Preparation of nanocellulose/reduced graphene oxide matrix loaded with cuprous oxide nanoparticles for efficient catalytic reduction of 4-nitrophenol.

The paper reports on the preparation of cellulose nanocrystals/reduced graphene oxide matrix loaded with cuprous oxide nanoparticles (CNC/rGO-Cu2O) through a simple solvothermal method and its application for 4-nitrophenol reduction to 4-aminophenol using sodium borohydride. The CNC/rGO-Cu2O nanocomposite was formed chemically by first mixing CNC and graphene oxide (GO) followed by complexation of the negatively charged functional groups of CNC/GO with Cu2+ ions and subsequent heating at 100°C. This resulted in the simultaneous reduction of GO to rGO and the formation of Cu2O nanoparticles. The as-elaborated nanocomposite was firstly characterized using different techniques such as atomic force microscopy, scanning electron microscopy, transmission electron microscopy, UV-Vis spectrophotometry, Raman spectroscopy and x-ray photoelectron spectroscopy. Then, it was successfully applied for efficient catalytic reduction of 4-nitrophenol to 4-aminophenol using sodium borohydride: the reduction was completed in about 6 min. After eight times use, the catalyst still maintained good catalytic performance. Compared to CNC/rGO, rGO/Cu2O and free Cu2O nanoparticles, the CNC/rGO-Cu2O nanocomposite exhibits higher catalytic activity even at lower copper loading.

Adsorption and antibacterial studies of a novel hydrogel adsorbent based on ternary eco-polymers doped with sulfonated graphene oxide developed from upcycled plastic waste.

A novel ternary blended polymer composed of cost-effective and readily available polymers was synthesized using poly (vinyl alcohol) (PVA), iota carrageenan (IC), and poly (vinyl pyrrolidone) (PVP). Sulfonated graphene oxide (SGO), prepared from recycled drinking water bottles, was utilized as a doping agent. Varying amounts (1-3 wt%) were combined into the polymer matrix. The produced hydrogel film was examined as a potential adsorbent hydrogel film for the removal of methylene blue (MB) and Gentamicin sulfate (GMS) antibiotic from an aqueous solution. The experimental results demonstrate that the presence of SGO significantly increased the adsorption efficiency of PVA/IC/PVP hydrogel film. The antimicrobial tests revealed that the PVA/IC/PVP-3% SGO hydrogel film exhibited the most potent activity against all the tested pathogenic bacteria. However, the adsorption results for MB and GMS showed that the addition of 3 wt% SGO resulted in a removal percentage that was a two fold increase in the removal percentage compared with the undoped PVA/IC/PVP hydrogel film. Furthermore, the response surface methodology (RSM) model was utilized to examine and optimize several operating parameters, including time, pH of the solution, and initial pollutant concentration. The adsorption kinetics were better characterized by the pseudo-second-order kinetics model. The composite film containing 3 wt% SGO had a maximum adsorption capacity of 606 mg g-1 for MB and 654 mg g-1 for GMS, respectively. The generated nanocomposite hydrogel film demonstrated promising potential for application in water purification systems.

Effects of Oxygenated Acids on Graphene Oxide: The Source of Oxygen-Containing Functional Group.

Graphene oxide is an important member of the graphene family which has a wide range of applications. The chemical method, especially the liquid phase method, is one of the most common and important methods for its preparation. However, the complex solution environment not only gives them rich structure, but also brings great challenges for its large-scale industrial synthesis. In order to better realize its industrial application, it is important to understand its structure, such as the source of oxygen-containing functional groups. Here we studied the contribution of four oxygenated acids to oxygen-containing functional groups in Hummers' method using first principles. We found that the permanganic acid molecules that exist instantaneously due to energy fluctuations can be the source of oxygen-containing functional group. In addition, Stone-Wales defect have a certain effect on the formation of oxygen-containing functional groups, but this effect is not as good as that of solvation effect. This work provides a guide for exploring the source of oxygen-containing functional groups on graphene oxide.

Electrodeposition and Corrosion Properties of Nickel-Graphene Oxide Composite Coatings.

Nickel-based composite electrochemical coatings (CEC) modified with multilayer graphene oxide (GO) were obtained from a sulfate-chloride electrolyte in the reverse electrolysis mode. The microstructure of these CECs was investigated by X-ray phase analysis and scanning electron microscopy. The corrosion-electrochemical behavior of nickel-GO composite coatings in a 0.5 M solution of H2SO4was studied. Tests in a 3.5% NaCl solution showed that the inclusion of GO particles into the composition of electrolytic nickel deposits makes their corrosion rate 1.40-1.50 times less.

Removal behaviors and mechanisms for series of azo dye wastewater by novel nano constructed macro-architectures material.

A novel macro-architectures material Fe3O4-N-GO@sodium alginate (SA) gel film was successfully produced, which was used to remove series azo dye wastewater. The optimal adsorption rates were attained, which achieved the maximum removal efficiency of 74.22%, 45.72%, 37.75% for Congo Red, Acid Orange 7 and Amino Black 10B respectively, under the condition that the mass ratio of Fe3O4-N-GO to sodium alginate was 0.11. The optimal adsorption temperature for three dyes was 30 ℃ and the adsorption equilibrium was reached at 150 min. The adsorption kinetic model of Fe3O4-N-GO@SA for the three azo dyes conformed to the quasi-second-order reaction model, and the adsorption isotherm was more in line with the Freundlich adsorption. The adsorption mechanism was multi-layer heterogeneous adsorption under the combined action of physical adsorption and chemisorption, and chemisorption was the main step of controlling the speed. The study would provide theoretical basis for the application of macro-architectures material in environment.

Multichannel Room-Temperature Gas Sensors Based on Magnetic-Field-Aligned 3D Fe3O4@SiO2@Reduced Graphene Oxide Spheres.

Reduced graphene oxide (rGO) is considered as one of the ideal sensing materials for high-performance room-temperature gas sensors owing to its large specific surface areas, numerous active sites, and high carrier mobility. However, the sensing performance cannot be maximized due to the inevitable sheet stacking and agglomeration. Herein, we firstdemonstrate multichannel room-temperature gas sensors using magnetic-field-induced alignment of three-dimensional (3D) Fe3O4@SiO2@rGO core-shell spheres. Moreover, the sensing channels composed of spheres can be tailored by changing the concentration of spheres and the magnetic field. Experimental results suggest that the multichannel 3D Fe3O4@SiO2@rGO sensor exhibits an ultrahigh sensitivity of 34.41 with a good response stability and high selectivity toward 5 ppm of NO2 at room temperature, which is ca. 7.96 times higher than that of the random 3D rGO gas sensor. The high performance can be mainly ascribed to a full utilization of their large specific surface area and active sites of rGO nanosheets. We believe that our results not only contribute to the development of high-performance rGO-based sensing devices, but also provide a general approach to maximize the sensing performance of other nanomaterials.

Capillary electrophoresis-integrated immobilized enzyme microreactor with graphene oxide as support: Immobilization of negatively charged L-lactate dehydrogenase via hydrophobic interactions.

We report the first application of hydrophobic interaction between graphene oxide (GO) and negatively charged enzymes to fabricate CE-integrated immobilized enzyme microreactors (IMERs) by a simple and reliable immobilization procedure based on layer by layer assembly. L-lactate dehydrogenase (L-LDH), which is negatively charged during the enzymatic reaction, is selected as the model enzyme. Various spectroscopic techniques, including SEM, FTIR, and UV-vis are used to characterize the fabricated CE-IMERs, demonstrating the successful immobilization of enzymes on the negatively charged GO layer in the capillary surface. The IMER exhibits excellent repeatability with RSDs of inter-day and batch-to-batch less than 3.49 and 6.37%, respectively, and the activity of immobilized enzymes remains about 90% after five-day usage. The measured Km values of pyruvate and NADH of the immobilized L-LDH are in good agreement with those obtained by free enzymes. The results demonstrate that the hydrophobic interactions and/or π-π stacking is significant between the GO backbone and the aromatic residues of L-LDH and favorable to fabrication of CE-integrated IMERs. Finally, the method is successfully applied to the determination of pyruvate in beer samples.

Gold nanoparticles decorated graphene oxide/nanocellulose paper for NIR laser-induced photothermal ablation of pathogenic bacteria.

A functionalized paper based on gold nanoparticles (Au NPs) conjugated graphene oxide (GO) was developed for near-infrared (NIR) laser triggered photothermal ablation against infectious bacterial pathogens. Firstly, quaternized carboxymethyl chitosan (QCMC) not only acted as reducing agent to synthesize Au NPs, but also functioned as coupling agent to link up Au NPs with GO. Au-QCMC-GO(+) was supposed to synergistically intensify the photothermal effect, which was then mixed with nanocellulose to form a functionalized paper via vacuum filtration. The photothermal efficiency, antibacterial treatment and mechanical property of Au-QCMC-GO(+)/nanocellulose paper were investigated. Excited by NIR laser irradiation, Au-QCMC-GO(+)/nanocellulose paper generated a temperature rise over 80 °C, sufficient for photothermal ablation upon both Gram-positive bacteria (Bacillus subtilis and Stapylococcus aureus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Additionally, Au-QCMC-GO(+)/nanocellulose paper showed a remarkable enhancement in tensile strength, bursting index and tear index compared to those of pure nanocellulose paper.

Biomacromolecules as carriers in drug delivery and tissue engineering.

Natural biomacromolecules have attracted increased attention as carriers in biomedicine in recent years because of their inherent biochemical and biophysical properties including renewability, nontoxicity, biocompatibility, biodegradability, long blood circulation time and targeting ability. Recent advances in our understanding of the biological functions of natural-origin biomacromolecules and the progress in the study of biological drug carriers indicate that such carriers may have advantages over synthetic material-based carriers in terms of half-life, stability, safety and ease of manufacture. In this review, we give a brief introduction to the biochemical properties of the widely used biomacromolecule-based carriers such as albumin, lipoproteins and polysaccharides. Then examples from the clinic and in recent laboratory development are summarized. Finally the current challenges and future prospects of present biological carriers are discussed.

Anti-fouling and thermosensitive ion-imprinted nanocomposite membranes based on grapheme oxide and silicon dioxide for selectively separating europium ions.

The increasing amount of europium in aqueous environment from rare earth industry has become a serious environmental challenge. Significant efforts have been focused on ion-imprinting membranes (IIMs) for selective separation of ions from analogues. Based on ion-imprinting technique, we have developed Eu3+-imprinted nanocomposite membranes (Eu-IIMs) for selectively separating Eu3+ from La3+, Gd3+ and Sm3+. Polydopamine (pDA) was previously synthesized on basal membranes to augment the interfacial adhesion. Grapheme oxide (GO) and modified silicon dioxide (kSiO2) were synergistically stacked on pDA-modified substrates to form hydrophilic nanocomposite membranes. Ag nanoparticles were modified on the surface to enhance anti-fouling performance. The temperature-controlled selective recognition sites were formed using N-isopropylacrylamide (NIPAm) and acrylamide (Am) as functional monomers as well as europium ions as templates by RAFT (reversible addition-fragmentation chain transfer) method. Large enhanced Eu3+-rebinding capacity (101.14 mg g-1), adsorptive selectivity (1.82, 1.57, 1.45 for Eu3+/La3+, Eu3+/Gd3+, Eu3+/Sm3+) and permselectivity (3.82, 3.47, 3.34 for La3+/Eu3+, Gd3+/Eu3+, Sm3+/Eu3+) were achieved on Eu-IIMs with superior regeneration performance. Additionally, the negligible damage of the membranes after buried for 20 d indicated the superior anti-fouling property of the Eu-IIMs. The ion-imprinted nanocomposite membranes synthesized in this work have shown great potentials for selective separation of rare earth ions.

Suspended graphene oxide nanoparticle for accelerated multilayer osteoblast attachment.

Mimicking bone tissues having layered structures is still a significant challenge because of the lack of technologies to assemble osteoblast cell types into bone structures. One of the promising and attractive materials in biomedical and different engineering fields is graphene and graphene-based nanostructures such as graphene oxide (GO) because of their unique properties. In most studies, GO was synthesized using chemical vapor deposition method, and was coated on the substrate. In this study, we proposed a simple technique for assembly of cells that facilitates the construction of osteoblast-like structures using suspended GO synthesized by graphite powder, H2 SO4 , and KMnO4 .Toxicity effects of GO on human mesenchymal stem cells (hMSCs) derived from bone marrow were analyzed. In addition to normal MSCs, toxicity effects of GO on human cancer cell line saos-2 as an abnormal cell line that possess several osteoblastic features, was examined. The attachment and expression of osteoblast cells genes were evaluated after differentiation of MSCs to osteoblast cells in presence of suspended GO by scanning electron microscopy and real time PCR. We found that the toxicity effects of GO are dose dependent and in oseogenic medium containing suspended GO the expression level of osteoblast genes osteopontin and osteocalcin and cell adhesion markers connexin were higher than control group. Interestingly, through this method GO was found to induce multilayer osteoblast cell morphology and enhance the number of cell layer. We expect that the presented method would become a highly useful approach for bone tissue engineering. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 293-303, 2018.

Influence of graphene-oxide nanosheets impregnation on properties of sterculia gum-polyacrylamide hydrogel formed by radiation induced polymerization.

Present work is an attempt, to explore the potential of graphene oxide nanoplates impregnation, on the mechanical and drug delivery properties of sterculia gum-polyacrylamide composite hydrogel formed by radiation induced polymerization. These polymers were characterized by SEM, cryo-SEM, AFM, FTIR's, 13C NMR and swelling studies. Release profile of an anticancer drug 'gemcitabine' was studied to determine the drug release mechanism and best fit kinetic model. Furthermore, some important biomedical properties of the polymers such as blood compatibility, mucoadhesion, antioxidant properties and gel strength were also studied. Impregnation of GO into sterculia gum-poly(AAm) hydrogels decreased the swelling of hydrogels but improved the mechanical, drug loading and drug release properties of the hydrogels. Release of gemcitabine from drug loaded hydrogels occurred through non-Fickian diffusion mechanism and release profile was best fitted in first order kinetic model. These hydrogels have been found as haemocompatible, mucoadhesive, and antioxidant in nature.

Highly sensitive determination of antimony in food by resonance Rayleigh scattering-energy transfer between grapheme oxide and I3(.).

Sb(III) was reduced to SbH3 gas and introduced to the I3(-)-grapheme oxide (GO) or I3(-)-silver nanorod (AgNR)-Victoria blue B (VBB) solutions. Resonance Rayleigh scattering energy transfer (RRS-ET) occurred between the donor GO and the acceptor I3(-) due to the overlap between the absorption peak of I3(-) and RRS peak of GO. When I3(-) was reduced by SbH3, RRS-ET weakened and the RRS intensity enhanced. The increased RRS intensity was linear to Sb concentration in the range of 2.1-376.6µg/L. In the I3(-)-AgNR-VBB solution, I3(-) combined with VBB to form VBB-I3 and there was a weak surface-enhanced Raman scattering (SERS) effect. When SbH3 reduced I3(-), the SERS intensity increased due to the release of SERS active VBB. The enhanced SERS intensity was linear for Sb concentration in the range of 8.4-292.9µg/L. The RRS-ET method was applied for determination of Sb in food with satisfactory results.

Chemiluminescence resonance energy transfer biosensing platform for site-specific determination of DNA methylation and assay of DNA methyltransferase activity using exonuclease III-assisted target recycling amplification.

Site-specific determination of DNA methylation and assay of MTase activity can be used for determining specific cancer types, providing insights into the mechanism of gene repression, and developing novel drugs to treat methylation-related diseases. Herein, we develop a simple and highly sensitive chemiluminescence (CL) biosensing platform for site-specific determination of DNA methylation using Exonuclease III (Exo III)-assisted target recycling signal amplification. After bisulfite treatment of mixture of methylated DNA and unmethylated DNA, methylated DNA can hybridize with fluorescein (FAM)-labeled probe DNA to form double-stranded DNA (dsDNA), removing the FAM-labeled probe DNA from the surface of grapheme oxide, and the chemiluminescence resonance energy transfer (CRET) sensing signal can be observed and then amplified using Exo III-based recycling strategy. The biosensing platform exhibits excellent high sensitivity, and it can ever distinguish as low as 0.002% methylation level from the mixture, which is superior to most currently reported methods used for DNA methylation assay. In addition, the proposed method can also be used to sensitively assay MTase activity with determination limit of 0.007 U/mL. This CL biosensing offers the advantages of being facile, sensitive, rapid and cost-effective. These features make the system promising for future use for early cancer diagnosis and discover of new anticancer drugs.