Engineering of Ultra-Thin Layer of MIL-125(Ti) Nanosheet\Zn-Tetracarboxy-Phthalocyanine S-Scheme Heterojunction as Photocatalytic CO2 Reduction Catalyst.

Metal-organic frameworks (MOFs) with ultrathin 2D structure have attracted remarkable attention in photocatalytic application owing to the accessibility of abundant active sites on the surface. But high charge recombination results in poor photocatalytic activity. Herein, the synthesis of ultrathin MIL-125(Ti) nanosheets is reported with a thickness of 1.3 nm through a simple chemical reaction route of precursor solution aging and subsequent solvothermal process for photocatalytic CO2 production. The maximal CO evolution rate achieves 200.8 µmol g-1 h-1, which is prominently higher than that (78.6 µmol g-1 h-1) of the bulk MIL-125(Ti) counterpart. Furthermore, the structurally stable Zn (II) tetracarboxy phthalocyanine (ZnTcPc) molecules assembly on ultrathin MIL-125(Ti) nanosheet (NS) to form MIL-125(Ti) NS\ZnTcPc S-scheme heterojunction through the strong interaction between the Ti3+ in MIL-125(Ti) and the COOH in ZnTcPc. The introduction of ZnTcPc greatly extends light absorption range and increases charge separation rate. The experimental and density functional theory calculation results validate that the MIL-125(Ti) NS\ZnTcPc S-scheme heterojunction can favor CO2 adsorption and effectively depress the formation energy of the intermediates, achieving a high CO evolution rate of 450.8 µmol g-1 h-1. This work provides a strategy of engineering 2D MOF-based heterostructure systems for photocatalytic application.

An out of box thinking: the changes of iron-porphyrin during meat processing and gastrointestinal tract and some methods for reducing its potential health hazard.

Iron-porphyrin is a very important substance in organisms, especially in animals. It is not only the source of iron in human body, but is also the catalytic center of many reactions. Previous studies suggested that adequate intake of iron was important for the health of human, especially for children and pregnant women. However, associated diseases caused by iron over-intake and excessive meat consumption suggested its potential harmfulness for human health. During meat processing, Iron-porphyrin will cause the oxidation of proteins and fatty acids. In the gastrointestinal tract, iron-porphyrin can induce the production of malondialdehyde, fats oxidation, and indirectly cause oxidation of amino acids and nitrates etc. Iron-porphyrin enters the intestinal tract and disturbs the balance of intestinal flora. Finally, some common measures for inhibiting its activity are introduced, including the use of chelating agent, antioxidants, competitive inhibitor, etc., as well as give the hypothesis that sodium chloride increases the catalytic activity of iron-porphyrin. The purpose of this review is to present an overview of current knowledge about the changes of iron-porphyrin in the whole technico- and gastrointesto- processing axis and to provide ideas for further research in meat nutrition.

Polyphenols and polyphenols-based biopolymer materials: Regulating iron absorption and availability from spontaneous to controllable.

Iron is an important trace element in the body, and it will seriously affect the body's normal operation if it is taken too much or too little. A large number of patients around the world are suffering from iron disorders. However, there are many problems using drugs to treat iron overload and causing prolonged and unbearable suffering for patients. Controlling iron absorption and utilization through diet is becoming the acceptable, safe and healthy method. At present, many literatures have reported that polyphenols can interact with iron ions and can be expected to chelate iron ions, depending on their types and structures. Besides, polyphenols often interact with other macromolecules in the diet, which may complicate this phenols-Fe behavior and give rise to the necessity of building phenolic based biopolymer materials. The biopolymer materials, constructed by self-assembly (non-covalent) or chemical modification (covalent), show excellent properties such as good permeability, targeting, biocompatibility, and high chelation ability. It is believed that this review can greatly facilitate the development of polyphenols-based biopolymer materials construction for regulating iron and improving the well-being of patients.

Property of mud and its application in cosmetic and medical fields: a review.

Mud is a semi-colloidal substance formed by the mixture of inorganic, organic and water under the influence of various physical and chemical factors through geological and biological processes. The chemical composition of mud is complex, rich in Ca2+, Zn2+, Mg2+, Na+ and other mineral elements, also contains organic matter such as humic acid, fulvic acid and acetic acid. In cosmetic field, mud can improve the activity of glutathione enzyme and superoxide dismutase in skin, which helps the skin anti-aging. Besides, it also can improve the skin microbial community, due to its distinctively physical properties, mineral ions, microorganisms, etc. In medical field, mud can treat osteoarthritis, especially knee osteoarthritis which has been studied extensively, and it can also increase the chemotaxis of macrophages. On the one hand, the use of clay (a kind of refined mud) can protect the gastrointestinal tract and treat some gastrointestinal diseases. On the other hand, clay is often used as carriers or composites in drug delivery, especially in skin drug delivery, showing very positive results. The purpose of this review is to present an overview of current knowledge about the application of mud in cosmetic and medical fields and to provide ideas for further research in mud.

Hierarchical S-scheme titanium dioxide@cobalt-nickel based metal-organic framework nanotube photocatalyst for selective carbon dioxide photoreduction to methane.

Efficient photocatalysts are of great importance for the photochemical conversion of CO2 into fuels. Herein, S-scheme titanium dioxide@cobalt-nickel based metal-organic framework (TiO2@CoNi-MOF) heterojunction photocatalysts with high surface area and porosity are designed and fabricated by a multi-step controllable strategy. The photocatalytic activity of the composites can be optimized by adjusting the loading content of CoNi-MOF in TiO2@CoNi-MOF and molar ratios of Co2+ and Ni2+ in CoNi-MOF. The optimized hybrid photocatalyst showed a much higher CO2 photoreduction activity than the control single-component samples (TiO2 and CoNi-MOF) with a high CH4 yield (41.65 µmol g-1 h-1) and selectivity (93.2%). The accelerated charge carrier separation induced by the S-scheme heterojunction significantly promoted the photocatalytic performance of TiO2@CoNi-MOF NTs. Meanwhile, the introduction of bimetallic CoNi-MOF nanosheets significantly resulted in the increase of active sites, CO2 adsorbability, visible-light utilization, and CH4 selectivity. Moreover, the S-scheme photoinduced charge transfer model of the TiO2@CoNi-MOF NTs photocatalyst was confirmed by photoluminescence spectroscopy, free radical trapping tests, and work function calculated from Kelvin probe. The work aims to design and fabricate heterojunction photocatalysts with high efficiency for solar fuel production.

Herbal smoke fumigation for controlling Penicillium crustosum in fresh walnuts.

Fresh walnuts have a high water content and are susceptible to decay, and controlling fungal contamination during storage is vital to walnut marketing. In this research, the dominant pathogenic fungus of fresh walnuts was first identified as Penicillium crustosum by morphological and molecular methods. The antifungal effect of herbal smoke fumigation was tested in vitro and in vivo, including Myristica fragrans Houtt., Aucklandia lappa Decne., Eugenia caryophyllata Thunb., Atractylodes lancea (Thunb.) DC., Shiraia bambusicola Henn., Artemisia argyi Lévl. et Vant. The results demonstrated that smoke from all six herbs successfully inhibited P. crustosum growth, and A. argyi smoke produced the best antifungal effect, which contained higher contents of phenol (17.1%), eugenol (13.7%), hexacosane, tetracontane, heneicosane, linolenic acid and other antimicrobial components by gas chromatography-mass spectrometry. Interestingly, optical transmittance data were found to correlate with antifungal capacity, revealing that a formed physical barrier combined with the above antimicrobial compositions, to participate in mold controlling together. Finally, fumigation with A. argyi smoke was tested in a real storage situation at proper dose, which not only dramatically controlled fungal contamination (>70%), but also maintained better odor and taste without oxidative rancidity or other adverse effects. This is the first report in which herbal smoke fumigation was adopted to preserve fresh walnut, providing a new way to reduce mold contamination and maintain quality of fresh walnuts in a natural and safe manner. More research on the application of herbal smoke fumigation to agricultural products in post-harvest storage is needed to explore the conditions and products for which it can be used successfully.

Sandwich-Structured Hybrid of NiCo Nanoparticles-Embedded Carbon Nanotubes Grafted on C3N4 Nanosheets for Efficient Photodehydrogenative Coupling Reactions.

Exploring cheap and efficient hybrid catalysts offers exciting opportunities for enhancing the performance of photocatalysts in the green organic synthesis field. Herein, a facile and effective approach is designed for the synthesis of a sandwich-structured hybrid in which NiCo bimetallic nanoparticles are embedded in the tip of nitrogen-doped carbon nanotubes (N-CNTs) grafted on both sides of a nitrogen deficient C3N4 (Nv-C3N4) nanosheet for photodehydrogenative coupling reactions. Such a brand-new type of sandwich-structured hybrid comprises Nv-C3N4 nanosheets and surrounding N-CNTs embedded with NiCo nanoparticles at their tips. Remarkably, the resultant hybrid exhibits integrated functionalities, abundant active sites, enhanced visible light absorption, and excellent interfacial charge transfer ability. As a result, the optimized NiCo@N-CNTs@Nv-C3N4 photocatalyst shows significantly improved photodehydrogenative coupling performance of amines to imines compared to the control single-metal-based catalysts (Ni@N-CNTs@Nv-C3N4 and Co@N-CNTs@Nv-C3N4). The mechanistic investigation through experimental and computational study demonstrates that, compared with single-metal-based hybrids, the NiCo bimetallic hybrid exhibits stronger amine adsorption and weaker photogenerated hydrogen atom adsorption, thus promoting the dehydrogenative activation of primary amines and fast generation of imines. This work presents a promising insight for designing and preparing efficient photocatalysts to trigger organic synthesis in high yields.

Multi-channel charge transfer of hierarchical TiO2 nanosheets encapsulated MIL-125(Ti) hollow nanodisks sensitized by ZnSe for efficient CO2 photoreduction.

Metal-organic frameworks-based hybrids with desirable components, structures, and properties have been proven to be promising functional materials for photocatalysis and energy conversion applications. Herein, we proposed and prepared ZnSe sensitized hierarchical TiO2 nanosheets encapsulated MIL-125(Ti) hollow nanodisks with sandwich-like structure (MIL-125(Ti)@TiO2\ZnSe HNDs) through a successive solvothermal and selenylation reaction route using the as-prepared MIL-125(Ti) nanodisks as precursor. In the ternary MIL-125(Ti)@TiO2\ZnSe HNDs hybrid, TiO2 nanosheets were transformed from MIL-125(Ti) and in situ grown on both sides of the MIL-125(Ti) shell, forming sandwich-like hollow nanodisks, and the ratio of MIL-125(Ti)/TiO2 can be tuned by changing the solvothermal time. The ternary hybrids possess the advantages of enhanced incident light utilization and abundant accessible active sites originating from bimodal pore-size distribution and hollow sandwich-like heterostructure, which can effectively promote CO2 photoreduction reaction. Especially, the formed multi-channel charge transfer routes in the ternary heterojunctions contribute to the charge transfer/separation and extend the lifespan of charge-separated state, thus boosting CO2 photoreduction performance. The CO (513.1 µmol g-1h-1) and CH4 (45.1 µmol g-1h-1) evolution rates over the optimized ternary hybrid were greatly enhanced compared with the single-component and binary hybrid photocatalysts.

Hierarchical CuS@ZnIn2S4 Hollow Double-Shelled p-n Heterojunction Octahedra Decorated with Fullerene C60 for Remarkable Selectivity and Activity of CO2 Photoreduction into CH4.

In this work, a hollow double-shelled architecture, based on n-type ZnIn2S4 nanosheet-coated p-type CuS hollow octahedra (CuS@ZnIn2S4 HDSOs), is designed and fabricated as a p-n heterojunction photocatalyst for selective CO2 photoreduction into CH4. The resulting hybrids provide rich active sites and effective charge migration/separation to drive CO2 photoreduction, and meanwhile, CO detachment is delayed to increase the possibility of eight-electron reactions for CH4 production. As expected, the optimized CuS@ZnIn2S4 HDSOs manifest a CH4 yield of 28.0 µmol g-1 h-1 and a boosted CH4 selectivity up to 94.5%. The decorated C60 both possesses high electron affinity and improves catalyst stability and CO2 adsorption ability. Thus, the C60-decorated CuS@ZnIn2S4 HDSOs exhibit the highest CH4 evolution rate of 43.6 µmol g-1 h-1 and 96.5% selectivity. This work provides a rational strategy for designing and fabricating efficient heteroarchitectures for CO2 photoreduction.

Free iron rather than heme iron mainly induces oxidation of lipids and proteins in meat cooking.

In this study, the relationship between different forms of iron (free or binding) and oxidation of lipids, proteins in meat system were investigated. Pork tenderloin was heated in 80 °C water bath for 0, 30, 60, 120, 180, 240, 300 min. Compared with control group, Equal and Treble deferiprone group confirmed that free iron was the main oxidizing substance. Moreover, adding exogenous heme caused slight increase of meat oxidation (p < 0.05). At the same time, the antioxidant properties of deferiprone were also evaluated and it shows few antioxidant properties. This study also found that the oxidation of lipid by free iron was more serious than protein. These results suggested that controlling free iron and production of free iron from heme is a potential approach for reducing the oxidative damage of lipid and protein in meat cooking.