Jiahai Wang

Recent Progress in Cobalt-Based Heterogeneous Catalysts for Electrochemical Water Splitting

Water electrolysis is considered as the most promising technology for hydrogen production. Much research has been devoted to developing efficient electrocatalysts for hydrogen production via the hydrogen evolution reaction (HER) and oxygen production via the oxygen evolution reaction (OER). The optimum electrocatalysts can drive down the energy costs needed for water splitting via lowering the overpotential. A number of cobalt (Co)-based materials have been developed over past years as non-noble-metal heterogeneous electrocatalysts for HER and OER. Recent progress in this field is summarized here, especially highlighting several important bifunctional catalysts. Various approaches to improve or optimize the electrocatalysts are introduced. Finally, the current existing challenges and the future working directions for enhancing the performance of Co-implicated electrocatalysts are proposed.

PVP-coated graphene oxide for selective determination of ochratoxin A via quenching fluorescence of free aptamer

In this paper, we developed a simple method to detect fungi toxin (ochratoxin A) produced by Aspergillus Ochraceus and Penicillium verrucosumm, utilizing graphene oxide as quencher which can quench the fluorescence of FAM (carboxyfluorescein) attached to toxin-specific aptamer. By optimizing the experimental conditions, we obtained the detection limit of our sensing platform based on bare graphene oxide to be 1.9 μM with a linear detection range from 2 μM to 35 μM. Selectivity of this sensing platform has been carefully investigated; the results showed that this sensor specifically responded to ochratoxin A without interference from other structure analogues (N-acetyl-l-phenylalanine and warfarin) and with only limited interference from ochratoxin B. Experimental data showed that ochratoxin A as well as other structure analogues could adsorb onto the graphene oxide. As compared to the non-protected graphene oxide based biosensor, PVP-protected graphene oxide reveals much lower detection limit (21.8 nM) by two orders of magnitude under the optimized ratio of graphene oxide to PVP concentration. This sensor has also been challenged by testing 1% red wine containing buffer solution spiked with a series of concentration of ochratoxin A.

Single-walled carbon nanotubes based quenching of free FAM-aptamer for selective determination of ochratoxin A

Ochratoxin A, a toxin produced by Aspergillus ochraceus and Penicillium verrucosum, is one of the most abundant food-contaminating mycotoxins in the world. It has been classified by the International Agency for Research on Cancer (IARC) as a possible human carcinogen. In this paper, a sensitive and selective fluorescent aptasensor for ochratoxin A (OTA) detection was constructed, utilizing single-walled carbon nanotubes (SWNTs) as quencher which can quench the fluorescence of free unfolded toxin-specific aptamer attached with FAM (carboxyfluorescein). Without any coating materials as compared to graphene-oxide based sensor, we obtained the detection limit of our sensing platform based on SWNTs to be 24.1 nM with a linear detection range from 25 nM to 200 nM. This technique responded specifically to OTA without interference from other analogues (N-acetyl-L-phenylalanine, warfarin and OTB). It has also been verified for real sample application by testing 1% beer containing buffer solution spiked with a series of concentration of OTA.

G-Quadruplex-Modulated Fluorescence Detection of Potassium in the Presence of a 3500-Fold Excess of Sodium Ions

A label-free detection of K(+) was developed using G-quadruplex DNA (c-Myc) modulated fluorescence enhancement of tetrakis-(diisopropylguanidino) zinc phthalocyanine (Zn-DIGP). Upon the addition of increasing concentrations of potassium, a detection limit of 0.8 μM for K(+) was easily achieved. Comparative titrations using sodium, lithium, ammonium, transition metal, or alkali earth salts revealed that the fluorescence enhancement was highly specific for potassium ions. This system has, for the first time, provided a means for detecting 40 μM of K(+) even in the presence of a 3500-fold excess of Na(+) ions.

A new drug-sensing paradigm based on ion-current rectification in a conically shaped nanopore.

AIMS To utilize the ion-current rectification phenomenon observed for conically shaped nanopores as the basis for designing sensors for drug molecules that adsorb to the walls of the nanopore. METHODS The conically shaped nanopore was prepared by the well-known track-etch method in a polyimide (Kapton) membrane. The ion current flowing through the nanopore was measured as a function of applied transmembrane potential in the presence of the analyte drug molecule, Hoechst 33258. RESULTS The pore walls in the Kapton membrane are hydrophobic yet have fixed carboxylate groups that give the walls a net negative charge. This fixed anionic surface charge causes the nanopore to rectify the ion current flowing through it. The analyte drug molecule, Hoechst 33258, is cationic yet also hydrophobic. When the membrane is exposed to this molecule, it adsorbs to the pore walls and neutralizes the anionic surface charge, thus lowering the extent of ion-current rectification. The change in rectification is proportional to the concentration of the drug. CONCLUSIONS This nanopore sensor is selective for hydrophobic cations relative to anions, neutral molecules and less hydrophobic cations. Future work will explore ways of augmenting this hydrophobic effect-based selectivity so that more highly selective sensors can be obtained.

G-Quadruplex as Signal Transducer for Biorecognition Events

G-rich nucleic acid oligomers can form G-quadruplexes built by G-tetrads stacked upon each other. The basic building block of the G-quadruplexes is similar, but the formation of different quadruplex structures is highly responsive to the strand stoichiometry, strand orientation, guanine glycosidic torsion angle, connecting loops, and the metal coordination. Because of its structural variations and different functions, G-quadruplex applied in biorecognition events can function as a versatile signaling component. A variety of strategies that incorporate G-quadruplex have also been reported. In this review, we mainly discuss G-quadruplex as signal transducer from the following aspects for biorecognition events: analyte-induced G-quadruplex reconfiguration and fluorescence enhancement of small ligand; analyte-induced G-quadruplex reconstruction and formation of DNAzyme; Stimulus-responsive G-quadruplex refolding and manipulation of electron transfer; Stimulus-responsive G-quadruplex and its combination with nanopore systems; Small ligand-responsive G-quadruplex stabilization for drug screening; Nanomaterial-reponsive G-quadruplex reformation; Target-triggered continuous formation of G-quadruplex by DNA nanomachine. We have comprehensively described the recent progress in our labs and others. Undoubtedly, bioanalytical technology and nanotechnology based on G-quadruplex will continue to grow, leading to develop new diagnostics, therapeutics and drug development.

An electrochemical aptasensor for chiral peptide detection using layer-by-layer assembly of polyelectrolyte-methylene blue/polyelectrolyte-graphene multilayer.

Here we demonstrate for the first time that by physically adsorbing aptamer onto conductive film assembled via alternate adsorption of graphene/polyelectrolyte and methylene blue/polyelectrolyte, a label-free electrochemical aptasensor with high sensitivity and selectivity for peptide detection is constructed. Graphene multilayer derived from layer-by-layer assembly has played significant roles in this sensing strategy: allowing accumulation of methylene blue, facilitating electron transfer and providing much more adsorption site. As compared to previous electrochemical aptasensors, the current sensor based on graphene multilayer alternated with electroactive molecule layer offers extremely high capability for sensitive detection of target without interference of environmental surrounding. This electroactive probe-confined graphene multilayer confers great flexibility to combine with differential pulse voltammetry (DPV) together. In the presence of target d entiomer of arginine vasopressin (D-VP), the binding of peptide to aptamer block the electron transfer process of MB, leading to decreased current peak of DPV. By this way, this electrochemical aptasensor based on electroactive molecule-intercalated graphene multilayer provide highly sensitive and specific detection of D-VP with the lowest detectable concentration of 1 ng mL(-1) and a wide detection range from 1 to 265 ng mL(-1).

Insertion approach: bolstering the reproducibility of electrochemical signal amplification via DNA superstructures.

For more than a decade, the backfilling approach for the immobilization of DNA probes has been routinely adopted for the construction of functional interfaces; however, reliably reproducing electrochemical signal amplification by this method is a challenge. In this research, we demonstrate that the insertion approach significantly bolsters the reproducibility of electrochemical signal amplification via DNA superstructures. The combination of the backfilling approach and the DNA superstructure formation poses a big challenge to reliably reproducing electrochemical signal amplification. In order to use the detection of Hg(2+) as a prototype of this new strategy, a thymine-rich DNA probe that is specific to mercury ion was applied in this study. The presence of Hg(2+) induces the folding of the DNA probes and inhibits the formation of DNA superstructures. By using electroactive probes ([Ru(NH3)6](3+)) that are electrostatically adsorbed onto the double strands, differential pulse voltammetry (DPV) could quantitatively confirm the presence of Hg(2+). A limit of detection (LOD) and a limit of quantification (LOQ) (LOQ) as low as 0.3 and 9.5 pM, respectively, were achieved. Furthermore, excellent selectivity and real sample analysis demonstrated the promising potential of this approach in future applications.

Label-free detection of nucleic acids by turn-on and turn-off G-quadruplex-mediated fluorescence

In this study we have used two fluorescent probes, tetrakis(diisopropylguanidino)-zinc-phthalocyanine (Zn-DIGP) and N-methylmesoporphyrin IX (NMM), to monitor the reassembly of “split” G-quadruplex probes on hybridization with an arbitrary “target” DNA. According to this approach, each split probe is designed to contain half of a G-quadruplex-forming sequence fused to a variable sequence that is complementary to the target DNA. Upon mixing the individual components, both base-pairing interactions and G-quadruplex fragment reassembly result in a duplex–quadruplex three-way junction that can bind to fluorescent dyes in a G-quadruplex-specific way. The overall fluorescence intensities of the resulting complexes were dependent on the formation of proper base-pairing interactions in the duplex regions, and on the exact identity of the fluorescent probe. Compared with samples lacking any “target” DNA, the fluorescence intensities of Zn-DIGP-containing samples were lower, and the fluorescence intensities of NMM-containing samples were higher on addition of the target DNA. The resulting biosensors based on Zn-DIGP are therefore termed “turn-off” whereas the biosensors containing NMM are defined as “turn-on”. Both of these biosensors can detect target DNAs with a limit of detection in the nanomolar range, and can discriminate mismatched from perfectly matched target DNAs. In contrast with previous biosensors based on the peroxidase activity of heme-bound split G-quadruplex probes, the use of fluorescent dyes eliminates the need for unstable sensing components (H2O2, hemin, and ABTS). Our approach is direct, easy to conduct, and fully compatible with the detection of specific DNA sequences in biological fluids. Having two different types of probe was highly valuable in the context of applied studies, because Zn-DIGP was found to be compatible with samples containing both serum and urine whereas NMM was compatible with urine, but not with serum-containing samples.

Revelation of the Excellent Intrinsic Activity of MoS2|NiS|MoO3 Nanowires for Hydrogen Evolution Reaction in Alkaline Medium

Loading an electrocatalyst on poorly conducting substrate can easily lead to undervaluation of its intrinsic property. In this study, the excellent activity of MoS2|NiS|MoO3 nanowires for hydrogen evolution is revealed. The precursor NiMoO4 synthesized on chemically polished Ti foil can be successfully converted to MoS2|NiS|MoO3 catalyst via gas-phase sulfurization. Without deep polish in sulfuric acid for 2 h, the as-synthesized materials do not show competitive results. After sulfurization, the surface morphology of the precursor is transformed into rough features, and the peripheries of these electrocatalysts are coated by multilayered and misaligned MoS2 with a high density of active sites and conductive component NiS. Further analysis shows that defect MoO3 is embedded inside each nanowire, which may facilitate fast electron transfer. Such nanostructured architecture shows promising results for hydrogen evolution reaction in alkaline medium with only 91 mV overpotential for the current density of 10 mA cm-2 and robust long-term stability during more than 20 h of tests.