A thermal receptor for nonvisual sunlight detection in myriapods.

Organisms from cyanobacteria to humans have evolved a wide array of photoreceptive strategies to detect light. Sunlight avoidance behavior is common in animals without vision or known photosensory genes. While indirect light perception via photothermal conversion is a possible scenario, there is no experimental evidence for this hypothesis. Here, we show a nonvisual and extraocular sunlight detection mechanism by identifying the broad-range thermal receptor 1 (BRTNaC1, temperature range = 33 to 48 °C) in centipede antennae. BRTNaC1, a heat-activated cation-permeable ion channel, is structurally related to members of the epithelial sodium channel family. At the molecular level, heat activation of BRTNaC1 exhibits strong pH dependence controlled by two protonatable sites. Physiologically, temperature-dependent activation of BRTNaC1 upon sunlight exposure comes from a striking photothermal effect on the antennae, where a slightly acidic environment (pH 6.1) of the body fluid leads to the protonation of BRTNaC1 and switches on its high thermal sensitivity. Furthermore, testosterone potently inhibits heat activation of BRTNaC1 and the sunlight avoidance behavior of centipedes. Taken together, our study suggests a sophisticated strategy for nonvisual sunlight detection in myriapods.

Cu2+ coordination-induced in situ photo-to-heat on catalytic sites to hydrolyze ß-lactam antibiotics pollutants in waters.

For degradation of ß-lactam antibiotics pollution in waters, the strained ß-lactam ring is the most toxic and resistant moiety to biodegrade and redox-chemically treat among their functional groups. Hydrolytically opening ß-lactam ring with Lewis acid catalysts has long been recognized as a shortcut, but at room temperature, such hydrolysis is too slow to be deployed. Here, we found when Cu2+ was immobilized on imine-linked COF (covalent organic framework) (Cu2+/Py-Bpy-COF, Cu2+ load is 1.43 wt%), as-prepared composite can utilize the light irradiation (wavelength range simulated sunlight) to in situ heat anchored Cu2+ Lewis acid sites through an excellent photothermal conversion to open the ß-lactam ring followed by a desired full-decarboxylation of hydrolysates. Under 1 W/cm2 simulated sunlight, Cu2+/Py-Bpy-COF powders placed in a microfiltration membrane rapidly cause a temperature rising even to ~211.7 °C in 1 min. It can effectively hydrolyze common ß-lactam antibiotics in waters and even antibiotics concentration is as high as 1 mM and it takes less than 10 min. Such photo-heating hydrolysis rate is ~24 times as high as under dark and ~2 times as high as Cu2+ homogenous catalysis. Our strategy significantly decreases the interference from generally coexisting common organics in waters and potential toxicity concerns of residual carboxyl groups in hydrolysates and opens up an accessible way for the settlement of ß-lactam antibiotics pollutants by the only energy source available, the sunlight.

Artificial-Cofactor-Mediated Hydrogen and Electron Transfer Endows AuFe/Polydopamine Superparticles with Enhanced Glucose Oxidase-Like Activity.

Various applications related to glucose catalysis have led to the development of functional nanozymes with glucose oxidase (GOX)-like activity. However, the unsatisfactory catalytic activity of nanozymes is a major challenge for their practical applications due to their inefficient hydrogen and electron transfer. Herein, we present the synthesis of AuFe/polydopamine (PDA) superparticles that exhibit photothermal-enhanced GOX-like activity. Experimental investigations and theoretical calculations reveal that the glucose oxidation process catalyzed by AuFe/PDA follows an artificial-cofactor-mediated hydrogen atom transfer mechanism, which facilitates the generation of carbon-centered radical intermediates. Rather than depending on charged Au surfaces for thermodynamically unstable hydride transfer, Fe(III)-coordinated PDA with abundant amino and phenolic hydroxyl groups serves as cofactor mimics, facilitating both hydrogen atom and electron transfer in the catalytic process. Finally, leveraging the photothermal-enhanced GOX-like and catalase-like activities of AuFe/PDA, we establish a highly sensitive and accurate point-of-care testing blood glucose determination with exceptional anti-jamming capabilities.

Thiacalix[4]arene-Protected Silver Nanoclusters Encapsulating Different Two-Electron Superatom Oligomers.

The subvalent silver kernel represents the nascent state of silver cluster formation, yet the growth mechanism has long been elusive. Herein, two silver nanoclusters (Ag30 and Ag34) coprotected by TC4A4- (H4TC4A = p-tert-butylthiacalix[4]arene) and TBPMT- (TBPMTH = 4-tert-butylbenzenemethanethiol) containing 6e and 4e silver kernels are synthesized and characterized. The trimer of the 2e superatom Ag14 kernel in Ag30 is built from a central Ag6 octahedron sandwiched by two orthogonally oriented Ag5 trigonal bipyramids through sharing vertexes, whereas a double-octahedral Ag10 kernel in Ag34 is a dimer of 2e superatoms. They manifest disparate polyhedron fusion growth patterns at the beginning of the silver cluster formation. Their excellent solution stabilities are contributed by the multisite and multidentate coordination fashion of TC4A4- and the special valence electron structures. This work demonstrates the precise control of silver kernel growth by the solvent strategy and lays a foundation for silver nanocluster application in photothermal conversion.

Metal-Loaded Synthetic Melanin via Oxidative Polymerization of Neurotransmitter Norepinephrine Exhibiting High Photothermal Conversion.

Polydopamine (PDA)-derived melanin-like materials exhibit significant photothermal conversion owing to their broad-spectrum light absorption. However, their low near-infrared (NIR) absorption and inadequate hydrophilicity compromise their utilization of solar energy. Herein, we developed metal-loaded poly(norepinephrine) nanoparticles (PNE NPs) by predoping metal ions (Fe3+, Mn3+, Co2+, Ca2+, Ga3+, and Mg2+) with norepinephrine, a neuron-derived biomimetic molecule, to address the limitations of PDA. The chelation between catechol and metal ions induces a ligand-to-metal charge transfer (LMCT) through the formation of donor-acceptor pairs, modulating the light absorption behavior and reducing the band gap. Under 1 sun illumination, the Fe-loaded PNE coated wood evaporator achieved a high seawater evaporation rate and efficiency of 1.75 kg m-2 h-1 and 92.4%, respectively, owing to the superior hydrophilicity and photothermal performance of PNE. Therefore, this study offers a comprehensive exploration of the role of metal ions in enhancing the photothermal properties of synthetic melanins.

Ultrahigh Transparent Safety Film for Spectrally Selective Photo/Electrothermal Conversion via Surface-Enhanced Plasma Resonance Dynamics.

Traditional deicing methods are increasingly insufficient for modern technologies like 5G infrastructure, photovoltaic systems, nearspace aerocraft, and terrestrial observatories. To address the challenge of combining anti-icing efficiency with operational performance, an innovative, spectrally selective, photo/electrothermic, ice-phobic film was prepared through a cost-effective mist deposition method. By manipulating the diameter ratio and density of nanowires, the local density of free electrons within this film is controlled to precisely dictate the position and intensity of surface plasmon resonance to achieve spectrally selective photo/electrothermal conversion. Additionally, the synthesized hydrophobic N-Boroxine-PDMS/SiO2 layer improves thermal stability and accelerates the deicing process. It achieves rapid deicing within 86 s under photothermal conditions and 65 s with Joule heating while maintaining high optical transmittance. The film improves the operational efficiency and thermal safety of equipment while preserving aesthetics and stability, thereby underscoring its broad suitability for advanced outdoor installations in cold environments.

Hybrid Nanogel-Wrapped Anisotropic Gold Nanoparticles Feature Enhanced Photothermal Stability.

Anisotropic gold nanoparticles (AuNPs) are renowned for their unique properties - including localized surface plasmon resonance (LSPR) and adjustable optical responses to light exposure - that enable the conversion of light into heat and make them a promising tool in cancer therapy. Nonetheless, their tendency to aggregate and consequently lose their photothermal conversion capacity during prolonged irradiation periods represents a central challenge in developing anisotropic AuNPs for clinical use. To overcome this issue, an innovative approach that facilitates the encapsulation of individual anisotropic AuNPs within thin nanogels, forming hybrid nanomaterials that mirror the inorganic core's morphology while introducing a negligible (2-8 nm) increase in overall diameter is proposed. The encapsulation of rod- and star-shaped anisotropic AuNPs within poly-acrylamide (pAA) or poly-(N-isopropylacrylamide) (pNIPAM) nanogels is successfully demonstrated. The ultrathin polymeric layers display remarkable durability, significantly enhancing the photothermal stability of anisotropic AuNPs during their interaction with near-infrared light and effectively boosting their photothermal capacities for extended irradiation periods. The outcomes of the research thus support the development of more stable and reliable AuNPs as hybrid nanomaterials, positioning them as promising nanomedicinal platforms.

An Asymmetric Layer Structure Enables Robust Multifunctional Wearable Bacterial Cellulose Composite Film with Excellent Electrothermal/Photothermal and EMI Shielding Performance.

Highly robust flexible multifunctional film with excellent electromagnetic interference shielding and electrothermal/photothermal characteristics are highly desirable for aerospace, military, and wearable devices. Herein, an asymmetric gradient multilayer structured bacterial cellulose@Fe3O4/carbon nanotube/Ti3C2Tx (BC@Fe3O4/CNT/Ti3C2Tx) multifunctional composite film is fabricated with simultaneously demonstrating fast Joule response, excellent EMI shielding effectiveness (EMI SE) and photothermal conversion properties. The asymmetric gradient 6-layer composite film with 40% of Ti3C2Tx possesses excellent mechanical performance with exceptional tensile strength (76.1 MPa), large strain (14.7%), and good flexibility. This is attributed to the asymmetric gradient multilayer structure designed based on the hydrogen bonding self-assembly strategy between Ti3C2Tx and BC. It achieved an EMI SE of up to 71.3 dB, which is attributed to the gradient "absorption-reflection-reabsorption" mechanism. Furthermore, this composite film also exhibits excellent low-voltage-driven Joule heating (up to 80.3 °C at 2.5 V within 15 s) and fast-response photothermal performance (up to 101.5 °C at 1.0 W cm-2 within 10 s), which is attributed to the synergistic effect of heterostructure. This work demonstrates the fabrication of multifunctional bacterial cellulose@Fe3O4/carbon nanotube/Ti3C2Tx composite film has promising potentials for next-generation wearable electronic devices in energy conversion, aerospace, and artificial intelligence.

Efficient Photothermal Sensor Based on Coral-Like Hollow Gold Nanospheres for the Sensitive Detection of Sulfonamides.

Gold nanoparticles (AuNPs), universally regarded as colorimetric signal reporters, are widely employed in lateral flow immunoassays (LFIAs). However, it is difficult for AuNPs-LFIA to achieve a wide range and sensitive detection. Herein, novel coral-like hollow gold nanospheres (CHGNPs) are synthesized. The growth of gold nanospheres can be regulated to obtain a multibranched and hollow construction. The obtained CHGNPs possess intense broadband absorption across the visible to near-infrared region, exhibiting a high molar extinction coefficient of 14.65 × 1011 M-1 cm-1 and a photothermal conversion efficiency of 79.75%. Thus, the photothermal/colorimetric dual-readout LFIA is developed based on CHGNPs (CHGNPs-PT-LFIA and CHGNPs-CM-LFIA) to effectively improve the detection sensitivity and broaden the detection range in regard to sulfonamides (SAs). The limits of detection of the CHGNPs-PT-LFIA and CHGNPs-CM-LFIA reached 1.9 and 2.8 pg mL-1 for the quantitative detection of sulfaquinoxaline, respectively, which are 6.3-fold and 4.3-fold lower than that of the AuNPs-LFIA. Meanwhile, the CHGNPs-PT-LFIA broadened the detection range to three orders of magnitude, which ranged from 2.5 to 5000 pg mL-1. The synthesized photothermal CHGNPs have been proven effective in improving the performance of the LFIA and provide a potential option for the construction of sensing platforms.

An Azulene-Based Crystalline Porous Covalent Organic Framework for Efficient Photothermal Conversion.

The designed synthesis of a crystalline azulene-based covalent organic framework (COF-Azu-TP) is presented and its photothermal property is investigated. Azulene, a distinctive 5-7 fused ring non-benzenoid aromatic compound with a large intramolecular dipole moment and unique photophysical characteristics, is introduced as the key feature in COF-Azu-TP. The incorporation of azulene moiety imparts COF-Azu-TP with broad-spectrum light absorption capability and interlayer dipole interactions, which makes COF-Azu-TP a highly efficient photothermal conversion material. Its polyurethane (PU) composite exhibits a solar-to-vapor conversion efficiency (97.2%) and displays a water evaporation rate (1.43 kg m-2 h-1) under one sun irradiation, even at a very low dosage of COF-Azu-TP (2.2 wt%). Furthermore, COF-Azu-TP is utilized as a filler in a polylactic acid (PLA)/polycaprolactone (PCL) composited shape memory material, enabling rapid shape recovery under laser stimulation. A comparison study with a naphthalene-based COF isomer further emphasizes the crucial role of azulene in enhancing photothermal conversion efficiency. This study demonstrates the significance of incorporating specific building blocks into COFs for the development of functional porous materials with enhanced properties, paving the way for future applications in diverse fields.

Multifunctional Wearable Electronic Based on Fabric Modified by PPy/NiCoAl-LDH for Energy Storage, Electromagnetic Interference Shielding, and Photothermal Conversion.

With the rapid advancement of electronic technology, traditional textiles are challenged to keep up with the demands of wearable electronics. It is anticipated that multifunctional textile-based electronics incorporating energy storage, electromagnetic interference (EMI) shielding, and photothermal conversion are expected to alleviate this problem. Herein, a multifunctional cotton fabric with hierarchical array structure (PPy/NiCoAl-LDH/Cotton) is fabricated by the introduction of NiCoAl-layered double hydroxide (NiCoAl-LDH) nanosheet arrays on cotton fibers, followed by polymerization and growth of continuous dense polypyrrole (PPy) conductive layers. The multifunctional cotton fabric shows a high specific areal capacitance of 754.72 mF cm-2 at 5 mA cm-2 and maintains a long cycling life (80.95% retention after 1000 cycles). The symmetrical supercapacitor assembled with this fabric achieves an energy density of 20.83 µWh cm-2 and a power density of 0.23 mWcm-2. Moreover, the excellent electromagnetic interference shielding (38.83 dB), photothermal conversion (70.2 °C at 1000 mW cm-2), flexibility and durability are also possess by the multifunctional cotton fabric. Such a multifunctional cotton fabric has great potential for using in new energy, smart electronics, and thermal management applications.

Multi-Functional 2D Covalent Organic Frameworks with Diketopyrrolopyrrole as Electron Acceptor.

2D covalent organic framework (COF) materials with extended conjugated structure and periodic columnar π-arrays exhibit promising applications in organic optoelectronics. However, there is a scarcity of reports on optoelectronic COFs, mainly due to the lack of suitable π-skeletons. Here, two multi-functional optoelectronic 2D COFs DPP-TPP-COF and DPP-TBB-COF are constructed with diketopyrrolopyrrole as electron acceptor (A), and 1,3,6,8-tetraphenylpyrene and 1,3,5-triphenylbenzene as electron donor (D) through imine bonds. Both 2D COFs showed good crystallinities and AA stacking with a rhombic framework for DPP-TPP-COF and hexagonal one for DPP-TBB-COF, respectively. The electron D-A and ordered intermolecular packing structures endow the COFs with broad UV-vis absorptions and narrow bandgaps along with suitable HOMO/LUMO energy levels, resulting in multi-functional optoelectronic properties, including photothermal conversion, supercapacitor property, and ambipolar semiconducting behavior. Among them, DPP-TPP-COF exhibits a high photothermal conversion efficiency of 47% under 660 nm laser irradiation, while DPP-TBB-COF exhibits superior specific capacitance of 384 F g-1. Moreover, P-type doping and N-type doping are achieved by iodine and tetrakis(dimethylamino)ethylene on a single host COF, resulting in ambipolar semiconducting behavior. These results provide a paradigm for the application of multi-functional optoelectronic COF materials.

Boosted Near-Infrared Photothermal Conversion in Rare Earth Ions-Doped 2D SnSe Nanosheets for Solar-Powered Water Evaporation Systems.

Solar-powered water evaporation as a clean and abundant renewable energy-efficient desalination technology provides a promising strategy to solve the shortage of freshwater resources. However, the development and application of solar vapor technology are hindered by the relatively low near-infrared photothermal conversion efficiency of existing materials and the lack of effective improvement strategies. In this work, the conductivity characteristics of 2D semiconductors are capitalized on the high visible light absorption and ultra-low thermal. Specifically, rare-earth ion dopants into SnSe nanosheets, significantly boosting their near-infrared photothermal conversion efficiency and solar water evaporation performance are introduced. Remarkably, the photothermal conversion efficiency of the doped SnSe nanosheets surged from 51.56% to 82.11%, surpassing many previously reported photothermal materials. Furthermore, leveraging these nanosheets with enhanced photothermal conversion efficiency, a solar interfacial evaporation system is constructed. The evaporation rate of 2.17 kg m-2 h-1 and the efficiency of 96.5% can be achieved at one solar irradiance, and it also has good salt-resistance properties. The findings demonstrate the potential of rare earth ion-doped 2D semiconductor nanosheets in solar water evaporation, paving the way for future sustainable desalination solutions.

Prussian Blue-Assisted NIR Triggered In-Situ Polymerized Nanocomposite Hydrogel for Wound Repair.

Hydrogels are commonly used as wound dressings to help maintain a moist environment around the wound and isolate contaminants, thus promoting healing. For irregular wounds, the slow healing process and even infection may occur due to the inability of dressings to adhere well to the wound. Prussian blue (PB) is a metal-organic framework (MOF) material with excellent photothermal conversion and superior stability. In this paper, a kind of near-infrared (NIR) light triggered in-situ polymerized antimicrobial hydrogel was prepared. The free radical initiator was encapsulated in the hollow PB by a phase change material (PCM) to maintain stability. The raised temperature triggered by NIR induced the release and decomposition of the initiator. The matrix was formed by the cross-linking of double bonds on modified chitosan. The quaternary amine groups of modified chitosan and the photothermal properties of PB enhanced the antimicrobial properties of the hydrogel. High-quality wound healing was demonstrated in the whole skin defect model. This study provides a new reference for the preparation of in-situ polymerized hydrogel dressings for irregular wounds.

Eight-Electron Copper Nanoclusters for Photothermal Conversion.

Owing to distinct physicochemical properties in comparison to gold and silver counterparts, atomically precise copper nanoclusters are attracting embryonic interest in material science. The introduction of copper cluster nanomaterials in more interesting fields is currently urgent and desired. Reported in this work are novel copper nanoclusters of [XCu54Cl12(tBuS)20(NO3)12] (X=S or none, tBuSH=2-methyl-2-propanethiol), which exhibit high performance in photothermal conversion. The clusters have been prepared in one pot and characterized by combinatorial techniques including ultraviolet-visible spectroscopy (UV-vis), electrospray ionization mass spectrometry (ESI-MS), and X-ray photoelectron spectroscopy (XPS). The molecular structure of the clusters, as revealed by single crystal X-ray diffraction analysis (SCXRD), shows the concentric three-shell Russian doll arrangement of X@Cu14@Cl12@Cu40. Interestingly, the [SCu54Cl12(tBuS)20(NO3)12] cluster contains 8 free valence electrons in its structure, making it the first eight-electron copper nanocluster stabilized by thiolates. More impressively, the clusters possess an effective photothermal conversion (temperature increases by 71 °C within ~50 s, λex=445 nm, 0.5 W cm-2) in a wide wavelength range (either blue or near-infrared). The photothermal conversion can be even driven under irradiation of simulated sunlight (3 sun), endowing the clusters with great potency in solar energy utilization.

Organic Photothermal Materials Obtained Using Thermally Activated Delayed Fluorescence Design Principles.

Organic small molecules with high photothermal conversion efficiencies that absorb near-infrared light are desirable for photothermal therapy due to their improved biocompatibility compared to inorganic materials and their ability to absorb light in the biological transparency window (650-1350 nm). Here we report three donor-acceptor organic materials DM-ANDI, O-ANDI, and S-ANDI that show high photothermal conversion efficiencies of 46-68 % with near-infrared absorption. The design of these molecules is based on the rational modification of a thermally activated delayed fluorescence material to favour a low photoluminescence quantum yield by reducing HOMO-LUMO overlap. Encapsulating these materials into either neat nanoparticles or aggregated organic dots modulates their photothermal conversion efficiencies, and also facilitates dispersion in water.

Synergistic antibacterial attributes of copper-doped polydopamine nanoparticles: an insight into photothermal enhanced antibacterial efficacy.

Antibiotic-resistant bacteria and associated infectious diseases pose a grave threat to human health. The antibacterial activity of metal nanoparticles has been extensively utilized in several biomedical applications, showing that they can effectively inhibit the growth of various bacteria. In this research, copper-doped polydopamine nanoparticles (Cu@PDA NPs) were synthesized through an economical process employing deionized water and ethanol as a solvent. By harnessing the high photothermal conversion efficiency of polydopamine nanoparticles (PDA NPs) and the inherent antibacterial attributes of copper ions, we engineered nanoparticles with enhanced antibacterial characteristics. Cu@PDA NPs exhibited a rougher surface and a higher zeta potential in comparison to PDA NPs, and both demonstrated remarkable photothermal conversion efficiency. Comprehensive antibacterial evaluations substantiated the superior efficacy of Cu@PDA NPs attributable to their copper content. These readily prepared nano-antibacterial materials exhibit substantial potential in infection prevention and treatment, owing to their synergistic combination of photothermal and spectral antibacterial features.

Near-Infrared Absorbing Para-Azaquinodimethane Conjugated Polymers Synthesized via the Transition-Metal-Free Route toward Efficient Photothermal Conversion.

Conjugated polymers with strong absorption in the second near-infrared (NIR-II) window have multiple applications. However, the development of new type of NIR-II conjugated polymers via facile and green methods remains challenging. Herein, this work reports a mild and convenient transition-metal-free method to synthesize near-infrared absorbing quinoidal conjugated polymers containing para-azaquinodimethane (AQM) moieties. The AQM quinoidal conjugated polymers with unique molecular structures and tunable optoelectronic properties can be synthesized by combining the Knoevenagel polycondensation of aromatic dialdehyde monomers with commercially available 1,4-diacetyl-2,5-piperazinedione and the following alkylation reaction. The resultant polymer PQ-DPP shows remarkable NIR-II absorption with a narrow band gap of about 1.08 eV. PQ-DPP nanoparticles exhibit high photothermal conversion efficiency of up to 48% under 1064 nm laser irradiation (1 W cm-2) endowing this polymer with potential in bio-related applications.

Self-Floating Nanoporous High-Entropy Oxides with Tunable Bandgap for Efficient Solar Seawater Desalination.

Nanoporous high-entropy oxide (np-HEO) powders with tunable composition are integrated with a poly(vinylidene fluoride) network to create self-floating solar absorber films for seawater desalination. By progressively increasing the element count, we obtain an optimized 9-component AlNiCoFeCrMoVCuTi-Ox. Density functional theory (DFT) calculations reveal a remarkable reduction in its bandgap, facilitating the light-induced migration of electrons to conduction bands to generate electron-hole pairs, which recombine to produce heat. Simultaneously, the intricate light reflection and refraction pathways, shaped by the nanoporous structure, coupled with the reduced thermal conductivity attributed to the suboptimal crystalline quality of the np-HEO ensure an effective conversion of captured light into thermal energy. Consequently, all these films demonstrate an impressive absorbance rate exceeding 93% across the 250-2500 nm spectral range. Under one sun, the surface temperature of the 9-component film rapidly rises to 110 °C within 90 s with a high pure water evaporation rate of 2.16 kg m-2 h-1.

Broadband and Spectrally Selective Photothermal Conversion through Nanocluster Assembly of Disordered Plasmonic Metasurfaces.

Plasmonic metasurfaces have been realized for efficient light absorption, thereby leading to photothermal conversion through nonradiative decay of plasmonic modes. However, current plasmonic metasurfaces suffer from inaccessible spectral ranges, costly and time-consuming nanolithographic top-down techniques for fabrication, and difficulty of scale-up. Here, we demonstrate a new type of disordered metasurface created by densely packing plasmonic nanoclusters of ultrasmall size on a planar optical cavity. The system either operates as a broadband absorber or offers a reconfigurable absorption band right across the visible region, resulting in continuous wavelength-tunable photothermal conversion. We further present a method to measure the temperature of plasmonic metasurfaces via surface-enhanced Raman spectroscopy (SERS), by incorporating single-walled carbon nanotubes (SWCNTs) as an SERS probe within the metasurfaces. Our disordered plasmonic system, generated by a bottom-up process, offers excellent performance and compatibility with efficient photothermal conversion. Moreover, it also provides a novel platform for various hot-electron and energy-harvesting functionalities.