Fully Conjugated Two-Dimensional sp -Carbon Covalent Organic Frameworks as Artificial Photosystem I with High Efficiency.
Zhao Yingjie,Liu Hui,Wu Chenyu,Zhang Zhaohui,Pan Qingyan,Hu Fan,Wang Ruiming,Li Piwu,Huang Xiaowen,Li Zhibo
Angewandte Chemie (International ed. in English)
The synthesis of fully conjugated sp -carbon covalent organic frameworks (COF) is extremely challenging given the difficulty of the formation of very stable carbon-carbon double bonds (-C=C-). Here, we report the successful preparation of a 2D COF (TP-COF) based on triazine as central planar units bridged by sp -carbon linkers through the -C=C- condensation reaction. High-resolution-transmission electron microscopy (HRTEM) clearly confirmed the tessellated hexagonal pore structure with a pore center-to-center distance of 2 nm. Powder X-ray diffraction (PXRD) together with structural simulations revealed an AA stacking mode of the obtained layered structure. TP-COF turned out to be an excellent semiconductor material with a LUMO energy of -3.23 eV and a band gap of 2.36 eV. Excitingly, this novel sp -carbon conjugated TP-COF exhibited unprecedented coenzyme regeneration efficiency and can significantly boost the coenzyme-assisted synthesis of l-glutamate to a record-breaking 97 % yield within 12 minutes.
10.1002/anie.201901194
Installing a Green Engine To Drive an Enzyme Cascade: A Light-Powered In Vitro Biosystem for Poly(3-hydroxybutyrate) Synthesis.
Li Fei,Wei Xinlei,Zhang Lin,Liu Cheng,You Chun,Zhu Zhiguang
Angewandte Chemie (International ed. in English)
Many existing in vitro biosystems harness power from the chemical energy contained in substrates and co-substrates, and light or electric energy provided from abiotic parts, leading to a compromise in atom economy, incompatibility between biological and abiotic parts, and most importantly, incapability to spatiotemporally co-regenerate ATP and NADPH. In this study, we developed a light-powered in vitro biosystem for poly(3-hydroxybutyrate) (PHB) synthesis using natural thylakoid membranes (TMs) to regenerate ATP and NADPH for a five-enzyme cascade. Through effective coupling of cofactor regeneration and mass conversion, 20 mM PHB was yielded from 50 mM sodium acetate with a molar conversion efficiency of carbon of 80.0 % and a light-energy conversion efficiency of 3.04 %, which are much higher than the efficiencies of similar in vitro PHB synthesis biosystems. This suggests the promise of installing TMs as a green engine to drive more enzyme cascades.
10.1002/anie.202111054
Enzymatic Electrosynthesis of Glycine from CO and NH.
Angewandte Chemie (International ed. in English)
Enzymatic electrosynthesis has gained more and more interest as an emerging green synthesis platform, particularly for the fixation of CO . However, the simultaneous utilization of CO and a nitrogenous molecule for the enzymatic electrosynthesis of value-added products has never been reported. In this study, we constructed an in vitro multienzymatic cascade based on the reductive glycine pathway and demonstrated an enzymatic electrocatalytic system that allowed the simultaneous conversion of CO and NH as the sole carbon and nitrogen sources to synthesize glycine. Through effective coupling and the optimization of electrochemical cofactor regeneration and the multienzymatic cascade reaction, 0.81 mM glycine was yielded with a highest reaction rate of 8.69 mg L h and faradaic efficiency of 96.8 %. These results imply a promising alternative for enzymatic CO electroreduction and expand its products to nitrogenous chemicals.
10.1002/anie.202218387
Microglia-Mediated Neuroinflammation: A Potential Target for the Treatment of Cardiovascular Diseases.
Journal of inflammation research
Microglia are tissue-resident macrophages of the central nervous system (CNS). In the CNS, microglia play an important role in the monitoring and intervention of synaptic and neuron-level activities. Interventions targeting microglia have been shown to improve the prognosis of various neurological diseases. Recently, studies have observed the activation of microglia in different cardiovascular diseases. In addition, different approaches that regulate the activity of microglia have been shown to modulate the incidence and progression of cardiovascular diseases. The change in autonomic nervous system activity after neuroinflammation may be a potential intermediate link between microglia and cardiovascular diseases. Here, in this review, we will discuss recent updates on the regulatory role of microglia in hypertension, myocardial infarction and ischemia/reperfusion injury. We propose that microglia serve as neuroimmune modulators and potential targets for cardiovascular diseases.
10.2147/JIR.S350109
Water flow promoted charge separation in piezoelectric BiTiO for the enhanced photocatalytic degradation of antibiotic.
Chemosphere
Addressing the issue of antibiotic residues in the environment is key to improving the quality of aquatic environments and reducing human health risks. In this study, piezoelectric bismuth titanate (BiTiO) nanosheets are synthesized and employed to conduct antibiotic degradation. The piezoelectric potential induced by the water flow shear force is utilized to facilitate charge separation and migration in the photocatalytic process and enhance the catalytic degradation of antibiotic wastewater. As a result, 85% of tetracycline hydrochloride (TC) is degraded within 90 min. The piezo-photocatalytic process exhibits a 2.4 times faster reaction rate and a 15% higher mineralization rate than photocatalysis. Different environmental factors are investigated for their effects on the catalytic activity in piezo-photocatalysis. In situ electrochemical measurement and photoluminescence (PL) spectroscopy under stress demonstrated that the piezoelectric potential shifted the energy band of BiTiO and promoted the charge migration and separation, which produce more active species that favor the efficient catalytic degradation. Finally, the intermediate products of the tetracycline hydrochloride degradation process are analyzed and possible degradation pathways are suggested. This study elucidates the degradation mechanism of BiTiO as a piezo-photocatalyst for antibiotic pollutants, and meticulously investigates the charge transfer mechanism of the catalyst material in response to micro-stress. Hence, it provides an efficient solution for organic wastewater treatment and can potentially provide theoretical support for the development and performance optimization of catalyst materials applied in natural environments.
10.1016/j.chemosphere.2023.140306
Dynamic defects boost in-situ HO piezocatalysis for water cleanup.
Proceedings of the National Academy of Sciences of the United States of America
Creating efficient catalysts for simultaneous HO generation and pollutant degradation is vital. Piezocatalytic HO synthesis offers a promising alternative to traditional methods but faces challenges like sacrificial reagents, harsh conditions, and low activity. In this study, we introduce a cobalt-loaded ZnO (CZO) piezocatalyst that efficiently generates HO from HO and O under ultrasonic (US) treatment in ambient aqueous conditions. The catalyst demonstrates exceptional performance with ~50.9% TOC removal of phenol and in situ generation of 1.3 mM HO, significantly outperforming pure ZnO. Notably, the CZO piezocatalyst maintains its HO generation capability even after multiple cycles, showing continuous improvement (from 1.3 mM to 1.8 mM). This is attributed to the piezoelectric electrons promoting the generation of dynamic defects under US conditions, which in turn promotes the adsorption and activation of oxygen, thereby facilitating efficient HO production, as confirmed by EPR spectrometry, XPS analysis, and DFT calculations. Moreover, the CZO piezocatalysts maintain outstanding performance in pollutant degradation and HO production even after long periods of inactivity, and the deactivated catalyst due to metal ion dissolution could be rejuvenated by pH adjustment, offering a sustainable solution for wastewater purification.
10.1073/pnas.2317435121
Pioneering Piezoelectric-Driven Atomic Hydrogen for Efficient Dehalogenation of Halogenated Organic Pollutants.
Environmental science & technology
The electrocatalytic hydrodehalogenation (EHDH) process mediated by atomic hydrogen (H*) is recognized as an efficient method for degrading halogenated organic pollutants (HOPs). However, a significant challenge is the excessive energy consumption resulting from the recombination of H* to H production in the EHDH process. In this study, a promising strategy was proposed to generate piezo-induced atomic H*, without external energy input or chemical consumption, for the degradation and dehalogenation of HOPs. Specifically, sub-5 nm Ni nanoparticles were subtly dotted on an N-doped carbon layer coating on BaTiO cube, and the resulted hybrid nanocomposite (Ni-NC@BTO) can effectively break C-X (X = Cl and F) bonds under ultrasonic vibration or mechanical stirring, demonstrating high piezoelectric driven dehalogenation efficiencies toward various HOPs. Mechanistic studies revealed that the dotted Ni nanoparticles can efficiently capture H* to form Ni-H* (H) and drive the dehalogenation process to lower the toxicity of intermediates. COMSOL simulations confirmed a "chimney effect" on the interface of Ni nanoparticle, which facilitated the accumulation of H and enhanced electron transfer for H* formation by improving the surface charge of the piezocatalyst and strengthening the interfacial electric field. Our work introduces an environmentally friendly dehalogenation method for HOPs using the piezoelectric process independent of the external energy input and chemical consumption.
10.1021/acs.est.3c09579
Protrudent Iron Single-Atom Accelerated Interfacial Piezoelectric Polarization for Self-Powered Water Motion Triggered Fenton-Like Reaction.
Lan Shenyu,Jing Binghua,Yu Chuan,Yan Dengming,Li Zhi,Ao Zhimin,Zhu Mingshan
Small (Weinheim an der Bergstrasse, Germany)
Water in motion presented in natural systems contains a rich source of renewable mechanical energy. Harvesting this water energy to trigger the generation of reactive oxygen species (ROS) for water purification is a desirable yet underexplored solution. Herein, the authors report a self-powered water motion triggered Fenton-like reaction system for wastewater treatment through the piezo-activation of peroxymonosulfate (PMS). Isolated protrudent Fe single atomic sites are immobilized on the surface of molybdenum disulfide (MoS ) nanosheet to improve piezoelectric polarization of MoS , to accelerate piezoelectric charge separation, and to enhance PMS activation for water purification. ROS ( OH, SO , O , and O ) generation for PMS piezo-activation are observed, and different water contaminants, including antibiotic, industrial chemicals, and dyes are efficiently removed under the natural water fluid. Aimed at solving concurrent issues of environmental pollution and energy crisis, this study provides a pathway for single atomic-mediated piezo-activation of Fenton-like reactions through ambient self-powered water motion for water purification.
10.1002/smll.202105279