Sonocatalytic degradation of EDTA in the presence of Ti and Ti@TiO2 nanoparticles

The sonocatalytic degradation of EDTA (C₀ = 5 10⁻³ M) in aqueous solutions was studied under 345 kHz (P_ac = 0.25 W mL⁻¹) ultrasound at 22–51 °C, Ar/20%O₂, Ar or air, and in the presence of metallic titanium (Ti⁰) or core-shell Ti@TiO₂ nanoparticles (NPs). Ti@TiO₂ NPs have been obtained using simultaneous action of hydrothermal conditions (100–214 °C, autogenic pressure P = 1.0–19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti⁰ NPs in pure water. Ti⁰ is composed of quasi-spherical particles (30–150 nm) of metallic titanium coated with a metastable titanium suboxide Ti₃O. SHT treatment at 150–214 °C leads to the oxidation of Ti₃O and partial oxidation of Ti⁰ and formation of nanocrystalline shell (10–20 nm) composed of TiO₂ anatase. It was found that Ti⁰ NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti⁰ NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti⁰ NPs and Ar/20%O₂ gas mixture. Coating of Ti⁰ with TiO₂ nanocrystalline shell reduces sonocatalytic activity. Pristine TiO₂ anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO₂ radicals in solution and (ii) EDTA oxidation at the surface of Ti⁰ NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti⁰/O₂ species at cavitation bubble/solution interface.     

Design,synthesis and evaluation of novel dehydroabietic acid-dithiocarbamate hybrids as potential multi-targeted compounds for tumor cytotoxicity

In the present study, novel representatives of the important group of biologically-active, dehydroabietic acid-bearing dithiocarbamate moiety, were synthesized and characterized by ¹H NMR, ¹³C NMR, HR-MS. The in vitro antiproliferative activity evaluation (MTT) indicated that these compounds exhibited potent inhibitory activities in various cancer cell lines (HepG-2, MCF-7, HeLa, T-24, MGC-803). Particularly, compound III-b possessed extraordinary cytotoxicity with low micromolar IC₅₀ values ranging from 4.07 to 38.84 µM against tested cancer cell lines, while displayed weak cytotoxicity on two normal cell lines (LO-2 and HEK 293 T). Subsequently, the potential mechanisms of representative compound III-b were elementarily investigated by Transwell experiment, which showed III-b can inhibit cancer cells migration. Annexin-V/PI dual staining showed that the compound can induce HepG-2 cells apoptosis in a dose-dependent manner. Meanwhile this apoptosis may be related to the upregulated protein expression of cleaved-caspase 3, cleaved-caspase 9, Bax and downregulated of Bcl-2 indicated by Western Blot. Later study further confirmed that ROS levels in HepG-2 cells increased significantly with the rise of concentrations. In addition, through the network pharmacology data analyzing, the core targets and signaling pathways of compound III-b for treatment of liver neoplasms were forecasted. Molecular docking model showed that compound III-b had high affinity with hub targets (CASP3, EGFR, HSP90AA1, MAPK1, ERBB2, MDM2), suggesting that compound III-b might target the hub protein to modulate signaling activity. Taken together, these data indicated that dehydroabietic acid structural modification following the “Molecular hybridization” principle is a feasible way to discover the potential multi-targeted antitumor compounds.     

Two-dimensional Covalent Organic Frameworks: Intrinsic Synergy Promoting Photocatalytic Hydrogen Evolution

Covalent organic frameworks(COFs) are emerging photocatalysts for hydrogen evolution in water splitting in recent years. They offer a pre-designable platform to design tailor-made structures and chemically adjustable functionality in terms of photocatalysis. In this review, we summarize the recent striking progress of COF-based photocatalysts in design and synthesis. Firstly, different approaches to functionalizing building blocks, diversifying linkages, extending π-conjugation and establishing D-A conjugation are illustrated for enhancing photocatalytic activity. Next, post-modification of backbones and pores is detailed for emphasizing the synergistic catalytic uniqueness of COFs. Besides, the strategy of preparing COF-related composites with various semiconductors is outlined for optimizing the electronic properties. Finally, we conclude with the current challenges and promising opportunities for the exploration of new COF-based photocatalysts.     

(Sm0.5Gd0.2Nd0.3)2(Hf0.3Ce0.7)2O7复合氧化物的热物理性能

为寻求新型热障涂层用陶瓷材料,本文采用高温固相烧结法制备了(Sm_0.5Gd_0.2Nd_0.3)₂(Hf_0.3Ce_0.7)₂O₇复合氧化物。利用XRD分析了其晶体结构,SEM分析其显微组织,膨胀仪测试其热膨胀性能,激光热导仪测试其热扩散系数。结果表明,成功制备了具有单一萤石晶体结构的(Sm_0.5Gd_0.2Nd_0.3)₂(Hf_0.3Ce_0.7)₂O₇复合氧化物。其显微组织结构致密,晶界清晰无其他相存在。由于复杂的元素组成和较大的原子量,其热导率明显低于7YSZ和Sm₂Ce₂O₇。其较低的热膨胀系数则归因于B位离子较小的离子半径,但其热膨胀系数依然满足热障涂层的要求。     

Pyridine solvated dioxouranium complex with salen ligand: Synthesis,characterization and luminescence properties

A new derivative of dioxouranium(VI) salen complex, [UO2(L)(pyridine)], where [L = N,N′-Bis(2-hydroxybenzylidene)-2,2-dimethyl-1,3-propanediamine] is synthesized and characterized by elemental analysis (C, H, N), FT-IR, ESI-MS spectrometry, UV/Vis, fluorescence, ¹H and ¹³C NMR spectroscopy and thermal gravimetric (TG) study. Furthermore, the single crystal X-ray diffraction measurements of the complex were carried out at 100 and 273 K. The crystal structure measurements revealed that the complex has distorted pentagonal bipyramidal geometry with uranium atom located at the centre and bonded to two phenoxy oxygen and two azomethine nitrogen in tetradenate fashion and one nitrogen from pyridine making it seven coordinated. In addition, the photoluminescence property of the complex was also recorded.     

Metamorphic InAs(Sb)/InGaAs/InAlAs nanoheterostructures grown on GaAs for efficient mid-IR emitters

High-efficiency semiconductor lasers and light-emitting diodes operating in the 3–5?μm mid-infrared (mid-IR) spectral range are currently of great demand for a wide variety of applications, in particular, gas sensing, noninvasive medical tests, IR spectroscopy etc. III-V compounds with a lattice constant of about 6.1?Å are traditionally used for this spectral range. The attractive idea to fabricate such emitters on GaAs substrates by using In(Ga,Al)As compounds is restricted by either the minimum operating wavelength of ～8?μm in case of pseudomorphic AlGaAs-based quantum cascade lasers or requires utilization of thick metamorphic In_xAl_1-xAs buffer layers (MBLs) playing a key role in reducing the density of threading dislocations (TDs) in an active region, which otherwise result in a strong decay of the quantum efficiency of such mid-IR emitters. In this review we present the results of careful investigations of employing the convex-graded In_xAl_1-xAs MBLs for fabrication by molecular beam epitaxy on GaAs (001) substrates of In(Ga,Al)As heterostructures with a combined type-II/type-I InSb/InAs/InGaAs quantum well (QW) for efficient mid-IR emitters (3–3.6?μm). The issues of strain relaxation, elastic stress balance, efficiency of radiative and non-radiative recombination at T?=?10–300?K are discussed in relation to molecular beam epitaxy (MBE) growth conditions and designs of the structures. A wide complex of techniques including in-situ reflection high-energy electron diffraction, atomic force microscopy (AFM), scanning and transmission electron microscopies, X-ray diffractometry, reciprocal space mapping, selective area electron diffraction, as well as photoluminescence (PL) and Fourier-transformed infrared spectroscopy was used to study in detail structural and optical properties of the metamorphic QW structures. Optimization of the growth conditions (the substrate temperature, the As₄/III ratio) and elastic strain profiles governed by variation of an inverse step in the In content profile between the MBL and the InAlAs virtual substrate results in decrease in the TD density (down to 3?×?10⁷ cm^?2), increase of the thickness of the low-TD-density near-surface MBL region to 250–300?nm, the extremely low surface roughness with the RMS value of 1.6–2.4?nm, measured by AFM, as well as rather high 3.5?μm-PL intensity at temperatures up to 300?K in such structures. The obtained results indicate that the metamorphic InSb/In(Ga,Al)As QW heterostructures of proper design, grown under the optimum MBE conditions, are very promising for fabricating the efficient mid-IR emitters on a GaAs platform.     

A review of recent advances in catalytic combustion of VOCs on perovskite-type catalysts

Along with the rapid development of industry, VOCs gradually move into the spotlight, and now become a kind of harmful environmental pollutants that cannot be overlooked. This paper introduces the hazards of VOCs and the common catalytic combustion catalysts, noble metal catalysts and non-noble metal catalysts, for the elimination of VOCs. Perovskite catalysts, as one of the non-noble catalysts, play an important role in the field of catalytic combustion in recent years. According to the classification of elements doping in perovskites, the research achievements in the past five years were analyzed and reviewed. In addition, this paper also analyzes and elaborates the reaction kinetics and QSAR/QSPR models for the introduction of structural properties and reaction mechanisms.     

In-chain functionalization through the combination of ring opening copolymerization and oxime “Click” reaction towards X-ray opaque polylactide copolymers

X-ray imaging functionalization of biodegradable polyesters is a great demand and challenge in biomedical applications.In this work,a strategy of in-chain functionalization through the combination of ring opening copolymerization and oxime "Click" postfunctionalization was developed towards X-ray opaque polylactide copolymers.A functionalized cyclic carbonate was first synthesized and used as comonomer of polylactide copolymers,which were subjected to postfunctionalization of oxime "Click" reaction towards iodinated polylactide copolymers.The chemical structure and physical properties of the target products were traced and confirmed.In vitro cytotoxicity evaluation with 3T3-Swiss albino by Alamar blue demonstrated a low cytotoxicity.The X-ray radiopacity was analyzed by Micro-CT and quantified by Hounsfield Units value,which could be tailorable by the feedstock.It is a promising X-ray visible implantable biomaterial in biomedical applications.     

MALDI MSI Reveals the Spatial Distribution of Protein Markers in Tracheobronchial Lymph Nodes and Lung of Pigs after Respiratory Infection

Respiratory infections are a real threat for humans, and therefore the pig model is of interest for studies. As one of a case for studies, Actinobacillus pleuropneumoniae (APP) caused infections and still worries many pig breeders around the world. To better understand the influence of pathogenic effect of APP on a respiratory system—lungs and tracheobronchial lymph nodes (TBLN), we aimed to employ matrix-assisted laser desorption/ionization time-of-flight mass spectrometry imaging (MALDI-TOF MSI). In this study, six pigs were intranasally infected by APP and two were used as non-infected control, and 48 cryosections have been obtained. MALDI-TOF MSI and immunohistochemistry (IHC) were used to study spatial distribution of infectious markers, especially interleukins, in cryosections of porcine tissues of lungs (necrotic area, marginal zone) and tracheobronchial lymph nodes (TBLN) from pigs infected by APP. CD163, interleukin 1β (IL-1β) and a protegrin-4 precursor were successfully detected based on their tryptic fragments. CD163 and IL-1β were confirmed also by IHC. The protegrin-4 precursor was identified by MALDI-TOF/TOF directly on the tissue cryosections. CD163, IL-1β and protegrin-4 precursor were all significantly (p < 0.001) more expressed in necrotic areas of lungs infected by APP than in marginal zone, TBLN and in control lungs.     

氧离子传导型固体氧化物电解池燃料电极的研究进展

固体氧化物电解池可高效地电解H₂O/CO₂制备燃料,越来越受到人们的重视. 本文对近年来在燃料电极（阴极）材料方面的研究进展进行了全面综述,指出各种阴极材料的优缺点及发展趋势,强调亟待解决的关键科学与技术问题.