Metal-assisted core-shell plasmonic nanoparticles for small molecule biothiol analysis and enantioselective recognition.

Cysteine (Cys) enantiomorphs, important small-molecule biothiols, participate in various antioxidative, flavoring, and poison-removing processes in the food industry. Current cysteine enantiomorph analysis methods require effective strategies for distinguishing them due to their similar structures and reactivity. Herein, we present a metal ion-assisted enantiomorph-selective surface-enhanced Raman scattering (SERS) biosensor based on an amphiphilic polymer matrix (APM), which can promote cysteine enantiomorph (L/D-Cys) identification. The highly selective molecular orientation is perhaps caused by the intermolecular hydrogen bonding with chiral isomers (metal centers). The experimental results show that the SERS biosensor has a sensitivity-distincting factor toward L-Cys and D-Cys. The linear range is from 1 mmol L-1 to 1 nmol L-1, along with a low limit of detection of 0.77 pmol L-1. Moreover, the fabricated Cu-APM biosensor exhibits remarkable stability and high repeatability, with an RSD of 3.7%. Real food cysteine enantiomorph detection was performed with L-Cys-containing samples of onion, cauliflower, garlic, and apple, and D-Cys-containing samples of vinegar, black garlic, cheese, and beer. The results show that the Cu-APM biosensor can be utilized as a powerful tool for real-time determination of Cys enantiomorphs in different food samples. Thus, the metal-ion-assisted enantiomorph-selective SERS biosensor has potential as an adaptable tool for enantiomorph detection and food sample analysis.

Anti-galvanic reaction induced interfacial engineering to reconstruct ternary colloid satellite platform for exceptionally high-performance redox-responsive sensor.

The anti-galvanic reaction (AGR), which is a classic galvanic reaction (GR) with an opposite effect, is a unique phenomenon associated with the quantum size effect. This reaction involves the interaction between metal ions and nanoclusters, offering opportunities to create well-defined nanomaterials and diverse reductive behavior. In hence, in our work, we utilize the AGR to generate gold (Au), silver (Ag), and copper (Cu) satellite nanoclusters which have superior electromagnetic properties for Surface-enhanced Raman spectroscopy (SERS) sensor. As the AGR process, weak oxidant Cu2+ is selected to etched matrix Au@Ag NPs, reduced to Cu(0) or Cu(1) and generated the ultrasmall metal nanoparticles (Ag). To facilitate the AGR, we introduce the nucleophilic thiol 4-mercaptopyridine (4-Mpy) to bridge the metal ions or ultrasmall metal nanoparticles to reconstruct the satellite nanoclusters. These experimental displays that the AGR based biosensors has highly sensitivity for reductive molecule glucose. The liner ranges from 1 mmol/L to 1 nmol/L and alongs with a correlation coefficient and detection limit (LOD) of 0.999 and 0.14 nmol/L. Moreover, the AGR based biosensors exhibits remarkable stability and high repeatability with RSD 1.3 %. The food samples are tested to further investigate the accuracy and reliability of the method, which provides a novel and effective SERS method for the reduction molecules detection.

Virus-Like Magnetic Heterostructure: an Outstanding Metal-Complex Active Platform Enables High-Efficiency Separation and Catalysis.

Assembled heterostructure systems, as emerging functional materials, have broad applications ranging from enzyme and drug payload to catalysis and purification. However, these require trial- and -error design process and complex experimental environment to generate heterostructure materials. Here, this study describes an easy-to-execute strategy to fabricate magnetic heterostructure as multifunctional delivery system. We utilize first-row transition metal copper and nitroso/amino ligand as modules to assemble around Fe3 O4 magnetic nanoparticles by excessed mild stimuli and fabricate the magnetic heterostructure materials (Fe3 O4 @ TACN NPs (tetraamminecopper (II) nitrate)). Notably, the Fe3 O4 @ TACN NPs present with cat's-whisker structure containing ligand and metal center. The nitroso-group ligands exhibit strong binding affinity to heme-structure enzyme, ensuring effective capture and isolate of cytochrome C (Cyt-c), resulting in their excellent isolation property. The copper complex-powered magnetic heterostructure materials can effectively isolation Cyt-c from complex biological sample (pork heart). Importantly, the Fe3 O4 @ TACN NPs coordinated with heme-structure, induced methionine 80 (Met80) disassociates from heme prosthetic group, and contributed to peroxidase-like (POD-like) activities increasing. These results exhibit that copper complex-powered magnetic heterostructure materials can not only satisfy the Cyt-c isolation and immobilization in an alkaline medium, but also be of the potential for improving the immobilization enzyme reactor performance.

Design of competition nanoreactor with shell-isolated colloidal plasmonic nanomaterials for quantitative sensor platform.

Shell-isolated colloid plasmonic nanomaterials-based nanoreactor is a well-established platform widely applied in catalyst or Surface Enhanced Raman Scattering (SERS) sensors. The potentials versatility of nanoreactor platform is mainly implemented by the well-defined and tailorable structure of colloid plasmonic nanomaterials. Currently, a competitive conjugative-mediated nanoreactor is introduced to determine glucose with SERS. Glucose-conjugating nanoreactor, as convertors of the sensors, are constructed by coordinated deposition colloidal gold nanoparticles with sodium nitroprusside framework (Au@SNF) and covalently bonded 4-mercaptopyridine (4-Mpy) with self-assembly strategy. The nanoreactor contained the signal-amplifier Au@SNF NPs, conjugative-mediated signal receiver 4-Mpy, and signal internal standard molecular CN-. In addition to well-defined morphology and functionality, conjugative-mediated and internal standards method are also employed to benefit the nanoreactor. The two-parameter strategy significantly improves the signal indication and correction. Using this proposed platform, the competitive-mediated nanoreactor provides a quantitative SERS detection of glucose, and extends the applicability of SERS in more complicated and reproducibility analysis. Meanwhile, the nanoreactor based sensors also exhibited better properties to detect glucose in various food samples and bio-samples which provided strongly appliance for glucose sensors.

Nanoenzyme Reactor-Based Oxidation-Induced Reaction for Quantitative SERS Analysis of Food Antiseptics.

Nanoenzyme reactors based on shell-isolated colloidal plasmonic nanomaterials are well-established and widely applied in catalysis and surface-enhanced Raman scattering (SERS) sensing. In this study, a "double wing with one body" strategy was developed to establish a reduced food antiseptic sensing method using shell-isolated colloidal plasmonic nanomaterials. Gold nano particles (Au NPs) were used to synthesize the colloidal plasmonic nanomaterials, which was achieved by attaching ferrous ions (Fe2+), ferric ions (Fe3+), nitroso (NO-) group, cyanogen (CN-) group, and dopamine (DA) via coordinative interactions. The oxidation-induced reaction was utilized to generate •OH following the Fe2+-mediated Fenton reaction with the shell-isolated colloidal plasmonic nanomaterials. The •OH generated in the cascade reactor had a high oxidative capacity toward acid preservatives. Importantly, with the introduction of the signal molecule DA, the cascade reactor exhibited also induced a Raman signal change by reaction with the oxidation product (malondialdehyde) which improved the sensitivity of the analysis. In addition, the stable shell-isolated structure was effective in realizing a reproducible and quantitative SERS analysis method, which overcomes previous limitations and could extend the use of nanoenzymes to various complex sensing applications.

Highly crosslinking core-shell magnetic nanocomposites based catalyst and heat free polymerization for isolation of glycoprotein.

New approaches for the engineering of well-defined, pore modality, and multi-chemical functionality nanocomposites are crucial to generate the next generation of functional materials with recoverable and easy preparation properties. Here, a catalyst and heat free polymerization reaction is exploited and fabricated zwitterionic system around magnetic nanoparticles. N-aminoethyl piperazine propane sulfonate (AEPPS) and dopamine (DA) are introduced as the zwitterionic system, which provided abundant zwitterionic groups (NH2, SO3-, N+) and strong adhesion and various oxidation state properties. And that, the zwitterionic engineering will assemble between AEPPS and DA whereby Schiff base formation or Michael type addition. Whereafter, a series of sophisticated array of microscopic, spectroscopic, and structure techniques verify the formation of highly crosslinking internal zwitterionic architectures, well-defined core-shell structure, and better porosity. The zwitterionic structure-function relationships and striking porous structure are explored in a multi-interaction adsorption assay. The adsorption capacity of the magnetic nanocomposites was 1065.8 mg/g. And that, the system exhibited with hydrophilic-hydrophobic activity towards glycoprotein and better performance to bioactive protein (Ig-G) isolation form human whole blood sample. The synergistic enhancement interaction in hydrophilic target enrichment, easy preparation, and soft substrate properties of the AEPPS-DA zwitterionic materials make them intriguing candidates for sustainable biomedical loading and chromatographic separation.

Construction of Metal Hydrate-Based Amorphous Magnetic Nanosheets for Enhanced Protein Enrichment and Immobilization.

Inspired by the hierarchical fabrication technique, many self-assembly procedures have improved the construction of nanomaterials with unique physicochemical characteristics and multiple functions. The generation of multiple complexes is always accompanied by hierarchical structures and intriguing properties that are distinct from their individual segments. An interesting composite is amorphous magnetic Zn-Zr phosphate hydrated nanosheets (Zn-Zr APHNs), generated using templated synthesis and nanoparticle codeposition. The special porous structure of this construct, together with the abundance of metal ions and hydrate present, endows it with many interaction sites for proteins, provides high loading efficiency, and enhances bioactivity. Then, a series of proteins, including enzymes, was immobilized by the Zn-Zr APHNs by multiple interactions, high ionization, and larger surface of the nanosheets. In this study, novel methods for the enrichment of bioactive proteins while retaining the activity of protein payloads are presented. As a verification method, it is indicated that the Zn-Zr APHNs can deliver enzyme proteins (i.e., Cyt-c) to increase the catalytic activity with their biological function and structural integrity, resulting in a highly increased activity to free proteins.

Three dimensional graphene materials doped with heteroatoms for extraction and adsorption of environmental pollutants in wastewater.

Environmental pollution by heavy metal ions, organic pollutants, oils, pesticides or dyes is a ubiquitous problem adversely affecting human health and environmental ecology. Development and application novel adsorbents in full-scale treatment systems with effectiveness properties could effective ways to facilitate the extraction and adsorption of environment pollutants from wastewater. Graphene materials have drawn much attention due to their extraordinary electron mobilities, high surface areas, good thermal conductivities, and excellent mechanical properties. Three-dimensional graphene materials can provide the inherent advantages of 2D graphene sheets and exhibit micro/nanoporous structures, increased specific surface areas, high electron conductivities, fast mass transport kinetics, and strong mechanical strength. Potential applications for 3D graphene materials include environmental remediation, chemical and biological sensing, catalysis, and super capacitors. Recent advances in the applications of 3D functionalized graphene materials (3D FGMs) doped with heteroatoms for the extraction and adsorption of environmental pollutants in wastewater are summarized in this review.

Colorimetric sensing of chloride in sweat based on fluorescence wavelength shift via halide exchange of CsPbBr3 perovskite nanocrystals.

Considering the high importance of the rapid detection of chloride ion (Cl-) in sweat for the diagnosis of fibrotic cysts, we have investigated the heterogeneous halide exchange between CsPbBr3 perovskite nanocrystals (PNCs) in n-hexane and Cl- in aqueous solution. The results show that CsPbBr3 PNCs could achieve fast halide exchange with Cl- in the aqueous phase under magnetic stirring at pH = 1, accompanied by a significant wavelength blue shift and vivid fluorescence color changes from green to blue. Therefore, a fluorescence wavelength shift-based colorimetric sensing of Cl- based on the halide exchange of CsPbBr3 PNCs has been developed to realize the rapid detection of Cl- in sweat. Compared with the conventional fluorescence intensity-based method, this method is of high convenience since the whole procedure could be achieved within 5 min without any sample pretreatment (even no dilution), demonstrating promising application prospects. Graphical Abstract Fluorescence wavelength-shift based colorimetric sensing of chloride in sweat via halide exchange of CsPbBr3 perovskite nanocrystals.

[Recent advances in the application of thin-film microextraction].

Thin-film microextraction (TFME), which is a new technique in solid-phase microextraction and correlational research, have gradually attracted the attention of scientists in the field of sample preparation. Because of the high surface area-to-volume ratio and the concurrent increase inthe extraction-phase volume, TFME shows enhanced sensitivity without sacrificing the sampling time, as opposed to other microextraction approaches. Recently, TFME in combination with sample analysis techniques has been widely used for the analysis of forbidden drugs, explosives, pesticides, and veterinary drugs in the pharmaceutical, foodstuff, and environmental industries. This review summarizes the fundamentals, formats, and applications of TFME, as well as its long-term prospects and potential applications.

A dichromatic label-free aptasensor for sulfadimethoxine detection in fish and water based on AuNPs color and fluorescent dyeing of double-stranded DNA with SYBR Green I.

A dichromatic label-free aptasensor was described for sulfadimethoxine (SDM) detection. Compared with the binding of SDM-aptamer to SDM, the higher affinity of aptamer to cDNA may result in the hybridization of dsDNA. In the presence of SDM, the aptamer specifically binds to SDM, leading to a blue color of AuNPs in deposit and fluorescence at 530 nm in supernatant after adding cDNA and SGI. With no target of SDM, AuNPs protected with the aptamer re-disperse in PBS with a red color, and no fluorescence occurs in supernatant. Based on the principle, SDM can be quantitatively detected through both fluorescent emission and AuNPs color changes with recoveries ranging from 99.2% to 102.0% for fish and from 99.5% to 100.5% for water samples. An analytical linear range of 2-300 ng mL-1 was achieved with the detection limits of 3.41 ng mL-1 for water and 4.41 ng g-1 for fish samples (3σ, n = 9).

A taurine-functionalized 3D graphene-based foam for electrochemical determination of hydrogen peroxide.

We present a synthesis approach of taurine-functionalized graphene foam (a-NSGF) using hydrothermal reduction, freeze-drying and high temperature annealing. The higher temperature in annealing allowed the N/S atoms of taurine enter into the graphene lattice, which improves its electrocatalytic activity greatly. The a-NSGF consisting of taurine that modified into 3D layers of graphene and endow is of the rapid sensitive to hydrogen peroxide (H2O2). The electrode using a-NSGF modification reveals highly sensitive and stable towards the concentration change of H2O2 due to the stable 3D structure and good electrical conductivity of a-NSGF. A linear correlation between H2O2 concentration and the electrochemical signal is found to be in a range from 1.5 to 300 µM and the correlation coefficient is R2 = 0.999. The modified electrode has been applied in the determination of H2O2 in rain samples and the results have been compared with the China National Standard Method. The recoveries range from 94.6% to 106.7%. These results show that the proposed sensor is promising for the development of novel electrochemical sensing for H2O2 determination.

Label-Free Fluorescence-Based Aptasensor for the Detection of Sulfadimethoxine in Water and Fish.

Fluorescence-based aptasensors possess high sensitivity but are complicated and usually require multistep labeling and modification in method design, which severely limit the practical applications. Here, a label-free fluorescence-based aptasensor, consisting of aptamer, gold nanoparticles (AuNPs), and cadmium telluride (CdTe) quantum dots (QDs), was developed for the detection of sulfadimethoxine (SDM) in water and fish based on the specific recognition of SDM-aptamer and the inner filter effect of QDs and AuNPs. In the absence of a target, AuNPs dispersed in salt solution because of the aptamer protection, which could effectively quench the fluorescence emission of QDs, while in the presence of SDM, AuNPs aggregated due to the specific recognition of SDM-aptamer to SDM, which resulted in fluorescence recovery. A linear response of SDM concentrations in the range of 10-250 ng mL-1 ( R2 = 0.99) was obtained, and the detection limit was 1.54 ng mL-1 (3σ, n = 9), far below the maximum residue limit (100 ng mL-1) of SDM in edible animal tissues regulated by China and the European Commission. The fluorescence-based aptasensor was applied to the detection of SDM in aquaculture water and fish samples with high accuracy, excellent precision, and ideal selectivity. The results indicated that the developed aptasensor was simple in design, easy to operate, and could be used to detect rapidly and accurately SDM in water and fish samples.

Ratiometric fluorescence probe of MIPs@CdTe QDs for trace malachite green detection in fish.

A facile and practical ratiometric fluorescence probe based on two CdTe quantum dots (QDs) coated with molecularly imprinted polymers (MIPs) was prepared for the detection of trace malachite green (MG) in fish. Two CdTe QDs coated with MIPs were fabricated by a one-pot method using MG, (3-aminopropyl) triethoxysilane (APTES) and tetraethyl orthosilicate (TEOS) as template, functional monomer, and cross-linker, respectively. CdTe QDs with λem 530 nm (gQDs) and 630 nm (rQDs) were used as the referential fluorophore and target sensitive fluorophore, respectively. The fluorescence intensity of gQDs remained unchanged in the presence of MG, while the fluorescence of rQDs could be quantitatively quenched by MG based on the strategy of fluorescence resonance energy transfer. The ratiometric fluorescence probe (MIPs@gQDs&rQDs) was characterized by transmission electron microscopy and Fourier transform infrared spectroscopy. The linear range of MG detection was 0.1-32 µmol L-1 with a detection limit of 8.8 µg kg-1. The constructed probe has been successfully applied to the detection of MG in fish with the recoveries of 92.3-109.1%, which were validated by the method of HPLC. The result indicated that the probe possessed rapid response, wide linear range, high sensitivity, and relatively high selectivity, and was low-cost and easy in operation in the detection of MG in fish samples.

An on-line solid-phase extraction disc packed with a phytic acid induced 3D graphene-based foam for the sensitive HPLC-PDA determination of bisphenol A migration in disposable syringes.

In this study, an on-line SPE-disc filled with phytic acid induced 3D graphene-based foam (PAGF) has been applied to the determination of the migration of bisphenol A (BPA) in disposable syringes. The approach is of quick, easy, sensitive and environmentally-friendly. Experimental conditions were investigated and optimized including the character of enriched material and the amount of migrated BPA under different temperature, time and pH conditions. The experimental results reveal that the approach presents a wide linear range between the signal response and the concentration of BPA from 1 to 1000ngmL-1, as well as the detection limit of 0.03ngmL-1. The recoveries from 73% to 117% are achieved. BPA could be found and detected in disposable syringe samples with the migration amount from 1.47 to 82.69ngmL-1, which is lower than the permissible values of National Standard People's Republic of China, GB 9685-2008.

Facile synthesis of a ratiometric oxygen nanosensor for cellular imaging.

A new type of cell-penetrating ratiometric fluorescence oxygen sensing nanoparticle was prepared through a facile co-precipitation method. Amphiphilic polymer poly (styrene-co-maleic anhydride) (PSMA) was firstly cooperated with polystyrene (PS) to envelop the highly photostable phosphorescent oxygen indicator, platinum(II)-tetrakis(pentafluorophenyl)porphyrin (PtTFPP, emission at 648nm), and the reference fluorophore, poly(9, 9-dioctylfluorene) (PFO, emission at 440nm ), via hydrophobic interaction in aqueous solution. To improve the sensor biocompatibility, the biomacromolecule poly-l-lysine (PLL) was selected to act as a shell via electrostatic forces. The as-prepared PtTFPP doped core-shell nanoparticles (called PPMA/PLL NPs) exhibited an excellent ratiometric luminescence response to O2 content with high quenching efficiency and full reversibility in the oxygen sensing. More importantly, these oxygen nanosensors passed across the cell membrane after co-incubation without external force. Labeled cells exhibited high brightness in the matching blue and red channels of a digital camera. And most nanosensors were found locating in cytoplasm rather than being trapped in endosomes.

A label-free electrochemiluminescent sensor for ATP detection based on ATP-dependent ligation.

In this work, we describe a new label-free, sensitive and highly selective strategy for the electrochemiluminescent (ECL) detection of ATP at the picomolar level via ATP-induced ligation. The molecular-beacon like DNA probes (P12 complex) are self-assembled on a gold electrode. The presence of ATP leads to the ligation of P12 complex which blocks the digestion by Exonuclease III (Exo III). The protected P12 complex causes the intercalation of numerous ECL indicators (Ru(phen)3(2+)) into the duplex DNA grooves, resulting in significantly amplified ECL signal output. Since the ligating site of T4 DNA ligase and the nicking site of Exo III are the same, it involves no long time of incubation for conformation change. The proposed strategy combines the amplification power of enzyme and the inherent high sensitivity of the ECL technique and enables picomolar detection of ATP. The developed strategy also shows high selectivity against ATP analogs, which makes our new label-free and highly sensitive ligation-based method a useful addition to the amplified ATP detection arena.

One-pot synthesis of fluorescent DHLA-stabilized Cu nanoclusters for the determination of H2O2.

A facile one-pot approach has been developed to prepare orange-emitting Cu nanoclusters (NCs) using tetrakis(hydroxymethyl)phosphonium chloride as a reducing agent and lipoic acid as a capping agent under an alkaline medium at room temperature. The as-prepared Cu NCs exhibited excellent water solubility, large Stokes shift, long lifetime and good dispersion. After the addition of polyvinyl pyrrolidone, the fluorescence intensity of dihydrolipoic acid-stabilized Cu NCs (DHLA-Cu NCs) was greatly enhanced, and their fluorescence signal remained stable for 5 weeks storage in the dark at room temperature. Based on H2O2-induced fluorescence quenching, DHLA-Cu NCs showed high sensitivity and selectivity for the detection of H2O2 in aqueous solution with a detection limit of 0.3µM, and were applied successfully to the detection of H2O2 in human urine samples.

Metal nanoclusters: applications in environmental monitoring and cancer therapy.

Metal nanoclusters (NCs), with dimensions between metal atoms and nanoparticles, have attracted more and more attention due to their unique physical and chemical properties. With their size approaching the Fermi wavelength of electrons, metal NCs possess molecule-like properties and excellent fluorescence emission. Owing to their ultrasmall size, strong fluorescence, and excellent biocompatibility, they have been widely studied in environmental and biological fields concerning their applications. In this review, we will introduce the properties of metal NCs, mainly focusing on the synthesis of metal alloy NCs and the recent progress in their applications in environmental monitoring and cancer therapy.

Highly fluorescent copper nanoclusters as a probe for the determination of pH.

A simple, one-pot synthetic route was developed for the preparation of green-emitting and pH-responsive Cu nanoclusters (NCs). The Cu NCs were obtained using cysteine (Cys) as both the reducing agent and the capping agent under alkaline conditions at room temperature. The Cu NCs were characterized using spectroscopic and microscopic techniques and exhibited excellent water solubility, ultrasmall size, good dispersion, bright fluorescence and good photostability. Moreover, the Cu NCs were stable even in a high ionic strength medium such as 1M NaCl. Interestingly, the Cys-Cu NCs showed an intrinsically reversible response toward pH change in the range 4-10, and thus can be utilized as an effective and reversible pH indicator.