Electrochromic materials, modulating their optical properties in response to electric fields, have shown widespread potential applications in displays, e-papers, camouflage, and smart windows, and so forth. However, conventional electrochromic materials based on chemical coloration mechanism exhibit noncontinuous color tuning ability and nontailorable color change and require high working voltages, significantly limiting their advanced applications. Recently, electrically responsive structural-color (ERSC) materials capable of addressing the above issues are regarded as the next-generation electrochromic materials and have attracted growing scientific interests. In this review, we summarize recent advances in ERSC materials through a seven-section framework. After introducing the background and significance of ERSC materials, we first classify representative structural platforms, including colloidal photonic crystals, inverse opals, liquid-crystal photonic structures, and plasmonic nanostructures. We then discuss the major electrically responsive mechanisms responsible for structural-color modulation, followed by an overview of fabrication strategies. Subsequently, key performance parameters, including color tuning range, color saturation, working voltage, response speed, hue stability, and cycling durability, are critically compared to clarify the merits and limitations of different ERSC systems. Finally, emerging applications, current challenges, and future prospects are discussed, aiming to provide guidance for the rational design and practical development of high-performance ERSC materials. This review will be helpful for facilitating the design and fabrication of outstanding ERSC materials and extend their advanced applications in color display, smart windows, information security, anticounterfeiting, dynamic camouflage, and so forth.
Red emitters suitable for solid-state applications are the subject of intense research. However, their development is delicate because, in general, the more the emission is red-shifted, the more its efficiency decreases. In this work, two series of phosphorescent tricarbonylrhenium complexes were synthesized and studied, both theoretically and experimentally. Their organic ligand is a phenyl-substituted quinoline or quinoxaline derivative. They also differ in their ancillary ligand, chloride or triphenylphosphine (TPP), and the presence of a bulky adamantyl substituent, initially introduced to improve the solid-state arrangement and thus the light emission efficiency. Unsurprisingly, chlorido complexes were not luminescent in solution, and only quinoline derivatives emitted faint red light in the solid state. In contrast, phosphino complexes were weakly phosphorescent in solution and showed strong solid-state luminescence enhancement. A red emission was observed for the microcrystalline powders of quinoxaline derivatives, with a PLQY up to 43%, a performance rarely achieved in this spectral region. This effect was attributed to the double intra- and intermolecular stabilization provided by the TPP moiety. The phosphino complexes were very well suited to aggregation-induced phosphorescence emission (AIPE) experiments. Their potential interest for related applications was shown. An adamantyl-substituted complex was used for the detection of sodium deoxycholate by taking advantage of the competition between these two compounds for a β-cyclodextrin. Until now, phosphino tricarbonylrhenium complexes have been mainly exploited for their photodecarbonylation properties useful in phototherapy. This work shows that they are photostable after proper chemical modifications, and that their unique spectroscopic properties make them the leaders of a new generation of red emitters.
Accurate tumor boundary delineation is critical for successful surgical resection, yet achieving high-contrast imaging of hepatocellular carcinoma (HCC) remains challenging due to nonspecific liver accumulation and high intrinsic fluorescence of optical agents. Herein, we reported a molecular design strategy exploiting enhanced cyanine H-aggregation by dimerization, which enabled glutathione (GSH) responsive high-contrast HCC imaging and precise surgical navigation. Four cyanine dimers with different side-chains were constructed via molecular engineering. Among them, the propyl-substituted dimer DCy-Pr exhibited exceptionally low intrinsic fluorescence quantum yield (Φf < 0.01%) due to strong H-aggregation-caused quenching, achieving the highest GSH-triggered fluorescence turn-on (151.0-fold). However, the other three cyanine dimers with hydrophilic side chains (polyethylene glycol, anionic SO3−, or cationic ammonium) showed unsatisfactory properties, such as absence of H-aggregation, no reactivity with GSH, and high intrinsic fluorescence. DCy-Pr displayed a remarkable fluorescence quenching, which outperformed its monomeric counterpart Cy-Azo (16.0-fold higher background fluorescence). Moreover, in vivo studies revealed that DCy-Pr efficiently accumulated in tumor regions, achieving remarkable fluorescence contrast with 9.7-fold tumor-to-normal tissue and 5.1-fold tumor-to-liver fluorescence ratios. Finally, DCy-Pr enabled precise delineation of orthotopic hepatic tumor margins and facilitated successful identification and resection of peritoneal metastatic nodules. In summary, this work not only presented a molecular design paradigm through modulating cyanine H-aggregation but also advanced precision surgery of HCC by providing credible real-time tumor margins.
Whereas aggregation-induced emission (AIE) is a useful tool to develop photofunctional host systems, its guest usability has been largely unexplored within well-defined host compounds so far, mainly owing to the absence of suitable cavities. Here we report the emission control of AIE-active anthracenes upon efficient encapsulation by a terpene-based micellar capsule in 100% water. Encapsulation of monopiperidyl-substituted anthracenes yields a well-defined host-guest composite, with an average diameter of ∼3 nm, displaying green emission with high quantum yield (ΦF = 53%). The yield is >50 and >10-fold higher than those of the AIE-dye in tetrahydrofuran (THF) and H2O/THF suspension (ΦF = 1 and 4%), respectively. This encapsulation-induced emission (EIE) is altered by changing the substituent number/shape on the aromatic framework, leading to up to ΦF = 65%. Co-encapsulation of the AIE-anthracenes with aggregation-caused quenching (ACQ) dyes (i.e., rubrene) enables strong yellow emission (up to ΦF = 55%) through high guest-to-guest Förster Resonance Energy Transfer (FRET) and antenna effect (up to 80% and 25, respectively) in the cavity. Furthermore, this strategy realizes strong pure-white emission (ΦF = 36%; CIE of (0.33, 0.33)) using other AIE-active molecules in water. The photofunctions of AIE-molecules can thus be largely expanded by the present capsule.
Living crystallization-driven self-assembly (CDSA) has evolved beyond fundamental morphological control, driving a paradigm shift toward an era of precise functional customization. This review highlights the transition of living CDSA from a structural fabrication tool to a highly modular platform for tailored functional nanomaterials. We highlight how living CDSA enables the precise construction of hierarchical nanostructures, such as one-dimensional nanofibers, two-dimensional platelets, and multicomponent micellar brushes through delicate tailoring of crystallizable cores and solvated coronas. We systematically evaluate the strategies for intrinsic material design, exogenous functionalization, and surface engineering. By integrating the precise architectures and highly designable functional modules, living CDSA facilitates the creation of various functional materials for catalysis, energy conversion, biomedicine, and so forth. This review emphasizes living CDSA as a universal platform to address key challenges in materials science, offering insights into scalable, application-driven nanomaterial fabrication.
Metal–polyphenol networks (MPNs), as supramolecular functional materials formed through coordination-driven self-assembly of polyphenol ligands and metal ions (Fe2+, Cu2+, etc.), have demonstrated broad application prospects in the biomedical field due to their structural designability, excellent biocompatibility, and stimulus-responsive degradation properties. MPNs allow for precise control over coordination kinetics, stability, and functionality through diverse combinations of polyphenols and metal ions. Various assembly methods, including the template method, nanoprecipitation, layer-by-layer self-assembly, and one-pot synthesis, have successfully led to the construction of diverse structures such as films, nanoparticles, hollow capsules, hydrogels, and metal–organic frameworks. By adjusting the metal-to-polyphenol ratio, pH, reaction time, and introducing functional molecules, the size, surface charge, mechanical properties, and dissociation behavior of MPNs can be effectively controlled to meet the demands of various biomedical applications. Leveraging the synergistic interaction between paramagnetic or fluorescent metal ions and polyphenol structures, MPNs are widely used in the design of probes for magnetic resonance imaging, fluorescence imaging, photoacoustic imaging, and multimodal imaging, enabling precise localization and real-time monitoring of pathological sites. MPNs not only serve as highly efficient drug delivery carriers, enabling targeted release in response to the micro acidic or high reactive oxygen species environments of tumors, but also play a critical role in synergistic disease therapy through the enzymatic-like catalytic activity, photothermal conversion capabilities, and radiosensitizing effects of metal ions. In this review, we summarize the advances of MPNs as a highly versatile and functionally integrated supramolecular assembly platform, and discuss their pivotal role in steering biomedical materials away from single-function designs and toward intelligent, unified diagnostic and therapeutic solutions.
Biomolecular condensates, formed via liquid–liquid phase separation (LLPS), play crucial roles in a range of cellular processes. Dysregulated or aberrant condensates are closely associated with diseases including neurodegeneration, cancer, metabolic disorders, and viral infections. Accumulating evidence demonstrates that LLPS is highly amenable to chemical regulation. Diverse chemical agents can modulate phase separation by directly or indirectly perturbing the weak, multivalent interactions that govern condensate formation, dissolution, size, material properties, and maturation. The identification of LLPS-modulating chemical regulators not only provides powerful probes for dissecting the physicochemical principles underlying condensate behavior, but also highlights emerging opportunities for the development of condensate-targeting strategies of potential therapeutic relevance. In this review, we summarize recent advances in the chemical regulation of LLPS, organizing regulatory strategies according to their dominant mechanistic level of action. We highlight how chemical perturbations reshape phase behavior by altering conformational ensembles, effective interaction valency, electrostatic and metabolic environments, or bulk solvent properties, thereby shifting phase boundaries or biasing pathological liquid-to-solid transitions. Finally, we discuss emerging opportunities and remaining challenges in the rational discovery of selective, mechanism-informed LLPS regulators.
The ability to synthesize well-defined and atomically precise nanoclusters is important both in advancing fundamental understanding of structure–property relationships of nanomaterials and for materials, energy, and biomedical applications. Nonetheless, incorporating bioactive ligands into the nanoclusters poses a significant challenge, mostly due to complex metallophilic interactions and incompatibility with typical synthetic conditions. In this work, we developed a straightforward method for the synthesis of an atomically precise gold nanocluster capped with a carbohydrate ligand, trehalose, Au25Tre18, in one step and in 55% yield. The formation of the nanocluster was enabled by using a mild reducing agent, t-butylamine borane, in a biphasic condition. The structure was confirmed by high-resolution mass spectrometry, optical absorption spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. 2D DOSY NMR gave a diffusion coefficient of 1.9 × 10−10 m2s−1 and the hydrodynamic diameter of 1.6 nm for Au25Tre18. The CD spectrum of Au25Tre18 indicated chirality, having features differing from other chiral Au25 nanoclusters. The aqueous solution of Au25Tre18 was stable and showed no degradation during a heating and cooling cycle from room temperature to 80°C. In a thiourea (TU)-triggered release assay, Au25Tre18 exhibited enhanced antimicrobial activity against Mycobacterium smegmatis, showing a minimal inhibitory concentration (MIC) four times lower than that of Au25 nanocluster capped with glutathione, Au25SG18. Treating the bacteria at 1 × MIC of Au25Tre18/TU resulted in complete eradication of bacteria, whereas bacteria treated with Au25SG18/TU at the same concentration continued to grow.
Achieving highly efficient purely organic room-temperature phosphorescence (RTP) remains a formidable challenge due to inherently weak spin–orbit coupling and slow intersystem crossing (ISC) between the singlet and triplet manifolds. To address this limitation, the involvement of higher-lying triplet states (Tn)—either through direct ISC (S1→Tn→T1) or indirect nonadiabatic spin–vibronic coupling (NA-SVC) enhanced ISC (Tn mediates S1→T1 without being populated)—has emerged as a powerful strategy to facilitate triplet harvesting. However, it remains unclear exactly how Tn participates in these two distinct pathways, and under which conditions one pathway dominates over the other. To address these questions, we develop a theoretical framework integrating the time-dependent generating function (TD-GF) algorithm with the multilayer energy-based fragment (MLEBF) method, enabling evaluation of NA-SVC contributions to ISC rate constants in the crystalline phase at the full quantum mechanical (QM) level. This computational protocol is applied to elucidate the competing ISC pathways in a series of carbazole derivatives (BeCbz, AcCbz, and PhCbz) in solution and crystalline phases. Quantitative evaluations reveal that the superior RTP performance of BeCbz is decisively governed by a direct, T2-mediated S1→T2→T1 pathway. Moreover, the significant NA-SVC enhancement drives an ultrafast S1→T2 ISC that effectively outcompetes fluorescence. In contrast, AcCbz primarily utilizes a direct spin–orbit coupling (DSO)-dominated S1→T1 pathway, whereas PhCbz exhibits solely fluorescence due to severely hindered ISC channels. Overall, this study demonstrates that explicit full QM modeling of environmental effects and NA-SVC is of great importance, providing a rigorous predictive tool for the rational design of high-performance organic phosphors.
The precise intraoperative delineation of gastric tumors and their micrometastases remains a major challenge in surgical oncology. To address this, we developed a novel NIR-II fluorescent probe named SPN01 targeting integrin αvβ3, a receptor upregulated in gastric cancer and associated tumor vasculature. SPN01 was constructed by conjugating RGD peptide to a high-performance cyanine fluorophore with net neutral charge. In multiple preclinical models, SPN01 enabled high-contrast visualization of sub-centimeter orthotopic tumors, detection of occult peritoneal micrometastases as small as 0.5 mm, and specific identification of metastatic lymph nodes. Concurrently, near-infrared II (NIR-II, 900–1880 nm) fluorescence guidance facilitated the complete resection of tumors with clear margins, owing to the superior brightness of SPN01 in the NIR-II window. Notably, ex vivo validation using human gastric cancer specimens confirmed target-specific binding. Comprehensive pharmacokinetic and safety studies demonstrated rapid dual-pathway clearance and no obvious toxicity. Following these findings, we conducted a first-in-human Phase I clinical trial involving 24 healthy volunteers, which demonstrated a favorable safety profile for SPN01. These findings support SPN01-assisted NIR-II fluorescence-guided surgery as a promising candidate for clinical translation with the potential to enhance the completeness of gastric cancer resection.
Perovskite solar cells (PSCs) are promising next-generation photovoltaics, yet their efficiency promotion from lab-scale prototypes to industrial application is fundamentally hindered by interfacial instability and non-radiative recombination. These critical bottlenecks stem from complex defect chemistry, ion migration, energetic mismatches and material degradation at the perovskite heterojunction interface, which conventional empirical strategies often fail to address systematically. This perspective evaluates two pivotal paradigms for multidimensional top interfacial regulation: multimolecular synergistic systems, which utilize cooperative interactions among diverse functional additives, and all-in-one molecular integration, which employs sophisticated, multifunctional single molecules. We analyze how these distinct philosophies influence defect passivation kinetics, energy level alignment, operational resilience against ionic migration and environmental stressors. While multimolecular systems offer modular versatility, all-in-one integration provides superior structural precision to suppress phase separation and interfacial delamination. Furthermore, we assess their comparison and applicable scenarios. Finally, we propose a transition from empirical trial-and-error to data-driven predictive design. By establishing a unified molecular engineering framework, this paper provides a strategic roadmap for bridging the gap between research breakthroughs and reliable, commercially viable perovskite modules.
We report a new chiral indaceno[1,2-b:5,6-b′]dithiophene bis-thiophenylpropynone (IDT-TPO) dye exhibiting very noticeable chiroptical properties in thin films. While freshly prepared samples are ECD-silent, aging triggers a giant dichroic response, with ellipticity values reaching approximately 18,000 mdeg, among the highest reported to date for thin films of chiral organic dyes as neat materials. This amplification is accompanied by an unusual flattening of the main UV-Vis absorption band, and the combination of these effects produces very large gabs values (exceeding 0.1). A thorough investigation, combining microscopy and spatially resolved chiroptical techniques with time-dependent density functional theory (TD-DFT) calculations, reveals that the intense chiroptical activity arises primarily from the consistent formation of right-handed three-dimensional (3D) helical architectures. Notably, the degree of circular polarization exhibits a non-monotonic dependence on film thickness: the maximum ECD intensity was found for a thinner film, rather than for the thickest one. This behavior is particularly promising for optoelectronic applications requiring efficient chiroptical responses in relatively thin active layers.
Liquid crystal elastomers (LCEs) have emerged as attractive soft actuators capable of undergoing large and reversible actuation. Their potential for practical applications, however, has been fundamentally constrained by an intrinsic trade-off: the chain flexibility required for reversible actuation inherently restricts molecular design toward achieving high mechanical strength and toughness. Here, we report a phase separation strategy that yields an LCE with a tensile strength of 92 MPa and toughness of 247 MJ m−3. This leads to 20-fold and 40-fold improvements compared with conventional LCEs without sacrificing their reversible actuation. Mechanistically, this superior mechanical performance is enabled by the incorporation of rigid polyamide acid segments into the network. During network formation, these segments self-assemble into phase-separated nanostructures that function as in situ-generated nanofillers, reinforcing the material and endowing it with outstanding work capacity. Our work suggests that leveraging microphase separation substantially broadens the design space for high-performance LCE actuators, paving the way toward mechanically robust and efficient soft actuation systems.
The aggregate form of interorganelle interaction is essential for the stable operation of cellular energy metabolism, signal transduction, as well as growth and development. Among these, the discovery of lipid droplet–mitochondria interactions (LDMIs) mediated by their aggregation has reshaped the understanding of how intracellular lipid metabolic networks operate within cells. Complex spatiotemporal interactions between lipid droplets and mitochondrial aggregates are commonly observed at the subcellular level, supporting the stable and efficient cycling of lipids and energy within the cell. Advanced techniques enabling organelle aggregation manipulation with high spatiotemporal precision have emerged as critical tools for investigating LDMIs and addressing diseases associated with LDMI dysregulation. This study aimed to summarize and update the distinctive characteristics of LDMIs and highlight the increasing understanding of their operational mechanisms, while also examining diseases caused by their dysfunction. Special emphasis was placed on the current challenges and prospects of strategies for the spatial aggregation manipulation of LDMIs, particularly the remarkable potential of optogenetic tools. With the continuous advancement of subcellular imaging and organelle aggregation manipulation technologies, LDMIs are poised to transform our understanding of cellular lipid metabolism networks and facilitate the effective manipulation of these complex networks at the organelle level.
Strong near-infrared-II (NIR-II, 1000–1700 nm) absorbers with high photothermal efficiency are highly desirable for deep-tissue photoacoustic imaging and photothermal therapy. However, donor–acceptor (D–A) molecular design strategies that simultaneously achieve structural robustness and intense NIR-II absorption remain scarce. Herein, we demonstrate that single-boron coordination can be implemented on the intrinsically strong acceptor [1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ), an unachieved regime by previously reported boron-engineered strategies, which have typically been based on weaker electron-deficient acceptors. Single intramolecular N→B–N coordination converts TQ into an even stronger electron-deficient motif than the widely used benzobis(thiadiazole) (BBT) acceptor. Through donor engineering and planarity modulation, the resulting borylated TQ derivative, BLD3, exhibits intense NIR-II absorption with a high molar extinction coefficient (ε > 3 × 104 M−1 cm−1) around 1000 nm in toluene. Featuring an ultrafast nonradiative decay of 2.1 ps, BLD3 nanoparticles (NPs) show a high photothermal conversion efficiency of 68% under 1060 nm laser irradiation, as well as a robust photoacoustic (PA) output under 1064 nm excitation. Combining excellent photo/thermal stability, favorable tumor accumulation, and good biocompatibility, BLD3 NPs enable effective NIR-II PA imaging-guided photothermal therapy with pronounced tumor ablation. This work expands the library of strong acceptors for boron-coordination chemistry, providing a general platform for constructing powerful electron-deficient building blocks and high-performance NIR-II phototheranostic materials.
Cancer is the leading cause of death worldwide, accounting for nearly 10 million deaths in 2020. The early diagnosis of cancer biomarkers is essential for improving prognosis and reducing the global disease burden. However, conventional diagnostic methods depend on sophisticated instrumentation, well-trained personnel, and complex workflows, which is usually time-consuming and costly. With programmable and sequence-specific nucleic acid recognition and cleavage, clustered regularly interspaced short palindromic repeats (CRISPR)-Cas systems have emerged as powerful tools for disease diagnostics. Their integration with engineering approaches, such as microfluidic devices including paper-based microfluidics, electrochemical, and smartphone-enabled platforms, has further enhanced cost-effectiveness, portability, and automation. This review presents the molecular mechanisms of CRISPR-Cas systems, recent advances in point-of-care testing (POCT) and its compatible technologies, and their applications in early cancer detection. We also discuss key challenges and future directions to enable accessible and reliable CRISPR-enabled diagnostics for improved global cancer diagnostics and provide the potential solution for effective treatment.
The tumor immune microenvironment (TIME) orchestrates a dynamic network of malignant, immune, and stromal cells, profoundly influencing cancer progression and therapeutic outcomes. Despite the transformative impact of immunotherapies, their efficacy remains limited by the immunosuppressive and heterogeneous nature of TIME. Overcoming these barriers requires platforms can both precisely visualizing immune–tumor interactions and actively modulating the local immune landscape. Aggregation-induced emission luminogens (AIEgens), proposed over two decades ago, have emerged as versatile and powerful tools that feature strong brightness in physiological environments and facile modulation of energy dissipation for phototherapy, enabling real-time monitoring of immune dynamics and induction of immunogenic responses. Herein, we summarize recent advances in AIEgen-based platforms for immunotherapy, with a particular emphasis on the emerging potential of AIEgens in immunotherapy, followed by rational design strategies for tailoring photophysical properties, high-fidelity mapping of immune–tumor interactions, and synergistic therapeutic modalities to reprogram the TIME. We further discuss the critical limitations that impede their clinical translation and outline future opportunities to accelerate their deployment in precision oncology. By positioning AIEgens systems at the interface of materials science and immunology, this review highlights their capacity to actively modulate the TIME and offers a framework to guide the design of next-generation precision immunotherapies.