DNA Framework-Guided Self-Limiting Aggregation for Highly Luminescent Metal Cluster Nanoaggregates.

The photoluminescent properties of atomically precise metal nanoclusters (MCs) have garnered significant attention in the fields of chemical sensing and biological imaging. However, the limited brightness of single-component nanoclusters hinders their practical applications, and the conventional ligand engineering approaches have proven insufficient in enhancing the emission efficiency of MCs. Here, we present a DNA framework-guided strategy to prepare highly luminescent metal cluster nanoaggregates. Our approach involves an amphiphilic DNA framework comprising a hydrophobic alkyl core and a rigid DNA framework shell, serving as a nucleation site and providing well-defined nanoconfinements for the self-limiting aggregation of MCs. Through this method, we successfully produced homogeneous MC nanoaggregates (10.1 ± 1.2 nm) with remarkable nanoscale precision. Notably, this strategy proves adaptable to various MCs, leading to a substantial enhancement in emission and quantum yield, up to 3011- and 87-fold, respectively. Furthermore, our investigation using total internal reflection fluorescence microscopy at the single-particle level uncovered a more uniform photon number distribution and higher photostability for MC nanoaggregates compared to template-free counterparts. This DNA-templating strategy introduces a conceptually innovative approach for studying the photoluminescent properties of aggregates with nanoscale precision and holds promise for constructing highly luminescent MC nanoparticles for diverse applications.

FedEYE: A scalable and flexible end-to-end federated learning platform for ophthalmology.

Data-driven machine learning, as a promising approach, possesses the capability to build high-quality, exact, and robust models from ophthalmic medical data. Ophthalmic medical data, however, presently exist across disparate data silos with privacy limitations, making centralized training challenging. While ophthalmologists may not specialize in machine learning and artificial intelligence (AI), considerable impediments arise in the associated realm of research. To address these issues, we design and develop FedEYE, a scalable and flexible end-to-end ophthalmic federated learning platform. During FedEYE design, we adhere to four fundamental design principles, ensuring that ophthalmologists can effortlessly create independent and federated AI research tasks. Benefiting from the design principles and architecture of FedEYE, it encloses numerous key features, including rich and customizable capabilities, separation of concerns, scalability, and flexible deployment. We also validated the applicability of FedEYE by employing several prevalent neural networks on ophthalmic disease image classification tasks.

Towards atom manufacturing with framework nucleic acids.

Atom manufacturing has become a blooming frontier direction in the field of material and chemical science in recent years, focusing on the fabrication of functional materials and devices with individual atoms or with atomic precision. Framework nucleic acids (FNAs) refer to nanoscale nucleic acid framework structures with novel properties distinct from those of conventional nucleic acids. Due to their ability to be precisely positioned and assembled at the nanometer or even atomic scale, FNAs are ideal materials for atom manufacturing. They hold great promise for the bottom-up construction of electronic devices by precisely arranging and integrating building blocks with atomic or near-atomic precision. In this review, we summarize the progress of atom manufacturing based on FNAs. We begin by introducing the atomic-precision construction of FNAs and the intrinsic electrical properties of DNA molecules. Then, we describe various approaches for the fabrication of FNAs templated materials and devices, which are classified as conducting, insulating, or semiconducting based on their electrical properties. We highlight the role of FNAs in the fabrication of functional electronic devices with atomic precision, as well as the challenges and opportunities for atom manufacturing with FNAs.

Clomiphene citrate treatment during perinatal development alters adult partner preference, mating behaviour and androgen receptor and vasopressin in the male mandarin vole Microtus mandarinus.

During development, many aspects of behaviour, including partner preferences and sexual behaviour, are "organized" by neural aromatization of androgen and oestrogen. This study aimed to analyse these processes in the mandarin vole (Microtus mandarinus); this is a novel mammalian model exhibiting strong monogamous pair bonds. Male pups were treated daily with a sesame oil only (MC) or the oestrogen receptor blocker-clomiphene citrate sesame oil mixture (MT) from prenatal day 14 to postnatal day 10. Female pups were treated daily with sesame oil only (FC). Partner preferences, sexual behaviour, and the expression of androgen receptor (AR) and arginine vasopressin (AVP) were examined when animals were 3 months old. The MT and FC groups exhibited male-directed partner preferences and feminized behaviour. AR-immunoreactive neurons (AR-IRs) in the medial preoptic area (mPOA), bed nucleus of stria terminalis (BNST), and medial amygdaloid nucleus (MeA) were reduced in MT males compared to MC males, and there was no significant difference in the number of AR-IRs between MT males and FC females. AVP-immunoreactive neurons (AVP-IRs) in the paraventricular nucleus (PVN) and supraoptic nucleus (SON) were reduced in MT males compared to MC males, and there were no significant differences in the number of AVP-IRs between MT males and FC females. The results indicate a significant role of hormone signalling in the development of male mate preference in the novel monogamous mammal model.

Halogen hydrogen-bonded organic framework (XHOF) constructed by singlet open-shell diradical for efficient photoreduction of U(VI).

Synthesis of framework materials possessing specific spatial structures or containing functional ligands has attracted tremendous attention. Herein, a halogen hydrogen-bonded organic framework (XHOF) is fabricated by using Cl- ions as central connection nodes to connect organic ligands, 7,7,8,8-tetraaminoquinodimethane (TAQ), by forming a Cl-···H3 hydrogen bond structure. Unlike metallic node-linked MOFs, covalent bond-linked COFs, and intermolecular hydrogen bond-linked HOFs, XHOFs represent a different kind of crystalline framework. The electron-withdrawing effect of Cl- combined with the electron-rich property of the organic ligand TAQ strengthens the hydrogen bonds and endows XHOF-TAQ with high stability. Due to the production of excited electrons by TAQ under light irradiation, XHOF-TAQ can efficiently catalyze the reduction of soluble U(VI) to insoluble U(IV) with a capacity of 1708 mg-U g-1-material. This study fabricates a material for uranium immobilization for the sustainability of the environment and opens up a new direction for synthesizing crystalline framework materials.

Amidoxime Group-Anchored Single Cobalt Atoms for Anti-Biofouling during Uranium Extraction from Seawater.

Marine biofouling is one of the most significant challenges hindering practical uranium extraction from seawater. Single atoms have been widely used in catalytic applications because of their remarkable redox property, implying that the single atom is highly capable of catalyzing the generation of reactive oxygen species (ROS) and acts as an anti-biofouling substance for controlling biofouling. In this study, the Co single atom loaded polyacrylamidoxime (PAO) material, PAO-Co, is fabricated based on the binding ability of the amidoxime group to uranyl and cobalt ions. Nitrogen and oxygen atoms from the amidoxime group stabilize the Co single atom. The fabricated PAO-Co exhibits a broad range of antimicrobial activity against diverse marine microorganisms by producing ROS, with an inhibition rate up to 93.4%. The present study is the first to apply the single atom for controlling biofouling. The adsorbent achieves an ultrahigh uranium adsorption capacity of 9.7 mg g-1 in biofouling-containing natural seawater, which decreased only by 11% compared with that in biofouling-removed natural seawater. These findings indicate that applying single atoms would be a promising strategy for designing biofouling-resistant adsorbents for uranium extraction from seawater.

Ultrasensitive Detection of Aqueous Uranyl Based on Uranyl-Triggered Protein Photocleavage.

The detection of environmental uranyl is attracting increasing attention. However, the available detection strategies mainly depend on the selective recognition of uranyl, which is subject to severe interference by coexisting metal ions. Herein, based on the unique uranyl-triggered photocleavage property, the protein BSA is labelled with fluorescent molecules that exhibit an aggregation-induced emission effect for uranyl detection. Uranyl-triggered photocleavage causes the separation of the fluorescent-molecule-labelled protein fragments, leading to attenuation of the emission fluorescence, which is used as a signal for uranyl detection. This detection strategy shows high selectivity for uranyl and an ultralow detection limit of 24 pM with a broad detection range covering five orders of magnitude. The detection method also shows high reliability and stability, making it a promising technique for practical applications in diverse environments.

In Situ Synthesis of Uranyl-Imprinted Nanocage for Selective Uranium Recovery from Seawater.

An adaptive coordination structure is vital for selective uranium extraction from seawater. By strategy of molecular imprinting, uranyl is introduced into a multivariate metal-organic framework (MOF) during the synthesis process to guide the in situ construction of proper nanocage structure for targeting uranyl binding. Except for the coordination between uranium with four oxygen from the materials, the axial oxygen of uranyl also forms hydrogen bonds with hydrogen from the phenolic hydroxyl group, which enhances the binding affinity of the material to uranyl. Attributing to the high binding affinity, the adsorbent shows high uranium binding selectivity to uranyl against not only the interfering metal ions, but also the carbonate group that coordinates with uranyl to form [UO2 (CO)3 ]4- in seawater. In natural seawater, the adsorbent realizes a high uranium adsorption capacity of 7.35 mg g-1 , together with an 18.38 times higher selectivity to vanadium.

Effects of treadmill exercise on anxiety-like behavior in association with changes in estrogen receptors ERα, ERß and oxytocin of C57BL/6J female mice.

Exercise can reduce the incidence of stress-related mental diseases, such as depression and anxiety. Control group was neither exposed to CVMS nor TRE (noCVMS/noTRE). Females were tested and levels of serum17-beta-oestradiol (E2), estrogen receptors α immunoreactive neurons (ERα-IRs), estrogen receptors ß immunoreactive neurons (ERß-IRs) and oxytocin immunoreactive neurons (OT-IRs) were measured. The results showed there's increased anxiety-like behaviors for mice from CVMS/noTRE, CVMS/higher speed TRE (CVMS/HTRE) and noCVMS/HTRE groups when they were put in open field and elevated maze tests. They had lower serum E2 levels than mice from CVMS/low-moderate speed TRE (CVMS/LMTRE), noCVMS/LMTRE and noCVMS/noTRE groups. The three groups of CVMS/noTRE, CVMS/HTRE and noCVMS/HTRE mice had more ERα-IRs and less ERß-IRs in the medial preoptic area (mPOA), bed nucleus of the stria terminalis (BNST) and medial amygdala (MeA), hypothalamic paraventricular nucleus (PVN) and supraoptic nucleus (SON). The number of OT-IRs in PVN and SON of CVMS/noTRE, CVMS/HTRE and noCVMS/HTRE mice was also lower than that of mice from CVMS/LMTRE, noCVMS/LMTRE and noCVMS/noTRE groups. Interestingly, CVMS/LMTRE and noCVMS/LMTRE mice were similar to noCVMS/noTRE mice in that they did not show anxiety, while CVMS/HTRE and noCVMS/HTRE mice did not, which were similar to the mice in CVMS/noTRE. We propose that LMTRE instead of HTRE changes the serum concentration of E2. ERß/ERα ratio and OT level in the brain may be responsible for the decrease in anxiety-like behavior in female mice exposed to anxiety-inducing stress conditions.

Accelerated Chemical Thermodynamics of Uranium Extraction from Seawater by Plant-Mimetic Transpiration.

The extraction of uranium from seawater, which is an abundant resource, has attracted considerable attention as a viable form of energy-resource acquisition. The two critical factors for boosting the chemical thermodynamics of uranium extraction from seawater are the availability of sufficient amounts of uranyl ions for supply to adsorbents and increased interaction temperatures. However, current approaches only rely on the free diffusion of uranyl ions from seawater to the functional groups within adsorbents, which largely limits the uranium extraction capacity. Herein, inspired by the mechanism of plant transpiration, a plant-mimetic directional-channel poly(amidoxime) (DC-PAO) hydrogel is designed to enhance the uranium extraction efficiency via the active pumping of uranyl ions into the adsorbent. Compared with the original PAO hydrogel without plant-mimetic transpiration, the uranium extraction capacity of the DC-PAO hydrogel increases by 79.33% in natural seawater and affords the fastest reported uranium extraction average rate of 0.917 mg g-1 d-1 among the most state-of-the-art amidoxime group-based adsorbents, along with a high adsorption capacity of 6.42 mg g-1 within 7 d. The results indicate that the proposed method can enhance the efficiency of solar-transpiration-based uranium extraction from seawater, particularly in terms of reducing costs and saving processing time.

Antibiofouling Ultrathin Poly(amidoxime) Membrane for Enhanced U(VI) Recovery from Wastewater and Seawater.

Although eco-friendly amidoxime-based adsorbents own an excellent uranium (U)-adsorption capacity, their U-adsorption efficiency is commonly reduced and even damaged by the biological adhesion from bacteria/microorganisms in an aqueous environment. Herein, we present an antibiofouling ultrathin poly(amidoxime) membrane (AUPM) with highly enhanced U-adsorption performance, through dispersing the quaternized chitosan (Q-CS) and poly(amidoxime) in a cross-linked sulfonated cellulose nanocrystals (S-CNC) network. The cross-linked S-CNC not only can elevate the hydrophilicity to improve the U-adsorption efficiency of AUPM but also can enhance the mechanical strength to form a self-supporting ultrathin membrane (17.21 MPa, 10 µm thickness). More importantly, this AUPM owns a good antibiofouling property, owing to the broad-spectrum antibacterial quaternary ammonium groups of the Q-CS. As a result, within the 1.00 L of low-concentration (100 ppb) U-added pure water (pH ≈ 5) and seawater (pH ≈ 8) for 48 h, 30 mg of AUPM can recover 93.7% U and 91.4% U, respectively. Furthermore, compared with the U-absorption capacity of a blank membrane without the Q-CS, that of AUPM can significantly increase 37.4% reaching from 6.39 to 8.78 mg/g after being in natural seawater for only 25 d. Additionally, this AUPM can still maintain almost constant tensile strength during 10 cycles of adsorption-desorption, which indicates the relatively long-term usability of AUPM. This AUPM will be a promising candidate for highly efficient and large-scale U-recovery from both U-containing waste freshwater/seawater and natural seawater, which will be greatly helpful to deal with the U-pollution and enrich U for the consumption of nuclear power. More importantly, the work will provide a new convenient but universal strategy to fabricate new highly enhanced low-cost U-adsorbents, through the introduction of both an antibacterial property and a high mechanical performance, which will be a good reference for the design of new highly efficient U-adsorbents.

Bio-inspired antibacterial cellulose paper-poly(amidoxime) composite hydrogel for highly efficient uranium(vi) capture from seawater.

A bio-inspired cellulose paper-poly(amidoxime) composite hydrogel is explored via UV-polymerization. This hydrogel has a highly efficient uranium capture capacity of up to 6.21 mg g-1 for WU/Wdry gel and 12.9 mg g-1 for WU/Wpoly(amidoxime) in seawater for 6 weeks, due to its enhanced hydrophilicity, good hydraulic/ionic conductivity and broad-spectrum antibacterial performance.

An Ion-Crosslinked Supramolecular Hydrogel for Ultrahigh and Fast Uranium Recovery from Seawater.

Large-scale uranium extraction from seawater is a crucial but challenging part of nuclear power generation. In this study, a new ion-crosslinked supramolecular Zn2+ -poly(amidoxime) (PAO) hydrogel that can super-efficiently adsorb uranium from seawater is explored. By simply mixing two solutions of zinc chloride and PAO, a supramolecular Zn2+ -PAO hydrogel is achieved via the interaction between zinc cations and amidoxime anions. In contrast with existing amidoxime-functionalized hydrogel-based adsorbents having low PAO contents and fiber-based adsorbents with weak hydrophilicity, the PAOs can be directly crosslinked using a small quantity of superhydrophilic zinc ion. Thus, a supramolecular hydrogel is formed, having both a high content of well-dispersed PAOs and good hydrophilicity. Relative to reported adsorbents, this low-cost hydrogel membrane exhibits outstanding uranium adsorption performance, reaching 1188 mg g-1 of MU /Mdry gel in 32 ppm uranium-spiked water. More importantly, after immersion in natural seawater for only 4 weeks, the uranium extraction capacity of the Zn2+ -PAO hydrogel membrane reaches 9.23 mg g-1 of MU /Mdry gel . This work can provide a general strategy for designing a new type of supramolecular hydrogel, crosslinked by various bivalent/multivalent cation-crosslinkers and even many other superhydrophilic supramolecular crosslinkers, for the high-efficient and massive extraction of uranium from seawater.

Sunlight Polymerization of Poly(amidoxime) Hydrogel Membrane for Enhanced Uranium Extraction from Seawater.

The uranium level in seawater is ≈1000 times as high as terrestrial ores and can provide potential near-infinite fuel for the nuclear energy industry. However, it is still a significant challenge to develop high-efficiency and low-cost adsorbents for massively extracting uranium from seawater. Herein, a simple and fast method through low-energy consumption sunlight polymerization to direct fabrication of a poly(amidoxime) (PAO) hydrogel membrane, which exhibits high uranium adsorption capacity, is reported. This PAO hydrogel owns semi-interpenetrating structure and a hydrophilic poly(acrylamide) 3D network of hydrogel which can disperse and fix PAOs well. As a result, the amidoxime groups of PAOs exhibit an outstanding uranium adsorption efficiency (718 ± 16.6 and 1279 ± 14.5 mg g-1 of m uranium/m PAO in 8 and 32 ppm uranium-spiked seawater, respectively) among reported hydrogel-based adsorbents. Most importantly, U-uptake capacity of this hydrogel can achieve 4.87 ± 0.38 mg g-1 of m uranium/m dry gel just after four weeks within natural seawater. Furthermore, this hydrogel can be massively produced through low-energy consumption and environmentally-friendly sunlight polymerization. This work will provide a high-efficiency and low-cost adsorbent for massive uranium extraction from seawater.

Cations Controlling the Chiral Assembly of Luminescent Atomically Precise Copper(I) Clusters.

Chiral assembly and asymmetric synthesis are critically important for the generation of chiral metal clusters with chiroptical activities. Here, a racemic mixture of [K(CH3 OH)2 (18-crown-6)]+ [Cu5 (St Bu)6 ]- (1⋅CH3 OH) in the chiral space group was prepared, in which the chiral red-emissive anionic [Cu5 (St Bu)6 ]- cluster was arranged along a twofold screw axis. Interestingly, the release of the coordinated CH3 OH of the cationic units turned the chiral 1⋅CH3 OH crystal into a mesomeric crystal [K(18-crown-6)]+ [Cu5 (St Bu)6 ]- (1), which has a centrosymmetric space group, by adding symmetry elements of glide and mirror planes through both disordered [Cu5 (St Bu)6 ]- units. The switchable chiral/achiral rearrangement of [Cu5 (St Bu)6 ]- clusters along with the capture/release of CH3 OH were concomitant with an intense increase/decrease in luminescence. We also used cationic chiral amino alcohols to induce the chiral assembly of a pair of enantiomers, [d/l-valinol(18-crown-6)]+ [Cu5 (St Bu)6 ]- (d/l-Cu5V ), which display impressive circularly polarized luminescence (CPL) in contrast to the CPL-silent racemic mixture of 1⋅CH3 OH and mesomeric 1.

Tandem Silver Cluster Isomerism and Mixed Linkers to Modulate the Photoluminescence of Cluster-Assembled Materials.

Silver chalcogenolate cluster assembled materials (SCAMs) are a category of promising light-emitting materials the luminescence of which can be modulated by variation of their building blocks (cluster nodes and organic linkers). The transformation of a singly emissive [Ag12 (SBut )8 (CF3 COO)4 (bpy)4 ]n (Ag12 bpy, bpy=4,4'-bipyridine) into a dual-emissive [(Ag12 (SBut )6 (CF3 COO)6 (bpy)3 )]n (Ag12 bpy-2) via cluster-node isomerization, the critical importance of which was highlighted in dictating the photoluminescence properties of SCAMs. Moreover, the newly obtained Ag12 bpy-2 served to construct visual thermochromic Ag12 bpy-2/NH2 by a mixed-linker synthesis, together with dichromatic core-shell Ag12 bpy-2@Ag12 bpy-NH2 -2 via solvent-assisted linker exchange. This work provides insight into the significance of metal arrangement on physical properties of nanoclusters.

Layer-sliding-driven crystal size and photoluminescence change in a novel SCC-MOF.

A novel silver-chalcogenolate cluster-based framework Ag12TPPA·AA with long-lived afterglow was successfully synthesized. It transformed into more densely packed Ag12TPPA·AB and Ag12TPPA·ABC by layer sliding accompanied by macroscopic crystal contraction and changing luminescence.

Self-Assembly of a Stable Silver Thiolate Nanocluster Encapsulating a Lacunary Keggin Phosphotungstate Anion.

A polyoxometalate-templated silver(I) thiolate nanocluster has been synthesized by a one-pot reaction in high yield. This novel and stable nanocluster exhibits a core-shell structure with a Ag67S36 shell and two lacunary Keggin [PW9O34]9- cores, which is fully characterized by X-ray crystallography, X-ray photoelectron spectroscopy, UV-vis, powder X-ray diffraction, and cyclic voltammetry.