Visible-Light-Assisted Photoelectrochemical Biosensing of Uric Acid Using Metal-Free Graphene Oxide Nanoribbons.

In this study, we demonstrate the visible-light-assisted photoelectrochemical (PEC) biosensing of uric acid (UA) by using graphene oxide nanoribbons (GONRs) as PEC electrode materials. Specifically, GONRs with controlled properties were synthesized by the microwave-assisted exfoliation of multi-walled carbon nanotubes. For the detection of UA, GONRs were adopted to modify either a screen-printed carbon electrode (SPCE) or a glassy carbon electrode (GCE). Cyclic voltammetry analyses indicated that all Faradaic currents of UA oxidation on GONRs with different unzipping/exfoliating levels on SPCE increased by more than 20.0% under AM 1.5 irradiation. Among these, the GONRs synthesized under a microwave power of 200 W, namely GONR(200 W), exhibited the highest increase in Faradaic current. Notably, the GONR(200 W)/GCE electrodes revealed a remarkable elevation (~40.0%) of the Faradaic current when irradiated by light-emitting diode (LED) light sources under an intensity of illumination of 80 mW/cm2. Therefore, it is believed that our GONRs hold great potential for developing a novel platform for PEC biosensing.

Antioxidant Graphene Oxide Nanoribbon as a Novel Whitening Agent Inhibits Microphthalmia-Associated Transcription Factor-Related Melanogenesis Mechanism.

In the melanin synthesis process, oxidative reactions play an essential role, and it is a good strategy to inhibit melanin production by reducing oxidative stress. Fullerene and its derivatives, or the complexes, were considered as strong free-radical scavengers, and we further applied multilayered sp2 nanocarbons to discover melanin synthesis inhibitory mechanisms. In the present study, we used novel nanomaterials, such as multiwalled carbon nanotubes (MWCNTs), short-type MWCNTs, graphene oxide nanoribbons (GONRs), and short-type GONRs, as anti-oxidative agents to regulate melanin production. The results showed that GONRs had better anti-oxidative capabilities in intracellular and extracellular oxidative stress analysis platforms than others. We proposed that GONRs have oxygen-containing functional groups. In the 2',7'-dichlorodihydrofluorescein diacetate assay, we found out GONR could chelate metal ions to scavenge reactive oxygen species. In the molecular insight view, we observed that these nanomaterials downregulated the melanin synthesis by decreasing microphthalmia-associated transcription factor-related gene expressions, and there were similar consequences in protein expressions. To sum up, GONRs is a potential agent as a novel antioxidant and skin-whitening cosmetology material.

Low-Temperature CVD Graphene Nanostructures on Cu and Their Corrosion Properties.

Chemical vapor deposition (CVD) graphene is reported to effectively prevent the penetration of outer factors and insulate the underneath metals, hence achieving an anticorrosion purpose. However, there is little knowledge about their characteristics and corresponding corrosion properties, especially for those prepared under different parameters at low temperatures. Using electron cyclotron resonance chemical vapor deposition (ECR-CVD), we can successfully prepare graphene nanostructures on copper (Cu) at temperatures lower than 600 °C. Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and potentiodynamic polarization measurements were used to characterize these samples. In simulated seawater, i.e., 3.5 wt.% sodium chloride (NaCl) solution, the corrosion current density of one graphene-coated Cu fabricated at 400 °C can be 1.16 × 10-5 A/cm², which is one order of magnitude lower than that of pure Cu. Moreover, the existence of tall graphene nanowalls was found not to be beneficial to the protection as a consequence of their layered orientation. These correlations among the morphology, structure, and corrosion properties of graphene nanostructures were investigated in this study. Therefore, the enhanced corrosion resistance in selected cases suggests that the low-temperature CVD graphene under appropriate conditions would be able to protect metal substrates against corrosion.

Soft Electrochemical Probes for Mapping the Distribution of Biomarkers and Injected Nanomaterials in Animal and Human Tissues.

Monitoring biomarkers and injected theranostic nanomaterials in tissues and organs plays a pivotal role in numerous medical applications ranging from cancer diagnostics to drug delivery. Scanning electrochemical microscopy has been demonstrated as a powerful tool to create highly resolved maps of the distributions of relevant biomolecules in cells and tissues without suffering from the optical interferences of conventional microscopy. We demonstrate for the first time the application of soft microelectrodes brushing in contact mode over large and thick tissues as well as organs that were immersed in an electrolyte solution. Amperometric currents were recorded based on the local flux of redox-active species locally and specifically generated by the biomarkers and nanomaterials to create maps of the biodistribution of graphene oxide nanoribbons in mouse livers, prognostic protein biomarkers in human melanoma and redox-active proteins in mouse heart.

Printed Combinatorial Sensors for Simultaneous Detection of Ascorbic Acid, Uric Acid, Dopamine, and Nitrite.

In this study, an effective and simple direct printing method was developed to create sensing devices on screen-printed carbon electrodes (SPCEs) to detect multiple species simultaneously. Two sensing materials, graphene oxide nanoribbons (GONRs) and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), were printed on one SPCE for detection of multiple biochemical substances. Printed layers of the GONRs and PEDOT:PSS mixture (GONRs & PEDOT:PSS) on SPCE showed embedment of GONRs in the PEDOT:PSS layer and diminished the electrochemical activity of GONRs. In contrast, by printing the GONRs and PEDOT:PSS at separate locations (GONRs + PEDOT:PSS) on the same SPCE, the electrochemical activities of both GONRs and PEDOT:PSS can be preserved. Thus, without synthesizing new materials, the modified electrode is able to simultaneously detect ascorbic acid (AA), uric acid (UA), dopamine (DA), and nitrite (NO2-), with high anodic oxidation currents and well-separated voltammetric peaks, in differential pulse voltammetry measurements. The detection limits for the four analytes are 41 nM (AA), 30 nM (DA), 11 nM (UA), and 18 nM (NO2-), respectively. The electrode can either detect single species separately or simultaneously determine specific concentrations of the four species in aqueous mixtures, and this can be further extended for many other electrochemical sensing applications.

Graphene Nanoribbon-Supported PtPd Concave Nanocubes for Electrochemical Detection of TNT with High Sensitivity and Selectivity.

In this work, PtPd concave nanocubes anchored on graphene nanoribbons (PtPd-rGONRs) were successfully fabricated through a hydrothermal process. The structural characterizations confirmed that PtPd concave cubes with an average size of around 11 nm have been successfully synthesized and they are uniformly assembled on the surface of rGONRs. The electrochemical measurements demonstrated that the PtPd-rGONRs composite-modified glassy carbon electrode (GCE) shows much enhanced current signals for TNT reduction, which is 4 and 12-fold higher than rGONRs and bare glassy carbon electrode, respectively. The PtPd-rGONRs exhibited a wide linear range for TNT detection from 0.01 to 3 ppm with the sensing limit of 0.8 ppb. Moreover, the PtPd-rGONRs showed excellent detection stability for the determination of TNT. Most importantly, the PtPd-rGONRs-based electrochemical detection platform can be successfully applied to TNT detection in tap water and real lake water samples. The present study indicates that graphene nanoribbon-supported nanocrystals are promising in designing high performance electrochemical sensors for explosives detection.

A reusable magnetic graphene oxide-modified biosensor for vascular endothelial growth factor detection in cancer diagnosis.

Early cancer diagnosis is critical for the prevention of metastasis. However, simple and efficient methods are needed to improve the diagnosis and evaluation of cancer. Here, we propose a reusable biosensor based on a magnetic graphene oxide (MGO)-modified Au electrode to detect vascular endothelial growth factor (VEGF) in human plasma for cancer diagnosis. In this biosensor, Avastin is used as the specific biorecognition element, and MGO is used as the carrier for Avastin loading. The use of MGO enables rapid purification due to its magnetic properties, which prevents the loss of bioactivity. Moreover, the biosensor can be constructed quickly, without requiring a drying process, which is convenient for proceeding to detection. Our reusable biosensor provides the appropriate sensitivity for clinical diagnostics and has a wide range of linear detection, from 31.25-2000 pg mL(-1), compared to ELISA analysis. In addition, in experiments with 100% serum from clinical samples, readouts from the sensor and an ELISA for VEGF showed good correlation within the limits of the ELISA kit. The relative standard deviation (RSD) of the change in current (ΔC) for reproducibility of the Au biosensor was 2.36% (n=50), indicating that it can be reused with high reproducibility. Furthermore, the advantages of the Avastin-MGO-modified biosensor for VEGF detection are that it provides an efficient detection strategy that not only improves the detection ability but also reduces the cost and decreases the response time by 10-fold, indicating its potential as a diagnosis product.

Synthesis of short graphene oxide nanoribbons for improved biomarker detection of Parkinson's disease.

We demonstrate the microwave-assisted synthesis of short graphene oxide nanoribbons (GONRs) through unzipping cut multiwalled carbon nanotubes (MWCNTs). Transmission electron microscopy and dynamic light scattering spectroscopy were used to examine the length, size, and morphology, i. e. unzipping level, of our various products. The nanotube core and nanoribbon shell can be observed from short GONRs via a modified unzipping recipe. Then the short GONRs were adopted to modify the glassy carbon electrode for the electrochemical detection of ascorbic acid (AA), uric acid (UA), and dopamine (DA). Compared to other nanomaterials, cyclic voltammograms of short GONRs show higher anodic oxidation currents for AA, UA, and DA. The detection limits of three analytes are 26, 98, and 24 nM, respectively, in amperometric current-time measurements. Especially, the sensitivity for DA is improved to be 40.86 µA µM(-1) cm(-2). The improved detection signals are due to the increased active sites of the open ends of short GONRs. Moreover, the width side of short GONRs could be more active than their length side. All above-mentioned results reveal that the short GONRs can provide a novel platform for electrochemically biomarker detection of Parkinson's disease.

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

The effects of ionic liquid on the electrochemical sensing performance of graphene- and carbon nanotube-based electrodes.

The electrochemical sensing properties of graphene-based and carbon nanotube (CNT)-based electrodes towards ascorbic acid, dopamine, uric acid, and glucose are systematically compared. Nano-sized Pd catalyst particles are uniformly dispersed on both carbon supports using a supercritical fluid deposition technique to increase the sensing performance. The CNT/Pd electrode shows higher detection current than that of the graphene/Pd electrode, which is attributed to the three-dimensional architecture interwoven by the CNTs that creates a larger number of reaction sites. With the incorporation of ionic liquid (IL), the detection sensitivity of the IL/graphene/Pd electrode significantly increases, becoming noticeably higher than that of the IL/CNT/Pd counterpart. The synergistic interactions between graphene and IL that lead to the superior sensing performance are demonstrated and discussed.

Microwave-assisted synthesis of a core-shell MWCNT/GONR heterostructure for the electrochemical detection of ascorbic acid, dopamine, and uric acid.

In this study, graphene oxide nanoribbons (GONRs) were synthesized from the facile unzipping of multiwalled carbon nanotubes (MWCNTs) with the help of microwave energy. A core-shell MWCNT/GONR-modified glassy carbon (MWCNT/GONR/GC) electrode was used to electrochemically detect ascorbic acid (AA), dopamine (DA), and uric acid (UA). In cyclic voltammograms, the MWCNT/GONR/GC electrode was found to outperform the MWCNT- and graphene-modified GC electrodes in terms of peak current. For the simultaneous sensing of three analytes, well-separated voltammetric peaks were obtained using a MWCNT/GONR/GC electrode in differential pulse voltammetry measurements. The corresponding peak separations were 229.9 mV (AA to DA), 126.7 mV (DA to UA), and 356.6 mV (AA to UA). This excellent electrochemical performance can be attributed to the unique electronic structure of MWCNTs/GONRs: a high density of unoccupied electronic states above the Fermi level and enriched oxygen-based functionality at the edge of the graphene-like structures, as revealed by X-ray absorption near-edge structure spectroscopy, obtained using scanning transmission X-ray microscopy.

The simultaneous electrochemical detection of ascorbic acid, dopamine, and uric acid using graphene/size-selected Pt nanocomposites.

In this study, a graphene/Pt-modified glassy carbon (GC) electrode was created to simultaneously characterize ascorbic acid (AA), dopamine (DA), and uric acid (UA) levels via cyclic voltammetry (CV) and differential pulse voltammetry (DPV). During the preparation of the nanocomposite, size-selected Pt nanoparticles with a mean diameter of 1.7 nm were self-assembled onto the graphene surface. In the simultaneous detection of the three aforementioned analytes using CV, the electrochemical potential differences among the three detected peaks were 185 mV (AA to DA), 144 mV (DA to UA), and 329 mV (AA and UA), respectively. In comparison to the CV results of bare GC and graphene-modified GC electrodes, the large electrochemical potential difference that is achieved via the use of the graphene/Pt nanocomposites is essential to the distinguishing of these three analytes. An optimized adsorption of size-selected Pt colloidal nanoparticles onto the graphene surface results in a graphene/Pt nanocomposite that can provide a good platform for the routine analysis of AA, DA, and UA.

Atomic-scale deformation in N-doped carbon nanotubes.

We present the N-doping induced atomic-scale structural deformation in N-doped carbon nanotubes by using density functional theory calculations. For substitutional N-doped nanotube clusters, the N dopant with an excess electron lone pair exhibits the high negative charge, and the homogeneously distributed dopants enlarge the tube diameter in both zigzag and armchair cases. On the other hand, in pyridine-like N-doped ones, the concentrated N atoms result in a positively curved graphene layer and, thus, can be responsible for tube wall roughness and the formation of interlinked structures.

Radius margin bounds for support vector machines with the RBF kernel.

An important approach for efficient support vector machine (SVM) model selection is to use differentiable bounds of the leave-one-out (loo) error. Past efforts focused on finding tight bounds of loo (e.g., radius margin bounds, span bounds). However, their practical viability is still not very satisfactory. Duan, Keerthi, and Poo (2003) showed that radius margin bound gives good prediction for L2-SVM, one of the cases we look at. In this letter, through analyses about why this bound performs well for L2-SVM, we show that finding a bound whose minima are in a region with small loo values may be more important than its tightness. Based on this principle, we propose modified radius margin bounds for L1-SVM (the other case) where the original bound is applicable only to the hard-margin case. Our modification for L1-SVM achieves comparable performance to L2-SVM. To study whether L1- or L2-SVM should be used, we analyze other properties, such as their differentiability, number of support vectors, and number of free support vectors. In this aspect, L1-SVM possesses the advantage of having fewer support vectors. Their implementations are also different, so we discuss related issues in detail.