Development and validation of a liquid chromatography-triple quadrupole mass spectrometry method for the determination of isopeptide ε-(γ-glutamyl) lysine in human urine as biomarker for transglutaminase 2 cross-linked proteins.

Determination of the levels of protein cross-linking catalysed by the activity of transglutaminase 2 in various disease states has remained a significant challenge. The ability to quantify the isopeptide ε-(γ-glutamyl) lysine, which can form as a heterogeneous bond within or between proteins has significant analytical and clinical potential as a biomarker in biofluids such as human urine. Increased transglutaminase 2 activity is associated with a number of diseases, such as fibrosis. Previously published methods have been based on classical amino acid analysis, however they require a complex multi-enzyme digestion in order to achieve complete protein digestion, whilst leaving the isopeptide cross link intact. These methods require high levels of enzymes, which contaminate the analysis and alter the dynamics of digestion. The amino acid analysis detection also lacked selectivity, especially where the levels of crosslink are expected to be low relative to the background protein levels. We have systematically addressed these challenges, by optimising the precipitation of the protein in urine, the use of innovative immobilised enzyme technology, which allows for efficient digestion without enzyme contamination and LC-MS/MS detection based on multiple reaction monitoring. This method was validated for its analytical performance characteristics, showing the method has a sensitivity of 0.1 ng/mL of ε-(γ-glutamyl) lysine in human urine with precision of less than 20% CV, and is selective as no interferences were observed that may adversely affect the analysis. As such this approach represents a significant advance in the ability to detect and quantify ε-(γ-glutamyl) lysine.

Enhanced CO2 Capture of Poly(amidoamine)-Modified Graphene Oxide Aerogels with the Addition of Carbon Nanotubes.

Innovative dendrimer-modified graphene oxide (GO) aerogels are reported by employing generation 3.0 poly(amidoamine) (PAMAM) dendrimer and a combined synthesis approach based on the hydrothermal method and freeze-casting followed by lyophilization. The properties of modified aerogels were investigated with the dendrimer concentration and the addition of carbon nanotubes (CNTs) in varying ratios. Aerogel properties were evaluated via scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The obtained results indicated a strong correlation of the N content with the PAMAM/CNT ratio, where optimum values were revealed. The CO2 adsorption performance on the modified aerogels increased with the concentration of the dendrimer at an appropriate PAMAM/CNT ratio, reaching the value of 2.23 mmol g-1 at PAMAM/CNT ratio of 0.6/0.12 (mg mL-1). The reported results confirm that CNTs could be exploited to improve the functionalization/reduction degree in PAMAM-modified GO aerogels for CO2 capture.

Magnetite Impregnated Lignocellulosic Biomass for Zn(II) Removal.

Magnetic composites obtained by impregnation of lignocellulosic biomass with magnetite nanoparticles were used for zinc(II) removal from aqueous synthetic solutions. Laurel, canelo and eucalyptus sawdust, with a particle size between 74 and 150 µm were used as support. Structural and morphological examinations of the composites confirmed the presence of magnetite nanoparticles in the lignocellulosic support. Transmission Electron Microscopy showed nanoparticles with diameters of about 20 nm. The maximum removal efficiencies for 7 g L-1 of modified adsorbent were increased to 98.9, 98.8 and 97.6% for laurel, canelo and eucalyptus magnetic composites, respectively, in comparison to 60.9, 46.0 and 33.3%, for corresponding unmodified adsorbents. Adsorption data was analyzed using pseudo-first, pseudo-second order and intra-particle diffusion kinetic models and various isotherm models. The results determined that Freundlich isotherm fits the Zn ions adsorption on magnetite modified adsorbents while chemisorption and boundary diffusion were dominating the process.

Hydrothermal-Freeze-Casting of Poly(amidoamine)-Modified Graphene Aerogels towards CO2 Adsorption.

This article presents novel poly(amidoamine) (PAMAM) dendrimer-modified with partially-reduced graphene oxide (rGO) aerogels, obtained using the combined solvothermal synthesis-freeze-casting approach. The properties of modified aerogels are investigated with varying synthesis conditions, such as dendrimer generation (G), GO:PAMAM wt. ratio, solvothermal temperature, and freeze-casting rate. Scanning electron microscopy, Fourier Transform Infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy are employed to characterize the aerogels. The results indicate a strong correlation of the synthesis conditions with N content, N/C ratio, and nitrogen contributions in the modified aerogels. Our results show that the best CO2 adsorption performance was exhibited by the aerogels modified with higher generation (G7) dendrimer at low GO:PAMAM ratio as 2:0.1 mg mL-1 and obtained at higher solvothermal temperature and freeze-casting in liquid nitrogen. The enclosed results are indicative of a viable approach to modify graphene aerogels towards improving the CO2 capture.

Chemical Modification of Agro-Industrial Waste-Based Bioadsorbents for Enhanced Removal of Zn(II) Ions from Aqueous Solutions.

Contamination of water by heavy metals is a major environmental concern due to the potential ecological impact on human health and aquatic ecosystems. In this work, we studied the chemical modification of various fruit peels such as banana (BP), granadilla (GP), and orange ones (OP) in order to obtain novel bio-adsorbents to improve the removal of Zn(II) ions from 50 mg·L-1 synthetic aqueous solutions. For this purpose, sodium hydroxide and calcium acetate were employed to modify the fruit peels. The moisture, extractives, lignin, hemicellulose, and cellulose contents of the raw materials were determined according to ASTM standards. The obtained bio-adsorbents were characterized by scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). The results showed the OP bio-adsorbents performed better, especially when the concentration of the modifier solutions increased, e.g., the OP particles modified using 0.8 M NaOH and Ca(CH3COO)2 solutions resulted in 97% removal of Zn(II) contaminating ions and reached a maximum adsorption capacity of 27.5 mg Zn per gram of bio-adsorbent. The adsorption processes were found to follow a pseudo-second order model. The error function sum of square error indicated the Freundlich isotherm (non-linear regression) as best fit model. The obtained results are particularly interesting for material selection in wastewater treatment technologies based on contaminant adsorption.

Effect of Varying Amine Functionalities on CO2 Capture of Carboxylated Graphene Oxide-Based Cryogels.

Graphene cryogels synthesis is reported by amine modification of carboxylated graphene oxide via aqueous carbodiimide chemistry. The effect of the amine type on the formation of the cryogels and their properties is presented. In this respect, ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), were selected. The obtained cryogels were characterized by Fourier Transformed Infrared spectroscopy, thermogravimetric analysis, X-ray spectroscopy, and Scanning electron microscopy. The CO2 adsorption performance was evaluated as a function of amine modification. The results showed the best CO2 adsorption performance was exhibited by ethylenediamine modified aerogel, reaching 2 mmol g-1 at 1 bar and 298 K. While the total N content of the cryogels increased with increasing amine groups, the nitrogen configuration and contributions were determined to have more important influence on the adsorption properties. It is also revealed that the residual oxygen functionalities in the obtained cryogels represent another paramount factor to take into account for improving the CO2 capture properties of amine-modified graphene oxide (GO)-based cryogels.

Graphene Oxide-Polypyrrole Coating for Functional Ceramics.

Ceramic substrates were metallized with a Ni-Mo-P electroless coating and further modified with a polypyrrole (PPy) coating by the electrodeposition method. The properties of the polypyrrole coating were studied with the addition of a graphene oxide (GO) nanomaterial prior to the electrodeposition and its reduction degree. Fourier Transform Infrared Spectroscopy, Field-Emission Scanning Electron Microscopy, Raman spectroscopy and cyclic voltammetry were employed to characterize the properties of the coatings. The results indicated the successful synthesis of conductive electrodes by the proposed approach. The electrodeposition of PPy and its charge storage properties are improved by chemically reduced GO. The surface capacitive contribution to the total stored charge was found to be dominant and increased 2-3 fold with the reduction of GO. The chemically reduced GO-modified PPy exhibits the highest capacitance of 660 F g-1 at 2 mV s-1, and shows a good cyclability of 94% after 500 charge/discharge cycles. The enclosed results indicate the use of an NiMoP electroless coating, and modification with a carbon nanomaterial and conducting polymer is a viable approach for achieving functional ceramics.

Improving Electrochemical Properties of Polypyrrole Coatings by Graphene Oxide and Carbon Nanotubes.

Nanostructured polypyrrole coating was applied on carbon paper via simple dip-coating and electrochemical approach. Hybridization with nanocarbon materials (graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs)) and their effect as an anchoring hybrid layer for the growth of polypyrrole towards improving electrochemical properties are studied. The loading of each component and their w/w ratio were evaluated. Fourier transform infrared spectroscopy, field emission scanning electron microscopy, and Raman spectroscopy were employed to characterize the properties of the coatings. The electrochemical properties were investigated by cyclic voltammetry. The results indicated the electrodeposition of polypyrrole is enhanced by the addition of MWCNTs to the GO layer due to the formation of a hierarchical network. The electrochemical performance of the modified electrode was shown to be highly dependent on the employed w/w ratio, reaching a capacitance value of about 40 mF cm-2 for a carbon paper substrate modified with GO:MWCNT in a w/w ratio of 1:2.5 and PPy layer deposited by cyclic voltammetry for 30 cycles. The contribution to total stored charge was found to be primary from the inner capacitance component of about 95.5% contribution.

Effect of Deposition Parameters on Electrochemical Properties of Polypyrrole-Graphene Oxide Films.

Graphene oxide (GO)-modified polypyrrole (PPy) coatings were obtained by electrochemical methods in the presence of the anionic surfactant, sodium dodecyl sulfate (SDS). The structure, morphology, and electrochemical properties of the coatings were assessed by Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, scanning electron microscopy (SEM) and cyclic voltammetry at varying scan rates, respectively. The properties of the obtained coatings were analyzed with the GO and PPy loadings and electrodeposition mode. The hybrid coatings obtained galvanostatically showed a coarser appearance than those deposited by cyclic voltammetry CV mode and improved performance, respectively, which was further enhanced by GO and PPy loading. The capacitance enhancement can be attributed to the SDS surfactant that well dispersed the GO sheets, thus allowing the use of lower GO content for improved contribution, while the choice of suitable electrodeposition parameters is highly important for improving the applicability of GO-modified PPy coatings in energy storage applications.

Tailoring the Performance of Graphene Aerogels for Oil/Organic Solvent Separation by 1-Step Solvothermal Approach.

Ultra-light eco-friendly graphene oxide (GO)-based aerogels are reported by simple one-step solvothermal self-assembly. The effect of varying parameters such as C/O ratio of GO; reducing agent amount; temperature; and duration on the properties of the aerogels was studied. The structural and vibrational features and hydrophobic surface properties of the obtained aerogels were obtained by XRD; FTIR; XPS; Raman; SEM; and contact angle measurements. The effect of synthesis conditions on the engine oil and organic solvent absorption properties was assessed. The results indicated that the lower the C/O ratio of GO, the better the absorption properties, with the best performance for oil uptake reaching 86 g g-1. The obtained results indicate the approach based on ice-templating and the tailoring of oxygen content in GO make the resulting aerogels potential candidates for use in oil spill and organic solvent treatments.

The Effect of Solvothermal Conditions on the Properties of Three-Dimensional N-Doped Graphene Aerogels.

Low-density three-dimensional (3D) N-doped graphene aerogels by a one-step solvothermal method in the presence of ethylenediamine (EDA) are reported. The gelation, formation, and properties of the aerogels were studied with solvothermal conditions, namely, operating temperature, time, graphene oxide (GO) concentration, and the GO/EDA w/w ratio. Two ranges of solvothermal conditions are employed: one involving an operating temperature below 100 °C and a conventional chemical reduction of GO with EDA at atmospheric pressure and a second one employing a higher temperature range up to 165 and a high pressure reduction with EDA. The results show that both solvothermal approaches allow for the fabrication of homogeneous N-doped 3D graphene aerogels with density values close to 10 mg cm-3. The measurements indicated that low values of GO concentration, temperature, and EDA are optimum for obtaining low-density 3D aerogels. N doping is improved with an EDA amount in lower temperature conditions. The N doping mechanism below 100 °C is dominated by the epoxy ring opening while at temperatures up to 165 °C both epoxy ring opening and amidation take place. The CO2 adsorption properties are strongly controlled by the nitrogen configuration, namely, pyridinic nitrogen in terms of its density.

In vitro and environmental toxicity of reduced graphene oxide as an additive in automotive lubricants.

Despite the ground-breaking potential of nanomaterials, their safe and sustainable incorporation into an array of industrial markets prompts a deep and clear understanding of their potential toxicity for both humans and the environment. Among the many materials with great potential, graphene has shown promise in a variety of applications; however, the impact of graphene based products on living systems remains poorly understood. In this paper, we illustrate that via exploiting the tribological properties of graphene nanosheets, we can successfully improve both the frictional behaviour and the anti-wear capacity of lubricant oil for mechanical transmission. By virtue of reducing friction and enhancing lubricant lifetimes, we can forecast a reduction in friction based energy loss, in addition to a decrease in the carbon footprint of vehicles. The aforementioned positive environmental impact is further strengthened considering the lack of acute toxicity found in our extensive in vitro investigation, in which both eukaryotic and prokaryotic cells were tested. Collectively, our body of work suggests that by the use of safe nanoadditives we could contribute to reducing the environmental impact of transportation and therein take a positive step towards a more sustainable automotive sector. The workflow proposed here for the evaluation of human and environmental toxicity will allow for the study of nanosized bare graphene material and can be broadly applied to the translation of graphene-based nanomaterials into the market.

Functionalized single-walled carbon nanotubes/polypyrrole composites for amperometric glucose biosensors.

This article reports an amperometric glucose biosensor based on a new type of nanocomposite of polypyrrole (PPY) with p-phenyl sulfonate-functionalized single-walled carbon nanotubes (SWCNTs-PhSO3-). An environmentally friendly functionalization procedure of the SWCNTs in the presence of substituted aniline and an oxidative species was adopted. The nanocomposite-modified electrode exhibited excellent electrocatalytic activities towards the reduction or oxidation of H2O2. This feature allowed us to use it as bioplatform on which glucose oxidase (GOx) was immobilized by entrapment in an electropolymerized PPY/SWCNTs-PhSO3- film for the construction of the glucose biosensor. The amperometric detection of glucose was assayed by applying a constant electrode potential value necessary to oxidize or reduce the enzymatically produced H2O2 with minimal interference from the possible coexisting electroactive compounds. With the introduction of a thin film of Prussian blue (PB) at the substrate electrode surface, the PPY/GOx/SWCNTs-PhSO3-/PB system shows synergy between the PB and functionalized SWCNTs which amplifies greatly the electrode sensitivity when operated at low potentials. The biosensor showed good analytical performances in terms of low detection (0.01 mM), high sensitivity (approximately 6 µA mM-1 cm-2), and wide linear range (0.02 to 6 mM). In addition, the effects of applied potential, the electroactive interference, and the stability of the biosensor were discussed. The facile procedure of immobilizing GOx used in the present work can promote the development of other oxidase-based biosensors which could have a practical application in clinical, food, and environmental analysis.