Graphene aerogels: part 1 - derived from graphene oxide and thermally reduced graphene oxide via supercritical carbon dioxide drying.

Graphene aerogels have become promising materials in many areas of industry, especially in energy applications due to their superior physical and electrochemical properties. Generally, graphene oxide (GO)-derived aerogels (A) are synthesized by using the hydrothermal method. In this study, both GO and reduced graphene oxide (RGO)-derived aerogels were synthesized by using the sol-gel method coupled with the supercritical carbon dioxide (SCCO2) drying process. It aims to examine the changes in the structure of the final aerogel by changing the amount (0.25-0.5-1% wt.) and type of graphene-based precursor materials used in the synthesis. Physical characterizations of graphene aerogels were conducted using Brunauer-Emmett-Teller (BET) analysis, scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis, transmission electron microscopy (TEM), micro-Raman spectroscopy, X-ray diffractometer (XRD) to highlight their structural properties. Additionally, X-ray photoelectron spectroscopy (XPS) analyses were performed to determine the oxidation levels on the surface of the RGO-1 aerogel. The cyclic voltammetry (CV) method was used to examine the electrochemical behavior of the graphene aerogels against corrosion. Specific capacitance values of the synthesized materials were calculated before and after corrosion. Furthermore, the surface charge changes that occur after corrosion were examined. GOAs displayed the highest specific capacitance value among graphene aerogels. Notably, the RGOA-1 aerogel exhibited the highest corrosion resistance. The pseudo-capacitive charge ratio of RGOA-1 after corrosion was measured at 0.5 mC cm-2.

Dependence of Electrical Conductivity on Phase Morphology for Graphene Selectively Located at the Interface of Polypropylene/Polyethylene Composites.

Conductive composites of polypropylene (PP) and polyethylene (PE) filled with thermally reduced graphene oxide (TRG) were prepared using two different processing sequences. One was a one-step processing method in which the TRG was simultaneously melt blended with PE and PP, called TRG/PP/PE. The second was a two-step processing method in which the TRG and the PP were mixed first, and then the (TRG/PP) masterbatch was blended with PE, called (TRG/PP)/PE. The phase morphology and localization of the TRG in TRG/PP/PE and (TRG/PP)/PE composites with different PP/PE compositions were observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The TRG was found to be selectively dispersed in the PE phase of the TRG/PP/PE composites, resulting in a low percolation threshold near 2.0 wt%. In the (TRG/PP)/PE composites, the TRG was selectively located at the PP/PE blend interface, resulting in a percolation threshold that was lower than 1.0 wt%. With the addition of 2.0 wt% TRG, the (TRG/PP)/PE composites exhibited a wide range of electrical conductivities at PP/PE weight ratios of 10 w/90 w to 80 w/20 w. Moreover, electrical and rheological measurements of the composites revealed that the co-continuous phase structure is the most efficient candidate for the fabrication of conductive composites.

Reagentless D-Tagatose Biosensors Based on the Oriented Immobilization of Fructose Dehydrogenase onto Coated Gold Nanoparticles- or Reduced Graphene Oxide-Modified Surfaces: Application in a Prototype Bioreactor.

As electrode nanomaterials, thermally reduced graphene oxide (TRGO) and modified gold nanoparticles (AuNPs) were used to design bioelectrocatalytic systems for reliable D-tagatose monitoring in a long-acting bioreactor where the valuable sweetener D-tagatose was enzymatically produced from a dairy by-product D-galactose. For this goal D-fructose dehydrogenase (FDH) from Gluconobacter industrius immobilized on these electrode nanomaterials by forming three amperometric biosensors: AuNPs coated with 4-mercaptobenzoic acid (AuNP/4-MBA/FDH) or AuNPs coated with 4-aminothiophenol (AuNP/PATP/FDH) monolayer, and a layer of TRGO on graphite (TRGO/FDH) were created. The immobilized FDH due to changes in conformation and spatial orientation onto proposed electrode surfaces catalyzes a direct D-tagatose oxidation reaction. The highest sensitivity for D-tagatose of 0.03 ± 0.002 µA mM-1cm-2 was achieved using TRGO/FDH. The TRGO/FDH was applied in a prototype bioreactor for the quantitative evaluation of bioconversion of D-galactose into D-tagatose by L-arabinose isomerase. The correlation coefficient between two independent analyses of the bioconversion mixture: spectrophotometric and by the biosensor was 0.9974. The investigation of selectivity showed that the biosensor was not active towards D-galactose as a substrate. Operational stability of the biosensor indicated that detection of D-tagatose could be performed during six hours without loss of sensitivity.

Synthesis of Nickel Spinel Ferrites Nanoparticles Coated with Thermally Reduced Graphene Oxide for EMI Shielding in the Microwave, UV, and NIR Regions.

The co-precipitation and in situ modified Hummers' method was used to synthesize Nickel Spinal Ferrites (NiFe) nanoparticles and NiFe coated with Thermally Reduced Graphene Oxide (TRGO) (NiFe-TRGO) nanoparticles, respectively. By using polyvinyl chloride (PVC), tetrahydrofuran (THF), and NiFe-TRGO, the nanocomposite film was synthesized using the solution casting technique with a thickness of 0.12-0.13 mm. Improved electromagnetic interference shielding efficiency was obtained in the 0.1-20 GHz frequency range. The initial assessment was done through XRD for the confirmation of the successful fabrication of nanoparticles and DC conductivity. The microstructure was analyzed with scanning electron microscopy. The EMI shielding was observed by incorporating a filler amount varying from 5 wt.% to 40 wt.% in three different frequency regions: microwave region (0.1 to 20 GHz), near-infrared (NIR) (700-2500 nm), and ultraviolet (UV) (200-400 nm). A maximum attenuation of 65 dB was observed with a 40% concentration of NiFe-TRGO in nanocomposite film.

Study of the Influence of Magnetite Nanoparticles Supported on Thermally Reduced Graphene Oxide as Filler on the Mechanical and Magnetic Properties of Polypropylene and Polylactic Acid Nanocomposites.

A study addressed to develop new recyclable and/or biodegradable magnetic polymeric materials is reported. The selected matrices were polypropylene (PP) and poly (lactic acid) (PLA). As known, PP corresponds to a non-polar homo-chain polymer and a commodity, while PLA is a biodegradable polar hetero-chain polymer. To obtain the magnetic nanocomposites, magnetite supported on thermally reduced graphene oxide (TrGO:Fe3O4 nanomaterial) to these polymer matrices was added. The TrGO:Fe3O4 nanomaterials were obtained by a co-precipitation method using two types of TrGO obtained by the reduction at 600 °C and 1000 °C of graphite oxide. Two ratios of 2.5:1 and 9.6:1 of the magnetite precursor (FeCl3) and TrGO were used to produce these nanomaterials. Consequently, four types of nanomaterials were obtained and characterized. Nanocomposites were obtained using these nanomaterials as filler by melt mixer method in polypropylene (PP) or polylactic acid (PLA) matrix, the filler contents were 3, 5, and 7 wt.%. Results showed that TrGO600-based nanomaterials presented higher coercivity (Hc = 8.5 Oe) at 9.6:1 ratio than TrGO1000-based nanomaterials (Hc = 4.2 Oe). PLA and PP nanocomposites containing 7 wt.% of filler presented coercivity of 3.7 and 5.3 Oe, respectively. Theoretical models were used to analyze some relevant experimental results of the nanocomposites such as mechanical and magnetic properties.

Enhanced Mechanical and Antibacterial Properties of Nanocomposites Based on Poly(vinyl Alcohol) and Biopolymer-Derived Reduced Graphene Oxide.

Functionalized graphene-polymer nanocomposites have gained significant attention for their enhanced mechanical, thermal, and antibacterial properties, but the requirement of multi-step processes or hazardous reducing agents to functionalize graphene limits their current applications. Here, we present a single-step synthesis of thermally reduced graphene oxide (TrGO) based on shellac, which is a low-cost biopolymer that can be employed to produce poly(vinyl alcohol) (PVA)/TrGO nanocomposites (PVA-TrGO). The concentration of TrGO varied from 0.1 to 2.0 wt.%, and the critical concentration of homogeneous TrGO dispersion was observed to be 1.5 wt.%, below which strong interfacial molecular interactions between the TrGO and the PVA matrix resulted in improved thermal and mechanical properties. At 1.5 wt.% filler loading, the tensile strength and modulus of the PVA-TrGO nanocomposite were increased by 98.7% and 97.4%, respectively, while the storage modulus was increased by 69%. Furthermore, the nanocomposite was 96% more effective in preventing bacterial colonization relative to the neat PVA matrix. The present findings indicate that TrGO can be considered a promising material for potential applications in biomedical devices.

In Vitro Hyperthermia Evaluation of Electrospun Polymer Composite Fibers Loaded with Reduced Graphene Oxide.

Electrospun meshes (EM) composed of natural and synthetic polymers with randomly or aligned fibers orientations containing 0.5% or 1% of thermally reduced graphene oxide (TrGO) were prepared by electrospinning (ES), and their hyperthermia properties were evaluated. EM loaded with and without TrGO were irradiated using near infrared radiation (NIR) at 808 nm by varying the distance and electric potential recorded at 30 s. Morphological, spectroscopic, and thermal aspects of EM samples were analyzed by using SEM-EDS, Raman and X-ray photoelectron (XPS) spectroscopies, X-ray diffraction (XRD), and NIR radiation response. We found that the composite EM made of polyvinyl alcohol (PVA), natural rubber (NR), and arabic gum (AG) containing TrGO showed improved hyperthermia properties compared to EM without TrGO, reaching an average temperature range of 42-52 °C. We also found that the distribution of TrGO in the EM depends on the orientation of the fibers. These results allow infering that EM loaded with TrGO as a NIR-active thermal inducer could be an excellent candidate for hyperthermia applications in photothermal therapy.

The Synergy of Thermally Reduced Graphene Oxide in Amperometric Urea Biosensor: Application for Medical Technologies.

Thermally reduced graphene oxide (TRGO) is a graphene-based nanomaterial that has been identified as promising for the development of amperometric biosensors. Urease, in combination with TRGO, allowed us to create a mediator-free amperometric biosensor with the intention of precise detection of urea in clinical trials. Beyond simplicity of the technology, the biosensor exhibited high sensitivity (2.3 ± 0.1 µA cm-2 mM-1), great operational and storage stabilities (up to seven months), and appropriate reproducibility (relative standard deviation (RSD) about 2%). The analytical recovery of the TRGO-based biosensor in urine of 101 ÷ 104% with RSD of 1.2 ÷ 1.7% and in blood of 92.7 ÷ 96.4%, RSD of 1.0 ÷ 2.5%, confirmed that the biosensor is acceptable and reliable. These properties allowed us to apply the biosensor in the monitoring of urea levels in samples of urine, blood, and spent dialysate collected during hemodialysis. Accuracy of the biosensor was validated by good correlation (R = 0.9898 and R = 0.9982) for dialysate and blood, utilizing approved methods. The advantages of the proposed biosensing technology could benefit the development of point-of-care and non-invasive medical instruments.

Thermally reduced graphene oxide as green and easily available adsorbent for Sunset yellow decontamination.

The release of synthetic food dyes, like Sunset yellow, into industrial effluents can cause serious environmental and health problems. Due to its aromatic structure, it is recalcitrant towards degradation into non-toxic intermediates and its removal by efficient adsorption represents a cheap and efficient method. Herein we propose the use of thermally reduced graphene oxide (TRGO) as effective Sunset yellow dye adsorbent with an adsorption maximum capacity comparable with other sophisticated, chemically synthesized carbon-based nanomaterials. The reduced graphene oxide and the Sunset yellow adsorbed one were characterized by FT-IR, XPS and XRD spectroscopy, N2 adsorption-desorption isotherm and TGA analysis. BET surface area reduced from 274.1 m2/g (for TRGO) to 39.9 m2/g (for TRGO-SY) showing that Sunset Yellow molecules occupied the corresponding active sites while the number of sheets resulted from the XRD spectra - from 3 to 8 in TRGO to 5 in TRGO-SY indicates the ordered intercalations in the graphene structure. The adsorption isotherm experimental data were better fitted with the Langmuir model than the Freundlich model, with the maximum adsorption capacity of the SY dye monolayer of 243.3 mg/g at pH = 6.0 and 189.0 mg/g from synthetic wastewater. The kinetic study revealed a perfect fit following the Pseudo-second order model with an equilibrium achieved within 30 min. The lack of adsorption on the starting graphene oxide is indicative for π-π interactions between the adsorbate and adsorbent.

Chemical modification of graphene with grape seed extract: Its structural, optical and antimicrobial properties.

Herein, we modified for the first time thermally reduced graphene oxide (TRG) using grape seed extract (GSE), by simple probe sonication method. The effect of GSE on the structural changes of TRG has been carefully analyzed through Fourier Transform Infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy and these spectral data proved that the TRG has been modified successfully. Furthermore, X-ray investigations proved the change in crystallinity and coherence length of TRG, which could be further, authenticated by Transmission electron microscopy (TEM). The optical properties of as prepared modified TRG (m-TRG) were investigated with the help of UV-Visible and photoluminescence spectroscopy. The band gap of m-TRG was found to be 4.1 eV and it exerted the luminescence in the visible region. Moreover, the antibacterial results showed that m-TRG has enhanced antibacterial activity and 80% of mortality was observed in both the gram positive and gram negative bacteria at a minimum concentration of 40 µg ml-1 and 60 µg ml-1. Thus, this m-TRG could find many applications in the future semiconductor and optoelectronic devices and it could be considered as a novel antibacterial agent that can find potential application in the areas of healthcare and engineering.

Polyvalent 2D Entry Inhibitors for Pseudorabies and African Swine Fever Virus.

African swine fever virus (ASFV) is one of the most dangerous viruses for pigs and is endemic in Africa but recently also spread into the Russian Federation and the Eastern border of the EU. So far there is no vaccine or antiviral drug available to curtail the infection. Thus, control strategies based on novel inhibitors are urgently needed. Another highly relevant virus infection in pigs is Aujeszky's disease caused by the alphaherpesvirus pseudorabies virus (PrV). This article reports the synthesis and biological evaluation of novel extracellular matrix-inspired entry inhibitors based on polyglycerol sulfate-functionalized graphene sheets. The developed 2D architectures bind enveloped viruses during the adhesion process and thereby exhibit strong inhibitory effects, which are equal or better than the common standards enrofloxacin and heparin as demonstrated for ASFV and PrV. Overall, the developed polyvalent 2D entry inhibitors are nontoxic and efficient nanoarchitectures, which interact with various types of enveloped viruses. Therefore they prevent viral adhesion to the host cell and especially target viruses that rely on a heparan sulfate-dependent cell entry mechanism.

Highly Efficient Multivalent 2D Nanosystems for Inhibition of Orthopoxvirus Particles.

Efficient inhibition of cell-pathogen interaction to prevent subsequent infection is an urgent but yet unsolved problem. In this study, the synthesis and functionalization of novel multivalent 2D carbon nanosystems as well as their antiviral efficacy in vitro are shown. For this reason, a new multivalent 2D flexible carbon architecture is developed in this study, functionalized with sulfated dendritic polyglycerol, to enable virus interaction. A simple "graft from" approach enhances the solubility of thermally reduced graphene oxide and provides a suitable 2D surface for multivalent ligand presentation. Polysulfation is used to mimic the heparan sulfate-containing surface of cells and to compete with this natural binding site of viruses. In correlation with the degree of sulfation and the grafted polymer density, the interaction efficiency of these systems can be varied. In here, orthopoxvirus strains are used as model viruses as they use heparan sulfate for cell entry as other viruses, e.g., herpes simplex virus, dengue virus, or cytomegalovirus. The characterization results of the newly designed graphene derivatives demonstrate excellent binding as well as efficient inhibition of orthopoxvirus infection. Overall, these new multivalent 2D polymer nanosystems are promising candidates to develop potent inhibitors for viruses, which possess a heparan sulfate-dependent cell entry mechanism.

Graphene oxide vs. reduced graphene oxide as carbon support in porphyrin peroxidase biomimetic nanomaterials.

The paper describes the preparation of supramolecular assemblies of tetrapyridylporphyrin (TPyP) and its metallic complexes with graphene oxide (GO) and thermally reduced graphene oxide (TRGO). The two carbon supports are introducing different characteristics in the absorption spectra of the investigated nanocomposites. Raman spectroscopy shows that the absorption of iron-tetrapyridylporphyrin is more efficient on GO than TRGO, suggesting that oxygen functionalities are involved in the non-covalent interaction between the iron-porphyrin and graphene. The biomimetic peroxidase activity is investigated and the two iron-containing composites exhibit a better catalytic activity than each component of the assembly, and their cobalt and manganese homologues, respectively. The main advantages of this work include the demonstration of graphene oxide as a very good support for graphene-based nanomaterials with peroxidase-like activity (K(M)=0.292 mM), the catalytic activity being observed even with very small amounts of porphyrins (the TPyP:graphene ratio=1:50). Its potential application in the detection of lipophilic antioxidants (vitamin E can be measured in the 10(-5)-10(-4) M range) is also shown.

Multivalency at Interfaces: Supramolecular Carbohydrate-Functionalized Graphene Derivatives for Bacterial Capture, Release, and Disinfection.

A supramolecular carbohydrate-functionalized two-dimensional (2D) surface was designed and synthesized by decorating thermally reduced graphene sheets with multivalent sugar ligands. The formation of host-guest inclusions on the carbon surface provides a versatile strategy, not only to increase the intrinsic water solubility of graphene-based materials, but more importantly to let the desired biofunctional binding groups bind to the surface. Combining the vital recognition role of carbohydrates and the unique 2D large flexible surface area of the graphene sheets, the addition of multivalent sugar ligands makes the resulting carbon material an excellent platform for selectively wrapping and agglutinating Escherichia coli (E. coli). By taking advantage of the responsive property of supramolecular interactions, the captured bacteria can then be partially released by adding a competitive guest. Compared to previously reported scaffolds, the unique thermal IR-absorption properties of graphene derivatives provide a facile method to kill the captured bacteria by IR-laser irradiation of the captured graphene-sugar-E. coli complex.