Anion Exchange in Semiconductor Magic-Size Clusters.

Ion exchange is an effective postsynthesis strategy for the design of colloidal nanomaterials with unique structures and properties. In contrast to the rapid development of cation exchange (CE), the study of anion exchange is still in its infancy and requires an in-depth understanding. Magic-size clusters (MSCs) are important reaction intermediates in quantum dot (QD) synthesis, and studying the ion exchange processes can provide valuable insights into the transformations of QDs. Here, we achieved anion exchange in Cd-based MSCs and elucidated the reaction pathways. We demonstrated that the anion exchange was a stepwise intermolecular transition mediated by covalent inorganic complexes (CICs). We proposed that this transition involved three essential steps: the disassembly of CdE1-MSCs into CdE1-CICs (step 1), an anion exchange reaction from CdE1-CICs to CdE2-CICs (step 2), and assembly of CdE2-CICs to CdE2-MSCs (step 3). Step 3 was the rate-determining step and followed first-order reaction kinetics (kobs = 0.01 min-1; from CdSe-MSCs to CdS-MSCs). Further studies revealed that the activity of foreign anions only affected the reaction kinetics without altering the reaction pathway. The present study provides a deeper insight into the anion exchange mechanisms of MSCs and will further shed light on the synthesis of QDs.

Anisotropic Growth of Covalent Inorganic Complexes to Nanoplatelets.

Colloidal II-VI semiconductor nanoplatelets (NPLs) provide a new platform in material science due to their unique growth mode and advanced optical properties. However, in contrast to the rapid development of zinc blend structured NPLs, studies on the formation of wurtzite (WZ) NPLs have been limited to the lamellar assembly of specific magic-sized nanoclusters (MSCs). Therefore, the study of new precursors is important for enriching the synthesis strategy, improving the study of two-dimensional (2D) nanocrystal growth mechanisms, and constructing complex nanostructures. Here, we demonstrated that covalent inorganic complexes (CICs), as novel functional intermediates, can be directly used to form NPLs without involving MSCs. Using in situ absorption spectra, we demonstrated that the evolution followed a pseudo-first-order kinetics (kobs = 0.02 min-1 (t1/2 = 34.7 min)). Several types of binary WZ NPLs, including CdSe, CdS, CdTe, and ZnS, have been directly prepared based on this mechanism through the anisotropic growth of CICs. In addition, CICs can also be used to prepare Mn-doped CdSe NPLs. The present study not only affords new precursors for the synthesis of WZ NPLs but also advances our understanding of the synthesis mechanism of nanocrystals.

Biofuel Cell-Driven Robust Electrochemiluminescence Biosensing Platform.

Electrochemiluminescence (ECL) is one powerful tool in the sensing field, in which the electrochemical workstation is necessary to achieve the electrical/optical signal conversion in the presence of luminescent agents. By contrast, biofuel cells (BFCs) can also provide electricity from renewable biofuels under moderate conditions. More importantly, BFCs with the features of adjustable voltage output and excellent compatibility would well meet the requirement of working voltages for different ECL devices. However, to the best of our knowledge, the BFC-driven luminous system has not been reported. In this work, we constructed, for the first time, a BFC-driven ECL system with fast and stable signal outputs. To demonstrate the proof-of-concept of the BFC-ECL system, the sensitive and selective detection of histidine was achieved, exhibiting great potential among point-of-care diagnoses in remote regions. Overall, this work not only paves a new way for the conversion of chemical energy, electrical energy, and luminous system but also explores the new application of BFC.

Self-Photocatalysis Boosted Electrochemiluminescence Signal Amplification via In Situ Generation of the Coreactant.

The classic luminol-based electrochemiluminescence (ECL) platform generally suffers from self-decomposition of the coreactant (i.e., H2O2) during the reaction process, seriously hampering the luminous signal stability, as well as its practical application. To address this issue, apart from the introduction of complex exogenous species, preoxidation of the luminophore, and electrocatalysis for ECL signal amplification, we proposed a novel ECL model to realize the signal enhancement via in situ self-photocatalytic generation of the coreactant H2O2. Interestingly, the luminescence of luminol was simultaneously utilized as the light source to promote the conversation of O2 to H2O2 with the assistance of the photocatalyst resorcinol-formaldehyde resin, which could further improve the luminescence of luminol in turn. In comparison with the traditional case, this new ECL model not only exhibited obvious signal amplification but also efficiently boosted its stability of signal output. To sum up, an exogenous coreactant-free, highly stable ECL platform was obtained via simply integrating the photocatalyst RF and the luminol-based system. This work will not only inspire the design of a new integrated ECL system with a coreactant translator but also provide an ingenious insight for the construction of a new generation of ECL models.

Self-Powered Biosensing Platform Based on "Signal-On" Enzymatic Biofuel Cell for DNA Methyltransferase Activity Analysis and Inhibitor Screening.

Aberrant DNA methylation catalyzed by DNA methyltransferases (MTase) has proved to be associated with human diseases such as cancers. Thus, the development of an efficient strategy to accurately detect DNA MTase is highly desirable in medical diagnostics. Herein, we proposed a robust "signal-on" enzymatic biofuel cell (EBFC)-based self-powered biosensing platform with excellent anti-interference ability for DNA MTase activity analysis and inhibitor screening. In the presence of target MTase, the MTase-catalyzed DNA methylation occurred and hindered the HpaII endonuclease-catalyzed dsDNA dissociation, which enabled more bilirubin oxidase (BOD) to immobilize at the cathode surface via amidation. Then, BOD-catalyzed oxygen reduction took place by accepting electrons generated at the anode via glucose oxidation, thus leading to an elevated open-circuit voltage value, the amplitude of which was directly related to MTase concentration. The direct detection limit of the M.SssI assay was down to 0.005 U/mL, which was lower than that of those reported results. Notably, the as-proposed protocol was competent to detect DNA MTase activity directly in human serum samples without enrichment and separation, and applicable to the screening of M.SssI inhibitors. Considering the virtues of the excellent anti-interference ability, no requirement of external power, simplicity, and high accuracy, the biosensing platform would hold great potential in DNA MTase bioassay and clinical diagnosis of cancers.

Enzymatic Biofuel-Cell-Based Self-Powered Biosensor Integrated with DNA Amplification Strategy for Ultrasensitive Detection of Single-Nucleotide Polymorphism.

Enzymatic biofuel cell (EBFC)-based self-powered biosensors could offer significant advantages: no requirement for an external power source, simple instruments, and easy miniaturization. However, they also suffered from the limitations of lower sensitivity or specific targets. In this study, a self-powered biosensor for the ultrasensitive and selective detection of single nucleotide polymorphisms (SNPs) produced by combining the toehold-mediated strand displacement reaction (SDR) and DNA hybridization chain reaction (HCR) was proposed. Herein, the capture probe (CP) with an external toehold was designed to switch on the sensing system. In the presence of target sequence, both SDR and DNA HCR reaction would happen to produce a long double-helix chain. Because of the electrostatic interaction between [Ru(NH3)6]3+ and the double-helix chain described above, the open circuit voltage ( EOCV) of the as-proposed biosensor was significantly elevated, thus realizing the detection of SNPs. Overall, in this work, an ingeniously constructed self-powered biosensor for the detection of SNPs was created by integrating EBFCs with a DNA amplification strategy. Furthermore, the as-proposed self-powered biosensor not only showed prominent specificity to distinguish the p53 gene fragment from random sequences (e.g., single-base mutant sequences) but exhibited excellent sensitivity with the detection limit of 20 aM. More importantly, the results obtained from the real cell lysate sample have laid a strong foundation for disease diagnostics and, potentially, as a powerful tool for even more fields.

Covalent inorganic complexes enabled zinc blende to wurtzite phase changes in CdSe nanoplatelets.

Phase changes in colloidal semiconductor nanocrystals (NCs) are essential in material design and device applications. However, the transition pathways have yet to be sufficiently studied, and a better understanding of the underlying mechanisms is needed. In this work, a complete ligand-assisted phase transition from zinc blende (ZB) to wurtzite (WZ) is observed in CdSe nanoplatelets (NPLs). By monitoring with in situ absorption spectra along with electrospray ionization mass spectrometry (ESI-MS), we demonstrated that the transition process is a ligand-assisted covalent inorganic complex (CIC)-mediated phase transition pathway, which involves three steps, ligand exchange on ZB CdSe NPLs (Step 1), dissolution of NPLs to form CICs (Step 2), and conversion of CdSe-CIC assemblies to WZ CdSe NPLs (Step 3). In particular, CICs can be directly anisotropically grown to WZ CdSe NPL without other intermediates, following pseudo-first-order kinetics (kobs = 9.17 × 10-5 s-1). Furthermore, we demonstrated that CICs are also present and play an essential role in the phase transition of ZnS NPLs from WZ to ZB structure. This study proposes a new crystal transformation pathway and elucidates a general phase-transition mechanism, facilitating precise functional nanomaterial design.

Biohybrid Cells for Photoelectrochemical Conversion Based on the HCOO--CO2 Circulation Approach.

Biohybrid photoelectrochemical systems could combine the light-harvesting ability of semiconductor photocatalysts and the CO2-processing capability of biocatalysts to realize CO2 reduction. How to develop the energy-utilized model can be of importance for the mechanism exploration of photosynthesis. Here, a biohybrid photoelectrochemical system based on HCOO--CO2 circulation was developed to realize the conversion both of solar-to-electric energy and chemical-to-electric energy. The device consists of a TiO2 nanoparticle photoanode and a laser-scribed graphene/formate dehydrogenase biocathode, which was utilized for the formic acid oxidation and the biocatalysis reduction of CO2 to HCOO-, respectively. The as-proposed biohybrid photoelectrochemical system exhibits good performance with an open-circuit potential of 0.93 V and a maximum power output density of 76 µW cm-2. This ingenious strategy not only exploits a robust carbon circulation system for the conversion of solar energy but also provides a way of constructing complex artificial photosynthesis systems.

Anode-Driven Controlled Release of Cathodic Fuel via pH Response for Smart Enzymatic Biofuel Cell.

Enzymatic biofuel cells (EBFCs) with or without a membrane to separate the anodic and cathodic compartments generally suffered from high internal resistance or interactive interference, both of which restricted the improvement of their performance. Herein, a smart membrane-less EBFC was engineered based on anode-driven controlled release of cathodic acceptor via pH-responsive metal-organic framework ([Fe(CN)6]3-@ZIF-8) nanocarriers. The glucose anodic oxidation would produce gluconic acid accompanied by the change in pH value from neutral to the acidic case, which could drive the degradation of [Fe(CN)6]3-@ZIF-8 nanocarriers and further realize the controlled release of cathodic acceptor [Fe(CN)6]3-. More importantly, compared with controlled EBFC with or without membrane, the power output of the as-proposed EBFC enhanced at least 700 times due to the seamless electronic communication. Therefore, the ingenious strategy not only realized the successful engineering of the membrane-less EBFC but also provided an appealing idea for constructing smart devices.

Photo-driven self-powered biosensor for ultrasensitive microRNA detection via DNA conformation-controlled co-sensitization behavior.

We successfully developed a photoelectrochemical enzymatic fuel cell (PEFC)-based self-powered biosensing platform for microRNA detection via DNA conformation change-controlled co-sensitization behavior, which could offer ultrasensitive detection of microRNA down to 0.05 fM and realize microRNA determination in human serum.