Unexpected High-Performance Photocatalytic Hydrogen Evolution in Co@NCNT@ZnIn2 S4 Triggered by Directional Charge Separation and Transfer.

The structural design of photocatalysts is highly related to the separation and transfer of photogenerated carriers, which is essential for the improvement of photocatalytic hydrogen evolution performance. Here, the hybrid photocatalyst M@NCNT@ZIS (M: Fe, Co, Ni; NCNT: nitrogen-doped carbon nanotube; ZIS: ZnIn2 S4 ) with a hierarchical structure is rationally designed and precisely synthesized. The unique hollow structure with a large specific surface area offers abundant reactive sites, thus increasing the adsorption of reactants. Importantly, the properly positioned metal nanoparticles realize the directional charge migration from ZIS to M@NCNT, which significantly improves the efficiency of charge separation. Furthermore, the intimate interface between M@NCNT and ZIS effectively facilitates charge migration by shortening the transfer distance and providing numerous transport channels. As a result, the optimized Co@NCNT@ZIS exhibits a remarkable photocatalytic hydrogen evolution efficiency (43.73 mmol g-1 h-1 ) without Pt as cocatalyst. Experimental characterizations and density functional theory calculations demonstrate that the synergistic effect between hydrogen adsorption and interfacial charge transport is of great significance for improving photocatalytic hydrogen production performance.

Characterization and high expression of recombinant Ustilago maydis xylanase in Pichia pastoris.

A recombinant xylanase gene (rxynUMB) from Ustilago maydis 521 was expressed in Pichia pastoris, and the enzyme was purified and characterized. Phylogenetic analysis demonstrated that rxynUMB belongs to glycosyl hydrolase family 11. The Trp84, Trp95, Glu93, and Glu189 residues are proposed to be present at the active site. The apparent molecular mass of the recombinant xylananse was approximately 24 kDa, and the optimum pH and temperature were 4.3 and 50 °C, respectively. Xylanase activity was enhanced by 166 and 115% with Fe(2+) and Mn(2+), respectively. The biochemical properties of this recombinant xylanase suggest that it may be a useful candidate for a variety of commercial applications.

Heterojunctions of Mercury Selenide Quantum Dots and Halide Perovskites with High Lattice Matching and Their Photodetection Properties.

Heterojunction semiconductors have been extensively applied in various optoelectronic devices due to their unique carrier transport characteristics. However, it is still a challenge to construct heterojunctions based on colloidal quantum dots (CQDs) due to stress and lattice mismatch. Herein, HgSe/CsPbBrxI3-x heterojunctions with type I band alignment are acquired that are derived from minor lattice mismatch (~1.5%) via tuning the ratio of Br and I in halide perovskite. Meanwhile, HgSe CQDs with oleylamine ligands can been exchanged with a halide perovskite precursor, acquiring a smooth and compact quantum dot film. The photoconductive detector based on HgSe/CsPbBrxI3-x heterojunction presents a distinct photoelectric response under an incident light of 630 nm. The work provides a promising strategy to construct CQD-based heterojunctions, simultaneously achieving inorganic ligand exchange, which paves the way to obtain high-performance photodetectors based on CQD heterojunction films.

In situ fabrication of MIL-68(In)@ZnIn2S4 heterojunction for enhanced photocatalytic hydrogen production.

Metal-organic frameworks (MOFs), as a class of semiconductor-like materials, are widely used in photocatalysis. However, the limited visible light absorption and poor charge separation efficiency are the main challenges restricting their photocatalytic performance. Herein, the type II heterojunction MIL-68(In)@ZIS was successfully fabricated by in situ growth of ZnIn2S4 (ZIS) on the surface of a representative MOF, i.e. MIL-68(In). After composition optimization, MIL-68(In)-20@ZIS shows an extraordinary photocatalytic hydrogen production efficiency of 9.09 mmol g-1 h-1 and good photochemical stability, which far exceeds those of most photocatalysts. The hierarchical loose structure of MIL-68(In)-20@ZIS is conducive to the adsorption of reactants and mass transfer. Meanwhile, a large number of tight 2D contact interfaces significantly reduce the obstruction of charge transfer, paving the way for high-perform photocatalytic hydrogen evolution. The experimental results demonstrate that the MIL-68(In)@ZIS heterojunction achieves intensive photoresponse and effective charge separation and transfer benefiting from unique charge transport paths of a type II heterojunction. This study opens an avenue toward MOF-based heterojunctions for solar energy conversion.

Mass Diffusion Metamaterials with "Plug and Switch" Modules for Ion Cloaking, Concentrating, and Selection: Design and Experiments.

The outstanding abilities of metamaterials to manipulate physical fields are extensively studied in both wave-based and diffusion-based fields. However, mass diffusion metamaterials, with the ability to manipulate diffusion with practical applications associated with chemical and biochemical engineering, have not yet been experimentally demonstrated. In this work, ion cloaking, concentrating, and selection in liquid solvents are verified by both simulations and experiments, and the concept of a "plug and switch" metamaterial is proposed based on scattering cancellation (SC) to achieve switchable functions by plugging modularized functional units into a functional motherboard. Plugging in any module barely affects the environmental diffusion field, but the module choice impacts different diffusion behaviors in the central region. Cloaking strictly hinds ion diffusion, and concentrating increase diffusion flux, while cytomembrane-like ion selection permits the entrance of some ions but blocks others. In addition, these functions are demonstrated in special applications like the catalytic enhancement by the concentrator and the protein protection by the ion selector. This work not only experimentally demonstrates the effective manipulation of mass diffusion by metamaterials, but also shows that the "plug and switch" design is extensible and reconfigurable. It facilitates novel applications including sustained drug release, catalytic enhancement, bioinspired cytomembranes, etc.

Characterization of congenital factor XII deficiency in Taiwanese patients: identification of one novel and one common mutation.

BACKGROUND: Factor XII (FXII) deficiency is an interesting condition that causes prolonged activated partial thromboplastin time without bleeding diathesis. FXII may be not important in hemostasis, but still plays roles in thrombosis and inflammation. In order to raise clinical awareness about this condition, we studied patients with severe FXII deficiency and their relatives. METHODS: Consecutive severely FXII deficient patients presenting from 1995 to 2020 were recruited from two medical centers in Taiwan. Index patients and their families were tested for FXII function, antigen and F12 gene. F12 variants were constructed into the pIRES-hrGFP vector and expressed on human embryonic kidney cells (HEK293T). FXII antigen and activity were analyzed. RESULTS: We found five severely FXII deficient patients, three women and two men, aged 44-71 years. FXII antigen results ranged from undetectable to 43.7%. Three different mutations were identified: c.1681C>A (p.Gly542Ser), c.1561G>A (p.Glu502Lys), and a novel mutation c.1556T>A (p.Leu500Gln). HEK293T cells expressed consistently low FXII activity with all mutations. FXII antigen expression was similar to the wild type in c.1681C>A (p.Gly542Ser), but reduced in c.1556T>A (p.Leu500Gln) and c.1561G>A (p.Glu502Lys). CONCLUSIONS: We report five unrelated patients with severe FXII deficiency, one of whom carried a novel, cross-reacting material negative mutation c.1556T>A (p.Leu500Gln).

Ultrahigh piezocatalytic capability in eco-friendly BaTiO3 nanosheets promoted by 2D morphology engineering.

Piezocatalysis, converting mechanical vibration into chemical energy, is an emerging technology to address environmental issues. In this work, we propose an efficient method to significantly improve the piezocatalytic activity by morphology engineering rather than composition design. The catalytic property in BaTiO3 nanocrystallites with diverse morphologies is investigated by dye degradation and hydrogen production under ultrasonic vibration. The BaTiO3 nanosheets exhibit an excellent piezocatalytic activity with a degradation rate of 0.1279 min-1 for Rhodamine B, far beyond those in previous piezocatalytic literature and even comparable to excellent photocatalysts, and also a high hydrogen production rate of 92 µmol g-1 h-1. Compared with nanowires and nanoparticles, the 2D morphology greatly enhances the piezocatalytic activity in nanosheets owing to much larger piezoelectric potential. This proves that the piezocatalytic property is dominated by the morphology-dependent piezoelectricity, rather than specific surface area as other catalysis. Dominated by bending vibrating mode, the piezocatalytic activity reaches a maximum at the piezoelectric resonating frequency, and it increases with the ultrasonic power. Moreover, it has good reusability and wide versatility for catalytic degradation. This work gives an in-depth understanding of piezocatalytic mechanism and provides a way to develop high performance and eco-friendly piezocatalysts.

Engineering of g-C3N4-based photocatalysts to enhance hydrogen evolution.

The technology of photocatalytic hydrogen production that converts abundant yet intermittent solar energy into an environmentally friendly alternative energy source is an attractive strategy to mitigate the energy crisis and environmental pollution. Graphitic carbon nitride (g-C3N4), as a promising photocatalyst, has gradually received focus in the field of artificial photosynthesis due to its appealing optical property, high chemical stability and easy synthesis. However, the limited light absorption and massive recombination of photoinduced carriers have hindered the photocatalytic activity of bare g-C3N4. Therefore, from the perspective of theoretical calculations and experiments, many valid approaches have been applied to rationally design the photocatalyst and ameliorate the hydrogen production performance, such as element doping, defect engineering, morphology tuning, and semiconductor coupling. This review summarized the latest progress of g-C3N4-based photocatalysts from two perspectives, modification of pristine g-C3N4 and interfacial engineering design. It is expected to offer feasible suggestions for the fabrication of low-cost and high-efficiency photocatalysts and the photocatalytic mechanism analyses assisted by calculation in the near future. Finally, the prospects and challenges of this exciting research field are discussed.

Residue mutations of xylanase in Aspergillus kawachii alter its optimum pH.

Aspergillus kawachii and Aspergillus niger have been traditionally used as molds for commercial microbial fermentation because of their capability to grow in extremely acidic environments and produce acid-stable enzymes. Endo-1,4-ß-xylanase cleaves the glycosidic bonds in the xylan backbone, consequently reducing the degree of polymerization of the substrate. The amino acid sequences of xylanases from A. kawachii and A. niger only differ in one amino acid residue. However, the xylanases from A. kawachii and A. niger show different optimum pH values of 2.0 and 3.0, respectively. In this study, we synthesized the A. kawachii xylanase gene (XynC) on the basis of the bias codon of yeast and mutated the gene in the dominating region related to optimum pH shifting during gene synthesis. After the overexpression of this gene in Pichia pastoris G115, the mutant (Thr64Ser) enzyme (XynC-C) showed an optimum pH of 3.8, which indicated partial alkalinity compared with the original xylanase from A. kawachii. Similar to that of the enzyme with one residue mutation (Asp48Asn), the optimum pH of the enzyme with two residue mutations (Thr64Ser and Asp48Asn) shifted to 5.0. The result indicated that mutation Asp48 was more important than mutation Thr64 in optimum pH shifting. We proposed a model that explains the lower optimum pH of XynC-C than other members of the xylanase family G. XynC-C showed similar proteolytic resistance and Km and Vmax values for beechwood xylan to other xylanases.