MWNTs and human cells. One important technique is the visualisation of the intracellular distribution of MWNTs. We exposed human macrophage cells to unpurified MWNTs and found that a decrease in cell viability was correlated with uptake of MWNTs due to mainly necrosis. Cells treated with purified MWNTs and the main contaminant Fe(2)O(3) itself yielded toxicity only from the nanotubes and not from the Fe(2)O(3). We used 3-D dark-field scanning transmission electron microscopy (DF-STEM) tomography of freeze-dried whole cells as well as confocal and scanning electron microscopy (SEM) to image the cellular uptake and distribution of unpurified MWNTs. We observed that unpurified MWNTs entered the cell both actively and passively frequently inserting through the plasma membrane into the cytoplasm and the nucleus. These suggest that MWNTs may cause incomplete phagocytosis or mechanically pierce through the plasma membrane and result in oxidative stress and cell death.