Near-infrared spectroscopy has gained extensive application across numerous fields owing to its distinct advantages in efficiency, non-destructiveness, and real-time online monitoring capabilities. However, its inherent characteristics of severe overlap of spectral bands and weak absorption signals have made the precise analysis of the correlation between spectral features and molecular structure a core challenge in this field. This review systematically examines research progress in near-infrared spectral band assignment. Building on the theoretical foundation of anharmonic vibration mechanisms, it categorizes three mainstream methodological approaches: experimental perturbation analysis, which separates overlapping bands by modulating external conditions such as temperature and concentration; data-driven methods that integrate chemometrics and explainable artificial intelligence to extract physically meaningful characteristic wavelengths from macroscopic spectral data; and theoretical computation, which employs quantum chemistry and anharmonic vibrational algorithms to achieve precise spectral predictions directly from molecular structures. The article further discusses representative applications of band assignment in quantitative composition analysis, process monitoring, material identification, and biomedical diagnostics, while illustrating how this approach can elevate spectral analysis from "black-box" prediction to the level of mechanistic insight. The article concludes by proposing future development avenues focused on the deep fusion of multi-paradigm approaches, the enhanced integration of artificial intelligence, and the advancement of miniaturized and interdisciplinary applications. Through the synergistic advancement of theory, computation, and data, the field of NIR spectral band assignment will continue to enable deeper breakthroughs across scientific and industrial domains.
Ubiquitously found in the Universe, atomic hydrogen represents up to 70% of the neutral gas composition of the Milky Way. As an adatom, hydrogen can physisorb or chemisorb onto interstellar dust grains and icy mantles, thereby contributing to the formation of H2 and, potentially, to the synthesis of more complex hydrogenated species. In addition, structures with relatively large specific surface areas - such as silicates, amorphous carbon, graphene sheets, or water ice - host heterogeneous chemistry that is thought to facilitate the emergence of complex organic matter in astrophysical environments. Although the fundamental physical and chemical processes occurring at dust/gas interfaces are well characterized, current understanding of dust properties governing the formation of H2 and complex molecules remains incomplete. In this context, we introduce graphitic-like two-dimensional carbon nitride monolayer structures (2D-CN) as a putative molecular family of potential relevance to astro-chemistry. The physicochemical and electronic properties of these materials have been extensively examined in recent years for industrial and technological applications. Here, we propose that their importance may likewise extend to interstellar and circumstellar environments. To explore this possibility, we employed density functional theory (DFT) calculations to investigate the characteristics and extent of H adsorption onto C2N1, C3N1, C3N2, C3N4, C4N3, C6N6, C6N8, C9N4, and C9N7 monolayer nanosheets. We identify multiple adsorption sites over C-C bonds, above C and N atoms, and hollow (macropore) locations at which energetically favorable binding of atomic hydrogen could occur in the interstellar medium (ISM). From an astrochemical perspective, these 2D-CN structures, if formed, could therefore contribute to the physicochemical processing and evolution of hydrogen in the ISM. As such, given their structural similarities to prebiotic nitrogen-bearing frameworks (many found in meteoritic samples and organic aerosols), 2D-CN molecules may emerge as promising candidates for exploring the complex interstellar chemistry of astrophysically relevant molecules.
Cell adhesion, fundamental to many physiopathological processes, is a tightly regulated multiscale phenomenon. In spite of immense advances in phenomenological description of the steps involved in adhesion, a full understanding of the coupling of bond kinetics and global dynamics of adhesion is still lacking even for model lipid membranes, especially when the adhesion is mediated by sparse and weak bonds. We report combined experimental and theoretical results showing that membrane adhesion dynamics depend strongly on binder concentration and only weakly on binder diffusion. A minimal adhesion system consisting of cadherin decorated giant unilamellar vesicles (GUVs) and supported lipid bilayers (SLBs) is imaged using Reflection Interference Contrast Microscopy (RICM) to follow the growth dynamics of the adhesion zone between the GUV and the SLB membranes. Cadherins diffuse on the GUV membrane, while on the SLB they are either laterally mobile within the bilayer or immobilized; the concentration of cadherins on both membranes is systematically varied. Quantitative analysis shows that both the equilibrium state and adhesion dynamics depend strongly on ligand concentration, with higher concentrations leading to faster and stronger adhesion. At fixed concentration, cadherin mobility further enhances and accelerates adhesion. To explain this result, we construct a multiscale Monte Carlo simulations of the GUV spreading dynamics, due to cadherin trans-binding using an adaptive Euler method. Simulations reveal that membrane-mediated trans interactions between cadherins lead to the recruitment of freely diffusing receptors into the adhesion zone. This is a result of the equilibration of the chemical potential difference that emerges when cadherins become part of large agglomerates of trans-bonds. These cooperative effects lead to a significant enhancement in adhesion when cadherins are mobile and diffuse on the SLB compared to when they are immobile, quantitatively matching the experiments. This comprehensive model sheds light on the complex coupling between force sensitive cadherin reaction kinetics and membrane mechanics during spreading of GUVs.
Direct interrogation of nanoscale chemical features on and within biological structures remains a major frontier challenge in biophysical and biomedical research. These nanoscale features govern molecular organization, structural dynamics, and cellular function, yet conventional non-invasive techniques such as Fourier-transform infrared spectroscopy (FTIR) are fundamentally limited by optical diffraction. Although hybrid approaches, including scattering-type scanning near-field optical microscopy (s-SNOM) and atomic force microscopy infrared spectroscopy (AFM-IR), have advanced spatial resolution, they remain insufficient to resolve individual macromolecular assemblies. Furthermore, precise control over the depth of analysis within biological architectures, where critical molecular information underpinning intra- and inter-cellular communication resides, has yet to be fully achieved. Here, we employ photo-induced force microscopy (PiFM), an atomic force microscopy (AFM) based technique that directly measures forces arising from light-induced polarization in the near-field region. These forces, typically on the order of piconewtons, are localized perpendicular to the sample surface. This localization enables a theoretical spatial resolution approaching 5 nm, with depth sensitivity spanning approximately 2-200 nm. Crucially, PiFM can operate under ambient and environmentally controlled conditions, preserving physiologically relevant architectures in vitro. Our findings demonstrate that aldehyde-based fixing, including formalin treatment, causes substantial chemical modifications and spectral overlap within the nuclear envelopes of oral mucosa lamina propria progenitor cells (OMLP-PCs). These effects highlight the necessity for rigorous validation of sample-preparation protocols in nano-spectroscopy. In contrast, live-cell PiFM imaging under controlled humidity conditions enables visualisation of native biomolecular states and dynamic cellular processes in OMLP-PCs. Our approach captured whole-cell and membrane-level phenomena, including extracellular vesicle (EV) biogenesis and nuclear stress responses. PiFM mapping of isolated human bone marrow stromal cell (hBMSC) EVs further uncovers nanoscale compositional heterogeneity at the single-EV level. This work demonstrates the application of PiFM as a transformative nano-spectroscopic tool for probing the structural and spatial chemical information of biological matter, potentially down to 5 nm resolution. By bridging physical chemistry and biophysics, PiFM enables direct visualisation of compositional heterogeneity under near-physiological conditions, offering a non-invasive and in situ pathway for nanoscale characterisation and mechanistic understanding of complex biological systems.
To elucidate the hydro-mechanical evolution of rainfall-triggered loess-mudstone interface landslides and improve monitoring and early warning, we conducted a large-scale indoor physical model test under artificial rainfall conditions. The model was instrumented with pore-water pressure and earth pressure sensors, as well as terrestrial laser scanning (TLS) for spatially continuous, hourly displacement mapping. XRF/XRD and mechanical tests were adopted to quantify the water-induced softening characteristics of mudstone.The results show a power-law increase in water absorption and rapid strength degradation, with the unconfined compressive strength decreasing from 4.90 MPa to 0.82 MPa within 3 h. Rainfall promotes the formation of an interfacial water film and argillation of mudstone, which weakens inter-particle bonding and significantly reduces the interface shear strength, representing the key trigger for sliding. Pore-water pressure evolves quasi-synchronously with rainfall but with a slight lag, exhibiting a three-stage pattern: stable - accelerated rise - rapid decline. TLS captured deformation precursors at the crest and slope surface at approximately 1560 min, providing a 140-min lead time over sensor-detected anomalies (approximately 1700 min).TLS-derived displacement fields cross-validate with pressure-based indicators to characterize progressive destabilization, which culminates in failure under continuous rainfall. This study clarifies the water-film-controlled softening mechanism and demonstrates the superior early-warning sensitivity of TLS for interface-type landslides, providing a scientific basis for multi-index fusion monitoring and the formulation of refined early-warning thresholds.
Cell migration is a fundamental process underlying the survival and function of both unicellular and multicellular organisms. Crawling motility in eukaryotic cells arises from cyclic protrusion and retraction driven by the cytoskeleton, whose organization is regulated by reaction-diffusion (RD) dynamics of Rho GTPases between the cytosol and the cortex. These dynamics generate spatial membrane patterning and establish front-rear polarity through the coupling of biochemical signalling and mechanical feedback. We develop a cross-scale mean-field framework that integrates RD signalling with cytosolic and cortical hydrodynamics to capture the evolution of cell shapes and emergent cellular locomotion. Our model reproduces diverse experimentally observed shape and motility phenotypes with small parameter changes, indicating that these behaviours correspond to self-organized limit cycles. Phase-space analysis reveals that coupling to both cytosolic flow and spatially varying surface tension is essential to recover the full spectrum of motility modes, providing a theoretical foundation for understanding amoeboid migration.
We investigate the nitrate reduction reaction (NO3 RR) on the Cu(100) surface using grand-canonical density functional theory (GC-DFT) under constant electrode potential. Ionic correction schemes are applied to both reactants and products to ensure an accurate representation of their physical states, and gas-phase reference error corrections are included to address known limitations of the generalized gradient approximation (GGA) in DFT simulations. The role of pH in modulating the binding energies of key intermediates and transition states governing the elementary steps of nitrate conversion is analyzed as a function of applied electrode potential. To validate the computational approach, DFT-based molecular dynamics simulations with explicit water molecules and activation energy calculations for proton-electron transfer steps are performed. Based on the modeling framework and computational strategy presented here, the results show that under acidic conditions, NO3RR on Cu(100) favors the formation of nitric oxide and ammonium at cathodic potentials (URHE < 0.1 V), whereas under alkaline conditions at comparable potentials, nitrite and hydroxylamine dominate. These findings are consistent with experimentally reported potential- and pH-dependent selectivity trends and suggest that the approach provides a general computational framework for modeling pH-dependent electrocatalytic reactions and predicting potential-dependent selectivity.
The impact of caffeine on strength and endurance performance is well acknowledged, yet its influence on skill performance remains contentious. A potential scenario in which caffeine augments the efficacy of practice could be useful for sports brokers who diligently pursue every nuance to enhance performance. Therefore, the primary objective of this study was to examine the impact of 3 mg·kg-1 of caffeinated coffee intake combined with deliberate (DP) or maintenance practice (MP) on passing performance in adolescent football players. The study also discusses how DP and MP affect passing accuracy without considering caffeine or placebo conditions, as well as how athletes perceive DP and MP and whether caffeine supplementation influences these perceptions. Fourteen adolescent male football players (14.07 ± 0.26 years; 174.28 ± 3.12 cm; 57.21 ± 8.40 kg) participated in a double-blind, randomized, counterbalanced, and crossover research design. For the experimental protocols, each participant visited an artificial turf pitch on four occasions, separated by 48 h. They received 3 mg·kg-1 of caffeine sourced from coffee with DP (1), caffeinated coffee intake with MP (2), decaffeinated coffee with DP (3), and decaffeinated coffee with MP (4). Upon concluding the practice regimes, the athletes promptly expressed their evaluations of the practice on a scale of 1-10. The Loughborough Soccer Passing Test (LSPT), the One-Touch Passing Test (OTPT), and the Long Passing Test (LPT) were administered to evaluate participants' passing proficiency at both the beginning and end of each session. There was no difference in LSPT, OTPT, or LPT values following caffeine (CAF) and placebo (PLA) supplementation after DP or MP. Regardless of CAF-PLA conditions, although both practices improve the LSPT original time, penalty time, and performance time, only MP increases the LPT score (21.9%; p = 0.03). Caffeine also has no additional modifier effect on practice perceptions. DP is considered more mentally challenging than MP (4.18 ± 2.3 & 1.9 ± 1.2; p > 0.05), but both practices are similar in terms of relevancy, enjoyment, and physicality. 3 mg·kg-1 of caffeinated coffee has no additional effects on DP or MP for passing performance. Regardless of CAF or PLA intake, both practices improve short-term passing, yet only MP appears effective for enhancing long-term passing in players with average technical ability. Accordingly, coaches may consider incorporating these strategies into pre-match warm-ups or structured training programs. Moreover, CAF did not influence players' perceptions of the training sessions, particularly when physical demand was minimal. Similarly, when comparing DP and MP, athletes reported similar perceptions, suggesting that the practical application of DP in field-based settings may diverge from its original theoretical framework. Further research needs to clarify how DP principles are implemented and perceived in real-world practice.
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The widespread coexistence of microplastics (MPs) and organic pollutants in water presents the challenges for advanced oxidation processes. Although the O3/H2O2 system demonstrated efficient degradation of various pollutants, its effectiveness with the background of microplastics (MPs), particularly those subjected to environmental aging, remains poorly understood and inadequately quantified. This work systematically investigated the inhibitory effects of pristine and aged MPs on the O3/H2O2 system and elucidated the underlying mechanisms through experimental and theoretical analyses. The findings revealed pollutant-specific dual oxidation pathways: electron-rich compounds underwent concurrent •OH-mediated oxidation and direct O3 molecular oxidation, whereas electron-deficient pollutants were degraded exclusively via •OH attack. Pristine MPs mainly suppressed degradation through physical adsorption. In contrast, aged MPs with oxygen-rich surfaces induced stronger inhibition by stabilizing O3, altering interfacial electron transfer and promoting inefficient surface consumption. Crucially, the O3/H2O2 system maintained high pollutant removal efficiency in real water matrices despite MPs-induced inhibition, and also exhibited no ecotoxicity in plant growth assays and yielded favorable life cycle outcomes. This study establishes a mechanistic foundation for optimizing advanced oxidation in microplastic-coexisted environments and demonstrated the practical feasibility of the O3/H2O2 system for such applications.
The emergence of multidrug-resistant (MDR) bacteria poses a serious threat to global public health. Enhancing the permeability across the physical barriers, including lipopolysaccharide (LPS) and extracellular polymeric substances (EPS), while simultaneously preventing drug resistance, remains a major challenge. To address this issue, we developed a novel biotin-conjugated cationic photosensitizer (PS), ACR-DM-Bio. It not only effectively binds to the bacterial outer membrane and EPS via electrostatic interactions but also facilitates active uptake through the biotin transport system. This dual mechanism promotes penetration through the physical barriers and destroys the outer membrane. Moreover, ACR-DM-Bio competitively disrupts biotin-dependent metabolism and inhibits fatty acid biosynthesis, thereby compromising outer membrane integrity. Besides, this metabolic interference further hinders the tricarboxylic acid (TCA) cycle, severely disrupting energy metabolism and biosynthetic precursor supply. This three-pronged strategy could efficiently overcome bacterial resistance evolution and prevent biofilm recurrence. In a murine biofilm infection model, ACR-DM-Bio-mediated photodynamic therapy (PDT) not only completely cleared biofilms but also promoted tissue repair by modulating inflammation and angiogenesis, outperforming the conventional antibiotic polymyxin B. This work not only presents a highly promising candidate for treating MDR bacterial infections, but also provides theoretical guidance for the rational design of next-generation antimicrobial PS.
Gas-permeable membranes (GPM) have emerged as a promising technology for recovering total ammoniacal nitrogen (TAN) from wastewater. However, simultaneous transport of ammonia and water across hydrophobic membranes dilute the trapping solution and reduces its value. Additionally, water transport hinders nitrogen transfer analysis, which is used to assess membrane performance. Existing modelling approaches often rely on osmotic pressure estimates or assume constant volumes, which limits their applicability when treating real wastewaters. This study presents a new modelling approach to describe the coupled transport of ammonia and water across GPM using only experimentally measurable variables such as TAN concentration and solution volume. A key feature of this model is its capacity to capture dilution effects caused by water flux and accurately estimate TAN diffusion without requiring chemical speciation data. Laboratory experiments with synthetic and waste-derived effluents, including anaerobic digestion supernatant, acidogenic fermentation liquid, and industrial wastewater accurately reproduced TAN concentration over time. For synthetic wastewater, the mean ammonia permeability was 1.26·10-6 m/s, while waste effluents showed broader values from 0.58·10-6 to 1.83·10-6 m/s due to matrix component interactions. This narrow distribution confirms the robustness of the model, as permeability is a membrane-intrinsic parameter. Water transport significantly increased trapping solution volume, up to 149% in synthetic media and 292% in high-strength effluents, increasing with the osmotic pressure gradient between solutions. The proposed model provides a practical tool to obtain membrane-intrinsic ammonia permeability and to model TAN recovery in GPM treating real effluents, helping to bridge the gap between theoretical transport models and experimental applications.
In the context of global energy transition and carbon neutrality goals, converting lignocellulosic biomass into high-value products is essential for a circular bioeconomy. This review systematically explores technological advancements in modern biorefineries, from feedstock deconstruction to precise valorization. Pretreatment strategies-physical, chemical, and integrated pretreatment strategies-effectively overcome lignocellulose recalcitrance, achieving high-purity fractionation of cellulose, hemicellulose, and lignin. Advanced conversion technologies, including electrocatalysis, photocatalysis, biological funneling, and bio-photoelectrochemical hybrid systems, offer superior selectivity, atom economy, and energy efficiency in biomass upgrading. Addressing economic and stability challenges in scale-up, the integration of artificial intelligence and digital twins promises intelligent, carbon-neutral biorefinery systems. This review provides theoretical guidance and technical roadmaps for closed-loop resource utilization and sustainable development.
The development of high-energy-density power sources with integrated energy harvesting capabilities is crucial for advancing wearable electronics. Herein, inspired by the homeostatic ion regulation mechanisms of plant roots in dynamic chemical environments, we developed a biomimetic starch-polyiodide solid polymer electrolyte for constructing an integrated photo-rechargeable energy storage system. The incorporation of functionalized starch-polyiodides reconfigures the PVDF matrix topology, modulates the all-trans (TTTT) conformation and anchors anions, thereby optimizing lithium-ion transport and enhancing ionic conductivity, while enabling interfacial dead-lithium self-healing at the anode and defect passivation of the photoelectrochemical storage cathode (PSC). In situ characterization and theoretical calculations revealed that the additive facilitated multi-electron transfer and formed a functional buffer layer, which synergistically stabilized the lithium metal anode interface while suppressing ion migration at the PSC. This mechanism established a robust solid electrolyte interphase and improved the overall energy storage efficiency of the integrated device. The resulting flexible integrated device demonstrated outstanding performance, retaining 85% capacity and 95.2% energy efficiency after 450 cycles at 1 C while preserving superior mechanical flexibility and efficient photo-electric conversion. This work provides a novel strategy for developing flexible energy storage systems that integrate high ionic conductivity, interfacial stability, and photo-electrochemical synergy.
Collapsibility of loess is a widespread, highly destructive geological hazard on the Chinese Loess Plateau. Malan loess exhibits distinct regional particle size variations, but the collapsible deformation characteristics and underlying microscopic mechanisms of loess with different particle sizes remain insufficiently understood. This study selected sandy (Jingbian), silty (Yan'an), and clayey (Jingyang) Malan loess in Shaanxi as representative samples to investigate collapsible deformation and clarify intrinsic mechanisms. Results show particle size and clay content significantly affect loess' physical-mechanical properties: particle shape transitions from angular to sub-rounded/rounded, with clay distributing as adhesion (sandy), bridging (silty), or filling (clayey). Collapse is dominated by clay softening, skeleton destruction, and void filling. Post-collapse, macropores (>50 μm) convert to mesopores (2-50 μm), porosity drops ~10%, and pore orientation homogenizes. Generalized collapse mechanism models for different particle size Malan loess are proposed, providing a theoretical basis for hazard mitigation.
The pursuit of high-specific-energy rechargeable batteries is increasingly hindered by persistent electrode polarization, interfacial instability, and parasitic side reactions that conventional material designs struggle to address across diverse battery chemistries (such as lithium batteries and non-lithium batteries). These challenges call for materials capable of actively regulating electrochemical environments under realistic operating conditions. Ferroelectric materials, characterized by switchable spontaneous polarization, intrinsic dipolar asymmetry, and strong multi-field coupling, represent a fundamentally distinct class of functional materials for battery systems. Rather than relying solely on static chemical composition or structural reinforcement, ferroelectrics introduce dynamically build-in electric fields that reshape ion transport behavior, redistribute interfacial charge, and modify reaction energetics throughout the battery architecture. In this review, we first outline the historical development and fundamental physical principles of ferroelectric materials, establishing the theoretical basis for their functionality in electrochemical systems. We then examine how polarization-driven effects manifest differently when ferroelectrics are integrated into a variety of battery components. Within electrodes, polarization can influence ion flux and alleviate concentration gradients; at reactive metal/electrolyte interfaces, dipole-induced charge redistribution helps stabilize interfacial chemistry; and within solid or quasi-solid electrolytes, polarization-modified space-charge structures can alter transport kinetics and interfacial resistance. From the cross-system and cross-component perspectives, we summarize chemistry-specific and architecture-aware design principles for ferroelectric materials in practical battery environments. Finally, we identify key mechanistic bottlenecks and future research directions, outlining pathways toward the rational deployment of ferroelectric-enabled strategies for safe, durable, and high-energy-density rechargeable batteries.
The equilibrium between hydrated and hydrolysed forms of CO2 in water is central to a multitude of processes in geology, oceanography and biology. Chemistry of the carbonate system is well understood in bulk solution, however processes such as mineral weathering and biomineralisation frequently occur in nano-confined spaces where carbonate chemistry is less explored. For confined systems, the speciation equilibria are expected to tilt due to surface reactivity, electric fields and reduced configurational entropy. In this discussion paper we provide measurements of interaction force between negatively charged aluminosilicate (mica) sheets across aqueous carbonate/bicarbonate solutions confined to nanoscale films in equilibrium with a reservoir of the solution. By fitting the measurements to a Poisson-Boltzmann equation modified to account for charge regulation at the bounding walls, we discuss features of the bicarbonate speciation in confinement. We find that (i) the presence of bicarbonate in the bulk reservoir causes a repulsive excess pressure in the slit compared to pH-neutral salt solutions at the same concentration, arising from a higher (negative) effective charge on the mica surfaces; (ii) the electrostatic screening length is lower for solutions of Na2CO3 compared to NaHCO3 at the same bulk concentration, due to a shift in the speciation equilibria with pH and in accordance with Debye-Hückel theory; (iii) hydration forces are observed at distances below 2 nm with features of size 0.1 nm and 0.3 nm; this was reproducible across the various bicarbonate electrolytes studied, and contrasts with hydration forces of uniform step size measured in pH-neutral electrolytes.
Coupled ion-electron interfacial reactivities on electroactive particles are complex and crucial to various battery chemistries and dynamics, yet direct visualization of these reactions remains elusive despite advances in operando imaging. Here we report ion-localization optical nanoscopy (ION) with single-ion, subparticle resolution that distinguishes microscopic static and dynamic disorder in ion-generation interfacial reactivity, offering nondestructive, real-time, non-equilibrium insights. We uncover diverse stripping dynamics of zinc anodes, revealing unexpected subparticle-level heterogeneity and challenging conventional views of uniform stripping on (002)-textured zinc. Mesoscale functional descriptors-intraparticle diffusive and electronic coupling strengths-that govern overall stripping uniformity are identified by ION, supported by computational methods and validated by in situ single-particle manipulation. Imaging-derived insights are further translated into ensemble-level strategies enabling exceptional anode reversibility. ION is cost-effective, high-throughput and broadly applicable to myriad ion-participated interfacial processes, including cathode (de)intercalation, solid-electrolyte interphase evolution, ion exchange and catalyst restructuring.
Atomically precise copper nanoclusters (Cu NCs) offer a compelling platform for elucidating structure-property relationships in quantum-confined materials, yet isolating ligand-induced electronic effects without altering core geometry remains a fundamental challenge. Herein, we report a systematic study of four compositionally identical Cu11 NCs in which the metal nuclearity and core architecture are strictly preserved, while only the substitution position and electronic nature of the thiolate ligands are varied. By employing methyl- and amino-substituted benzenethiols (ABT) in para and meta configurations, we precisely modulate the ligand-to-metal electronic communication without perturbing the Cu11 architecture. Despite their nearly identical atomic structures, these NCs exhibit strikingly different photoluminescence behaviors. Comprehensive steady-state and time-resolved spectroscopic analyses, complemented by transient absorption measurements and theoretical calculations, reveal that subtle changes in ligand substitution govern excited-state relaxation pathways, long-lived triplet-like excited-state stabilization, and oxygen sensitivity. Among the series, Cu11-3ABT achieves an exceptional photoluminescence quantum yield of 26.1% under inert conditions, arising from effective excited-state stabilization. This work establishes ligand positional engineering as a powerful and general strategy to control emission dynamics in atomically precise Cu NCs, providing fundamental insights into their excited-state physics and offering new design principles for highly emissive, earth-abundant metal NC systems.
The scattering and transport processes of electrons with initial kinetic energies ranging from 0.2 eV to 10 keV in liquid-phase water are studied using a Monte Carlo (MC) simulation. This study aims to identify a set of scattering cross sections and physical assumptions regarding angular deflection and energy loss that ensure computational results align with available data across the entire energy range of interest. These data include thermalization distances derived from photoinjection measurements in the very low energy regime (<2.5 eV) and theoretical approximations, including continuously slowing down approximation (CSDA) values, up to 10 keV. In particular, incorporating an assumption for track termination events-such as transient negative anion (TNA) formation at resonance peaks followed by dissociative electron attachment (DEA) processes-may resolve the longstanding discrepancy in geminate separation distance of secondary electrons, which has been reported to vary over the rather broad range of 6-14 nm. This discrepancy arises between stochastic models fitted to diffusive spur recombination data from radiolysis measurements and those directly calculated using MC track simulations with measured scattering cross sections. By accounting for secondary electron tracks and electron autodetachment (EAD) from TNA states, as well as autoionization of neutral excited water molecules, the model also reproduces the reported G-value of pre-solvated electrons.