Dynamic defects boost in-situ H2O2 piezocatalysis for water cleanup.

Creating efficient catalysts for simultaneous H2O2 generation and pollutant degradation is vital. Piezocatalytic H2O2 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 H2O2 from H2O and O2 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 H2O2, significantly outperforming pure ZnO. Notably, the CZO piezocatalyst maintains its H2O2 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 H2O2 production, as confirmed by EPR spectrometry, XPS analysis, and DFT calculations. Moreover, the CZO piezocatalysts maintain outstanding performance in pollutant degradation and H2O2 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.

Hydrogen Nanobubbles Generated In Situ from Nanoscale Zerovalent Iron with Water to Further Enhance Selenite Sequestration.

Gas nanobubbles used for water treatment and recovery give rise to great concern for their unique advantages of less byproducts, higher efficiency, and environmental friendliness. Nanoscale zerovalent iron (nZVI), which has also been widely explored in the field of environmental remediation, can generate gas hydrogen by direct reaction with water. Whether nanoscale hydrogen bubbles can be produced to enhance the pollution removal of the nZVI system is one significant concern involved. Herein, we report direct observations of in situ generation of hydrogen nanobubbles (HNBs) from nZVI in water. More importantly, the formed HNBs can enhance indeed the reduction of Se(IV) beyond the chemical reduction ascribed to Fe(0), especially in the anaerobic environment. The possible mechanism is that HNBs enhance the reducibility of the system and promote electron transport in the solution. This study demonstrates a unique function of HNBs combined with nZVI for the pollutant removal and a new approach for in situ HNB generation for potential applications in the fields of in situ remediation agriculture, biotechnology, medical treatment, health, etc.

In Situ Production of Hydroxyl Radicals via Three-Electron Oxygen Reduction: Opportunities for Water Treatment.

The electro-Fenton (EF) process is an advanced oxidation technology with significant potential; however, it is limited by two steps: generation and activation of H2O2. In contrast to the production of H2O2 via the electrochemical two-electron oxygen reduction reaction (ORR), the electrochemical three-electron (3e-) ORR can directly activate molecular oxygen to yield the hydroxyl radical (⋅OH), thus breaking through the conceptual and operational limitations of the traditional EF reaction. Therefore, the 3e- ORR is a vital process for efficiently producing ⋅OH in situ, thus charting a new path toward the development of green water-treatment technologies. This review summarizes the characteristics and mechanisms of the 3e- ORR, focusing on the basic principles and latest progress in the in situ generation and efficient utilization of ⋅OH through the modulation of the reaction pathway, shedding light on the rational design of 3e- ORR catalysts, mechanistic exploration, and practical applications for water treatment. Finally, the future developments and challenges of efficient, stable, and large-scale utilization of ⋅OH are discussed based on achieving optimal 3e- ORR regulation and the potential to combine it with other technologies.

Horseradish peroxidase (HRP) and glucose oxidase (GOX) based dual-enzyme system: Sustainable release of H2O2 and its effect on the desirable ping pong bibi degradation mechanism.

In this study, an adaptable HRP/GOX-Glu system was established due to the trait, efficient degradation of pollutants in the catalytic process of HRP named the ping-pong bibi mechanism and a sustained release of H2O2 in-situ under the catalysis of glucose oxidase (GOX). Compared with the traditional HRP/H2O2 system, the HRP was more stable in the HRP/GOX-Glu system based on the feature of persistent releasing H2O2 in-situ. Simultaneously, the high valent iron was found out to give a greater contribution to Alizarin Green (AG) removal through ping-pong mechanism, whereas the hydroxyl radical and superoxide free radical generated by Bio-Fenton were also the main active substances for AG degradation. Furthermore, on the basis of effect evaluation of the co-existence of two different degradation mechanisms in the HRP/GOX-Glu system, the degradation pathways of AG were proposed. Moreover, the optimum reaction conditions preferentially triggering ping-pong bibi mechanism instead of Bio-Fenton were determined by single factor analysis and degradation mechanism elaboration. This study would provide a reference for how to give full play to the advantages of ping-pong bibi mechanism in the dual-enzyme system based on HRP to degrade pollutants with high efficiency.

In situ enzymatic generation of Au/Pt nanoparticles as an analytical photometric system: proof of concept determination of tyramine.

In situ enzymatic generation of bimetallic nanoparticles, mainly Au/Pt, overcomes the drawbacks (continuous absorbance drift, modest LOQ, and long-time reaction) observed when AuNP alone are produced. In this study, Au/Pt nanoparticles have been characterized by EDS, XPS, and HRTEM images using the enzymatic determination of tyramine with tyramine oxidase (TAO) as a model. Under experimental conditions, the Au/Pt NPs show an absorption maximum at 580 nm which can be related to the concentration of tyramine in the range 1.0 × 10-6M to 2.5 × 10-4M with a RSD of 3.4% (n = 5, using 5 × 10-6M tyramine). The Au/Pt system enables low LOQ (1.0 × 10-6 M), high reduction of the absorbance drift, and a significant shortening of the reaction time (i.e., from 30 to 2 min for a [tyramine] = 1 × 10-4M); additionally, a better selectivity is also obtained. The method has been applied to tyramine determination in cured cheese and no significant differences were obtained compared to a reference method (HRP:TMB). The effect of Pt(II) seems to involve the previous reduction of Au(III) to Au(I) and NP generation from this oxidation state. Finally, a three-step (nucleation-growth-aggregation) kinetic model for the generation of NPs is proposed; this has enabled us to obtain a mathematical equation which explains the experimentally observed variation of the absorbance with time.

Self-Regulating Solar Steam Generators Enable Volatile Organic Compound Removal through In Situ H2O2 Generation.

Interfacial solar steam generation for clean water production suffers from volatile organic compound (VOC) contamination during solar-to-steam conversion. Here, we present a solar steam generator based on the integration of melamine foam (MF), polydopamine (PDA), and Ag/AgCl particles. Together with the high photothermal conversion efficiency (ca. 87.8%, 1 kW/m2) achieved by the PDA thin film, the Ag/AgCl particles can efficiently activate the localized generation of H2O2 and •OH in situ, thus degrading the VOCs during the rapid vapor generation. The generation of H2O2 and •OH in situ also facilitates the creation of a buffer zone containing H2O2 and •OH for the rapid removal of organic pollutants in the surrounding water attracted to the solar vapor generator, demonstrating a self-cleaning steam generator toward various volatile compounds such as phenol, aniline, 2,4-dichlorophenol, and N,N-dimethylformamide in a wide range of concentrations.

Enhancement of solar-driven photocatalytic activity of oxygen vacancy-rich Bi/BiOBr/Sr2LaF7:Yb3+,Er3+ composites through synergetic strategy of upconversion function and plasmonic effect.

For better use of solar energy, the development of efficient broadband photocatalyst has attracted extraordinary attention. In this study, a ternary composite consisting of Sr2LaF7:Yb3+,Er3+ upconversion (UC) nanocrystals and Bi nanoparticles loaded BiOBr nanosheets with oxygen vacancies (OVs, SLFBB) was designed and synthesized by multistep solvent-thermal method. Mechanisms of in-situ formation of Bi nanoparticles and OVs in BiOBr/Sr2LaF7:Yb3+,Er3+ composites (SFLB) are clarified. The Bi metal and OVs enhanced the light-harvesting capacity in the region of visible-near-infrared (Vis-NIR), and promoted the separation of electron-hole (e-/h+) pairs. Furthermore, the surface plasmon resonance (SPR) effect of Bi metal can improve the energy transfer from Sr2LaF7:Yb3+,Er3+ to BiOBr via nonradiative energy transfer process, resulting in enhancing the light utilization from upconverting NIR into Vis light. Due to the synergistic effects of UC function, SPR and OVs, the SFLBB exhibited obviously enhanced photocatalytic ability for the degradation of BPA with a rate of 8.9 × 10-3 min-1, which is about 2.78 times higher than 3.2 × 10-3 min-1 of BiOBr (BOB) under UV-Vis-NIR light irradiation. This work provides a novel strategy for the project of high-efficiency Bismuth-based broadband photocatalysts, which is helpful to further understand the mechanism of enhanced photocatalysis by UC function and plasmonic effect.

Spiropyran-Appended Cucurbit[6]uril Enabling Direct Generation of 2D Materials inside Living Cells.

The unique structural advantage and physicochemical properties render some 2D materials emerging platforms for intracellular bioimaging, biosensing, or disease theranostics. Despite recent advances in this field, one major challenge lies in bypassing the endocytic uptake barrier to allow internalization of very large 2D materials that have longer retention time in cells, and hence greater potency as intracellular functional platforms than small, endocytosable counterparts. Here, an engineered cucurbit[6]uril carrying at its periphery multiple spiropyran pendants that readily translocates into cytosol, and then polymerizes laterally and non-covalently in a controlled manner, enabling direct generation of 2D materials inside living cells, is reported. The resultant 2D materials are single-monomer-thick and can in situ grow up to 0.8-1.2 µm in lateral size, experimentally proved too large to be endocytosed from outside the cells even after surface engineered with biorecognition entities. A Förster resonance energy transfer assay is further devised for real-time visualization of the polymerization dynamics in vivo, clearly demonstrating the rationale in this study. With the otherwise non-endocytosable large 2D materials gaining access to cytosol, potent intracellular signaling or theranostic platform that surpasses the intrinsic performance limit of conventional small counterparts are in sight.

In-Situ Formed Protecting Layer from Organic/Inorganic Concrete for Dendrite-Free Lithium Metal Anodes.

In this work, a separator modified by composite material of graphite fluoride nanosheets and poly(vinylidene difluoride) (GFNs-PVDF) is fabricated to in-situ construct a protective layer on Li metal anodes. The much-improved mechanical properties of this organic/inorganic protecting layer ensure efficient restriction on the growth of Li dendrites. The LiF and graphene nanosheets generated by the reaction of GFNs with lithium metal can not only provide fast transport channels for Li ions but also protect the Li metal anode from continuous corrosion of electrolytes. In addition, GFNs' lithiophilic nature guarantees the uniform Li nucleation site and perfect contact between li metal and the protecting layer without void space, leading to a low interfacial impedance and layer-by-layer lithium deposition. Together with the scalable method and cheap raw materials, this strategy provides new insights toward practical applications of Li metal batteries.

Fenton-like oxidation of 4-chlorophenol using H2O2 in situ generated by Zn-Fe-CNTs composite.

In this paper, a zinc-iron-carbon nanotubes (Zn-Fe-CNTs) composite was prepared, characterized and used to develop a Fenton-like system of Zn-Fe-CNTs/O2 for the degradation of 4-chlorophenol (4-CP), in which H2O2 was generated in situ from zinc-carbon galvanic cells and oxygen in aqueous solution was activated by iron attached on the surface of CNTs to produce ·OH radicals for the oxidation of 4-CP. The experimental results showed that the particles of Zn and Fe in Zn-Fe-CNTs composite were adhered to the surface of CNTs, which accelerated the electron transfer process. The BET area of Zn-Fe-CNTs composite was 32.9 m2/g. The contents of Zn and Fe (% w) in the composite were 44.7% and 4.2%, respectively. The removal efficiency of 4-CP and TOC in Zn-Fe-CNTs/O2 system was 90.8% and 52.9%, respectively, with the initial pH of 2.0, O2 flow rate of 800 mL/min, Zn-Fe-CNTs dosage of 1.0 g/L, 4-CP concentration of 50 mg/L and reaction time of 20 min. Based on the analysis of the degradation intermediate products with LC-MS and IC, a possible degradation pathway of 4-CP in Zn-Fe-CNTs/O2 system was proposed.

In-situ generation of gold nanoparticles on MnO2 nanosheets for the enhanced oxidative degradation of basic dye (Methylene Blue).

In this work, the gold nanoparticles (Au-NPs) were in-situ generated on the surface of MnO2 nanosheets to form MnO2/Au-NPs nanocomposite in a simple and cost-effective way. Multiple experiments were carried out to optimize the oxidation of basic dye (Methylene Blue (MB)), including the molar ratio of MnO2 to chloroauric acid (HAuCl4), the pH of the solution and the effect of initial material. Under the optimal condition, the highest degradation efficiency for MB achieved to 98.9% within 60 min, which was obviously better than commercial MnO2 powders (4.3%) and MnO2 nanosheets (74.2%). The enhanced oxidative degradation might attribute to the in-situ generation of ultra-small and highly-dispersed Au-NPs which enlarged the synergistic effect and/or interfacial effect between MnO2 nanosheets and Au-NPs and facilitated the uptake of electrons by MnO2 from MB during the oxidation, thus validating the application of MnO2/Au-NPs nanocomposite for direct removal of organic dyes from wastewater in a simple and convenient fashion.

Generation of C(2)F(5)CHN(2) in situ and its first reaction: [3+2] cycloaddition with alkenes.

The novel chemical reagent, C2 F5 CHN2 , is generated in situ from C2 F5 CH2 NH2 ⋅HCl and sodium nitrite. It reacts with mono- and disubstituted electron-deficient alkenes at room temperature to afford C2 F5 -pyrazolines in excellent yields.

In Situ Construction of Morphologically Different Hydroxyapatite-Mineralized Structures on a Three-Dimensional Bionic Chitin Scaffold.

Slow healing at the tendon-bone interface is a prominent factor in the failure of tendon repair surgeries. The development of functional biomaterials with 3D gradient structures is urgently needed to improve tendon-bone integration. The crystalline form of hydroxyapatite (HAP) has a crucial impact on cell behavior, which directly influences protein adsorption, such as bone morphogenetic protein 2, the adhesion, proliferation, and osteogenic differentiation with cells. This work aimed to generate gradient mineral structures in situ by stabilizing calcium and phosphate ions using a polymer-induced liquid precursor process. To regulate the crystalline growth of HAP at the interface of ß-chitin, this work made use of the surface properties of the organic matrix found in cuttlefish bone. These techniques allowed us to prepare an organic-inorganic composite gradient scaffold comprising plate-like HAP mineralized in situ on the surface of the scaffold and fibrous HAP in the scaffold's interior. Organic-inorganic composite gradient materials are anticipated for use in tendon-bone healing produced via the in situ construction of gradient-distributed HAP mineralization layers having varying crystalline morphologies on chitin scaffolds that possess a three-dimensional bionic structure.

CYP116B5-SOX: An artificial peroxygenase for drug metabolites production and bioremediation.

CYP116B5 is a class VII P450 in which the heme domain is linked to a FMN and 2Fe2S-binding reductase. Our laboratory has proved that the CYP116B5 heme domain (CYP116B5-hd) is capable of catalyzing the oxidation of substrates using H2O2. Recently, the Molecular Lego approach was applied to join the heme domain of CYP116B5 to sarcosine oxidase (SOX), which provides H2O2 in-situ by the sarcosine oxidation. In this work, the chimeric self-sufficient fusion enzyme CYP116B5-SOX was heterologously expressed, purified, and characterized for its functionality by absorbance and fluorescence spectroscopy. Differential scanning calorimetry (DSC) experiments revealed a TM of 48.4 ± 0.04 and 58.3 ± 0.02°C and a enthalpy value of 175,500 ± 1850 and 120,500 ± 1350 cal mol-1 for the CYP116B5 and SOX domains respectively. The fusion enzyme showed an outstanding chemical stability in presence of up to 200 mM sarcosine or 5 mM H2O2 (4.4 ± 0.8 and 11.0 ± 2.6% heme leakage respectively). Thanks to the in-situ H2O2 generation, an improved kcat/KM for the p-nitrophenol conversion was observed (kcat of 20.1 ± 0.6 min-1 and KM of 0.23 ± 0.03 mM), corresponding to 4 times the kcat/KM of the CYP116B5-hd. The aim of this work is the development of an engineered biocatalyst to be exploited in bioremediation. In order to tackle this challenge, an E. coli strain expressing CYP116B5-SOX was employed to exploit this biocatalyst for the oxidation of the wastewater contaminating-drug tamoxifen. Data show a 12-fold increase in tamoxifen N-oxide production-herein detected for the first time as CYP116B5 metabolite-compared to the direct H2O2 supply, equal to the 25% of the total drug conversion.

Stable detection of diazinon residues in vegetables by an electrochemiluminescent aptasensor based on the in-situ production of H2O2 from dual-catalytic glucose.

Stable detection of diazinon (DZN) residues in vegetables is important for food safety. In this work, an electrochemiluminescence (ECL) aptasensor with dual-catalytic glucose in-situ production of H2O2 was constructed for the stable detection of DZN in vegetables. Firstly, MWCNTs@MB was prepared using π-π stacking interactions between methylene blue (MB) and multi-walled carbon nanotubes (MWCNTs) to enhance the loading of MB on an electrode and thus catalyze the generation of H2O2 from glucose. Secondly, Cu2O@AuNPs was formed by loading AuNPs on the surface of Cu2O through spontaneous reduction reaction, which improved the interfacial charge transfer, Cu2O nano-enzyme had glucose oxidase mimicking activity and could further catalyze the production of more H2O2 from glucose. MWCNTs@MB and Cu2O@AuNPs played a key role in the in-situ generation of co-reacting reagent H2O2, which solved the problem of unstable detection caused by the easy decomposition of the H2O2 solution added to the luminescence system. In addition, the aptamer was immobilized on the electrode surface by forming Au-S bonds with Cu2O@AuNPs. As a result, the ECL aptasensor performed good linearity in 1.00 pg mL-1-1.00 µg mL-1 and a low limit of detection (LOD) to 0.39 pg mL-1 (S/N = 3). This work provided an effective method for the accurate and stable detection of DZN residues in vegetables, which was of great significance in ensuring food safety and assessing the environmental risk of DZN.

Spark plasma sintered porous Ni as a novel substrate of Ni3Se2@Ni self-supporting electrode for ultra-durable hydrogen evolution reaction.

Developing efficient and durable self-supporting catalytic electrodes is an important way for industrial applications of hydrogen evolution reaction. Currently, commercial nickel foam (NF)-based electrode has been widely used due to its good catalytic performance. However, the NF consisting of smooth skeleton surface and large pores not only exhibits poor conductivity but also provides insufficient space for catalyst decoration and sufficient adhesion, resulting in inadequate catalytic performance and poor durability of NF-based electrodes. In this paper, a novel three-dimensional porous Ni substrate with multangular skeleton surface and small pore structure was prepared by a modified spark plasma sintering technique, and subsequently Ni3Se2@Porous Ni electrode with a large number of Ni3Se2 nanosheets uniformly distributed on the surface was obtained by one-step in-situ selenization. The electrode exhibits outstanding conductivity and catalytic hydrogen evolution reaction, providing a low overpotential of 183 mV at a current density of 100 mA cm-2. Due to the strong interfacial bonding between Ni and Ni3Se2, the Ni3Se2@Porous Ni electrode shows strong durability, which can work stably at 85 mA cm-2 for more than 200 h. This work provides an effective strategy for the rational preparation of metal substrates for efficient and durable self-supporting catalytic electrodes.

Enhancing Lithium-Ion Diffusion Kinetics in a 3D Lithium Metal Host through Surface Modification with Hierarchical Multimetal Oxides.

Lithium metal is a promising anode candidate to achieve high-energy-density lithium metal batteries (LMBs) due to its ultrahigh theoretical capacity (3860 mA h g-1) and low electrochemical potential (-3.04 V vs S.H.E). Unfortunately, the commercialization of lithium metal anodes is hindered by the growth of Li dendrites and the infinite Li volume changes during the cycling process. Herein, we introduce a 3D hierarchical multimetal oxide nanowire framework as a current collector for Li metal anodes. The hierarchical metal oxide layers of CoO and CuxO provide abundant Li nucleation sites and thus offer uniform Li plating and regulate Li nucleation during the charge/discharge process. As a result, half cells present a prolonging Coulombic efficiency of 97% at 1 mA cm-2 with a capacity of 1 mA h cm-2 for over 300 cycles. A stable cyclability of symmetric cells is demonstrated under 1 mA cm-2 with a capacity of 1 mA h cm-2 for 1500 h. Full cells paired with an LFP cathode show a stable capacity of 131.5 mA h g-1 with a capacity retention of 92% for 200 cycles. These results will shed insights into the design of 3D Cu current collectors for high-performance composite Li metal anodes.

Organism-Generated Biological Vesicles In Situ: An Emerging Drug Delivery Strategy.

Biological vesicles, containing genetic materials and proteins of the original cells, are usually used for local or systemic communications among cells. Currently, studies on biological vesicles as therapeutic strategies or drug delivery carriers mainly focus on exogenously generated biological vesicles. However, the limitations of yield and purity caused by the complex purification process still hinder their clinical transformation. Recently, it has been reported that living organisms, including cells and bacteria, can produce functional/therapeutic biological vesicles within body automatically. Therefore, using organisms to produce endogenous biological vesicles in body as drug/bio-information delivery carriers has become a potential therapeutic strategy. In this review, the current development status and application prospects of in situ organism-produced biological vesicles are introduced. The advantages and effects of this endogenous biological vesicles-based strategy in drug delivery and disease treatments are analyzed. According to the type of endogenous biological vesicles, they are divided into four categories: exosomes, platelet-derived microparticles, apoptotic bodies, and bacteria-released outer membrane vesicles. And finally, the shortcomings of current research and future development are analyzed. This review is believed to open up the application of endogenous biological vesicles in the field of biomedicine and shed light on current research.

In Situ Programming of CAR-T Cells: A Pressing Need in Modern Immunotherapy.

Chimeric antigen receptor-T (CAR-T) cell-based therapy has become a successful option for treatment of numerous hematological malignancies, but also raises hope in a range of non-malignant diseases. However, in a traditional approach, generation of CAR-T cells is associated with the separation of patient's lymphocytes, their in vitro modification, and expansion and infusion back into patient's bloodstream. This classical protocol is complex, time-consuming, and expensive. Those problems could be solved by successful protocols to produce CAR-T cells, but also CAR-natural killer cells or CAR macrophages, in situ, using viral platforms or non-viral delivery systems. Moreover, it was demonstrated that in situ CAR-T induction may be associated with reduced risk of the most common toxicities associated with CAR-T therapy, such as cytokine release syndrome, immune effector cell-associated neurotoxicity syndrome, and "on-target, off-tumor" toxicity. This review aims to summarize the current state-of-the-art and future perspectives for the in situ-produced CAR-T cells. Indeed, preclinical work in this area, including animal studies, raises hope for prospective translational development and validation in practical medicine of strategies for in situ generation of CAR-bearing immune effector cells.

Reuse of used paper egg carton boxes as a source to produce hybrid AgNPs- carboxyl nanocellulose through bio-synthesis and its application in active food packaging.

The proper disposal of disposable synthetic plastic food packaging materials presents a significant challenge for both the environment and the solid waste management community. To address this issue, an antibacterial-based high-strength bio-composite serves as the optimal alternative to conventional packaging materials. This study aims to produce a hybrid material of AgNPs-carboxyl cellulose nanocrystals (AgNPs-CCNCs), obtained from used egg carton boxes (UECBs), through bio acid hydrolysis and an in-situ generation process. Furthermore, AgNPs- carboxyl cellulose nanofibers (AgNPs-CCNFs) will be synthesized through a combination of bio acid hydrolysis and ball milling, followed by an additional in-situ generation step. The AgNPs-carboxyl nanocellulose (AgNPs-CCNCs, and AgNPs-CCNFs) exhibited excellent crystallinity index, morphology, thermal, and antibacterial properties. The morphological analysis was performed by electron microscopy, and the results showed the uniform distribution and spherical form of AgNPs appearing over the carboxyl nanocellulose through the in-situ generation process, which was confirmed through XRD analysis. The study further explores the impact of AgNPs-carboxyl nanocellulose on the mechanical, chemical, antibacterial, and thermal properties of the PVA matrix. The results demonstrate that the bio-nanocomposite film offers opportunities for utilization in active packaging applications.