Development of surface-enhanced Raman scattering-sensing Method by combining novel Ag@Au core/shell nanoparticle-based SERS probe with hybridization chain reaction for high-sensitive detection of hepatitis C virus nucleic acid.

The ultrasensitive detection of hepatitis C virus (HCV) nucleic acid is crucial for the early diagnosis of hepatitis C. In this study, by combining Ag@Au core/shell nanoparticle (Ag@AuNP)-based surface-enhanced Raman scattering (SERS) tag with hybridization chain reaction (HCR), a novel SERS-sensing method was developed for the ultrasensitive detection of HCV nucleic acid. This SERS-sensing system comprised two different SERS tags, which were constructed by modifying Ag@AuNP with a Raman reporter molecule of 4-ethynylbezaldehyde, two different hairpin-structured HCR sequences (H1 or H2), and a detection plate prepared by immobilizing a capture DNA sequence onto the Ag@AuNP layer surface of the detection wells. When the target nucleic acid was present, the two SERS tags were captured on the surface of the Ag@AuNP-coated detection well to generate many "hot spots" through HCR, forming a strong SERS signal and realizing the ultrasensitive detection of the target HCV nucleic acid. The limit of detection of the SERS-sensing method for HCV nucleic acid was 0.47 fM, and the linear range was from 1 to 105 fM.

Ag@AuNP-Functionalized Capillary-Based SERS Sensing Platform for Interference-Free Detection of Glucose in Urine Using SERS Tags with Built-In Nitrile Signal.

A Ag@AuNP-functionalized capillary-based surface-enhanced Raman scattering (SERS) sensing platform for the interference-free detection of glucose using SERS tags with a built-in nitrile signal has been proposed in this work. Capillary-based SERS capture substrates were prepared by connecting 4-mercaptophenylboronic acid (MBA) to the surface of the Ag@AuNP layer anchored on the inner wall of the capillaries. The SERS tags with a built-in interference-free signal could then be fixed onto the Ag@AuNP layer of the capillary-based capture substrate based on the distinguished feature of glucose, which can form a bidentate glucose-boronic complex. Thus, many "hot spots" were formed, which produced an improved SERS signal. The quantitative analysis of glucose levels was realized using the interference-free SERS intensity of nitrile at 2222 cm-1, with a detection limit of about 0.059 mM. Additionally, the capillary-based disposable SERS sensing platform was successfully employed to detect glucose in artificial urine, and the new strategy has great potential to be further applied in the diagnosis and control of diabetes.

Atomic-Level and Modulated Interfaces of Photocatalyst Heterostructure Constructed by External Defect-Induced Strategy: A Critical Review.

Despite the existence of numerous photocatalyst heterostructures, their separation efficiency and charge flow precision remain low due to the poor study on interfacial properties. The photocatalysts with confined defects can effectively control the photogenerated carrier migration, but the metastability of such defects considerably decreases the photocatalyst stability. Meanwhile, the introduction of defective region can increase the coordinative unsaturation and delocalize local electrons to promote their interactions with the molecules/ions in that region. The selective growth of modulated heterogeneous interface by defect-induced strategy may not only increase the stability of defective structures, but also enhance the migration of interfacial charges. Using this method, photocatalytic heterostructures with low contact resistances and intimate interfaces are constructed to achieve the optimal charge migration in terms of efficiency and accuracy. In this work, the point, linear, and planar heterogeneous interfaces and related defect engineering techniques are discussed. Particularly, it is focused on the external, defect-induced interfacial heterogeneities with various spatial and dimensional configurations, which exhibit modulated and controllable interfacial properties. Furthermore, the main aspects of fabricating photocatalyst heterostructures by the defect-induced strategy, including the i) controllable generation of defects, ii) advanced characterization methods, and iii) elaborate construction of the minimal interface, are described.

Target MicroRNA-Responsive DNA Hydrogel-Based Surface-Enhanced Raman Scattering Sensor Arrays for MicroRNA-Marked Cancer Screening.

On the basis of a target microRNA (miRNA)-responsive DNA hydrogel, a novel surface-enhanced Raman scattering (SERS) sensor array with nine sensor units that can detect multiple cancer-related miRNAs in one sample was developed. The target miRNA-responsive DNA hydrogel was first formed in each sensor unit to realize the construction of the DNA hydrogel-based SERS sensor array. Initially, because of the blocking of the streptavidin (SA)-modified sensor units by the formed DNA hydrogel, the SERS tags (biotin/4-mercaptobenzonitrile-functionalized AuAg alloy nanoparticles (B/M-AuAgNPs)) could not pass through the hydrogel and bind to the SA-modified sensor surface; thus, obvious Raman signals could not be observed. After the introduction of the target miRNA, DNA hydrogels of the corresponding sensor unit were disintegrated accordingly, and SERS tags were able to pass through the hydrogel to be captured onto the SA-modified detection surface, thus resulting in strong Raman signals and the detection of target miRNA. The assay is validated under clean buffer conditions as well as in serum. This target miRNA-responsive DNA hydrogel-based SERS sensor array has attractive application prospects in cancer typing via blood miRNA measurements.

Alkyne/Ruthenium(II) Complex-Based Ratiometric Surface-Enhanced Raman Scattering Nanoprobe for In Vitro and Ex Vivo Tracking of Carbon Monoxide.

Here, we report a surface-enhanced Raman scattering (SERS) nanosensor for real-time ratiometric detection of carbon monoxide (CO) based on a ligand displacement mechanism. This nanoprobe consists of a gold-silver (Au-Ag) alloy nanoparticle core as the highly active SERS substrate, an alkyne/ruthenium(II) (alkyne/Ru(II)) complex immobilized on the surface as the CO-sensing element, and a porous silica shell to improve the stability and biocompatibility of the particle. Displacement of the alkyne ligand by CO results in a decrease of the alkyne vibrations and an increase of the metal carbonyl complex signals, thus allowing the effective ratiometric detection of CO in real-time. The great potential of this assay for CO detection is validated in clean buffer environments, live cells, and tissue slices.

Nanoconjugates of Ag/Au/Carbon Nanotube for Alkyne-Meditated Ratiometric SERS Imaging of Hypoxia in Hepatic Ischemia.

We report a ratiometric surface-enhanced Raman scattering (SERS) nanoprobe for imaging hypoxic living cells or tissues, using azo-alkynes assembled on a single-walled carbon nanotube (SWCNT) surface-functionalized with Ag/Au alloy nanoparticles (SWCNT/Ag/AuNPs). Under a hypoxic condition, azobenzene derivatives preassembled on the surface of the nanostructures are reduced stepwise by various reductases and eventually removed from the surface of the SWCNT/Ag/AuNPs, resulting in the loss of characteristic alkyne Raman bands at 2207 cm-1. Using 2D-band of SWCNTs at 2578 cm-1 as the internal standard, we are able to determine the hypoxia level based on the ratio of two peak intensities ( I2578/ I2207) as demonstrated by the successful detection in different cell lines and rat liver tissue samples derived from hepatic ischemia surgery. By combining the outstanding anti-interference property of alkynes as SERS reporters and the distinct Raman responses of alkynes and SWCNTs in complex systems, this novel ratiometric SERS strategy holds promise in becoming a very useful tool for in vitro and in vivo monitoring of hypoxia in research and clinical settings.

Alkyne-DNA-Functionalized Alloyed Au/Ag Nanospheres for Ratiometric Surface-Enhanced Raman Scattering Imaging Assay of Endonuclease Activity in Live Cells.

A novel ratiometric surface-enhanced Raman scattering (SERS) nanosensor has been developed to probe the activity of endonuclease under in vitro and in living cells conditions. The optimized alloyed Au/Ag nanoparticles (NPs) were synthesized as the SERS substrate, which combined the superior properties of both pure Au and pure Ag nanoparticles: they exhibit excellent plasmonic property with high chemical stability and low cytotoxicity. They were then employed for quantitative detection of endonuclease through functionalization with single-stranded DNA (ssDNA) carrying 3-[4-(phenylethynyl)benzylthio]propanoic acid (PEB) as endonuclease-responsive SERS signaling molecule and 4-thiophenylacetylene (TPA) as the internal standard SERS signaling molecule. In the presence of endonuclease, the ssDNA was cleaved, releasing PEB molecules from the particle surface and decreasing the SERS signal at 2215 cm-1 from PEB. Since the SERS signal at 1983 cm-1 from alkynyl TPA remained the same, quantitative detection of endonuclease was achieved, based on the ratiometric peak intensity of I1983/ I2215, with a detection limit as low as 0.056 unit/mL. A highly biocompatible and antijamming ratiometric SERS sensor was established by combining the alloyed Au/AgNPs with two unique alkynes molecules with Raman signals in the cellular silent region. The ratiometric sensor was successfully employed to detect intracellular endonuclease activity as well as endonuclease in living cells for the first time.

[Characteristics of molecular genetics and research progress on mitochondrial diseases].

Mitochondrial diseases is a group of metabolic disorders caused by abnormal structure and dysfunction of mitochondrial DNA (mtDNA). Abnormalities of mtDNA include point mutations, deletions, and rearrangements and depletion of mtDNA. These may affect the ability of mitochondria to generate energy in cells of various tissues and organs. As many factors are involved in the regulation of mtDNA mutations, most mitochondrial diseases may manifest great genetic heterogeneity and a wide spectrum of clinical manifestations. On the other hand, for the low prevalence of single disease, these disorders may be easily missed or with delayed diagnosis. This review focuses on the pathological mutations and benign variations of mtDNA, and research progress on such disorders.

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.

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.

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.

Combined fabrication of zeolitic imidazolate framework-8 and lanthanide towards coordination polymers: A dual-signal fluorescent probe for sensing Cu2+ based on synergistic effect of aggregation-induced emission and antenna effect.

Copper ion (Cu2+) detection remains an important task for monitoring water quality because of its specific toxicity. Herein, a new dual-signal fluorescent probe was developed by combining zeolitic imidazolate framework-8 (ZIF-8) and lanthanide for the detection of Cu2+ for the first time. The lanthanide coordination polymer (guanosine monophosphate and Eu3+, GMP/Eu) was initially incorporated into ZIF-8 to yield ZIF-8/GMP/Eu nanomaterials with extremely weak single emission fluorescence at 618 nm. It was found that the resulted nanomaterials could display a dual emission fluorescence at 515 nm and 618 nm after the introduction of tetracycline (TC) due to the synergistic effect of aggregation-induced emission effect (AIE, TC induced by ZIF-8) and antenna effect (AE, between TC and GMP/Eu). Interestingly, in the presence of Cu2+, the AIE of TC was destroyed because of the interaction of Cu2+ with ZIF-8 and TC. The AE between TC and GMP/Eu disappeared due to the formation of complex between TC and Cu2+. A dual-signal fluorescent probe of ZIF-8/GMP/Eu/TC was thereby established for sensing Cu2+ in the range of 0.5-100 µM. Such a dual-signal response strategy that intelligently utilized the "ON"/"OFF" of AIE and AE can not only eliminate the background interference, but also ensure the improved selectivity of Cu2+ sensing. Subsequently, the dual-signal fluorimetric strategy was applied for the detection of Cu2+ in environmental water samples, indicating the potential feasibility of applications for water quality monitoring.

Rational design of a functionalized metal-organic framework for ratiometric fluorimetric sensing of Hg2+ in environmental water.

A target-responsive ratiometric fluorimetric sensing strategy for Hg2+ has been rationally designed. The sensing probe was established based on a functionalized metal-organic framework, which was prepared with 3,5-dicarboxyphenylboronic acid (DCPB) as the functional ligand and Eu3+ as the metal junction. The porous nano-spheres of Eu-MOF with an arylboronic acid as the functional recognition group for Hg2+ exhibited tunable optical properties with dual emission fluorescence signals at 338 nm and 615 nm. In the presence of Hg2+, arylmercury was formed by a specific transmetalation reaction between Hg2+ and arylboronic acid groups, which blocks the energy transfer between the ligand and Eu3+. Thereby, the fluorescence signal of Eu-MOF/BA at 615 nm decreased, while the fluorescence signal at 338 nm remained almost constant. The ratiometric fluorimetric sensing for Hg2+ was achieved by calculating the peak intensity ratio of F615/F338 based on the reference signal at 338 nm and the response signal at 615 nm. The detection limit of Hg2+ was as low as 0.0890 nM, and the recovery rate of the actual environmental water sample ranged from 90.92% to 118.50%. Therefore, the excellent performance of the ratiometric fluorimetric sensing method for Hg2+ makes it attractive for the detection of heavy metal ions in environmental monitoring.

A microdots array-based fluoremetric assay with superwettability profile for simultaneous and separate analysis of iron and copper in red wine.

A microdots array-based fluoremetric method with superwettability profile has been developed for the simultaneous and separate detection of Fe3+ and Cu2+ ions in red wine samples. A wettable micropores array was initially designed with high density by using polyacrylic acid (PAA) and hexadecyltrimethoxysilane (HDS), followed by the NaOH etching route. Zinc metal organic frameworks (Zn-MOFs) were fabricated as the fluorescent probes to be immobilized into the micropores array to obtain the fluoremetric microdots array platform. It was found that the fluorescence of Zn-MOFs probes could decrease significantly in the presence of Fe3+ and/or Cu2+ ions towards their simultaneous analysis. Yet, the specific responses to Fe3+ ions could be expected if using histidine to chelate Cu2+ ions. Moreover, the developed Zn-MOFs-based microdots array with superwettability profile can enable the accumulation of targeting ions from the complicated samples without any tedious pre-processing. Also, the cross-contamination of different samples droplets can be largely avoided so as to facilitate the analysis of multiple samples. Subsequently, the feasibility of simultaneous and separate detection of Fe3+ and Cu2+ ions in red wine samples was demonstrated. Such a design of microdots array-based detection platform may promise the wide applications in analyzing Fe3+ and/or Cu2+ ions in the fields of food safety, environmental monitoring, and medical diseases diagnostics.

Zeolitic imidazolate framework-8 for ratiometric fluorescence sensing tetracyclines in environmental water based on AIE effects.

A ratiometric fluorimetric sensing strategy with Zeolitic imidazolate framework-8 (ZIF-8) has been developed for the analysis of tetracycline (TC) in environmental water samples. ZIF-8 with polyhedral structure was synthesized at room temperature exhibiting blue fluorescence at 445 nm. Especially, the as-prepared ZIF-8 could conduct the aggregation-induced emission (AIE) effect in the presence of TC through electrostatic, hydrogen bond, π-π stacking, and coordination interactions. As a result, a strong yellow-green fluorescence appeared and a new fluorescence peak at 505 nm was observed, although the initial fluorescence peak at 445 nm of ZIF-8 was almost unchanged. A ZIF-8-based fluorimetric platform was thereby designed for sensing TC by using ZIF-8 as the fluorescent probe with the peak at 445 nm as the reference and the one at 505 nm as the changing signal, which should increase with the increasing concentrations of TC. Moreover, the quantitative analysis of TC could be carried out through the ratiometric peak intensities of F505/F445, with a detection limit as low as 14.7 nM. Additionally, the ratiometric fluorescent analysis method was successfully employed to detect TC in environmental water samples, indicating that ZIF-8 might be a good luminescent sensor for probing the pollutants in the environmental water.

High-throughput lateral and basal interface in CeO2@Ti3C2TX: Reverse and synergistic migration of carrier for enhanced photocatalytic CO2 reduction.

Rational construction of heterogeneous interfaces that maximize carrier flux and allow carrier separation for achieving efficient photocatalytic CO2 reduction still remain a challenge. In this work, high-throughput and intimate interfaces that allow efficient carrier separation and flux are designed by depositing high-density CeO2 nanoparticles on large-area Ti3C2TX (T = terminal group) nanosheets. Oxygen-containing functional groups of Ti3C2TX nanosheets facilitate the anchoring of CeO2 nanoparticles on the nanosheets via the formation of interfacial Ce-O-Ti bonds, which serve as effective channels for reverse and synergistic migration of electrons and holes to achieve spatial separation. The light absorption of the CeO2@Ti3C2TX composites is extended to the infrared (IR) region due to narrow bandgaps of Ti3C2TX. High-density lateral and basal interfaces enhance carrier migration, which ultimately aids the CeO2@Ti3C2TX composites to exhibit excellent activity for reducing CO2 to alcohols (i.e., methanol and ethanol) under both visible (vis) and IR irradiations. The total amount of produced alcohol under visible irradiation is 109.9 µmol•gcatal-1 (methanol and ethanol: 76.2 and 33.7 µmol•gcatal-1, respectively), which is 4.3 times higher than that obtained using CeO2 (methanol and ethanol: 19.8 and 6 µmol•gcatal-1, respectively). The yields of methanol and ethanol using the optimized CeO2@Ti3C2TX were 102.24 and 59.21 µmol•gcatal-1, respectively, after 4 h under the vis-IR irradiation.

Covalent organic framework-loaded silver nanoparticles as robust mimetic oxidase for highly sensitive and selective colorimetric detection of mercury in blood.

Covalent organic frameworks (COFs) were fabricated with a hierarchical flower-like hollow structure, possessing a large specific surface area, high porosity, and excellent environmental stability. In situ growth of noble silver nanoparticles (AgNPs) onto COFs was conducted yielding COF-Ag nanozymes. The structural advantages of COFs can ensure the uniform dispersion and effective size control of AgNPs. More interestingly, the oxidase-like catalytic activity of the obtained COF-Ag nanozymes could be enhanced in the presence of Hg2+ ions, which could specifically interact with AgNPs to form Ag-Hg alloys. A COF-Ag catalysis-based colorimetric platform was thereby constructed for highly selective and sensitive analysis of Hg2+ ions, showing a linear concentration range from 0.050 to 10.0 µM, with a limit of detection of about 3.7 nM. Besides, the developed colorimetric strategy was successfully applied for detecting Hg2+ ions in human blood with favorable detection recoveries, indicating its potential for applications in the biomedical analysis, environmental monitoring, and food safety fields.

Hierarchical Ag3PO4@ZnIn2S4 nanoscoparium: An innovative Z-scheme photocatalyst for highly efficient and predictable tetracycline degradation.

Z-scheme photocatalyst preserved with superior oxidicability is an innovative photocatalyst system that can be used for efficient photocatalytic detoxification of antibiotics. In this study, Z-scheme Ag3PO4@ZnIn2S4 photocatalyst was constructed by decorating Ag3PO4 nanoparticles on ZnIn2S4 nanoscopariums. ZnIn2S4 nanoscopariums were prepared by self-templated strategy and given hierarchical structures. The hierarchical Ag3PO4@ZnIn2S4 provides more active sites for generating photogenerated carriers and large surface area for capturing tetracycline. The study results show that Ag3PO4@ZnIn2S4 performed excellently well in the photocatalytic degradation of tetracycline and also in protecting Ag3PO4 nanoparticles from photo-corrosion. The highest removal efficiency (up to 92.3%) was achieved from the optimal composites of Ag3PO4 and ZnIn2S4. In stability tests, Ag3PO4@ZnIn2S4 did not reduce the photocatalytic activity of degrading tetracycline after five successive runs. Active radical identification proves that the transfer behavior of electron and hole over Ag3PO4@ZnIn2S4 follows a direct Z-scheme mechanism. Furthermore, the transformation pathway for degrading tetracycline was proposed by combining the Fukui index prediction with Mass Spectra identification of intermediates. This work presents in-depth sights into a regulated degradation pathway from theoretical prediction and practical identification based on innovative Z-scheme photocatalyst.

Gradient Hydrogen Migration Modulated with Self-Adapting S Vacancy in Copper-Doped ZnIn2S4 Nanosheet for Photocatalytic Hydrogen Evolution.

It is a challenge to regulate charge flow synergistically at the atomic level to modulate gradient hydrogen migration (H migration) for boosting photocatalytic hydrogen evolution. Herein, a self-adapting S vacancy (Vs) induced with atomic Cu introduction into ZnIn2S4 nanosheets was fabricated elaborately, which can tune charge separation and construct a gradient channel for H migration. Detailed experimental results and theoretical simulations uncover the behavior mechanism of Vs generation with Cu introduction after substituting a Zn atom tendentiously. Cu-S bond shrinkage and Zn-S bond distortion are presented around Vs areas. Besides, Vs induced by Cu introduction lowers the internal electric field to restrain electron transmission between layers, which are enriched on the Vs area because of the lower surface electrostatic potential. Atomic Cu and Vs show a synergistic effect for regulating regional charge separation due to the Cu dopant being a hole trap and Vs being an electron trap. The channels for H migration with gradient ΔGH0 are constructed by different S atom sites, which are modulated by Vs. Gradient H migration driven by a photothermal effect occurs on an identical surface without striding across a heterogeneous interface, which is a valid pathway with lower resistance for boosting H2 release. Ultimately, 5 mol % Cu confined in ZnIn2S4 nanosheets achieves an optimum photocatalytic hydrogen evolution activity of 9.8647 mmol g-1 h-1, which is 14.8 times higher than 0.6640 mmol g-1 h-1 for ZnIn2S4, and apparent quantum efficiency reaches 37.11% at 420 nm. This work demonstrates the behavior mechanism of atomic substitution and provides cognition for hydrogen evolution mechanism deeply.