A review on synthesis, properties, and biomedical applications of graphene quantum dots (GQDs).

A new type of 0-dimensional carbon-based materials called graphene quantum dots (GQDs) is gaining significant attention as a non-toxic and eco-friendly nanomaterial. GQDs are nanomaterials composed of sp2hybridized carbon domains and functional groups, with their lateral size less than 10 nm. The unique and exceptional physical, chemical, and optical properties arising from the combination of graphene structure and quantum confinement effect due to their nano-size make GQDs more intriguing than other nanomaterials. Particularly, the low toxicity and high solubility derived from the carbon core and abundant edge functional groups offer significant advantages for the application of GQDs in the biomedical field. In this review, we summarize various synthetic methods for preparing GQDs and important factors influencing the physical, chemical, optical, and biological properties of GQDs. Furthermore, the recent application of GQDs in the biomedical field, including biosensor, bioimaging, drug delivery, and therapeutics are discussed. Through this, we provide a brief insight on the tremendous potential of GQDs in biomedical applications and the challenges that need to be overcome in the future.

Graphene Quantum Dots Alleviate Impaired Functions in Niemann-Pick Disease Type C in Vivo.

While the neuropathological characteristics of Niemann-Pick disease type C (NPC) result in a fatal diagnosis, the development of clinically available therapeutic agent remains a challenge. Here we propose graphene quantum dots (GQDs) as a potential candidate for the impaired functions in NPC in vivo. In addition to the previous findings that GQDs exhibit negligible long-term toxicity and are capable of penetrating the blood-brain barrier, GQD treatment reduces the aggregation of cholesterol in the lysosome through expressed physical interactions. GQDs also promote autophagy and restore defective autophagic flux, which, in turn, decreases the atypical accumulation of autophagic vacuoles. More importantly, the injection of GQDs inhibits the loss of Purkinje cells in the cerebellum while also demonstrating reduced activation of microglia. The ability of GQDs to alleviate impaired functions in NPC proves the promise and potential of the use of GQDs toward resolving NPC and other related disorders.

Threshold Voltage Control of Multilayered MoS2 Field-Effect Transistors via Octadecyltrichlorosilane and their Applications to Active Matrixed Quantum Dot Displays Driven by Enhancement-Mode Logic Gates.

In recent past, for next-generation device opportunities such as sub-10 nm channel field-effect transistors (FETs), tunneling FETs, and high-end display backplanes, tremendous research on multilayered molybdenum disulfide (MoS2 ) among transition metal dichalcogenides has been actively performed. However, nonavailability on a matured threshold voltage control scheme, like a substitutional doping in Si technology, has been plagued for the prosperity of 2D materials in electronics. Herein, an adjustment scheme for threshold voltage of MoS2 FETs by using self-assembled monolayer treatment via octadecyltrichlorosilane is proposed and demonstrated to show MoS2 FETs in an enhancement mode with preservation of electrical parameters such as field-effect mobility, subthreshold swing, and current on-off ratio. Furthermore, the mechanisms for threshold voltage adjustment are systematically studied by using atomic force microscopy, Raman, temperature-dependent electrical characterization, etc. For validation of effects of threshold voltage engineering on MoS2 FETs, full swing inverters, comprising enhancement mode drivers and depletion mode loads are perfectly demonstrated with a maximum gain of 18.2 and a noise margin of ≈45% of 1/2 VDD . More impressively, quantum dot light-emitting diodes, driven by enhancement mode MoS2 FETs, stably demonstrate 120 cd m-2 at the gate-to-source voltage of 5 V, exhibiting promising opportunities for future display application.

Continuous Films of Self-Assembled Graphene Quantum Dots for n-Type Doping of Graphene by UV-Triggered Charge Transfer.

The demands to examine components serving as one of the active layers in heterostructures of 2D materials have been recently increasing. Nanomaterials synthesized from a solution process and their self-assembly can provide a promising route to build a new type of mixed dimensional heterostructures, and several methodologies have been reported previously to construct 2D assemblies from colloidal nanostructures in solution. Graphene quantum dots (GQDs), receiving much interest due to the tunable optical band gap and the capability of chemical functionalization, are considered as emerging nanomaterials for various optoelectronic and biological applications. This study fabricates a closely packed GQDs film (GQDF) from colloidal solutions using a solvent-assisted Langmuir Blodgett method, and investigates the optical and electrical characteristics of the heterostacked graphene/GQD film (G/GQDF) structures. It is observed that the GQDF plays a role not only as a buffer layer that isolates Chemical Vapor Deposited graphene (CVD graphene) from undesired p-doping but also as a photoactive layer that triggers n-doping of the heterostacked CVD graphene film. The n-doping density of the G/GQDF device is proportional to UV irradiation time, but its carrier mobility remains constant regardless of doping densities, which are unique characteristics that have not been observed in other doping methods.

Multiscale Modulation of Nanocrystalline Cellulose Hydrogel via Nanocarbon Hybridization for 3D Neuronal Bilayer Formation.

Bacterial biopolymers have drawn much attention owing to their unconventional three-dimensional structures and interesting functions, which are closely integrated with bacterial physiology. The nongenetic modulation of bacterial (Acetobacter xylinum) cellulose synthesis via nanocarbon hybridization, and its application to the emulation of layered neuronal tissue, is reported. The controlled dispersion of graphene oxide (GO) nanoflakes into bacterial cellulose (BC) culture media not only induces structural changes within a crystalline cellulose nanofibril, but also modulates their 3D collective association, leading to substantial reduction in Young's modulus (≈50%) and clear definition of water-hydrogel interfaces. Furthermore, real-time investigation of 3D neuronal networks constructed in this GO-incorporated BC hydrogel with broken chiral nematic ordering revealed the vertical locomotion of growth cones, the accelerated neurite outgrowth (≈100 µm per day) with reduced backward travel length, and the efficient formation of synaptic connectivity with distinct axonal bifurcation abundancy at the ≈750 µm outgrowth from a cell body. In comparison with the pristine BC, GO-BC supports the formation of well-defined neuronal bilayer networks with flattened interfacial profiles and vertical axonal outgrowth, apparently emulating the neuronal development in vivo. We envisioned that our findings may contribute to various applications of engineered BC hydrogel to fundamental neurobiology studies and neural engineering.

Strain Relaxation of Graphene Layers by Cu Surface Roughening.

The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by ∼1.41% and ∼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene.

Distortion in Two-Dimensional Shapes of Merging Nanobubbles: Evidence for Anisotropic Gas Flow Mechanism.

Two nanobubbles that merge in a graphene liquid cell take elliptical shapes rather than the ideal circular shapes. This phenomenon was investigated in detail by using in situ transmission electron microscopy (TEM). The results show that the distortion in the two-dimensional shapes of the merging nanobubbles is attributed to the anisotropic gas transport flux between the nanobubbles. We also predicted and confirmed the same phenomenon in a three-nanobubble system, indicating that the relative size difference is important in determining the shape of merging nanobubbles.

Correction: Graphene-catalyzed photoreduction of dye molecules revealed by graphene enhanced Raman spectroscopy.

Correction for 'Graphene-catalyzed photoreduction of dye molecules revealed by graphene enhanced Raman spectroscopy' by Bora Lee et al., Phys. Chem. Chem. Phys., 2016, 18, 3413-3415.

Graphene-catalyzed photoreduction of dye molecules revealed by graphene enhanced Raman spectroscopy.

The unique electrical and optical properties of graphene have enabled its application in various photocatalysis reactions. However, graphene needs to be combined with photosensitizing co-catalysts such as TiO2 due to its negligible visible light absorption. Here, we report that the single layer graphene by itself is capable of catalyzing the photoreduction of dye molecules, which has been revealed by graphene-enhanced Raman spectroscopy studies. The proposed mechanism involves the electron transfer from graphene to temporarily empty HOMO states of photoexcited dye molecules, which can be interpreted as ultrafast hole transfer from dyes to graphene. We also confirm that graphene-encapsulated nitrobenzene dyes show less photoreduction, implying that the ambient hydrogen molecules are the important source of photoreduction into aniline dyes. The photocatalytic reactivity of graphene would find numerous energy and environmental applications in the future.

Graphene-based nanomaterials for versatile imaging studies.

Over the last decade, interest in graphene has surged because of its unprecedented physical, chemical, electrical, and mechanical properties. In recent years, researchers' interests have gradually shifted to other notable properties of graphene - its environmentally-friendly nature with outstanding optical properties. Thus, graphene is considered to be a promising and attractive candidate for various biomedical applications such as NIR-responsive cancer therapy and fluorescence bio-imaging. To that end, appropriate preparation and novel approaches to utilize graphene-based materials such as graphene oxides (GOs), reduced graphene oxides (rGOs), and graphene quantum dots (GQDs) in biology and medical science are gaining growing interest. In this review, we highlight recent applications of graphene-based materials as novel prospects for versatile imaging studies with a brief perspective on their future applications.

Ultraclean patterned transfer of single-layer graphene by recyclable pressure sensitive adhesive films.

We report an ultraclean, cost-effective, and easily scalable method of transferring and patterning large-area graphene using pressure sensitive adhesive films (PSAFs) at room temperature. This simple transfer is enabled by the difference in wettability and adhesion energy of graphene with respect to PSAF and a target substrate. The PSAF-transferred graphene is found to be free from residues and shows excellent charge carrier mobility as high as ∼17,700 cm(2)/V·s with less doping compared to the graphene transferred by thermal release tape (TRT) or poly(methyl methacrylate) (PMMA) as well as good uniformity over large areas. In addition, the sheet resistance of graphene transferred by recycled PSAF does not change considerably up to 4 times, which would be advantageous for more cost-effective and environmentally friendly production of large-area graphene films for practical applications.

Fluorinated CYTOP passivation effects on the electrical reliability of multilayer MoS2 field-effect transistors.

We demonstrated highly stable multilayer molybdenum disulfide (MoS2) field-effect transistors (FETs) with negligible hysteresis gap (ΔV(HYS) ∼ 0.15 V) via a multiple annealing scheme, followed by systematic investigation for long-term air stability with time (∼50 days) of MoS2 FETs with (or without) CYTOP encapsulation. The extracted lifetime of the device with CYTOP passivation in air was dramatically improved from 7 to 377 days, and even for the short-term bias stability, the experimental threshold voltage shift, outstandingly well-matched with the stretched exponential function, indicates that the device without passivation has approximately 25% larger the barrier distribution (ΔE(B) = k(B)T(o)) than that of a device with passivation. This work suggests that CYTOP encapsulation can be an efficient method to isolate external gas (O2 and H2O) effects on the electrical performance of FETs, especially with low-dimensional active materials like MoS2.

Stable n-type doping of graphene via high-molecular-weight ethylene amines.

We demonstrate a stable and strong n-type doping method to tune the electrical properties of graphene via vapor phase chemical doping with various high-molecular-weight ethylene amines. The resulting carrier concentration after doping with pentaethylenehexamine (PEHA) is as high as -1.01 × 10(13) cm(-2), which reduces the sheet resistance of graphene by up to ∼400% compared to pristine graphene. Our study suggests that the branched structure of the dopant molecules is another important factor that determines the actual doping degree of graphene.

Large-scale pattern growth of graphene films for stretchable transparent electrodes.

Problems associated with large-scale pattern growth of graphene constitute one of the main obstacles to using this material in device applications. Recently, macroscopic-scale graphene films were prepared by two-dimensional assembly of graphene sheets chemically derived from graphite crystals and graphene oxides. However, the sheet resistance of these films was found to be much larger than theoretically expected values. Here we report the direct synthesis of large-scale graphene films using chemical vapour deposition on thin nickel layers, and present two different methods of patterning the films and transferring them to arbitrary substrates. The transferred graphene films show very low sheet resistance of approximately 280 Omega per square, with approximately 80 per cent optical transparency. At low temperatures, the monolayers transferred to silicon dioxide substrates show electron mobility greater than 3,700 cm(2) V(-1) s(-1) and exhibit the half-integer quantum Hall effect, implying that the quality of graphene grown by chemical vapour deposition is as high as mechanically cleaved graphene. Employing the outstanding mechanical properties of graphene, we also demonstrate the macroscopic use of these highly conducting and transparent electrodes in flexible, stretchable, foldable electronics.

Graphene enhances the cardiomyogenic differentiation of human embryonic stem cells.

Graphene has drawn attention as a substrate for stem cell culture and has been reported to stimulate the differentiation of multipotent adult stem cells. Here, we report that graphene enhances the cardiomyogenic differentiation of human embryonic stem cells (hESCs) at least in part, due to nanoroughness of graphene. Large-area graphene on glass coverslips was prepared via the chemical vapor deposition method. The coating of the graphene with vitronectin (VN) was required to ensure high viability of the hESCs cultured on the graphene. hESCs were cultured on either VN-coated glass (glass group) or VN-coated graphene (graphene group) for 21 days. The cells were also cultured on glass coated with Matrigel (Matrigel group), which is a substrate used in conventional, directed cardiomyogenic differentiation systems. The culture of hESCs on graphene promoted the expression of genes involved in the stepwise differentiation into mesodermal and endodermal lineage cells and subsequently cardiomyogenic differentiation compared with the culture on glass or Matrigel. In addition, the culture on graphene enhanced the gene expression of cardiac-specific extracellular matrices. Culture on graphene may provide a new platform for the development of stem cell therapies for ischemic heart diseases by enhancing the cardiomyogenic differentiation of hESCs.

Biomedical applications of graphene and graphene oxide.

Graphene has unique mechanical, electronic, and optical properties, which researchers have used to develop novel electronic materials including transparent conductors and ultrafast transistors. Recently, the understanding of various chemical properties of graphene has facilitated its application in high-performance devices that generate and store energy. Graphene is now expanding its territory beyond electronic and chemical applications toward biomedical areas such as precise biosensing through graphene-quenched fluorescence, graphene-enhanced cell differentiation and growth, and graphene-assisted laser desorption/ionization for mass spectrometry. In this Account, we review recent efforts to apply graphene and graphene oxides (GO) to biomedical research and a few different approaches to prepare graphene materials designed for biomedical applications. Because of its excellent aqueous processability, amphiphilicity, surface functionalizability, surface enhanced Raman scattering (SERS), and fluorescence quenching ability, GO chemically exfoliated from oxidized graphite is considered a promising material for biological applications. In addition, the hydrophobicity and flexibility of large-area graphene synthesized by chemical vapor deposition (CVD) allow this material to play an important role in cell growth and differentiation. The lack of acceptable classification standards of graphene derivatives based on chemical and physical properties has hindered the biological application of graphene derivatives. The development of an efficient graphene-based biosensor requires stable biofunctionalization of graphene derivatives under physiological conditions with minimal loss of their unique properties. For the development graphene-based therapeutics, researchers will need to build on the standardization of graphene derivatives and study the biofunctionalization of graphene to clearly understand how cells respond to exposure to graphene derivatives. Although several challenging issues remain, initial promising results in these areas point toward significant potential for graphene derivatives in biomedical research.

Carbon nanostructure-based saturable absorber mirror for a diode-pumped 500-MHz femtosecond Yb:KLu(WO4)2 laser.

We report a diode-pumped Yb:KLu(WO(4))(2) (Yb:KLuW) laser passively mode-locked by employing a carbon nanostructure-based multi-functional saturable absorber mirror. Two types of carbon nanostructures, single-walled carbon nanotubes (SWCNTs) and graphene, were deposited on a single dielectric mirror and applied both for stable mode-locking of the Yb:KLuW laser near 1050 nm in a compact cavity configuration. The carbon nanostructure mode-locked laser delivers 157-fs pulses with output powers of up to 85 mW at a repetition rate of 500 MHz.

Highly uniform growth of monolayer graphene by chemical vapor deposition on Cu-Ag alloy catalysts.

One of the major challenges for the practical application of graphene is the large scale synthesis of uniform films with high quality at lower temperature. Here, we demonstrate the use of Ag-plated Cu substrates in the synthesis of high-quality graphene films via chemical vapor deposition (CVD) of methane gas at temperatures as low as 900 °C. Various experimental analyses show that the plated Ag diffuses into Cu to form a uniform Cu-Ag alloy that suppresses the formation of multilayer nucleation and decreases the activation energy of precursor formation, leading to a lower synthesis temperature with enhanced monolayer coverage. In addition, we also observed an unusual Ag-assisted abnormal grain growth of Cu into the cube texture with larger grain sizes and reduced grain boundaries, which is believed to provide the homogeneous environment needed for uniform graphene growth.

Engineering functionalization and properties of graphene quantum dots (GQDs) with controllable synthesis for energy and display applications.

Graphene quantum dots (GQDs), a new type of 0D nanomaterial, are composed of a graphene lattice with sp2 bonding carbon core and characterized by their abundant edges and wide surface area. This unique structure imparts excellent electrical properties and exceptional physicochemical adsorption capabilities to GQDs. Additionally, the reduction in dimensionality of graphene leads to an open band gap in GQDs, resulting in their unique optical properties. The functional groups and dopants in GQDs are key factors that allow the modulation of these characteristics. So, controlling the functionalization level of GQDs is crucial for understanding their characteristics and further application. This review provides an overview of the properties and structure of GQDs and summarizes recent developments in research that focus on their controllable synthesis, involving functional groups and doping. Additionally, we provide a comprehensive and focused explanation of how GQDs have been advantageously applied in recent years, particularly in the fields of energy storage devices and displays.

Sub-100-fs Cr:YAG laser mode-locked by monolayer graphene saturable absorber.

We report on mode-locking of a Cr:YAG laser at 1516 nm using a monolayer graphene-based saturable absorber of transmission type generating 91 fs pulses with a Fourier product of 0.38 at an average output power exceeding 100 mW. Stable single-pulse mode-locked operation without any sign of Q-switching instabilities or multiple pulses is achieved.