Examining Concentration-Reliant Zn Deposition/Stripping Behavior in Organic Alcohol/Sulfones-Modified Aqueous Electrolytes.

The practical application of Zn metal anodes in electronic devices is hindered by dendrite growth and parasitic reactions. Electrolyte optimization, particularly the introduction of organic co-solvents, is widely used to circumvent these challenges. Various organic solvents in a wide range of concentrations have been reported; however, their influences and corresponding working mechanisms at different concentrations are largely unexplored in the same organic species. Herein, economical, low-flammable ethylene glycol (EG) is used as a model co-solvent in aqueous electrolytes to examine the relationship between its concentration, anode-stabilizing effect, and mechanism. Two maximal values are observed for the lifetime of Zn/Zn symmetric batteries under EG concentrations from 0.05 vol% to 48 vol%. Zn metal anodes can stably run for over 1700 h at a low EG content (0.25 vol%) and high EG content (40 vol%). Based on the complementary experimental and theoretical calculations, the enhancements in low- and high-content EG are ascribed to the specific surface adsorption for suppressed dendrite growth and the regulated solvation structure for inhibited side reactions, respectively. Intriguingly, a similar concentration-reliant bimodal phenomenon is observed in other low-flammable organic solvents (e.g., glycerol and dimethyl sulfoxide), thereby suggesting universality of this study and providing insight into electrolyte optimization.

Chlorination-Mediated π-π Stacking Enhances the Photodynamic Properties of a NIR-II Emitting Photosensitizer with Extended Conjugation.

NIR-II-emitting photosensitizers (PSs) have attracted great research interest due to their promising clinical applications in imaging-guided photodynamic therapy (PDT). However, it is still challenging to realize highly efficient PDT on NIR-II PSs. In this work, we develop a chlorination-mediated π-π organizing strategy to improve the PDT of a PS with conjugation-extended A-D-A architecture. The significant dipole moment of the carbon-chlorine bond and the strong intermolecular interactions of chlorine atoms bring on compact π-π stacking in the chlorine-substituted PS, which facilitates energy/charge transfer and promotes the photochemical reactions of PDT. Consequently, the resultant NIR-II emitting PS exhibits a leading PDT performance with a yield of reactive oxygen species higher than that of previously reported long-wavelength PSs. These findings will enlighten the future design of NIR-II emitting PSs with enhanced PDT efficiency.

Direct Atomic-Scale Structure and Electric Field Imaging of Triazine-Based Crystalline Carbon Nitride.

Crystalline carbon nitrides (CNs) have recently attracted considerable attention owing to their superior photocatalytic activity. However, the electron-beam-sensitive nature of crystalline CNs hinders atomic-resolution imaging of their local structures by conventional (scanning) transmission electron microscopy ((S)TEM) techniques. Here, the atomic structure of a triazine-based crystalline CN, poly(triazine imide) (PTI) incorporated with lithium and chloride ions, is unambiguously revealed using the emerging imaging technique of differential phase contrast STEM under a low dose. The lightest-element Li/H configuration is resolved within framework cavities of PTI and significantly affects the electronic structure for photoabsorption. The atomic electric field of PTI crystal directly determined in real space provides a fundamental evidence for the chemical bonding of Li ions and adjacent atoms for the migration of photogenerated carriers. These results facilitate the comprehension on local atomic configuration and chemical bonding state of crystalline CNs and can lead to a deeper understanding of the photocatalytic mechanism.

Sulfate modified g-C3N4 with enhanced photocatalytic activity towards hydrogen evolution: the role of sulfate in photocatalysis.

Sulfate modified graphitic carbon nitride (g-C3N4) was prepared by simple co-pyrolysis of dicyandiamide and ammonium sulfate, and shows seven times higher photocatalytic activity towards hydrogen production than pristine g-C3N4. The origin of its improved photocatalytic activity was comprehensively investigated, and it was found that there are two kinds of sulfate (strongly adsorbed sulfate and a weakly adsorbed one) in the modified sample, both of which play important but slightly different roles in the photocatalysis. Compared to the strongly adsorbed one, the weakly adsorbed sulfate is more beneficial for charge separation and thus promotes more electrons to participate in the photocatalytic reaction. By applying the above synthesis method, most sulfate in our best photocatalyst exists as weakly adsorbed species, which is confirmed by advanced characterization techniques as well as DFT calculations. The increased number of electrons and improved charge separation, which are induced by the weakly adsorbed sulfate, are key to boosting the photocatalytic activity of g-C3N4. Hence, this work provides comprehensive insights into the effect of sulfate on the photocatalytic activity of g-C3N4, which help in the design of more efficient photocatalysts by suitable surface modification.

Controllable local electronic migration induced charge separation and red-shift emission in carbon nitride for enhanced photocatalysis and potential phototherapy.

Electronic migration can be tailored by carefully manipulating the local electron donating and withdrawing nature of carbon nitride for charge separation and red-shift emission. A high yield of H2 (5 mmol h-1 g-1) with an apparent quantum yield of 20.98% at 420 nm and a preliminary study on phototherapy by labeling cell membranes are simultaneously provided.

Intramolecular Charge Transfer and Extended Conjugate Effects in Donor-π-Acceptor-Type Mesoporous Carbon Nitride for Photocatalytic Hydrogen Evolution.

Inspired by donor-acceptor (D-A) polymers in organic solar cell and the extended conjugation effect, a conceptual design of D-π-A-type mesoporous carbon nitride with benzene or thiophene as a π-spacer is proposed as an efficient photocatalyst for hydrogen evolution. The photocatalyst was successfully synthesized by a one-pot thermopolymerization based on nucleophilic substitution and a Schiff-base chemical reaction. On the molecular level, the insertion of an in-plane benzene as a π-spacer by forming covalent bonds C=N (acceptor) and C-N (donor) interrupts the continuity of tri-s-triazine units and maintains the intrinsic π-π conjugated electronic system. Synchronously, the enlarged electron delocalization and the intramolecular charge transfer induced by polarization provide force-directed migration of electrons, leading to boosted optical absorption capability and enhanced photogenerated carrier separation. With the synergistic effects of the mesoporous structure and excellent optical and electronic properties, a fivefold increase in the H2 evolution rate compared with that of pristine g-C3 N4 was achieved with robust performance. In addition, other simple aromatic heterocyclic compounds (e.g., pyridine, thiophene and furan)-based D-π-A structures with a higher hydrogen evolution rate (up to sevenfold increase) were also explored to broaden the application for the design of novel photocatalysts.

Silver nanoclusters with enhanced fluorescence and specific ion recognition capability triggered by alcohol solvents: a highly selective fluorimetric strategy for detecting iodide ions in urine.

Alcohol solvents especially isopropanol were demonstrated for the first time to endow silver nanoclusters (AgNCs) in water with dramatically enhanced red fluorescence. More importantly, the specific iodide recognition capability of the AgNCs could thus be obtained towards a highly selective fluorimetric assay for detecting iodide ions in urine.

Super-hydrophobic Silver-Doped TiO2 @ Polycarbonate Coatings Created on Various Material Substrates with Visible-Light Photocatalysis for Self-Cleaning Contaminant Degradation.

In the present work, a facile and efficient fabrication method has been developed for creating super-hydrophobic coatings of silver-doped TiO2@polycarbonate (TiO2 (Ag)@PC) on the substrates of different materials with photocatalytic self-cleaning performances simply by the "dipping and drying" process. The substrates were first patterned with glue and then deposited with the dopamine-capped TiO2 (Ag)@PC (DA-TiO2 (Ag)@PC) nanocomposites, followed by the further etching with dimethylbenzene. The so prepared super-hydrophobic E-DA-TiO2(Ag)@PC coatings could present the lotus leaf-like porous architectures, high adhesion stability, and especially the visible-light photocatalysis for organic contaminant degradation, thus promising the wide outdoor and indoor applications like water proofing, metal erosion protection, and surface self-cleaning.

Encapsulating chromogenic reaction substrates with porous hydrogel scaffolds onto arrayed capillary tubes toward a visual and high-throughput colorimetric strategy for rapid occult blood tests.

A porous hydrogel scaffold was fabricated for the first time to encapsulate chromogenic reaction substrates onto arrayed capillary tubes, resulting in a visual and high-throughput colorimetric method for rapid occult blood tests (OBTs) based on the hemoglobin (Hgb)-catalyzed chromogenic reactions. Gelatin (Gel), a biodegradable and biocompatible polymer, was introduced to couple with p-hydroxyphenyl-propionic acid (HPA) yielding the Gel-HPA hydrogel scaffold. Chromogenic reaction substrates of 3,3,5,5-tetramethylbenzidine and H2O2 were then encapsulated into the Gel-HPA matrix and further attached onto the amine-derivatized capillary tubes by forming porous chromogenic composites through the HPA-mediated bridging of Gel by the oxidization of H2O2. The developed Hgb catalysis-based OBT platform can facilitate the detection of Hgb with the level down to 0.125 µg mL-1 in human excreta (i.e., saliva, urine, and feces) through capillarity-enabled automatic sampling. This simple, sensitive, selective, and high-throughput colorimetric method may be promising for the bedside OBT for point-of-care monitoring and rapid diagnostics of clinical bleeding diseases.

A high-throughput fluorimetric microarray with enhanced fluorescence and suppressed "coffee-ring" effects for the detection of calcium ions in blood.

A rapid, ultrasensitive, and high-throughput fluorimetric microarray method has been developed using hydrophobic pattern as the microarray substrate and 3-aminopropyltriethoxysilane-coupled carboxylic acid calcium (APS-CCA) as the fluorescent probes for sensing Ca2+ ions in blood. The hydrophobic pattern of the developed Ca2+ analysis microarray could largely suppress the "coffee-ring" effects to facilitate the better distribution density of testing microspots toward the high-throughput detections, and especially prevent the cross-contamination of the multiple samples between adjacent microspots. Moreover, the use of APS matrix could endow the CCA probe the enhanced environmental stability and fluorescence intensity, which is about 2.3-fold higher than that of free CCA. The interactions between APS-CCA and Ca2+ ions were systematically characterized by UV-vis and fluorescence measurements including microscopy imaging. It was demonstrated that the fluorimetric microarray could display the strong capacity of specifically sensing Ca2+ ions with the minimal interferences from blood backgrounds. Such an APS-CCA-based fluorimetric microarray can allow for the analysis of Ca2+ ions down to 0.0050 mM in blood, promising a highly sensitive and selective detection candidate for Ca2+ ions to be applied in the clinical laboratory.

Silver Nanoclusters with Specific Ion Recognition Modulated by Ligand Passivation toward Fluorimetric and Colorimetric Copper Analysis and Biological Imaging.

Silver nanoclusters were synthesized and passivated by glutathione (GSH) ligand, with high aqueous stability and powerful red fluorescence and UV-vis yellow colour. Importantly, the specific recognition of the AgNCs was modulated from Hg(2+) ions to Cu(2+) ions upon the GSH passivation, of which the unique GSH-Cu(2+) chelating reaction could conduct the fluorescence quenching of AgNCs. Strong UV-vis absorbance of GSH-passivated AgNCs could also be realized depending on the Cu(2+) levels. Moreover, the Cu(2+)-induced loss of fluorescence and UV-vis absorbance of GSH-passivated AgNCs could be well restored by using stronger Cu(2+) chelating agent. A simultaneous and reversible fluorimetric and colorimetric sensing method was thereby developed for probing Cu(2+) ions in blood with high sensitivity and selectivity. Subsequently, the fluorescence-trackable imaging for live tissues and cells was demonstrated towards the analysis Cu(2+) ions using GSH-passivated AgNCs as the fluorescent probes. This study indicates that the use of functional ligands like GSH could not only modulate the specific ion recognition of AgNCs, but also endow them the high aqueous stability and powerful red fluorescence towards the wide applications for ion sensing and biological imaging in the complicated media like blood.

ZnO nanocomposites modified by hydrophobic and hydrophilic silanes with dramatically enhanced tunable fluorescence and aqueous ultrastability toward biological imaging applications.

Multicolor ZnO quantum dots (QDs) were synthesized and further modified with hydrophobic hexadecyltrimethoxysilane (HDS) and then hydrophilic aminopropyltriethoxysilane (APS) bilayers, resulting in amine-functionalized ZnO@HDS@APS nanocomposites with tunable fluorescence from blue to green yellow. Systematic investigations verify that the resulting ZnO@HDS@APS could display extremely high stability in aqueous media and unexpectedly, dramatically-enhanced fluorescence intensities, which are about 10-fold higher than those of bare ZnO QDs. The feasibility of the as-prepared ZnO nanocomposites for blood, cell, and tissue imaging was preliminarily demonstrated, promising the wide bio-applications for cell or tissue imaging, proteome analysis, drug delivery, and molecular labeling.

Rapid, selective, and ultrasensitive fluorimetric analysis of mercury and copper levels in blood using bimetallic gold-silver nanoclusters with "silver effect"-enhanced red fluorescence.

Bimetallic alloying gold-silver nanoclusters (Au-AgNCs) have been synthesized by a one-pot biomineralization synthesis route at a vital molar ratio of Au/Ag precursors in the protein matrix. Unexpectedly, the prepared Au-AgNCs could exhibit dramatically enhanced red fluorescence, which is about 6.5-fold and 4.7-fold higher than that of common AuNCs and core-shell Au@AgNCs, respectively. A rapid, selective, and ultrasensitive fluorimetric method has thereby been developed using Au-AgNCs as fluorescent probes toward the separate detections of Hg(2+) and Cu(2+) ions in blood. The interactions of Au-AgNCs with Hg(2+) and Cu(2+) ions were systematically characterized by microscopy imaging, UV-vis, and fluorescence measurements. It is demonstrated that the "silver effect" gives the Au-AgNCs probes not only greatly enhanced red fluorescence but also the strong capacity to specifically sense Cu(2+) ions in addition to improved response to Hg(2+) ions. Moreover, aided by a Cu(2+) chelating agent, exclusive detection of Hg(2+) ions could also be expected with the coexistence of a high level of Cu(2+) ions, as well as reversible Cu(2+) analysis by restoring the fluorescence of Au-AgNCs. Additionally, Au-AgNCs with strong red fluorescence could facilitate fluorimetric analysis with minimal interference from blood backgrounds. Such an Au-AgNCs-based fluorimetric method can allow for the selective analysis of Hg(2+) and Cu(2+) ions down to 0.30 nM and 0.60 nM in blood, respectively, promising a novel detection method to be applied in the clinical laboratory.

Ultrasensitive electroanalysis of low-level free microRNAs in blood by maximum signal amplification of catalytic silver deposition using alkaline phosphatase-incorporated gold nanoclusters.

An ultrasensitive sandwich-type analysis method has been initially developed for probing low-level free microRNAs (miRNAs) in blood by a maximal signal amplification protocol of catalytic silver deposition. Gold nanoclusters (AuNCs) were first synthesized and in-site incorporated into alkaline phosphatase (ALP) to form the ALP-AuNCs. Unexpectedly, the so incorporated AuNCs could dramatically enhance the catalysis activities of ALP-AuNCs versus native ALP. A sandwiched hybridization protocol was then proposed using ALP-AuNCs as the catalytic labels of the DNA detection probes for targeting miRNAs that were magnetically caught from blood samples by DNA capture probes, followed by the catalytic ligation of two DNA probes complementary to the targets. Herein, the ALP-AuNC labels could act as the bicatalysts separately in the ALP-catalyzed substrate dephosphorylation reaction and the AuNCs-accelerated silver deposition reaction. The signal amplification of ALP-AuNCs-catalyzed silver deposition was thereby maximized to be measured by the electrochemical outputs. The developed electroanalysis strategy could allow for the ultrasensitive detection of free miRNAs in blood with the detection limit as low as 21.5 aM, including the accurate identification of single-base mutant levels in miRNAs. Such a sandwich-type analysis method may circumvent the bottlenecks of the current detection techniques in probing short-chain miRNAs. It would be tailored as an ultrasensitive detection candidate for low-level free miRNAs in blood toward the diagnosis of cancer and the warning or monitoring of cancer metastasis in the clinical laboratory.

A phosphorylation-sensitive tyrosine-tailored magnetic particle for electrochemically probing free organophosphates in blood.

A simple, rapid, sensitive, selective, and field-deployable detection protocol has been initially proposed for the early warning and diagnosis of exposure to organophosphates (OPs) by electrochemically monitoring the direct biomarkers of free OPs in blood. Phosphorylation-sensitive tyrosine (Tyr), which was tested with unique electroactivity, was bound onto Fe3O4 particles mediated by the mussel-inspired dopamine to form Fe3O4@Tyr particles with well-defined shape and well-retained Tyr electroactivities, as characterized separately by electron microscopy and electrochemical measurements. A "lab-on-a-particle"-based detection procedure combined with a magnetic electrode was thus developed by employing Fe3O4@Tyr particles as capturing probes for detecting free OPs in blood, dimethyl-dichloro-vinyl phosphate (DDVP) as an example. A significant difference in electrochemical responses could be obtained for Fe3O4@Tyr particles before and after DDVP exposure, based on the phosphorylation-induced inhibition of electroactivities of loaded Tyr. Investigation results indicate that highly specific and sensitive phosphorylation for the inhibition of Tyr electroactivities by sensitive electrochemical outputs could endow the OP detection with high selectivity and sensitivity (i.e., down to about 0.16 nM DDVP in blood). Moreover, strong and stable Tyr-OP bindings especially irreversible electrochemical oxidization of the Tyr probe could facilitate the OP evaluation with high reproducibility and stability over time. In particular, the simple "lab-on-a-particle"-based detection procedure equipped with a portable electrochemical transducer can be tailored for the field-deployable or on-site monitoring of the exposure to various nerve agents and pesticides.

Lab-on-a-drop: biocompatible fluorescent nanoprobes of gold nanoclusters for label-free evaluation of phosphorylation-induced inhibition of acetylcholinesterase activity towards the ultrasensitive detection of pesticide residues.

A simple, sensitive, selective, and "lab-on-a-drop"-based fluorimetric protocol has been proposed using biocompatible fluorescent nanoprobes of gold nanoclusters (AuNCs) for the label-free evaluation of the catalytic activity and phosphorylation of acetylcholinesterase (AChE) under physiologically simulated environments. Protein-stabilized AuNCs were prepared and mixed with acetylthiocholine (ATC) serving as "a drop" of fluorimetric reaction substrate. The AChE-catalyzed hydrolysis of ATC releases thiocholine to cause the aggregation of the AuNCs towards a dramatic decrease in fluorescence intensities, which could be curbed by the phosphorylation-induced inhibition of AChE activity when exposed to organophosphorus compounds (OPs). The reaction procedures and conditions of AChE catalysis and phosphorylation were monitored by fluorimetric measurements and electron microscopy imaging. Moreover, a selective and ultrasensitive fluorimetric assay has been tailored for the detection of pesticide residues using dimethyl-dichloro-vinyl phosphate (DDVP) as an example. Investigation results indicate that the specific catalysis and irreversible OP-induced phosphorylation of AChE, in combination with sensitive fluorimetric outputs could facilitate the detection of total free OPs with high selectivity and sensitivity. A linear concentration of DDVP ranging from 0.032 nM to 20 nM could be obtained with a detection limit of 13.67 pM. Particularly, pesticide residues of DDVP in vegetable samples were quantified down to ~36 pM. Such a label-free "lab-on-a drop"-based fluorimetry may promise wide applications for the evaluation of the physiological catalytic activity of various enzymes (i.e., cholinesterase), and especially for monitoring the direct phosphorylation biomarkers of free OPs towards rapid and early warning, and accurate diagnosis of OP exposure.

High-throughput colorimetric assays for mercury(II) in blood and wastewater based on the mercury-stimulated catalytic activity of small silver nanoparticles in a temperature-switchable gelatin matrix.

A catalysis-based, label-free, and high-throughput colorimetric protocol has been initially proposed for detecting mercury(II) in blood and wastewater with 96-cell plates, based on the mercury-enhanced catalytic activity of small silver nanoparticles synthesized in a gelatin matrix with unique temperature switchable sol-gel transition.

Platinum nanocatalysts loaded on graphene oxide-dispersed carbon nanotubes with greatly enhanced peroxidase-like catalysis and electrocatalysis activities.

A powerful enzymatic mimetic has been fabricated by employing graphene oxide (GO) nanocolloids to disperse conductive carbon supports of hydrophobic carbon nanotubes (CNTs) before and after the loading of Pt nanocatalysts. The resulting GOCNT-Pt nanocomposites could present improved aqueous dispersion stability and Pt spatial distribution. Unexpectedly, they could show greatly enhanced peroxidase-like catalysis and electrocatalysis activities in water, as evidenced in the colorimetric and electrochemical investigations in comparison to some inorganic nanocatalysts commonly used. Moreover, it is found that the new enzyme mimetics could exhibit peroxidase-like catalysis activity comparable to natural enzymes; yet, they might circumvent some of their inherent problems in terms of catalysis efficiency, electron transfer, environmental stability, and cost effectiveness. Also, sandwiched electrochemical immunoassays have been successfully conducted using GOCNT-Pt as enzymatic tags. Such a fabrication avenue of noble metal nanocatalysts loaded on well-dispersed conductive carbon supports should be tailored for the design of different enzyme mimics promising the extensive catalysis applications in environmental, medical, industrial, and particularly aqueous biosensing fields.

Recyclable enzyme mimic of cubic Fe3O4 nanoparticles loaded on graphene oxide-dispersed carbon nanotubes with enhanced peroxidase-like catalysis and electrocatalysis.

Fe3O4 nanoparticles as nanocatalysts may present peroxidase-like catalysis activities and high electrocatalysis if loaded on conductive carbon nanotube (CNT) supports; however, their catalysis performances in an aqueous system might still be challenged by the poor aqueous dispersion of hydrophobic carbon supports and/or low stability of loaded iron catalysts. In this work, amphiphilic graphene oxide nanosheets were employed as "surfactant" to disperse CNTs to create stable graphene oxide-dispersed CNT (GCNT) supports in water for covalently loading cubic Fe3O4 nanoparticles with improved distribution and binding efficiency. Compared with original Fe3O4 nanos and CNT-loaded Fe3O4 nanocomplex, the prepared GCNT-Fe3O4 nanocomposite could achieve higher aqueous stability and, especially, much stronger peroxidase-like catalysis and electrocatalysis to H2O2, presumably resulting from the synergetic effects of two conductive carbon supports and cubic Fe3O4 nanocatalysts effectively loaded. Colorimetric and direct electrochemical detections of H2O2 and glucose using the GCNT-Fe3O4 nanocomposite were conducted with high detection sensitivities, demonstrating the feasibility of practical sensing applications. Such a magnetically recyclable "enzyme mimic" may circumvent some disadvantages of natural protein enzymes and common inorganic catalysts, featuring the multi-functions of high peroxidase-like catalysis, strong electrocatalysis, magnetic separation/recyclability, environmental stability, and direct H2O2 electrochemistry.