Constructing an Ultra-Rapid Nanoconfinement-Enhanced Fluorescence Clinical Detection Platform by Using Machine Learning and Tunable DNA Xerogel "Probe".

Low mass transfer efficiency and unavoidable matrix effects seriously limit the development of rapid and accurate determination of biosensing systems. Herein, we have successfully constructed an ultra-rapid nanoconfinement-enhanced fluorescence clinical detection platform based on machine learning (ML) and DNA xerogel "probe", which was performed by detecting neutrophil gelatinase-associated lipocalin (NGAL, protein biomarker of acute kidney injury). By regulating pore sizes of the xerogels, the transfer of NGAL in xerogels can approximate that in homogeneous solution. Due to electrostatic attraction of the pore entrances, NGAL rapidly enriches on the surface and inside the xerogels. The reaction rate of NGAL and aptamer cross-linked in xerogels is also accelerated because of the nanoconfinement effect-induced increasing reactant concentration and the enhanced affinity constant KD between reactants, which can be promoted by ∼667-fold than that in bulk solution, thus achieving ultra-rapid detection (ca. 5 min) of human urine. The platform could realize one-step detection without sample pretreatments due to the antiligand exchange effect on the surface of N-doped carbon quantum dots (N-CQDs) in xerogels, in which ligand exchange between -COOH and underlying interfering ions in urine will be inhibited due to higher adsorption energy of -COOH on the N-CQD surface relative to the interfering ions. Based on the ML-extended program, the real-time analysis of the urine fluorescence spectra can be completed within 2 s. Interestingly, by changing DNA, aptamer sequences, or xerogel fluorescence intensities, the detection platform can be customized for targeted diseases.

Instantly Detecting Catalysts' Hot Spots Temperature In Situ during Photocatalysis by Operando Raman Spectroscopy.

Precisely detecting the catalysts' hot spots temperature in situ instantly during photocatalysis is a great challenge but extremely important for chemical reactions. However, no efficient method has been developed to instantly detect the hot spots temperature in situ during photocatalysis. Herein, we designed a simple and convenient method to measure the instant hot spots temperature in situ on the nanostructure surface during photocatalysis by operando Raman spectroscopy using 4-methoxyphenyl isocyanide (MI) as the probe molecule. The νN≡C frequency of MI varied linearly with temperature, which is caused by the orientation change of the MI induced by temperature, leading to the change in the frequency of the νN≡C bond that directly interacts with the nanostructure surface. Using in situ surface-enhanced Raman spectroscopy (SERS), the surface temperature of the catalysts illuminating for each time can be measured instantly. Interestingly, the catalytic activity of the hydrogen evolution reaction (HER) for the Au-Ag/Ag2S heterojunction nanorods (HJNRs) are higher than that for the Ag-Au-Ag HJNRs, although they have a lower surface temperature during photocatalysis; therefore, hot carriers and electronic structure contributed more to the catalytic activity of the Au-Ag/Ag2S HJNRs than that of the Ag-Au-Ag HJNRs. Such an instant hot spots temperature detecting method of catalysts can greatly facilitate the analysis of the mechanism of catalytic processes.

Controlling alloy to core-shell structure transformation of Au-Pd icosahedral nanoparticles.

The structure transformation between Au-Pd alloy and core-shell icosahedral nanoparticles was achieved by a one-step aqueous-phase strategy. This strategy provided a way to tune the structure and atomic distribution of Au-Pd icosahedral nanoparticles. It could modulate the electronic structure of Pd, achieving promoted electrocatalytic ability toward the hydrogen evolution reaction.

Segmented Ag-Au-Ag Heterojunction Nanorods: Pressure-Assisted Aqueous-Phase Synthesis and Engineered Femtosecond-to-Nanosecond Dynamics.

Segmented metal-metal heterostructure nanorods/nanowires are very promising for development in photoelectric devices, wearable electronics, biomedicine, and energy storage due to unique surface and interface and adjustable electronic and optical properties. Regretfully, most of the segmented heterojunctions are presently synthesized in organic solvent, and its electronic dynamics is still rarely studied and poorly understood. Here, we reported a pressure-assisted one-step aqueous-phase strategy to successfully synthesize segmented Ag-Au-Ag heterojunction nanorods (HJNRs), the aspect ratios and heterojunction contents of which can be well controlled by varying pressure value. The heterojunction-induced femtosecond-to-nanosecond dynamics in 1D direction of the Ag-Au-Ag HJNRs were for the first time acquired and presented a unique regularity tendency (e.g., electron-phonon scattering time). The unprecedented aqueous-phase strategy opens up horizons of synthesis of other segmented metal-metal HJNRs, and the fascinating Ag-Au-Ag HJNRs are hopeful for the development of a new class devices in photothermal and photoelectronic fields.

Controlling Shape and Plasmon Resonance of Pt-Etched Au@Ag Nanorods.

Pt-based catalysts with novel structure have attracted great attention due to their outstanding performance. In this work, H2PtCl6 was used as both precursor and etching agent to realize the shape-controlled synthesis of Pt-modified Au@Ag nanorods (NRs). During the synthesis, the as-prepared Ag shell played a crucial role in both protecting the Au NRs from being etched away by PtCl62- and leading to an unusual growth mode of Pt component. The site-specified etching and/or growth depended on the concentration of H2PtCl6, where high-yield core-shell structure or dumbbell-like structure could be obtained. The shape-controlled synthesis also led to a tunable longitudinal surface plasmon resonance from ca. 649 to 900 nm. Meanwhile, the core-shell Pt-modified Au@Ag NRs showed approximately 4-fold enhancement in catalytic reduction reaction of p-nitrophenol than that of the Au NRs, suggesting the great potential for photocatalytic reaction.