Modification Strategies Research Articles

Polymorphism of CL-20 and the Modification and Inhibition Strategies for Its Crystal Transformation

Polymorphism of CL-20 and the Modification and Inhibition Strategies for Its Crystal Transformation

HZSM-5 supported with N-doped Fe for microwave catalytic pyrolysis of lignin

Microwave catalytic pyrolysis of lignin is one of emerging technologies for efficiently converting lignin into fuels and chemicals. Molecular sieves (HZSM-5) are widely used as carriers to load metallic components for biomass pyrolysis but often encounter challenges such as high diffusion resistance and insufficient acidity of acidic sites. Traditionally, HZSM-5 is directly modified to enhance the activity of the acidic sites, but this modification is ineffective in improving the metallic components’ activity. Instead, we made nitrogen doping on Fe and then supported on HZSM-5 to construct Fe-N25/HZSM-5 catalysts for microwave catalytic pyrolysis of lignin. The N-doped Fe has the effect of “killing two birds with one stone” on enhancing the catalytic activity. The characterization results indicated that N replaced C of the graphitic carbon network to form carbon nitride structure, and further combined with Fe to generate Fe-N bonds, improving the electronegativity of the metallic component. Besides, the loading of N-doped Fe increased the acidity of the catalyst. The utilization of 1.00Fe-N25/HZSM-5 obtained the greatest bio-gas yield (35.2 wt%), a hydrogen yield of 27.8 mL/min, bio-oil yield (36.4 wt%) and phenol selectivity of 46.2 %. The likely pathway of microwave catalytic pyrolysis on Fe-N25/HZSM-5 was proposed through DFT calculation, using guaiacol as a model compound. The results suggested that N-doped Fe on HZSM-5 8 T tended to break the side-chain methoxy during pyrolysis of guaiacol, with energy barrier of 0.14 eV. This paper provides a promising strategy for modification of microwave pyrolysis catalysts.

High-Performance, High-Resolution Quantum Dot Light-Emitting Diodes with Self-Assembly Single-Molecular Interface Modification.

With the development of near-eye displays, the demands for display resolution and performance are increasing. Quantum dot performance is virtually independent of pixel size, making it an efficient way to display ultrahigh resolution. However, the low efficiency of high-resolution quantum dot devices has been an urgent technical bottleneck to be solved. Here, we constructed a dense single-molecule modification layer and a leakage current blocking layer for high-resolution devices using self-assembly, thereby realizing ultrahigh-resolution, high-efficiency, and stable high-resolution quantum dot light-emitting diodes (QLEDs). The peak external quantum efficiencies of the red devices are 24.68% (8759 PPI) and 19.54% (26075 PPI), respectively, with an exceptional long lifetime (T95@1000 nit) up to 4871 h. In addition, we explored the feasibility of this modification strategy on non-Cd-based quantum dots. In conclusion, our strategy effectively improves the performance of high-resolution devices and provides a superior approach for realizing near-eye display applications.

Fundamentals and Challenges of Ligand Modification in Heterogeneous Electrocatalysis.

The development of efficient catalytic materials in the energy field could promote the structural transformation from traditional fossil fuels to sustainable energy. In heterogeneous catalytic reactions, ligand modification is an effective way to regulate both electronic and steric structures of catalytic sites, thus paving a prospective avenue to design the interfacial structures of heterogeneous catalysts for energy conversion. Although great achievements have been obtained for the study and applications of heterogeneous ligand-modified catalysts, the systematical refinements of ligand modification strategies are still lacking. Here, we reviewed the ligand modification strategy from both the mechanistic and applicable scenarios by focusing on heterogeneous electrocatalysis. We elucidated the ligand-modified catalysts in detail from the perspectives of basic concepts, preparation, regulation of physicochemical properties of catalytic sites, and applications in different electrocatalysis. Notably, we bridged the electrocatalytic performance with the electronic/steric effects induced by ligand modification to gain intrinsic structure-performance relations. We also discussed the challenges and future perspectives of ligand modification strategies in heterogeneous catalysis.

Rotational, orbital atherectomy and intravascular lithotripsy for coronary calcified nodules: insights from optical coherence tomography.

The optimal treatment strategy for coronary calcified nodules (CN) remains uncertain. We aimed to evaluate the efficacy and safety of different calcium modification strategies, including rotational atherectomy (RA), orbital atherectomy (OA), and intravascular lithotripsy (IVL) for managing CN with optical coherence tomography (OCT) guidance. Consecutive patients undergoing OCT-guided percutaneous coronary intervention (PCI) for severely calcified lesions using RA, OA, or IVL between January 2017 and December 2022 were included. Primary endpoint was minimum stent area (MSA) post-PCI. Secondary endpoints included MSA at CN site and 1-year target vessel failure (TVF), defined as a composite of cardiac death, target-vessel myocardial infarction, or target vessel revascularization. Among 154 patients and 158 lesions, CN was identified in 54 lesions (34.2%) and managed with RA (39%, n = 21), OA (33%, n = 18), or IVL (28%, n = 15). The IVL group exhibited a larger minimal lumen diameter, maximum calcium arc, and maximum calcium thickness. Post-PCI OCT demonstrated comparable MSA (RA: 6.23 ± 0.34 mm², OA: 5.75 ± 0.39 mm², IVL: 6.24 ± 0.46 mm²; p = 0.62) and MSA at CN site (7.17 ± 0.43 mm², 6.46 ± 0.49 mm², 7.86 ± 0.56 mm², respectively; p = 0.55) after adjusting for morphologic factors. The incidence of TVF at 1 year was similar among the group (RA: 19.0%, OA: 22.2%, IVL: 13.3%, p = 0.81). In patients undergoing PCI for CN, similar procedural and clinical outcomes can be achieved using RA, OA, or IVL. These findings warrant further investigation in larger, prospective trials.

Medium bandgap A-DA’D-A type small molecule acceptors prepared by synergetic modification strategy for efficient indoor organic photovoltaic devices

Medium bandgap A-DA’D-A type small molecule acceptors prepared by synergetic modification strategy for efficient indoor organic photovoltaic devices

Enhanced nonlinear optical properties of MXene (Ti3C2Tx) via surface-covalent functionalization with porphyrin

The surface terminations (=O, -OH, and -F) play a key role in determining the physical and chemical properties of MXenes, which have been demonstrated with significant potential in field-effect transistors, humidity sensors, energy storage, and photocatalysis, etc. It is therefore crucial to modify these active functional groups on the surface of MXenes in order to optimize the applicability of these materials. In this study, we introduce a covalent modification strategy to successfully construct a porphyrin-functionalized Ti3C2Tx organic-inorganic nanohybrid (TPP-Ti3C2Tx) by covalently attaching porphyrin molecules to the surface groups on Ti3C2Tx nanosheets for the first time. As revealed by steady-state fluorescence spectra, transient fluorescence spectra, and DFT calculations, the robust covalent bonds between TPP and Ti3C2Tx can effectively promote the photon-induced electron and/or energy transfer within the TPP-Ti3C2Tx nanohybrid. The investigation on the nonlinear optical (NLO) properties of TPP-Ti3C2Tx nanohybrid as well as its precursors, reveals that the TPP-Ti3C2Tx nanohybrid exhibits the highest nonlinear absorption coefficient and the lowest optical limiting threshold among the tested samples at both 532 and 1064 nm, indicating its great potential as a broadband optical limiter for visible and near-infrared wavelengths. This work not only demonstrates the significant promise of covalently-linked TPP-Ti3C2Tx nanohybrid in optical limiting applications but also provides a paradigm for engineering high-performance NLO MXenes-based materials through the covalent modification strategy.

Electrochemical pre-treatment of graphite electrode as a green modification strategy for sensitive voltammetric determination of pyrazinamide

Electrochemical pre-treatment of graphite electrode as a green modification strategy for sensitive voltammetric determination of pyrazinamide

Modification of bamboo fiber for reinforcing cement-based composites and durability improvement

This study tackled the issue of inferior fiber-matrix adhesion in bamboo fiber (BF) reinforced cement-based composites, a critical factor impacting their performance and service life. Our approach introduces a novel application of silane coupling agents (SCAs) to improve the compatibility of BF with cement matrices. We utilized isocyanate propyl triethoxy silane (IPTS) in a pioneering manner, and used γ-glycidyl ether oxypropyl trimethoxysilane (KH560), respectively, to chemically modify the BFs. This modification strategy was designed to enhance the adhesion between BFs and the cement matrix through the SCAs' interaction with hydroxyl groups on the BF surface and their involvement in the cement hydration process. Our findings reveal that the modified BFs, when incorporated into cement composites, not only match the compressive strength of the control but also show a remarkable increase of over 20 % in flexural strength and over 30 % in tensile strength. Additionally, the modified BFs reduce drying shrinkage by more than 19 % after 90-day curing, and similarly significant reductions are observed in chloride ion penetration and freeze−thaw cycle failure rates. Notably, IPTS outperforms KH560 in enhancing mechanical strengths and durability, likely due to the formation of more siloxane bonds on the fiber surface, leading to stronger cement matrix interaction. This research presents a cost-effective method to improve the performance of BF/cement composites, paving the way for broader utilization of BFs in sustainable construction materials.

Promoting Layered Oxide Cathodes Based on Structural Reconstruction for Sodium‐Ion Batteries: Reversible Phase Transition, Stable Interface Regulation, and Multifunctional Intergrowth Structure

AbstractLayered transition‐metal oxides (NaxTMO2) are one of the most promising cathode materials for sodium‐ion batteries due to their high theoretical specific capacities, good conductivity, and environmental friendliness. However, several key scientific issues of NaxTMO2 cathode materials still persist in practical applications: i) complex phase transitions during the charge/discharge process owing to the slip of the transition‐metal layer; ii) the tendency for the interface to react with the electrolyte, resulting in structure degradation, and iii) reactions between active materials and H2O as well as CO2 on exposure to air in the environment to form alkaline substances on the surface. To understand electrochemical storage mechanisms and solve these problems, several modification strategies of NaxTMO2 have been reported recently, including bulk doping, concentration gradient structure design, interface regulation, and intergrowth structure construction. This review focuses on reversible phase transitions, stable interface regulation, and multifunctional intergrowth structure of the NaxTMO2 material from the inside to the outside. The future research directions for NaxTMO2 are also analyzed, providing guidance for the development of commercial layered oxides for next‐generation energy storage systems.

Differential regulation of glucosinolate-myrosinase mediated defense determines host-aphid interaction in Indian mustard Brassica juncea L.

India's oilseed economy falls short of self-sufficiency and is supplemented by huge imports every year. Increasing national productivity of the major oilseeds is confronted with yield losses due to diverse biotic and abiotic stresses. The productivity of Indian mustard (Brassica juncea Linnaeus), belonging to the family Brassicaceae, is significantly reduced due to damage caused by mustard aphids (Lipaphis erysimi Kaltenbach, Hemiptera: Aphididae). Rapid colonization by the nymphs makes it difficult to protect the crop through agrochemicals. Aphids release effector molecules to modulate the host-defence responses. Glucosinolates (GSLs) extensively found in Brassicaceae family, are hydrolysed by myrosinase into toxic compounds that deter herbivore insects. Here, we investigated the differential activation of the glucosinolate-myrosinase pathway in mustard manifesting susceptibility and resistance to different aphid species. Mustard plants were challenged by two different aphid species mustard aphid and cowpea aphid (Aphis craccivora Koch, Hemiptera: Aphididae) leading to complete host-susceptibility in one case and resistance in the other, respectively. Differential regulation of the GSL biosynthetic pathway and myrosinase activity was assessed by gene expression study and ultra-performance liquid chromatography quadrupole time-of-flight tandem mass spectrometry (UPLC- QToF-ESL-MS). Gene expression study identified selective transcriptional attenuation of the key GSL biosynthetic and myrosinase gene in mustard when challenged with mustard aphid. In contrary, the activation of GSL biosynthetic genes in conjunction with myrosinase at the transcriptional level was profound in mustard, when challenged with cowpea aphid. UPLC-MS analysis showed higher turnover in the hydrolysis of glucosinolates by myrosinase which led to concomitant generation of glucose as byproduct in response to cowpea aphid in mustard plants. GSL-myrosinase pathway is specifically attenuated by the successful aphid species in mustard and thus plays a pivotal role in determining the outcome of the B. juncea-aphid interaction. The results open up a new genetic modification strategy for developing resistance against aphids.

MgF2 Interface Engineering Promotes the Growth and Stability of LiF-Rich Solid-Electrolyte Interphases on Si-C.

Volume expansion of the Si-C anode during the charging/discharging process causes continuous fracture/formation of the solid electrolyte interface (SEI), which leads to rapid capacity fading. Here, we designed a MgF2-modified separator (MF-PP) to construct a fluorine-rich SEI layer by generating more LiF. The robust SEI layer formed can alleviate the volume stress and prevent crack growth in Si-C electrodes. After 450 cycles, the Si-C||MF-PP half cell retained a reversible capacity of 543.2 mAh g-1, while the LFP||MF-PP||Si-C full cell maintained a reversible capacity of 103.4 mAh g-1 with high Coulombic efficiency after 100 cycles. This facile and low-cost separator modification strategy provides an easily scalable approach to develop stable Si-based anodes for next-generation high-energy-density systems.

Zwitterionic covalent organic framework membranes for efficient liquid molecular separations

Covalent organic frameworks (COFs) featuring uniform topological structure and devisable functionality have emerged as promising membrane materials. The design and precise manipulation of COF membranes with advanced spatial structure to achieve efficient liquid molecular separations are of great necessity. Herein, zwitterionic COF membranes have been in-situ fabricated on porous polymeric substrates using an interfacial polymerization modification strategy. The continuous defect-free COF membranes with two-dimensional in-plane dominant growth can be achieved by optimizing the fabrication parameters including reaction time, monomer concentration, and catalyst concentration. Subsequent zwitterionic modification thereon not only favors the formation of hydrophilic surface but also improves the sieving capability by sheltering effect. Attributed to the synergistic contribution, the optimized zwitterionic COF membrane possesses a superior separation factor of 2839 with the water content in the permeate up to 99.7 wt%, while maintaining a comparable permeation flux of 3309 g m−2 h−1 during the ethanol dehydration process, outperforming most of other representative membranes. Furthermore, the excellent durability of the zwitterionic COF membrane in the ethanol dehydration process and its efficient separation performance towards other alcohol dehydration systems demonstrate its potential practical applications. The easy scalability of the fabrication and regulation method offers crucial guidance for the engineering of advanced COF membranes in efficient liquid molecular separations.

Site-specificQuadruple-Functionalised Antibodies.

Antibody-drug conjugates (ADCs) are a growing class of chemotherapeutic agents that have yielded striking clinical successes. However, the efficacy of ADCs often suffers from issues associated with tumor heterogeneity and resistance. To overcome these problems, a new generation of ADCs comprising a single monoclonal antibody with multiple different payloads attached, termed multi-payload ADCs, have been developed. Here we deploy multiple orthogonal site-specific protein modification strategies to generate highly homogeneous multi-functionalised antibody conjugates comprising up to four different functionalities installed at four unique sites on the antibody. This work, which includes the use of a site-specific cyclopropenone (CPO)-based reagent, represents the first example of a homogeneous multi-payload ADC with a payload count greater than two, and thereby facilitates the development of the next generation of ADCs.

Site‐specific Quadruple‐Functionalised Antibodies

Antibody–drug conjugates (ADCs) are a growing class of chemotherapeutic agents that have yielded striking clinical successes. However, the efficacy of ADCs often suffers from issues associated with tumor heterogeneity and resistance. To overcome these problems, a new generation of ADCs comprising a single monoclonal antibody with multiple different payloads attached, termed multi‐payload ADCs, have been developed. Here we deploy multiple orthogonal site‐specific protein modification strategies to generate highly homogeneous multi‐functionalised antibody conjugates comprising up to four different functionalities installed at four unique sites on the antibody. This work, which includes the use of a site‐specific cyclopropenone (CPO)‐based reagent, represents the first example of a homogeneous multi‐payload ADC with a payload count greater than two, and thereby facilitates the development of the next generation of ADCs.

A MnO2 nanosheets doping double crosslinked hydrogel for cartilage defect repair through alleviating inflammation and guiding chondrogenic differentiation

The inflammatory microenvironment and inferior chondrogenesis are major symptoms after cartilage defect. Although various modifications strategies associated with hydrogels exhibit remarkable capacity of pro-cartilage regeneration, the adverse effect by prolonging inflammation is still formidable to hamper potential biomedical applications of different hydrogel implants. Herein, inspired by the repair microenvironment of articular cartilage defects, an injectable, immunomodulatory, and chondrogenic L-MNS-CMDA hydrogel is prepared through grafting vinyl and catechol groups to chitosan macromolecules using amide reaction, then further loading MnO2 nanosheets (MNS). The double crosslinking of photopolymerization and catechol oxidative polymerization endows L-MNS-CMDA hydrogel with preferable mechanical property, affording a suitable mechanical support for cartilage defect repair. Additionally, the robust tissue adhesion capability stemming from catechol groups guarantees the long-term retention of the hydrogel in the defect site. Meanwhile, L-MNS-CMDA hydrogel decomposes exogenous and intracellular H2O2 into O2 and H2O, to effectively alleviate cellular oxidative stress caused by long-term hypoxia. Under the synergies of catechol groups and MNS, L-MNS-CMDA hydrogel not only inhibits macrophages polarizing into M1 phenotype, but encourages them turn into M2 phenotype, thereby, reconstructing an immunization friendly microenvironment to ultimately enhance cartilage regeneration. Predictably, the hydrogel markedly induces rat bone marrow mesenchymal stem cells differentiating into chondrocytes by expressing abundant glycosaminoglycan and type II collagen. A cartilage defect model of rat knee joint indicates that L-MNS-CMDA hydrogel visually regulate the early inflammatory response of post-implantation, and facilitate cartilage regeneration and recovery of joint function after 12 weeks of post-implantation. All in all, this multifunctional L-MNS-CMDA hydrogel exhibits superior immunomodulatory and chondrogenic properties, holding immense clinical potential in the treatment of cartilage defects.

The Introduction of a BaTiO3 Polarized Coating as an Interface Modification Strategy for Zinc-Ion Batteries: A Theoretical Study.

Aqueous zinc-ion batteries (AZIBs) have become a promising and cost-effective alternative to lithium-ion batteries due to their low cost, high energy, and high safety. However, dendrite growth, hydrogen evolution reactions (HERs), and corrosion significantly restrict the performance and scalability of AZIBs. We propose the introduction of a BaTiO3 (BTO) piezoelectric polarized coating as an interface modification strategy for ZIBs. The low surface energy of the BTO (110) crystal plane ensures its thermodynamic preference during crystal growth in experimental processes and exhibits very low reactivity toward oxidation and corrosion. Calculations of interlayer coupling mechanisms reveal a stable junction between BTO (110) and Zn (002), ensuring system stability. Furthermore, the BTO (110) coating also effectively inhibits HERs. Diffusion kinetics studies of Zn ions demonstrate that BTO effectively suppresses the dendrite growth of Zn due to its piezoelectric effect, ensuring uniform zinc deposition. Our work proposes the introduction of a piezoelectric material coating into AZIBs for interface modification, which provides an important theoretical perspective for the mechanism of inhibiting dendrite growth and side reactions in AZIBs.

Prussian Blue Analogue‐Based Materials: Synthesis and Their Application in Peroxymonosulfate Activation for Wastewater Treatment

Peroxymonosulfate (PMS) based advanced oxidation processes (AOPs) are effective in degrading refractory organic pollutants in water. The unique internal chemical tunability of Prussian blue analogues (PBAs), a type of metal‐organic framework materials (MOFs), makes them promising catalysts for PMS‐AOPs. However, the pristine PBA is limited in practical application due to its structural instability and easy leaching of metal ions. To this end, various methods have been developed to enhance the catalytic performance of PBAs. In this paper, the recent advances in the modification and composite strategies of PBA catalysts are systematically reviewed. PBA modification by the regulation of synthesis conditions and post‐synthesis treatment, along with composite strategies involving metal and non‐metal based materials are introduced. The structural morphology improvement, physical and chemical property adjustment, vacancy design and crystal surface modulation of PBAs induced by these modification and composite strategies are discussed in depth. In addition, the performance of the modified and composite catalysts to activate PMS for organic pollutant degradation is demonstrated. The radical pathway via SO4•‐, •OH and O2•‐, non‐radical pathway through 1O2, electron transfer process and high‐valence metal‐oxygen species, or a combination of radical and non‐radical pathways are revealed in PMS‐AOPs with PBAs and their derivatives as catalysts.

Revealing the Dynamic Evolution of Electrolyte Configuration on the Cathode‐Electrolyte Interface by Visualizing (De) Solvation Processes

AbstractElectrolyte engineering is crucial for improving cathode electrolyte interphase (CEI) to enhance the performance of lithium‐ion batteries, especially at high charging cut‐off voltages. However, typical electrolyte modification strategies always focus on the solvation structure in the bulk region, but consistently neglect the dynamic evolution of electrolyte solvation configuration at the cathode‐electrolyte interface, which directly influences the CEI construction. Herein, we reveal an anti‐synergy effect between Li+‐solvation and interfacial electric field by visualizing the dynamic evolution of electrolyte solvation configuration at the cathode‐electrolyte interface, which determines the concentration of interfacial solvated‐Li+. The Li+ solvation in the charging process facilitates the construction of a concentrated (Li+‐solvent/anion‐rich) interface and anion‐derived CEI, while the repulsive force derived from interfacial electric field induces the formation of a diluted (solvent‐rich) interface and solvent‐derived CEI. Modifying the electrochemical protocols and electrolyte formulation, we regulate the “inflection voltage” arising from the anti‐synergy effect and prolong the lifetime of the concentrated interface, which further improves the functionality of CEI architecture.

High Performance Memristors Based on Imine‐Linked Covalent Organic Frameworks Obtained Using a Protonation Modification Strategy

AbstractImine‐linked covalent organic frameworks (COFs) are garnering substantial interest in resistive random‐access memory, attributed to their superior crystallinity, excellent chemical and thermal stability, and modifiable molecular structures. However, the development of high‐performance COF‐based memristors impeded by challenges such as low conjugation degree of imine bonds and poor electron delocalization ability. Herein, we report a protonation strategy to modify the imine bonds of donor‐acceptor (D‐A) type COFs. This modification significantly enhances the electron delocalization capability of imine bonds, lowers the energy barriers for electron injection from electrodes, and stabilizes the conductive charge transfer state, thus markedly improving device performance. The protonated COF‐BTT‐BPy and COF‐BTT‐TAPT thin films‐based memristors show remarkable device performance with a high ON/OFF current ratio of 105, a low driving voltage, and outstanding endurance exceeding 600 and 1300 cycles, respectively, which is nearly twice the durability of analogous non‐protonated COFs‐based memristors. Notably, the protonated COF‐BTT‐TAPT‐based memristor exhibit the highest number of cycles reported at present. This work not only unprecedentedly enhances the performance of COF‐based memristors, but also provides a universal and promising approach for the molecular design and potential application of D‐A type imine‐linked COFs.