Pore-Forming Toxin-Driven Recovery of Peroxidase-Mimicking Activity in Biomass Channels for Label-Free Electrochemical Bacteria Sensing.

The development of sensitive, selective, and rapid methods to detect bacteria in complex media is essential to ensuring human health. Virulence factors, particularly pore-forming toxins (PFTs) secreted by pathogenic bacteria, play a crucial role in bacterial diseases and serve as indicators of disease severity. In this study, a nanochannel-based label-free electrochemical sensing platform was developed for the detection of specific pathogenic bacteria based on their secreted PFTs. In this design, wood substrate channels were functionalized with a Fe-based metal-organic framework (FeMOF) and then protected with a layer of phosphatidylcholine (PC)-based phospholipid membrane (PM) that serves as a peroxidase mimetic and a channel gatekeeper, respectively. Using Staphylococcus aureus (S. aureus) as the model bacteria, the PC-specific PFTs secreted by S. aureus perforate the PM layer. Now exposed to the FeMOF, uncharged 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) molecules in the electrolyte undergo oxidation to cationic products (ABTS•+). The measured transmembrane ionic current indicates the presence of S. aureus and methicillin-resistant S. aureus (MRSA) with a low detection limit of 3 cfu mL-1. Besides excellent specificity, this sensing approach exhibits satisfactory performance for the detection of target bacteria in the complex media of food.

Electrochemically Triggered Self-Adaptive Reconstruction of an all-Purpose Electrode for Photothermally Enhanced Capacitors.

Large-capacity energy storage devices are attracting widespread research attention. However, the decreased capacity of these devices due to cold weather is a huge obstacle for their practical use. In this study, an electrochemical self-adaptive reconstructed Cux S/Cu(OH)2 -based symmetric energy storage device is proposed. This device provides a satisfactorily enhanced photothermal capacity under solar irradiation. After electrochemical reconstruction treatment, the morphological structure is rearranged and the Cux S component is partially converted to electrochemically active Cu(OH)2 with the introduction of a large number of active sites. The resulting Cux S/Cu(OH)2 electrode provides a significant capacitance of 115.2 F cm-2 at 5 mA cm-2 . More importantly, its wide working potential range and superior photo-to-thermal conversion ability endow Cux S/Cu(OH)2 with superb performance as full-purpose photothermally enhanced capacitance electrodes. Under solar irradiation, the surface temperature of Cux S/Cu(OH)2 is elevated by 76.6 °C in only 30 s, and the capacitance is boosted to 230.4% of the original capacitance at a low temperature. Furthermore, the assembled symmetric energy storage device also delivers a photothermal capacitance enhancement of 200.3% under 15 min solar irradiation.

Enantioselective Target Transport-Mediated Nanozyme Decomposition for the Identification of Reducing Enantiomers in Asymmetric Nanochannel Arrays.

Enantioselective identification of chiral molecules is regarded as one of the key issues in biological and medical sciences because of their configuration-dependent effects on biological systems. In this study, we developed an electrochemical platform based on a tandem recognition-reaction zone design in TiO2 nanochannels for the specific recognition of reducing enantiomers. In this system, MIL-125(Ti) Ti-metal-organic frameworks, in situ grown in TiO2 nanochannels, provided a homochiral recognition environment via postmodification with l-tartaric acid (l-TA); MnO2 nanosheets possessing both glucose oxidase (GOD)- and peroxidase (POD)-mimicking activities served as the target-reactive zone at the end of the nanochannels. The use of penicillamine (Pen) enantiomers as model-reducing targets facilitated the passage of d-Pen through the homochiral recognition zone, owing to its lower affinity with l-TA. The passed Pen molecules reached the responsive zone and induced a target concentration-dependent MnO2 disassembly. Such target recognition event impaired the cascade GOD- and POD-like activities of MnO2. Combining the enantioselectivity of the recognition nanochannels with the cascade enzyme-like activity of MnO2 toward glucose and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate), the quantitative identification of l- and d-Pen was achieved through the changes in transmembrane ionic current induced by the generated charged products. This recognition-reaction zone design paves an effective way for developing a promising electrochemical platform for the identification of reducing enantiomers with improved selectivity and sensitivity.

Water Evaporation-Driven Arginine Enantiomer Recognition on a Self-Powered Flexible Chip with High Specificity.

Chiral recognition is a crucial issue in the biomedical and pharmaceutical research communities. Due to the need for expensive equipment, reagents, and external energy, enantiomer identification is difficult to perform outside of a laboratory. Based on water evaporation-induced hydrovoltaic effect, a power-free sensing platform with sensitive chiral recognition capability is proposed for the discrimination of enantiomers. The chiral recognizer was bovine serum albumin (BSA), a naturally occurring protein. Using arginine (Arg) enantiomers as the sensing targets, the difference in enantioselectivity between l-Arg and d-Arg on a BSA-modified porous carbon substrate can be measured directly from the output voltage. By combining the cyclization reaction between NO and O-phenylenediamine (OPD), it has been discovered that the sensitivity and specificity of enantioselective identification can be significantly enhanced based on the surface charges. The limit of detection (LOD) could be as low as 76.0 nM. In addition, the proposed chips are extremely flexible and can function under deformation without sacrificing output performance. This self-powered chiral recognition chip paves a new path for the detection of chiral molecules at any time, any place, and it also has excellent potential for use in flexible wearable technology.

Target Recognition-Triggered Peroxidase-Mimicking Activity Depression in Homochiral Nanochannels for Identifying Cystine Enantiomers.

Enantioselective identification of chiral molecules is of paramount importance in medical science, biochemistry, and pharmaceutics owing to the configuration-dependent activities of enantiomers. However, the identical physicochemical properties of enantiomers remain challenging in chiral sensing. In this study, inspired by the peroxidase-mimicking activity of Fe(III)-based nanomaterials, an enantioselective artificial architecture is constructed on TiO2 nanochannels. Homochiral Ti-based metal-organic frameworks (MOFs) use a 2,2'-bipyridine-5,5'-dicarboxylic acid ligand as the artificial enzyme skeleton, Fe(III) as peroxidase-mimicking centers, and l-tartaric acid (TA) as a chiral recognition selector. Using l-/d-cystine as model enantiomers, the chiral moieties of l-TA on Ti-MOFs allow stereoselective recognition of guest molecules through hydrogen bonds formed between chiral cystine and the host. In a tris(2-carboxyethyl)phosphine hydrochloride-containing environment, the disulfide bonds in cystine molecules are further cleaved, and the HS-tails react with Fe(III) active sites, causing the loss of peroxidase-like performance of nanochannels. Benefitting from the nanochannel architecture's current-potential (I-V) properties, the selective recognition of cystine enantiomers is directly monitored through the peroxidase-like activity change-induced ionic current signatures. This study provides a new and universal strategy for distinguishing disulfide- and thiol-containing chiral molecules.

Improved Sensitivity and Selectivity of Glutathione Detection through Target-Driven Electron Donor Generation in Photoelectrochemical Electrodes.

Glutathione (GSH) plays a vital role in many physiological processes, and its abnormal levels have been found to be associated with several diseases. In contrast to traditional methods using electron donor-containing electrolytes for photoelectrochemical (PEC) sensing, in this study, a target-driven electron donor generation in a PEC electrode was developed to detect GSH. Using well-aligned TiO2 nanotube arrays (TNTs) as the PEC substrate, mesoporous MIL-125(Ti) was grown in the TNTs through an in situ solvothermal method and subsequent two-step annealing treatment. The accommodation capacity of mesoporous MIL-125(Ti) allows a well loading of cystine and Pt nanoclusters (NCs). Taking advantage of the specific cleavage ability of disulfide bonds by GSH, cystine was converted to cysteine, which served as the electron donor for the PEC process. Benefiting from the confinement effect of mesoporous MIL-125(Ti), cysteine was effectively oxidized to cysteine sulfinic acid by the photogenerated holes. Importantly, the highly active Pt NCs decorated in the mesopores not only improved the charge transfer but also accelerated the above oxidation reaction. The synergistic effect of these factors enabled the efficient separation of the photogenerated electron-hole pairs, which induced a significant photocurrent increase and in turn led to the high-sensitivity detection of GSH. Consequently, the proposed PEC biosensor exhibited excellent performance in the detection of GSH in serum specimens. The target-driven electron donor generation designed in this study might open a new route for developing sensitive and selective PEC biosensors with application in complex biological environments.

Single-Nanoparticle-Level Understanding of Oxidase-like Activity of Au Nanoparticles on Polymer Nanobrush-Based Proton Reservoirs.

Enzyme-mimicking nanoparticles play a key role in important catalytic processes, from biosensing to energy conversion. Therefore, understanding and tuning their performance is crucial for making further progress in biological applications. We developed an efficient and sensitive electrochemical method for the real-time monitoring of the glucose oxidase (GOD)-like activity of single nanoparticle through collision events. Using brush-like sulfonate (-SO3-)-doped polyaniline (PANI) decorated on TiO2 nanotube arrays (TiNTs-SPANI) as the electrode, we fabricated a proton reservoir with excellent response and high proton-storage capacity for evaluating the oxidase-like activity of individual Au nanoparticles (AuNPs) via instantaneous collision processes. Using glucose electrocatalysis as a model reaction system, the GOD-like activity of individual AuNPs could be directly monitored via electrochemical tests through the nanoparticle collision-induced proton generation. Furthermore, based on the perturbation of the electrical double layer of SPANI induced by proton injection, we investigated the relationship between the measured GOD-like activities of the plasmonic nanoparticles (NPs) and the localized surface plasmon resonance (LSPR) as well as the environment temperature. This work introduces an efficient platform for understanding and characterizing the catalytic activities of nanozymes at the single-nanoparticle level.

Cascade-Gates Guarded Asymmetrical Nanochannel Membrane: An Interference-Free Device for Straightforward Detection of Trace Biomarker in Undiluted Serum.

Accurate detection of trace biomarkers in biological samples is a key task in diagnostic testing, but it remains challenging due to the high concentration of other physiologically relevant interferences. This work presents a new electrochemiluminescence (ECL) sensing device based on a bio-inspired nanochannel membrane (NM) guarded with two differential gates. The recognition event at the aptamer gate is followed by the permitting of stimulator transport toward the metal-organic framework (MOF) gate. Proof of concept application is evaluated using cytochrome C (Cytc) as the analyte, and glucose, a commonly existing nutriment as the stimulator. The oxidase-mimic plasmonic nanoparticles induce an effective release of ECL luminophore from the MOF gate. This cascade-gates guarded NM can effectively separate biological matrices from the detection cell. Consequently, the proposed system can achieve direct sensing of 1.0 nm Cytc in undiluted serum within the threshold concentrations of leukemia and lymphoma, making it attractive for point-of-care applications.

Plasmon-Mediated Peroxidase-like Activity on an Asymmetric Nanotube Architecture for Rapid Visual Detection of Bacteria.

Rapid and sensitive detection of bacteria from a complex real media remains a challenge. Herein, we report a visual bacterial sensing assay with excellent specificity, anti-interference ability, and sensitivity based on a surface plasmon resonance (SPR)-enhanced peroxidase (POD) mimetic. The POD mimetic based on Pt nanoparticles (NPs) asymmetrically decorated on Au/TiO2 magnetic nanotubes (Au/Pt/MTNTs) is designed by combining the intrinsic photocatalytic activity of TiO2 and the limited transport depth of light. It is revealed that the localized surface plasmon resonance (LSPR) effect of the asymmetric nanotubes is more effective in facilitating the generation of hot electrons, which are subsequently transferred to Pt and MTNTs, thus greatly promoting the catalytic performance. Using Staphylococcus aureus (S. aureus) as a model of Gram-positive bacteria, the dependence of the colorimetric reaction on the active sites of the POD mimetic is used for the sensing of target bacteria. Owing to the specific recognition between S. aureus and peptide, the fluorescein isothiocyanate (FITC) labeled peptide probes are captured by S. aureus and removed from the Au/Pt/MTNTs, leading to the recovery of POD-like activity and fluorescence emission of S. aureus. Particularly, benefiting from the Au-SPR effect and the magnetic feature of the Au/Pt/MTNTs, the recovery of catalytic activity induced an improved colorimetric assay with a wider linear response for S. aureus qualification and a detection limit of four cells, as well as satisfactory selectivity and feasibility for application in real samples. The plasmon-enhanced POD activity would provide a simple-yet-effective approach to achieve a colorimetric bioassay with high efficiency and sensitivity. This asymmetric design can also be utilized to engineer nanozymes in colorimetric assays for the specific detection of biotoxins, biomarkers, and cancer cells.

Near Infrared Light-Driven Photothermal Effect on Homochiral Au/TiO2 Nanotube Arrays for Enantioselective Desorption.

Chiral enantiomers have different effects on biological processes. Enantiomer separation is significant and necessary. Herein, a photothermal (PT) effect-derived enantioselective desorption strategy based on homochiral Au/TiO2 nanotubes (NTs) is developed. Using 3,4-dihydroxyphenylalanine (DOPA) as the model enantiomer, an obvious selective desorption of L/D-DOPA can be achieved by the NIR light-triggered local temperature enhancement. Molecular docking simulation further verifies that the distinct affinity precipitated by the different hydrogen bonds between homochiral sorbent and target enantiomers is the origin of enantioselective desorption. This desorption strategy provides a green and alternative approach for the selective separation of chiral molecules.

Target-Modulated Hydrophobic Precipitation in Photocatalytic Nanochannels for Sensitive Detection of Alpha Fetoprotein.

It is important to detect cancer biomarkers at an early stage of tumor development for the effective diagnosis and treatment of cancer. As a well-known probe for detecting superoxide (·O2-) radicals, nitro blue tetrazolium (NBT) can rapidly react with ·O2- to form a hydrophobic formazan precipitate. In this study, by deliberately utilizing this reaction, Pt asymmetrically decorated on a TiO2 nanochannel membrane (Pt/TiNM) is explored to fabricate an electrochemical immunosensing platform with outstanding selectivity and ultrahigh sensitivity. Using NBT as the substrate, hydrophobic formazan precipitation induces a substantial block of ionic diffusion flux in nanochannels. Using alpha fetoprotein (AFP) as the target analyte, the established immunorecognition event was used to induce MoS2-Ab2 conjugates. Thanks to the excellent light-shielding ability of MoS2 nanosheets, the production of ·O2- radicals from the photocatalysis of Pt/TiNM is effectively depressed because of the attenuated arrival of light. The reduced formazan precipitation results in ionic transport changes in nanochannels, which in turn enables the selective recognition of AFP down to 2 ng mL-1. This target-modulated sensing strategy is also capable of sensing other immune targets, thus paving a new way for designing nanochannel-based sensing platforms.

Photocatalysis engineered hydrophilic reactors on hydrophobic paper for the visual and colorimetric assay of alkaline phosphatase activity.

Taking advantage of the intrinsic photocatalysis of TiO2, hydrophilic reactor arrays were lithographically patterned on a hydrophobic paper via a simple UV irradiation. As a proof-of-concept, alkaline phosphatase (ALP) was used as the model analyte for colorimetric analysis. As ALP can induce hydrolysis of pyrophosphate-Zn(II) framework, the released Zn2+ ions are subsequently coordinated with red-colored zincon to form blue-colored zincon-Zn(II) chelate complex, and these color differences were applied for further colorimetric assay. The sensing platform showed response to ALP ranging from 20 ~ 800 U L-1 with a detection limit of 3 U L-1, and the recoveries of ALP in serum samples were in the range 95.7 ~ 104.5% with relative standard deviations from 2.10 to 3.84%. Additionally, the distinct wettability features of the proposed sensing platform effectively prevent lateral fluid spread out of hydrophilic reactors, thus allowing not only the use of minimum amount of analyte but it has also a high potential for simultaneous quantification of multiple samples.

Construction of Peroxidase-like Metal-Organic Frameworks in TiO2 Nanochannels: Robust Free-Standing Membranes for Diverse Target Sensing.

The high cost and easy denaturation of natural enzymes under environmental conditions hinder their practical usefulness in sensing devices. In this study, peroxidase (POD)-like metal-organic frameworks (MOFs) were in situ grown in the nanochannels of an anodized TiO2 membrane (TiO2NM) as an electrochemical platform for multitarget sensing. By directly using a nanochannel wall as the precursor of metal nodes, Ti-MOFs were in situ derived on the nanochannel wall. Benefitting from the presence of bipyridine groups on the ligands, the MOFs in the nanochannels provide plenty of sites for Fe3+ anchoring, thus endowing the resulting membrane (named as Fe3+:MOFs/TiO2NM) with remarkable POD-like activity. Such Fe3+-induced POD-like activity is very sensitive to thiol-containing molecules owing to the strong coordination effect of thiols on Fe3+. Most importantly, the POD-like activity of nanochannels can be in situ characterized by the current-potential (I-V) properties via catalyzing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) substrate to the corresponding positively charged product ABTS•+. As a proof-of-concept application, the free-standing POD-like membranes were applied as a label-free assay in sensing cysteine, as well as monitoring acetylcholinesterase (AChE) activity through the generated thiol-containing product. Furthermore, based on the toxicity effect of organophosphorus (OP) compounds on AChE, the robust membranes were successfully utilized to evaluate the toxicity of diverse OP compounds. The POD-like nanochannels open up an innovative way to expand the application of nanochannel-based electrochemical sensing platforms in drug inspection, food safety, and environmental pollution.

Fabrication of Homochiral Metal-Organic Frameworks in TiO2 Nanochannels for In Situ Identification of 3,4-Dihydroxyphenylalanine Enantiomers.

Enantioselective identification of chiral molecules is important for biomedical and pharmaceutical research. However, owing to identical molecular formulas and chemical properties of enantiomers, signal transduction and amplification are still the two major challenges in chiral sensing. In this study, we developed an enantioselective membrane by integrating homochiral metal-organic frameworks (MOFs) with nanochannels for the sensitive identification and quantification of chiral compounds. The membrane was designed using a TiO2 nanochannel membrane (TiNM) as the metal ion precursor of MOFs (using MIL-125(Ti)) and incorporating l-glutamine (l-Glu) into the framework of MIL-125(Ti). Using 3,4-dihydroxyphenylalanine (DOPA) as the model analyte, the as-prepared homochiral l-Glu/MIL-125(Ti)/TiNM exhibits a remarkable chiral recognition to d-DOPA than l-DOPA. More importantly, benefiting from the highly enlarged surface area and confinement effect provided by the MOFs-in-nanochannel architecture, the discrimination for chiral recognition is largely amplified through the chelation interaction of Fenton-like activity of Fe3+ onto DOPA. Using 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as the substrate, the positively charged ABTS•+ product via Fenton-like reaction induces significant ionic transport changes in nanochannels, which in turn provides information about chiral recognition. This innovative signal amplification strategy on homochiral nanochannels might pave a new way for sensitive monitoring and chiral recognition.

Deployment of MIL-88B(Fe)/TiO2 Nanotube-Supported Ti Wires as Reusable Electrochemiluminescence Microelectrodes for Noninvasive Sensing of H2O2 from Single Cancer Cells.

As one of the significant intracellular signaling molecules, hydrogen peroxide (H2O2) regulates some vital biological processes. However, it remains a challenge to develop noninvasive electrodes that can be used for sensing trace H2O2 at the cellular level. Here, we evaluated a high-performance solid-state electrochemiluminescence (ECL) H2O2 sensor based on MIL-88B(Fe) nanocrystal-anchored Ti microwires. Semiconducting TiO2 nanotubes (TiNTs) vertically grown around a Ti wire via an anodization technique act as an intrinsic ECL luminophore. By integrating with MIL-88B(Fe), the synergistic effect of the TiO2 luminophore and the remarkable peroxidase-like activity of MIL-88B(Fe) enable the resulting H2O2 sensor an ultrahigh sensitivity featuring a minimum detection limit of 0.1 nM (S/N = 3), long-term stability, high durativity, and wide-range linear response to a concentration of up to 10 mM. To demonstrate the concept of a MIL-88B(Fe)@TiO2 microelectrode for single-cell sensing, the electrode was used to detect intracellular H2O2 in a single cell. Moreover, benefiting from the heterojunction of MIL-88B(Fe)/TiO2, the microelectrode was found to exhibit excellent photocatalytic activity in the visible-light range, that is, the sensor surface can be self-cleaning after a short visible-light treatment. These advanced sensor characteristics involving easy reusability reveal that the MIL-88B(Fe)@TiO2 microelectrode is a new platform for cytosensing. This study provides a new strategy to design semiconductor materials with arbitrary shape and size, allowing for profound applications in biomedical and clinical analysis.

Engineering Homochiral MOFs in TiO2 Nanotubes as Enantioselective Photoelectrochemical Electrode for Chiral Recognition.

Enantioselective sensing of chiral molecules is an important issue for both biomedical research and the pharmaceutical industry. Here, an enantioselective photoelectrochemical (PEC) sensor was constructed by integrating TiO2 nanotubes (NTs) with metal-organic frameworks (MOFs) for the identification of enantiomers. TiO2 NTs prepared by electrochemical anodization can not only be used as the PEC platform but also as the metal-ion precursor to react with terephthalic acid (BDC) to form MIL-125(Ti) in situ. A postsynthetic exchange (PSE) method was used for exchanging the ligand of MIL-125 by 2-aminoterephthalic acid (BDC-NH2) for further functionalization. Homochirality was then successfully introduced into achiral MIL-125-NH2 by postsynthetic modification (PSM) with l-histidine (l-His). The resulting homochiral metal-organic frameworks (MOF)-in-NT architecture exhibits excellent discrimination ability for the chiral recognition of 3,4-dihydroxyphenylalanine (l/d-DOPA) enantiomers. Moreover, by adjusting the charge-carrier separation-induced photocurrent variation mechanism, the as-proposed homochiral PEC electrode exhibits a broad application potential for the discrimination of enantiomers. Because of the construction of binder-free monochiral MOF-in-NT structure directly on a Ti-metal substrate, the valuable feature is that the PEC sensing platform can be used directly, thereby providing a stable, simplified, and low-cost sensing device for the recognition of chiral enantiomers.

Wireless Battery-Free Generation of Electric Fields on One-Dimensional Asymmetric Au/ZnO Nanorods for Enhanced Raman Sensing.

Wearable electronics have great potential in enhancing health monitoring, disease diagnosis, and environmental pollution tracking. Development of wearable surface-enhanced Raman spectroscopy (SERS) substrates with target sampling and sensitive sensing functions is a promising way to obtain physical and chemical information. This study describes a facile and effective approach for constructing an electrically modulated SERS (E-SERS) substrate as a wearable and wireless battery-free substrate with improved sensitivity. By integrating zinc oxide nanorods (ZnO NRs) with asymmetric gold decoration, controllable enhanced piezoelectric potentials were achieved using magnets to supply the adjustable pressure force. Owing to spatially oriented electron-hole pair separation on the asymmetric NRs, the local hotspot intensity at the Au tips is significantly improved, increasing the SERS signal by 6.7 times. This mechanism was quantitatively analyzed using Raman spectra by in situ formation of Prussian blue (PB). As a proof-of-concept, the E-SERS substrate was further used as a wearable flexible device to directly collect the sweat on a runner's skin and then monitor the lactate status of the runner. This study offers new insight into the development of E-SERS substrates and provides new design options for the construction of wearable sampling and sensing devices for the noninvasive monitoring of metabolites in healthcare and biomedical fields.

TiO2 Nano-test tubes as a solid visual platform for sensitive Pb2+ ion detection based on a fluorescence resonance energy transfer (FRET) process.

A cost-effective, facile, and sensitive fluorescence sensing strategy for Pb2+ ion detection has been developed based on the fluorescence resonance energy transfer (FRET) between carbon quantum dots (CQDs) and Au nanoparticles (NPs). Glutathione (GSH)-synthesized CQDs acted as both the fluorescence donor and the sorbent to extract Pb2+ ions from the solution via Pb-GSH complexes. Pb2+ ions on CQDs reacted with -SH groups on AuNPs to generate sandwich-type Au-PdS-CQDs, leading to a dramatic decrease in the fluorescence of the CQDs. To expand the potential applications of this strategy, we constructed a sensing strategy using self-organized TiO2 nanotube arrays (TiNTs). The high aspect ratio and transparency for light emitted from the CQDs enabled the TiNTs to serve as a sensitive solid visual platform for the highly selective detection of Pb2+ ions with a detection limit as low as 4.1 × 10-8 mg mL-1. More importantly, the long observation length combined with a small volume enabled a sample acquisition volume of only 2.1 × 10-3 µL, which is smaller than the traditional fluorescence analysis in solution and on commercially available test paper, thus endowing this visual platform with the potential for use in single-cell diagnostics.

Intracellular Metal-Organic Frameworks: Integrating an All-In-One Semiconductor Electrode Chip for Therapy, Capture, and Quantification of Circulating Tumor Cells.

Capture, analysis, and inactivation of circulating tumor cells (CTCs) have emerged as important issues for the early diagnosis and therapy of cancer. In this study, an all-in-one sensing device was developed by integrating magnetic metal-organic framework (magMOF) nanoparticles (NPs) and TiO2 nanotube arrays (TiNTs). The magMOF NPs are composed of a magnetic Fe3O4 core and a MIL-100(Fe) shell, which is loaded with glucose oxidase (GOD) and provides an intensive starvation therapy by catalyzing the consumption of cellular nutrients, thus accelerating the generation of intracellular iron ions by MIL-100(Fe) dissolution. Importantly, these iron ions not only lead to an intensive Fenton-like reaction but also establish an excellent correlation of electrochemical intensities with cancer cell numbers. Owing to the intracellular magMOF NPs, the CTCs were magnetically collected onto TiNTs. The exogenous ·OH radicals generated by TiNT photocatalysis trigger iron ions to be rapidly released out and subsequently detected via differential pulse voltammetry using TiNTs as the electrode. An excellent correlation of differential pulse voltammetry intensities with CTC numbers is obtained from 2 to 5000 cell mL-1. This nanoplatform not only paves a way to combine starvation therapy agents with Fenton-like reaction for chemodynamic therapy but also opens up new insights into the construction of all-in-one chips for CTC capture and diagnosis.

Target-Driven Nanozyme Growth in TiO2 Nanochannels for Improving Selectivity in Electrochemical Biosensing.

Nanozymes have been used in colorimetric and electrochemical sensing because of their low cost and high stability. However, the wide applications of nanozymes in sensing devices are largely limited due to their poor selectivity. In this study, unlike traditional methods using prepared nanozymes for target detection, we designed a target-driven nanozyme growth strategy in TiO2 nanochannels to detect analytes. Using telomerase as an example, the established recognition event was used to expand the photocatalytic activity of TiO2 to visible-light region, thus triggering Prussian blue nanoparticle (PBNP) growth in visible light. Benefiting from the peroxidase (POD)-like activity of PBNPs, the uncharged 3,5,3',5'-tetramethylbenzidine (TMB) is oxidized to positively charged oxTMB, which induces significant ionic transport changes in nanochannels, and thus in turn provides information about telomerase activity. Such a nanozyme-triggered sensing system exhibited excellent performance in telomerase detection in urine specimens from patients with bladder cancer. This innovative target-driven signal generation strategy might provide a new method for applying nanozymes in developing sensitive, rapid, and accurate biological sensing systems.