Stable and Photothermally Efficient Antibody-Covered Cu3(PO4)2@Polydopamine Nanocomposites for Sensitive and Cost-Effective Immunoassays.

Polydopamine (PDA)-coated or encapsulating Cu3(PO4)2 (Cu3(PO4)2@PDA) nanosheets were synthesized, allowing the C-reaction protein (CRP) antibody to be attached electrostatically for immunosensing of CRP with simple photothermal detection. The antibody-covered Cu3(PO4)2@PDA nanosheets replace the antibody-conjugated enzyme in the enzyme-linked immunosorbant assays. Owing to the high surface area of the 2-D-structured Cu3(PO4)2@PDA nanosheets and the coabsorption of light in the near-IR spectrum by Cu3(PO4)2 and PDA, a small amount of Cu3(PO4)2@PDA confined in the wells of a titer plate generates an easily detectable temperature change after irradiation at 808 nm. The temperature changes, measured by an inexpensive pen-type thermometer, increased linearly with the analyte concentration from 0.42 to 16 pM. We found that the linear relationship can be fitted by the isotherm derived from responses collected from heterogeneous sensors covered with different ligand or antibody densities. The low detection limit (0.11 pM) is largely due to the attachment of a great number of antibodies onto the flat nanosheets. The antibody-covered Cu3(PO4)2@PDA nanosheets are stable and can be used under conditions that are generally unfavorable to enzymatic activities. The excellent agreement between our results and immunoturbidimetric assays of CRP in serum samples from patients and healthy donors demonstrates its utility for disease diagnosis in clinical settings. This cost-effective, biocompatible, and convenient photothermal immunosensor affords a range of possibilities for detecting diverse protein biomarkers.

Ratiometric fluorescent immunoassay for the cardiac troponin-I using carbon dots and palladium-iridium nanocubes with peroxidase-mimicking activity.

A nanozyme-linked immunosorbent assay is described for cardiac troponin I which is a biomarker for myocardial infarction. The method is based on the use of Pd-Ir nanocubes with excellent peroxidase-like activity. The nanocubes catalyze the oxidization of nonfluorescent o-phenylenediamine (OPD) by H2O2 to form a yellow fluorescent product (oxOPD) with excitation/emission maxima at 400/570 nm. Carbon dots are added as a reference fluorophore. Under the same excitation wavelength, they display blue fluorescence (450 nm). The ELISA uses the Pd-Ir nanocubes as a label for the secondary antibody and OPD as substrate. The ratio of fluorescence intensities at 570 and 450 nm increases in the 1 pg·mL-1 to 1 ng·mL-1 cardiac troponin I concentration range, and the detection limit is 0.31 pg·mL-1. The method was applied to analyze spiked serum samples, and the results compared well with those obtained by a commercial chemiluminescence assay. Graphical abstract Schematic presentation of the ratiometric fluorescence immunoassay for cardiac troponin-I. Pd-Ir nanocubes were employed to fabricate nanozyme-based signal labels for its excellent peroxidase-mimicking activity.

Catalyst-free synthesis of 3-sulfone nitrile from sulfonyl hydrazides and acrylonitrile in water.

A novel catalyst-free sulfonation reaction for synthesizing 3-sulfone nitrile compounds from sulfonyl hydrazides and acrylonitriles in water, without any metal catalyst, ligand or organic solvent, was demonstrated. This catalyst-free protocol provides a new synthetic method for the construction of 3-sulfone nitrile compounds with excellent yields. The D2O experiment adequately proved that the catalyst-free sulfonation reaction occurs via a Michael addition mechanism and that the hydrogen of 3-sulfone nitrile comes from water.

Near-infrared light-induced homogeneous photoelectrochemical biosensor based on 3D walking nanomotor-assisted CRISPR/Cas12a for ultrasensitive microRNA-155 detection.

The dysregulation of microRNA (miRNA) expression levels is intricately linked to a myriad of human diseases, and the precise and delicate detection thereof holds paramount significance in the realm of clinical diagnosis and therapy. Herein, a near-infrared (NIR) light-mediated homogeneous photoelectrochemical (PEC) biosensor was constructed for miRNA-155 detection based on NaYF4: Yb, Tm@ZnIn2S4 (NYF@ ZIS) coupled with a three-dimensional (3D) walking nanomotor-assisted CRISPR/Cas12a strategy. The upconverted light emitted by the NYF in the visible and UV region upon NIR light excitation could be utilized to excite ZIS to produce a photocurrent response. The presence of target miRNA-155 initiated an amplification reaction within the 3D walking nanomotor, resulting in the production of multiple nucleic acid fragments. These fragments could activate the collateral cleavage capability of CRISPR/Cas12a, leading to the indiscriminate cleavage of single-stranded DNA (ssDNA) on ALP-ssDNA-modified magnetic beads and the subsequent liberation of alkaline phosphatase (ALP). The released ALP facilitated the catalysis of ascorbic acid 2-phosphate to generate ascorbic acid as the electron donor to capture the photogenerated holes on the NYF@ZIS surface, resulting in a positively correlated alteration in the photocurrent response. Under optimal conditions, the NIR light-initiated homogeneous PEC biosensor had the merits of good linear range (0.1 fM to 100 pM), an acceptable limit of detection (65.77 aM) for miRNA-155 detection. Considering the pronounced sensitivity, light stability, and low photodamage, this strategy presents a promising platform for detecting various other miRNA biomarkers in molecular diagnostic practice.

Regio- and Stereoselective Syn-Boronation of Terminal Alkynes Catalyzed by Copper Nanospheres on Graphene Nanosheets.

Evenly distributed copper nanospheres on reduced graphene oxide were prepared and showed high heterogeneous catalytic activity in converting varying terminal alkynes into (E)-ß-styrene boronate esters. The excellent catalytic performance was achieved through the synergistic catalysis between Cu nanospheres and rGO. This work not only is a supplement for preparing (E)-ß-styrene boronate esters but also provides a way for the rational designing of high-performance graphene-based catalysts. Meanwhile, the advancement of graphene-based nanomaterials will be motivated to promote their applications in the development of green catalytic chemistry.

Fabrication of a fluorescent probe for in-situ and ratiometric visualization of autophagy.

In situ and real-time visualization of autophagy process is of vital importance for fundamental researches in biology. However, fluorescent probes for autophagy were rarely reported, which greatly hindered the study on autophagy. In this work, a fluorescent probe was rationally designed and fabricated for the ratiometric visualization of autophagy. The probe targeted non-lysosome organelles in healthy cells, and gave blue emission. During autophagy, the organelles together with the probe were delivered into acid lysosomes, and gave red fluorescence. In this way, the autophagy process could be monitored in ratiometric manner. The starvation induced autophagy was successfully visualized by means of the probe, and the inhibition effect of chloroquine to autophagy was also observed. We expect that the probe can serve as a powerful tool for the investigation of autophagy and relative areas.

Self-supporting hierarchical PdCu aerogels for enhanced catalytic reduction of 4-nitrophenol.

This work reports a new kind of self-assembled PdCu monolithic aerogels via a mild reduction process, which exhibits highly efficient catalytic reduction activity towards 4-nitrophenol. The enhanced catalytic reduction performance can be contributed the following unique features of PdCu aerogels: 1) the interconnected channels and three-dimensional network provide a platform for accelerating mass transfer during catalysis; 2) metallic aerogels combined with stretching ultrathin nanowires has a large surface area and good crystallinity affording sufficient reactive sites and high atom utilization; 3) the introduction of nonprecious Cu not only drastically cuts down the cost but also attains the excellent catalytic activity due to the bimetallic intrinsic synergetic effect; 4) the self-supporting feature is good for improving the durability of the catalyst. This study pushes a new avenue to develop robust catalysts for heterogeneous catalytic reactions.

A radical capture mechanism for immediate Csp2-H bond hydroxylation via a heterogeneous Cu-graphene catalyst.

A radical capture mechanism via a synergistic heterogeneous Cu2O-rGO catalyst for Csp2-H bond immediate hydroxylation has been developed. This protocol suggests the involvement of a C-centered radical (˙C), generated through an O-centered radical (˙OH) initiated hydrogen atom transfer (HAT) process.

A novel route with a Cu(ii)-MOF-derived structure to synthesize Cu/Cu2O NPs@graphene: the electron transfer leads to the synergistic effect of the Cu(0)-Cu(i) phase for an effective catalysis of the Sonogashira cross-coupling reactions.

A uniformly dispersed two-phase Cu/Cu2O NPs@graphene was obtained via an innovative "take" and "off" synthesis strategy with a Cu-MOF-derived jacket structure. The electron transfer between the Cu phase and Cu2O phase leads to the synergistic effect of the Cu(0)-Cu(i) phase for an efficient catalysis of the Sonogashira cross-coupling reactions.

A naphthalene benzimidazole-based chemosensor for the colorimetric and on-off fluorescent detection of fluoride ion.

A novel naphthalene benzimidazole (NBI)-based chemosensor (D2) was developed for fluoride ion (F-) detection. The absorption spectrum of D2 changed dramatically from yellow to blue in the visible region accompanied with a 225nm red shift of its absorption maximum upon the addition of F- in DMSO. D2 also exhibited a fluorescence turn-off response towards the fluoride ion. The emission intensity of D2 decreased drastically along the increasing F- concentration and the detection limit for F- was as low as 3.2×10-9mol/L. 1H NMR and HRMS-ESI results indicated that the formation of NBI-O- through the desilylation reaction of F- with NBI-OSi was responsible for the spectral changes. Overall, this kind of NBI-type molecules represent a new type chemosensor for the spectral detection of fluoride ion in solution.

[Fluorescence property of OBBE and its application].

The effects of acidity and temperature on the fluorescent characteristics of N-N-bis-(O-Carboxylphenyl)-Oxamide (OBBE) have been studied in details. And the quantum efficiency of fluorescence has been measured. In a pH 8-9.5 buffer medium of H3BO3-NaOH, OBBE has a maximum excitation wavelength at 210 nm and a maximum emission wavelength at 395 nm. The nitrate reacts with OBBE and quenches the fluorescent intensity of OBBE. Thus a new sensitive method using the quenching of synchronous fluorimetry has been developed for the direct determination of nitrate in water. The linear calibration curve was obtained in the range of 0.0028 and 0.16 mg.L-1, the detection limit was 0.0028 mg.L-1. The proposed method has been applied to the determination of nitrate in water with satisfactory results.