Biomass fuels related-PM2.5 promotes lung fibroblast-myofibroblast transition through PI3K/AKT/TRPC1 pathway.

Emerging evidence has suggested that exposure to PM2.5 is a significant contributing factor to the development of chronic obstructive pulmonary disease (COPD). However, the underlying biological effects and mechanisms of PM2.5 in COPD pathology remain elusive. In this study, we aimed to investigate the implication and regulatory effect of biomass fuels related-PM2.5 (BRPM2.5) concerning the pathological process of fibroblast-to-myofibroblast transition (FMT) in the context of COPD. In vivo experimentation revealed that exposure to biofuel smoke was associated with airway inflammation in rats. After 4 weeks of exposure, there was inflammation in the small airways, but no significant structural changes in the airway walls. However, after 24 weeks, airway remodeling occurred due to increased collagen deposition, myofibroblast proliferation, and tracheal wall thickness. In vitro, cellular immunofluorescence results showed that with stimulation of BRPM2.5 for 72 h, the cell morphology of fibroblasts changed significantly, most of the cells changed from spindle-shaped to star-shaped irregular, α-SMA stress fibers appeared in the cytoplasm and the synthesis of type I collagen increased. The collagen gel contraction experiment showed that the contractility of fibroblasts was enhanced. The expression level of TRPC1 in fibroblasts was increased. Specific siRNA-TRPC1 blocked BRPM2.5-induced FMT and reduced cell contractility. Additionally, specific siRNA-TRPC1 resulted in a decrease in the augment of intracellular Ca2+ concentration ([Ca2+]i) induced by BRPM2.5. Notably, it was found that the PI3K inhibitor, LY294002, inhibited enhancement of AKT phosphorylation level, FMT occurrence, and elevation of TRPC1 protein expression induced by BRPM2.5. The findings indicated that BRPM2.5 is capable of inducing the FMT, with the possibility of mediation by PI3K/AKT/TRPC1. These results hold potential implications for the understanding of the molecular mechanisms involved in BRPM2.5-induced COPD and may aid in the development of novel therapeutic strategies for pathological conditions characterized by fibrosis.

High-Valence Metal Doping Induced Lattice Expansion for M-FeNi LDH toward Enhanced Urea Oxidation Electrocatalytic Activities.

The precise design of low-cost, efficient, and definite electrocatalysts is the key to sustainable renewable energy. The urea oxidation reaction (UOR) offers a promising alternative to the oxygen evolution reaction for energy-saving hydrogen generation. In this study, by tuning the lattice expansion, a series of M-FeNi layered double hydroxides (M-FeNi LDHs, M: Mo, Mn, V) with excellent UOR performance are synthesized. The hydrolytic transformation of Fe-MIL-88A is assisted by urea, Ni2+ and high-valence metals, to form a hollow M-FeNi LDH. Owing to the large atomic radius of the high-valence metal, lattice expansion is induced, and the electronic structure of the FeNi-LDH is regulated. Doping with high-valence metal is more favorable for the formation of the high-valence active species, NiOOH, for the UOR. Moreover, the hollow spindle structure promoted mass transport. Thus, the optimal Mo-FeNi LDH showed outstanding UOR electrocatalytic activity, with 1.32 V at 10 mA cm-2 . Remarkably, the Pt/C||Mo-FeNi LDH catalyst required a cell voltage of 1.38 V at 10 mA·cm-2 in urea-assisted water electrolysis. This study suggests a new direction for constructing nanostructures and modulating electronic structures, which is expected to ultimately lead to the development of a class of auxiliary electrocatalysts.

Electroenzymatic cascade reaction on a biohybrid boosts the chiral epoxidation reaction.

The chiral epoxidation of styrene and its derivatives is an important transformation that has attracted considerable scientific interest in the chemical industry. Herein, we integrate enzymatic catalysis and electrocatalysis to propose a new route for the chiral epoxidation of styrene and its derivatives. Chloroperoxidase (CPO) functionalized with 1-ethyl-3-methylimidazolium bromide (ILEMB) was loaded onto cobalt nitrogen-doped carbon nanotubes (CoN@CNT) to form a biohybrid (CPO-ILEMB/CoN@CNT). H2O2 species were generated in situ through a two-electron oxygen reduction reaction (2e-ORR) at CoN@CNT to initiate the following enzymatic epoxidation of styrene by CPO. CoN@CNT had high electroactivity for the ORR to produce H2O2 at a more positive potential, prohibiting the conversion of FeIII to FeII in the heme of CPO to maintain enzymatic activity. Meanwhile, CoN@CNT could serve as an ideal carrier for the immobilization of CPO-ILEMB. Hence, the coimmobilization of CPO-ILEMB and CoN@CNT could facilitate the diffusion of intermediate H2O2, which achieved 17 times higher efficiency than the equivalent amounts of free CPO-ILEMB in bulk solution for styrene epoxidation. Notably, an enhancement (∼45%) of chiral selectivity for the epoxidation of styrene was achieved.

Substituent Engineering in Pore-Space-Partitioned Metal-Organic Frameworks for CO2 Selective Adsorption and Fixation.

Comprehensive understanding of substituent groups located on the pore surface of metal-organic frameworks (which we call substituent engineering herein) can help to promote gas adsorption and catalytic performance through ligand functionalization. In this work, pore-space-partitioned metal-organic frameworks (PSP MOFs) were selected as a platform to evaluate the effect of organic functional groups on CO2 adsorption, separation, and catalytic conversion. Twelve partitioned acs metal-organic frameworks (pacs-MOFs, named SNNU-25-Rn here) containing different functional groups were synthesized, which can be classified into electron-donor groups (-OH, -NH2, -CH3, and -OCH3) and electron-acceptor groups (-NO2, -F, -Cl, and -Br). The experimental results showed that SNNU-25-Rn with electron donors usually perform better than those with electron acceptors for the comprehensive utilization of CO2. The CO2 uptake of the 12 SNNU-25-Rn MOFs ranged from 30.9 to 183.6 cm3 g-1 at 273 K and 1 bar, depending on the organic functional groups. In particular, SNNU-25-OH showed the highest CO2 adsorption, SNNU-25-CH3 had the highest IAST of CO2/CH4 (36.1), and SNNU-25-(OH)2 showed the best catalytic activity for the CO2 cycloaddition reaction. The -OH functionalized MOFs with excellent performance may be attributed to the Lewis acid-base and hydrogen-bonding interactions between -OH groups and the CO2 molecules. This work modulated the effect of the microenvironment of MOFs on CO2 adsorption, separation, and catalysis in terms of substituents, providing valuable information for the precise design of porous MOFs with a comprehensive utilization of CO2.

Population-based heteropolymer design to mimic protein mixtures.

Biological fluids, the most complex blends, have compositions that constantly vary and cannot be molecularly defined1. Despite these uncertainties, proteins fluctuate, fold, function and evolve as programmed2-4. We propose that in addition to the known monomeric sequence requirements, protein sequences encode multi-pair interactions at the segmental level to navigate random encounters5,6; synthetic heteropolymers capable of emulating such interactions can replicate how proteins behave in biological fluids individually and collectively. Here, we extracted the chemical characteristics and sequential arrangement along a protein chain at the segmental level from natural protein libraries and used the information to design heteropolymer ensembles as mixtures of disordered, partially folded and folded proteins. For each heteropolymer ensemble, the level of segmental similarity to that of natural proteins determines its ability to replicate many functions of biological fluids including assisting protein folding during translation, preserving the viability of fetal bovine serum without refrigeration, enhancing the thermal stability of proteins and behaving like synthetic cytosol under biologically relevant conditions. Molecular studies further translated protein sequence information at the segmental level into intermolecular interactions with a defined range, degree of diversity and temporal and spatial availability. This framework provides valuable guiding principles to synthetically realize protein properties, engineer bio/abiotic hybrid materials and, ultimately, realize matter-to-life transformations.

Au Nanowires Decorated Ultrathin Co3 O4 Nanosheets toward Light-Enhanced Nitrate Electroreduction.

Nitrate is a reasonable alternative instead of nitrogen for ammonia production due to the low bond energy, large water-solubility, and high chemical polarity for good absorption. Nitrate electroreduction reaction (NO3 RR) is an effective and green strategy for both nitrate treatment and ammonia production. As an electrochemical reaction, the NO3 RR requires an efficient electrocatalyst for achieving high activity and selectivity. Inspired by the enhancement effect of heterostructure on electrocatalysis, Au nanowires decorated ultrathin Co3 O4 nanosheets (Co3 O4 -NS/Au-NWs) nanohybrids are proposed for improving the efficiency of nitrate-to-ammonia electroreduction. Theoretical calculation reveals that Au heteroatoms can effectively adjust the electron structure of Co active centers and reduce the energy barrier of the determining step (*NO → *NOH) during NO3 RR. As the result, the Co3 O4 -NS/Au-NWs nanohybrids achieve an outstanding catalytic performance with high yield rate (2.661 mg h-1 mgcat -1 ) toward nitrate-to-ammonia. Importantly, the Co3 O4 -NS/Au-NWs nanohybrids show an obviously plasmon-promoted activity for NO3 RR due to the localized surface plasmon resonance (LSPR) property of Au-NWs, which can achieve an enhanced NH3 yield rate of 4.045 mg h-1 mgcat -1 . This study reveals the structure-activity relationship of heterostructure and LSPR-promotion effect toward NO3 RR, which provide an efficient nitrate-to-ammonia reduction with high efficiency.

Monodispersed Pt Sites Supported on NiFe-LDH from Synchronous Anchoring and Reduction for High Efficiency Overall Water Splitting.

Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for PtII . Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm-2 for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm-2 for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm-2 , which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design.

Oxygen-Vacancy-Rich Cu2O Hollow Nanocubes for Nitrate Electroreduction Reaction to Ammonia in a Neutral Electrolyte.

The electrocatalytic nitrate reduction reaction (NO3--ERR) to ammonia (NH3) is a promising strategy for NH3 production. Cu-based nanomaterials have been regarded as a kind of effective NO3--ERR catalysts. In this work, high-quality hollow Cu2O nanocubes (Cu2O h-NCs) are facilely synthesized by a simple one-step reduction method. The as-prepared Cu2O h-NCs reveal high selectivity and activity for NO3--ERR, which is ascribed to abundant oxygen vacancies, high surface area, hollow architecture, low mass transfer resistance, and strong adsorbing ability toward NO3-. In fact, Cu2O h-NCs can achieve a Faradic efficiency of 92.9% and an NH3 yield of 56.2 mg h-1 mgcat-1 for NH3 production at -0.85 V (vs RHE) potential, which exceeds those of other transition-metal-based NO3--ERR electrocatalysts.

Iron-Doped Cobalt Phosphide Nanohoops for Electroreduction of Nitrate to Ammonia.

Heteroatom doping can effectively tune the electronic structure of an electrocatalyst to accelerate the adsorption/desorption of reaction intermediates, which sharply increases their intrinsic electroactivity. Herein, we successfully prepare iron (Fe)-doped cobalt phosphide (CoP) nanohoops (Fe/CoP NHs) with different Fe/Co atomic ratios as highly active electrocatalysts for the nitrate electrocatalytic reduction reaction (NIT-ERR). Electrochemical measurements reveal that appropriate Fe doping can improve the electroactivity of cobalt phosphide nanohoops for the NIT-ERR. In a 1 M KOH electrolyte, the Fe/CoP NHs with the optimized chemical composition can achieve an efficient ammonia (NH3) generation rate of 27.6 mg h-1 mgcat-1 for the conversion of NO3- into NH3 and a Faradaic efficiency of 93.3% at a -0.25 V potential, which exceed the values of various previously reported nanomaterials in an alkaline electrolyte.

Micropore Regulation in Ultrastable [Sc3O]-Organic Frameworks for Acetylene Storage and Purification.

High storage capacity, high separation selectivity, and high structure stability are essential for an idea gas adsorbent. However, it is not easy to achieve all three at the same time, even for the promising metal-organic framework (MOF) adsorbents. We demonstrate herein that robust [Sc3O]-organic frameworks could be regulated by a micropore combination strategy for high-performance acetylene adsorption. Under the same solvent system with formic acid as a modulator, similar tritopic ligands extend [Sc3O(COO)6] trigonal-prismatic clusters to generate SNNU-5-Sc and SNNU-150-Sc adsorbents. Notably, the two Sc-MOFs can keep their architectures over 24 h in water at different pH values (2-12) or at 90 °C. Modulated by the linker symmetry, the final stacking metal-organic polyhedral cages produce open window sizes of about 10 Å for SNNU-5-Sc and 5 Å + 7 Å for SNNU-150-Sc. Due to such micropore combinations, SNNU-5-Sc exhibits a top-level C2H2 uptake of 211.2 cm3 g-1 (1 atm and 273 K) and SNNU-150-Sc shows high C2H2/CH4, C2H2/C2H4, and C2H2/CO2 selectivities of 80.65, 4.03, and 8.19, respectively, under ambient conditions. Dynamic breakthrough curves obtained on a fixed-bed column and grand canonical Monte Carlo (GCMC) simulations further support their prominent acetylene storage and purification performance. High framework stability, storage capacity, and separation selectivity make SNNU-5-Sc and SNNU-150-Sc ideal acetylene adsorbents in practical applications.

Competitive Coordination-Oriented Monodispersed Ruthenium Sites in Conductive MOF/LDH Hetero-Nanotree Catalysts for Efficient Overall Water Splitting in Alkaline Media.

Rational exploration of efficient, inexpensive, and robust electrocatalysts is critical for the efficient water splitting. Conjugated conductive metal-organic frameworks (cMOFs) with multicomponent layered double hydroxides (LDHs) to construct bifunctional heterostructure catalysts are considered as an efficient but complicated strategy. Here, the fabrication of a cMOF/LDH hetero-nanotree array catalyst (CoNiRu-NT) coupled with monodispersed ruthenium (Ru) sites via a controllable grafted-growth strategy is reported. Rich-amino hexaiminotriphenylene linkers coordinate with the LDH nanotrunk to form cMOF nanobranches, providing numerous anchoring sites to precisely confine and stabilize RuN4 sites. Moreover, monodispersed and reduced Ru moieties facilitate H2 O adsorption and dissociation, and the heterointerface between the cMOF and the LDH further modifies the chemical and electronic structures. Optimized CoNiRu-NT displays a significant increase in electrochemical water-splitting properties in alkaline media, affording low overpotentials of 22 mV at 10 mA cm-2 and 255 mV at 20 mA cm-2 for the hydrogen evolution reaction and oxygen evolution reaction, respectively. In an actual electrochemical system, CoNiRu-NT drives an overall water splitting at a low cell voltage of 1.47 V to reach 10 mA cm-2 . This performance is comparable to that of pure noble-metal-based materials and superior to most reported MOF-based catalysts.

Amide-Functionalized Metal-Organic Frameworks Coupled with Open Fe/Sc Sites for Efficient Acetylene Purification.

Acetylene (C2H2) purification is of great importance for many chemical synthesis and processes. Metal-organic frameworks (MOFs) are widely used for gas adsorption and separation due to their variable structure and porosity. However, the exploitation of ideal MOF adsorbents for C2H2 keeps a challenging task. Herein, a combination of open metal sites (OMSs) and Lewis basic sites (LBSs) in robust MOFs is demonstrated to effectively promote the C2H2 purification performance. Accordingly, SNNU-37(Fe/Sc), two isostructural MOFs constituted by [Fe3O(COO)6] or [Sc3O(COO)6] trinuclear clusters and amide-functionalized tricarboxylate linkers, were designed with extra-stable 3,6-connected new architectures. Derived from the coexistence of high-density OMSs and LBSs, the C2H2 adsorption amounts of SNNU-37(Fe/Sc) are much higher than those values for C2H4 and CO2. Theoretical IAST selectivity values of SNNU-37(Fe) are 2.4 for C2H2/C2H4 (50/50, v/v) and 9.9 for C2H2/CO2 (50/50, v/v) at 298 K and 1 bar, indicating an excellent C2H2 separation ability. Experimental breakthrough curves also revealed that SNNU-37(Fe) could effectively separate C2H2/C2H4 and C2H2/CO2 under ambient conditions. GCMC simulations further indicate that open Fe or Sc sites and amide groups mainly contribute to stronger adsorption sites for C2H2 molecules.

Cobalt phosphide nanorings towards efficient electrocatalytic nitrate reduction to ammonia.

High-quality CoP nanorings (CoP NRs) are easily achieved using a phosphorating treatment of CoOOH nanorings, and reveal high activity towards the hydrogen evolution reaction and the nitrate electrocatalytic reduction reaction due to substantial coordinately unsaturated active sites, a high surface area, and available mass transfer pathways. Consequently, the CoP NRs can achieve a faradaic efficiency of 97.1% towards NO3--to-NH3 conversion and provide an NH3 yield of 30.1 mg h-1 mg-1cat at a -0.5 V potential.

Efficient Nitrate-to-Ammonia Electroreduction at Cobalt Phosphide Nanoshuttles.

The nitrate electroreduction reaction (NO3--ERR) is an efficient and green approach for nitrate remediation, which requires a highly active and selective electrocatalyst. In this work, porous and amorphous cobalt phosphide nanoshuttles (CoP PANSs) are successfully synthesized by using Mg2+ ion-doped calcium carbonate nanoshuttles (Mg-CaCO3 NSs) as the initial reaction precursor via precipitation transformation and a high-temperature phosphidation strategy. Various physical characterizations show that CoP PANSs have porous architecture, amorphous crystal structure, and big surface area. Electrochemical measurements reveal for the first time that CoP PANSs have outstanding electroactivity for NO3--ERR in a neutral electrolyte. At an applied potential of -0.5 V vs reversible hydrogen electrode, CoP PANSs can achieve a high Faraday efficiency (94.24 ± 2.8%) and high yield rate (19.28 ± 0.53 mg h-1 mgcat-1) for ammonia production, which exceeds most reported values at various electrocatalysts for NO3--ERR. Thus, the present result indicates that cobalt phosphide nanomaterials have promising application for NO3--ERR.

Ultrahigh-Uptake Capacity-Enabled Gas Separation and Fruit Preservation by a New Single-Walled Nickel-Organic Framework.

High gas-uptake capacity is desirable for many reasons such as gas storage and sequestration. Moreover, ultrahigh capacity can enable a practical separation process by mitigating the selectivity factor that sometimes compromises separation efficiency. Herein, a single-walled nickel-organic framework with an exceptionally high gas capture capability is reported. For example, C2H4 and C2H6 uptake capacities are at record-setting levels of 224 and 289 cm3 g-1 at 273 K and 1 bar (169 and 110 cm3 g-1 at 298 K and 1 bar), respectively. Such ultrahigh capacities for both gases give rise to an excellent separation performance, as shown for C2H6/C2H4 with breakthrough times of 100, 60 and 30 min at 273, 283 and 298 K and under 1 atm. This new material is also shown to readily remove ethylene released from fruits, and once again, its ultrahigh capacity plays a key role in the extraordinary length of time achieved in the preservation of the fruit freshness.

Precise Pore Space Partitions Combined with High-Density Hydrogen-Bonding Acceptors within Metal-Organic Frameworks for Highly Efficient Acetylene Storage and Separation.

The high storage capacity versus high selectivity trade-off barrier presents a daunting challenge to practical application as an acetylene (C2 H2 ) adsorbent. A structure-performance relationship screening for sixty-two high-performance metal-organic framework adsorbents reveals that a moderate pore size distribution around 5.0-7.5 Šis critical to fulfill this task. A precise pore space partition approach was involved to partition 1D hexagonal channels of typical MIL-88 architecture into finite segments with pore sizes varying from 4.5 Š(SNNU-26) to 6.4 Š(SNNU-27), 7.1 Š(SNNU-28), and 8.1 Š(SNNU-29). Coupled with bare tetrazole N sites (6 or 12 bare N sites within one cage) as high-density H-bonding acceptors for C2 H2 , the target MOFs offer a good combination of high C2 H2 /CO2 adsorption selectivity and high C2 H2 uptake capacity in addition to good stability. The optimized SNNU-27-Fe material demonstrates a C2 H2 uptake of 182.4 cm3 g-1 and an extraordinary C2 H2 /CO2 dynamic breakthrough time up to 91 min g-1 under ambient conditions.

Lattice Matching Growth of Conductive Hierarchical Porous MOF/LDH Heteronanotube Arrays for Highly Efficient Water Oxidation.

The conjugation of metal-organic frameworks (MOFs) into different multicomponent materials to precisely construct aligned heterostructures is fascinating but elusive owing to the disparate interfacial energy and nucleation kinetics. Herein, a promising lattice-matching growth strategy is demonstrated for conductive MOF/layered double hydroxide (cMOF/LDH) heteronanotube arrays with highly ordered hierarchical porous structures enabling an ultraefficient oxygen evolution reaction (OER). CoNiFe-LDH nanowires are used as interior template to engineer an interface by inlaying cMOF and matching two crystal lattice systems, thus conducting a graft growth of cMOF/LDH heterostructures along the LDH nanowire. A class of hierarchical porous cMOF/LDH heteronanotube arrays is produced through continuously regulating the transformation degree. The synergistic effects of the cMOF and LDH components significantly promote the chemical and electronic structures of the heteronanotube arrays and their electroactive surface area. Optimized heteronanotube arrays exhibit extraordinary OER activity with ultralow overpotentials of 216 and 227 mV to deliver current densities of 50 and 100 mA cm-2 with a small Tafel slope of 34.1 mV dec-1 , ranking it among the best MOF and non-noble-metal-based catalysts for OER. The robust performance under high current density and vigorous gas bubble conditions enable such hierarchical MOF/LDH heteronanotube arrays as promising materials for practical water electrolysis.

Hydrogen and Potassium Acetate Co-Production from Electrochemical Reforming of Ethanol at Ultrathin Cobalt Sulfide Nanosheets on Nickel Foam.

The sluggish reaction kinetics of the anodic oxygen evolution reaction increases the energy consumption of the overall water electrolysis for high-purity hydrogen generation. In this work, ultrathin cobalt sulfide nanosheets (Co3S4-NSs) on nickel foam (Ni-F) nanohybrids (termed as Co3S4-NSs/Ni-F) are synthesized using cyanogel hydrolysis and a sulfurization two-step approach. Physical characterizations reveal that Co3S4-NSs with a 1.7 nm thickness have abundant holes, implying the big surface area, abundant active edge atoms, and sufficient active sites. Electrochemical measurements show that as-synthesized Co3S4-NSs/Ni-F have excellent electrocatalytic activity and selectivity for ethanol oxidation reaction and hydrogen evolution reaction. Due to their bifunctional property of Co3S4-NSs/Ni-F nanohybrids, a symmetric Co3S4-NSs/Ni-F∥Co3S4-NSs/Ni-F ethanol electrolyzer can be effectively constructed, which only requires a 1.48 V electrolysis voltage to reach a current density of 10 mA cm-2 for high-purity hydrogen generation at the cathode as well as value-added potassium acetate generation at the anode, much lower than the electrolysis voltage of traditional electrochemical water splitting (1.64 V).