Harnessing NIR-II-responsive Rh single-atom nanozymes for photothermal-catalytic immunomodulation and eradication of drug-resistant biofilms in deep tissues.

Silicon doping-engineered asymmetric coordination and electronic structure modulation for amplified single-atom nanozyme catalytic therapy.

Coordination Number Regulation of Molybdenum Single-Atom Nanozyme Peroxidase-like Specificity

Single-atom nanozymes (SAzymes) generally trigger catalytic reactions in situ within tumor cells, generating toxic reactive oxygen species (ROS) that induce cell death through oxidative stress, thereby achieving catalytic tumor therapy. However, therapeutic efficacy is often limited by insufficient ROS levels and intrinsic cellular antioxidant defenses. This study developed a spherical mesoporous iron-based single-atom nanozyme (Fe-SAzyme) modified with polyethylene glycol (PEG) and (4-carboxybutyl)triphenylphosphonium bromide (TPP), achieving photothermal amplification of catalytic activities to deliver antitumor therapeutic effects. Fe-SAzyme exhibited triple enzyme-mimetic activities-peroxidase-like, glutathione peroxidase-like, and catalase-like activity. It simultaneously generated ROS and oxygen while oxidizing glutathione to oxidized glutathione. This elevation in ROS levels and weakening of antioxidant defenses disrupted intracellular redox homeostasis, ultimately triggering a process known as ferroptosis. Density functional theory (DFT) calculations revealed that Fe-SAzyme exhibited a low energy barrier for hydroxyl radical generation and possessed a viable cyclic catalytic pathway. Additionally, Fe-SAzyme-TPP exhibited exceptional photothermal conversion capabilities under second near-infrared (NIR-II) irradiation, enabling its use in photothermal therapy (PTT), while simultaneously enhancing catalytic activity and thereby significantly improving tumor treatment efficacy. In vitro and in vivo experiments demonstrated that PEG and TPP-modified Fe-SAzyme exhibited outstanding antitumor efficacy, along with enhanced biocompatibility and targeting capabilities. Under NIR-II irradiation, photothermal therapy synergized with catalytic activities, significantly amplifying tumor suppression effects. This study proposed a combined antitumor strategy based on iron-based SAzymes, utilizing photothermal amplification to enhance catalytic activities in conjunction with PTT, thereby achieving ferroptosis-based antitumor effects.

Increasing cellular immunogenicity and reshaping the immune tumor microenvironment (TME) are crucial for antitumor immunotherapy. Herein, this work develops a novel single-atom nanozyme pyroptosis initiator: UK5099 and pyruvate oxidase (POx)-co-loaded Cu-NS single-atom nanozyme (Cu-NS@UK@POx), that not only trigger pyroptosis through cascade biocatalysis to boost the immunogenicity of tumor cells, but also remodel the immunosuppressive TME by targeting pyruvate metabolism. By replacing N with weakly electronegative S, the original spatial symmetry of the Cu-N4 electron distribution is changed and the enzyme-catalyzed process is effectively regulated. Compared to spatially symmetric Cu-N4 single-atom nanozymes (Cu-N4 SA), the S-doped spatially asymmetric single-atom nanozymes (Cu-NS SA) exhibit stronger oxidase activities, including peroxidase (POD), nicotinamide adenine dinucleotide (NADH) oxidase (NOx), L-cysteine oxidase (LCO), and glutathione oxidase (GSHOx), which can cause enough reactive oxygen species (ROS) storms to trigger pyroptosis. Moreover, the synergistic effect of Cu-NS SA, UK5099, and POx can target pyruvate metabolism, which not only improves the immune TME but also increases the degree of pyroptosis. This study provides a two-pronged treatment strategy that can significantly activate antitumor immunotherapy effects via ROS storms, NADH/glutathione/L-cysteine consumption, pyruvate oxidation, and lactic acid (LA)/ATP depletion, triggering pyroptosis and regulating metabolism. This work provides a broad vision for expanding antitumor immunotherapy.

Carbon-supported CoS4-C single-atom nanozyme for dramatic improvement in CO2 electroreduction to HCOOH: A DFT study combined with hybrid solvation model

Cs0.33WO3 nanoparticles have been prepared successfully by a stirred bead milling process. By grinding micro-sized coarse powder with grinding beads of 50 μm in diameter, the mean hydrodynamic diameter of Cs0.33WO3 powder could be reduced to about 50 nm in 3 h, and a stable aqueous dispersion could be obtained at pH 8 via electrostatic repulsion mechanism. After grinding, the resulting Cs0.33WO3 nanoparticles retained the hexagonal structure and had no significant contaminants from grinding beads. Furthermore, they exhibited a strong characteristic absorption and an excellent photothermal conversion property in the near-infrared (NIR) region, owing to the free electrons or polarons. Also, the NIR absorption and photothermal conversion property became more significant with decreasing particle size or increasing particle concentration. When the concentration of Cs0.33WO3 nanoparticles was 0.08 wt.%, the solution temperature had a significant increase of above 30°C in 10 min under NIR irradiation (808 nm, 2.47 W/cm2). In addition, they had a photothermal conversion efficiency of about 73% and possessed excellent photothermal stability. Such an effective NIR absorption and photothermal conversion nanomaterial not only was useful in the NIR shielding, but also might find great potential in biomedical application.

Photogenerated radicals are an indispensable member of the state-of-the-art photochromic material family, as they can effectively modulate the photoluminescence and photothermal conversion performance of radical-induced photochromic complexes. Herein, two novel radical-induced photochromic metal-organic frameworks (MOFs), [Ag(TEPE)](AC) ⋅ 7/4H2O ⋅ 5/4EtOH (1) and [Ag(TEPE)](NC) ⋅ 3H2O ⋅ EtOH (2), are reported. Distinctly different topological networks can be obtained by judiciously introducing alternative π-conjugated anionic guests, including a new topological structure (named as sfm) first reported in this work, describing as 4,4,4,4-c net. EPR data and UV-Vis spectra prove the radical-induced photochromic mechanism. Dynamic photochromism exhibits tunability in a wide CIE color space, with a linear segment from yellow to red for 1, while a curved coordinate line for 2, resulting in colorful emission from blue to orange. Moreover, photogenerated TEPE* radicals effectively activate the near-infrared (NIR) photothermal conversion effect of MOFs. Under 1 W cm-2 808 nm laser irradiation, the surface temperatures of photoproducts 1* and 2* can reach ~160 °C and ~120 °C, respectively, with competitive NIR photothermal conversion efficiencies η=51.8 % (1*) and 36.2 % (2*). This work develops a feasible electrostatic compensation strategy to accurately introduce photoactive anionic guests into MOFs to construct multifunctional radical-induced photothermal conversion materials with tunable photoluminescence behavior.

The incorporation of donor-acceptor components into metal-organic frameworks (MOFs) is an effective approach for developing efficient near-infrared (NIR) photothermal conversion materials; yet, their precise structural design and synthetic methodologies still present significant challenges. In this work, we present a distinctive MOF material Zn2(bpPDI)(TTFTB)·solvent (MOF 1) constructed by the coordinated assembly of donor-acceptor components, featuring a tetrathiafulvalene tetrabenzoate (TTFTB) electron donor and a bis-pyridyl-substituted pyromellitic diimide (bpPDI) electron acceptor. The material demonstrates significant intrinsic intermolecular electron-transfer capability and possesses a long-lived TTFTB•+ radical cation and a bpPDI•- radical anion. These characteristics enable panchromatic absorption spanning the visible to the second near-infrared (NIR-II) region, thus allowing efficient NIR photothermal conversion. Under NIR light irradiation, MOF 1 achieves efficient photothermal conversion (ΔTmax = 137 °C under 0.5 W cm-2 laser exposure), including rare NIR-II photothermal conversion capabilities, while exhibiting excellent thermal stability and cycling durability.

This review focuses on the active site microenvironment engineering of metal-nitrogen-carbon single-atom nanozymes (M-N-C SANs), a frontier subfield of nanozymes renowned for their exceptional catalytic activity, selectivity, and cycling stability due to the synergistic effects of highly dispersed metal single atoms and carbon-based carriers, making them a core research focus in the nanozyme field. This paper systematically reviews the regulatory mechanisms and catalytic principles governing the active site microenvironment of M-N-C nanozymes. Focusing on three core components (carbon carrier defects, metal coordination environments, and surface functional groups), this paper elucidates the structural characteristics, action mechanisms, and targeted regulation strategies for each element. By integrating advanced characterization techniques such as in situ X-ray absorption fine structure (XAFS) and transmission electron microscopy (TEM) with density functional theory (DFT) calculations, the structure-electronic-catalytic performance relationship within the microenvironment is elucidated, revealing the intrinsic logic of microenvironmental regulation in optimizing catalytic pathways. Current research still faces challenges such as the difficulty of precise microenvironment regulation, insufficient understanding of dynamic catalytic mechanisms, and unclear multi-factor synergistic mechanisms. Future efforts should focus on innovative precision control technologies, high spatiotemporal resolution characterization techniques, multi-factor synergistic regulation systems, and interdisciplinary integration. This will propel M-N-C nanozymes from empirical regulation to precision design, providing theoretical foundations and technical references for their large-scale applications in biomedicine, environmental remediation, and energy conversion.

Single-atom nanozymes (SAzymes) precisely emulate enzyme catalytic centers at the atomic level, offering exceptional catalytic efficiency and selectivity. Inspired by the heme structure of natural enzymes, this study introduces chlorine axial coordination into the Fe-N3O single-atom nanozyme, constructing a unique Fe-N3O-Cl catalytic site (Fe-N/O/Cl-C SA). As a result, the Fe-N/O/Cl-C SA demonstrates remarkable peroxidase-like activity toward the substrate 3,3',5,5'-tetramethylbenzidine (TMB), achieving a catalytic efficiency 1.96-fold greater than horseradish peroxidase (HRP). Density functional theory (DFT) calculations further reveal that axial chlorine coordination significantly reduces the reaction energy barrier, complementing the planar oxygen coordination, which shortens the activation pathway for H2O2. Moreover, the Fe-N/O/Cl-C SA efficiently catalyzes the oxidative depolymerization of birch lignin under mild conditions, producing high-value aromatic monomers such as vanillin and cinnamaldehyde. These findings underscore the critical role of chlorine axial coordination in enhancing catalytic performance and highlight the great potential of single-atom nanozymes in biomass conversion and renewable energy applications.

Simple and powerful: The reaction kinetics at surfaces of heterogeneous catalysts is reformulated in terms of the involved chemical potentials. Based on this formulism, an approach of searching for good catalysts is proposed without recourse to extensive calculations of reaction barriers and detailed kinetic analyses. (see picture; R=reactant, I=surface intermediate, P=product, and =standard chemical potential). Catalysis is of paramount importance in our daily life. In particular, heterogeneous catalysts which speed up reactions on their solid surfaces play a vital role in a wide range of industries, such as petroleum, energy, and environment-related industries. There is no doubt that rational design of new catalysts is a major endeavor in chemistry. A key to achieve this goal is reaction kinetics, bridging the gap between microscopic elementary chemical reactions and macroscopic performance of catalysts. Although great progress in understanding reaction kinetics has been made, rational design of new catalysts remains one of the profound challenges. Here, we present a new formulism of reaction kinetics at surfaces in terms of the involved chemical potentials, which simplifies the reaction kinetics significantly. Furthermore, within this formulism we propose a new approach of searching for new catalysts. The effectiveness and universality of this theory are discussed. There have been several major related developments in this field. First, density functional theory (DFT) approaches have been developed to such a level that the barriers of elementary steps are determined routinely. Many total-energy profiles of reaction systems from DFT calculations were reported. Second, with the energy profiles from first-principles calculations in hand, kinetic information, such as reaction rates and coverages of surface intermediates, are obtained by kinetic Monte Carlo simulations1, 2 and microkinetic calculations.3 Third, the linear relationship between the reaction barrier and the reaction-enthalpy change, the so-called Brønsted–Evans–Polanyi (BEP) relations,4 was found to be followed by a wide range of surface reactions.5–8 Based on the BEP relations, some successful examples of catalyst design from first-principles calculations, that is, the activities were plotted against the adsorption energies of key intermediates (see, for example, Refs. 9, 10), were reported.11, 12 Fourth, Nørskov and co-workers9, 13 observed that for many surface reactions on the best catalysts the adsorption energies of key intermediates locate in a small window of −2 to −1 eV (negative energy means the adsorption is exothermic). Significantly, this energy window appears to be universal. This is somewhat surprising, considering that the catalytic systems are very different and each of them possesses unique, complicated kinetics. However, the computation of the reaction barrier of each elementary step is time-consuming, and moreover the understanding of the catalytic systems from the total-energy profiles obtained consequently is not straightforward, let alone rational design of new catalysts. As a result, new catalysts are traditionally developed using experimental trial-and-error methods. Therefore, to have better approaches, in particular better kinetic theories directed towards the design of catalysts, is essential to further develop the subject. Here, we introduce chemical potentials, which are widely used in electrochemistry under the name of electrochemical potential, to surface-catalytic reactions to reformulate the reaction kinetics. It will be manifested below that the chemical potentials of surface intermediates implicitly take into account surface coverages and temperature effects, and therefore reveal more chemical meanings. More importantly, we show that chemical potentials of surface intermediates can be used as a guide in searching for new catalysts without detailed kinetic analyses, and the interesting observation of the universal energy window can be understood using our approach. where θi and θ* are coverages of adsorbed species i and free sites * on a surface, respectively, and is the standard chemical potential of species i at temperature T and is readily obtained from the total energy Etot, routinely computed using DFT, at 0 K with a small thermal correction term Δµi(T). Energy diagram of a model for heterogeneous catalytic reactions. The black curve stands for the profile of total energies calculated from DFT, and the gray curve represents the profile of chemical potentials. TS1 and TS2 are the transition states (TSs) of adsorption and desorption, respectively. Etot is the total energy, and µ is the chemical potential (subscript R, I and P refer to reactant, intermediate, and product). and are the total energy and standard chemical potential of the TS of adsorption, respectively, and have the same meanings for the TS of desorption. The correction of the chemical potential because of the temperature effect is given by Δµ. The thermal corrections for gaseous molecules (ΔµR and ΔµP) are quite large because of large entropy effects, whereas the corrections for surface species (, ΔµI and ) are much smaller. R Tln(θi/θ*) is the coverage-dependent term in the expression of the chemical potential of surface species [see Eq. (1)], and likewise R Tln(p/po) is the pressure-dependent term for gaseous molecules [see Eq. (S1) in the Supporting Information]. Unlike intermediate state, the standard chemical potentials for the TSs appear in the profile of chemical potentials. This equation can be generalized to any sequential multistep reaction system, namely . Its significance will be revealed later. Second, the magnitude of the decrease of each step, which is related to the reversibility according to Equations (5) and (7), indicates the thermodynamic driving force for the step. Third, the heights of the TSs with respect to the reactant states (the barriers of the chemical potentials) are direct measures of the reaction rates, unlike the barriers of total energies in which the entropic effects and coverages are not taken into account. This is best manifested by the fact that for adsorption processes the sole use of the barriers of total energies as measures will significantly overestimate the reaction rates because of the lack of large negative entropic effects. There are some significant implications in the above results for understanding heterogeneous catalysis. First, if the standard chemical potential of a TS of a prior step is smaller than the later step, that is, , then µR≈µI is approximately satisfied (see the Supporting Information), indicating that the former step reaches a quasi-equilibrium at steady states. This result can be readily extended to other sequential elementary reactions, such as the multistep hydrogenation reaction C+4 H→CH4 in the CO hydrogenation on metal surfaces.18, 19 For a series of sequential reactions if the last step has the highest chemical potential at the TS, the previous steps can be approximately treated as being in quasi-equilibrium, and the last step is the rate-determining. Second, for a given reaction condition and a catalyst surface, the levels of the chemical potentials of reactant and product (µR and µP) and TSs ( and ) are fixed in a reaction profile of chemical potentials. However, the chemical potential of the surface intermediate (µI) consists of two terms, and R Tln(θi/θ*), where is invariant for a given catalyst and R Tln(θi/θ*) is the coverage-dependent term. Namely, µI is varied around the by θ*, considering that θ* is a variable whereas θI is not an independent variable because of θI+θ*=1 in our two-step model (but generally, θI+θ*≈1 if there are more than one intermediate and intermediate I is the main one). Upon approaching a steady state, however, the level of µI must reside between µR and µP to satisfy Equation (8). Now we are in a position to illustrate an important application of our chemical potential kinetics theory for searching for new catalysts. In the Supporting Information, using a simple kinetic model we show that the coverage of free sites θ* on the surface can be derived to be around 10−1 monolayer (ML) for the optimal catalysts, which is supported by experimental results: When catalytic reactions take place on good catalysts, θ* is usually in the order of magnitude of 10−1 to 10−2 ML at steady states. For example, kinetic analyses showed that θ* is around 0.08 ML for hydrogenation of isobutene on Pt,17 and around 0.01 ML for the synthesis of ammonia on Fe and Ru catalysts.7, 17 This is also consistent with a general consensus in the field: 1) If θ* is low, it is usually a sign of blockage of surface sites, leading to low activities. This often happens when the surface–adsorbate bonding interaction is too strong. 2) If θ* is high and approaches 1 ML, it is difficult for molecules to adsorb on the surface. Namely, the surface is too inert to catalyze the reaction. In principle the coverage-dependent term RT ln(θi/θ*) varies in the range from −∞ to +∞ and approaches the infinity limits when the surface coverage is extremely low (no adsorption) and high (1 ML). Thus, µI can be changed by θ* to locate anywhere in the diagrams of chemical potentials no matter where is. However, upon approaching the two limits the total reaction rates will be reduced dramatically because of the inertness of the surface or blockage of surface sites. For good catalysts RT ln(θi/θ*) should be small, and hence µI is mainly determined by . Equation (11) may partially justify the assumption of a downhill requirement for the free-energy diagrams in the model for electrocatalytic reactions reported by Nørskov, Rossmeisl, and co-workers.20 Then, the searching procedure of catalysts, as illustrated in Figure 2, can be devised: First, based on the gas-phase energetics of an overall reaction under a certain reaction condition (i.e. temperature and pressure) which can be very easily obtained, determine the positions of the chemical potentials of the reactants and products in the diagram of chemical potentials, which approximately establishes the upper and lower boundaries of the standard chemical potentials of the key intermediates on the surface (zone 1 in Figure 2). Second, according to Equation (11), we slightly relax the boundaries (e.g. by 0.2 eV) and search for the appropriate catalyst surfaces which are able to offer the standard chemical potentials of the surface intermediates lying between the relaxed boundaries (zone 2 in Figure 2). As can be seen from Figure 2, and satisfy the requirement and the corresponding catalysts are most likely good catalysts. However, and are too high or too low to locate in the zone even including the small variation because of the coverage term, and hence the corresponding catalysts cannot be good catalysts. This approach is extremely simple, but its effectiveness and universality can be seen later. Searching for good catalysts by means of the involved chemical potentials. The chemical potentials of reactant and product (µR and µP) set the boundaries for the chemical potential of the surface intermediate (µI, zone 1). On good catalysts, this zone can only be slightly relaxed for the standard chemical potential of the surface intermediate (, zone 2). Thus, surfaces of catalysts related to and are very likely to be good catalysts, whereas surfaces related to and cannot be good catalysts. Since the standard chemical potential of a key surface intermediate consists of a dominating total-energy term , related to the adsorption energy on the surface and a small thermal correction term ΔµI(T) according to Equation (1), a good catalyst must have an appropriate binding energy of the key intermediate lying between the boundaries set by the chemical potentials of the reactant and the product. This coincides with the idea of adsorption-energy windows proposed by Nørskov and co-workers, stating that the optimal catalyst should be one with an chemisorption energy of the adsorbate in the range of −2 to −1 eV.9, 13 Taking ε as 0.2 eV as suggested above, we will have adsorption energies of N2 in the range of around −1.7 to −0.8 eV for optimal catalysts, which is in good agreement with the observed energy window (around −2 to−1 eV).9, 13 This agreement is extraordinary: In predicting the optimal range of the adsorption energy, we only use the data from gas-phase reaction energetics, without recourse to detailed DFT calculations on surfaces except the small corrections of and the ZPE. A universal upper boundary of optimal adsorption energy can be estimated and understood using our formulation. Heterogeneous catalytic reactions start with adsorption of reactants on surfaces, which must satisfy µR>µI. Applying Equation (1) and ignoring small concentration and thermal correction terms, we can obtain −T SR>ΔER, where SR is the entropy of the reactant in the gas phase and ΔER is the adsorption energy of the reactant. Therefore, the upper boundary is mainly set by the entropy of the reactant, that is, the adsorption energy of the reactant must be strong enough to outweigh the decrease in entropy upon adsorption. Bearing in mind the fact that many small molecules have the entropies of around 200 J mol−1 K (e.g. N2 in the ammonia synthesis, CO in its hydrogenation reaction and O2 in the CO oxidation), we reach the upper boundary of adsorption energy of around −0.6 to −1.0 eV at a typical temperature range of 300–500 K. This estimate also agrees with the upper boundary of the observed energy window.9, 13 The lower boundary of optimal adsorption energy may be not that obvious as the upper boundary, but should readily be obtained, as already shown in the ammonia synthesis. Finally, we wonder why this method works by considering only reaction energetics (i.e. chemical potentials of reactants and products and standard chemical potential of key intermediates) without taking reaction kinetics into account (reaction barriers are not involved). In fact, the kinetic information is implicitly folded by the fact that the coverage-dependent term R Tln(θi/θ*) in Equation (1) is small for good catalysts. In summary, here we have applied chemical potentials to catalytic reactions on surfaces; reaction kinetics of surface processes, for example, the reaction rate and reversibility, has been reformulated in terms of the involved chemical potentials. The total energy profiles of surface reactions usually computed from DFT simulations can be readily converted to profiles of chemical potentials. The new formulation is simple but powerful to understand surface reactions both thermodynamically and kinetically. We have estimated with approximations that for many catalytic reactions the coverage of free site on surfaces of the best catalysts is usually in a medium range. Combining this simple, but important result and our formulation, a procedure in searching for good catalyst has been proposed. Our formulation has also provided the explanation of the universality of the adsorption-energy window in heterogeneous catalysis. We have further shown our method by using the ammonia synthesis as an example. Our method is not only able to predict the range of optimal adsorption energies, in agreement with reported values, but it also is very simple without the need of extensive calculations of reaction barriers and detailed kinetic analyses. Detailed facts of importance to specialist readers are published as "Supporting Information". Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Tetrathiafulvalene (TTF) and Ni-bis(dithiolene) are typical conductive units widely studied in electronics, optics, and photochemistry. However, their applications in near-infrared (NIR) photothermal conversion are often limited by insufficient NIR absorption and low chemical/thermal stability. Herein, we integrate TTF and Ni-bis(dithiolene) into a covalent organic framework (COF) with stable and efficient NIR and solar photothermal conversion performance. Two isostructural COFs, namely Ni-TTF and TTF-TTF, are successfully isolated which are composed of TTF and Ni-bis(dithiolene) units as donor-acceptor (D-A) pairs or TTF units only. Both COFs show high BET surface areas and good chemical/thermal stability. Notably, compared with TTF-TTF, the periodic D-A arrangement in Ni-TTF significantly lowers the bandgap, leading to unprecedented NIR and solar photothermal conversion performance.

Constructing ultra-stable photothermal plastics assisted by carbon dots with photocaged reactivity

Gold–silver hybrid nanostructures have emerged as promising candidates for efficient near-infrared (NIR) photothermal conversion due to their unique optical and electronic properties. In this study, we report on the synthesis and characterization of gold–silver core–shell nanostructures with Au multipods as the core and Ag hollow cage as the shell, exhibiting strong absorption in the NIR region, which is attributed to the coupled localized surface plasmon resonance (LSPR) effect. Benefiting from its large surface area and porous structure, an optimized photothermal conversion efficiency of 68.5% is achieved, evaluated using a water suspension under an 808 nm laser at a power density of 1.0 W cm–2. The photothermal stability was also investigated, revealing good durability after multiple cycles of heating and cooling. Our study demonstrates the potential of gold–silver core–shell hybrid nanostructures involving both multipods and hollow cages for efficient NIR photothermal conversion applications. These findings pave the way for further optimization of these nanostructures for various biomedical and industrial applications.

Flexible and hydrophobic CoFe-LDH @Co MOF @biomass-derived carbon fabrics for effective near-infrared photothermal conversion and electromagnetic attenuation