Phenanthroline-functionalized donor-acceptor covalent organic frameworks as photo-responsive nanozymes for visual colorimetric detection of isoniazid.

Development of metal-free nanozymes has raised concern for their extensive applications in photocatalysis and sensing fields. As novel metal-free nanomaterials, covalent organic frameworks (COFs) have engendered intense interest in the construction of nanozymes due to their structural controllability and molecular functionality. The formation of the molecular arrangement by embedding orderly donor-acceptors (D-A) linked in the framework topology to modulate material properties for highly efficient enzyme mimicking activity is of importance but challenging. Here, a strong D-A type of COF was designed and synthesized by integrating electron donor units (pyrene) and electron acceptor units (phenanthroline), named Py-PD COF. Using experiments and theoretical calculations, the introduction of a phenanthroline ring endowed the Py-PD COF with a narrowed band gap, and efficient charge transfer and separation. Further, the Py-PD COF exhibited a superior light-responsive oxidase-mimicking characteristic under visible light irradiation, which could catalyze the oxidation of 3,3',5,5-tetramethylbenzidine (TMB) and give the corresponding evolution of color. The nanoenzymatic activity of the Py-PD COF was light-regulated, which offers a fascinating advantage because of its high efficiency and spatial controllability. Based on previously mentioned characteristics, an "on-off" sensing platform for the colorimetric analysis of isoniazid (INH) could be constructed with a good linear relationship (2-100 µM) and a low limit of detection (1.26 µM). This research shows that not only is Py-PD COF an environmentally friendly compound for the colorimetric detection of INH, but it is also capable of providing the interesting D-A type COF-based material for designing an excellent nanozyme.

Enhanced Adsorption of Methyl Orange from Aqueous Phase Using Chitosan-Palmer Amaranth Biochar Composite Microspheres.

To develop valuable applications for the invasive weed Palmer amaranth, we utilized it as a novel biochar source and explored its potential for methyl orange adsorption through the synthesis of chitosan-encapsulated Palmer amaranth biochar composite microspheres. Firstly, the prepared microspheres were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy and were demonstrated to have a surface area of 19.6 m2/g, a total pore volume of 0.0664 cm3/g and an average pore diameter of 10.6 nm. Then, the influences of pH, dosage and salt type and concentration on the adsorption efficiency were systematically investigated alongside the adsorption kinetics, isotherms, and thermodynamics. The results reveal that the highest adsorption capacity of methyl orange was obtained at pH 4.0. The adsorption process was well fitted by a pseudo-second-order kinetic model and the Langmuir isotherm model, and was spontaneous and endothermic. Through the Langmuir model, the maximal adsorption capacities of methyl orange were calculated as 495.0, 537.1 and 554.3 mg/g at 25.0, 35.0 and 45.0 °C, respectively. Subsequently, the adsorption mechanisms were elucidated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy investigations. It is indicated that electrostatic interactions, hydrogen bonding, π-π interactions and hydrophobic interactions between methyl orange and the composite microspheres were pivotal for the adsorption process. Finally, the regeneration studies demonstrated that after five adsorption-desorption cycles, the microspheres still maintained 93.6% of their initial adsorption capacity for methyl orange. This work not only presents a promising method for mitigating methyl orange pollution but also offers a sustainable approach to managing Palmer amaranth invasion.

Exceptional piezocatalytic H2 production of nitrogen-doped TiO2@carbon nanosheets induced by engineered piezoelectricity.

Piezocatalytic hydrogen evolution is a promising strategy to generate sustainable energy. In this report, nitrogen-doped (N-doped) TiO2@ carbon nanosheets (N-TiO2@C NSs) was successfully synthesized using C3N4 as a multifunctional template. During the synthesis, the two-dimensional (2D) architecture of C3N4 nanosheets directed the synthesis of TiO2 nanosheets. In addition, nitrogens of C3N4 were doped into the TiO2 lattice. Simultaneously, C3N4 was transformed into N-doped carbon nanosheets. N doping broke the crystal symmetry of TiO2, which endowed TiO2 with promising piezoelectric properties. The N-doped carbon nanosheets derived from C3N4 improved charge carrier separation efficiency and served as a flexible support to inhibit structural damage under sonication. Therefore, the N-TiO2@C NSs exhibited highly efficient activity for piezocatalytic H2 production (6.4 mmol·g-1·h-1) in the presence of methanol, much higher than those of the previously reported piezocatalysts. Our method is hoped to provide a new strategy for designing highly efficient piezocatalysts.

Inhibition of phase transition from δ-MnO2 to α-MnO2 by Mo-doping and the application of Mo-doped MnO2 in aqueous zinc-ion batteries.

MnO2 is an oxide with many crystalline phases and is often used as a cathode material for aqueous zinc-ion batteries. However, its poor electrical conductivity and structural instability limit its further application. In the present work, Mo-doped MnO2 microflowers are successfully prepared by a facile hydrothermal method. Interestingly, it is found that the doping of Mo inhibits the phase transition from δ-MnO2 to α-MnO2, which may be related to the low crystallinity of Mo doped MnO2. Compared with undoped MnO2, Mo-doped MnO2 maintains two-dimensional morphology with a large specific surface area and mesoporous structure. In addition, the electronic conductivity and reversibility of Zn2+ insertion/extraction are improved in Mo doped MnO2. Therefore, Mo-doped MnO2 exhibits high reversible capacity and long cycling stability. For example, a high reversible capacity of 72.6 mA h g-1 can be achieved at a current density of 2000 mA g-1 after 2500 cycles.

Facile synthesis of hierarchical CdS nanoflowers for efficient piezocatalytic hydrogen evolution.

Piezocatalytic hydrogen evolution has emerged as a promising field for the collection and utilization of mechanical energy, as well as for generating sustainable energy throughout the day. Hexagonal CdS, an established semiconductor photocatalyst, has been widely investigated for its ability to split water into H2. However, its piezocatalytic performance has received less attention, and the relationship between its structure and piezocatalytic activity remains unclear. In this study, we prepared 3D ultrathin CdS nanoflowers with high voltage electrical response and low impedance. In pure water, without the use of any cocatalyst, CdS exhibited a piezoelectric catalytic hydrogen production rate of 1.46 mmol h-1 g-1, which was three times higher than that of CdS nanospheres (0.46 mmol h-1 g-1). Furthermore, the value-added oxidation product H2O2 was produced during the process of piezoelectric catalysis. These findings provide new insights for the design of high-efficiency piezoelectric catalytic hydrogen production.

Mechanistic insights into gel formation of egg-based yoghurt: The dynamic changes in physicochemical properties, microstructure, and intermolecular interactions during fermentation.

This study aimed to elucidate the mechanism of acid-induced gelation in egg-based yoghurt by investigating the dynamic changes in physicochemical properties, texture, rheology, and microstructure of the gel during fermentation, combined with the role of intermolecular forces in gel formation. Results showed that protein aggregation and cross-linking increased as pH decreased during fermentation. Gel hardness increased with fermentation, eventually reaching 11.36 g, while maintaining low fracturability. Water holding capacity (WHC) decreased from 91.77% to 73.13% during fermentation. Rheological testing demonstrated a significant increase in viscosity and dynamic moduli (G' and G''), consistent with the observation of a more compact microstructure by scanning electron microscopy (SEM) and particle size analysis. Furthermore, dynamic changes of surface hydrophobicity, sulfhydryl content, and intermolecular forces suggested that hydrophobic interactions were likely the main driving force for gel formation, as well as that hydrophobic interactions and disulfide bonds played an important role in the maintenance and construction of the gel network structure. Although ionic bonds and hydrogen bonds also had an effect on the gel formation of egg-based yoghurt, their contributions were not significant. The study provided new insights for the development of novel egg-based fermentation foods and the research of acid-induced protein gels, and also contributed to the deep exploitation and utilization of poultry eggs.

2D MXenes polar catalysts for multi-renewable energy harvesting applications.

The synchronous harvesting and conversion of multiple renewable energy sources for chemical fuel production and environmental remediation in a single system is a holy grail in sustainable energy technologies. However, it is challenging to develop advanced energy harvesters that satisfy different working mechanisms. Here, we theoretically and experimentally disclose the use of MXene materials as versatile catalysts for multi-energy utilization. Ti3C2TX MXene shows remarkable catalytic performance for organic pollutant decomposition and H2 production. It outperforms most reported catalysts under the stimulation of light, thermal, and mechanical energy. Moreover, the synergistic effects of piezo-thermal and piezo-photothermal catalysis further improve the performance when using Ti3C2TX. A mechanistic study reveals that hydroxyl and superoxide radicals are produced on the Ti3C2TX under diverse energy stimulation. Furthermore, similar multi-functionality is realized in Ti2CTX, V2CTX, and Nb2CTX MXene materials. This work is anticipated to open a new avenue for multisource renewable energy harvesting using MXene materials.

Spatial Separation of Electrons and Holes among ZnO Polar {0001} and {101Ì 0} Facets for Enhanced Photocatalytic Performance.

Spatial separation of electrons and holes is critical for improving their photocatalytic performance, which is ascribed to the suppressed photoinduced carriers' recombination among facets. In this work, the ZnO-Au-MnO x heterogeneous nanostructure photocatalyst was prepared by photodepositing Au and MnO x on the ZnO polar {0001} and {101̅0} crystal facets, respectively. The photocatalytic performance of ZnO-Au-MnO x was higher than ZnO and ZnO-Au for the degradation of rhodamine B dye under UV light irradiation. Due to the potential difference between different crystal planes of zinc oxide, electrons and holes will migrate to different crystal planes of zinc oxide. This will lead to the deposition of Au and MnO x on different crystal facets of zinc oxide. The efficient photoinduced carrier separation of ZnO-Au-MnO x resulted in the high photocatalytic activity, which is well supported by photoelectrochemical and photoluminescence analyses. The intermediated species formed during the reaction were investigated by high performance liquid chromatography. The reaction mechanism was investigated by radical trapping experiments and electron spin resonance analysis. The special structure of selective deposition of redox cocatalysts on the different facets should be promising and intriguing for designing highly efficient photocatalysts.

Palladium decoration directed synthesis of ZIF-8 nanocubes with efficient catalytic activity for nitrobenzene hydrogenation.

A palladium precursor (H2PdCl4) has been utilized as a novel structure-directing agent for controlling the morphology of ZIF-8. Using reverse micelles as nanoreactors, the Pd/ZIF-8 nanocomposite with a uniform size distribution is obtained. It is revealed that Pd(II) can selectively coordinate with the (100) plane of ZIF-8. As a result, the morphology of ZIF-8 is transformed from rhombic dodecahedral to cubic. After hydrogen treatment, the as-obtained Pd NPs/ZIF-8 nanocubes show efficient catalytic activity for nitrobenzene hydrogenation, which is higher than that of the commercially available Pd/C catalyst.

Seventeen novel angiotensin converting enzyme (ACE) inhibitory peptides from the protein hydrolysate of Mytilus edulis: isolation, identification, molecular docking study, and protective function on HUVECs.

In the study, seventeen angiotensin converting enzyme (ACE) inhibitory peptides were isolated from the protein hydrolysate of blue mussel (Mytilus edulis) and identified as MFR, MFV, FV, KP, QP, QVK, IK, YKV, IRK, MLKV, NFRPQ, YEGDP, WF, GPE, SWISS, SVEWK, and FKWH, respectively. Among them, IK, YEGDP, WF, and SWISS showed the strongest ACE inhibitory activity with IC50 values of 0.77 ± 0.020, 0.19 ± 0.010, 0.40 ± 0.015, and 0.32 ± 0.017 mg mL-1, respectively. Molecular docking study indicated that IK, YEGDP, WF, and SWISS exhibited better inhibitory activity attributed to its effective interaction with the active site of ACE by hydrogen bonding, electrostatic force and hydrophobic interaction. Furthermore, IK, YEGDP and WF perform an important protective function on human umbilical vein endothelial cells (HUVECs) by increasing nitric oxide (NO) content, decreasing endothelin-1 (ET-1) secretion, and antagonizing the adverse impact of norepinephrine on the secretion of NO and ET-1. In addition, YEGDP and WF could provide protection to HUVECs against H2O2 damage by increasing superoxide dismutase (SOD), glutathione peroxidase (GSH-Px) and NO levels to decrease the contents of reactive oxygen species (ROS) and malondialdehyde. Therefore, seventeen ACE inhibitory peptides, especially YEGDP and WF, might be used as natural ingredients for the development of products with antihypertensive functions.

Photocatalytic Anaerobic Oxidation of Aromatic Alcohols Coupled With H2 Production Over CsPbBr3/GO-Pt Catalysts.

Metal halide perovskites (MHPs) have been widely investigated for various photocatalytic applications. However, the dual-functional reaction system integrated selective organic oxidation with H2 production over MHPs is rarely reported. Here, we demonstrate for the first time the selective oxidation of aromatic alcohols to aldehydes integrated with hydrogen (H2) evolution over Pt-decorated CsPbBr3. Especially, the functionalization of CsPbBr3 with graphene oxide (GO) further improves the photoactivity of the perovskite catalyst. The optimal amount of CsPbBr3/GO-Pt exhibits an H2 evolution rate of 1,060 µmol g-1 h-1 along with high selectivity (>99%) for benzyl aldehyde generation (1,050 µmol g-1 h-1) under visible light (λ > 400 nm), which is about five times higher than the CsPbBr3-Pt sample. The enhanced activity has been ascribed to two effects induced by the introduction of GO: 1) GO displays a structure-directing role, decreasing the particle size of CsPbBr3 and 2) GO and Pt act as electron reservoirs, extracting the photogenerated electrons and prohibiting the recombination of the electron-hole pairs. This study opens new avenues to utilize metal halide perovskites as dual-functional photocatalysts to perform selective organic transformations and solar fuel production.

Titanate-derived Nb-doped TiO2 nanoparticles displaying improved lithium storage performance.

In the present work, a facile synthetic method has been used to prepare Nb-doped TiO2 nanoparticles with titanate as the precursor. The synthesized electrode materials were characterized using X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, inductively coupled plasma optical emission spectrometry and X-ray photoelectron spectroscopy. Furthermore, the Nb-doped TiO2 nanoparticles were used as anode materials for lithium-ion batteries and exhibited improved lithium-ion storage properties. For instance, Nb-doped TiO2 showed a high capacity of 134.1 mA h g-1 at 30 C, while undoped TiO2 exhibited a low capacity of 76.8 mA h g-1. These improvements may be associated with enhanced conductivity due to Nb doping.

Recent Progress in Pd-Based Nanocatalysts for Selective Hydrogenation.

Selective hydrogenation plays an important role in the chemical industry and has a wide range of applications, including the production of fine chemicals and petrochemicals, pharmaceutical synthesis, healthcare product development, and the synthesis of agrochemicals. Pd-based catalysts have been widely applied for selective hydrogenation due to their unique electronic structure and ability to adsorb and activate hydrogen and unsaturated substrates. However, the exclusive and comprehensive summarization of the size, composition, and surface and interface effect of metal Pd on the performance for selective hydrogenation is still lacking. In this perspective, the research progress on selective hydrogenation using Pd-based catalysts is summarized. The strategies for improving the catalytic hydrogenation performance over Pd-based catalysts are investigated. Specifically, the effects of the size, composition, and surface and interfacial structure of Pd-based catalysts, which could influence the dissociation mode of hydrogen, the adsorption, and the reaction mode of the catalytic substrate, on the performance have been systemically reviewed. Then, the progress on Pd-based catalysts for selective hydrogenation of unsaturated alkynes, aldehydes, ketones, and nitroaromatic hydrocarbons is revealed based on the fundamental principles of selective hydrogenation. Finally, perspectives on the further development of strategies for chemical selective hydrogenation are provided. It is hoped that this perspective would provide an instructive guideline for constructing efficient heterogeneous Pd-based catalysts for various selective hydrogenation reactions.

Novel covalent organic framework/PVDF ultrafiltration membranes with antifouling and lead removal performance.

Membrane separation technology is recognized as a competitive approach to remove Pb2+ from water system due to its high efficiency and low operating cost. In present study, a simple and facile approach was developed to fabricate covalent organic framework (COF) modified PVDF ultrafiltration membranes with comprehensive antifouling property and superior Pb2+ removal ability. Herein, COF was synthesised in a homogenous PVDF/DMAc solution to fabricate hydrophilic COF modified PVDF ultrafiltration membranes with the Pb2+ removal property. The filtration test demonstrated that the COF modified PVDF ultrafiltration membranes exhibited excellent antifouling property and high water flux. Moreover, the membranes showed remarkable potential for treating Pb2+-containing water. The removal efficiency was determined at 92.4%, and its removal efficiency was 87.5% at the fourth treatment cycle with Pb2+-containing water. The present work provides a valuable platform for further development of efficient composite membranes for the treatment of Pb2+-containing water.

Remarkable adsorption performance of MOF-199 derived porous carbons for benzene vapor.

Volatile organic compounds (VOCs) are perceived as serious pollutants due to their great threat to both environment and human health. Recovery and removal of VOCs is of great significance. Herein, novel MOF-199 derived porous carbon materials (MC-T-n) were prepared by using MOF-199 as precursor, glucose as additional carbon source and KOH as activator, and then characterized. Adsorption performance of MC-T-n materials for benzene vapor was investigated. Isotherms of MC-T-n samples towards benzene and water vapor were measured. The adsorption selectivities of benzene/water were estimated by DIH (difference of the isosteric heats) equation. Results indicated that BET surface area and pore volume of MC-T-n materials reached separately 2320 m2/g and 1.05 m3/g. Benzene adsorption capacity of MC-T-n materials reached as high as 12.8 mmol/g at 25 °C, outperforming MOF-199 and some conventional adsorbents. Moreover, MC-T-n materials presented type-V isotherms of water vapor, suggesting their excellent water resistance. The isosteric heats of benzene adsorption on MC-500-6 were much greater than that of water adsorption, leading to a preferential adsorption for C6H6 over H2O. The adsorption selectivity of C6H6/H2O on MC-500-6 reached up to 16.3 superior to some previously reported MOFs. Therefore, MC-500-6 was a promising candidate for VOC adsorption and seperation. This study provides a strong foundation for MOF derived porous carbons as adsorbents for VOC removal.

A redox-active support for the synthesis of Au@SnO2 core-shell nanostructure and SnO2 quantum dots with efficient photoactivities.

A defect pyrochlore-type Sn1.06Nb2O5.59F0.97 (SnNbOF) nano-octahedron is used as a redox-active support for fabricating Au@SnO2 core-shell and SnO2 quantum dots at room temperature without the use of organic species or foreign reducing reagents. Gold (Au) and SnO2 components were obtained through an in situ redox reaction between the HAuCl4 and reductive Sn2+ ions incorporated in SnNbOF. The composition and morphology of the resulting nanocomposites (denoted as Au-SnNbOF) could be controlled by adjusting the Au/SnNbOF ratio. The Au-SnNbOF nanocomposites exhibited efficient photoactivities for methyl orange (MO) degradation under the visible light irradiation (λ > 420 nm), during which the MO was almost completely degraded within 8 min. Among all the samples, the 5wt% Au-SnNbOF nanocomposite had the highest rate constant (0.43 min-1), which was 40 times higher than that of the blank SnNbOF.

Novel Hierarchical Fe(III)-Doped Cu-MOFs With Enhanced Adsorption of Benzene Vapor.

New hierarchical Fe(III)-doped Cu-MOFs (Fe-HK) were developed via introduction of Fe3+ ions during HKUST-1 synthesis. The obtained products were characterized by N2 adsorption, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, FTIR spectroscopy, and thermal analysis. The adsorption isotherms and kinetics of benzene vapor were measured and consecutive adsorption-desorption cycles were performed. It was found that the hierarchical-pore Fe-HK-2 exhibited optimal textural properties with high BET surface area of 1,707 m2/g and total pore volume of 0.93 cm3/g, which were higher than those of the unmodified HKUST-1. Significantly, the hierarchical-pore Fe-HK-2 possessed outstanding benzene adsorption capacity, which was 1.5 times greater than the value on HKUST-1. Benzene diffusivity of Fe-HK-2 was 1.7 times faster than that of parent HKUST-1. Furthermore, the benzene adsorption on Fe-HK-2 was highly reversible. The hierarchical-pore Fe-HK-2 with high porosity, outstanding adsorption capacity, enhanced diffusion rate, and excellent reversibility might be an attractive candidate for VOCs adsorption. This may offer a simple and effective strategy to synthesize hierarchical-pore MOFs by doping with other metal ions.

Core-Shell Au@SnO2 Nanostructures Supported on Na2Ti4O9 Nanobelts as a Highly Active and Deactivation-Resistant Catalyst toward Selective Nitroaromatics Reduction.

Catalysis using gold (Au) nanoparticles has become an important field of chemistry. However, activity loss caused by aggregation or leaching of Au nanoparticles greatly limits their application in catalytic reaction. Herein, we report a facile and green synthesis of a core-shell Au@SnO2 nanocomposite, exhibiting excellent activity toward selective nitroaromatics reduction under mild conditions. The core-shell Au@SnO2 nanocomposite (Au size = ∼50 nm; shell thickness = ca. 16 nm) is conceived and validated by a direct redox reaction between HAuCl4 and SnF2. Optimization of the core size, shell thickness, and dispersion of Au@SnO2 has been introduced by an alkaline surface supported by negatively charged metal oxide Na2Ti4O9. The as-obtained Au-Sn-Na2Ti4O9 catalyst with much smaller Au cores (ca. 5 nm) and thinner SnO2 nondensed shells (ca. 4 nm) exhibits highly improved catalytic activities for nitro reduction compared to most of the known Au-based catalysts. Moreover, the core-shell Au@SnO2 structure inhibits the leaching and agglomeration of Au nanoparticles and thus leads to superior catalytic durability.

Four Antioxidant Peptides from Protein Hydrolysate of Red Stingray (Dasyatis akajei) Cartilages: Isolation, Identification, and In Vitro Activity Evaluation.

In the work, water-soluble proteins of red stingray (Dasyatis akajei) cartilages were extracted by guanidine hydrochloride and hydrolyzed using trypsin. Subsequently, four antioxidant peptides (RSHP-A, RSHP-B, RSHP-C, and RSHP-D) were isolated from the water-soluble protein hydrolysate while using ultrafiltration and chromatographic techniques, and the amino acid sequences of RSHP-A, RSHP-B, RSHP-C, and RSHP-D were identified as Val-Pro-Arg (VPR), Ile-Glu-Pro-His (IEPH), Leu-Glu-Glu--Glu-Glu (LEEEE), and Ile-Glu-Glu-Glu-Gln (IEEEQ), with molecular weights of 370.46 Da, 494.55 Da, 647.64 Da, and 646.66 Da, respectively. VPR, IEPH, LEEEE, and IEEEQ exhibited good scavenging activities on the DPPH radical (EC50 values of 4.61, 1.90, 3.69, and 4.01 mg/mL, respectively), hydroxyl radical (EC50 values of 0.77, 0.46, 0.70, and 1.30 mg/mL, respectively), superoxide anion radical (EC50 values of 0.08, 0.17, 0.15, and 0.16 mg/mL, respectively), and ABTS cation radical (EC50 values of 0.15, 0.11, 0.19, and 0.18 mg/mL, respectively). Among the four isolated antioxidant peptides, IEPH showed the strongest reducing power and lipid peroxidation inhibition activity, but LEEEE showed the highest Fe2+-chelating ability. The present results suggested that VPR, IEPH, LEEEE, and IEEEQ might have the possibility of being an antioxidant additive that is used in functional food and pharmaceuticals.

A New Defect Pyrochlore Oxide Sn1.06Nb2O5.59F0.97: Synthesis, Noble Metal Hybrids, and Photocatalytic Applications.

Noble metal nanoparticles have attracted considerable attention due to their useful capabilities as heterogeneous catalysts. However, they are usually prepared using various organic stabilizing agents that negatively affect their catalytic activities. Herein, we report a facile, clean, and effective method for synthesizing supported ultrafine noble metal nanoparticles by utilizing the reductive property of a new pyrochlore oxide: Sn1.06Nb2O5.59F0.97 (SnNbOF). Ultrafine Au, Pd, and Pt nanoparticles or clusters are homogeneously distributed on the SnNbOF surface. In addition, the atomic cavities and ion-exchange properties of pyrochlore-type SnNbOF can facilitate the synthesis of atomic Ag dispersed within the framework of SnNbOF. Noble metal-SnNbOF hybrids can be obtained in one step at room temperature, and no foreign reducing agents or stabilizing organics are required for the synthesis. We also show that the fabricated hybrids exhibit promising photocatalytic properties for ethylene oxidation and CO2 reduction.