Showing papers in "ACS Nano in 2011"
TL;DR: In this article, the present knowledge about point and line defects in graphene are reviewed and particular emphasis is put on the unique ability of graphene to reconstruct its lattice around intrinsic defects, leading to interesting effects and potential applications.
Abstract: Graphene is one of the most promising materials in nanotechnology. The electronic and mechanical properties of graphene samples with high perfection of the atomic lattice are outstanding, but structural defects, which may appear during growth or processing, deteriorate the performance of graphene-based devices. However, deviations from perfection can be useful in some applications, as they make it possible to tailor the local properties of graphene and to achieve new functionalities. In this article, the present knowledge about point and line defects in graphene are reviewed. Particular emphasis is put on the unique ability of graphene to reconstruct its lattice around intrinsic defects, leading to interesting effects and potential applications. Extrinsic defects such as foreign atoms which are of equally high importance for designing graphene-based devices with dedicated properties are also discussed.
2,828 citations
TL;DR: In this paper, the antibacterial activity of four types of graphene-based materials (graphite (Gt), graphite oxide (GtoO), reduced graphene oxide (rGO), and reduced GtO) toward a bacterial model (Escherichia coli) was investigated.
Abstract: Health and environmental impacts of graphene-based materials need to be thoroughly evaluated before their potential applications. Graphene has strong cytotoxicity toward bacteria. To better understand its antimicrobial mechanism, we compared the antibacterial activity of four types of graphene-based materials (graphite (Gt), graphite oxide (GtO), graphene oxide (GO), and reduced graphene oxide (rGO)) toward a bacterial model—Escherichia coli. Under similar concentration and incubation conditions, GO dispersion shows the highest antibacterial activity, sequentially followed by rGO, Gt, and GtO. Scanning electron microscope (SEM) and dynamic light scattering analyses show that GO aggregates have the smallest average size among the four types of materials. SEM images display that the direct contacts with graphene nanosheets disrupt cell membrane. No superoxide anion (O2•–) induced reactive oxygen species (ROS) production is detected. However, the four types of materials can oxidize glutathione, which serves ...
2,279 citations
TL;DR: A facile, catalyst-free thermal annealing approach for large-scale synthesis of NG using low-cost industrial material melamine as the nitrogen source is proposed, which can completely avoid the contamination of transition metal catalysts, and thus the intrinsic catalytic performance of pure NGs can be investigated.
Abstract: The electronic and chemical properties of graphene can be modulated by chemical doping foreign atoms and functional moieties. The general approach to the synthesis of nitrogen-doped graphene (NG), such as chemical vapor deposition (CVD) performed in gas phases, requires transitional metal catalysts which could contaminate the resultant products and thus affect their properties. In this paper, we propose a facile, catalyst-free thermal annealing approach for large-scale synthesis of NG using low-cost industrial material melamine as the nitrogen source. This approach can completely avoid the contamination of transition metal catalysts, and thus the intrinsic catalytic performance of pure NGs can be investigated. Detailed X-ray photoelectron spectrum analysis of the resultant products shows that the atomic percentage of nitrogen in doped graphene samples can be adjusted up to 10.1%. Such a high doping level has not been reported previously. High-resolution N1s spectra reveal that the as-made NG mainly contai...
2,242 citations
TL;DR: In this paper, the stiffness and breaking strength of monolayer MoS2, a new semiconducting analogue of graphene, was investigated. But the results were limited to the case of single and bilayer membranes, and the strength of strongest membranes was only 11% of its Young's modulus.
Abstract: We report on measurements of the stiffness and breaking strength of monolayer MoS2, a new semiconducting analogue of graphene. Single and bilayer MoS2 is exfoliated from bulk and transferred to a substrate containing an array of microfabricated circular holes. The resulting suspended, free-standing membranes are deformed and eventually broken using an atomic force microscope. We find that the in-plane stiffness of monolayer MoS2 is 180 ± 60 Nm–1, corresponding to an effective Young’s modulus of 270 ± 100 GPa, which is comparable to that of steel. Breaking occurs at an effective strain between 6 and 11% with the average breaking strength of 15 ± 3 Nm–1 (23 GPa). The strength of strongest monolayer membranes is 11% of its Young’s modulus, corresponding to the upper theoretical limit which indicates that the material can be highly crystalline and almost defect-free. Our results show that monolayer MoS2 could be suitable for a variety of applications such as reinforcing elements in composites and for fabricat...
2,111 citations
TL;DR: The unique two-dimensional structure, disordered surface morphology, heteroatomic defects, better electrode/electrolyte wettability, increased intersheet distance, improved electrical conductivity, and thermal stability of the doped graphene are beneficial to rapid surface Li(+) absorption and ultrafastLi(+) diffusion and electron transport, and thus make the doping materials superior to those of pristine chemically derived graphene and other carbonaceous materials.
Abstract: [Wu, Zhong-Shuai; Ren, Wencai; Xu, Li; Li, Feng; Cheng, Hui-Ming] Chinese Acad Sci, Shenyang Natl Lab Mat Sci, Inst Met Res, Shenyang 110016, Peoples R China.;Ren, WC (reprint author), Chinese Acad Sci, Shenyang Natl Lab Mat Sci, Inst Met Res, 72 Wenhua Rd, Shenyang 110016, Peoples R China;wcren@imr.ac.cn cheng@imr.ac.cn
1,847 citations
TL;DR: The superior electrochemical performances of MoS(2)/G composites as Li-ion battery anodes are attributed to their robust composite structure and the synergistic effects between layered MoS (2) and graphene.
Abstract: A facile process was developed to synthesize layered MoS2/graphene (MoS2/G) composites by an l-cysteine-assisted solution-phase method, in which sodium molybdate, as-prepared graphene oxide (GO), and l-cysteine were used as starting materials. As-prepared MoS2/G was then fabricated into layered MoS2/G composites after annealing in a H2/N2 atmosphere at 800 °C for 2 h. The samples were systematically investigated by X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy. Electrochemical performances were evaluated in two-electrode cells versus metallic lithium. It is demonstrated that the obtained MoS2/G composites show three-dimensional architecture and excellent electrochemical performances as anode materials for Li-ion batteries. The MoS2/G composite with a Mo:C molar ratio of 1:2 exhibits the highest specific capacity of ∼1100 mAh/g at a current of 100 mA/g, as well as excellent cycling stability and hig...
1,516 citations
TL;DR: Improved wet transfer onto perforated substrates with 2.7 μm diameter holes yields 98% coverage of holes covered with continuous films, allowing the ready use of Raman spectroscopy and transmission electron microscopy to study the intrinsic properties of CVD-grown monolayer graphene.
Abstract: Reproducible dry and wet transfer techniques were developed to improve the transfer of large-area monolayer graphene grown on copper foils by chemical vapor deposition (CVD). The techniques reported here allow transfer onto three different classes of substrates: substrates covered with shallow depressions, perforated substrates, and flat substrates. A novel dry transfer technique was used to make graphene-sealed microchambers without trapping liquid inside. The dry transfer technique utilizes a polydimethylsiloxane frame that attaches to the poly(methyl methacrylate) spun over the graphene film, and the monolayer graphene was transferred onto shallow depressions with 300 nm depth. The improved wet transfer onto perforated substrates with 2.7 μm diameter holes yields 98% coverage of holes covered with continuous films, allowing the ready use of Raman spectroscopy and transmission electron microscopy to study the intrinsic properties of CVD-grown monolayer graphene. Additionally, monolayer graphene transfer...
1,391 citations
TL;DR: This report reports on the first integrated circuit based on a two-dimensional semiconductor MoS(2) transistors, capable of operating as inverters, converting logical "1" into logical "0", with room-temperature voltage gain higher than 1, making them suitable for incorporation into digital circuits.
Abstract: Logic circuits and the ability to amplify electrical signals form the functional backbone of electronics along with the possibility to integrate multiple elements on the same chip. The miniaturization of electronic circuits is expected to reach fundamental limits in the near future. Two-dimensional materials such as single-layer MoS2 represent the ultimate limit of miniaturization in the vertical dimension, are interesting as building blocks of low-power nanoelectronic devices, and are suitable for integration due to their planar geometry. Because they are less than 1 nm thin, 2D materials in transistors could also lead to reduced short channel effects and result in fabrication of smaller and more power-efficient transistors. Here, we report on the first integrated circuit based on a two-dimensional semiconductor MoS2. Our integrated circuits are capable of operating as inverters, converting logical “1” into logical “0”, with room-temperature voltage gain higher than 1, making them suitable for incorporat...
1,244 citations
TL;DR: The synthesis approach presents a promising route for a large-scale production of RG-O platelet/metal oxide nanoparticle composites as electrode materials for Li-ion batteries.
Abstract: Reduced graphene oxide/Fe2O3 composite was prepared using a facile two-step synthesis by homogeneous precipitation and subsequent reduction of the G-O with hydrazine under microwave irradiation to yield reduced graphene oxide (RG-O) platelets decorated with Fe2O3 nanoparticles. As an anode material for Li-ion batteries, the RG-O/Fe2O3 composite exhibited discharge and charge capacities of 1693 and 1227 mAh/g, respectively, normalized to the mass of Fe2O3 in the composite (and ∼1355 and 982 mAh/g, respectively, based on the total mass of the composite), with good cycling performance and rate capability. Characterization shows that the Fe2O3 nanoparticles are uniformly distributed on the surface of the RG-O platelets in the composite. The total specific capacity of RG-O/Fe2O3 is higher than the sum of pure RG-O and nanoparticle Fe2O3, indicating a positive synergistic effect of RG-O and Fe2O3 on the improvement of electrochemical performance. The synthesis approach presents a promising route for a large-sca...
1,236 citations
TL;DR: Graphene films grown by chemical vapor deposition are demonstrated for the first time to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation, allowing pure metal surfaces only one atom away from reactive environments.
Abstract: The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. In particular, graphene prevents the formation of any oxide on the protected metal surfaces, thus allowing pure metal surfaces only one atom away from reactive environments. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 °C in air for up to 4 h. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth.
1,190 citations
TL;DR: Under the irradiation of 980 nm laser with the conservative and safe power density over a short period, cancer cells in vivo can be efficiently killed by the photothermal effects of the Cu(9)S(5) NCs.
Abstract: Photothermal ablation (PTA) therapy has a great potential to revolutionize conventional therapeutic approaches for cancers, but it has been limited by difficulties in obtaining biocompatible photothermal agents that have low cost, small size (<100 nm), and high photothermal conversion efficiency. Herein, we have developed hydrophilic plate-like Cu(9)S(5) nanocrystals (NCs, a mean size of ∼70 nm × 13 nm) as a new photothermal agent, which are synthesized by combining a thermal decomposition and ligand exchange route. The aqueous dispersion of as-synthesized Cu(9)S(5) NCs exhibits an enhanced absorption (e.g., ∼1.2 × 10(9) M(-1) cm(-1) at 980 nm) with the increase of wavelength in near-infrared (NIR) region, which should be attributed to localized surface plasmon resonances (SPR) arising from p-type carriers. The exposure of the aqueous dispersion of Cu(9)S(5) NCs (40 ppm) to 980 nm laser with a power density of 0.51 W/cm(2) can elevate its temperature by 15.1 °C in 7 min; a 980 nm laser heat conversion efficiency reaches as high as 25.7%, which is higher than that of the as-synthesized Au nanorods (23.7% from 980 nm laser) and the recently reported Cu(2-x)Se NCs (22% from 808 nm laser). Importantly, under the irradiation of 980 nm laser with the conservative and safe power density over a short period (∼10 min), cancer cells in vivo can be efficiently killed by the photothermal effects of the Cu(9)S(5) NCs. The present finding demonstrates the promising application of the Cu(9)S(5) NCs as an ideal photothermal agent in the PTA of in vivo tumor tissues.
TL;DR: Plasmonic effects influence the characteristics of polymer photovoltaic devices (OPVs) incorporating a blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C(61)-butyric acid methyl ester to trigger localized surface plasmon resonance (LSPR), which enhanced the performance of the OPVs without dramatically sacrificing their electrical properties.
Abstract: We have systematically explored how plasmonic effects influence the characteristics of polymer photovoltaic devices (OPVs) incorporating a blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). We blended gold nanoparticles (Au NPs) into the anodic buffer layer to trigger localized surface plasmon resonance (LSPR), which enhanced the performance of the OPVs without dramatically sacrificing their electrical properties. Steady state photoluminescence (PL) measurements revealed a significant increase in fluorescence intensity, which we attribute to the increased light absorption in P3HT induced by the LSPR. As a result, the rate of generation of excitons was enhanced significantly. Furthermore, dynamic PL measurements revealed that the LSPR notably reduced the lifetime of photogenerated excitons in the active blend, suggesting that interplay between the surface plasmons and excitons facilitated the charge transfer process. This phenomenon reduced the recombination level...
TL;DR: It is shown that the photothermal effect of graphene can be utilized to promote the delivery of Ce6 molecules by mild local heating when exposed to a near-infrared laser at a low power density, further enhancing the PDT efficacy against cancer cells.
Abstract: Graphene with unique physical and chemical properties has shown various potential applications in biomedicine. In this work, a photosensitizer molecule, Chlorin e6 (Ce6), is loaded on polyethylene glycol (PEG)-functionalized graphene oxide (GO) via supramolecular π–π stacking. The obtained GO-PEG-Ce6 complex shows excellent water solubility and is able to generate cytotoxic singlet oxygen under light excitation for photodynamic therapy (PDT). Owing to the significantly enhanced intracellular trafficking of photosensitizers, our GO-PEG-Ce6 complex offers a remarkably improved cancer cell photodynamic destruction effect compared to free Ce6. More importantly, we show that the photothermal effect of graphene can be utilized to promote the delivery of Ce6 molecules by mild local heating when exposed to a near-infrared laser at a low power density, further enhancing the PDT efficacy against cancer cells. Our work highlights the promise of using graphene for potential multifunctional cancer therapies.
TL;DR: It is reported that the strong noncovalent binding abilities of G allow it to act as a preconcentration platform for osteogenic inducers, which accelerate MSCs growing on it toward the osteogenic lineage.
Abstract: The culture of bone marrow derived mesenchymal stem cells (MSCs), as well as the control of its differentiation toward different tissue lineage, is a very important part of tissue engineering, where cells are combined with artificial scaffold to regenerate tissues. Graphene (G) and graphene oxide (GO) sheets are soft membranes with high in-plane stiffness and can potentially serve as a biocompatible, transferable, and implantable platform for stem cell culture. While the healthy proliferation of stem cells on various carbon platforms has been demonstrated, the chemical role of G and GO, if any, in guiding uncommitted stem cells toward differentiated cells is not known. Herein, we report that the strong noncovalent binding abilities of G allow it to act as a preconcentration platform for osteogenic inducers, which accelerate MSCs growing on it toward the osteogenic lineage. The molecular origin of accelerated differentation is investigated by studying the binding abilities of G and GO toward different grow...
TL;DR: A simple and fast electrochemical method to exfoliate graphite into thin graphene sheets, mainly AB-stacked bilayered graphene with a large lateral size, which exhibit ultratransparency and sheet resistance superior to those based on reduced graphene oxide or graphene sheets by other exfoliation methods are demonstrated.
Abstract: Flexible and ultratransparent conductors based on graphene sheets have been considered as one promising candidate for replacing currently used indium tin oxide films that are unlikely to satisfy future needs due to their increasing cost and losses in conductivity on bending. Here we demonstrate a simple and fast electrochemical method to exfoliate graphite into thin graphene sheets, mainly AB-stacked bilayered graphene with a large lateral size (several to several tens of micrometers). The electrical properties of these exfoliated sheets are readily superior to commonly used reduced graphene oxide, which preparation typically requires many steps including oxidation of graphite and high temperature reduction. These graphene sheets dissolve in dimethyl formamide (DMF), and they can self-aggregate at air-DMF interfaces after adding water as an antisolvent due to their strong surface hydrophobicity. Interestingly, the continuous films obtained exhibit ultratransparency (∼96% transmittance), and their sheet resistance is <1k Ω/sq after a simple HNO3 treatment, superior to those based on reduced graphene oxide or graphene sheets by other exfoliation methods. Raman and STM characterizations corroborate that the graphene sheets exfoliated by our electrochemical method preserve the intrinsic structure of graphene.
TL;DR: Graphene chemical vapor deposition growth on copper foil using methane as a carbon source is strongly affected by hydrogen, which appears to serve a dual role: an activator of the surface bound carbon that is necessary for monolayer growth and an etching reagent that controls the size and morphology of the graphene domains.
Abstract: We show that graphene chemical vapor deposition growth on copper foil using methane as a carbon source is strongly affected by hydrogen, which appears to serve a dual role: an activator of the surface bound carbon that is necessary for monolayer growth and an etching reagent that controls the size and morphology of the graphene domains. The resulting growth rate for a fixed methane partial pressure has a maximum at hydrogen partial pressures 200–400 times that of methane. The morphology and size of the graphene domains, as well as the number of layers, change with hydrogen pressure from irregularly shaped incomplete bilayers to well-defined perfect single layer hexagons. Raman spectra suggest the zigzag termination in the hexagons as more stable than the armchair edges.
TL;DR: It is suggested that Coulomb potential from trapped charges in the substrate is the dominant source of disorder in MoS(2) field-effect devices, which leads to carrier localization, as well, in low-temperature electrical transport experiments.
Abstract: We present low-temperature electrical transport experiments in five field-effect transistor devices consisting of monolayer, bilayer, and trilayer MoS(2) films, mechanically exfoliated onto Si/SiO(2) substrate. Our experiments reveal that the electronic states in all films are localized well up to room temperature over the experimentally accessible range of gate voltage. This manifests in two-dimensional (2D) variable range hopping (VRH) at high temperatures, while below ∼30 K, the conductivity displays oscillatory structures in gate voltage arising from resonant tunneling at the localized sites. From the correlation energy (T(0)) of VRH and gate voltage dependence of conductivity, we suggest that Coulomb potential from trapped charges in the substrate is the dominant source of disorder in MoS(2) field-effect devices, which leads to carrier localization, as well.
TL;DR: It is shown that graphene provides a promising biocompatible scaffold that does not hamper the proliferation of human mesenchymal stem cells and accelerates their specific differentiation into bone cells, demonstrating graphene's potential for stem cell research.
Abstract: Current tissue engineering approaches combine different scaffold materials with living cells to provide biological substitutes that can repair and eventually improve tissue functions. Both natural and synthetic materials have been fabricated for transplantation of stem cells and their specific differentiation into muscles, bones, and cartilages. One of the key objectives for bone regeneration therapy to be successful is to direct stem cells’ proliferation and to accelerate their differentiation in a controlled manner through the use of growth factors and osteogenic inducers. Here we show that graphene provides a promising biocompatible scaffold that does not hamper the proliferation of human mesenchymal stem cells (hMSCs) and accelerates their specific differentiation into bone cells. The differentiation rate is comparable to the one achieved with common growth factors, demonstrating graphene’s potential for stem cell research.
TL;DR: This work demonstrates a green and facile approach to the synthesis of graphene nanosheets based on Fe reduction of exfoliated graphite oxide, resulting in a substantial removal of oxygen functionalities of thegraphite oxide.
Abstract: The synthesis of graphene nanosheets from graphite oxide typically involves harmful chemical reductants that are undesirable for most practical applications of graphene. Here, we demonstrate a green and facile approach to the synthesis of graphene nanosheets based on Fe reduction of exfoliated graphite oxide, resulting in a substantial removal of oxygen functionalities of the graphite oxide. More interestingly, the resulting graphene nanosheets with residual Fe show a high adsorption capacity of 111.62 mg/g for methylene blue at room temperature, as well as easy magnetic separation from the solution. This approach offers a potential for cost-effective, environmentally friendly, and large-scale production of graphene nanosheets.
TL;DR: The application of conducting polymer to minimize the diffusion of polysulfides out of the mesoporous carbon matrix by coating poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) onto mesoporus carbon/sulfur particles.
Abstract: Rechargeable lithium–sulfur (Li–S) batteries hold great potential for next-generation high-performance energy storage systems because of their high theoretical specific energy, low materials cost, and environmental safety. One of the major obstacles for its commercialization is the rapid capacity fading due to polysulfide dissolution and uncontrolled redeposition. Various porous carbon structures have been used to improve the performance of Li–S batteries, as polysulfides could be trapped inside the carbon matrix. However, polysulfides still diffuse out for a prolonged time if there is no effective capping layer surrounding the carbon/sulfur particles. Here we explore the application of conducting polymer to minimize the diffusion of polysulfides out of the mesoporous carbon matrix by coating poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) onto mesoporous carbon/sulfur particles. After surface coating, coulomb efficiency of the sulfur electrode was improved from 93% to 97%, and capaci...
TL;DR: This study shows experimentally that the retention loss in a nanoscale memristor device bears striking resemblance to memory loss in biological systems and confirms that not only the shape or the total number of stimuli is influential, but also the time interval between stimulation pulses plays a crucial role in determining the effectiveness of the transition.
Abstract: “Memory” is an essential building block in learning and decision-making in biological systems. Unlike modern semiconductor memory devices, needless to say, human memory is by no means eternal. Yet, forgetfulness is not always a disadvantage since it releases memory storage for more important or more frequently accessed pieces of information and is thought to be necessary for individuals to adapt to new environments. Eventually, only memories that are of significance are transformed from short-term memory into long-term memory through repeated stimulation. In this study, we show experimentally that the retention loss in a nanoscale memristor device bears striking resemblance to memory loss in biological systems. By stimulating the memristor with repeated voltage pulses, we observe an effect analogous to memory transition in biological systems with much improved retention time accompanied by additional structural changes in the memristor. We verify that not only the shape or the total number of stimuli is i...
TL;DR: Using density functional theory coupled with Boltzmann transport equation with relaxation time approximation, the electronic structure is investigated and the charge mobility for a new carbon allotrope, the graphdiyne for both the sheet and nanoribbons is predicted.
Abstract: Using density functional theory coupled with Boltzmann transport equation with relaxation time approximation, we investigate the electronic structure and predict the charge mobility for a new carbon allotrope, the graphdiyne for both the sheet and nanoribbons. It is shown that the graphdiyne sheet is a semiconductor with a band gap of 0.46 eV. The calculated in-plane intrinsic electron mobility can reach the order of 10(5) cm(2)/(V s) at room temperature, while the hole mobility is about an order of magnitude lower.
TL;DR: The observation of this FBS-mitigated GO cytotoxicity effect may provide an alternative and convenient route to engineer nanomaterials for safe biomedical and environmental applications.
Abstract: Graphene is a single layer of sp(2)-bonded carbons that has unique and highly attractive electronic, mechanical, and thermal properties. Consequently, the potential impact of graphene and its derivatives (e.g., graphene oxide, GO) on human and environmental health has raised considerable concerns. In this study, we have carried out a systematic investigation on cellular effects of GO nanosheets and identified the effect of fetal bovine serum (FBS), an often-employed component in cell culture medium, on the cytotoxicity of GO. At low concentrations of FBS (1%), human cells were sensitive to the presence of GO and showed concentration-dependent cytotoxicity. Interestingly, the cytotoxicity of GO was greatly mitigated at 10% FBS, the concentration usually employed In cell medium. Our studies have demonstrated that the cytotoxicity of GO nanosheets arises from direct Interactions between the cell membrane and GO nanosheets that result in physical damage to the cell membrane. This effect is largely attenuated when GO is incubated with FBS due to the extremely high protein adsorption ability of GO. The observation of this FBS-mitigated GO cytotoxicity effect may provide an alternative and convenient route to engineer nanomaterials for safe biomedical and environmental applications.
TL;DR: A "modified RCA clean" transfer method is developed that has much better control of both contamination and crack formation and does not degrade the quality of the transferred graphene.
Abstract: We present the results of a thorough study of wet chemical methods for transferring chemical vapor deposition grown graphene from the metal growth substrate to a device-compatible substrate. On the basis of these results, we have developed a “modified RCA clean” transfer method that has much better control of both contamination and crack formation and does not degrade the quality of the transferred graphene. Using this transfer method, high device yields, up to 97%, with a narrow device performance metrics distribution were achieved. This demonstration addresses an important step toward large-scale graphene-based electronic device applications.
TL;DR: Results show that PEGylated NGS mainly accumulate in the reticuloendothelial system (RES) including liver and spleen after intravenous administration and can be gradually cleared, likely by both renal and fecal excretion.
Abstract: Graphene has emerged as interesting nanomaterials with promising applications in a range of fields including biomedicine. In this work, for the first time we study the long-term in vivo biodistribution of 125I-labeled nanographene sheets (NGS) functionalized with polyethylene glycol (PEG) and systematically examine the potential toxicity of graphene over time. Our results show that PEGylated NGS mainly accumulate in the reticuloendothelial system (RES) including liver and spleen after intravenous administration and can be gradually cleared, likely by both renal and fecal excretion. PEGylated NGS do not cause appreciable toxicity at our tested dose (20 mg/kg) to the treated mice in a period of 3 months as evidenced by blood biochemistry, hematological analysis, and histological examinations. Our work greatly encourages further studies of graphene for biomedical applications.
TL;DR: Hematology, serum biochemistry, and histopathology results indicate that MSNs would not cause significant toxicity in vivo, but there is potential induction of biliary excretion and glomerular filtration dysfunction.
Abstract: In our previous study we reported that the interaction of nanoparticles with cells can be influenced by particle shape, but until now the effect of particle shape on in vivo behavior remained poorly understood. In the present study, we control the fabrication of fluorescent mesoporous silica nanoparticles (MSNs) by varying the concentration of reaction reagents especially to design a series of shapes. Two different shaped fluorescent MSNs (aspect ratios, 1.5, 5) were specially designed, and the effects of particle shape on biodistribution, clearance and biocompatibility in vivo were investigated. Organ distributions show that intravenously administrated MSNs are mainly present in the liver, spleen and lung (>80%) and there is obvious particle shape effects on in vivo behaviors. Short-rod MSNs are easily trapped in the liver, while long-rod MSNs distribute in the spleen. MSNs with both aspect ratios have a higher content in the lung after PEG modification. We also found MSNs are mainly excreted by urine an...
TL;DR: The complexity of the plasma corona is demonstrated and its still unresolved physicochemical regulation is demonstrated, which need to be considered in nanobioscience in the future.
Abstract: In biological fluids, proteins associate with nanoparticles, leading to a protein “corona” defining the biological identity of the particle. However, a comprehensive knowledge of particle-guided protein fingerprints and their dependence on nanomaterial properties is incomplete. We studied the long-lived (“hard”) blood plasma derived corona on monodispersed amorphous silica nanoparticles differing in size (20, 30, and 100 nm). Employing label-free liquid chromatography mass spectrometry, one- and two-dimensional gel electrophoresis, and immunoblotting the composition of the protein corona was analyzed not only qualitatively but also quantitatively. Detected proteins were bioinformatically classified according to their physicochemical and biological properties. Binding of the 125 identified proteins did not simply reflect their relative abundance in the plasma but revealed an enrichment of specific lipoproteins as well as proteins involved in coagulation and the complement pathway. In contrast, immunoglobul...
TL;DR: This study developed a simple technique to produce transferrin-coated gold nanoparticle aggregates of different sizes and characterized their uptake and toxicity in three different cell lines and found that cell type and the mechanism of interactions may play a significant role.
Abstract: Aggregation appears to be a ubiquitous phenomenon among all nanoparticles and its influence in mediating cellular uptake and interactions remain unclear. Here we developed a simple technique to produce transferrin-coated gold nanoparticle aggregates of different sizes and characterized their uptake and toxicity in three different cell lines. While the aggregation did not elicit a unique toxic response, the uptake patterns were different between single and aggregated nanoparticles. There was a 25% decrease in uptake of aggregated nanoparticles with HeLa and A549 cells in comparison to single and monodisperse nanoparticles. However, there was a 2-fold increase in MDA-MB 435 cell uptake for the largest synthesized aggregates. These contrasting results suggest that cell type and the mechanism of interactions may play a significant role. This study highlights the need to investigate the behavior of aggregates with cells on a case-by-case basis and the importance of aggregation in mediating targeting and intrac...
TL;DR: DOX-Hyd@AuNPs represents a model with dual roles in overcoming MDR in cancer cells and probing the intracellular release of drug from its delivery system.
Abstract: Multidrug resistance (MDR) is a major impediment to the success of cancer chemotherapy. Through the development of a drug delivery system that tethers doxorubicin onto the surface of gold nanoparticles with a poly(ethylene glycol) spacer via an acid-labile linkage (DOX-Hyd@AuNPs), we have demonstrated that multidrug resistance in cancer cells can be significantly overcome by a combination of highly efficient cellular entry and a responsive intracellular release of doxorubicin from the gold nanoparticles in acidic organelles. DOX-Hyd@AuNPs achieved enhanced drug accumulation and retention in multidrug resistant MCF-7/ADR cancer cells when it was compared with free doxorubicin. It released doxorubicin in response to the pH of acidic organelles following endocytosis, opposite to the noneffective drug release from doxorubicin-tethered gold nanoparticles via the carbamate linkage (DOX-Cbm@AuNPs), which was shown by the recovered fluorescence of doxorubicin from quenching due to the nanosurface energy transfer ...
TL;DR: The results confirm that significant evolution of the corona occurs in the second biological solution, but that the final corona contains a "fingerprint" of its history, which could be evolved to map the transport pathways utilized by nanoparticles, and eventually to predict nanoparticle fate and behavior.
Abstract: The importance of the protein corona formed around nanoparticles upon entering a biological fluid has recently been highlighted. This corona is, when sufficiently long-lived, thought to govern the particles’ biological fate. However, even this long-lived “hard” corona evolves and re-equilibrates as particles pass from one biological fluid to another, and may be an important feature for long-term fate. Here we show the evolution of the protein corona as a result of transfer of nanoparticles from one biological fluid (plasma) into another (cytosolic fluid), a simple illustrative model for the uptake of nanoparticles into cells. While no direct comparison can be made to what would happen in, for example, the uptake pathway, the results confirm that significant evolution of the corona occurs in the second biological solution, but that the final corona contains a “fingerprint” of its history. This could be evolved to map the transport pathways utilized by nanoparticles, and eventually to predict nanoparticle f...