Valence-Engineered Oxidase-Mimicking Nanozyme with Specificity for Aromatic Amine Oxidation and Identification.

Oxidase-mimicking nanozymes with specificity for catalyzing oxidation of aromatic amines are of great significance for recognition of aromatic amines but rarely reported. Herein, Cu-A nanozyme (synthesized with Cu2+ as a node and adenine as a linker) could specifically catalyze oxidation of o-phenylenediamine (OPD) in Britton-Robinson buffer solution. Such a specific catalytic performance was also corroborated with other aromatic amines, such as p-phenylenediamine (PPD), 1,5-naphthalene diamine (1,5-NDA), 1,8-naphthalene diamine (1,8-NDA), and 2-aminoanthracene (2-AA). Moreover, the presence of salts (1 mM NaNO2, NaHCO3, NH4Cl, KCl, NaCl, NaBr, and NaI) greatly mediated the catalytic activity with the order of NaNO2 < blank ≈ NaHCO3 < NH4Cl ≈ KCl ≈ NaCl < NaBr < NaI, which was due to anions sequentially increasing interfacial Cu+ content via anionic redox reaction, while the effect of cations was negligible. With the increased Cu+ content, Km decreased and Vmax increased, indicating valence-engineered catalytic activity. Based on high specificity and satisfactory activity, a colorimetric sensor array with NaCl, NaBr, and NaI as sensing channels was constructed to identify five representative aromatic amines (OPD, PPD, 1,5-NDA, 1,8-NDA, and 2-AA) as low as 50 µM, quantitatively analyze single aromatic amine (with OPD and PPD as model analysts), and even identify 20 unknown samples with an accuracy of 100%. In addition, the performance was further validated through accurately recognizing various concentration ratios of binary, ternary, quaternary, and quinary mixtures. Finally, the practical applications were demonstrated by successfully discriminating five aromatic amines in tap, river, sewage, and sea water, providing a simple and feasible assay for large-scale scanning aromatic amine levels in environmental water samples.

Carbon Dots with Guanidinium and Amino Acid Functional Groups for Targeted Small Interfering RNA Delivery toward Tumor Gene Therapy.

Small interfering RNA (siRNA)-based gene therapy represents a promising strategy for tumor treatment. Novel gene vectors that can achieve targeted delivery of siRNA to the tumor cells without causing any side effects are urgently needed. To this end, the large amino acid mimicking carbon dots with guanidinium functionalization (LAAM GUA-CDs) are designed and synthesized by choosing arginine and dopamine hydrochloride as precursors. LAAM GUA-CDs can load siRNA through the multiple hydrogen bonds between their guanidinium groups and phosphate groups in siRNA. Meanwhile, the amino acid groups at the edges of LAAM GUA-CDs endow them the capacity to target tumors. After loading siBcl-2 as a therapeutic agent, LAAM GUA-CDs/siBcl-2 has a high tumor inhibition rate of up to 68%, which is twice more than that of commercial Lipofectamine 2000. Furthermore, LAAM GUA-CDs do not cause side effect during antitumor treatment owing to their high tumor-targeting ability, thus providing a versatile strategy for tumor-targeted siRNA delivery and cancer therapy.

Carbon Quantum Dots with Near-Unity Quantum Yield Bandgap Emission for Electroluminescent Light-Emitting Diodes.

Carbon quantum dots (CQDs) feature bright and tunable photoluminescence, solution processability, and low toxicity, showing great potential in optoelectronics. However, the large-scale synthesis of CQDs with near-unity photoluminescence quantum yield (PLQY) has not been achieved so far. In this study, we perform radical-assisted synthesis of hexagon-shaped CQDs (H-CQDs) delivering near-unity PLQY (96 %). Experimental and theoretical analyses revealed that the large vertically oriented transition dipole moment of H-CQDs originating from high symmetry results in nearly 100 % PLQY. The H-CQDs also exhibited a high electron mobility of up to 0.07 cm2  V-1 s-1 . These properties enable the H-CQD-based light-emitting diodes with a high external quantum efficiency of 4.6 % and a record maximum brightness of over 11 000 cd m-2 . This study represents a significant advance that CQDs-based electroluminescent device can be utilized for potential display and lighting applications.

Red Phosphorescent Carbon Quantum Dot Organic Framework-Based Electroluminescent Light-Emitting Diodes Exceeding 5% External Quantum Efficiency.

Carbon quantum dots (CQDs) have developed into prospective nanomaterials for next-generation lighting and displays due to their intrinsic advantages of high stability, low cost, and environmental friendliness. However, confined by the spin-forbidden nature of triplet state transitions, the highest theoretical value of external quantum efficiency (EQE) of fluorescent CQDs is merely 5%, which fundamentally limits their further application in electroluminescent light-emitting diodes (LEDs). Soluble phosphorescent CQDs offer a means of breaking the shackle to achieve efficient monochromatic electroluminescence, especially red emission, which is a pivotal constituent in full-color displays. Here, the synthesis of red (625 nm) phosphorescent carbon quantum dot organic frameworks (CDOFs) with a quantum yield of up to 42.3% and realization of high-efficiency red phosphorescent electroluminescent LEDs are reported. The LEDs based on the CDOFs exhibited a red emission with a maximum luminance of 1818 cd m-2 and an EQE of 5.6%. This work explores the possibility of a new perspective for developing high-performance CQD-based electroluminescent LEDs.

Glucose oxidase decorated fluorescent metal-organic frameworks as biomimetic cascade nanozymes for glucose detection through the inner filter effect.

Metal-organic frameworks (MOFs) as a peroxidase mimic have been integrated with glucose oxidase (GOx) to achieve one-step glucose detection. However, limited by the loading amount of GOx, the performances of the developed glucose sensing assays still remain to be further improved to meet sensing requirements in diverse biological samples. Herein, with Fe3+ as the metal ion and 2-amino-benzenedicarboxylic acid as a ligand, a fluorescent Fe-based organic framework (NH2-MIL-101) with peroxidase-like activity was synthesized. Due to the large specific surface area (791.75 m2 g-1), 68 µg mg-1 GOx could be immobilized through the amidation coupling reaction, and the product was designated GOx@NH2-MIL-101. With OPD as the substrate, Gox@NH2-MIL-101 achieved highly efficient biomimetic cascade catalysis for one-step glucose detection through an inner filter effect: upon reacting with glucose, GOx@NH2-MIL-101 catalytically oxidized glucose using dissolved O2, and the produced H2O2 concurrently oxidized o-phenylenediamine (OPD) to oxidized OPD (oxOPD), accompanied by the fluorescence of GOx@NH2-MIL-101 at 456 nm being quenched and that of oxOPD at 565 nm being enhanced. With the fluorescent ratio F565/F456 used as a readout signal, a wide linear range of 0.1-600 µM was obtained, and the detection limit was 0.0428 µM. Based on the excellent selectivity and high stability of GOx@NH2-MIL-101, the developed assay was successfully applied to glucose detection in human serum and saliva, presenting potential applications in diverse biological samples and even medical diagnosis.

Fe-N/C single-atom nanozyme-based colorimetric sensor array for discriminating multiple biological antioxidants.

Identifying the species and concentrations of antioxidants is really important because antioxidants play important roles in various biological processes and numerous diseases. Compared with an individual sensor detecting a single antioxidant with limited specificity, a sensor array could simultaneously identify various antioxidants, in which 3-5 types of nanomaterials with peroxidase-like activity are absolutely necessary. Herein, as a single-atom nanozyme, Fe-N/C with oxidase-mimicking activity was applied to construct a triple-channel colorimetric sensor array: (1) Fe-N/C catalytically oxidized three substrates 3,3',5,5'-tetramethylbenzidine (TMB), 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and o-phenylenediamine (OPD) to produce blue oxidized TMB (oxTMB), green oxidized ABTS (oxABTS) and yellow oxidized OPD (oxOPD), respectively; (2) with oxTMB, oxABTS and oxOPD as three sensing channels, a colorimetric sensor array was constructed for simultaneously discriminating glutathione (GSH), l-cysteine (l-Cys), ascorbic acid (AA), uric acid (UA), and melatonin (MT), even quantifying concentrations (with GSH as a model analyst). The performance of the sensor array was validated through accurately identifying 15 blind samples containing GSH, l-Cys, AA, UA and MT in buffer solution and human serum samples, and also in binary and ternary mixtures. This work proved that fabricating a single nanozyme-based sensor array was a simplified and reliable strategy for simultaneously probing multiple antioxidants.

Gram-Scale Synthesis of Highly Efficient Rare-Earth-Element-Free Red/Green/Blue Solid-State Bandgap Fluorescent Carbon Quantum Rings for White Light-Emitting Diodes.

The negative impact of rare-earth elements (REEs) on the environment, limited supply and high cost prompt the need for REE-free phosphor-converted white light-emitting diodes (LEDs). Here, we report the gram-scale synthesis of red/green/blue solid-state bandgap fluorescent carbon quantum rings (R/G/B-SBF-CQRs) with high quantum yields up to 30-46 %. This was achieved using cyano-group-bearing p-phenyldiacetonitrile as precursor and forming carbon quantum rings of different diameters through the linkage of curved carbon quantum ribbons of different lengths. The results show the role of cyano groups in inducing the curvature of the carbon quantum ribbons for CQR formation and emission of stable solid-state bandgap fluorescence. R/G/B-SBF-CQRs-phosphor-based LEDs emitted warm white light with low CCT (3576 K), high CRI (96.6), and high luminous efficiency (48.7 lm W-1 ), comparable to REE-phosphor-based LEDs.

A versatile fluorometric in situ hybridization method for the quantitation of hairpin conformations in DNA self-assembled monolayers.

As the performance of hairpin DNA (hpDNA)-based biosensors is highly dependent on the yield of stem-loop (hairpin) conformations, we report herein a versatile fluorometric in situ hybridization protocol for examining hpDNA self-assembled monolayers (SAMs) on popularly used biochip substrates. Specifically, the ratio of fluorescence (FL) intensities of hpDNA SAMs (in an array format) before and after hybridization was adopted as the key parameter for performing such a determination. Upon confirming the existence of mixed and tunable DNA conformations in binary deposition solutions and efficient hybridization of the hairpin strands with the target DNA via gel electrophoresis assays, we tested the fluorometric protocol for determining the coverages of hpDNA in hpDNA/ssDNA SAMs prepared on gold; its accuracy was validated by Exonuclease I (Exo I)-assisted electrochemical quantitation. To further confirm its versatility, this FL protocol was adopted for quantifying hairpin conformations formed on glass and polycarbonate (PC) substrates. The molar ratios of surface-tethered hairpin conformations on the three different substrates were all found to be proportional to but less than those in the binary deposition solutions, and were dependent on the substrate morphology. The findings reported herein are beneficial for the construction of highly efficient DNA hairpin-based sensing surfaces, which essentially facilitates the creation of hpDNA-based biosensors with optimal detection performance.

Solution Grown Single-Unit-Cell Quantum Wires Affording Self-Powered Solar-Blind UV Photodetectors with Ultrahigh Selectivity and Sensitivity.

As crystalline semiconductor nanowires are thinned down to a single-unit-cell thickness, many fascinating properties could arise pointing to promising applications in various fields. A grand challenge is to be able to controllably synthesize such ultrathin nanowires. Herein, we report a strategy, which synergizes a soft template with oriented attachment (ST-OA), to prepare high-quality single-unit-cell semiconductor nanowires (SSNWs). Using this protocol, we are able to synthesize for the first time ZnS and ZnSe nanowires (NWs) with only a single-unit-cell thickness (less than 1.0 nm) and a cluster-like absorption feature (i.e., with a sharp, strong, and significantly blue-shifted absorption peak). Particularly, the growth mechanism and the single-unit-cell structure of the as-prepared ZnS SSNWs are firmly established by both experimental observations and theoretical calculations. Thanks to falling into the extreme quantum confinement regime, these NWs are found to only absorb the light with wavelengths shorter than 280 nm (i.e., solar-blind UV absorption). Utilizing such a unique property, self-powered photoelectrochemical-type photodetectors (PEC PDs) based on the ZnS SSNWs are successfully fabricated. The PDs after interface modification with TiO2 exhibit an excellent solar-blind UV photoresponse performance, with a typical on/off ratio of 6008, a detectivity of 1.5 × 1012 Jones, and a responsivity of 33.7 mA/W. This work opens the door to synthesizing and investigating a new dimension of nanomaterials with a wide range of applications.

Thioflavin T specifically brightening "Guanine Island" in duplex-DNA: a novel fluorescent probe for single-nucleotide mutation.

Here, we found that Thioflavin T (ThT) could specifically bind with a G-GGG unit (named as "Guanine Island") in double stranded DNA (ds-DNA). Through stacking with G base via hydrogen bonds, the rotation of ThT was restricted and concurrently its planarization was enforced. Such a binding mode produced a significantly enhanced ThT fluorescence. Based on this discovery, with ThT as a lighting-up probe for "Guanine Island" in ds-DNA, the fluorescent detection of single-nucleotide mutation (C mutation) was investigated. With C base in target DNA mutating to G, A or T and further hybridizing with a probe DNA containing a GGG unit at the mutated point, ds-DNA including G-GGG, A-GGG or T-GGG islands was formed, respectively. After binding with ThT, C mutation was clearly recognized. With C mutating to G as an example, the detection limit was as low as 3 nM. Importantly, the developed assay could be applied to recognize C mutating to G in a DNA sequence related to dilated cardiomyopathy for diluted human serum. As a sensing unit ("Guanine Island" in ds-DNA lighting up ThT), it is expected to be applied for various biological or environmental systems.

Systematic truncating of aptamers to create high-performance graphene oxide (GO)-based aptasensors for the multiplex detection of mycotoxins.

Graphene oxide (GO)-based aptasensors are currently one of the most popular sensing platforms for the simple and rapid detection of various targets. Unfortunately, the GO-based aptasensors with long aptamer strands typically show unsatisfactory performance resulting from insignificant structural transformations upon target binding. We report herein the utilization of an aptamer-truncating strategy to combat such a challenge. Taking a pre-selected anti-aflatoxin B1 (AFB1) aptamer (P-AFB1-50) as a trial system, we sequentially remove the extraneous nucleotides within the aptamer by means of circular dichroism (CD) spectroscopy and binding affinity analysis. Particularly, the ratio of the quenching constants between the GO sheets and the truncated aptamers (labelled with fluorophores) in the absence and presence of the target was determined for each of the truncated aptamers to evaluate the optimal sequence. As a result, the truncated aptamer comprising 40 nucleotides was confirmed to show the highest FL output and the best detection limit upon conjugation with GO sheets. More importantly, we demonstrated that this truncating strategy is versatile, i.e., it can be easily extended to other aptamer systems (anti-ochratoxin A (OTA) aptamer, P-OTA-61, as an example) for extraneous nucleotide identification. Impressively, the two optimal truncated aptamers can work together on GO sheets to achieve a simultaneous detection of two different mycotoxins (i.e., AFB1 and OTA) in one single test. Essentially, this research opens a new avenue for the design and testing of aptamer-/GO-based-sensing platforms for rapid, low-cost and multiplex quantification of analytical targets of interest.

Na+-Induced Conformational Change of Pb2+-Stabilized G-Quadruplex and Its Influence on Pb2+ Detection.

Here, we first find that Na+ can induce Pb2+-stabilized T30695 undergoing conformational transition from partly parallel to completely parallel, and further forming a dimeric G-quadruplex, which was characterized by circular dichroism (CD) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and native polyacrylamide gel electrophoresis (PAGE). Thermal denaturation experiments show that the transforming process is a thermodynamics-driven process. Furthermore, the presence of Na+ further improves the binding efficiency of Pb2+-stabilized T30695 with the fluorescent probe (such as ZnPPIX). Based on the fact, with a partially hybridized double-stranded DNA (ds-DNA) containing T30695 as a sensing probe and ZnPPIX as a fluorescence probe, the effect of Na+ on Pb2+ detection is subsequently investigated. The presence of Na+ (varied from 0.3 mM to 500 mM) simultaneously increases the read-out and background fluorescence, which results in a decreased signal-to-noise ratio and further leads to a decreased sensing performance (detection limits is increased to 120 nM). In order to avoid Na+ interference, a fully matched ds-DNA containing T30695 is utilized as a sensing probe to fix the background fluorescence, regardless of whether Na+ is present or not. Thus, a relatively lower detection limit (10 nM) in all Na+-containing real samples is achieved, respectively. Therefore, the paper provides a novel insight into the conformational changes in G-quadruplex and presents an efficient step to resolve the challenging problem about Pb2+ detection in Na+-containing real samples.

Synthesis and photophysical properties of a Sc3N@C80 -corrole electron donor-acceptor conjugate.

Embedding endohdedral metallofullerenes (EMFs) into electron donor-acceptor systems is still a challenging task owing to their limited quantities and their still largely unexplored chemical properties. In this study, we have performed a 1,3-dipolar cycloaddition reaction of a corrole-based precursor with Sc3 N@C80 to regioselectively form a [5,6]-adduct (1). The successful attachment of the corrole moiety was confirmed by mass spectrometry. In the electronic ground state, absorption spectra suggest sizeable electronic communications between the electron acceptor and the electron donor. Moreover, the addition pattern occurring at a [5,6]-bond junction is firmly proven by NMR spectroscopy and electrochemical investigations performed with 1. In the electronically excited state, which is probed in photophysical assays with 1, a fast electron-transfer yields the radical ion pair state consisting of the one-electron-reduced Sc3 N@C80 and of the one-electron-oxidized corrole upon its exclusive photoexcitation. As such, our results shed new light on the practical work utilizing EMFs as building blocks in photovoltaics.

A gold nanoparticle-based colorimetric probe for rapid detection of 1-hydroxypyrene in urine.

Direct and rapid detection of 1-hydroxypyrene (1-OHP) is of great importance owing to its high carcinogenicity, teratogenicity and toxicity. In this study, a simple colorimetric assay for rapid determination of 1-OHP is reported, which is based on non-crosslinking aggregation of gold nanoparticles (Au NPs) induced by 1-OHP in the presence of formic acid (FA). Initially, Au NPs were synthesized with citrate as the capping agent and exhibited red color. Subsequently, the addition of FA did not cause aggregation of Au NPs, but a proton transfer process occurred from FA to carboxylic anions on the surface of Au NPs with a decreased zeta potential. The subsequent addition of 1-OHP resulted in a further decreased zeta potential and an intensely hydrophobic environment, which led to a strong and rapid non-crosslinking aggregation of Au NPs within 5 min with the color changing from red to violet blue. Based on this principle, sensitive and selective detection of 1-OHP was achieved. The detection limit was 3.3 nM. Finally, the colorimetric assay was successfully applied to detect 1-OHP in a urine sample. This strategy provides new insights into developing colorimetric methods for on-site and real-time detection of polycyclic aromatic hydrocarbons.

Binary DNA hairpin-based colorimetric biochip for simultaneous detection of Pb(2+) and Hg(2+) in real-world samples.

A microarray-format colorimetric biochip was constructed on plastic using two specially-designed DNA hairpin strands as binary probes and a binding-induced conformational switching strategy as the signal generation protocol. Coupled with single- or dual-color staining, we were able to simultaneously detect and quantitate the trace amounts of Pb(2+) and Hg(2+) in various real-world samples.

Aggregation-induced preparation of ultrastable zinc sulfide colloidal nanospheres and their photocatalytic degradation of multiple organic dyes.

Monodispersed and ultrastable colloidal ZnS nanospheres (NPs) composed of tiny nanoparticles were successfully synthesized by using a limited ligand-induced in situ aggregation strategy. With such a strategy, the whole size as well as the particle size of those ZnS NPs could be tuned simultaneously by appropriately varying the reaction conditions. Three representative ZnS NP samples with different sphere sizes and particle sizes were thus obtained, which were all proven to possess rather large surface areas, robust structures and excellent colloidal stability. Furthermore, the photocatalytic activities of the as-prepared ZnS NPs toward the photodegradation of eosin B, methylene blue and their binary mixture were explored respectively. An interesting size-dependent degradation performance associated with the ZnS NPs was observed in all the photodegradation cases. Finally, their degradation mechanism was fully elucidated according to the control experiments under different atmospheres in combination with the related energy level information. We believe that the control strategy for tuning the fine and whole structures of spherical nanostructures in a synergistic manner together with the structure-dependent photodegradation performance revealed herein will definitely benefit the fabrication of highly efficient photocatalysts as well as the nanocomplexes with hierarchical architectures.

Efficiency enhancement of perovskite solar cells through fast electron extraction: the role of graphene quantum dots.

We report on a significant power conversion efficiency improvement of perovskite solar cells from 8.81% to 10.15% due to insertion of an ultrathin graphene quantum dots (GQDs) layer between perovskite and TiO2. A strong quenching of perovskite photoluminescence was observed at ∼760 nm upon the addition of the GQDs, which is pronouncedly correlated with the increase of the IPCE and the APCE of the respective cells. From the transient absorption measurements, the improved cell efficiency can be attributed to the much faster electron extraction with the presence of GQDs (90-106 ps) than without their presence (260-307 ps). This work highlights that GQDs can act as a superfast electron tunnel for optoelectronic devices.

Sulfur-doped graphene quantum dots as a novel fluorescent probe for highly selective and sensitive detection of Fe(3+).

Sulfur-doped graphene quantum dots (S-GQDs) with stable blue-green fluorescence were synthesized by one-step electrolysis of graphite in sodium p-toluenesulfonate aqueous solution. Compared with GQDs, the S-GQDs drastically improved the electronic properties and surface chemical reactivities, which exhibited a sensitive response to Fe(3+). Therefore, the S-GQDs were used as an efficient fluorescent probe for highly selective detection of Fe(3+). Upon increasing of Fe(3+) concentration ranging from 0.01 to 0.70 µM, the fluorescence intensity of S-GQDs gradually decreased and reached a plateau at 0.90 µM. The difference in the fluorescence intensity of S-GQDs before and after adding Fe(3+) was proportional to the concentration of Fe(3+), and the calibration curve displayed linear regions over the range of 0-0.70 µM. The detection limit was 4.2 nM. Finally, this novel fluorescent probe was successfully applied to the direct analysis of Fe(3+) in human serum, which presents potential applications in clinical diagnosis and may open a new way to the design of effective fluorescence probes for other biologically related targets.

Electrochemical preparation of N-doped cobalt oxide nanoparticles with high electrocatalytic activity for the oxygen-reduction reaction.

Nitrogen-doped CoO (N-CoO) nanoparticles with high electrocatalytic activity for the oxygen-reduction reaction (ORR) were fabricated by electrochemical reduction of CoCl2 in acetonitrile solution at cathodic potentials. The initially generated, highly reactive nitrogen-doped Co nanoparticles were readily oxidized to N-CoO nanoparticles in air. In contrast to their N-free counterparts (CoO or Co3 O4 ), N-CoO nanoparticles with a N content of about 4.6 % exhibit remarkable ORR electrocatalytic activity, stability, and immunity to methanol crossover in an alkaline medium. The CoNx active sites in the CoO nanoparticles are held responsible for the high ORR activity. This work opens a new path for the preparation of nitrogen-doped transition metal oxide nanomaterials, which are promising electrocatalysts for fuel cells.