Constructing 2D/3D bilayer structured all-inorganic perovskites through cation exchange is critically challenging. So far, only a few reports have claimed 2D/3D heterostructure formation via in situ surface reconstruction or cation interdiffusion. Yet, the underlying mechanism remains elusive and a fundamental understanding is still lacking from both thermodynamic and mechanistic perspectives: why and how organic cations displace Cs+ ions. This work presents a detailed mechanistic study encompassing molecular design, experimental validation, and theoretical verification to elucidate the cation exchange mechanism behind this surface reconstruction process. We have specifically developed a novel ammonium iodide salt, namely, DMA-BzAI, by incorporating a strong electron-donating dimethylamino moiety on the para position of the benzene ring in the most commonly used benzylammonium iodide (BzAI). This design aims to decrease the polarization force of the spacer cation toward octahedral inorganic slabs, providing stronger driving forces for ionic substitution. In situ X-ray scattering analysis confirms the dynamic evolution of n = 1 2D perovskites on CsPbI2Br perovskites by treating with DMA-BzAI, contrasting sharply to the case of BzAI. A comprehensive theoretical investigation, including Bader charge analysis, formation energy, and nudged elastic band calculations, further demonstrates that both thermodynamic favorability and low activation barriers allow DMA-BzA+ cations to go through cation exchange reactions to substitute the strongly bound Cs+ ions in the inorganic perovskite lattice, leading to in situ formation of 2D/3D bilayer structure, in alignment with experimental observations. These mechanistic results provide fundamental insights into the cation exchange mechanism behind 2D/3D heterojunction formation in inorganic perovskites, offering rational ligand design principles for future research.
Inorganic-biological hybrid cell factories couple cellular metabolism with inorganic ions and nanomaterials, enabling (i) biosynthesis of functional nanomaterials under mild aqueous conditions and (ii) biohybrid systems in which inorganic components modulate cellular redox, light harvesting and catalysis. This review summarizes nano-bio-interface mechanisms that govern ion uptake, trafficking and intracellular nucleation, and highlights synthetic-biology and metabolic-engineering strategies for improving yield, compositional control and biocompatibility. We survey representative material classes-including semiconductor quantum dots, carbon quantum dots and graphene-family 2D materials derived from microbial feedstocks, rare earth nanophosphors, noble metal nanostructures, and emerging perovskite-type and metal/metalloid materials-and discuss how bio-derived surface chemistries and dynamic interfaces support applications in biosensing, bioimaging, antimicrobial/therapeutic platforms, bioelectronics, and biohybrid production of fuels and chemicals. We conclude by outlining translational constraints relevant to Biomaterials Science, including reproducibility, scale-up, and safety/regulatory drivers that favor toxic-metal-free, stable, and sustainable materials.
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Hyperpolarized (HP) xenon-129 (129Xe) chemical exchange saturation transfer (HyperCEST) provides the opportunity to perform high-sensitivity molecular magnetic resonance imaging (MRI) due to superior signal enhancement. One of the most recently discovered candidates for future development of HyperCEST-active biosensors, resorcinarene trimer methanesulfonate (R3-Noria-MeSO3H), possesses unique complex molecular dynamics resulting in its aggregation around metal cations. To study and understand this behavior of R3-Noria-MeSO3H and its potential interaction with large biological molecules, we conducted time series of UV-vis spectroscopies of different R3-Noria-MeSO3H concentrations in deionized water, phosphate buffer saline, saline, solutions of potassium chloride, choline, and bovine serum albumin (BSA). For the first time, we have acquired R3-Noria-MeSO3H UV-vis spectra and identified the origin of all absorption bands. Our data suggested that Na+ promoted R3-Noria-MeSO3H aggregation the most, while choline hinders it, albeit did not stop it completely. The absorption bands around 353 and 497 nm are the most indicative of the aggregation process and, therefore, may be utilized in future studies of R3-Noria-MeSO3H molecular dynamics. Furthermore, using UV-vis spectroscopy and electrophoretic analysis, we discovered rapid aggregation of R3-Noria-MeSO3H around BSA, forming supramolecular assemblies that persist as dynamic but macroscopically stable populations.
Functional interfaces between magnetic oxides and organic semiconductors have led to a wealth of spin-dependent phenomena, enriching the fundamental understanding of spintronics and offering new routes for next-generation spintronic device engineering. However, modulation of carrier injection at such interfaces, particularly through non-invasive methods, has yet to be thoroughly investigated. This limitation hinders precise control over interfacial charge injection and restricts overall device efficiency. In this work, we construct an LPCMO/P3HT-based organic magnetoresistive diode and demonstrate highly efficient rectification of interfacial carrier transport by exploiting the electronic phase separation (EPS) in the magnetic electrode LPCMO. By tuning the internal EPS of LPCMO, we achieve distinct resistance switching states in the device. Notably, the observed change in device resistance exceeds that of the LPCMO electrode by a factor of 60, revealing a pronounced amplification effect at the interface. This giant modulation originates from the EPS-induced Fermi level shift in LPCMO, which reduces the interfacial energy barrier and significantly enhances carrier injection efficiency across the oxide/organic semiconductor interface. Our findings present a new strategy for precise and in situ control of carrier injection processes, which may further advance both the scientific and technological frontiers of organic spintronics.
Molecular-scale integration of non-natural functional components into living systems for precise manipulation, monitoring, and enhancement of organisms remains a great challenge. Here, we achieved the geneticable synthesis of functional inorganic nanomaterials with molecular-level spatial precision within live mammalian cells. By genetically encoding a cysteine-rich protein tag named 1DFS, and tuning its intracellular inherent metabolic pathways, organic molecules can be precisely synergized with inorganic molecules at a specific site of the protein of interest within live cells to grow a single inorganic semiconductor nanocrystal-specifically quantum dot (QD). This, in turn, endows the protein with unique fluorescent functions for precise and stable protein labeling even after multiple cell passages. This approach is flexible and universal, and QD can not only integrate into the specific protein in live cells but also synchronously grow on the delicate viral nucleoprotein (NP) during the natural replication and assembly of virions in the host cells. The labeled NPs then accurately assemble into viral ribonucleoproteins deep inside virions, resulting in fluorescent virions with full infectivity that exceeds capabilities of conventional genetic manipulation. This work provides a programmable platform for geneticable growth of inorganic nanomaterials at specific molecular sites, opening a new frontier in precise inorganic-enabled synthetic biology.
Quantum dots (QDs), a remarkable inorganic semiconductor nanocrystal capable of converting light energy into electrical, chemical, thermal, and other forms of energy, can be used to create super living systems through their fusion with cells, which hold tremendous potential for biomedical applications. Although considerable efforts have been devoted to delivering in vitro synthesized QDs into cells via endocytosis or electroporation, these approaches often suffer from poor biocompatibility, uncontrolled uptake pathways, and nonspecific intracellular interactions. Moreover, to satisfy the stringent demands of biological environments, QDs produced through conventional synthetic routes typically require extensive postsynthetic treatments, such as phase transfer into aqueous media and surface functionalization, which can irreversibly disrupt their surface structure and substantially compromise their photoluminescence quantum yield and photostability. Consequently, the exceptional optical properties of QDs are difficult to fully maintain when applied in physiological environments. Live-cell synthesis of QDs provides an innovative strategy to overcome these intrinsic limitations. By harnessing the intracellular spatiotemporally organized biochemical metabolic networks, this strategy enables the controlled synthesis of QDs while synchronously accomplishing in situ labeling. The resulting QDs are naturally coated with endogenous biomolecules and can be directed to form at specific subcellular locations, which inherently ensures high biocompatibility and precise integration with local cellular structures. This method establishes a robust foundation for in situ labeling of delicate cellular components and opens new avenues for high-fidelity acquisition of dynamic information within complex biological processes. Moreover, this flexible and universal strategy to fuse inorganic nanocrystals with live cells can endow organisms with enhanced or novel functionalities, holding significant promise for diverse applications in the fields of biomedicine and energy conversion. In this Account, we systematically summarize our efforts in the field of the live-cell synthesis of QDs. Our discussion encompasses the development of the "space-time-coupled" synthetic strategy, the elucidation of the key molecular mechanisms underlying the intracellular synthesis of QDs, and the diverse applications of this technique in pathogen detection, microvesicle labeling, site-specific protein labeling, and in vivo tumor imaging. Furthermore, inspired by the live-cell synthetic pathways, we introduce a cell-free "quasi-biosynthesis" system that enables controllable synthesis of near-infrared Ag2Se QDs and supports surface-chemistry-based strategies for precise modulation of photoluminescence properties. Finally, we outline the key challenges and future opportunities in this field, emphasizing that the synergistic integration of genetic engineering with precision materials science will profoundly advance the intracellular synthesis of nanocrystals and unlock new possibilities in high-precision sensing, dynamic regulation, and functional augmentation of biological systems. We believe that, with a deepened understanding of the synthetic mechanisms and continued innovation in synthetic methods, the spatial precision, operational reliability, and functional integration of QDs within living systems will be significantly enhanced, thereby providing a powerful toolkit for revealing biological mechanisms and advancing precise disease diagnosis and treatment strategies.
ConspectusThe innovative exploration of non-fullerene acceptors (NFAs) such as ITIC, Y6, and others, has boosted the power conversion efficiencies (PCEs) of organic solar cells (OSCs) surpassing 21%. However, organic photovoltaics still suffer from significant efficiency gaps compared to inorganic photovoltaics, particularly in open-circuit voltage under similar bandgaps. This notable disparity is largely driven by the stark difference in nonradiative recombination energy losses: OSCs typically incur losses exceeding 0.2 eV, whereas their inorganic counterparts suffer only minimal losses, ranging from a mere 0.03 to 0.04 eV. This insurmountable nonradiative recombination is closely associated with some intrinsic features of organic photovoltaic light-harvesting materials: relatively flexible molecular frameworks, loose and disordered molecular aggregates, large exciton binding energies, etc. Therefore, a multiscale regulation spanning single-molecular properties and aggregation behaviors in further molecular design is required, if a remarkable PCE improvement is expected.In this Account, we first present a brief review of the development of electron acceptor materials, with a focus on analyzing the prominent merits of current high-efficiency acceptor molecular skeletons (especially Y6 analogs) in terms of intermolecular packing modes, photodynamic, etc. Meanwhile, great challenges for further material design also arises from the quite limited structural optimization room for Y-series backbones. In order to break through the dilemma of molecular design, we developed CH-series NFAs with multi-functionalized central units and an "acceptor-donor-acceptor" architecture. Subsequently, a systematic discussion about CH-series NFAs will be made to reveal their advantages in (1) inducing a directional transformation of molecular packing mode toward a more favorable one, through multiple intermolecular weak interactions such as fluorine-hydrogen/sulfur/π bonds, thus rendering multidimensional long-range ordered molecular stacking to minimize energy loss pathways in OSCs; (2) breaking through the limitations of traditional dimeric/trimeric/polymeric acceptor design by pioneering the construction of relatively rigid central-units-linked dimeric/trimeric NFAs with multiple free terminals to enhance intermolecular packings; (3) proposing a novel "functional reconfiguration" strategy for the central units, aiming to explore new photoelectric conversion mechanisms in organic photovoltaic materials.Thus far, CH-series NFAs based binary OSCs have achieved the highest PCE of approaching 21%, ranking among the best NFAs. If further considering their great structural modification possibilities, CH-series NFAs hold exceptional promise as a versatile platform for developing OSCs with record-breaking PCEs. Therefore, we further propose some perspectives for CH-series NFAs, for example, more precise structural and packing optimization to reduce exciton binding energies and improve molecular packing ordering; further in-depth exploration of a "functional reconfiguration" strategy to apply new photoelectric conversion mechanisms, such as triplet excitons, singlet fission, etc.; extending the absorption edge of NFAs to near-infrared II region to harvest more low-energy photons, especially for tandem OSCs. These strategies may have the potential to overcome the critical challenge existing in OSCs and shrink the PCE gap comparing to inorganic platforms.
Traditional sulfoxide synthesis often relies on toxic oxidants and harsh conditions. Photocatalytic oxidation using inorganic semiconductors provides a greener approach but is limited by low catalytic efficiency. Herein, we developed a heterostructure catalyst enriched with cadmium vacancies (denoted as CdvSx/Ti3CN). The optimized CdvS4/Ti3CN exhibited a high sulfoxide production rate of 21.85 mmol·gcat -1·h-1, outperforming most reported catalytic systems. Comprehensive characterization revealed that sulfur dosage was precisely tuned during synthesis to generate abundant cadmium vacancies and expose active crystal facets. In particular, the presence of cadmium vacancies enhances substrate adsorption via unsaturated coordination sites, lowers the energy barrier for bond activation, and promotes the activation of O2 into superoxide radicals. Moreover, Ti3CN further facilitates photogenerated electron transfer and enhances superoxide radical concentration by enabling favorable band alignment with CdS. In addition, the catalyst demonstrates excellent substrate compatibility and recyclability. This work offers a new approach for improving the performance of CdS-based inorganic semiconductor catalysts in sulfoxide synthesis through Cd defect engineering.
Circularly polarized luminescence (CPL) in the ultraviolet B (UVB) region holds great potential applications in asymmetric catalysis, enantioselective polymerization, and polarization-based optical anticounterfeiting and information encryption. However, to date, the CPL materials in the UVB region remain unexplored. In this study, the first chiral gadolinium-based organic-inorganic hybrid metal halides, (R/S-C3H7NF3)3GdCl6 (R/S-3F-Gd), were constructed, which exhibit efficient CPL in the UVB region. Owing to the unique 4f-4f transition of Gd3+ ions, R/S-3F-Gd shows a high photoluminescent quantum yield of 18%, a narrow full width at half maximum (∼3 nm) and a ultralong photoluminescence lifetime (∼6.6 ms). Additionally, their CPL can be further tuned by applying the external magnetic field. Then the light-emitting diode (LED) chips coated with R- or S-3F-Gd were also fabricated, which exhibit high dissymmetry factor of + 9.1 × 10-3 and -8.2 × 10-3, further demonstrate their potential as circularly polarized light source in the UVB region. Our work offers a novel strategy for designing the chiral luminescent materials with efficient CPL response in the UVB region and broadens the family of chiral organic-inorganic hybrid rare-earth halides.
Ion exchange chromatography (IEC) and mixed-mode chromatography are highly effective for the separation of polar and ionic compounds, including inorganic ions, proteins, peptides, pharmaceuticals, nucleotides, and organic acids, owing to their unique ion exchange or mixed-mode retention mechanisms. As the core component of chromatographic system, the stationary phase directly determines separation selectivity and column efficiency. Therefore, the rational design and development of novel stationary phases remain a focal in modern separation science. In response to the increasing complexity of sample matrices, recent advances have driven the evolution of high‑performance IEC stationary phases that are shifting from a single ion exchange mechanism toward sophisticated multifunctional designs. To better elucidate the critical structure-performance relationships governing the chromatographic behavior, this review provides a comprehensive overview of the evolution of substrates and surface modification strategies (e.g., click chemistry, controlled radical polymerization, and hyperbranched modification) employed in preparing of modern stationary phases over the past decade. Furthermore, this review concludes with a critical discussion of the current challenges and future development trends of chromatographic packing materials.
Ruddlesden-Popper perovskites are promising photovoltaic materials because their enhanced structural and environmental stability relative to their three-dimensional counterparts. However, weak interactions between organic spacer and the adjacent inorganic framework often undermine structural stability and impede charge transport. Here, we demonstrate that the hydrazide-based spacer, thiophene-2-hydrazide (ThCH), unexpectedly induces strong interlayer orbital coupling in 2D RP perovskites despite its monocyclic aromatic structure. It is found that the hydrazide group extends electronic conjugation and promotes orbital hybridization between ThCH and the adjacent inorganic framework, a phenomenon not observed in conventional single-ring aromatic spacers. This effect is further verified by benzo hydrazide, which shares a similar structural motif. Beyond promoting electronic coupling, the hydrazide functionality enhances film formation, yielding enhanced crystallization uniformity and facilitating efficient charge transport. Consequently, ThCH-based RP perovskite (nominal n = 4) devices achieve record efficiencies of 22.41% (certified 21.74%, 0.074 cm2) for small-area devices and 20.74% (certified 20.01%, 1.015 cm2) for large-area devices, the highest reported for quasi-2D RP PSCs. This study establishes a molecular design strategy that uses multifunctional hydrazide modules to overcome the electronic insulation of single-ring aromatic spacers, enabling robust and efficient RP PSCs.
All-solid-state lithium batteries (ASSLBs) offer improved energy density and safety over traditional liquid-electrolyte systems. However, their practical use is limited by the rigidity of inorganic lithium superionic conductors, which require impractically high stack pressures (>50 MPa) to maintain close solid-solid contacts during cycling. We introduce the idea of incorporating nonmetal-chlorine chemical bonds into the conductive network to make rigid conductors more flexible. Because nonmetal-chlorine chemical bonds (e.g., P-Cl, Si-Cl) exhibit low bond dissociation energies, they can undergo facile rotation and torsion, thereby facilitating Li+ migration and framework deformability. A liquid SiCl4 activation method is developed to introduce these chemical bonds, yielding a soft superionic conductor, Li3P0.58Si1.25Zr1.78Cl10.86O3.58. This material shows a high room-temperature Li+ conductivity of 4.55 mS cm-1 and a low Young's modulus of 2.09 GPa. This combination enables over 3000 cycles of ultrahigh-nickel cathode LiNi0.92Co0.05Mn0.03O2 at a high current density of 3 mA cm-2, and even allows for stable operation of ASSLBs with no capacity decay after 300 cycles under a low stack pressure of 5 MPa, much lower than the usual 50 MPa needed for most inorganic superionic conductors. Additionally, this chemical-bond-tuning method works with various nonmetal centers (P, Si, C, S), providing a flexible strategy for designing deformable superionic conductors suitable for low-pressure ASSLBs.
Dimensionality engineering has been proven as a pivotal approach to the modulation of chemical and electronic structures of organic-inorganic hybrid metal halides (OIHMHs) for advanced optoelectronic applications. However, prevailing methods primarily rely on altering chemical composition, which limits the precision and predictability of fine-tuning. Herein, we propose a new conformational modulation strategy to direct the self-assembly of chiral OIHMHs without changing their chemical compositions. By steering the conformation of the cyclic chiral cation, R/S-2-methylpyrrolidinium, we achieve precise control over the connectivity and dimensionality of inorganic units. Designing mixed conformational systems by introducing axial-conformation into equatorial-conformation structures successfully enables efficient chiral amplification and enhances linear and nonlinear chiroptical responses. The resulting OIHMHs exhibit a photoluminescence quantum yield exceeding 86%, high anisotropy factors in linear and nonlinear optical circular dichroism, circularly polarized luminescence, and an enhanced second-harmonic generation intensity by two orders of magnitude. Such a simultaneous enhancement in both linear and nonlinear chiroptical properties arises from the modulation of steric hindrance and electronic structure in organic cations mediated by molecular conformation. This work highlights the contribution of conformational modulation to structural design and performance optimization, broadening the prospects for precise modulation of high-performance optoelectronic functions in chiral OIHMHs.
Since 2007, recurrent green tide blooms caused by Ulva prolifera have been observed in the Yellow Sea of China; however, their temporal window and spatial scale remain unknown. This study constructed a downscaling numerical reconstruction method associated with the spatiotemporal correspondence of green tides to elucidate the key processes underlying U. prolifera blooms. Based on spatiotemporal downscaling analysis, green tide block drift paths and the growth extinction processes of U. prolifera in the Yellow Sea from 2008 to 2021 were identified. U. prolifera growth extinction processes were reproduced well using a three-box Nutrient-U. prolifera-Debris (NUD) model. U. prolifera green tides exhibited gradual earlier onset characteristics, accompanied by an increase in global temperatures. Dissolved inorganic nitrogen (DIN) and dissolved inorganic phosphorus (DIP) pools regulate the scale of green tides, exhibiting significantly positive correlations with DIN (p < 0.01) and DIP loads (p < 0.01) in molar amounts. These results offer further insights into the mechanisms regulating U. prolifera green tide blooms in the context of global warming and coastal eutrophication.
Organic cathode materials (OCMs), with their inherent structural diversity, elemental sustainability, and environmental compatibility, present a promising pathway to overcome the energy density and resource limitations of conventional inorganic cathodes. As such, they are regarded as highly promising candidates for next-generation rechargeable batteries. Nevertheless, the simultaneous achievement of high-energy density and robust stability in OCMs remains a significant challenge. High energy density depends on the high capacity and high voltage of the material, while robust stability relies on the low solubility of the material. In this review, we begin by systematically examining the fundamental causes of the low capacity, low voltage, and strong solubility in OCMs. On this basis, we summarize recent advances in enhancing the energy density of OCMs, including molecular-level material design, electrode-level engineering, and electrolyte-level optimization. Meanwhile, we offer forward-looking perspectives on the future development of organic electrodes for next-generation battery technologies.
Chiral mesostructured In2S3 particles with nanoflake morphology were fabricated via a hydrothermal method, using cysteine as both the symmetry-breaking agent and the sulphur source. The pH-dependent inversion of their optical activity was observed, which was speculated by the dynamic interfacial interactions between organic molecules and inorganic precursors.
Molecularly imprinted technology (MIT) represents an advanced synthetic strategy that emulates biological recognition mechanisms, such as antigen-antibody or enzyme-substrate interactions, by creating three-dimensional cavity-like structures through the directional assembly of functional monomers around a template molecule. This process generates spatial and functional complementarity, enabling highly selective recognition of target species. Molecularly imprinted polymers (MIPs), often described as "synthetic antibodies", overcome the intrinsic limitations of natural biomolecules by offering superior selectivity, robustness, cost-effectiveness, and structural tunability. These features position MIPs as promising alternatives to natural antibodies in targeted sensing and drug delivery, with broad applications across biomedical, environmental, and pharmaceutical domains, including pollutant detection, and food safety monitoring. Despite substantial progress, key challenges remain, such as uneven imprinting layers, template residue, and limited aqueous compatibility in macromolecular imprinting. Furthermore, issues of industrial scalability, unclear recognition mechanisms, and insufficient integration with emerging fields such as microfluidics and artificial intelligence have hindered large-scale translation. In recent years, our research team has systematically advanced MIT through a tri-dimensional strategy encompassing high-throughput monomer screening, mechanistic elucidation of molecular recognition, and directional assembly of functional units. By establishing a standardized monomer library and integrating molecular dynamics simulations, we achieved precise material design under complex conditions. Through process optimization and material innovation, we developed a highly efficient solid-phase surface imprinting method that enables the fabrication of smart MIPs with stimuli-responsive properties (e.g., temperature and pH). These MIPs exhibit markedly enhanced binding affinity, with equilibrium dissociation constant (KD) reaching 10-12 mol/L, over four orders of magnitude higher than those of non-imprinted polymers (NIPs). Building on these advances, we established cross-disciplinary application platforms, including affinity-based protein separation and purification systems capable of efficient dual-enzyme cascade immobilization and inactivated enzyme renaturation. In the biomedical domain, we developed ultrasensitive biosensing methods achieving picogram-level detection of heart failure biomarkers and single-digit (≈5 cells/mL) detection of cancer cells in whole blood, extending these methods toward integrated tumor theranostics and microbial community regulation. This paper comprehensively summarizes our team's recent innovations in the rational design, functionalized fabrication, and cross-disciplinary applications of MIPs, spanning biosensing, biocatalysis, and biomedical diagnostics/therapeutics, while contextualizing these within the latest global advances in biomedicine and catalysis. Looking forward, we identify three strategic research frontiers for next-generation MIT. (i) Smart responsive material systems: design MIPs capable of multi-stimuli responsiveness (e.g., magnetic, photothermal, and pH cues) to enable programmable drug release, real-time signal monitoring, and dynamic feedback regulation. (ii) Quantitative modeling of dynamic recognition: establish multi-scale theoretical frameworks to elucidate coupling between cavity flexibility and target conformational dynamics, guiding structure optimization and function-oriented design of adaptive MIPs. (iii) Integrated intelligent theranostic platforms: integrate microfluidics and biomimetic recognition modules into closed-loop systems capable of biomarker detection, targeted delivery, and real-time therapeutic feedback, bridging the gap between in vitro sensing and in vivo precision intervention. Synergistic advancement along these trajectories will empower MIT to transcend its role as a "static recognition material" and evolve into an intelligent, adaptive, and systematic biomedical platform. Such evolution will accelerate the translation of MIT innovations from laboratory to clinic and industry, propelling progress in personalized medicine, point-of-care diagnostics, and synthetic biology, and yielding profound scientific and societal impact. 分子印迹技术(MIT)因设计灵活、适用广泛,已在疾病诊断、环境监测与食品安全等领域展现出重要应用潜力。然而,传统本体聚合法仍存在传质效率低、模板残留严重及大分子印迹效率不足等问题,同时受制于成本、标准化及跨学科融合等因素,限制了MIT的规模化应用。针对上述问题,本团队围绕功能单体的高通量筛选与识别机制解析,建立了标准化功能单体库,并结合粗粒化模拟,实现了复杂体系中印迹聚合物(MIPs)的精准设计与可控合成。通过技术路径优化与材料体系升级,开发出高效固相模板表面印迹及具温度/pH响应特性的智能印迹材料,其结合亲和力显著提升,平衡解离常数(K D)可达10-12 mol/L,较非印迹聚合物提升逾万倍。在应用层面,团队构建了MIPs的多维交叉体系:在生物分离纯化中实现复杂体系中蛋白质的高效富集;在生物催化中搭建双酶级联系统以提升催化效率与酶活复性;在生物医学方向开发出皮克(pg)级灵敏度的生物标志物检测与超低浓度肿瘤细胞(5个细胞/mL全血)识别平台,拓展至肿瘤诊疗一体化与微生物群落干预等前沿领域。本文综述了近5年MIT在生物医学与生物催化领域的研究进展,系统总结了本团队在MIPs理性设计、制备方法及交叉应用方面的成果,并展望其在智能响应材料与集成化诊疗系统中的发展方向。
Arsenic (As) and bisphenol A (BPA), representing conventional inorganic and emerging organic pollutants respectively, are ubiquitous in coastal environments and pose potential ecological threats. Given the semi-enclosed nature and intense anthropogenic pressures of the Bohai Sea, region-specific ecological risk assessments (ERA) are imperative for effective management. This study prioritized 24 representative native aquatic species from the Bohai Sea and curated a robust acute toxicity database for As and BPA through integrated literature mining and acute toxicity experiments. Based on species sensitivity distribution (SSD) models, hazardous concentrations for 5% of species (HC5) were derived, resulting in acute predicted no-effect concentrations (PNECacute) of 1.69 μg/L for As and 100.7 μg/L for BPA. The Risk Quotient (RQ) analysis revealed that As poses a moderate ecological risk in the three major semi-enclosed bays, while BPA currently exhibits low risk levels. These findings underscore the necessity of utilizing locally-derived toxicity data for accurate ERA and provide a scientific foundation for site-specific pollution control strategies in the Bohai Sea.
Anthropogenic activities pose increasingly significant nitrate (NO3-N) pollution to surface water. The NO3-N source tracking is key to effective pollutant control and policy development. Nitrate dual isotopes (δ15N-NO3-, δ18O-NO3-) and long-term NO3-N concentrations in the Yellow River were used to identify NO3-N sources, transformations, and driving factors. The NO3-N concentrations and proportional contributions from different sources varied considerably from upper reaches to lower reaches in the high flow season. The NO3-N concentrations were high in the reach downstream of Lanzhou relative to the headwater area, driven by intensive agricultural and urban inputs; soil organic nitrogen dominated in the upper (54.8%) and lower (35.2%) reaches, whereas manure and sewage constituted the primary source in the middle reaches (43.3%). The NO3-N concentrations along the Yellow River decreased over a decade of environmental regulations, but key transformations remained unchanged, with nitrification still being the dominant process. The NO3-N and dissolved inorganic nitrogen (DIN) concentrations in the lower Yellow River significantly increased from 1981 to 2005 but decreased from 2005 to 2021. The increases in NO3-N and DIN concentrations were mainly attributed to agricultural activities and sewage discharge, while the reduction in fertilizer application accounted for approximately 62% of the DIN decrease. The study reveals that continued fertilizer management, strict wastewater discharge control, and sub-regional cooperation in the Yellow River are crucial for reducing nitrate, which has implications for effective pollutant control of nitrate pollution.