Microenvironment reconstitution of highly active Ni single atoms on oxygen-incorporated Mo2C for water splitting.

The rational design of efficient bifunctional single-atom electrocatalysts for industrial water splitting and the comprehensive understanding of its complex catalytic mechanisms remain challenging. Here, we report a Ni single atoms supported on oxygen-incorporated Mo2C via Ni-O-Mo bridge bonds, that gives high oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) bifunctional activity. By ex situ synchrotron X-ray absorption spectroscopy and electron microscopy, we found that after HER, the coordination number and bond lengths of Ni-O and Ni-Mo (Ni-O-Mo) were all altered, yet the Ni species still remain atomically dispersed. In contrast, after OER, the atomically dispersed Ni were agglomerated into very small clusters with new Ni-Ni (Ni-O-Ni) bonds appeared. Combining experimental results and DFT calculations, we infer the oxidation degree of Mo2C and the configuration of single-atom Ni are both vital for HER or OER. This study provides both a feasible strategy and model to rational design highly efficient electrocatalysts for water electrolysis.

Augmentations in Hypergraph Contrastive Learning: Fabricated and Generative.

This paper targets at improving the generalizability of hypergraph neural networks in the low-label regime, through applying the contrastive learning approach from images/graphs (we refer to it as HyperGCL). We focus on the following question: How to construct contrastive views for hypergraphs via augmentations? We provide the solutions in two folds. First, guided by domain knowledge, we fabricate two schemes to augment hyperedges with higher-order relations encoded, and adopt three vertex augmentation strategies from graph-structured data. Second, in search of more effective views in a data-driven manner, we for the first time propose a hypergraph generative model to generate augmented views, and then an end-to-end differentiable pipeline to jointly learn hypergraph augmentations and model parameters. Our technical innovations are reflected in designing both fabricated and generative augmentations of hypergraphs. The experimental findings include: (i) Among fabricated augmentations in HyperGCL, augmenting hyperedges provides the most numerical gains, implying that higher-order information in structures is usually more downstream-relevant; (ii) Generative augmentations do better in preserving higher-order information to further benefit generalizability; (iii) HyperGCL also boosts robustness and fairness in hypergraph representation learning. Codes are released at https://github.com/weitianxin/HyperGCL.

Detection of 17ß-estradiol in water samples by a novel double-layer molecularly imprinted film-based biosensor.

This study reports a novel double-layer molecularly imprinted film (MIF)-based biosensor for rapid, sensitive and highly selective detection of small molecule 17ß-estradiol (E2) that is frequently detected in environmental water samples. In this system, the modification of gold surface of SPR chip was performed by 1-dodecanethiol. Then double-layer MIF was generated on the 1-dodecanethiol modified gold surface. The non-modified and imprinted surfaces were characterized by atomic force microscopy (AFM), scanning electron microscope (SEM) and contact angle measurements. Analysis of surface plasmon resonance (SPR) spectroscopy showed that the imprinted sensing film displayed good selectivity for E2 compared to other analog molecules and NIF. A good linear relationship was obtained between the SPR angle and E2 concentrations over a range of 2.50×10(-13)-2.50×10(-)(9)mol/L (R(2)=0.993) with the lowest measurable concentration of 2.50×10(-13)mol/L. The sensor can be regenerated with the mixture of acetic acid and PBS buffer (v/v=1:9) as a desorption agent over tens of times without significant deterioration of the sensor performance. Potential interference of real environmental sample matrix was assessed by spiked samples in several waste seawater effluents. This portable sensor system can be successfully applied for on-site real-time inexpensive and easy-to-use monitoring of E2 or other small molecule pollutants in environmental samples such as effluents or water bodies.

Surface plasmon resonance sensor for femtomolar detection of testosterone with water-compatible macroporous molecularly imprinted film.

A novel water-compatible macroporous molecularly imprinted film (MIF) has been developed for rapid, sensitive, and label-free detection of small molecule testosterone in urine. The MIF was synthesized by photo copolymerization of monomers (methacrylic acid [MAA] and 2-hydroxyethyl methacrylate [HEMA]), cross-linker (ethylene glycol dimethacrylate, EGDMA), and polystyrene nanoparticles (PS NPs) in combination with template testosterone molecules. The PS NPs and template molecules were subsequently removed to form an MIF with macroporous structures and the specific recognition sites of testosterone. Incubation of artificial urine and human urine on the MIF and the non-imprinted film (NIF), respectively, indicated undetectable nonspecific adsorption. Accordingly, the MIF was applied on a surface plasmon resonance (SPR) sensor for the detection of testosterone in phosphate-buffered saline (PBS) and artificial urine with a limit of detection (LOD) down to 10(-15)g/ml. To the best of our knowledge, the LOD is considered as one of the lowest among the SPR sensors for the detection of small molecules. The control experiments performed with analogue molecules such as progesterone and estradiol demonstrated the good selectivity of this MIF for sensing testosterone. Furthermore, this MIF-based SPR sensor shows high stability and reproducibility over 8months of storage at room temperature, which is more robust than protein-based biosensors.

Biosensor based on hydrogel optical waveguide spectroscopy for the detection of 17ß-estradiol.

Rapid detection of hormones at sub-ng/ml concentrations is of tremendous importance for diagnostic purposes, quality control, and environmental monitoring. In this respect, we report a novel label-free biosensor based on hydrogel optical waveguide spectroscopy (HOWS) for the sensitive detection of 17ß-estradiol (E2). This approach was implemented by using a thin hydrogel layer of a carboxylated poly(N-isoproprylacrylamide) (PNIPAAm) terpolymer that was attached to a metallic sensor surface in order to simultaneously serve as a binding matrix and an optical waveguide. Refractive index changes that are accompanied with the specific capture of biomolecules from an aqueous sample on the sensor surface were probed by resonantly excited hydrogel optical waveguide modes. To optically excite and interrogate these waves, an optical setup based on Kretschmann configuration of attenuated total reflection (ATR) method that is compatible with surface plasmon resonance (SPR) was used. We demonstrate that HOWS offers a higher binding capacity, good anti-fouling properties, improved figure of merit, and E2 detection limit of 50 pg/ml which is seven times better than that obtained by a regular surface plasmon resonance (SPR) biosensor.

Adsorption behaviors of cationic surfactants and wettability in polytetrafluoroethylene-solution-air systems.

Measurements of the advancing contact angle (θ) and adsorption properties were carried out for aqueous solutions of four cationic surfactants, hexadecanol glycidyl ether ammonium chloride (C(16)PC), Guerbet alcohol hexadecyl glycidyl ether ammonium chloride (C(16)GPC), hexadecanol polyoxyethylene(3) glycidyl ether ammonium chloride(C(16)(EO)(3)PC), and Guerbet alcohol hexadecyl polyoxyethylene(3) glycidyl ether ammonium chloride (C(16)G(EO)(3)PC), on the polytetrafluoroethylene (PTFE) surface using the sessile drop analysis. The obtained results indicate that the contact angle decreases to a minimum with the increasing concentration for all cationic surfactants. Surfactants with branched chain show lower θ values. Moreover, an increase of adhensional tension on the PTFE-water interface has been observed for the four cationic surfactants, and the branched ones have larger increases of adhensional tension. It is very interesting that the sharp decrease of θ appears mainly after critical micelle concentration (cmc) for C(16)GPC, C(16)(EO)(3)PC, and C(16)G(EO)(3)PC, which is quite different from traditional cationic surfactants reported in the literature. Especially for C(16)G(EO)(3)PC, there are two saturated adsorption stages on PTFE surface after cmc (which means the saturated adsorption film at air-solution interface has been formed). In the first saturated stage, the C(16)G(EO)(3)PC molecules are oriented parallel to the PTFE surface with saturated monolayer formed through hydrophobic interaction and hydrogen bond. In the second saturated stage, the hemimicelle has been formed on the PTFE surface, which can be supported by the QCM-D and SPR measurements.

Enhanced light harvesting in plasmonic dye-sensitized solar cells by using a topologically ordered gold light-trapping layer.

Dye-sensitized solar cells (DSSCs) are promising low-cost, high-efficiency devices with low environmental impact. One of the important methods to improve their efficiencies involves increasing the light-harvesting efficiency. Earlier work has focused on varying the morphology of the photoanode. With such a hierarchical structured photoanode in hand, we modify herein the structure of the counter electrode to enhance the optical path length through the plasmonic and reflecttion effects. With the introduced topological gold layer, the photocurrent and efficiency are increased by 16 % and 18 %, respectively, due to the increased light collection. Besides, this effect is effective at both high and low levels of solar irradiation.

Dye-sensitized solar cell based on blood mimetic thixotropy sol-gel electrolyte.

Blood mimetic thixotropy sol-gel electrolytes were prepared and sandwiched between dye-coated porous TiO(2) and a platinum counter-electrode to form a dye-sensitized solar cell. The highest overall conversion efficiency of 6.45%, and the fill factor of 0.74 under the white light irradiation AM 1.5 (100 mW cm(-2)) were obtained.

Biosensor based on hydrogel optical waveguide spectroscopy.

A novel label-free biosensor based on the measurement of binding-induced refractive index changes by hydrogel optical waveguide spectroscopy (HOWS) is reported. This biosensor is implemented by using a surface plasmon resonance (SPR) optical setup in which a carboxylated poly(N-isoproprylacrylamide) (PNIPAAm) hydrogel film is attached on a metallic surface and modified by protein catcher molecules through amine coupling chemistry. The swollen hydrogel with micrometer thickness serves both as a binding matrix and optical waveguide. We show that compared to regular SPR biosensor with thiol self-assembled monolayer (SAM), HOWS provides an order of magnitude improved resolution in the refractive index measurements and enlarged binding capacity owing to its low damping and large swelling ratio, respectively. A model immunoassay experiment revealed that HOWS allowed detection of IgG molecules (molecular weight 150 kDa) with a 10 pM limit of detection that was 5-fold lower than that achieved for SPR with thiol SAM. For the high capacity hydrogel matrix, the affinity binding was mass transport limited. Therefore, we envisage that HOWS will provide further improved detection limit for low molecular weight analytes or for assays employing lower affinity catcher molecules.

Bio-inspired fabrication of lotus leaf like membranes as fluorescent sensing materials.

A fluorescent organic small molecule, hexaphenylsilole (HPS), has been used as a sensing material, while a HPS/polymethyl methacrylate composite film with a lotus leaf like structure is prepared by a simple electrospin method. The film shows high stability and excellent sensitivity for the metal ions Fe(3+) and Hg(2+), respectively. The special surface morphology containing micro-/nanocomposite structure is attributed to the exhibition of these unusual properties.