Sustainable hygroelectricity generation has emerged as a revolutionary technology capable of harvesting the latent heat from ambient environments and converting it into direct-current electricity. Recently, microbial biofilms have been regarded as promising hydrovoltaic materials for their low-cost, facile fabrication and environmentally friendly nature. However, external moisture dependence and ultra-high internal resistance have greatly limited the output performance of microbial biofilm-based hydrovoltaic electricity generators (BioHEGs). Herein, a core@shell structured biohybrid system (S. o@PPy) was constructed by in situ polymerization of pyrrole monomers on the surface of Shewanella oneidensis (S. o) cells. The presence of polymer-biofilm interfaces resulted in an exceptional performance of hygroelectricity generation originated from the built-in conductivity of hole-doped polypyrrole (PPy), as well the reduced internal resistance and improved water adsorption capacity of S. o biofilms. Hence, the S. o@PPy BioHEG generated a stable short-circuit current of ca. 33.5 μA at the optimal condition, which is significantly higher than all BioHEGs documented hitherto. Moreover, a novel mechanism of asymmetric charge redistribution was confirmed by density function theory (DFT) calculations. These results support a new perspective of hydrovoltaic effects and provide a viable strategy for advancing BioHEGs towards more practical scenarios.
Circularly polarized luminescence (CPL) has become a cornerstone in the study of fluorescent materials, offering transformative potential for applications such as autostereoscopic 3D displays, optical information storage and processing, biological encoding and sensing, and anti-counterfeiting technologies. In this work, two sets of chiral-symmetric, low-dimensional organometallic halides were synthesized through a self-assembly process, resulting in unique 0D molecular architectures. These materials exhibit exceptional optical activity, particularly in chiral luminescence, which can be finely tuned by substituting Cu+ with Ag+. A striking feature is their temperature-dependent behavior: across a range of 80-350 K, the materials display both thermal expansion and negative thermal expansion, accompanied by anomalous luminescence variations driven by changes in excitonic dynamics. Remarkably, temperature-dependent single-crystal analyses reveal negligible structural changes, suggesting that the observed luminescent shifts primarily stem from exciton recombination processes. Furthermore, the luminescence dissymmetry factor (g lum) remains stable across this temperature range, highlighting its structural origin and affirming the materials' robustness in thermally variable environments. These findings deepen the understanding of chiral luminescent materials and enhance their potential for advanced optical applications, particularly in designing temperature-resilient systems for cutting-edge technologies.
Electrical field-assisted thermophilic composting (eTC) is considered a promising technology for enhancing compost maturation, while membrane-covered composting is an effective strategy for reducing harmful gas emissions. However, the combined application of membrane and electric field to simultaneously enhance organic matter humification and mitigate greenhouse gas emissions during composting has rarely been explored. In this study, we constructed membrane and electric field co-assisted thermophilic composting (m-eTC) and confirmed its effect on promoting organic matter humification and greenhouse gas emissions reduction, respectively. The results showed that humic acid content in m-eTC was 1.22- and 1.15-fold higher than that in ordinary thermophilic composting (oTC) and eTC, respectively. Moreover, the global warming potential, expressed as CO2-equivalent emissions, was reduced by 11.9% and 9.8% compared with oTC and eTC. Microbial analyses revealed selective enrichment of humification-related bacteria (e.g., Nocardiopsis and Saccharomonospora) and regulation of key functional genes related to greenhouse gas emissions (e.g., pmoA and norB) in the m-eTC system. Interactive Mantel test and partial least-squares path modeling further demonstrated that m-eTC significantly enhanced the positive effects of composting properties and small-molecule organic acids on organic matter humification. In contrast, m-eTC attenuated the positive effects of composting properties and bacterial activity on greenhouse gas emissions. This study indicated that m-eTC is an effective strategy for simultaneously reducing greenhouse gas emissions and promoting organic matter humification, offering a promising pathway for efficient and sustainable organic solid waste management.
Microbial biofilm-based hydrovoltaic electricity generators (BioHEGs) exemplify low-cost and facile manufacturing platforms for hydrovoltaic energy, albeit with relatively low power output that is unsatisfactory for practical applications. Herein, in situ surface polymerization of polyaniline (PAni) on Shewanella oneidensis (S. o o) is verified to boost the hydrovoltaic performance of the biohybrid system. Notably, the S. o o@PAni BioHEG unit achieves an ultra-high stable power density of ca. 168.6 mW & sdot;m(-2), which outperforms all BioHEGs hitherto documented by an order of magnitude. Specifically, the output voltage and current density of S. o o@PAni BioHEG are significantly enhanced due to the formation of Schottky junctions at the interface between the microbial biofilm and electrode. Moreover, the synergistic effect of extracellular polymeric substances and PAni induces accelerated electron transfer, thereby lowering the electrical resistance in the system. This work unambiguously provides a reliable strategy for advancing the performance of BioHEGs toward more comprehensive and practical scenarios.
Nucleotide-binding, leucine-rich repeat (NLR) receptors are widespread intracellular immune sensors across kingdoms. Plant G10-type coiled-coil (CCG10)-NLRs constitute a distinct phylogenetic clade that remains poorly characterized. Here, we identified a gain-of-function mutant of wheat autoimmunity 3 (WAI3GOF), which encodes a constitutively active CCG10-NLR resulting from a residue substitution in the leucine-rich repeat (LRR) domain. Cryo-electron microscopy (cryo-EM) analysis reveals that activated WAI3 assembles into a distinctive octameric resistosome. Arabidopsis RPS2, another CCG10-NLR, also forms an octamer, indicating a conserved structural property across monocot and dicot plants. The WAI3 resistosome induces a prolonged and sustained increase in cytosolic calcium, likely facilitated by a unique channel architecture arising from its divergent coiled-coil (CC) domain configuration. Notably, this domain arrangement may be shared by plant NLRs that lack the conserved EDVID (Glu-Asp-Val-Ile-Asp) motif in their CC domains. Together, our findings uncover a conserved yet previously uncharacterized NLR resistosome structure and provide insights into the plant immune receptor plasticity.
The low efficiency of photogenerated charge separation significantly hinders the photocatalytic nitrogen (N2) fixation. Local polarization electric field (LPEF) induced by defects has been known to enhance charge separation, yet the synergistic effects and mechanisms related to different types of defects in pure phases remain poorly understood. In this study, defect-free bismuth oxybromide (BiOBr; BOB), together with single vacancy (BOB-VBr and BOB-VO) and dual vacancy (BOB-VBrO) analogues, were successfully synthesized, and the presence of these specific vacancies was comprehensively characterized. Notably, the dual vacancy BOB-VBrO exhibited the highest photocatalytic NH3 generation rate of 266 mu mol g-1 h-1 in a liquid-solid biphasic system, which was 6.1, 1.5, and 1.4 times higher than those of BOB, BOB-VBr, and BOB-VO, respectively. Furthermore, the NH3 generation capacity of BOB-VBrO reached an impressive rate of 978 mu mol g-1 h-1 in a gas-liquid-solid triphasic system. Photoelectrochemical tests revealed that BOB-VBrO demonstrated the highest light conversion efficiency, followed by BOB-VO, BOB-VBr, and BOB. The relative intensity of the internal electric field in BOB-VBrO was also significantly high, being 1.8, 2.4, and 3.9 times greater than those of BOB-VO, BOB-VBr, and BOB, respectively. The Br and O vacancies synergistically induced LPEF between the [O]/[Br] and [Bi] layers. In situ irradiation X-ray photoelectron spectroscopy indicated that O and Br vacancies of the oligomers could synergistically enhance the LPEF, thereby facilitating the transfer of photogenerated electrons from O/Br to Bi. Additionally, the practical feasibility of BOB-VBrO in photocatalytic N2 fixation was validated to produce liquid nitrogenous fertilizer for plant growth, revealing its potential application in agricultural production.
Photocatalytic conversion of chemical fuels has emerged as a most challenging subject in photocatalysis which is considered as one of the sustainable solutions for environmental issues related to the energy shortage and anthropogenic carbon emissions. Herein, unique heterostructures of ZnCdS nanoplates with Bi2S3-terminated edges were prepared through a facile cation exchange pathway, by which the controlled photocatalytic CO2 conversion was achieved. The optimized BZCS-NS-5 photocatalyst exhibited an excellent capacity of CO2 photoreduction with a CO production rate of ca. 513.2 f 5.1 mu mol g-1 h-1 and a selectivity of ca. 91.0%, which were among the highest activities for sulfide photocatalysts documented in the literature. The outstanding photocatalytic performance was attributable to the formation of Z-scheme heterostrucutres between Bi2S3 and ZnCdS, in a way the separation and migration of photocarriers were accelerated. This work thus provides a feasible strategy for the construction of heterostructures to enhance the activity and selectivity of CO2-to-CO conversion via delicate design and controlled synthesis of photocatalysts.
Blue light-emitting materials are crucial for the commercialization of OLEDs, especially in dark display applications. However, a comprehensive understanding of the relationship between blue light emission and material structure remains lacking. In this study, we synthesized three organic phosphonium salts with blue light emissions using a one-step methylation method. The correlation between molecular structure and light emission was investigated, revealing that the position of the methyl group on the benzene ring introduces varying degrees of steric hindrance, which in turn affects the spatial arrangement and energy level distribution of the compounds. This research paves a significant development in blue light-emitting materials for future OLEDs and facilitates the commercialization of organic phosphonium cationic salts. Moreover, the usage of the position isomerization of methylated organophosphorus salts can achieve stereoscopic controlled blue emissions, providing a low-cost alternative to precious metal-based systems.
Microbial biofilm-based hydrovoltaic electricity generators (BioHEGs) have recently been developed as promising and readily available platforms for green energy harvesting, despite their unsatisfactory output performances and unspecified mechanisms regarding electric current production. Herein, carbon quantum dots (CQDs) were used to construct a nano-biohybrid system with Shewanella oneidensis MR-1 (S. oneidensis), through which the CQDs/S. oneidensis BioHEG achieved a maximum open-circuit voltage of ca. 0.65 V and short-circuit current density of ca. 5.23 μA·cm-2. In addition, both the hydrovoltaic effect and electrical conductivity of CQDs/S. oneidensis nano-biohybrids were noticeably improved due to enhanced secretion of extracellular polymeric substances (EPS) and accelerated electron transfer upon CQDs implantation, thereby leading to a nearly 14-fold increase in output power density compared to the bare S. oneidensis cells. Studies aimed to elucidate the underlying mechanism indicated that the hybridization of CQDs and S. oneidensis greatly promoted the metabolic synthesis of outer membrane c-type cytochromes (OM c-Cyts) and the extracellular secretion of riboflavin (RF), which was demonstrated to be decisive in the current producing process of the CQDs/S. oneidensis BioHEG. This work thus proposes a viable strategy to boost the hydrovoltaic electricity generation capacity of microbial biofilms and provides a new perspective on the mechanism of accelerated electron transfer pathways inside BioHEGs.
Circularly polarized luminescent (CPL) materials are essential for advanced optoelectronics, especially wide-color-gamut OLED displays. Here, BINAP-based enantiomers were synthesized via one-step methylation, yielding deep blue emission (CIEy < 0.08) with high thermal stability and antioxidative properties, thus addressing the challenges in designing blue-emitting CPL materials for efficient, stable, and commercializable applications.
The notion of spontaneous and persistent energy generation from omnipresent atmospheric moisture presents an alluring prospect in the realm of next-generation energy sources. Here, an ultra-durable and all-weather energy generator (UAEG) predicated on interface-induced proton migration derived from enhanced proton dissociation by charge transfer and ion occupation is reported, which reduces the diffusion barrier of protons in chromatogram-like mass transfer by avoiding the rebinding of dissociated protons with charged polyelectrolyte chains, thus leading to efficient and continuous proton migration through heterogeneously hygroscopic interface and delivering ultra-durable direct-current output. Deep insight into underlying mechanisms is demonstrated by theoretical calculations and in situ investigations toward molecular interactions and charge distribution. A UAEG unit with 4 cm2 in size can generate an impressive electric output (0.88 V and 37.58 mu A) across extensive relative humidity (10-90%) and ambient temperature (-30-50 & ring;C), capable of generating energy in all-weather conditions (e.g., sunny, cloudy, overcast, and rainy) regardless of day and night. Importantly, it is the first time that a commercial electronic is continuously driven for over 200 days in all-weather conditions just depending on ambient moisture. This work provides a novel perspective for the development of ultra-durable and all-weather moisture-enabled energy generators. An ultra-durable and all-weather energy generator (UAEG) is developed based on interface-induced proton migration. Charge transfer between hygroscopic salt ions and polyelectrolyte leads to the efficient proton dissociation from polyelectrolyte chains, while ion occupation effect of hygroscopic salt ions reduces the diffusion barrier of protons, thus leading to continuous proton migration through heterogeneously hygroscopic interface and delivering ultra-durable direct-current output. image
The substantial presence of antibiotics in aquatic environments remains as a critical environmental issue that needs to be urgently addressed. In this study, mimetics of C-Dots/siderite heteroaggregates (CSI) were studied in a visible-light-responsive Fenton system as a platform for the degradation of antibiotics in contaminated water. By virtue of the excellent electron transfer of C-Dots, the sustained conversion cycles of Fe(II) -* Fe(III) -* Fe(II) in CSI were greatly accelerated, and meanwhile the H2O2 utilization was enhanced. The optimized CSI-3 nanocomposite displayed a prominent degradation efficiency towards a series of tetracycline analogs at ppb levels. Density functional theory (DFT) calculations indicated the excellent photo-Fenton catalytic performance of CSI originated from the increased d-band center and electron density, which considerably improves the utilization of H2O2. Both experimental and theoretical studies revealed that the correlated toxicity of degradation intermediates was significantly decreased. Additionally, a continuous flow device integrating the CSI photoFenton system maintained a high degradation efficiency after long-term treatment of simulated chlortetracycline wastewater. The presented work thereby confirms a spontaneous remediation process for the decontamination and detoxification of persistent organic pollutants under the action of heteroaggregates formed by engineered nanoparticles and natural minerals.
Regulating the photo-response region of iron metal-organic frameworks (Fe-MOFs) is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process. This study developed a novel pyrazine-based Fe-MOFs (MIL-101(Fe)-Pz) by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe) with 2,5-pyrazinedicarboxylic acid (PzDC), in which sodium acetate was used as coordinative modulator to control the crystal size (2-3 µm). The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap (1.45 eV) than MIL-101(Fe) (2.54 eV) resulting in improved visible-light adsorption capacity (λ > 420 nm), and also increased the proportion of Fe(II) in the Fe-clusters. Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation. The MIL-101(Fe)-Pz/H2O2/Vis system could degrade 99% of sulfamethoxazole within 30 min, which was 10-fold faster than that of the pristine MIL-101(Fe), it also effectively removed other organic micropollutants with high durability and stability. Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe), giving MIL-101(Fe)-Pz appropriate band structure (-0.40∼1.05 V vs. NHE) which can cover several light-driven process for the generation of reactive oxygen species, including Fe(III) reduction and H2O2 activation for accelerating •OH generation, as well as oxygen reduction reaction for generating H2O2, O2•- and 1O2. This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs, providing valuable guidance for the design of Fe-MOFs photocatalysts.
Scintillators can convert the ionizing radiation into visible light and are crucial in X/gamma-ray detectors. Commercial detectors often use multiple scintillators with photodetector arrays, where optical crosstalk can degrade the performance. Chiral scintillators, emitting circularly polarized light, offer a promising solution for regulating the direction of light propagation to enhance X-ray detecting merits. Here novel chiral metal-organic polymers have been developed via photopolymerization, using chiral polymeric monomers and 0D Mn(II)-based organic-metal halide hybrid scintillators, achieving luminescence dissymmetry factors (glum) of 5.823 x 10-2 and -2.877 x 10-2. Two such scintillators, (atpp)2MnCl40.5H2O (MnCl4-1) and (atpp)2MnBr4 (MnBr4-2), exhibit excellent X-ray scintillation rooted in tetrahedral [MnX4]2- crystal field. Compound MnBr4-2, with heavier bromine atoms, shows superior performance with a detection limit of 0.117 mu Gyair s-1, compared to 0.330 mu Gyair s-1 of MnCl4-1, both surpassing the medical diagnostic standard of 5.50 mu Gyair s-1. The chiral metal-organic polymer film derived from MnBr4-2 has achieved a resolution up to 14.84 lp mm-1, exceeding medical standards for dental (2.0 lp mm-1) and breast cancer (10.0 lp mm-1) imaging. These advancements in chiral scintillators hold significant promise for high-resolution X-ray medical imaging applications. Through photo-polymerization reactions, 0 D manganese-based organic-metal halides can polymerize with chiral monomers to form a novel chiral metal-organic polymer, which has integrated the advantages of excellent scintillation properties from the metal halides and the circularly polarized characteristics from the chiral groups, further serving as outstanding scintillation films in high-resolution X-ray imaging for reducing the light scattering. image
Scintillators, essential for applications in nuclear medicine, radiation detection, and industrial inspection, convert high-energy radiation into visible light. Manganese (Mn)-based inorganic-organic hybrid materials are distinguished by their thermal stability, mechanical strength, and flexibility. However, the effects of temperature on Mn(II)-based hybrid scintillators have not been clearly analyzed, making the elucidation of their temperature-dependent luminescence mechanisms particularly important. A notable advancement is the synthesis of Mn-1 nanocrystals (NCs) using methyltriphenylphosphonium chloride (mtppCl) and MnCl2. These NCs exhibit distinctive temperature-dependent photoluminescence luminescence: the intensity decreases from 77 to 150 K but paradoxically increases at higher temperatures due to anomalous thermal exciton behavior in the [MnCl4]2(-) tetrahedra. Besides, Mn-1 NCs achieve a detection limit of 1.01 mu Gyair/s, surpassing medical diagnostic standards and outperforming commercial scintillators such as Bi4Ge3O12 (BGO). Additionally, they show exceptional stability under continuous irradiation and can be incorporated into a flexible scintillating film with a resolution of 11.3 lp/mm at an MTF of 0.2. The current study has further refined the luminescence mechanism of Mn(II)-based materials and optimizes their properties for a wider range of applications.
Fiber-based photochromic wearables have attracted growing attention in sustainable photo-patterning information displays, information security encryption, and optical data recording/storage. Molybdenum trioxide (MoO3) is one of the key photochromic materials that possesses good photochromic performance, nevertheless, it faces considerable challenges in preparing photochromic textiles with stable, scalable, and long color-retention properties. In this work, a new kind of fiber-based photochromic wearables is designed and developed by combining cotton fabric with a MoO3-based self-adhesive polymer network and long chain silyl group. The prepared photochromic wearable has exhibited excellent fatigue resistance and favorable reversibility (> 40 cycles), rapid light response (reach color saturation with a UV dose of 60 kJ m(-2)), outstanding color retention capability (> 90 days), and desirable biocompatibility (cell viability > 100%). In addition, the prepared photochromic textiles could maintain a fast light response and excellent color retention even after experiencing repeated washing (20 cycles). Moreover, the photo-patterning photochromic wearables are verified by resisting the deterioration of acid solution, alkali solution, and sweat (pH 2.0-9.0) as well as keeping clear patterns under sunlight irradiation. As a demonstration of the application, fiber-based photochromic wearables are made and employed for the sustainable applications of rewritable photo-patterning and information security encryption.
Fluorescence imaging can be employed in fields of medical treatment, astronomical exploration, and national defense security. Traditional fluorescence imaging often takes the single-photon techniques, which is vulnerable to background interference and photobleaching. Remedially, two-photon fluorescence imaging can achieve much higher-resolution fluorescence imaging for reducing scattering and deeper depth. Hence, by assembling the tetraphenylethylene backbones with nontoxic and non-noble K+ ions, compound 1 ([(Hdma)K(H2ettc)]n, H4ettc = 4 ',4 ''',4 ''''',4 '''''''(ethene-1,1,2,2-tetrayl)tetrakis(([1,1 '-biphenyl]-4-carboxylic acid))) with the crystallization-induced emissions exhibited charming fluorescence imaging under two-photon excitation microscopy (TPEM). Besides, luminescent powders based on compound 1 can achieve high-resolution fingerprint recognition, providing secure access control and identification for a novel authentication method. Compared with the commercial fluorescent dyes coumarin-6, the as-synthesized compound 1 showed great solvent stability, indicating its durability against harsh environment. Moreover, compound 1 shows mechanoluminescent properties for the perturbation of weak supramolecular interactions within ordered arrangements of the H2ettc2- ligands. This novel compound has provided an important insight to the development of two-photon fluorescence imaging and advanced external-stimuli responsive materials.
Scintillators are essential in converting ionizing X-rays and gamma-rays into visible light, with applications in medical diagnosis, security inspection, and non-invasive detection. However, current scintillating materials exhibit unclear structure-function relationships. The performance of scintillators is intricately linked to their electronic band structure, particularly the intrinsic properties of excited states. Therefore, investigating the structural factors affecting scintillation performance is crucial for developing new scintillators. Therefore, Ba-SMOF 1 ([Ba2(PyTS)(CH3OH)2(H2O)4]n) is synthesized using a pyrene-based organic motif and metal Ba(II) ions, where PyTS4- refers to pyrene-1,3,6,8-tetrasulfonate. For the first time, the excited state of a pyrene-based X-ray scintillating metal-organic framework (MOF) is determined through comprehensive all-electron excitation studies, including in situ experimental electron density and wave-function analysis. The electron density maps exhibit a continuous overlap, attributed to the associative exciton behaviors among the closely packed PyTS4- linkers. These linkers are identified as the sources of both static and dynamic excimer emissions. The electron density studies reveal the role of excimers in pyrene-based luminophores, highlighting that interchromophoric interactions are key to enhancing the performance of scintillating MOFs. This discovery opens new avenues for the practical application of scintillating MOFs. Groundbreaking insights into the excited state of a pyrene-based X-ray scintillating metal-organic frameworks (MOFs) via the experimental in situ electron density study unveil the associate exciton behaviors for the coexistence of static excimer emission and dynamic excimer.image
The study of facile-synthesis and low-cost X-ray scintillators with high light yield, low detection limit and high X-ray imaging resolution plays a vital role in medical and industrial imaging fields. However, the optimal balance between X-ray absorption, decay lifetime and excitonic utilization efficiency of scintillators to achieve high-resolution imaging is extremely difficult due to the inherent contradiction. Here two thermally activated delayed fluorescence (TADF)-actived coinage-metal clusters M 6 S 6 L 6 (M=Ag or Cu) were synthesized by simple solvothermal reaction, where the cooperation of heavy atom-rich character and TADF mechanism supports strong X-ray absorption and rapid luminescent collection of excitons. Excitingly, Ag 6 S 6 L 6 ( SC-Ag ) displays a high photoluminescence quantum yield of 91.6 % and scintillating light yield of 17420 photons MeV −1 , as well as a low detection limit of 208.65 nGy s −1 that is 26 times lower than the medical standard (5.5 μGy s −1 ). More importantly, a high X-ray imaging resolution of 16 lp/mm based on SC-Ag screen is demonstrated. Besides, rigid core skeleton reinforced by metallophilicity endows clusters M 6 S 6 L 6 strong resistance to humidity and radiation. This work provides a new view for the design of efficient scintillators and opens the research door for silver clusters in scintillation application.