Jiali Zhang

Biocompatibility of Graphene Oxide

Herein, we report the effects of graphene oxides on human fibroblast cells and mice with the aim of investigating graphene oxides biocompatibility. The graphene oxides were prepared by the modified Hummers method and characterized by high-resolution transmission electron microscope and atomic force microscopy. The human fibroblast cells were cultured with different doses of graphene oxides for day 1 to day 5. Thirty mice divided into three test groups (low, middle, high dose) and one control group were injected with 0.1, 0.25, and 0.4 mg graphene oxides, respectively, and were raised for 1 day, 7 days, and 30 days, respectively. Results showed that the water-soluble graphene oxides were successfully prepared; graphene oxides with dose less than 20 μg/mL did not exhibit toxicity to human fibroblast cells, and the dose of more than 50 μg/mL exhibits obvious cytotoxicity such as decreasing cell adhesion, inducing cell apoptosis, entering into lysosomes, mitochondrion, endoplasm, and cell nucleus. Graphene oxides under low dose (0.1 mg) and middle dose (0.25 mg) did not exhibit obvious toxicity to mice and under high dose (0.4 mg) exhibited chronic toxicity, such as 4/9 mice death and lung granuloma formation, mainly located in lung, liver, spleen, and kidney, almost could not be cleaned by kidney. In conclusion, graphene oxides exhibit dose-dependent toxicity to cells and animals, such as inducing cell apoptosis and lung granuloma formation, and cannot be cleaned by kidney. When graphene oxides are explored for in vivo applications in animal or human body, its biocompatibility must be considered.

Graphene Oxide as a Matrix for Enzyme Immobilization

Graphene oxide (GO), having a large specific surface area and abundant functional groups, provides an ideal substrate for study enzyme immobilization. We demonstrated that the enzyme immobilization on the GO sheets could take place readily without using any cross-linking reagents and additional surface modification. The atomically flat surface enabled us to observe the immobilized enzyme in the native state directly using atomic force microscopy (AFM). Combining the AFM imaging results of the immobilized enzyme molecules and their catalytic activity, we illustrated that the conformation of the immobilized enzyme is mainly determined by interactions of enzyme molecules with the functional groups of GO.

The immunotoxicity of graphene oxides and the effect of PVP-coating

Graphene oxide (GO) immunotoxicity is not clarified well up to date. Herein we reported the effects of GOs with and without polyvinylpyrrolidone (PVP) coating on human immune cells such as dendritic cells (DCs), T lymphocytes and macrophages. Human immune cells such as dendritic cells (DCs), T lymphocytes and macrophages were isolated from health donated bloods, PVP-coating GO (PVP-GO) exhibited lower immunogenicity compared with pure GO on the aspect of inducing differentiation and maturation of dendritic cells (DCs), the levels of secreted TNF-α and IL-1β had no obvious difference between two groups, yet the secretion of IL-6 remained in PVP-coating GO group. In addition, PVP-coating GO delayed significantly the apoptotic process of T lymphocytes, at the same time, and exhibited anti-phagocytosis ability against macrophages and markedly enhanced the physiological activity of macrophages. In conclusion, PVP-coating GO possesses good immunological biocompatibility and immunoenhancement effects in vitro, and is likely to be an available candidate of immunoadjuvant in the future.

DNA cleavage system of nanosized graphene oxide sheets and copper ions.

The exploration of efficient DNA intercalative agents (intercalators) is essential for understanding DNA scission, repair, and signal transduction. In this work, we explored systematically the graphene oxide (GO) interaction with DNA molecules using fluorescence spectroscopic (FL) and circular dichroism (CD) studies, gel electrophoresis, and DNA thermal denaturation. We demonstrated that the GO nanosheets could intercalate efficiently into DNA molecules. Significantly, we illustrated that the scission of DNA by GO sheets combining with copper ions could take place pronouncedly. The scission of DNA by the GO/Cu(2+) system is critically dependent on the concentrations of GO and Cu(2+) and their ratio. DNA cleavage ability exhibited by the GO with several other metal ions and the fact that GO/Cu(2+)-cleaved DNA fragments can be partially relegated suggest that the mechanism of DNA cleavage by the GO/metal ion system is oxidative and hydrolytic. The result reveals that the GO/Cu(2+) could be used as a DNA cleaving system that should find many practical applications in biotechnology and as therapeutic agents.

Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation

In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO) were prepared and separated to individual sheets using Hummers method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future.

Individual nanocomposite sheets of chemically reduced graphene oxide and poly(N-vinyl pyrrolidone): preparation and humidity sensing characteristics

Individual nanocomposite sheets of chemically reduced graphene oxide (CRG) and poly(N-vinyl pyrrolidone) (PVP), namely CRG/PVP, have been fabricated through a simple one-pot procedure. The structure and composition of the as-prepared CRG/PVP sheets were complementarily characterized using solid-state 13C NMR, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and other spectroscopic measurements, demonstrating that the PVP molecules were chemically grafted on the CRG surfaces. The electrical conductivity of the individual CRG/PVP sheets was measured at different levels of relative humidity (RH) using a conductive atomic force microscopy (CAFM) system, revealing that the electrical conductivity of a CRG/PVP sheet is sensitive to RH variation with a response time of a few seconds. Given the easy mass scale production and improved electrical conductivity, we envisage that the CRG/PVP nanocomposite sheets should have a broad spectrum of applications in electrical conductivity based sensors.

Metastable intermolecular composites of Al and CuO nanoparticles assembled with graphene quantum dots

Metastable intermolecular composites (MICs) have attracted great attention during the last two decades owing to their potential applications for both civilian and military purposes. In this work, a novel category of MICs are assembled using Al and CuO nanoparticles (NPs), and graphene quantum dots (GQDs) as building blocks. It has been demonstrated that the as-assembled Al/GQDs/CuO MICs show unique energetic performance in contrast to the physical mixture of Al and CuO NPs. More specifically, the MICs assembled at relatively higher temperature and with proper Alu2006:u2006GQDsu2006:u2006CuO ratio of 20u2006:u20061u2006:u200690 (in weight) exhibit overall better energetic performances, including a higher heat releasing rate and larger specific heat. It was also illustrated that the specific heat amount released during the reaction can be lifted by whittling the oxide layer of the Al NPs surface, revealing that the inactive oxide layer on Al NPs should be one of the main reasons influencing the energetic performances of the MICs. Nevertheless, this work shows that the GQDs should be a useful media for MICs assembling.

Graphene Quantum Dots Downregulate Multiple Multidrug-Resistant Genes via Interacting with Their C-Rich Promoters

Multidrug resistance (MDR) is the major factor in the failure of many forms of chemotherapy, mostly due to the increased efflux of anticancer drugs that mediated by ATP-binding cassette (ABC) transporters. Therefore, inhibiting ABC transporters is one of effective methods of overcoming MDR. However, high enrichment of ABC transporters in cells and their broad substrate spectra made to circumvent MDR are almost insurmountable by a single specific ABC transporter inhibitor. Here, this study demonstrates that graphene quantum dots (GQDs) could downregulate the expressions of P-glycoprotein, multidrug resistance protein MRP1, and breast cancer resistance protein genes via interacting with C-rich regions of their promoters. This is the first example that a single reagent could suppress multiple MDR genes, suggesting that it will be possible to target multiple ABC transporters simultaneously with a single reagent. The inhibitory ability of the GQDs to these drug-resistant genes is validated further by reversing the doxorubicin resistance of MCF-7/ADR cells. Notably, GQDs have superb chemical and physical properties, unique structure, low toxicity, and high biocompatibility; hence, their capability of inhibiting multiple drug-resistant genes holds great potential in cancer therapy.

Three-dimensional composite of Co3O4 nanoparticles and nitrogen-doped reduced graphene oxide for lignin model compound oxidation

A three-dimensional composite of Co3O4 nanoparticles and nitrogen-doped reduced graphene oxide (3D Co3O4/N-rGO) with a unique 3D porous structure was prepared, and its catalytic activity in lignin model compound oxidation was explored. The 3D Co3O4/N-rGO composite exhibits improved catalytic performance as compared to Co3O4 nanoparticles or 3D N-rGO in the oxidation of lignin model compounds. The higher catalytic activity of the 3D Co3O4/N-rGO composite is attributed to the combination of its porous structural features, large surface area that is provided by the 3D N-rGO matrix, and active Co3O4 nanoparticles doped on the N-rGO surface. The structural features of the 3D Co3O4/N-rGO are beneficial to reactant and product diffusion and transportation, and also are helpful in preventing aggregation of Co3O4 nanoparticles. In addition, the introduction of N atoms in rGO is also favorable for the formation of active oxygen species for the oxidation of model compounds. Given the high activity and the easy recovery from the reaction system, the 3D Co3O4/N-rGO composite should be applicable to non-noble metal catalytic systems for lignin model compounds.

Composites of Graphene Quantum Dots and Reduced Graphene Oxide as Catalysts for Nitroarene Reduction

Composites of graphene quantum dots (GQDs) and reduced graphene oxide (rGO) with unique three-dimensional (3D) structure are prepared and their catalytic activities for reduction of nitroarenes are explored. We demonstrate that the 3D GQDs/rGO composites are more active in nitroarene reduction than GQDs and rGO. Some of them are even more active than the Ag-embedded calcium alginate (Ag/CA) or Au-embedded calcium alginate (Au/CA) catalysts. Interestingly, their catalytic property is closely related to the ratio of GQDs to rGO in the 3D GQDs/rGO composites and GQDs-to-rGO mass ratio of 1/4 exhibits the highest catalytic activity. Raman spectra of the composites show that GQDs-to-rGO ratio is related to the number of the surface/edge defects, indicating that the sites of defect and edges are active sites. In addition, the catalytic performance of the 3D GQDs/rGO composites is also contributed by their unique 3D network structures that are beneficial for the reactant adsorption and product diffusion. Given also the long cycling duration and the easy recovery from the reaction system, 3D GQDs/rGO composites are potential applicable metal-free catalytic system for nitorarene reduction.