Konggang Qu

Graphene Oxide: Intrinsic Peroxidase Catalytic Activity and Its Application to Glucose Detection

Carboxyl-modified graphene oxide (GO-COOH) possesses intrinsic peroxidase-like activity that can catalyze the reaction of peroxidase substrate 3,3,5,5-tetramethyl-benzidine (TMB) in the presence of H2O2 to produce a blue color reaction. A simple, cheap, and highly sensitive and selective colorimetric method for glucose detection has been developed and will facilitate the utilization of GO-COOH intrinsic peroxidase activity in medical diagnostics and biotechnology.

Microwave assisted one-step green synthesis of cell-permeable multicolor photoluminescent carbon dots without surface passivation reagents

A facile, economic and green one-step microwave synthesis route towards photoluminescent carbon dots is proposed. The preparation requires a carbohydrate (glycerol, glycol, glucose, sucrose, etc.) and a tiny amount of an inorganic ion, and can finish in just a few minutes, no surface passivation reagent is needed. The carbon dots are biologically compatible and show favorable optical properties and have potential applications in biolabeling and bioimaging.

Label-free colorimetric detection of single nucleotide polymorphism by using single-walled carbon nanotube intrinsic peroxidase-like activity.

Single-walled carbon nanotubes (SWNTs) have been considered to be leading candidates for nanodevice applications and novel drug delivery. Intriguingly, recent studies have shown that SWNTs have catalytic activity even in the absence of catalytic factors. Since hydrogen peroxide is an important oxidizing agent in biological systems, the catalytic reaction of SWNTs with H2O2 has received much attention. The SWNT catalytic mechanism is much debated, but it has been suggested that it is related to trace amounts of metal catalyst in SWNTs. H2O2 is a major reactive oxygen species in living organisms, and its overproduction is implicated in the development of numerous inflammatory diseases, such as atherosclerosis, chronic obstructive pulmonary disease, and hepatitis. Furthermore, as a product of many enzyme-catalyzed reactions, H2O2 can act as an indicator to monitor the quantity of biologically important molecules, such as glucose. Therefore, studying the catalytic reaction of SWNTs with H2O2 might offer a promising application for disease diagnosis and for the design of SWNT-based sensors. In this work, we report that SWNTs possess intrinsic peroxidase-like activity. That the catalytic activity does not depend on trace amounts of metal catalyst in the SWNTs is evidenced by energy-dispersive X-ray (EDX) analysis. In the presence of H2O2, SWNTs catalyze the reaction of the peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) thereby producing a color change (Scheme 1). Our results indicate that the catalytic efficiency of SWNTs is strongly dependent on pH, temperature, and H2O2 concentration, similar to horseradish peroxidase (HRP). More importantly, we compared the catalytic efficiency of SWNTs containing different amounts of cobalt residues. The results clearly show that the observed “catalytic” effect of SWNTs can be attributed to their intrinsic properties rather than metal residues. Peroxidase activity has a great potential for practical application and has been used in the bioremediation of waste water or as diagnostic kits. As peroxidase mimics, SWNTs were used here for label-free colorimetric detection of disease-associated single-nucleotide polymorphism (SNP) with a direct detection limit of 1 nm based on the color reaction of TMB. It is well known that SNP detection is very important, and different kinds of detection methods have been reported; however, to our knowledge, this is the first demonstration of applying intrinsic SWNT peroxidase-like activity and color change for this purpose. This work will provide new insights into the utilization of SWNT peroxidase-like activity. To increase SWNT solubility in aqueous solution, we treated SWNTs with a mixture of concentrated sulfuric and nitric acids, as described previously. Figure S1 in the Supporting Information shows the mixed solution of H2O2 and TMB in the presence or absence of SWNTs. In the absence of SWNTs, the color of the solution does not change in 12 h; however, in the presence of SWNTs, the color changes from black to blue immediately. This result suggests that SWNTs can catalyze the reaction of TMB in the presence of [a] Y. Song, X. Wang, C. Zhao, K. Qu, Dr. J. Ren, Prof. X. Qu Laboratory of Chemical Biology Division of Biological Inorganic Chemistry State Key Laboratory of Rare Earth Resource Utilization Graduate School of the Chinese Academy of Sciences Changchun Institute of Applied Chemistry Chinese Academy of Sciences Changchun, Jilin 130022 (China) Fax: (+86)431-85262656 E-mail : xqu@ciac.jl.cn Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/chem.20090902643. Scheme 1. Schematic illustration of SWNTs catalyzing the reaction of peroxidase substrate TMB in the presence of H2O2 to give the blue product oxidized TMB (oxTMB).

Using Graphene Oxide High Near-Infrared Absorbance for Photothermal Treatment of Alzheimer's Disease

A novel strategy to dissociate amyloid aggregation is presented, using localised heat generation from a clinically used amyloid staining dye, thioflavin-S (ThS)-modified graphene oxide (GO) under NIR laser irradiation. Compared to traditional chemotherapies, photothermal therapy shows reduced side effects and improved selectivity and safety.

A Reusable DNA Single‐Walled Carbon‐Nanotube‐Based Fluorescent Sensor for Highly Sensitive and Selective Detection of Ag+ and Cysteine in Aqueous Solutions

Here we report a reusable DNA single-walled carbon nanotube (SWNT)-based fluorescent sensor for highly sensitive and selective detection of Ag(+) and cysteine (Cys) in aqueous solution. SWNTs can effectively quench the fluorescence of dye-labeled single-stranded DNA due to their strong pi-pi stacking interactions. However, upon incubation with Ag(+), Ag(+) can induce stable duplex formation mediated by C-Ag(+)-C (C=cytosine) coordination chemistry, which has been further confirmed by DNA melting studies. This weakens the interactions between DNA and SWNTs, and thus activates the sensor fluorescence. On the other hand, because Cys is a strong Ag(+) binder, it can remove Ag(+) from C-Ag(+)-C base pairs and deactivates the sensor fluorescence by rewrapping the dye-labeled oligonucleotides around the SWNT. In this way, the fluorescence signal-on and signal-off of a DNA/SWNT sensor can be used to detect aqueous Ag(+) and Cys, respectively. This sensing platform exhibits high sensitivity and selectivity toward Ag(+) and Cys versus other metal ions and the other 19 natural amino acids, with a limit of detection of 1 nM for Ag(+) and 9.5 nM for Cys. Based on these results, we have constructed a reusable fluorescent sensor by using the covalent-linked SWNT-DNA conjugates according to the same sensing mechanism. There is no report on the use of SWNT-DNA assays for the detection of Ag(+) and Cys. This assay is simple, effective, and reusable, and can in principle be used to detect other metal ions by substituting C-C base pairs with other native or artificial bases that selectively bind to other metal ions.

Insights into the biomedical effects of carboxylated single-wall carbon nanotubes on telomerase and telomeres

Both human telomeric G-rich and C-rich DNA have been considered as specific drug targets for cancer therapy. However, due to i-motif structure instability and lack of specific binding agents, it remains unclear whether stabilization of telomeric i-motif can inhibit telomerase activity. Single-walled carbon nanotubes (SWNTs) have been reported as the first ligand that can selectively stabilize human telomeric i-motif DNA. Here we report that SWNTs can inhibit telomerase activity through stabilization of i-motif structure. The persistence of i-motif and the concomitant G-quadruplex eventually leads to telomere uncapping and displaces telomere-binding proteins from telomere. The dysfunctional telomere triggers DNA damage response and elicits upregulation of p16 and p21 proteins. This is the first example that SWNTs can inhibit telomerase activity and interfere with the telomere functions in cancer cells. These results provide new insights into understanding the biomedical effects of SWNTs and the biological importance of i-motif DNA.

pH-responsive NIR enhanced drug release from gold nanocages possesses high potency against cancer cells

We report a smart therapeutic nanoplatform based on Fe(3)O(4)@CaP capped gold nanocages, which integrates magnetic targeting, photothermal therapy and chemotherapy for killing cancer cells. Combining photothermal- and chemo-therapy results in a synergistic effect in cancer treatment.

Chiral detection using reusable fluorescent amylose-functionalized graphene

By using DNA or a peptide as a common probe, graphene-based biosensing has made significant progress. However, to the best of our knowledge, a graphene-based chiral sensor has not been reported. Chiroselective recognition is perhaps the most subtle to achieve because of the similarity of the optical enantiomers. Therefore, besides using DNA or peptides as probes, developing graphene-based sensors with chiral selectivity is highly desirable. Here a reusable natural cheap polysaccharide, amylose-functionalized graphene was developed for highly sensitive and visual fluorescent chiral sensing. The detection sensitivity toward L-Trp is over 100-times higher than that of recently reported electrochemical sensors and colorimetric sensors. In comparison with commonly used DNA or peptides as a probe, natural amylose is more attractive because of its low cost, ready availability, simple manipulation and renewability. The specific selectivity for tryptophan (Trp) enantiomers towards other essential amino acids allows potential chiroselective analysis of Trp in complex samples such as biological fluids. This design can, in principle, be implemented for other slender target molecules that can form an inclusion complex with amylose.

Nanocomposite Incorporating V2O5 Nanowires and Gold Nanoparticles for Mimicking an Enzyme Cascade Reaction and Its Application in the Detection of Biomolecules

Artificial enzyme mimics are a current research interest, and many nanomaterials have been found to display enzyme-mimicking activity. However, to the best of our knowledge, there have not hitherto been any reports on the use of pure nanomaterials to construct a system capable of mimicking an enzyme cascade reaction. Herein, we describe the construction of a novel nanocomposite consisting of V2O5 nanowires and gold nanoparticles (AuNPs) through a simple and facile chemical method, in which V2O5 and AuNPs possess intrinsic peroxidase and glucose oxidase (GOx)-like activity, respectively. Results suggest that this material can mimic the enzyme cascade reaction of horseradish peroxidase (HRP) and GOx. Based on this mechanism, a direct and selective colorimetric method for the detection of glucose has been successfully designed. Because single-strand and double-strand DNA (ssDNA and dsDNA) have different deactivating effects on the GOx-like activity of AuNPs, the sensing of target complementary DNA can also be realized and disease-associated single-nucleotide polymorphism of DNA can be easily distinguished. Our study opens a new avenue for the use of nanomaterials in enzyme mimetics, and holds promise for the further exploration of nanomaterials in creating alternative catalytic systems to natural enzymes.

Triplex inducer-directed self-assembly of single-walled carbon nanotubes: a triplex DNA-based approach for controlled manipulation of nanostructures

As a promising strategy for artificially control of gene expression, reversible assembly of nanomaterials and DNA nanomachine, DNA triplex formation has received much attention. Carbon nanotubes as gene and drug delivery vector or as ‘building blocks’ in nano/microelectronic devices have been successfully explored. Therefore, studies on triplex DNA-based carbon nanotube hybrid materials are important for development of smart nanomaterials and for gene therapy. In this report, a small molecule directed single-walled carbon nanotubes (SWNTs) self-assembly assay has been developed by disproportionation of SWNTs–dT22·dA22 duplex into triplex dT22·dA22·dT22 and dA22 by a triplex formation inducer, coralyne. This has been studied by circular dichroism, light scattering (LS) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), electrophoretic mobility shift assay and supported by using DNA random sequence. In contrast, SWNTs do not aggregate under the same experimental conditions when the small molecules used can not induce dT22·dA22·dT22 triplex formation. Therefore, this novel small molecule-directed SWNTs self-assembly assay has also been used for screening of triplex inducers in our studies.