Tailoring strategies of SERS tags-based sensors for cellular molecules detection and imaging.

As an emerging nanoprobe, surface enhanced Raman scattering (SERS) tags hold significant promise in sensing and bioimaging applications due to their attractive merits of anti-photobleaching ability, high sensitivity and specificity, multiplex, and low background capabilities. Recently, several reviews have proposed the application of SERS tags in different fields, however, the specific sensing strategies of SERS tags-based sensors for cellular molecules have not yet been systematically summarized. To provide beneficial and comprehensive insights into the advanced SERS tags technique at the cellular level, this review systematically elaborated on the latest advances in SERS tags-based sensors for cellular molecules detection and imaging. The general SERS tags-based sensing strategies for biomolecules and ions were first introduced according to molecular classes. Then, aiming at such molecules located in the extracellular, cellular membrane and intracellular regions, the tailored strategies by designing and manipulating SERS tags were summarized and explored through several key examples. Finally, the challenges and perspectives of developing high performance of advanced SERS tags were briefly discussed to provide effective guidance for further development and extended applications.

Luminescent carbon dots-rooted polysaccharide crosslinked hydrogel adsorbent for sensitive determination and efficient removal of Cu2.

In this study, a novel luminescent carbon dot-rooted polysaccharide hydrogel (CDs@CCP hydrogel) was prepared by crosslinking cellulose, chitosan (CS), and polyvinyl alcohol (PVA) for simultaneous fluorescent sensing and adsorption of Cu2+. The crosslinking of these low-cost, polysaccharide polymers greatly enhance the mechanical strength of the composite hydrogel while making the polysaccharide-based adsorbent easy to reuse. This composite hydrogel exhibited an excellent adsorption capacity (124.7 mg∙g-1) for residual Cu2+ in water, as well as a sensitive and selective fluorescence response towards Cu2+ with a good linear relationship (R2 > 0.97) and a low detection limit (LOD) of 0.02 µM. The adsorption isotherms, adsorption kinetics, and thermodynamics studies were also conducted to investigate the adsorption mechanism. This composite hydrogel offers an efficient tool for simultaneous monitoring and treatment of Cu2+ from wastewater.

A novel molecularly expanded covalent triazine framework heterojunction with significantly enhanced molecular oxygen activation and photocatalysis performance under visible light.

The activation capacity of molecular oxygen is an important indicator to evaluate the photocatalytic efficiency of photocatalysts. In this paper, WS2 nanosheet was deposited on hyper-crosslinked CTF-1-G (obtained by molecular expansion from covalent triazine framework CTF-1) to form a C-GW heterojunction, which promoted the photodegradation of pollutants and the activation of molecular oxygen. This novel C-GW heterojunction exhibited excellent degradation property for organic pollutants (tetracycline (TC), rhodamine B (RhB)) and activating molecular oxygen under visible light irradiation. Among them, C-GW15 could degrade 98% of 20 ppm TC in 60 min and 99% of 30 ppm RhB in 30 min, and it had the highest hydrogen generation rate and hydrogen production amount in 4 hours, which were 8.74 mmol h-1 g-1 and 34.94 mmol g-1, respectively. Meanwhile, C-GW15 had the strongest 3,3',5,5'-tetramethylbenzidine oxidation capacity and could generate 1.83 µmol of ˙O2- in 60 min and the production of H2O2 was 20.8 µmol L-1 in 40 min. The results of this study clearly indicated that the combination of WS2 and CTF-1-G can enhance the visible light absorption capacity and photogenerated carrier separation efficiency, thus promoting the photocatalytic performance. Finally, a Z-type photocatalytic mechanism was proposed based on radical capture, molecular oxygen activation experiments and electron spin resonance analysis. These findings will extend the fundamental understanding of the Z-type photocatalytic mechanism and provide new opportunities for the rational design of CTF heterojunctions for the treatment of environmental pollution and clean energy conversion.

MOF-derived CdS/CoO S-type heterojunctions for improving the efficiency of photocatalytic evolution.

The aggravating extreme climate changes and environmental pollution problems have stimulated the exploration of green alternatives to conventional fossil fuels and green environmental treatments. Photocatalysis is recognized as an outstanding green tool for solving the energy crisis and environmental rehabilitation issues. Restricted by the high cost of precious metals, researchers expect to obtain low-cost, efficient and stable photocatalysts. Herein, CdS materials were derived through MOFs and subsequently combined with CoO to form CdS/CoO heterojunctions. The catalytic ability was evaluated by the photocatalytic degradation of tetracycline hydrochloride (TC) and the photocatalytic production of hydrogen. With the integration of CoO, in terms of TC degradation, CdS/CoO heterojunctions can degrade over 90% of TC within 1 hour. In terms of hydrogen production, compared to CdS alone, the hydrogen production efficiency of the CdS/CoO heterojunction increased by 1.7 times. The initial analysis of the reasons for the enhancement of photocatalytic efficiency was conducted by TEM, XPS and other characterization means. Density functional theory (DFT) calculations verified the existence of a built-in electric field in the CdS/CoO heterojunction, which was the essential reason for the improved catalytic performance, and finally, the presence of ˙O2- and ˙OH in the photocatalytic system was demonstrated by the ESR technique. Based on the carrier separation/transfer pathway in the heterojunction, a simple and novel S-type heterojunction scheme was proposed.

Surface-enhanced Raman scattering based determination on sulfamethazine using molecularly imprinted polymers decorated with silver nanoparticles.

Molecularly imprinted polymers (MIPs) were combined with surface-enhanced Raman scattering (SERS) and AgNPs were prepared by in situ reduction within the MIP for selective and sensitive detection of sulfamethazine (SMZ). The MIP@AgNPs composites were characterized in detail by several analytical techniques, showing the generation of polymers and the formation of AgNPs hot spots. The specific affinity and rapid adsorption equilibrium rates of MIP@AgNPs composites were verified by static and kinetic adsorption studies. The MIP@AgNPs with high selectivity and excellent sensitivity were used as SERS substrates to detect SMZ. A good linear correlation (R2 = 0.996) in rang of 10-10-10-6 mol L-1 was observed between the Raman signal (1596 cm-1) and the concentration of SMZ. The limit of detection (LOD) was as low as 8.10 × 10-11 mol L-1 with relative standard deviations (RSD) of 6.32%. The good stability and reproducibility are also fully reflected in the SERS detection based on MIP@AgNPs. The method was successfully applied to the analysis of lake water samples, with recoveries in the range 85.1% to 102.5%. In summary, SERS detection based on MIP@AgNPs can be developed for a wider and broader range of practical applications. Schematic illustration of MIP@AgNPs sensor for the SERS detection of sulfamethazine.

Construction of a direct Z-scheme CeO2/UiO-66-NH2 heterojunction for boosting photocatalytic organic pollutant degradation and H2 evolution performance.

In this study, hollow CeO2 nanospheres were grown on UIO-66-NH2 nanosheets to form a novel CeO2/UiO-66-NH2 (abbreviation, CUx) Z-scheme heterojunction photocatalyst by calcination and hydrothermal method for hydrogen production and photocatalytic degradation of organic pollutants. Under visible light, the H2 generation rate of the CU0.50 composite was 5662.1 µmol g-1 h-1, which was 22 and 7 fold than that of pure CeO2 and pure UiO-66-NH2, respectively. In addition, compared with CeO2 and UiO-66-NH2, the as-prepared CUx composites exhibited enhanced photo-degradation efficiencies for tetracycline (TC) and 2,4-dichlorophenol (DCP) under simulated solar light irradiation. Among them, the CU0.50 composite demonstrated the highest photocatalytic performance and reached 91.5% for TC, and 94.3% for DCP. In addition, a logical solid-state Z-type electron transfer mechanism is presented with the results of radical scavenging and ESR experiments to illustrate the intensive decomposed ability of the photocatalytic system. The enhanced photocatalytic performance of CUx heterostructures can be attributed to the formation of a band-position-matched hollow structure heterojunction between CeO2 and UIO-66-NH2, which can effectively inhibit the recombination of carriers and increase the specific surface area as well as the light absorption. Moreover, the oxidation and reduction ability of the charge carriers was also increased. This work resulted in a feasible idea for removing organic pollutants and hydrogen production by traditional inorganic semiconductor/MOF-based heterostructured photocatalysts.

Routine analysis of pesticides in foodstuffs: Emerging ambient ionization mass spectrometry as an alternative strategy to be on your radar.

Pesticides residues in foodstuffs are longstanding of great concern to consumers and governments, thus reliable evaluation techniques for these residues are necessary to ensure food safety. Emerging ambient ionization mass spectrometry (AIMS), a transformative technology in the field of analytical chemistry, is becoming a promising and solid evaluation technology due to its advantages of direct, real-time and in-situ ionization on samples without complex pretreatments. To provide useful guidance on the evaluation techniques in the field of food safety, we offered a comprehensive review on the AIMS technology and introduced their novel applications for the analysis of residual pesticides in foodstuffs under different testing scenarios (i.e., quantitative, screening, imaging, high-throughput detection and rapid on-site analysis). Meanwhile, the creative combination of AIMS with high-resolution mass analyzer (e.g., orbitrap and time-of-flight) was fundamentally mentioned based on recent studies about the detection and evaluation of multi-residual pesticides between 2015 and 2021. Finally, the technical challenges and prospects associated with AIMS operation in food industry were discussed.

Advances on removal of organophosphorus pesticides with electrochemical technology.

Widespread use of organophosphorus pesticides (OPs), especially superfluous and unreasonable use, had brought huge harm to the environment and food chain. It is because only a small part of the pesticides sprayed reached the target, and the rest slid across the soil, causing pollution of groundwater and surface water resources. These pesticides accumulate in the environment, causing environmental pollution. Therefore, in recent years, the control and degradation of OPs have become a public spotlight and research hotspot. Due to its unique advantages such as versatility, environmental compatibility, controllability, and cost-effectiveness compatibility, electrochemical technology has become one of the most promising methods for degradation of OPs. The fundamental knowledge about electrochemical degradation on OPs was introduced in this review. Then, a comprehensive overview of four main types of practical electrochemical technologies to degrade pesticides were presented and evaluated. The knowledge contained herein should conduce to better understand the degradation of pesticides by electrochemical technology, and better exploit the degradation of pesticides in the environment and food. Overall, the objective of this review is to provide comprehensive guidance for rational design and application of electrochemical technology in the degradation of OPs for the safety of the environment and food chain in the future.

Enhanced photocatalytic performance over PANI/NH2-MIL-101(Fe) with tight interfacial contact.

Constructing a suitable heterojunction structure while maintaining a tight interface to promote the separation of photogenerated electrons is of great significance for improving the photocatalytic activity. In this paper, a new PANI/NH2-MIL-101(Fe) II-scheme heterojunction was prepared by a hydrothermal method. PANI with a porous structure was firstly obtained by the template method, and then PANI fragments were loaded on the surface of NH2-MIL-101(Fe) crystals under hydrothermal conditions to obtain a PANI/NH2-MIL-101(Fe) photocatalyst. The photocatalytic degradation of TC under simulated sunlight can reach 90% within an hour, and the maximum hydrogen evolution rate is 7040 µmol g-1 h-1 under visible light. The enhanced catalytic performance of PANI/NH2-MIL-101(Fe) was attributed to the appropriate matching of the VB and CB of PANI and NH2-MIL-101(Fe), and secondly, the coordination bonds formed between PANI and NH2-MIL-101(Fe) provided a channel for charge separation and transfer. Finally, a possible mechanism of the photocatalytic system was proposed through a free radical capture experiment and characterization analysis. More importantly, the experiment proved that the heterojunction formed by PANI and NH2-MIL-101(Fe) can achieve the effect of complementing each other, which provides a feasible idea and method for the design of efficient heterojunction photocatalysts.

Highly sensitive sensing and quantitative detection of sulfate ion with a SERS chip-based on boric acid's Lewis effect.

Based on the Lewis acid's coordination principle, a surface-enhanced Raman scattering (SERS) chip strategy had been developed for the ultrasensitive quantitation of SO42-. Through the immobilization of silver nanoparticles (Ag NPs) and the construction of the boric acid-based sensing unit, the chip system displayed outstanding merits on the direct sensing of SO42-, e.g., simple operation, ultra-high sensitivity, reproducibility, excellent selectivity and specificity. Moreover, an accurate evaluation was obtained by ratiometric calculations on characteristic peaks (1382 and 1070 cm-1) for quantitative detection of SO42-. The detection limit was down to 10 nM. Tap water, beer, and mineral water samples were tested, and high recoveries were achieved (97.12-110.12%). Besides, such SERS chip also displayed strong applicability for the evaluation of SO32-. Therefore, this SERS chip provided a promising idea for the quantification of trace amounts of SO42- and SO32- in the fields of food safety and environmental monitoring.

A novel analytical strategy for the determination of perfluoroalkyl acids in various food matrices using a home-made functionalized fluorine interaction SPME in combination with LC-MS/MS.

In this study, a fluorine-fluorine interaction approach through fluoridating boron nitride nanosheets (BNNs) for sensing perfluoroalkyl acids (PFAAs) in multiple food matrices was developed. Through a facile hydrothermal fluorination modification, the BNNs were transferred into homogeneous fluorinated boron nitride nanoparticles (F-BNNs) with robust networks and specific surface area. After morphological modification, the particles displayed strong adsorption and sensing capabilities on PFAAs in both solid and liquid food matrix. Under the evaluation of mass spectrometry, F-BNNs based microextraction approach exhibited low method detection limits (MDLs) in the ranges of 0.9-3.9 pg mL-1 and 3.6-15.8 pg g-1 for milk and meat matrices, respectively, with satisfactory repeatability (RSD% <13.5%) and recoveries (77.7-110.5%). This work not only depicted a facile approach for preparing F-BNNs based SPME fiber, but also provided a routine analysis protocol for monitoring PFAAs in food systems.

A Competitive "On-Off-Enhanced On" AIE Fluorescence Switch for Detecting Biothiols Based on Hg2+ Ions and Gold Nanoclusters.

In this study, a novel "on-off-enhanced on" approach to highly sensitive rapid sensing of biothiols was developed, based on competitive modulation of gold nanoclusters (AuNCs) and Hg2+ ions. In our approach, the AuNCs were encapsulated into a zeolite imidazole framework (ZIF) for predesigned competitive aggregation-induced luminescence (AIE) emission. To readily operate this approach, the Hg2+ ions were selected as mediators to quench the fluorescence of AuNCs. Then, due to the stronger affinities between the interactions of Hg2+ ions with -SH groups in comparison to the AuNCs with -SH groups, the quenched probe of AuNCs@ZIF-8/Hg2+ displayed enhanced fluorescence after the Hg2+ ions were competitively interacted with -SH groups. Based on enhanced fluorescence, the probe for AuNCs@ZIF-8/Hg2+ had a sensitive and specific response to trace amounts of biothiols. The developed fluorescence strategy had limit of quantification (LOQ) values of 1.0 µM and 1.5 µM for Cys and GSH molecules in serum, respectively. This competitive AIE strategy provided a new direction for developing biological probes and a promising method for quantifying trace amounts of biothiols in serum. It could promote progress in disease diagnosis.

Ultrasensitive and turn-on homogeneous Hg2+ sensing based on a target-triggered isothermal cycling reaction and dsDNA-templated copper nanoparticles.

In this work, an ultrasensitive and turn-on sensor for homogeneous Hg2+ detection has been constructed based on a target-triggered isothermal cycling reaction and rapid label-free signal output with dsDNA-templated copper nanoparticles (CuNPs). As the key component of the sensor, a hairpin DNA without any labels was designed to contain different functional sequence segments and to resist digestion by exonuclease due to the protruding 3'-terminus. In the presence of Hg2+, the formation of a T-Hg2+-T structure turned the protruding 3'-terminus of the hairpin DNA to a blunt end that could be efficiently digested by Exo III, accompanied by Hg2+ release, followed by another digestion cycle. Hence, the Hg2+-triggered isothermal cycling reaction accumulated numerous dsDNA templates that facilitated fluorescent CuNP generation and finally output an amplified signal used to identify the target. This protocol is capable of Hg2+ sensing in a concentration range of 5 orders of magnitude with a detection limit down to 3.9 pM. The as-constructed sensor also revealed high selectivity, as well as satisfactory results in recovery experiments of Hg2+ detection in real water samples.

A versatile fluorescent nanobeacon lighted by DNA-templated copper nanoparticles and the application in isothermal amplification detection.

In this work, an environmentally-friendly and versatile nanobeacon was constructed by utilizing DNA-templated copper nanoparticles (CuNPs) as fluorescence signal source. As the key component of the nanobeacon, a hairpin DNA was designed to contain four segments: two segments for CuNPs template sequence, a target recognition segment and a blocking segment. At room temperature, the target recognition segment partly hybridizes with the blocking segment and thus prohibits the formation of double stranded DNA template, so that no CuNPs can be generated on the hairpin DNA. While a target is introduced, the specific binding of target with recognition sequence triggers off the conformational transformation of the hairpin DNA, which contributes to the formation of the CuNPs template. As a result, the in-situ generation of CuNPs gives birth to the fluorescence signal readout that can be used to identify the target. By reasonably varying the recognition sequence within hairpin DNA, a series of nanobeacons in response to corresponding targets, such as DNA, microRNA, thrombin, and ATP, were put forward with satisfactory sensitivity and selectivity. Moreover, this nanobeacon was also integrated with the strategy of enzyme-assisted target-recycling to realize signal amplification and ultrasensitive detection, which further demonstrated the versatility of the nanobeacon. This novel nanobeacon is expected to be a promising alternative to classical dye-labeled molecular beacon and provide new perspective on ultrasensitive fluorescence sensing.

Carbon nitride-doped melamine-silver adsorbents with peroxidase-like catalysis and visible-light photocatalysis: Colorimetric detection and detoxification removal of total mercury.

Mesoporous melamine-silver (MA-Ag) nanocomposites doped with carbon nitride quantum dots (CNQDs) were fabricated simply by the controlled supramolecular self-assembly. It was discovered that the resulting nanoflower-like CNQDs@MA-Ag nanocomposites could exhibit the peroxidase-like catalysis, which could be specifically enhanced by Hg2+ by forming Ag@Hg alloys. A double catalysis-based colorimetric method was thereby developed for the fast detecting of Hg2+ and Hg0 in wastewater samples, with the levels down to 0.050 nM and 18.3 nM, respectively. Moreover, strong visible-light-driven photocatalysis of the nanocomposites was demonstrated for oxidizing Hg0 into Hg2+ through photocatalytic H2O2 production so as to realize the detoxification of Hg0 in the environmental wastewater. Besides, the fabricated mesoporous CNQDs@MA-Ag nanocomposites with large specific surface areas might facilitate the high Hg adsorption through the powerful MA-Hg chelate interaction, showing the efficient adsorption and/or removal of total Hg. The catalysis-selective colorimetric analysis and photocatalysis-based detoxification removal of total mercury may promise for wide applications in the environmental monitoring and wastewater treatment of toxic heavy metals of mercury.

A selective colorimetric and efficient removal strategy for mercury (II) using mesoporous silver-melamine nanocomposites synthesized by controlled supramolecular self-assembly.

Mesoporous silver-melamine (Ag-MA) nanocomposites were synthesized by controlled supramolecular self-assembly with various structural morphologies. It was discovered that the rod-like Ag-MA nanocomposites could present the larger Hg2+-enhanced catalysis by forming Ag-Hg alloys. Also, they could display large surface-to-volume area and high aqueous stability for the selective Hg2+ enrichment and absorption of Hg2+ ions by yielding the stable coordination complexes. A catalysis-based colorimetric method was thus developed using 96-wells plates to probe Hg2+ ions in blood and wastewater with the linear Hg2+ concentrations ranging from 1.0 nM to 600 nM and 0.50 nM to 700 nM, respectively. Besides, mesoporous Ag-MA absorbents could facilitate the removal of Hg2+ ions in wastewater with the removal efficiency up to 99.76 % and the absorption capacity of 598.99 mg g-1.

Fe3O4 Nanozymes with Aptamer-Tuned Catalysis for Selective Colorimetric Analysis of ATP in Blood.

In this work, a simple and highly selective colorimetric method has been developed for quantifying trace-level ATP using Fe3O4 nanoparticles (Fe3O4 NPs). It was discovered that Fe3O4 NPs could present the dramatically enhanced catalysis once anchored with ATP-specific aptamers (Apts), which is about 6-fold larger than that of bare Fe3O4 NPs. In the presence of ATP, however, the Apts would be desorbed from Fe3O4 NPs due to the Apts-target binding event, leading to the decrease of catalysis rationally depending on ATP concentrations. A colorimetric strategy was thereby developed to facilitate the highly selective detection of ATP, showing the linear concentrations ranging from 0.50 to 100 µM. Subsequently, the developed ATP sensor was employed for the evaluation of ATP in blood with the analysis performances comparably better than those of the documented detection methods, showing the potential applications in the clinical laboratory for the detective diagnosis of some ATP-indicative diseases. Importantly, such a catalysis-based detection strategy should be extended to other kinds of nanozymes with intrinsic catalysis properties (i.e., peroxidase and oxidase-like activities), promising as a universal candidate for monitoring various biological species simply by using target-specific recognition elements like Apts and antibodies.

A highly selective "turn-on" electroanalysis strategy with reduced copper metal-organic frameworks for sensing histamine and histidine.

A highly selective and sensitive electroanalysis strategy has been developed for sensing histamine (HTA) and histidine (His) with "turn-on" signal outputs using copper nanocomposites (Cu NCs) of reduced copper metal-organic frameworks (Cu MOFs). It was discovered that the Cu NC-modified electrodes could display the sharp and stable oxidation peaks of solid-state CuCl electrochemistry at a low potential (about -0.10 V). More interestingly, once HTA or His was introduced, the peaking currents of the electrodes would increase due to the specific interaction between Cu2+ and imidazole groups of HTA or His. A highly selective electroanalysis method was thereby developed for the detection of both HTA and His in the concentration range of 0.010-100 µM. Besides, the application feasibility of the developed electroanalysis strategy was demonstrated for the evaluation of HTA and His separately in red wine and urine samples. Such an electroanalysis candidate for HTA and His holds great potential for wide applications in the fields of food analysis and clinical disease diagnosis.

A selective colorimetric strategy for probing dopamine and levodopa through the mussel-inspired enhancement of Fe3O4 catalysis.

Mussel-inspired enhancement of Fe3O4 catalysis was discovered towards a highly selective and sensitive colorimetric strategy for the magnetic separation-based evaluation of dopamine and/or levodopa in urine, in which the specific interaction of bis-catechol-containing analytes and mesoporous Fe3O4 NPs would form highly stable complexes of bis-catechol-Fe coordination.

One-step rapid synthesis of fluorescent silicon nanodots for a hydrogen peroxide-related sensitive and versatile assay based on the inner filter effect.

In this work, a kind of environment-friendly and water-dispersible silicon nanodot (SiND) was rapidly synthesized by using the mild reagents (3-aminopropyl)triethoxysilane (APTES) and glucose. It was found that the fluorescence of the as-prepared SiNDs can be quenched obviously by permanganate due to the inner filter effect. Inspired by this finding, a novel fluorescent sensor for sensitive detection of hydrogen peroxide (H2O2) was developed through the oxidation-reduction reaction between permanganate and H2O2. The detection limit of H2O2 is down to 2.8 nM. Since H2O2 is an important molecule and involved in various studies, this sensor could be applied in various H2O2-related biological analyses. As a proof-of-application demonstration, a sensitive biosensor for glucose detection was constructed through the catalytic oxidation of glucose to generate H2O2. The as-constructed sensor showed good linear response to glucose over the range from 0.16 to 16 µM with a detection limit of 0.11 µM. Moreover, the biosensor can be readily extended to other sensors for different targets, which indicates the broad applications of the proposed sensing strategy in biomedical analysis.