Label-Free Electrogenerated Chemiluminescence Aptasensing Method for Highly Sensitive Determination of Dopamine via Target-Induced DNA Conformational Change.

A label-free electrogenerated chemiluminescence (ECL) aptasensing method for highly sensitive determination of dopamine (DA) was developed based on target-induced DNA conformational change. After anti-DA specific aptamer, as molecular recognition element, was hybridized with a capture ss-DNA (complementary with the aptamer), the formed double-strand DNA (ds-DNA) was self-assembled onto the surface of a gold electrode, and then Ru(phen)32+, as ECL reagent, was intercalated into ds-DNA to form an ECL biosensing platform. In the presence of DA, DA bound with its aptamer and target-induced DNA conformational change occurred, resulting in the dissociation of ds-DNA, the release of intercalated Ru(phen)32+ from the electrode surface, and the decrease of ECL intensity. For comparison, an ECL aptamer-based biosensing method using an ECL reagent-labeled aptamer was also developed for DA assay based on target-induced DNA conformational change. Because of the increase in the amount of ECL reagent into ds-DNA over that of the single-site ECL reagent-labeled aptamer, an obvious increase of ECL intensity was found at the ds-DNA modified electrode over the aptamer modified electrode. DA can be sensitively detected with a lower detection limit of 0.05 nM in the range from 0.1 to 100 nM. With the recognition of the aptamer for DA, DA can be selectively and sensitively detected in artificial cerebrospinal fluid and serum samples without interference from common small molecules. This work demonstrates that the combination of the direct transduction of specific recognition of DA and its aptamer into an ECL signal with Ru(phen)32+ intercalated ds-DNA amplification provides a promising strategy for the development of a simple, sensitive, and selective method for DA assay, which is of great importance in neurochemical assays and clinical diagnosis.

Boron-Doped and Ketonic Carbonyl Group-Enriched Graphdiyne as a Dual-Site Carbon Nanozyme with Enhanced Peroxidase-Like Activity.

We demonstrate the preparation of a dual-site carbon nanozyme, boron-doped and ketonic carbonyl (-C=O) group-enriched graphdiyne (B-GDY), with an enhanced peroxidase-like activity. Taking advantage of acidic oxidation treatment, GDY oxide (GDYO) with abundant surface oxygen-containing groups is obtained from pristine bulk GDY. Upon further thermal annealing of GDYO with H3BO3 under an inert atmosphere, B is introduced into GDY, while the loading of -C=O groups is increased onto B-GDY. We discover that boron-doped and ketonic carbonyl group-enriched graphdiyne as a dual-site carbon nanozyme endows it with an enhanced peroxidase-like activity, which is nearly 4.2-fold higher than that of GDY without B atoms and 6.6-fold higher than that of GDYO without B atoms and with low loading of -C=O groups. The high peroxidase-like activity of B-GDY is ascribed to the dual active sites (-C=O group and B atom) within it, which facilitates the adsorption and decomposition of H2O2 into hydroxyl radicals revealed by experimental and theoretical studies. Moreover, B-GDY is successfully employed to develop a colorimetric method for the detection of glucose with good sensitivity and selectivity. This work probes into the intrinsic peroxidase activity and structure-reactivity correlation, creating effective strategies for the preparation of GDY-based nanozymes.

Self-Terminated Electroless Deposition of Surfactant-Free and Monodispersed Pt Nanoparticles on Carbon Fiber Microelectrodes for Sensitive Detection of H2O2 Released from Living Cells.

We report a self-terminated electroless deposition method to prepare surfactant-free and monodispersed Pt nanoparticle (NP)-modified carbon fiber microelectrodes (Pt NP/CFEs) for electrochemical detection of hydrogen peroxide (H2O2) released from living cells. The surfactant-free and monodispersed Pt NPs with a uniform size of 65 nm are spontaneously deposited on a CFE surface by immersing an exposed carbon fiber (CF) of CFE in the PtCl42- solution, in which an exposed CF can be used as the reducing agent and stabilizer. A self-terminated electroless deposition method is demonstrated, in which the density and size of Pt NPs on a CFE surface do not increase when the reaction time increases from 20 to 60 min. The self-terminated electroless deposition process not only can effectively avoid any manual electrode modification and thus largely minimize person-to-person and electrode-to-electrode deviations but also can avoid the use of any extra reductant or surfactant in the fabrication process. Therefore, Pt NPs/CFEs, with good reproducibility and sensitivity, not only exhibit high electrocatalytic activity toward the oxidation of H2O2 but also maintain the spatial resolution of CFEs. Moreover, Pt NPs/CFEs can detect H2O2 with a wide linear range of 0.5-80 µM and a low detection limit of 0.17 µM and then can be successfully applied in the monitoring of H2O2 released from RAW 264.7 cells. The self-terminated electroless deposition method can also be extended to selectively prepare other metal NP-modified CFEs, such as Au NPs/CFEs or Ag NPs/CFEs, by choosing the metal ions with higher reduction potential as precursors. This work provides a simple, straightforward, and general method for the preparation of small, surfactant-free, and monodispersed metal NP-modified CFEs with high sensitivity, reproducibility, and spatial resolution.

Highly dispersive Pt-Pd nanoparticles on graphene oxide sheathed carbon fiber microelectrodes for electrochemical detection of H2O2 released from living cells.

We report a facile strategy for the synthesis of surfactant-free, small and highly dispersive Pt-Pd nanoparticles on graphene oxide (Pt-Pd NPs/GO) by an electroless deposition method, which is sheathed on carbon fiber microelectrodes (CFMs) as an electrochemical sensing platform for highly sensitive and selective detection of hydrogen peroxide (H2O2) released from the living cells. GO serves as the reducing agent and stabilizer for electroless deposition of Pd NPs on the surface of GO owing to its low work function (4.38 eV) and highly conjugated electronic structure. The obtained Pd NPs/GO have a relatively high work function (4.64 eV), and thereby could be used as stabilizer for synthesis of surfactant-free, small and highly dispersive Pt-Pd NPs/GO by chemical reduction of K2PtCl4. The obtained Pt-Pd NPs have a uniform size of 4.0 ± 0.6 nm on the surface of GO. Moreover, the Pt-Pd NPs/GO sheathed CFMs exhibit an excellent electrocatalytic activity for the reduction of H2O2 with a low detection limit of 0.3 µM and good selectivity. These good properties enable the modified microelectrode to detect the H2O2 released from living cells.

Synthesis of multiple-color emissive carbon dots towards white-light emission.

Multiple-color emissive carbon dots (C-dots) are gaining increasing attention in various fields. Herein, we report a facile solvothermal method for the synthesis of multiple-color emissive C-dots with the aim of white-light emission. Under single ultraviolet-light excitation, three C-dots emit a easily controlled fluorescent emission wavelength at 440 nm, 500 nm and 610 nm by using different three amines (either ammonium hydroxide, ethylenediamine or p-phenylenediamine, respectively) and pyromellitic dianhydride as molecular precursors while another three C-dots emit a controllable fluorescent emission wavelength at 500 nm, 550 nm and 585 nm by using same three amines and naphthalene-1,4,5,8-tetracarboxylic dianhydride as molecular precursors. The maximum fluorescence wavelength of these C-dots is red-shifted by changing three different amines molecular precursors from ammonium hydroxide, ethylenediamine, to p-phenylenediamine. Furthermore, these C-dots have shown promising applications in the fields of white-light-emitting diodes devices and color printing.

Electroless deposition of gold nanoparticles on carbon nanopipette electrode for electrochemical detection of catecholamines released from PC12 cells.

An electroless deposition method is reported for the fabrication of gold nanoparticles (Au NPs) modified carbon nanopipette electrode (CNPE) for sensitive electrochemical detection of dopamine (DA) in aqueous solution and catecholamines released from PC12 cells. A CNPE is fabricated by chemical vapor deposition with a carbon layer onto nanocapillary and then contacted with copper (Cu) wire. Cu wire of CNPE is able to serve as reducing agent for electroless deposition of Au NPs on the CNPE because the potential of Cu2+/Cu is more negative than that of AuCl4-/Au. The method is simple, time-saving, and environmentally friendly. Field emission scanning electron microscopy, energy-dispersive X-ray analysis, and electrochemical techniques confirm the successful fabrication of the Au NPs/CNPE. Furthermore, Au NPs/CNPE exhibits a good sensing activity for DA oxidation with a wide linear determination range of 0.1-8 µmol/L and a low detection limit of 6 nmol/L. The Au NPs/CNPE can be potentially applied for measurement of catecholamines released from PC12 cells. This present work is believed to be beneficial to the design and development of active metal catalysts onto nanoelectrodes for the detection of electroactive biological molecules in living cells.Graphical abstract An electroless deposition method was developed for the fabrication of gold nanoparticles onto the carbon nanopipette electrode, which was served as an enhanced electrochemical sensing platform for highly sensitive detection of dopamine with a linear range of 0.1-8 µmol/L and a detection limit of 6 nmol/L, and was also applied in the detection of catecholamines released from PC12 cells.

Rapid "turn-on" photoluminescence detection of bisulfite in wines and living cells with a formyl bearing bis-cyclometalated Ir(iii) complex.

A new photoluminescence (PL) probe based on a formyl bearing bis-cyclometalated Ir(iii) complex, [Ir(ppy)2phen-CHO]+PF6- (1), is synthesized and applied to the selective detection of a bisulfite anion (HSO3-). Probe 1 is prepared using 2-phenylpyridine (ppy) as the C^N main ligand and 1,10-phenanthroline-5-carboxaldehyde (phen-CHO) as the N^N ancillary ligand. Probe 1 displayed excellent selective PL enhancement in response to HSO3- in acetic acid-sodium acetate buffer solution (pH = 5.0). The increase of PL signal is directly proportional to the concentration of HSO3- in the range of 2 µM to 45 µM with a detection limit of 0.9 µM using 50 µM probe 1 and in the range of 0.5 µM to 6 µM with a detection limit of 0.3 µM using 10 µM probe 1. More importantly, probe 1 can respond to HSO3- rapidly within 40 s. Furthermore, probe 1 was successfully applied to detect HSO3- in real white wines and the bioimaging of HSO3- in living cells. The superior properties of probe 1 make it of great potential use for studying the effects of HSO3- in other biosystems.

Graphdiyne oxides as excellent substrate for electroless deposition of Pd clusters with high catalytic activity.

Graphdiyne (GDY), a novel kind of two-dimensional carbon allotrope consisting of sp- and sp(2)-hybridized carbon atoms, is found to be able to serve as the reducing agent and stabilizer for electroless deposition of highly dispersed Pd nanoparticles owing to its low reduction potential and highly conjugated electronic structure. Furthermore, we observe that graphdiyne oxide (GDYO), the oxidation form of GDY, can be used as an even excellent substrate for electroless deposition of ultrafine Pd clusters to form Pd/GDYO nanocomposite that exhibits a high catalytic performance toward the reduction of 4-nitrophenol. The high catalytic performance is considered to benefit from the rational design and electroless deposition of active metal catalysts with GDYO as the support.

Effective visualization assay for alcohol content sensing and methanol differentiation with solvent stimuli-responsive supramolecular ionic materials.

This study demonstrates a rapid visualization assay for on-spot sensing of alcohol content as well as for discriminating methanol-containing beverages with solvent stimuli-responsive supramolecular ionic material (SIM). The SIM is synthesized by ionic self-assembling of imidazolium-based dication C10(mim)2 and dianionic 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) in water and shows water stability, a solvent stimuli-responsive property, and adaptive encapsulation capability. The rationale for the visualization assay demonstrated here is based on the combined utilization of the unique properties of SIM, including its water stability, ethanol stimuli-responsive feature, and adaptive encapsulation capability toward optically active rhodamine 6G (Rh6G); the addition of ethanol into a stable aqueous dispersion of Rh6G-encapsulated SIM (Rh6G-SIM) destructs the Rh6G-SIM structure, resulting in the release of Rh6G from SIM into the solvent. Alcohol content can thus be visualized with the naked eyes through the color change of the dispersion caused by the addition of ethanol. Alcohol content can also be quantified by measuring the fluorescence line of Rh6G released from Rh6G-SIM on a thin-layer chromatography (TLC) plate in response to alcoholic beverages. By fixing the diffusion distance of the mobile phase, the fluorescence line of Rh6G shows a linear relationship with alcohol content (vol %) within a concentration range from 15% to 40%. We utilized this visualization assay for on-spot visualizing of the alcohol contents of three Chinese commercial spirits and discriminating methanol-containing counterfeit beverages. We found that addition of a trace amount of methanol leads to a large increase of the length of Rh6G on TLC plates, which provides a method to identify methanol adulterated beverages with labeled ethanol content. This study provides a simple yet effective assay for alcohol content sensing and methanol differentiation.

Improving the fluorescence detection limit with positively charged carbon nanostructures as a low background signal platform.

We have demonstrated a new strategy to improve the fluorescence detection limit by enhancing the energy transfer efficiency between carbon structures and fluorescent dyes using polyimidazolium-functionalized carbon nanostructures as a low background signal platform. Based on this, a highly sensitive method for thrombin was proposed with a detection limit as low as 2.79 pM without any amplification.

Anion-exchange-based amperometric assay for heparin using polyimidazolium as synthetic receptor.

This study demonstrates a facile yet effective strategy for amperometric assay of electrochemically inactive heparin based on an anion-exchange mechanism with polyimidazolium (Pim) as the synthetic receptor. The rationale for the amperometric heparin assay is essentially based on the different binding affinity of the synthetic Pim receptor toward electrochemically active ferricyanide (Fe(CN)6(3-)) and electrochemically inactive heparin. To accomplish the amperometric assay, Pim is first synthesized and used as the artificial receptor to recognize the anions (i.e., Fe(CN)6(3-) and heparin). The stronger binding affinity of the synthetic Pim receptor toward heparin than toward Fe(CN)6(3-) essentially validates the amperometric heparin assay through an anion-exchange mechanism with the decrease in the redox peak current of Fe(CN)6(3-) adsorbed onto the Pim film as the signal readout. The anion exchange between Fe(CN)6(3-) and heparin on the Pim receptor is verified by cyclic voltammetry and Fourier transform IR and UV-visible spectroscopies. The ratio of the current decrease shows a linear relationship with heparin concentration with a concentration range from 0.5 to 10 µM. With animal experiments by dosing intraperitoneally and collecting the serum sample, the method is demonstrated to be potentially useful for investigating heparin metabolism in the biological system. This study not only provides a simple yet effective route to a heparin assay but also opens a new way to developing amperometric methods for electrochemically inert species by fully utilizing the supramolecular principles.

Rationally Designed Matrix-Free Carbon Dots with Wavelength-Tunable Room-Temperature Phosphorescence.

We report the rational design of the matrix-free carbon dots (C-dots) with long wavelength and wavelength-tunable room-temperature phosphorescence (RTP). Taking advantage of microwave-assisted heating treatment, three RTP C-dots in boric acid (BA) composites are synthesized by using diethylenetriaminepentakis (methylphosphonic acid) as a multiple-sites crosslink agent, a moderately acid catalyst and P source; phenylenediamines (either o-PD, m-PD, or p-PD, respectively) as building block while BA as a carbonization-retardant matrix. After the water-soluble BA matrix is removed by dialysis, three matrix-free C-dots are obtained with RTP emission at 540, 550 and 570 nm under an excitation wavelength of 365 nm. Alterations of RTP emission of three matrix-free C-dots are ascribed to the difference in their particle size and band gap from n-π* transition. Furthermore, the application of three matrix-free C-dots are successfully performed in information encryption and decryption.

Matrix-Free and Highly Efficient Room-Temperature Phosphorescence Carbon Dots towards Information Encryption and Decryption.

Designing efficient room-temperature phosphorescence (RTP) carbon dots (C-dots) without the need of an additional matrix is important for various applications. Herein, matrix-free and highly efficient C-dots with yellow-green RTP emission have been successfully synthesized towards information encryption and decryption. Phytic acid (PA) and triethylenetetramine are used as molecular precursors, and a facile microwave-assisted heating method is selected as synthesis method. The obtained C-dots exhibit a maximum phosphorescence emission at around 535 nm under an excitation wavelength of 365 nm and a long average lifetime up to 750 ms (more than 9 s to the naked eye). PA containing six phosphate groups and serving as P source plays a significant role in producing the RTP C-dots. Furthermore, potential applications of the RTP C-dots in the field of information encryption and decryption are successfully demonstrated.

Cyclometalated Iridium Complex as Off-On-Off Reversible Photoluminescence Probe for Redox Cycle HSO3-/H2O2 in Living Cells.

The development of new methods for the detection of redox cycle is important for biological and clinical diagnoses. Here, a new cyclometalated iridium complex, (4-(2-pyridyl) benzaldehyde)2Ir (5-chloro-1,10-phenanthroline) ([(4-pba)2Ir(5-Cl-phen)]PF6, probe 1), has been synthesized and applied to rapid, sensitive, and reversible detection and imaging of redox cycle HSO3-/H2O2 in living cells. The probe 1 is synthesized by using 4-(2-pyridyl) benzaldehyde as main ligand and 5-chloro-1,10-phenanthroline as ancillary ligand. Probe 1 exhibited "off-on-off" photoluminescence (PL) signal change in response to HSO3- and H2O2 in aqueous solution within 1 min. The change of PL intensity is proportional to HSO3- concentration from 40 µM to 300 µM and to H2O2 concentration from 40 µM to 260 µM. The detection limit is 10 µM for HSO3- and 20 µM for H2O2. Additionally, probe 1 was applied to detect HSO3- in food samples with satisfactory results. More importantly, PL imaging of HeLa cells indicates that probe 1 is able to image redox cycle HSO3-/H2O2 in living cells.

Water-stable, adaptive, and electroactive supramolecular ionic material and its application in biosensing.

Developing water-stable and adaptive supramolecular materials is of great importance in various research fields. Here, we demonstrate a new kind of water-stable, adaptive, and electroactive supramolecular ionic materials (SIM) that is formed from the aqueous solutions of imidazolium-based dication and dianionic dye (i.e., 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), ABTS) through ionic self-assembly. The formed SIM not only shows good thermostability and unique optical and electrochemical properties that are raised from precursors of the SIM, but also exhibits good water-stability, salt-stability, and adaptive encapsulation properties toward some heterocyclic cationic dye molecules. UV-vis and FT-IR results demonstrate that this encapsulation property is essentially based on the electrostatic interactions between the guest dye molecules and ABTS in the SIM. The application of the SIM prepared here is illustrated by the development of a new electrochemical sensor for NADH sensing at a low potential. This study not only opens a new avenue to the preparation of the supramolecular materials, but also provides a versatile platform for electrochemical (bio)sensing.

Determination of explosives based on novel type of sensor using porphyrin functionalized carbon nanotubes.

The hydroxide of meso-tetraphenylporphyrin derivatives functionalized carbon nanotubes (CNTs) was fabricated in our research to explore the interaction between porphyrin and explosive. It was turned out that in the formation of grid porphyrin film, carbon nanotubes as a cruciul base materials promoted the electron transfer rate. Most of important, the results also showed that the electrochemical response was enhanced through increasing the number of -OH substitution in porphyrin. Such information provides the platform for a practical strategy for rational design of the sensor of explosives.

Highly dispersive Ag nanoparticles on functionalized graphene for an excellent electrochemical sensor of nitroaromatic compounds.

A facile carbon radical reaction procedure and a chemical reduction method were proposed to synthesize Ag nanoparticles on functionalized graphene with uniform, high dispersion and excellent stability. The resultant material showed excellent electrocatalytic activity to nitroaromatic compounds and high sensitivity to the detection of nitroaromatic compounds.