Synthesis of Microscopic 3D Graphene for High-Performance Supercapacitors with Ultra-High Areal Capacitance.

Despite graphene being considered an ideal supercapacitor electrode material, its use in commercial devices is limited because few methods exist to produce high-quality graphene at a large scale and low cost. A simple method is reported to synthesize 3D graphene by graphenization of coal tar pitch with a K2CO3 catalyst. This produces 3D graphenes with high specific surface areas up to 2113 m2 g-1 and exceptional crystallinity (Raman ID/IG as low as ≈0.15). The material has an outstanding specific capacitance of 182.6 F g-1 at a current density of 1.0 A g-1. This occurs at a mass loading of 30 mg cm-2 which is 3 times higher than commercial requirements, yielding an ultra-high areal capacitance of 5.48 F cm-2. The K2CO3 is recycled and reused over 10 cycles with material quality and electrocapacitive performance of 3D graphene retained and verified after each cycle. The synthesis method and resulting electrocapacitive performance properties create new opportunities for using 3D graphene more broadly in practical supercapacitor devices.

High-performance cementitious composites containing nanostructured carbon additives made from charred coal fines.

Carbon-based nanomaterials, such as carbon nanoplatelets, graphene oxide, and carbon quantum dots, have many possible end-use applications due to their ability to impart unique mechanical, electrical, thermal, and optical properties to cement composites. Despite this potential, these materials are rarely used in the construction industry due to high material costs and limited data on performance and durability. In this study, domestic coal is used to fabricate low-cost carbon nanomaterials that can be used economically in cement formulations. A range of chemical and physical processing approaches are employed to control the size, morphology, and chemical functionalization of the carbon nanomaterial, which improves its miscibility with cement formulations and its impact on mechanical properties and durability. At loadings of 0.01 to 0.07 wt.% of coal-derived carbon nanomaterial, the compressive and flexural strength of cement samples are enhanced by 24% and 23%, respectively, in comparison to neat cement. At loadings of 0.02 to 0.06 wt.%, the compressive and flexural strength of concrete composites increases by 28% and 21%, respectively, in comparison to neat samples. Additionally, the carbon nanomaterial additives studied in this work reduce cement porosity by 36%, permeability by 86%, and chloride penetration depth by 60%. These results illustrate that low-loadings of coal-derived carbon nanomaterial additives can improve the mechanical properties, durability, and corrosion resistance of cement composites.

Optimization of Oligomer Chitosan/Polyvinylpyrrolidone Coating for Enhancing Antibacterial, Hemostatic Effects and Biocompatibility of Nanofibrous Wound Dressing.

A synergistic multilayer membrane design is necessary to satisfy a multitude of requirements of an ideal wound dressing. In this study, trilayer dressings with asymmetric wettability, composed of electrospun polycaprolactone (PCL) base membranes coated with oligomer chitosan (COS) in various concentrations of polyvinylpyrrolidone (PVP), are fabricated for wound dressing application. The membranes are expected to synergize the hygroscopic, antibacterial, hemostatic, and biocompatible properties of PCL and COS. The wound dressing was coated by spraying the solution of 3% COS and 6% PVP on the PCL base membrane (PVP6-3) three times, which shows good interaction with biological subjects, including bacterial strains and blood components. PVP6-3 samples confirm the diameter of inhibition zones of 20.0 ± 2.5 and 17.9 ± 2.5 mm against Pseudomonas aeruginosa and Staphylococcus aureus, respectively. The membrane induces hemostasis with a blood clotting index of 74% after 5 min of contact. In the mice model, wounds treated with PVP6-3 closed 95% of the area after 10 days. Histological study determines the progression of skin regeneration with the construction of granulation tissue, new vascular systems, and hair follicles. Furthermore, the newly-growth skin shares structural resemblances to that of native tissue. This study suggests a simple approach to a multi-purpose wound dressing for clinical treatment.

Potency of bisresorcinol from Heliciopsis terminalis on skin aging: in vitro bioactivities and molecular interactions.

BACKGROUND: A bisresorcinol was isolated as the main constituent of Heliciopsis terminalis's trunk (Proteaceae). Recently, resorcinol is applied as an active whitening agent in various cosmetic products. Because of the structural mimic to resorcinol, benefits of the bisresorcinol as an aging-enzyme antagonist were demonstrated in this study. METHODS: The bisresorcinol was purified from the crude ethanolic extract of H. terminalis's trunk by solvent extraction and preparative chromatography, respectively. Inhibitory activity on collagenase, elastase, and tyrosinase of the compound was investigated by using a different spectroscopic technique. Molecular docking was carried out to predict possible interactions of the substance around the enzyme active sites. RESULTS: The IC50 values on collagenase of the bisresorcinol and caffeic acid were 156.7 ± 0.7 and 308.9 ± 1.6 µmole L-1, respectively. For elastase activity, the IC50 of 33.2 ± 0.5 and 34.3 ± 0.3 µmole L-1 was respectively determined for the bisresorcinol and ursolic acid. The bisresorcinol was inhibitory to tyrosinase by exhibiting the IC50 of 22.8 µmole L-1, and that of 78.4 µmole L-1 was present for ß-arbutin. The bisresorcinol bound to collagenase, elastase, and tyrosinase with the respective binding energies of -5.89, -5.69, and -6.57 kcal mol-1. These binding energies were in the same ranges of tested inhibitors. The aromatic phenol groups in the structure were responsible for principle as well as supporting binding interactions with enzymes. Hydrogen binding due to hydroxyl groups and π-related attractive forces from an aromatic ring(s) provided binding versatility to bisresorcinol. CONCLUSION: The bisresorcinol purified from H. terminalis might be useful for inclusion in cosmetic products as an aging-enzyme antagonist.

Site-Specific Sodiation Mechanisms of Selenium in Microporous Carbon Host.

We combined advanced TEM (HRTEM, HAADF, EELS) with solid-state (SS)MAS NMR and electroanalytical techniques (GITT, etc.) to understand the site-specific sodiation of selenium (Se) encapsulated in a nanoporous carbon host. The architecture employed is representative of a wide number of electrochemically stable and rate-capable Se-based sodium metal battery (SMB) cathodes. SSNMR demonstrates that during the first sodiation, the Se chains are progressively cut to form an amorphous mixture of polyselenides of varying lengths, with no evidence for discrete phase transitions during sodiation. It also shows that Se nearest the carbon pore surface is sodiated first, leading to the formation of a core-shell compositional profile. HRTEM indicates that the vast majority of the pore-confined Se is amorphous, with the only localized presence of nanocrystalline equilibrium Na2Se2 (hcp) and Na2Se (fcc). A nanoscale fracture of terminally sodiated Na-Se is observed by HAADF, with SSNMR, indicating a physical separation of some Se from the carbon host after the first cycle. GITT reveals a 3-fold increase in Na+ diffusivity at cycle 2, which may be explained by the creation of extra interfaces. These combined findings highlight the complex phenomenology of electrochemical phase transformations in nanoconfined materials, which may profoundly differ from their "free" counterparts.

Growth in children infected with HIV receiving anti-retroviral therapy in Vietnam.

BACKGROUND: There are currently two markers used to monitor treatment response to anti-retroviral therapy (ART) in HIV-infected children: CD4 T-cell count and HIV viral load; but analysis of these could be challenging in resource-poor countries. The aim of this study was therefore to determine whether change in growth parameters such as weight-for-age Z score (WAZ), height-for-age Z score (HAZ) and body mass index-for-age Z score (BMIZ) is associated with treatment response in HIV-infected children. METHODS: This was a nested case-control study, in which the data were collected at enrolment and then periodically every 6 months for a total 36 month follow up of 107 HIV-infected children enrolled and treated at National Hospital of Pediatrics, Vietnam. RESULTS: At treatment initiation, WAZ, HAZ and BMIZ were not significantly higher in the treatment success (TS) group compared with the treatment failure (TF) group. After ART initiation, WAZ and HAZ increased, and this was significant in the TS group (from -1.5 to -0.54, P < 0.01 and from -2.06 to -0.84, P < 0.01, respectively). Low HAZ was significantly associated with TF (HR, 0.71; 95% CI: 0.54-0.92). CONCLUSION: Height-for-age Z score was the most sensitive growth parameter in prediction of the treatment response. In order to use growth parameters, particularly HAZ as a prognosis marker for TF in clinical practice, further research should be conducted to evaluate the role of growth parameters and their effects on treatment response.

Elevation of immunoglobulin levels is associated with treatment failure in HIV-infected children in Vietnam.

BACKGROUND: HIV-infected children suffer from higher levels of treatment failure compared to adults. Immunoactivation, including humoral immunoactivation reflected by increased immunoglobulin levels, is believed to occur early during HIV infection. Therefore, we wanted investigate alteration in immunoglobulin levels in association with treatment response in HIV-infected children. METHODS: A nested case-control study was conducted using clinical data collected from 68 HIV-infected children enrolled at the National Hospital of Pediatrics, Vietnam. RESULTS: The results showed that immunoglobulin levels, CD4 T-cell counts, CD4 T-cell percentage, and HIV load were significantly higher in the treatment-failure group than the treatment-success group at treatment initiation. IgG and IgA levels were negatively correlated with CD4 T-cell counts (P=0.049 and P<0.01, respectively) and positively correlated with HIV load (P=0.04 and P=0.02, respectively). In addition, IgG and IgA levels were independently associated with treatment response, analyzed by Cox regression analysis (HR 1.19 [P=0.049] and HR 1.69 [P<0.01], respectively). CONCLUSION: Elevation of IgA levels occurred early during HIV infection, and might have a prognostic role in treatment response.

Clinical characteristics of pediatric HIV-1 patients treated with first-line antiretroviral therapy in Vietnam: a nested case-control study.

OBJECTIVES: Over the past decades, Vietnam has made great strides in reducing the rate of mortality in HIV-related deaths, due to increased access of antiretroviral therapy (ART); however, given the significantly high level of treatment failure (TF), it is essential to identify markers that describe the failure of ART in HIV-1 infected children. METHODS: A nested case-control study was conducted with clinical data collected from 101 HIV-infected children [26 TF and 75 treatment success (TS)] at National Hospital of Pediatrics, Vietnam (2008-2012). RESULTS: The results showed that certain factors including height, weight, vaccination with Hepatitis B, and platelet were significantly different between TF and TS before starting the treatment. In addition, age to start the treatment, CD4 percentage, and opportunistic infection were found to significantly predict treatment outcome most frequently, implying the importance of clinical markers in the treatment response by Cox regression analysis. CONCLUSIONS: There is an inherent complexity within clinical markers that is challenging to determine HIV-pediatric failure and further research is needed to build a complete picture to guide clinical, evidence-based practice.

Insight into Nanoparticle Charging Mechanism in Nonpolar Solvents To Control the Formation of Pt Nanoparticle Monolayers by Electrophoretic Deposition.

We report on the formation of Pt nanoparticle monolayers by electrophoretic deposition from nonpolar solvents. First, the growth kinetics of Pt nanoparticles prepared by the reverse micelle technique are described in detail. Second, a model of nanoparticle charging in nonpolar media is discussed and methods to control the nanoparticle charging are proposed. Finally, essential parameters of the electrophoretic deposition process to control the deposition of nanoparticle monolayers are discussed and mechanisms of their formation are analyzed.

Facile electrodeposition of reduced graphene oxide hydrogels for high-performance supercapacitors.

We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g(-1) at a current density of 10 A g(-1) when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively.

Superhydrophobic silanized melamine sponges as high efficiency oil absorbent materials.

Superhydrophobic sponges and sponge-like materials have attracted great attention recently as potential sorbent materials for oil spill cleanup due to their excellent sorption capacity and high selectivity. A major challenge to their broad use is the fabrication of superhydrophobic sponges with superior recyclability, good mechanical strength, low cost, and manufacture scalability. In this study, we demonstrate a facile, cost-effective, and scalable method to fabricate robust, superhydrophobic sponges through the silanization of commercial melamine sponges via a solution-immersion process. The silanization was achieved through secondary amine groups on the surface of the sponge skeletons with alkylsilane compounds, forming self-assembled monolayers on the surface of sponge skeletons. This resulted in our ability to tune the surface properties of the sponges from being hydrophilic to superhydrophobic with a water contact angle of 151.0°. The superhydrophobic silanized melamine sponge exhibited excellent sorption capacity for a wide range of organic solvents and oils, from 82 to 163 times its own weight, depending on the polarity and density of the employed organic solvents and oils, and high selectivity and outstanding recyclability with an absorption capacity retention greater than 90% after 1000 cycles. These findings offer an effective approach for oil spill containment and environmental remediation.

Effects of the alkylamine functionalization of graphene oxide on the properties of polystyrene nanocomposites.

Alkylamine-functionalized graphene oxides (FGOs) have superior dispersibility in low-polar solvents and, as a result, they interact with low-polar polymers such as polystyrene. In this work, the functionalization of graphene oxide using three types of alkylamines, octylamine (OA), dodecylamine (DDA), and hexadecylamine (HDA), was performed, and nanocomposites of polystyrene (PS) and FGOs were prepared via solution blending. Different dispersions of FGOs over PS were obtained for the three alkylamines, and the properties of the PS composites were influenced by the length of the alkylamine. A better thermal stability was observed with a longer chain length of the alkylamine. On the other hand, functionalization with the shortest chain length alkylamine resulted in the highest increase in the storage modulus (3,640 MPa, 140%) at a 10 wt.% loading of FGO.

Dispersibility of reduced alkylamine-functionalized graphene oxides in organic solvents.

The alkylamine functionalization of graphene oxide is well known as an efficient approach to prepare reduced functionalized graphene oxide (RFGO) that is highly dispersible in organic solvents. Herein, we systematically investigated the effects of long-chain alkylamine functionalization of graphene oxide on the organic solvent dispersibility and electrical conductivity of RFGO. Three kinds of alkylamines, octylamine, dodecylamine and hexadecylamine, were chosen as functionalization agents. The alkylamine functionalization of graphene oxide was characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis and X-ray diffraction. RFGO using octylamine exhibited the best electrical conductivity of greater than 180 S/m. All of the RFGOs had excellent dispersibility, up to 3.0 mg/mL, in organic solvents, with Hansen solubility parameters in the range of 6.3<(δ(p)+δ(h))<13.7.

Highly efficient reduction of graphene oxide using ammonia borane.

We introduce ammonia borane, a versatile reducing agent for graphene oxide (GO) reduction in both aqueous and organic solvents; it is nontoxic and more effective than hydrazine. More interestingly, ammonia borane reduction of GO tetrahydrofuran produced higher nitrogen- and boron-doped graphene that exhibited high supercapacitor performance.

Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15.

The adsorption of a complex mixture of 12 selected pharmaceuticals to trimethylsilylated mesoporous SBA-15 (TMS-SBA-15) has been investigated by batch adsorption experiments. The adsorption of pharmaceuticals to TMS-SBA-15 was highly dependent on the solution pH and pharmaceutical properties (i.e., hydrophobicity (logKow) and acidity (pKa)). Good log-log linear relationships between the adsorption (Kd) and pH-dependent octanol-water coefficients (Kow(pH)) were then established among the neutral, anionic, and cationic compounds, suggesting hydrophobic interaction as a primary driving force in the adsorption. In addition, the neutral species of each compound accounted for a major contribution to the overall compound adsorption onto TMS-SBA-15. The adsorption kinetics of pharmaceuticals was evaluated by the nonlinear first-order and pseudo-second-order models. The first-order model gave a better fit for five pharmaceuticals with lower adsorption capacity, whereas the pseudo-second-order model fitted better for seven pharmaceuticals having higher adsorption capacity. In the same group of properties, pharmaceuticals having higher adsorption capacity exhibited faster adsorption rates. The rate-limiting steps for adsorption of pharmaceuticals onto TMS-SBA-15 are boundary layer diffusion and intraparticle diffusion including diffusion in mesopores and micropores. In addition, the adsorption of pharmaceuticals to TMS-SBA-15 was not influenced by the change of initial pharmaceutical concentration (10-100µgL(-1)) and the presence of natural organic matter.

Nanostructured graphene/Fe3O4 incorporated polyaniline as a high performance shield against electromagnetic pollution.

The development of high-performance shielding materials against electromagnetic pollution requires mobile charge carriers and magnetic dipoles. Herein, we meet the challenge by building a three-dimensional (3D) nanostructure consisting of chemically modified graphene/Fe3O4(GF) incorporated polyaniline. Intercalated GF was synthesized by the in situ generation of Fe3O4 nanoparticles in a graphene oxide suspension followed by hydrazine reduction, and further in situ polymerization with aniline to form a polyaniline composite. Spectroscopic analysis demonstrates that the presence of GF hybrid structures facilitates strong polarization due to the formation of a solid-state charge-transfer complex between graphene and polyaniline. This provides proper impedance matching and higher dipole interaction, which leads to the high microwave absorption properties. The higher dielectric loss (ε'' = 30) and magnetic loss (µ'' = 0.2) contribute to the microwave absorption value of 26 dB (>99.7% attenuation), which was found to depend on the concentration of GF in the polyaniline matrix. Moreover, the interactions between Fe3O4, graphene and polyaniline are responsible for superior material characteristics, such as excellent environmental (chemical and thermal) degradation stability and good electric conductivity (as high as 260 S m(-1)).

Morphology and properties of segregated-network chemically converted graphene-poly(vinyl chloride) composite.

The poly(vinyl chloride)-chemically converted graphene (PVC-CCG) composite prepared using colloidal blending, filtration and drying, and followed by compression molding at 175 degrees C, exhibited an electrical percolation threshold as low as 0.4 wt% and an electrical conductivity as high as 46.5 S/m corresponding to 4.0 wt% of CCG. The high electrical conductivity of the PVC-CCG composite was the result of minimizing the amount of surfactant using various methods. For example, the PVC latex was prepared using miniemulsion polymerization, and the CCG was synthesized via hydrazine reduction of graphene oxide at ambient temperature in order to diminish the irreversible agglomeration of CCG sheets during reduction. The morphology of the PVC-CCG composite, characterized using scanning electron microscopy in charge contrast mode, revealed that the CCG sheets created a segregated network in the PVC matrix.

Superior dispersion of highly reduced graphene oxide in N,N-dimethylformamide.

Here, we report the effect of temperature on the extent of hydrazine reduction of graphene oxide in N,N-dimethylformamide (DMF)/water (80/20 v/v) and the dispersibility of the resultant graphene in DMF. The highly reduced graphene oxide (HRG) had a high C/O ratio and good dispersibility in DMF. The good dispersibility of HRGs is due to the solvation effect of DMF on graphene sheets during the hydrazine reduction, which diminishes the formation of irreversible graphene sheet aggregates. The dispersibility of the HRGs was varied from 1.66 to 0.38 mg/mL when the reduction temperature increased from 25 °C to 80 °C. The dispersibility of the HRGs was inversely proportional to the electrical conductivity of the HRGs, which varied from 17,400 to 25,500 S/m. The relationships between the C/O ratio, electrical conductivity, and dispersibility of the HRGs were determined and these properties were found to be easily controlled by manipulating the reduction temperature.

Highly conductive poly(methyl methacrylate) (PMMA)-reduced graphene oxide composite prepared by self-assembly of PMMA latex and graphene oxide through electrostatic interaction.

We report a simple, environmentally friendly approach for preparing highly conductive poly(methyl methacrylate)-reduced graphene oxide (PMMA-RGO) composites by self-assembly of positively charged PMMA latex particles and negatively charged graphene oxide sheets through electrostatic interactions, followed by hydrazine reduction. The PMMA latex was prepared by surfactant-free emulsion polymerization using a cationic free radical initiator, which created the positive charges on the surface of the PMMA particle. By mixing PMMA latex with a graphene oxide dispersion, positively charged PMMA particles easily assembled with negatively charged graphene oxide sheets through electrostatic interaction. The obtained PMMA-RGO exhibited excellent electrical properties with a percolation threshold as low as 0.16 vol % and an electrical conductivity of 64 S/m at only 2.7 vol %. Moreover, the thermomechanical properties of PMMA-RGO were also significantly improved. The storage modulus of PMMA-RGO increased by about 30% at 4.0 wt % RGO at room temperature while the glass transition temperature of PMMA-RGO increased 15 °C at only 0.5 wt % RGO.

Uniform distribution of TiO2 nanocrystals on reduced graphene oxide sheets by the chelating ligands.

Reduced graphene oxide-TiO(2) hybrids were successfully prepared by the hydrothermal approach using triethanolamine and acetylacetone as the chelating agents. Without any additive, large aggregated TiO(2) clusters were randomly distributed dominantly at the edge and less on the basil plane of coagulated reduced graphene oxide (RGO) layers. The presence of chelating ligands remarkably facilitated the selective growth and regular spread of TiO(2) nanocrystals onto individually exfoliated RGO sheet. Such sandwich-like structure with stronger coupling and chemical interaction resulted in the surface area increase, the rearrangement of energy level, the enhanced concentration of oxygen vacancies, leading to much higher adsorbability and photocatalytic degradation of Rhodamine B under both UV and visible irradiations. These RGO-TiO(2) hybrid systems are potentially beneficial for widely practical applications in air/water purification, electronic devices, batteries, solar cells or supercapacitors.