In-situ construction of hollow double-shelled CoSx@CdS nanocages with prominent photoelectric response for highly sensitive photoelectrochemical biosensor.

In this work, we demonstrate a delicate design and construction of hollow double-shelled CoSx@CdS nanocages (CoSx@CdS-HDSNCs) as an efficient and stable photoactive material of photoelectrochemical (PEC) biosensor for detecting cardiac troponin I (cTnI). The novel self-templated strategy started with ZIF-67, in which two distinct sulfide semiconductors were integrated into a hollow heterojunction with uniform interfacial contacts after sequential anion and cation exchange. The unique thin double shell hollow structure, suitable energy band arrangement and stable electron transmission vastly enhanced the ability of light capture and photogenerated electron-hole separation of biosensor. Subsequently, the photoelectric performance of the heterojunction was further enhanced by the deposition of Au nanoparticles (NPs) on the surface of the CoSx@CdS-HDSNCs resulting in surface plasmon resonance (SPR) effect. Based on the excellent CoSx@CdS-HDSNCs, the biosensor exhibits a high sensitivity for detection of cTnI with a wide linear range (0.00016-16 ng mL-1) and low detection limit (38.6 fg mL-1). Besides, the PEC biosensor exhibited satisfactory stability, selectivity, and reproducibility in human serum. And more importantly, our work may provide more unique inspiration for the design of photoactive materials for the future PEC sensing applications.

Rational Design of PDA/P-PVDF@PP Janus Membrane with Asymmetric Wettability for Switchable Emulsion Separation.

Water pollution caused by oil spills or sewage discharges has become a serious ecological environmental issue. Despite the membrane separation technique having a promising application in wastewater purification, the membrane fabrication method and separation robustness have remained unsatisfactory until now. Herein, we developed a novel strategy, spacer-assisted sequential phase conversion, to create a patterned polyvinylidene fluoride@polypropylene (P-PVDF@PP) substrate membrane with a multiscale roughened surface. Based on that surface structure, the underwater oil resistance behavior of the P-PVDF@PP membrane was improved. Moreover, owing to the abundant active sites on the P-PVDF@PP surface, the polydopamine/P-PVDF@PP (PDA/P-PVDF@PP) Janus membrane could be readily fabricated via wet chemical modification, which exhibited excellent switchable oil-water separation performance. Regarding surfactant-stabilized oil-water emulsion, the as-prepared PDA/P-PVDF@PP Janus membrane also had robust separation efficiency (as high as 99% in the n-hexane/water, chloroform/water, and toluene/water emulsion separation cases) and desirable reusability. Finally, the underlying mechanism of emulsion separation in the PDA/P-PVDF@PP Janus membrane was specified. The as-designed PDA/P-PVDF@PP Janus membrane with high-efficiency oil-water separation shows potential application in oily wastewater treatment, and the developed fabrication method has implications for the fabrication of advanced separation membranes.

An enhanced photoelectrochemical biosensor for colitoxin DNA based on HKUST-1/TiO2 and derived HKUST-CuO/TiO2 heterogeneous composites.

HKUST-1 MOFs and its derivative HKUST-CuO were coupled with TiO2 nanoparticles to form the heterogeneous composites of HKUST-1/TiO2 and HKUST-CuO/TiO2 based on their well-suitable bandgap energies (Eg). Compared with mono-component HKUST-1 or HKUST-CuO, the prepared composites displayed photoelectrochemical (PEC) response due to the synergistic effect from their heterogeneous structure. Higher photocurrent response was obtained on HKUST-CuO/TiO2-modified ITO electrode (HKUST-CuO/TiO2/ITO), which could be attributed to the hollow structure with a thin shell of HKUST-CuO greatly enhancing visible spectra harvesting. The CuO component in HKUST-CuO not only could accelerate electron transfer on the heterojunction interface but also effectively separate the photo-generated charge carriers (e-1/h+). Based on the excellent PEC performance of prepared photoactive composite material, under visible-light excitation (λ ≥ 420 nm) and with a working potential of 0 V (vs. Ag/AgCl), the S1 (probe DNA)/HKUST-CuO/TiO2/ITO PEC platform was successfully fabricated for colitoxin DNA detection without using ascorbic acid (AA) as an electron donor. Compared with the analysis results on S1/HKUST-1/TiO2/ITO electrode, S1/HKUST-CuO/TiO2/ITO displayed a wider linear response range from 1.0 × 10-6 to 4.0 × 10-1 nM with a lower detection limit of 3.73 × 10-7 nM (S/N = 3), the linear regression equation was ΔI (10-6 A) =0.5549-0.1858 log (CS2/M), which confirmed the HKUST-CuO could improve sensitivity because of its prominent PEC property. The relative standard deviation (RSD) of the PEC sensor for target DNA detection of 2.0 × 10-4 nM was 7.4%. The proposed DNA biosensor also possessed good specificity and stability. Hence, this reported work was a promising strategy for molecular diagnosis in the bio-analysis field. (A) Schematic illustration of the preparation process of the proposed PEC biosensors for colitoxin DNA detection. (B) The preparation process of HKUST-1 and HKUST-CuO.

Design of ultrathin nanosheet subunits ZnIn2S4 hollow nanocages with enhanced photoelectric conversion for ultrasensitive photoelectrochemical sensing.

Herein, a high-efficiency photoactive material, hollow ZnIn2S4 nanocages (ZIS-HNCs) composed of ultrathin nanosheets were creatively synthesized via a metal-organic framework (MOF) derived solvothermal method. It had been specified the underlying mechanism of the ZIS-HNCs evolution under the MOF templated surface. Subsequently, the obtained ZIS-HNCs combined with annealing TiO2 modified electrode (ZIS-HNCs@TiO2), and the ZIS-HNCs@TiO2 exhibited intense transient photocurrent. The enhanced photocurrent signal benefited from the multiple light capture effect of ZIS-HNCs, ultrathin nanosheet subunits of ZIS-HNCs, and typical type Ⅱ heterojunction, which could effectively retard the photoexcited electron-hole pairs recombination, and accelerated charge separation and transfer. Taking antibiotic lincomycin (Lin) as a model, a signal-off photoelectrochemical (PEC) aptasensor based on the ZIS-HNCs@TiO2 was established and manifested a high sensitive detection for Lin with a linear response range from 0.0001 to 0.1 nM as well as an ultralow detection limit of 0.084 pM. Additionally, the proposed PEC aptasensor showed acceptable stability and remarkable selectivity. Therefore, this study provides a promising strategy to design nanomaterials with superior photoelectric activity for PEC sensing applications.

Porous hollow carbon nanobubbles@ZnCdS multi-shelled dodecahedral cages with enhanced visible-light harvesting for ultrasensitive photoelectrochemical biosensors.

Herein, novel photoactive materials, MOF-derived porous hollow carbon nanobubbles@ZnCdS multi-shelled dodecahedral cages (C@ZnCdS MSDCs)， were synthesized via continuous chemical etching, sulfurization, cation-exchange and calcination strategies. Due to the synergistic effect between the porous shells and the carbon-layer coating， C@ZnCdS MSDCs displayed superior photoelectrochemical (PEC) performance. The synthesized C@ZnCdS MSDCs were assembled onto TiO2 modified ITO electrodes to form a type-II heterostructures. Then, Au nanoparticles (NPs) were deposited on the surface of ITO/TiO2/C@ZnCdS MSDCs. Benefiting from the unique structure and performance merits of photoactive materials, a label-free PEC sensing platform based on ITO/TiO2/C@ZnCdS MSDCs/Au was successfully constructed for CEA detection. Under optimal conditions, the PEC biosensor exhibited a wide linear range (0.00005-500 ng mL-1) and low detection limit (2.28 fg mL-1). The proposed PEC biosensor also showed good stability, specificity, reproducibility and acceptability in human serum. The prepared C@ZnCdS MSDCs would be a promising photoactive material for PEC biosensors. Most importantly, this work opens up new horizons for the application of MOFs-derived hollow carbon materials in sensing.