Tensile properties of graphene nanotube hybrid structures : a molecular dynamics study

Graphene has been reported with record-breaking properties which have opened up huge potential applications. A considerable research has been devoted to manipulate or modify the properties of graphene to target a more smart nanoscale device. Graphene and carbon nanotube hybrid structure (GNHS) is one of the promising graphene derivates, while their mechanical properties have been rarely discussed in literature. Therefore, such a studied is conducted in this paper basing on the large-scale molecular dynamics simulation. The target GNHS is constructed by considering two separate graphene layers that being connected by single-wall carbon nanotubes (SWCNTs) according to the experimental observations. It is found that the GNHSs exhibit a much lower yield strength, Young’s modulus, and earlier yielding comparing with a bilayer graphene sheet. Fracture of studied GNHSs is found to fracture located at the connecting region between carbon nanotubes (CNTs) and graphene. After failure, monatomic chains are normally observed at the front of the failure region, and the two graphene layers at the failure region without connecting CNTs will adhere to each other, generating a bilayer graphene sheet scheme (with a layer distance about 3.4 Å). This study will enrich the current understanding of the mechanical performance of GNHS, which will guide the design of GNHS and shed lights on its various applications.

Atomistic simulation of surface functionalization on the interfacial properties of graphene-polymer nanocomposites

Graphene has been increasingly used as nano sized fillers to create a broad range of nanocomposites with exceptional properties. The interfaces between fillers and matrix play a critical role in dictating the overall performance of a composite. However, the load transfer mechanism along graphene-polymer interface has not been well understood. In this study, we conducted molecular dynamics simulations to investigate the influence of surface functionalization and layer length on the interfacial load transfer in graphene polymer nanocomposites. The simulation results show that oxygen-functionalized graphene leads to larger interfacial shear force than hydrogen-functionalized and pristine ones during pull-out process. The increase of oxygen coverage and layer length enhances interfacial shear force. Further increase of oxygen coverage to about 7% leads to a saturated interfacial shear force. A model was also established to demonstrate that the mechanism of interfacial load transfer consists of two contributing parts, including the formation of new surface and relative sliding along the interface. These results are believed to be useful in development of new graphene-based nanocomposites with better interfacial properties.

Gas sensing of ruthenium implanted tungsten oxide thin films

Different amounts of Ru were implanted into thermally evaporated WO3 thin films by ion implantation. The films were subsequently annealed at 600oC for 2 hours in air to remove defects generated during the ion implantation. The Ru concentrations of four samples have been quantified by Rutherford Backscattering Spectrometry as 0.8, 5.5, 9 and 11.5 at%. The un-implanted WO3 films were highly porous but the porosity decreased significantly after ion implantation as observed by Transmission Electron Microscopy and Scanning Electron Microscopy. The thickness of the films also decreased with increasing Ru-ion dose, which is mainly due to densification of the porous films during ion implantation. From Raman spectroscopy two peaks at 408 and 451 cm-1 (in addition to the typical vibrational peaks of the monoclinic WO3 phase) associated with Ru were observed. Their intensity increased with increasing Ru concentration. X-Ray Photoelectron Spectroscopy showed a metallic state of Ru with binding energy of Ru 3d5/2 at 280.1 eV. This peak position remained almost unchanged with increasing Ru concentration. The resistances of the Ru-implanted films were found to increase in the presence of NO2 and NO with higher sensor response to NO2. The effect of Ru concentration on the sensing performance of the films was not explicitly observed due to reduced film thickness and porosity with increasing Ru concentration. However, the results indicate that the implantation of Ru into WO3 films with sufficient film porosity and film thickness can be beneficial for NO2 sensing at temperatures in the range of 250°C to 350°C.

Optical coupling of Au nanoparticles on vertical graphenes to maximize SERS response

Gold particle interaction with few-layer graphenes is of interest for the development of numerous optical nanodevices. The results of numerical studies of the coupling of gold nanoparticles with few-layer vertical graphene sheets are presented. The field strengths are computed and the optimum nanoparticle configurations for the formation of SERS hotpots are obtained. The nanoparticles are modeled as 8 nm diameter spheres atop 1.5 nm (5 layers) graphene sheet. The vertical orientation is of particular interest as it is possible to use both sides of the graphene structure and potentially double the number of particles in the system. Our results show that with the addition of an opposing particle a much stronger signal can be obtained as well as the particle separation can be controlled by the number of atomic carbon layers. These results provide further insights and contribute to the development of next-generation plasmonic devices based on nanostructures with hybrid dimensionality.

Comparative study of photocatalytic performance of titanium oxide spheres assembled by nanorods, nanoplates and nanosheets

TiO2 spheres assembled by nanorods, nanoplates and nanosheets were fabricated by facile hydrothermal/solvothermal methods. The three samples were thoroughly characterised by scanning electron microscopy, X-ray diffraction, the Brunauer–Emmett–Teller method and UV spectroscopy. The surface area of spheres assembled by nanosheets was 83.9 m2g–1, which is larger than that obtained for nanorods (10.8 m2g–1) and nanoplates (6.31 m2g–1). Their photocatalytic performance was evaluated in terms of the decomposition rate of methyl orange in these three samples under UV irradiation. The best photoactivity was observed in the samples constructed from nanosheets.

One-step synthesis of titanium oxide with trilayer structure for dye-sensitized solar cells

Titanium oxide films with trilayer structure grown on fluorine doped tin oxide substrate were prepared from one-step hydrothermal process. The trilayer structure consists of microflowers, nanorod array and compact nanoparticulates, which is expected to possess the merits of good light harvesting, a high electron transport rate, while avoiding the issues of electron shunting. The photovoltaic performance was comprehensively studied and a 60% enhancement in short circuit photocurrent density was found from microflowers contribution as a light scattering layer. This unique trilayer structure exhibits great potential application in future dye-sensitized solar cells.

Tensile properties of a boron/nitrogen-doped carbon nanotube–graphene hybrid structure

Doping is an effective approach that allows for the intrinsic modification of the electrical and chemical properties of nanomaterials. Recently, a graphene and carbon nanotube hybrid structure (GNHS) has been reported, which extends the excellent properties of carbon-based materials to three dimensions. In this paper, we carried out a first-time investigation on the tensile properties of the hybrid structures with different dopants. It is found that with the presence of dopants, the hybrid structures usually exhibit lower yield strength, Young’s modulus, and earlier yielding compared to that of a pristine hybrid structure. For dopant concentrations below 2.5% no significant reduction of Young’s modulus or yield strength could be observed. For all considered samples, the failure is found to initiate at the region where the nanotubes and graphene sheets are connected. After failure, monatomic chains are normally observed around the failure region. Dangling graphene layers without the separation of a residual CNT wall are found to adhere to each other after failure with a distance of about 3.4 Å. This study provides a fundamental understanding of the tensile properties of the doped graphene–nanotube hybrid structures, which will benefit the design and also the applications of graphene-based hybrid materials.

Electron capture of tetracyanoethylene oxide in the gas phase. Rearrangement of the parent radical anion to form [(NC)(3)C](-). A joint experimental and ab initio study

Capture of an electron by tetracyanoethylene oxide can initiate a number of decomposition pathways. One of these decompositions yields [(NC)3C]− as the ionic product. Ab initio calculations (at the B3LYP/6-31+G∗ level of theory) indicate that the formation of [(NC)3C]− is initiated by capture of an electron into the LUMO of tetracyanoethylene oxide to yield the anion radical [(NC)2C–O–C(CN)2]−· that undergoes internal nucleophilic substitution to form intermediate [(NC)3C–OCCN]−·. This intermediate dissociates to form [(NC)3C]− (m/z 90) as the ionic product. The radical (NC)3C· has an electron affinity of 4.0 eV (385 kJ mol−1). Ab initio calculations show that [(NC)3C]− is trigonal planar with the negative charge mainly on the nitrogens. A pictorial representation of this structure is the resonance structure formed from three degenerate contributing structures (NC)2–CCN−. The other product of the reaction is nominally (NCCO)·, but there is no definitive experimental evidence to indicate whether this radical survives intact, or decomposes to NC· and CO. The overall process [(NC)2C–O–C(CN)2]−· → [(NC)3C]− + (NCCO)· is calculated to be endothermic by 21 kJ mol−1 with an overall barrier of 268 kJ mol−1.

Tailored interventions based on exhaled nitric oxide versus clinical symptoms for asthma in children and adults

Background The measurement of severity and control of asthma in both children and adults can be based on subjective or objective measures. It has been advocated that fractional exhaled nitric oxide (FeNO) can be used to monitor airway inflammation as it correlates with some markers of asthma. Interventions for asthma therapies have been traditionally based on symptoms and/or spirometry. Objectives To evaluate the efficacy of tailoring asthma interventions based on exhaled nitric oxide in comparison to clinical symptoms (with or without spirometry/peak flow) for asthma related outcomes in children and adults. Search methods We searched the Cochrane Airways Group Specialised Register of Trials, the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE, EMBASE and reference lists of articles. The last search was completed in February 2009. Selection criteria All randomised controlled comparisons of adjustment of asthma therapy based on exhaled nitric oxide compared to traditional methods (primarily clinical symptoms and spirometry/peak flow). Data collection and analysis Results of searches were reviewed against pre-determined criteria for inclusion. Relevant studies were independently selected in duplicate. Two authors independently assessed trial quality and extracted data. Authors were contacted for further information with response from one. Main results Two studies have been added for this update, which now includes six (2 adults and 4 children/adolescent) studies; these studies differed in a variety of ways including definition of asthma exacerbations, FeNO cut off levels, the way in which FeNO was used to adjust therapy and duration of study. Of 1053 participants randomised, 1010 completed the trials. In the meta-analysis, there was no significant difference between groups for the primary outcome of asthma exacerbations or for other outcomes (clinical symptoms, FeNO level and spirometry). In post-hoc analysis, a significant reduction in mean final daily dose inhaled corticosteroid per adult was found in the group where treatment was based on FeNO in comparison to clinical symptoms, (mean difference -450 mcg; 95% CI -677 to -223 mcg budesonide equivalent/day). However, the total amount of inhaled corticosteroid used in one of the adult studies was 11% greater in the FeNO arm. In contrast, in the paediatric studies, there was a significant increase in inhaled corticosteroid dose in the FeNO strategy arm (mean difference of 140 mcg; 95% CI 29 to 251, mcg budesonide equivalent/day). Authors' conclusions Tailoring the dose of inhaled corticosteroids based on exhaled nitric oxide in comparison to clinical symptoms was carried out in different ways in the six studies and found only modest benefit at best and potentially higher doses of inhaled corticosteroids in children. The role of utilising exhaled nitric oxide to tailor the dose of inhaled corticosteroids cannot be routinely recommended for clinical practice at this stage and remains uncertain.

A systematic review and meta-analysis : tailoring asthma treatment on eosinophilic markers (exhaled nitric oxide or sputum eosinophils)

Asthma severity and control can be measured both subjectively and objectively. Traditionally asthma treatments have been individualised using symptoms and spirometry/peak flow. Increasingly treatment tailored in accordance with inflammatory markers (sputum eosinophil counts or fractional exhaled nitric oxide (FeNO) data) is advocated as an alternative strategy. The objective of this review was to evaluate the efficacy of tailoring asthma interventions based on inflammatory markers (sputum analysis and FeNO) in comparison with clinical symptoms (with or without spirometry/peak flow) for asthma-related outcomes in children and adults. Cochrane Airways Group Specialised Register of Trials, the Cochrane Central Register of Controlled Trials (CENTRAL), MEDLINE, EMBASE and reference lists of articles were searched. The last searches were in February 2009. All randomised controlled comparisons of adjustment of asthma treatment based on sputum analysis or FeNO compared with traditional methods (primarily clinical symptoms and spirometry/peak flow) were selected. Results of searches were reviewed against predetermined criteria for inclusion. Relevant studies were selected, assessed and data extracted independently by at least two people. The trial authors were contacted for further information. Data were analysed as 'intervention received' and sensitivity analyses performed. Six (2 adults and 4 children/adolescent) studies utilising FeNO and three adult studies utilising sputum eosinophils were included. These studies had a degree of clinical heterogeneity including definition of asthma exacerbations, duration of study and variations in cut-off levels for percentage of sputum eosinophils and FeNO to alter management in each study. Adults who had treatment adjusted according to sputum eosinophils had a reduced number of exacerbations compared with the control group (52 vs. 77 patients with >=1 exacerbation in the study period; p=0.0006). There was no significant difference in exacerbations between groups for FeNO compared with controls. The daily dose of inhaled corticosteroids at the end of the study was decreased in adults whose treatment was based on FeNO in comparison with the control group (mean difference -450.03 mug, 95% CI -676.73 to -223.34; p<0.0001). However, children who had treatment adjusted according to FeNO had an increase in their mean daily dose of inhaled corticosteroids (mean difference 140.18 mug, 95% CI 28.94 to 251.42; p=0.014). It was concluded that tailoring of asthma treatment based on sputum eosinophils is effective in decreasing asthma exacerbations. However, tailoring of asthma treatment based on FeNO levels has not been shown to be effective in improving asthma outcomes in children and adults. At present, there is insufficient justification to advocate the routine use of either sputum analysis (due to technical expertise required) or FeNO in everyday clinical practice.

Cough and exhaled nitric oxide levels : what happens with exercise?

Cough associated with exertion is often used as a surrogate marker of asthma. However, to date there are no studies that have objectively measured cough in association with exercise in children. Our primary aim was to examine whether children with a pre-existing cough have an increase in cough frequency during and post-exercise. We hypothesized that children with any coughing illness will have an increase in cough frequency post-exercise regardless of the presence of exercise-induced broncho-constriction (EIB) or atopy. In addition, we hypothesized that Fractional exhaled nitric oxide (FeNO) levels decreases post-exercise regardless of the presence of EIB or atopy. Children with chronic cough and a control group without cough undertook an exercise challenge, FeNO measurements and a skin prick test, and wore a 24-h voice recorder to objectively measure cough frequency. The association between recorded cough frequency, exercise, atopy, and presence of EIB was tested. We also determined if the change in FeNO post exercise related to atopy or EIB. Of the 50 children recruited (35 with cough, 15 control), 7 had EIB. Children with cough had a significant increase in cough counts (median 7.0, inter-quartile ranges, 0.5, 24.5) compared to controls (2.0, IQR 0, 5.0, p = 0.028) post-exercise. Presence of atopy or EIB did not influence cough frequency. FeNO level was significantly lower post-exercise in both groups but the change was not influenced by atopy or EIB. Cough post-exertion is likely a generic response in children with a current cough. FeNO level decreases post-exercise irrespective of the presence of atopy or EIB. A larger study is necessary confirm or refute our findings.

Modeling nitrous oxide emissions from irrigated agriculture : testing DayCent with high-frequency measurements

A unique high temporal frequency dataset from an irrigated cotton-wheat rotation was used to test the agroecosystem model DayCent to simulate daily N2O emissions from sub-tropical vertisols under different irrigation intensities. DayCent was able to simulate the effect of different irrigation intensities on N2O fluxes and yield, although it tended to overestimate seasonal fluxes during the cotton season. DayCent accurately predicted soil moisture dynamics and the timing and magnitude of high fluxes associated with fertilizer additions and irrigation events. At the daily scale we found a good correlation of predicted vs. measured N2O fluxes (r2 = 0.52), confirming that DayCent can be used to test agricultural practices for mitigating N2O emission from irrigated cropping systems. A 25 year scenario analysis indicated that N2O losses from irrigated cotton-wheat rotations on black vertisols in Australia can be substantially reduced by an optimized fertilizer and irrigation management system (i.e. frequent irrigation, avoidance of excessive fertiliser application), while sustaining maximum yield potentials.

Resonance of graphene nanoribbons doped with nitrogen and boron : a molecular dynamics study

Based on its enticing properties, graphene has been envisioned with applications in the area of electronics, photonics, sensors, bioapplications and others. To facilitate various applications, doping has been frequently used to manipulate the properties of graphene. Despite a number of studies conducted on doped graphene regarding its electrical and chemical properties, the impact of doping on the mechanical properties of graphene has been rarely discussed. A systematic study of the vibrational properties of graphene doped with nitrogen and boron is performed by means of a molecular dynamics simulation. The influence from different density or species of dopants has been assessed. It is found that the impacts on the quality factor, Q, resulting from different densities of dopants vary greatly, while the influence on the resonance frequency is insignificant. The reduction of the resonance frequency caused by doping with boron only is larger than the reduction caused by doping with both boron and nitrogen. This study gives a fundamental understanding of the resonance of graphene with different dopants, which may benefit their application as resonators.

Monocyte chemoattractant protein-1 and nitric oxide promote adipogenesis in a model that mimics obesity

Objective: An increasing body of evidence is emerging linking adipogenesis and inflammation. Obesity, alone or as a part of the metabolic syndrome, is characterized by a state of chronic low-level inflammation as revealed by raised plasma levels of inflammatory cytokines and acute-phase proteins. If inflammation can, in turn, increase adipose tissue growth, this may be the basis for a positive feedback loop in obesity. We have developed a tissue engineering model for growing adipose tissue in the mouse that allows quantification of increases in adipogenesis. In this study, we evaluated the adipogenic potential of the inflammogens monocyte chemoattractant protein (MCP)-I and zymosan-A (Zy) in a murine tissue engineering model. Research Methods and Procedures: MCP-I and Zy were added to chambers filled with Matrigel and fibroblastgrowth factor 2. To analyze the role of inducible nitric oxide synthase (iNOS), the iNOS inhibitor aminoguanidine was added to the chamber. Results: Our results show that MCP-I generated proportionally large quantities of new adipose tissue. This neoadipogenesis was accompanied by an ingrowth of macrophages and could be mimicked by Zy. Aminoguanidine significantly inhibited the formation of adipose tissue. Discussion: Our findings demonstrate that low-grade inflammation and iNOS expression are important factors in adipogenesis, Because fat neoformation in obesity and the metabolic syndrome is believed to be mediated by macrophage-derived proinflammatory cytokines, this adipose tissue engineering system provides a model that could potentially be used to further unravel the pathogenesis of these two metabolic disorders.

Tuneable resonance properties of graphene by nitrogen-dopant

Doping as one of the popular methods to manipulate the properties of nanomaterials has received extensive application in deriving different types of graphene derivates, while the understanding of the resonance properties of dopant graphene is still lacking in literature. Based on the large-scale molecular dynamics simulation, reactive empirical bond order potential, as well as the tersoff potential, the resonance properties of N-doped graphene were studied. The studied samples were established according to previous experiments with the N atom’s percentage ranging from 0.43%-2.98%, including three types of N dopant locations, i.e., graphitic N, pyrrolic N and pyridinic N. It is found that different percentages of N-dopant exert different influence to the resonance properties of the graphene, while the amount of N-dopant is not the only factor that determines its impact. For all the considered cases, a relative large percentage of N-dopant (2.98% graphitic N-dopant) is observed to introduce significant influence to the profile of the external energy, and thus lead to an extremely low Q-factor comparing with that of the pristine graphene. The most striking finding is that, the natural frequency of the defective graphene with N-dopant appears uniformly larger than that of the pristine defective graphene. While for the perfect graphene, the N-dopant shows less influence to its natural frequency. This study will enrich the current understanding of the influence of dopants on graphene, which will eventually shed lights on the design of different molecules-doped graphene sheet.