Search

Circulating microRNAs (miRNAs) play a pivotal role in the occurrence and development of acute myocardial infarction (AMI), and precise detection of them holds significant clinical implications. The development of luminol-based luminophores in the field of electrochemiluminescence (ECL) for miRNA detection has been significant, while their effectiveness is hindered by the instability of co-reactant hydrogen peroxide (H2O2). In this work, an iron single-atom catalyst (Fe-PNC) was employed for catalyzing the luminol-O2 ECL system to achieve ultra-sensitive detection of myocardial miRNA. Target miRNA triggers a hybridization chain reaction (HCR), resulting in the generation of a DNA product featuring multiple sticky ends that facilitate the attachment of Fe-PNC probes to the electrode surface. The Fe-PNC catalyst exhibits high promise and efficiency for the oxygen reduction reaction (ORR) in electrochemical energy conversion systems. The resulting ECL biosensor allowed ultrasensitive detection of myocardial miRNA with a low detection limit of 0.42 fM and a wide linear range from 1 fM to 1.0 nM. Additionally, it demonstrates exceptional performance when evaluated using serum samples collected from patients with AMI. This work expands the application of single-atom catalysis in ECL sensing and introduces novel perspectives for utilizing ECL in disease diagnosis. [ABSTRACT FROM AUTHOR]

Humic acid–based carbon dots (HACDs) have excellent properties and are widely used in environmental detection, bioimaging, and optoelectronic materials. Herein, we investigated the structure–activity relationship between the morphology and optical properties of HACDs, and reported on a novel strategy for metronidazole (MNZ) and ornidazole (ONZ) sensing in multiple real samples. It was found that the average particle size decreased from 3.28 to 2.44 nm, optimal emission wavelength was blue-shifted from 500 to 440 nm, and the quantum yield (QY) improved from 5 to 23% with the temperature increasing from 110 to 400 °C. Under the oxidation of hydrogen peroxide (H2O2) and potassium permanganate (KMnO4), the UV–vis spectra of HACD aqueous solution showed time-dependent behavior, and the fluorescence emission of HACDs achieved spectrally tunable multi-color luminescence in the temporal dimension. The surface of HACDs contained a large number of hydroxyl (–OH) and carboxyl (–COOH) fluorophores, resulting in excellent pH sensing. Meanwhile, the synthesized HACDs revealed sensitive response to MNZ and ONZ with the limit of detection (LOD) of 60 nM and 50 nM in aqueous solutions, which had also been successfully applied in various actual samples such as lake water, honey, eggs, and milk with satisfactory results because of the inner filter effect (IFE). Our research is advantageous to enhance the potential applications of HACDs in advanced analytical systems. [ABSTRACT FROM AUTHOR]

Carbon dots (CDs) have attracted widespread attention because of their excellent properties and various preparation methods. Solvothermal methods have the advantages of simple operations, high product yields, and low costs, which have become the most commonly used methods to synthesize CDs. Understanding the effects of the solvent on the properties of CDs will allow the advantages of CDs to be fully utilized and promote their applications. This review summarizes the effects of reaction solvents on the morphology and properties of CDs, as well as the regulation mechanism of the dispersion solvent on the optical properties of CDs. On this basis, the applications of solvent-engineered CDs in sensing, imaging, optoelectronics and photocatalysis are introduced. Furthermore, we discuss the existing problems and prospects of solvent-engineered CDs. [Display omitted] • Classify the mechanism of solvent-engineered CDs. • Establish the structure-activity relationship between solvent and CDs. • Summarize the applications for sensing, imaging, optoelectronics and photocatalysis. • Discuss the research progress, challenges, and outlook of solvent-engineered CDs. [ABSTRACT FROM AUTHOR]

Carbon dots are zero‐dimensional carbon nanomaterials with quantum confinement effects and edge effects, which have aroused great interests in many disciplines such as energy, chemistry, materials, and environmental applications. They can be prepared by chemical oxidation, electrochemical synthesis, hydrothermal preparation, arc discharge, microwave synthesis, template method, and many other methods. However, the raw materials' high cost, the complexity and environmental‐unfriendly fabrication process limit their large‐scale production and commercialization. Herein, we review the latest developments of coal‐based carbon dots about selecting coal‐derived energy resources (bituminous coal, anthracite, lignite, coal tar, coke, etc.) the developments of synthesis processes, surface modification, and doping of carbon dots. The coal‐based carbon dots exhibit the advantages of unique fluorescence, efficient catalysis, excellent water solubility, low toxicity, inexpensive, good biocompatibility, and other advantages, which hold the potentiality for a wide range of applications such as environmental pollutants sensing, catalyst preparation, chemical analysis, energy storage, and medical imaging technology. This review aims to provide a guidance of finding abundant and cost‐effective precursors, green, simple and sustainable production processes to prepare coal‐based carbon dots, and make further efforts to exploit the application of carbon dots in broader fields. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are a new type of porous crystal materials that have been widely used in various fields. Owing to their adjustable porous structure, MOF photocatalysts with high catalytic activity have become a research hotspot. In this study, NH2-MIL-125/CoSx samples were investigated as a novel visible light-responsive catalyst for the removal of organic dye. The NH2-MIL-125/CoSx-20 composites showed the best photodegradation efficiency, where photodegradation of the rhodamine B reached 95.4% in 45 min. CoSx was able to effectively extend the wavelength absorption range of NH2-MIL-125 and effectively separate the photogenerated electrons and holes and that could lead to the improved photocatalytic performance of the composites. The reactive superoxide radical (·O2−) was identified as the main active species using reactive species capture experiments, and a reasonable photocatalytic mechanism was proposed. This paper is intended to guide the development of organic–inorganic hybrid materials for environmental remediation. [ABSTRACT FROM AUTHOR]

This review focuses on emerging applications of surface-enhanced Raman spectroscopy (SERS) optical nanosensors for miRNA analysis, in which the key enhancement factors of the SERS signal, i.e. SERS-active substrates, SERS nanoprobes and nano-assembly strategy, are emphasized. This article includes many nanomaterials for miRNA analysis by the SERS technique. We summarize these reported nanomaterials mainly according to their function in the miRNA assay biosensor. We also briefly summarize the research progress of these nanomaterials in SERS detection of intracellular miRNA. Finally, we discussed the prospect and limitations of SERS nanosensors for analyzing miRNA. [ABSTRACT FROM AUTHOR]

We report a new signal readout mechanism for DNA molecular sensing devices using ligand-free fluorogenic G-quadruplexes in which the propeller-like loops are distinguished from the diagonal and lateral loops with incorporated 2-aminopurine (2-AP, a fluorescent analogue of adenine). We study the fluorescence behavior of looped-out 2-AP in duplexes and G-quadruplexes and demonstrate that it shows better fluorescence properties in shorter loops. In particular, 2-AP in the propeller-like loops of parallel or hybrid G-quadruplexes displays a perfect fluorescence emission whereas that in the diagonal and lateral loops does not. This loop-environment-sensitive feature allows 2-AP to probe the propeller-like loops of G-quadruplexes, illustrated by an ion-tuned allosteric G-quadruplex FG9A and a (3 + 1) hybrid human telomeric DNA. In the presence of K+, FG9A folds into a parallel structure where 2-AP is in the propeller-like loops and shows a high fluorescence signal, which can probe K+ concentrations down to 25 μM. Upon addition of Pb2+, the folded FG9A converts into an antiparallel structure which is revealed by a sharp decrease in 2-AP fluorescence, which can easily be reset with EDTA. This process is utilized to reversibly sense Pb2+ with a detection limit of 100 nM. Furthermore, its ability to probe the propeller-like loops may allow 2-AP to identify the folding topologies of unknown G-quadruplexes in human gene regions. [ABSTRACT FROM AUTHOR]

Anisotropic noble-metal structures are attracting increasing attention because of interesting size- and shape-dependent properties and have emerging applications in the fields of optics and catalysis. However, it remains a significant challenge to overcome chemical contributions and acquire molecular insight into the relationship between Raman enhancement and photocatalytic activity. This study gives visualized experimental evidence of the anisotropic spatial distribution of Raman signals and photocatalytic activity at the level of single nanometer-thin Au microtriangles and microhexagons. Theoretical simulations indicate an anisotropic spatial distribution and sharpness-dependent strength of the electric-field enhancement. Analysis by using statistical surface-enhanced Raman scattering (SERS) supports this view, that is, Raman enhancement is on the order of corner>edge>face for a single microplate, but SERS measurements at different depths of focus also imply a concentration-dependent feature of SERS signals, especially at the corners and edges. Similarly, the SERS signals of product molecules in plasmonic photocatalysis also exhibit asymmetrical strengths at different corners of the same microplate. However, by examining the variations in the relative intensities of the SERS peaks, the difference in the photocatalytic activities at the corners, edges, and faces has been successfully calculated and is highly consistent with electric-field simulations, thus indicating that an increased number of molecules adsorbed at specific sites does not necessarily lead to a higher conversion ratio in noble-metal photocatalysis. Our strategy weakens the assumed impact of plasmonic local heating and, to a certain extent, excludes the influence of concentration effects and chemical contributions in noble-metal photocatalysis, thus clearly profiling plasmon-related characteristics. This study also promises a new research direction to understand the enhancement mechanism of SERS-active structures. [ABSTRACT FROM AUTHOR]

Surface-enhanced resonance Raman scattering (SERRS) is not realized for most molecules of interest. Here, we developed a new SERRS platform for the fast and sensitive detection of 2,4,6-trinitrotoluene (TNT), a molecule with low Raman cross section. A cationic surfactant, cetylpyridinium chloride (CPC) was modified on the surface of silver sols (CP-capped Ag). CPC not only acts as the surface-seeking species to trap sulfite-sulfonated TNT, but also undergoes complexation with it, resulting in the presence of two charge-transfer bands at 467 and 530 nm, respectively. This chromophore absorbs the visible light that matches with the incident laser and plasmon resonance of Ag sols by the use of a 532.06 nm laser, and offered large resonance Raman enhancement. This SERRS platform evidenced a fast and accurate detection of TNT with a detection limit of 5×10−11 M under a low laser power (200 μW) and a short integration time (3 s). The CP-capped Ag also provides remarkable sensitivity and reliable repeatability. This study provides a facile and reliable method for TNT detection and a viable idea for the SERS detection of various non-resonant molecules. [ABSTRACT FROM AUTHOR]

Difficult, but excellent surface‐enhanced resonance Raman scattering (SERRS) provides a fast and accurate method for the detection of ultra‐small traces of trinitrotoluene (TNT) under low laser power and in a short integration time. In their Full Paper on page 8789 ff., H. L. Liu, L. B. Yang, J. H. Liu et al. describe how cetylpyridinium chloride modified on Ag sols not only acts as the surface‐seeking species to trap sulfite‐sulfonated TNT, but also undergoes complexation with the sulfonated TNT, resulting in the appearance of two charge‐transfer bands at 467 and 530 nm. [ABSTRACT FROM AUTHOR]

Portable chemiluminescence (CL) imaging with a smartphone has shown a great promise for point-of-care testing of diseases, especially for acute myocardial infarction (AMI), which may occur abruptly. A challenge remains how to improve the imaging sensitivity that usually is several orders of magnitude lower than those of counterpart methodologies using the sophisticated equipment. Toward this goal, here, we report the target-triggered in situ growth of AuNP@hairpin-DNA nanoprobes into spherical nucleic acid enzymes (SNAzymes), which serve as both nanolabels and amplifiers for portable CL imaging of microRNAs (miRNAs) with an ultrahigh sensitivity comparable to that of the instrumental measurement under same conditions. A G-quadruplex (G4) DNA dense layer is dynamically produced on the gold nanocore via a DNAzyme machine-driven hairpin cleaving and captures the cofactor hemin to form the SNAzymes with higher peroxidase activity and stronger nuclease resistance than the commonly used G4 DNAzymes. The matured SNAzymes are then utilized as catalytic labels in a luminol-artesunate CL system for miRNA imaging with a smartphone as the portable detector. In this way, two AMI-related miRNAs, miRNA-499 and miRNA-133a, are successfully detected in real patients' serum with a naked eye-visualized CL change at 10 fM, showing a 5 order of magnitude improvement on the sensitivity of visualizing the same disease markers in clinical circulating blood as compared to the reported strategy. In addition, a good selectivity of our developed CL imaging platform is demonstrated. These unique features make it promising to employ this portable imaging platform for clinical AMI diagnosis.

Developing ultrasensitive probes holds great significance for simultaneous detection of multiplexed cancer-associated nucleic acids. Bimetallic nanoparticles containing silver may be exploited as nanoprobes for disease detection, which can produce stable and strong surface-enhanced Raman scattering (SERS) signals. However, it remains extremely challenging that such SERS nanoprobes are directly synthesized. Herein gold-silver nanosnowmen, grown via a DNA-mediated approach and attached to thiol-containing Raman dyes, are successfully synthesized. Stable SERS-enhanced gold substrates are also prepared and used as the enriching containers, where the capture DNAs are tethered to sense the target genes jointly enhanced by the SERS nanoprobes in a sandwich hybridization assay. This means detection of the target gene can obtain a limit of detection close to 0.839 fM. Such double-enhanced SERS nanosensors are further employed to simultaneously detect the three types of prostate carcinoma-related genes with high sensitivity and specificity, which meanwhile exhibit robust capacity of resisting disturbance in practical samples. Simultaneous and multiplexed detection of cancer-related genes may provide further biomedical applications with new opportunity.

The "fixed" or "flexible" design of plasmonic hotspots is a frontier area of research in the field of surface-enhanced Raman scattering (SERS). Most reported SERS hotspots have been shown to exist in zero-dimensional point-like, one-dimensional linear, or two-dimensional planar geometries. Here, we demonstrate a novel three-dimensional (3D) hotspot matrix that can hold hotspots between every two adjacent particles in 3D space, simply achieved by evaporating a droplet of citrate-Ag sols on a fluorosilylated silicon wafer. In situ synchrotron-radiation small-angle X-ray scattering (SR-SAXS), combined with dark-field microscopy and in situ micro-UV, was employed to explore the evolution of the 3D geometry and plasmonic properties of Ag nanoparticles in a single droplet. In such a droplet, there is a distinct 3D geometry with minimal polydispersity of particle size and maximal uniformity of interparticle distance, significantly different from the dry state. According to theoretical simulations, the liquid adhesive force promotes a closely packed assembly of particles, and the interparticle distance is not fixed but can be balanced in a small range by the interplay of the van der Waals attraction and electrostatic repulsion experienced by a particle. The "trapping well" for immobilizing particles in 3D space can result in a large number of hotspots in a 3D geometry. Both theoretical and experimental results demonstrate that the 3D hotspots are predictable and time-ordered in the absence of any sample manipulation. Use of the matrix not only produces giant Raman enhancement at least 2 orders of magnitude larger than that of dried substrates, but also provides the structural basis for trapping molecules. Even a single molecule of resonant dye can generate a large SERS signal. With a portable Raman spectrometer, the detection capability is also greatly improved for various analytes with different natures, including pesticides and drugs. This 3D hotspot matrix overcomes the long-standing limitations of SERS for the ultrasensitive characterization of various substrates and analytes and promises to transform SERS into a practical analytical technique.

Surface-enhanced resonance Raman scattering (SERRS) is not realized for most molecules of interest. Here, we developed a new SERRS platform for the fast and sensitive detection of 2,4,6-trinitrotoluene (TNT), a molecule with low Raman cross section. A cationic surfactant, cetylpyridinium chloride (CPC) was modified on the surface of silver sols (CP-capped Ag). CPC not only acts as the surface-seeking species to trap sulfite-sulfonated TNT, but also undergoes complexation with it, resulting in the presence of two charge-transfer bands at 467 and 530 nm, respectively. This chromophore absorbs the visible light that matches with the incident laser and plasmon resonance of Ag sols by the use of a 532.06 nm laser, and offered large resonance Raman enhancement. This SERRS platform evidenced a fast and accurate detection of TNT with a detection limit of 5×10(-11) M under a low laser power (200 μW) and a short integration time (3 s). The CP-capped Ag also provides remarkable sensitivity and reliable repeatability. This study provides a facile and reliable method for TNT detection and a viable idea for the SERS detection of various non-resonant molecules., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)