Designing of multifunctional graphene quantum dot-polyvinyl alcohol-polyglycerol luminescent film for fluorescence detection of pH in sweat.

BACKGROUND: Wound infection, skin disease, renal failure, cancer, cystic fibrosis, and other pathologies may induce obvious pH changes in sweat. Thus, tracking skin pH changes can help monitor human health in a convenient manner. Owing to their biocompatibility, easy preparation, and sensitive response to pH changes, graphene quantum dots (GQDs) have received increased attention in the optical detection of pH changes. However, their poor luminescent efficiency under visible light excitation and lack of functional diversification limit their application in skin pH monitoring. Therefore, the development of GQDs with excellent ultraviolet protection ability and antibacterial and luminescence performance is essential. RESULTS: Folic acid-, histidine-, and serine-functionalized boron-doped graphene quantum dots (FHSB-GQDs) were designed and synthesized via thermal treatment. The resulting FHSB-GQDs exhibit strong yellow fluorescence emission under excitation with 490-nm visible light and sensitive pH responsiveness. The peak fluorescence intensity linearly decreases with increasing pH from 4 to 9. Furthermore, the FHSB-GQDs were integrated with polyvinyl alcohol and polyglycerol to form a luminescent film via hydrogen bond interactions. The film exhibits high transparency, mechanical flexibility, ultraviolet protection ability, and antibacterial activity. The presence of polyvinyl alcohol and polyglycerol restricts the free movement of the FHSB-GQDs and improves fluorescence behavior. The film was successfully applied in an intelligent pH-sensing system for monitoring pH changes in human sweat. SIGNIFICANCE: The graphene quantum dot-polyvinyl alcohol-polyglycerol luminescent film offers excellent transparency, mechanical flexibility, ultraviolet protection ability, antibacterial activity, and luminescence performance. It was successfully applied in an intelligent pH sensing system for the detection of pH changes in human sweat. This study provides a new strategy for the design and construction of wearable sensing systems for health monitoring, facial masks, and medical dressings.

Excitation-depended fluorescence emission of boron-doped graphene quantum dot as an optical probe for detection of oxytetracycline in food and information encryption patterns.

The boron-doped graphene quantum dot (HSE-GQD-B) was prepared by thermal pyrolysis of the mixture of citric acid, histidine, serine and ethylenediamine and boric acid. The resulting HSE-GQD-B is composed of tiny graphene sheets with an average sheet size of 4.2 ± 0.16 nm and exhibits an excitation-depended fluorescence emission behavior. The HSE-GQD-B produces the strongest blue fluorescence of 450 nm wavelength under the excitation of 365-nm ultraviolet light and the strongest yellow fluorescence of 550-nm wavelength under the excitation of 470-nm visible light. The interaction of HSE-GQD-B with oxytetracycline molecule induces a sensitive blue fluorescence quenching process. Based on this characteristic, a fluorescence method was established for optical detection of oxytetracycline. The analytical method offers a better sensitivity, selectivity, and repeatability compared with previously reported methods. The detection of oxytetracycline attains a wide linear range of 0.02-50 µM and a detection limit of 0.0067 µM. It has been successfully applied to fluorescence detection of oxytetracycline in food samples. In addition, the HSE-GQD-B was also used as a multicolor fluorescence probe for information encryption patterns.

Electrochemical detection of uric acid in human serum based on ultrasmall Ta2O5 nanoparticle anchored Pt atom with ultrahigh uricase and catalase activities.

The synthesis of ultrasmall Ta2O5 nanoparticle anchored Pt atom using aspartic acid-functionalized graphene quantum dot (Asp-GQD) is reported. The Asp-GQD was combined with tantalic acid and chloroplatinic acid to rapidly form water-soluble Ta-Asp-GQD and Pt-Asp-GQD complex. Followed by thermal annealing at 900 °C in N2 to obtain Ta2O5-Asp-GQD-Pt. The study shows that the introduction of Asp-GQD as a chelating agent and p-type semiconductor achieves to the formation of ultrasmall Ta2O5 nanoparticle, PN junction at the interface and Pt single atom anchored on the surface of Ta2O5 nanocrystals. The unique structure realizes ultrahigh uricase activity and catalase activities of Ta2O5-Asp-GQD-Pt. The Ta2O5-Asp-GQD-Pt was used as the bifunctional sensing material for the construction of an electrochemical uric acid sensor. The differential pulse voltammetric current at 0.45 V linearly increases with the increase of uric acid concentration in the range 0.001-5.00 mM with the detection limit of 0.41 µM (S/N = 3). The sensor exhibits a much better sensitivity compared with the reported methods for the detection of uric acid. The proposed analytical method has been applied to the electrochemical detection of uric acid in human serum with a spiked recovery of 95-105%. The study also offers one way to design and synthesize multifunctional sensing materials with high catalytic activity.

Highly sensitive and selective electrochemical aptasensor with gold-aspartic acid, glycine acid-functionalized and boron-doped graphene quantum dot nanohybrid for detection of α-amanitin in blood.

Poisonous mushroom may cause fatal harm to human and animal, but its rapid detection still faces a great challenge. The paper reports synthesis of gold-aspartic acid, glycine acid-functionalized and boron-doped graphene quantum dot nanohybrid (AGB-GQD@Au) for the electrochemical detection of α-amanitin. AGB-GQD was prepared by pyrolysis and then reacted with chloroauric acid to produce gold nanoparticles. AGB-GQD@Au offers 12.5 nm-sized particles and Schottky heterojunction, improving the catalytic activity. AGB-GQD@Au connected with hairpin DNA and thionine by Au-S bonds was used as redox probe for electrochemical detection of α-amanitin coupled with one target-induced DNA cycle amplification strategy. α-Amanitin specifically hybridizes with aptamer in duplex DNA to release auxiliary strand DNA. The released DNA triggers one DNA cycle process and brings one redox probe to the electrode surface. By the DNA cycle, one target brings many redox probes to the electrode surface, producing a significant signal amplification. The detection signal was further enhanced by the catalysis of AGB-GQD@Au towards redox of thionine. Differential pulse voltammetric current increases linearly with the increasing α-amanitin in the range from 4 to 4 × 105 fM with the detection limit of 1.2 fΜ (S/N = 3). The analytical method provides advantages of sensitivity, selectivity and repeatability. It has been successfully applied in electrochemical detection of α-amanitin in blood.

Switchable two-color graphene quantum dot as a promising fluorescence probe to highly sensitive pH detection and bioimaging.

Graphene quantum dots have been widely applied in biosensing, fluorescence imaging, biomedicine, energy storage and conversion and catalysis, but design and synthesis of polychromatic graphene quantum dot with high luminous efficiency still faces great challenges. The study reports synthesis of histidine, serine and pentaethylenehexamine-functionalized and boron-doped graphene quantum dot (HSPB-GQD) via one-step pyrolysis. The resulting HSPB-GQD consists of graphene sheets of 2-5 nm with carboxyl, hydroxyl, amino, imino and imidazole. Synergy of histidine, serine, pentaethylenehexamine and boron atoms improves the luminescence behavior. This realizes unique switchable two-color luminescence. UV excitation of 370 nm produces one strong blue fluorescence with the maximum emission wavelength of 455 nm and quantum yield of 72.34%. Vis. excitation of 480 nm produces one strong yellow fluorescence with the maximum emission wavelength of 560 nm and quantum yield of 72.59%. The multiple proton dissociation system constructed by nitrogen-containing and oxygen-containing groups makes yellow fluorescence sensitive to environmental pH value. The intensity linearly increases with increasing pH in the range of 4.5-10.0. Organic molecules and inorganic ions do not interfere pH detection. HSPB-GQD as a promising fluorescence probe with negligible effect on cell viability was successfully applied to pH detection in biological and environmental water samples and cell imaging.

Electrochemical detection of carbendazim with mulberry fruit-like gold nanocrystal/multiple graphene aerogel and DNA cycle amplification.

An aptasensor for electrochemical detection of carbendazim is reported with mulberry fruit-like gold nanocrystal (MF-Au)/multiple graphene aerogel (MGA) and DNA cycle amplification. HAuCl4 was reduced by ascorbic acid in a CTAC solution containing KBr and KI and formed trioctahedron gold nanocrystal. The gold nanocrystal underwent structural evolution under enantioselective direction of L-cysteine. The resulting MF-Au shows a mulberry fruit-like nanostructure composed of gold nanocrystals of about 200 nm as the core and many irregular gold nanoparticles of about 30 nm as the shell. The exposure of high-index facets improves the catalytic activity of MF-Au. MF-Au/MGA was used for the construction of an aptasensor for electrochemical detection of carbendazim. The aptamer hybridizes with assistant strand DNA to form duplex DNA. Carbendazim binds with the formed duplex DNA to release assistant strand DNA, triggering one three-cascade DNA cycle. The utilization of a DNA cycle allows one carbendazim molecule to bring many methylene blue-labeled DNA fragments to the electrode surface. This promotes significant signal amplification due to the redox reaction of methylene blue. The detection signal is further enhanced by the catalysis of MF-Au and MGA towards the redox of methylene blue. A differential pulse voltammetric signal, best measured at - 0.32 V vs. Ag/AgCl, increases linearly with the carbendazim concentration ranging from 1.0 × 10-16 to 1.0 × 10-11 M with a detection limit of 4.4 × 10-17 M. The method provides ultrahigh sensitivity and selectivity and was successfully applied to the electrochemical detection of carbendazim in cucumber. This study reports on an ultrasensitive aptasensor for electrochemical detection of carbendazim in cucumber based on mulberry fruit-like gold nanocrystal-multiple graphene aerogel and DNA cycle double amplification.

Colorimetric detection of chlorpyrifos in peach based on cobalt-graphene nanohybrid with excellent oxidase-like activity and reusability.

Cobalt nanocrystal has been widely used as nano-enzyme for sensing and catalysis due to its high stability and low cost, but poor catalytic activity limits its applications in bioanalysis. The study reports one strategy for synthesis of cobalt-graphene nanohybrid. Histidine-functionalized graphene quantum dot (His-GQD) was bound to graphene sheet via π-π stacking and then combined with cobalt ions in the presence of cetyltrimethylammonium chloride to form stable complex and finally reduced under nitrogen to obtain Co-His-GQD-G. The as-synthesized nanohybrid offers well-defined three-dimensional structure and quasi-superparamagnetism. The cobalt nanoparticles were well dispersed on graphene sheets. The unique structure improves oxidase-like activity of Co-His-GQD-G. Further, Co-His-GQD-G was used as the nanozyme for colorimetric detection of chlorpyrifos. Co-His-GQD-G catalyzes oxidization of 3,3',5,5'-tetramethylbenzidine into blue product. Thiocholine produced by hydrolysis of acetylthiocholine under catalysis of acetylcholinesterase inhibits catalytic activity of Co-His-GQD-G and leads to a reduced oxidization rate. Chlorpyrifos inhibits activity of acetylcholinesterase and brings an enhanced absorbance of blue product. The absorbance at 652 nm linearly increases with increasing chlorpyrifos concentration in the range of 2-20 ng mL-1 with detection limit of 0.57 ng mL-1 (S/N = 3). The method was successfully applied in determination of chlorpyrifos in peach by preparing Co-His-GQD-G magnetic gel sheet.

Highly sensitive electrochemical detection of circulating tumor DNA in human blood based on urchin-like gold nanocrystal-multiple graphene aerogel and target DNA-induced recycling double amplification strategy.

Detection of circulating tumor DNA (ctDNA) is important approach to risk stratification and treatment response monitoring of cancer patients, but current method lacks of enough sensitivity and repeatability. The paper repors shape-controlled synthesis of gold nanocrystals via reduction of HAuCl4 with ascorbic acid. The synergy of CTAC, KBr, KI and L-glutathione creates urchin-like gold nanocrystals (U-Au) with more exposed high-index facets. Preparation of electrochemical sensing platform for ctDNA involves modification of U-Au-multiple graphene aerogel for target DNA-induced recycle amplification. DNA probe 1 (P1) with methylene blue (MB) hybridizes with DNA probe 2 with ferrocene (Fc) to form duplex DNA, which was attached to U-Au through Au-S bond. The ctDNA hybridizes with hairpin DNA 1 to open hairpin structure, triggering target DNA-induced recycle. Utilization of target DNA-induced recycling allows one target DNA to approach many MB probes to electrode surface and to leave many Fc probes from electrode surface, promoting significant signal amplification. The detection signal is enhanced by catalyzed redox of Fc and MB. Electrochemical response increases with ctDNA concentration from 0.1 to 1 × 106 fM with detection limit of 0.033 fM. The biosensor provides ultrahigh sensitivity, specificity and stability and was successfully applied in detection of ctDNA in human blood.

Dual amplification in a fluorometric acetamiprid assay by using an aptamer, G-quadruplex/hemin DNAzyme, and graphene quantum dots functionalized with D-penicillamine and histidine.

D-penicillamine and histidine-functionalized graphene quantum dot (DPA-GQD-His) was synthesized and applied in a fluorometric method for determination of acetamiprid using a G-quadruplex DNAzyme. At first DNA probe (probe 1) consists of a target-specific aptamer with two arms of DNA segments. Probe 1 was hybridized with DNA probe 2 composed of a single DNA sequence with two split G-rich DNA sequences. This leads to the formation of a triplex-to-G-quadruplex (TPGQ). Next, acetamiprid was hybridized with the aptamer in the TPGQ to release free DNA probe 2. The released probe 2, in the presence of of K+, undergoes a structural change into a stem-loop structure (by self-complementary hybridization and Hoogsteen hydrogen bonding) that bears a G-quadruplex structure. This is followed by conjugation with hemin to form the G-quadruplex/hemin DNAzyme. The DNAzyme catalyzes the oxidation of o-phenylenediamine by H2O2 to produce a yellow fluorescent product with excitation/emission maxima at 420/560 nm. The oxidation product interacts with DPA-GQD-His to achieve a rapid energy transfer between DPA-GQD-His and oxidation product. This increases the fluorescence of the oxidation product and quenches the fluorescence of DPA-GQD-His. DPA-GQD-His also improves the catalytic activity of DNAzyme towards oxidation of ophenylenediamine oxidization and enhances fluorometric response to acetamiprid. The assay works in the 1.0 fM to 1.0 nM acetamiprid concentration range and has a 0.38 fM detection limit. It was successfully applied to the determination of acetamiprid in tea. Graphical abstractThe study reported one double amplification strategy for ultrasensitive fluorescence detection of acetamiprid in tea with D-penicillamine and histidine-functionalized graphene quantum dots and G-quadruplex/heminDNAzyme. The analtyical method exhibits ultra high sensitivity, selectivity and rapidity of fluorescence response to acetamiprid.

Molecular machine and gold/graphene quantum dot hybrid based dual amplification strategy for voltammetric detection of VEGF165.

Graphene quantum dots (GQDs) were prepared via pyrolysis of citric acid and glutamic acid, then reacted with chlorauric acid to form a gold/graphene quantum dot hybrid (Au/GQD), and finally connected with hairpin DNA probe 1 (H1) and thionine (Thi). The H1-Au/GQD-Thi composite is found to be a viable redox probe for electrochemical and aptamer-based determination of vascular endothelial growth factor VEGF165. A dual amplification strategy is employed based on the use of molecular machine and the Au/GQD. Each single VEGF165 molecule can bind two DNA probes via specific aptamer-target recognition to produce a molecular machine. Surface-tethered hairpin DNA 2 (H2) hybridizes with the molecular machine through proximity effect, and the prelocked toehold domain of H2 becomes exposed. This part binds to H1-Au/GQD-Thi to release the molecular machine which then moves to the neighboring H2 upon which a surface programmatic chain reaction is initiated. By continuous molecular machine travel, many H1-Au/GQD-Thi probes are present on the gold electrode surface. This implies an efficient signal amplification capability. The Au/GQD based redox probes in-situ catalyzes the redox activity of thionine and further enhances the detection signal. The aptasensor exhibits ultrahigh sensitivity and selectivity for VEGF165. The square wave voltammetric signal, best measured at -0.18 V vs. Ag/AgCl, increases linearly in the 1.0 fM to 120 pM VEGF165 concentration range, and the detection limit is 0.3 fM. Conceivably, the method may be applied to other target proteins if the corresponding high-affinity aptamers are available. Graphical abstract This study report one dual amplification strategy for ultrasensitive electrochemical detection of VEGF165 based on gold-graphene quantum dot hybrid (Au/GQD) and bipedal molecular machine (BMM) powered surface programmatic chain reaction (SPCR).

The impact of carbon emission and forest activities on health outcomes: empirical evidence from China.

The higher economic growth of China intensifies the consumption of fossil fuel, such as coal and oil, for electricity generation, transportation etc., which is responsible for environmental degradation through the emissions of carbon, sulfur, and nitrogen etc. The objectives of this study are to investigate the impact of greenhouse gas emission on health issues and provide the effective solution to overcome health-related issues, caused by carbon, sulfur, and nitrogen emission. For this purpose, we propose that higher afforestation activities can help to mitigate the carbon emission and can help to reduce the health diseases. The findings of quantile regressions reported that an increase in carbon emission causes significantly higher health issues. On the contrary, afforestation activities reported a negative coefficient, suggesting that growth of forests can be useful measure in control of health issues. The findings of the current study can be utilized in policy making and to explore the nexus between greenhouse gas emission, afforestation, and health issues.

Electrochemical sensor for detection of cancer cell based on folic acid and octadecylamine-functionalized graphene aerogel microspheres.

Early diagnosis of cancers is critical for prevention of metastasis and early treatment. The study reports an electrochemical sensor for detection of cancer cell based on folic acid (FA) and octadecylamine (OA)-functionalized graphene aerogel microspheres (FA-GAM-OA). Citric acid was mixed with FA and OA and heated at 180 °C for 4 h to form FA and OA-functionalized graphene oxide. The graphene oxide was employed as solid particle surfactant for stabilizing toluene-in-water emulsion. The graphene oxide sheets in the emulsion were self-assembled into graphene oxide gel microspheres on the water/toluene interfaces. Followed by free drying and reduction in H2 at 400 °C for 5 h. The resulted FA-GAM-OA shows a sphere-like structure with an average diameter of 1.2 µm, the rich of open-pores and folic acid groups. Small particle size and good hydrophilicity make FA-GAM-OA can be dispersed in water for sensor preparation. The small size of graphene sheets and their self-assembly avoid a serious agglomeration of graphene sheets. The FA-GAM-OA offers a large surface area (1723.6 m2 g-1) and high electronic conductivity (2978.2 S m-1). The covalent linkage and ordered alignment of folic acid groups at FA-GAM-OA surface achieve to specific cancer cell capture with high capture efficiency. The electrochemical sensor based on FA-GAM-OA exhibits extremely good analytical performances in detection of liver cancer cells with a linear range of 5-105 cell mL-1 giving a low detection limit of 5 cells mL-1 (S/N = 3). The method was successfully applied to electrochemical detection of liver cancer cells in whole blood.

Pentaethylenehexamine and d-penicillamine co-functionalized graphene quantum dots for fluorescent detection of mercury(II) and glutathione and bioimaging.

Pentaethylenehexamine and d-penicillamine co-functionalized graphene quantum dots (PEHA-GQD-DPA) was made via one two-step thermal pyrolysis. The resulting PEHA-GQD-DPA is composed of the graphene sheets with an average size of 3.16 nm and the rich of functional groups. It gives an ultra strong fluorescence emission with the fluorescent quantum yield of 90.91% and sensitive and selective optical response towards Hg2+. The fluorescence intensity linearly decreases with the increase of Hg2+ in the range of 1.0 × 10-10-2 × 10-4 M with the detection limit of 4.6 × 10-11 M (S/N = 3). No species tested interfere with detection of Hg2+. The fluorescence quenched by Hg2+ can be well recovered by glutathione. The fluorescence intensity linearly increases with the increase of glutathione in the range of 5 × 10-8-2.5 × 10-6 M with the detection limit of 1.7 × 10-8 M (S/N = 3). The PEHA-GQD-DPA as a fluorescence probe has been successfully applied in determination of Hg2+ in natural water and glutathione in human serum and SW480 cell imaging.

Electrochemical determination of acetaminophen using a glassy carbon electrode modified with a hybrid material consisting of graphene aerogel and octadecylamine-functionalized carbon quantum dots.

The study reports on the synthesis of a graphene aerogel@octadecylamine-functionalized carbon quantum dots (GA@O-CQDs). The graphene oxide aqueous dispersion, O-CQDs aqueous dispersion and toluene were strongly mixed to make a toluene-in-water Pickering emulsion. The graphene oxide sheets in the aqueous phase are reduced by hydrazine hydrate, diffuse into the toluene droplets, and self-assemble into graphene oxide microgels. This is followed by freeze-drying and thermal annealing to obtain the GA@O-CQDs hybrid that has a three-dimensional structure of several microns. It was dispersed in ethanol and deposited on a glassy carbon electrode. The modified electrode was applied to differential pulse voltammetric determination of acetaminophen, best at a peak potential of 0.15 V (vs. Ag/AgCl). Figures of the merit include a wide linear response range (0.001-10 µM) and a 0.38 nM of the detection limit (S/N = 3). The assay has been applied to the determination of acetaminophen in tablets. Graphical abstract Schematic presentation of the synthesis of graphene aerogel@octadecylamine-functionalized carbon quantum dots. The synthesis achieves to the intimate chemical and electrical contact between graphene and carbon quantum dots. An electrode modified with the hybrid exhibits ultra high sensitivity for detection of acetaminophen.

Synthesis of dodecylamine-functionalized graphene quantum dots and their application as stabilizers in an emulsion polymerization of styrene.

Pickering emulsions have attracted considerable interest due to their potential applications in many fields, such as the food, pharmaceutical, petroleum and cosmetics industries. The study reports the synthesis of dodecylamine-functionalized graphene quantum dots (d-GQDs) and their implementation as stabilizers in an emulsion polymerization of styrene. First, d-GQDs are prepared by thermal pyrolysis of citric acid and dodecylamine in 0.1M ammonium hydroxide. The resulting d-GQDs consist of small graphene sheets with abundant amino, carboxyl, acylamino, hydroxyl and alkyl chains on the edge. The amphiphilic structure gives the d-GQDs high surface activity. The addition of d-GQDs can reduce the surface tension of water to 30.8mNm-1 and the interfacial tension of paraffin oil/water to 0.0182mNm-1. The surface activity is much better than that of previously reported solid particle surfactants for Pickering emulsions and is close to that of sodium dodecylbenzenesulfonate, which is, a classical organic surfactants. Then, d-GQDs are employed as solid particle surfactants for stabilizing styrene-in-water emulsions. The emulsions exhibit excellent stability at pH 7. However, stability is lost when the pH is more than 9 or less than 4. The pH-switchable behaviour can be attributed to the protonation of amino groups in a weak acid medium and dissociation of carboxyl groups in a weak base medium. Finally, 2,2'-azobis(2-methylpropionitrile) is introduced into the Pickering emulsions to trigger emulsion polymerization of styrene. The as-prepared polystyrene spheres display a uniform morphology with a narrow diameter distribution. The fluorescent d-GQDs coated their surfaces. This study presents an approach for the fabrication of amphiphilic GQDs and GQDs-based functional materials, which have a wide range of potential applications in emulsion polymerization, as well as in sensors, catalysts, and energy storage.

Histidine-functionalized carbon-based dot-Zinc(II) nanoparticles as a novel stabilizer for Pickering emulsion synthesis of polystyrene microspheres.

Carbon-based dots (CDs) are nanoparticles with size-dependent optical and electronic properties that have been widely applied in energy-efficient displays and lighting, photovoltaic devices and biological markers. However, conventional CDs are difficult to be used as ideal stabilizer for Pickering emulsion due to its irrational amphiphilic structure. The study designed and synthesized a new histidine-functionalized carbon dot-Zinc(II) nanoparticles, which is termed as His-CD-Zn. The His-CD was made via one-step hydrothermal treatment of histidine and maleic acid. The His-CD reacted with Zn2+ to form His-CD-Zn. The as-prepared His-CD-Zn was used as a solid particle surfactant for stabilizing styrene-in-water emulsion. The Pickering emulsion exhibits high stability and sensitive pH-switching behaviour. The introduction of S2O82- triggers the emulsion polymerization of styrene. The resulted polystyrene microsphere was well coated with His-CDs on the surface. It was successfully used as an ideal adsorbent for removal of heavy metallic ions from water with high adsorption capacity. The study also provides a prominent approach for fabrication of amphiphilic carbon-based nanoparticles for stabilizing Pickering emulsion.

Fabrication of valine-functionalized graphene quantum dots and its use as a novel optical probe for sensitive and selective detection of Hg2.

The functionalization of graphene quantum dots has become a powerful method to modulate its chemical, electronic and optical properties for various applications. In the study, we reported a facile synthesis of valine-functionalized graphene quantum dots (Val-GQDs) and its use as a novel fluorescent probe for optical detection of Hg2+. Herein, Val-GQDs was synthesized by the thermal pyrolysis of citric acid and valine. The resulting Val-GQDs has an average size of 3nm and the edge of graphene sheets contains the rich of hydrophilic groups, leading to a high water-solubility. Compared to the GQDs prepared by thermal pyrolysis of citric acid, Val-GQDs exhibits a stronger fluorescence (>10-fold) and better photostability (>4-fold). Interestingly, the existence of valine moieties in the Val-GQDs results in a more sensitive fluorescent response to Hg2+. The fluorescent signal will linearly decrease with the increase of Hg2+ concentration in the range from 0.8nM to 1µM with the correlation coefficient of 0.992. The detection limit is 0.4nM (S/N=3), which the sensitivity is >14-fold that of GQDs. The analytical method provides the prominent advantage of sensitivity, selectivity and stability. It has been successfully applied in the optical detection of Hg2+ in real water samples. The study also provides a promising approach for the design and synthesis of functionalized GQDs to meet the needs of further applications in sensing and catalysis.

Improved activity and thermo-stability of the horse radish peroxidase with graphene quantum dots and its application in fluorometric detection of hydrogen peroxide.

Graphene quantum dots (GQDs) have received extensive concern in many fields such as optical probe, bioimaging and biosensor. However, few reports refer on the influence of GQDs on enzyme performance. The paper reports two kinds of graphene quantum dots (termed as GO-GQDs and N,S-GQDs) that were prepared by cutting of graphene oxide and pyrolysis of citric acid and l-cysteine, and their use for the horse radish peroxidase (HRP) modification. The study reveals that GO-GQDs and N,S-GQDs exhibit an opposite effect on the HRP performance. Only HRP modified with GO-GQDs offers an enhanced activity (more than 1.9 times of pristine enzyme) and thermo-stability. This is because GO-GQDs offer a larger conjugate rigid plane and fewer hydrophilic groups compared to N,S-GQDs. The characteristics can make GO-GQDs induce a proper conformational change in the HRP for the catalytic performance, improving the enzyme activity and thermo-stability. The HRP modified with green luminescent GO-GQDs was also employed as a biocatalyst for sensing of H2O2 by a fluorometric sensor. The colorless tetramethylbenzidine (TMB) is oxidized into blue oxidized TMB in the presence of H2O2 by the assistance of HRP/GO-GQDs, leading to an obvious fluorescence quenching. The fluorescence intensity linearly decreases with the increase of H2O2 concentration in the range from 2×10-9 to 2×10-4M with the detection limit of 6.8×10-10M. The analytical method provides the advantage of sensitivity, stability and accuracy compared with present H2O2 sensors based on the pristine HRP. It has been successfully applied in the determination of H2O2 in real water samples. The study also opens a new avenue for modification of enzyme activity and stability that offers great promise in applications such as biological catalysis, biosensing and enzyme engineering.

Nitrogen-doped multiple graphene aerogel/gold nanostar as the electrochemical sensing platform for ultrasensitive detection of circulating free DNA in human serum.

Graphene aerogel has attracted increasing attention due to its large specific surface area, high-conductivity and electronic interaction. The paper reported a facile synthesis of nitrogen-doped multiple graphene aerogel/gold nanostar (termed as N-doped MGA/GNS) and its use as the electrochemical sensing platform for detection of double stranded (dsDNA). On the one hand, the N-doped MGA offers a much better electrochemical performance compared with classical graphene aerogel. Interestingly, the performance can be enhanced by only increasing the cycle number of graphene oxide gelation. On the other hand, the hybridization with GNS further enhances the electrocatalytic activity towards Fe(CN)6(3-/4-). In addition, the N-doped MGA/GNS provides a well-defined three-dimensional architecture. The unique structure make it is easy to combine with dsDNA to form the electroactive bioconjugate. The integration not only triggers an ultrafast DNA electron and charge transfer, but also realizes a significant synergy between N-doped MGA, GNS and dsDNA. As a result, the electrochemical sensor based on the hybrid exhibits highly sensitive differential pulse voltammetric response (DPV) towards dsDNA. The DPV signal linearly increases with the increase of dsDNA concentration in the range from 1.0×10(-)(21) g ml(-)(1) to 1.0×10(-16) g ml(-1) with the detection limit of 3.9×10(-22) g ml(-1) (S/N=3). The sensitivity is much more than that of all reported DNA sensors. The analytical method was successfully applied in the electrochemical detection of circulating free DNA in human serum. The study also opens a window on the electrical properties of multiple graphene aerogel and DNA as well their hybrids to meet the needs of further applications as special nanoelectronics in molecule diagnosis, bioanalysis and catalysis.

Synthesis of Novel Water-Soluble Silicon Quantum Dots with Imidazole Groups and Its Application in Fluorescent Detection of / 分析化学

Silicon quantum dot has become an attractive nanomaterial due to their excellent biocompatibility and optical performance. However, poor water-solubility of the traditional silicon quantum dot limits its wide application. In this study, we reported the synthesis of water-soluble silicon quantum dots with imidazole groups by using hydrothermal method, in which N-trimethysilylimidazole was used as a precursor of silicon. Compared with sodium borohydride, ascorbic acid, bovine serum protein, cysteine and citric acid, the as-prepared silicon quantum dots offered the strongest fluorescence intensity when sodium citrate was used as the reducing agent and stabilizer for the synthesis. The reaction could complete within 2 h at 220℃. The obtained silicon quantum dots showed good water-solubility with an average particle size of 2. 6 nm, and the result of infrared spectroscopic analysis verified the existence of free imidazole groups on the surface. By means of the investigation of the fluorescence quenching behavior of copper ions towards the silicon quantum dots at different temperatures, we found that the degree of fluorescence quenching increased with the increase of temperature. There results proved that the fluorescence decrease belongs to static quenching. Namely, the interaction of Cu2+ with imidazole groups on the surface of silicon quantum dots formed stable complex. In addition, the resonance light scattering analysis also showed that the fluorescence quenching process was accompanied by the agglomeration of particles. Based on the fluorescence quenching behavior of silicon quantum dots, we established a method for the fluorescent detection of Cu2+. When the concentration of Cu2+was in the range of 0. 04-2400 μmol/L, the fluorescence intensity would linearly decrease with the increase of Cu2+ concentration, and the detection limit (S/N=3) reached 1. 29×10-8 mol/L. The method provided high sensitivity, selectivity and reproducibility, and was successfully applied to the determination of trace copper in fruits and vegetables.