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The Diels-Alder reactions of sulfolenodipyrrins prove to be an efficient way to construct aromatic ring-fused dipyrrins. However, adjustable annulation is still hard to achieve. To address this, molecular engineering on the H-bond has been employed. The α-position aryl group-modified sulfolenodipyrrins have been synthesized to react with various dienophiles in Diels-Alder reactions, affording the monoannulation products with different regioselectivity in good yields (45-76%). The remaining sulfolenopyrrole in monoadducts can undergo further fusion in the presence of dienophiles and TEMPO, giving the bisadducts with a lactam subunit in an appropriate yield. According to the crystal structures and theoretical calculations, the intramolecular H-bonds between the α-substituent and the nearby pyrrole confine the conjugation pathway of the dipyrrin core. With respect to the normal NH-sulfolenopyrrole, the imino-type one features low aromaticity, from which SO 2 extrusion generates more stable dipyrrin-diene, achieving regioselectivity. In addition, aromatic ring fusion results in red-shifted absorption and emission spectra, and the annulation units regulate the emission intensity. This work shows the versatility of intramolecular H-bonds in regulating the reaction through confinement of the conjugation system.

Glyphosate, the most popular herbicide globally, has long been considered safe for mammals. However, whether glyphosate can disturb gut microbiota via inhibiting aromatic amino acid (AAA) synthesis has been under debate recently. Here, we evaluated the impacts of chronic exposure to Roundup on gut health with the addition of AAA and explored the mechanism behind Roundup-induced gut dysfunction by performing fecal microbiota transplantation. 500 mg/kg·bw of Roundup, independent of AAA deficiency, caused severe damage to gut function, as characterized by gut microbial dysbiosis, oxidative stress damage, intestinal inflammation, and histopathological injury, particularly in female rats. Notably, similar to Roundup, Roundup-shaped gut microbiome evidently damaged serum, cecum, and colon profiling of oxidative stress biomarkers (malonaldehyde (MDA), glutathione peroxidase (GSH-Px), superoxide dismutase (SOD), glutathione (GSH), and H 2 O 2 ). Moreover, it induced 0.65-, 3.29-, and 2.36-fold increases in colonic IL-1β, IL-6, and TNF-α levels, and 0.34-fold decreases in the IL-10 level. Upon transplanting healthy fecal microbiota to Roundup-treated rats, they exhibited a healthier gut microenvironment with mitigated inflammation, oxidative damage, and intestinal injury. Overall, our findings provide new insights into the safety of Roundup, highlight the crucial role of gut microbiota in Roundup-induced gut dysfunction, and pave the way for developing gut-microbiota-based strategies to address Roundup-related safety issues.

Large quantities of uranium-containing radioactive wastewater are typically generated during nuclear fuel cycle processes. Despite significant efforts, efficient capture of migratable hexavalent uranium U(VI) is still a huge challenge due to its acidity, radioactivity, coexisting organics, and high impurity cation abundance in wastewater. Herein, we have fabricated all-polymer-based 0D/2D C 4 N/C 6 N 7 homostructure hybrids with an S-scheme electronic configuration by coordinating the band engineering of semiconductors to enrich uranium species from the complex wastewater environment. The sample can capture over 97% of U(VI) in the actual concentration of nuclear industrial reprocessing wastewater; also, the U(VI) enrichment ratio still exceeds 95% when the irradiation dose (including α, β, and γ) is up to 100 kGy. Density functional theory and X-ray absorption spectroscopy demonstrate that the aggregation of charge carriers on the surface of the sample regulates the electron-rich microenvironment, thus accelerating the reduction conversion of single electron reaction uranium disproportionation. It is expected that this work can provide more insight into other functional materials, thereby promoting uranium removal advancements in nuclear wastewater.

The development and exploration of uranium decorporation agents with straightforward synthesis, high removal ability, and low toxicity are crucial guarantees for the safety of workers in the nuclear industry and the public. Herein, we report the use of traditional Chinese medicine licorice for uranium decorporation. Licorice has good adsorption performance and excellent selectivity for uranium in the simulated human environment. Glycyrrhizic acid (GL) has a high affinity for uranium (p(UO 2 ) = 13.67) and will complex with uranium at the carbonyl site. Both licorice and GL exhibit lower cytotoxicity compared to the commercial clinical decorporation agent diethylenetriamine pentaacetate sodium salts (CaNa 3 -DTPA). Notably, at the cellular level, the uranium removal efficiency of GL is eight times higher than that of CaNa 3 -DTPA. Administration of GL by prophylactic intraperitoneal injection demonstrates that its uranium removal efficiency from kidneys and bones is 55.2 and 23.9%, while CaNa 3 -DTPA shows an insignificant effect. The density functional theory calculation of the bonding energy between GL and uranium demonstrates that GL exhibits a higher binding affinity (-2.01 vs -1.15 eV) to uranium compared to DTPA. These findings support the potential of licorice and its active ingredient, GL, as promising candidates for uranium decorporation agents.

Uranium accumulation in the kidneys and bones following internal contamination results in severe damage, emphasizing the pressing need for the discovery of actinide decorporation agents with efficient removal of uranium and low toxicity. In this work, cinnamic acid (3-phenyl-2-propenoic acid, CD), a natural aromatic carboxylic acid, is investigated as a potential uranium decorporation ligand. CD demonstrates markedly lower cytotoxicity than that of diethylenetriaminepentaacetic acid (DTPA), an actinide decorporation agent approved by the FDA, and effectively removes approximately 44.5% of uranyl from NRK-52E cells. More importantly, the results of the prompt administration of the CD solution remove 48.2 and 27.3% of uranyl from the kidneys and femurs of mice, respectively. Assessments of serum renal function reveal the potential of CD to ameliorate uranyl-induced renal injury. Furthermore, the single crystal of CD and uranyl compound (C 9 H 7 O 2 ) 2 ·UO 2 (denoted as UO 2 -CD) reveals the formation of uranyl dimers as secondary building units. Thermodynamic analysis of the solution shows that CD coordinates with uranyl to form a 2:1 molar ratio complex at a physiological pH of 7.4. Density functional theory (DFT) calculations further show that CD exhibits a significant 7-fold heightened affinity for uranyl binding in comparison to DTPA.

Polar molecules are a promising platform for achieving scalable quantum information processing because of their long-range electric dipole-dipole interactions. Here, we take the coupled ultracold CaF molecules in an external electric field with gradient as qubits and concentrate on the creation of intermolecular entanglement with the method of deep reinforcement learning (RL). After sufficient training episodes, the educated RL agents can discover optimal time-dependent control fields that steer the molecular systems from separate states to two-qubit and three-qubit entangled states with high fidelities. We analyze the fidelities and the negativities (characterizing entanglement) of the generated states as a function of training episodes. Moreover, we present the population dynamics of the molecular systems under the influence of control fields discovered by the agents. Compared with the schemes for creating molecular entangled states based on optimal control theory, some conditions (e.g., molecular spacing and electric field gradient) adopted in this work are more feasible in the experiment. Our results demonstrate the potential of machine learning to effectively solve quantum control problems in polar molecular systems.

Constructing a three-dimensional (3D) structure along with Zn (002) texture selective exposure is a promising strategy to tackle the issues faced by Zn metal anodes. Herein, for the first time, we proposed an electrochemical stripping strategy to achieve controlled modification of the texture and microstructure of zinc foils in one step, building a hierarchical structure with (002) texture preferred exposed Zn (SZ). The SZ with favorable zincophilic properties not only can reduce the concentration polarization at the interface but also allow Zn to grow horizontally on the edge of the (002) texture by guiding the adsorption sites for Zn 2+ . Moreover, the honeycomb-like structure is beneficial to rearrange the distribution of the Zn 2+ flux as well as alleviating stress changes during cycling. Thus, the SZ||Cu cell exhibits excellent stability with a Coulombic efficiency of 99.76% over 1800 cycles. The SZ||NaV 3 O 8 · x H 2 O cell with inconspicuous self-discharge effect maintains a high areal capacity of 3.67 mA h cm -2 even after 700 cycles with a low N/P ratio of 3.6. This work achieves texture architecture and structure designing on Zn foils simultaneously by metallurgical electrochemical methods and opens up a potential strategy to implement the practicality of zinc metal anodes.

Constipation, a common gastrointestinal dysfunction, damages patients' life quality and predisposes them to other serious diseases. Current strategies against constipation often cause drug dependency and side effects. Here, we demonstrated that broccoli-derived exosome-like nanoparticles (BENs), a natural product with high gastrointestinal stability, ameliorated LOP-induced constipation in mice. Specifically, orally administered BENs (17.5 mg/kg/d) effectively shortened defecation time, sped up intestinal propulsion rate, and increased feces amount in constipated mice. BENs also raised excitatory neurotransmitters SP and MTL and reduced inhibitory neurotransmitters VIP and ET-1. Mechanistically, BENs were taken up by gut microbes, restored LOP-disordered gut microbiota, and altered microbial metabolism of SCFAs and tryptophan, as evidenced by the results of fluorescence microscopy, 16S rRNA gene sequencing, and nontargeted metabolomics. Thereinto, BEN-enriched SCFA-producing microorganisms are closely associated with the feces amount and SP and VIP levels and BEN-elevated indole-3-pyruvic acid and 3-indoleacetic acid are highly linked to ET-1, SP, and MTL levels. Conclusively, BENs, mitigating constipation by regulating gut microbiota and microbial tryptophan metabolism, showed high potential to be developed as alternative regimens for constipation.

The effective capture and deposition of radioactive iodine in the spent fuel reprocessing process is of great importance for nuclear safety and environmental protection. Three-dimensional (3D) fiber felt with structural diversity and tunability is applied as an efficient adsorbent with easy separation for iodine capture. Here, a bismuth-based silica aerogel fiber felt (Bi@SNF) was synthesized using a facile hydrothermal method. Abundant and homogeneous Bi nanoparticles greatly enhanced the adsorption and immobilization of iodine. Notably, Bi@SNF demonstrated a high capture capacity of 982.9 mg/g by forming stable BiI 3 and Bi 5 O 7 I phases, which was about 14 times higher than that of the unloaded material. Fast uptake kinetics and excellent resistance to nitric acid and radiation were exhibited as a result of the 3D porous interconnected network and silica aerogel fiber substrate. Adjustable size and easy separation and recovery give the material potential as a radioactive iodine gas capture material.

The efficient capture and immobilization of radioiodine (I - , IO 3 - ) is of great importance in radioactive waste management. Here, a Cu 2 O-loaded three-dimensional bulk cationic hydrogel composite (Cu 2 O@CH) was successfully prepared by simple redox reactions and UV photopolymerization, which realized the rapid enrichment and efficient immobilization of I - and IO 3 - . The adsorption experiments showed that the maximum adsorption capacity of Cu 2 O@CH for I - in the solution at pH = 3 reached 416.5 mg/g, and the adsorption capacity of IO 3 - in the solution at pH = 6 could reach 313.4 mg/g. It exhibited extremely fast adsorption kinetics for I - and IO 3 - . In addition, Cu 2 O@CH also exhibited efficient I - and IO 3 - removal from simulated high-level liquid waste. The rapid capture and effective immobilization of radioiodine (I - , IO 3 - ) were realized by the electrostatic interaction of -N + (CH 3 ) 3 groups in Cu 2 O@CH with I - and IO 3 - , as well as the chemical reactions between Cu 2 O and I - . The bulk cationic hydrogel composite explored the multifunctional role toward fast, high adsorption capability and easy handling, highlighting its superiority compared to the powder adsorbent, which renders it a potential adsorbent for the removal of radioactive iodine (I - , IO 3 - ) in nuclear wastewater treatment.

The capture of the radionuclides strontium and cesium is of great importance to the environment, human health, and the sustainable development of nuclear energy, and zirconium phosphate with excellent ion exchange capacity has potential application in this field. In this work, we organically granulated zirconium phosphate to induce the formation of composite bead materials (CA@ZrP) with a calcium-containing phase with selectivity for Sr 2+ and Cs + higher than that of pure ZrP in low-pH environments and competing ionic environments. The adsorption performance of the material was systematically investigated. It was concluded that the adsorption performance of CA@ZrP improved with an increase in temperature, and under the dynamic adsorption experimental conditions, the treatment capacity of CA@ZrP for Sr 2+ and Cs + reached 404.79 and 302.2 bed volumes, respectively. The systematic study and characterization showed that the generation of the calcium-containing phase [Ca 0.55 ZrH 0.9 (PO 4 ) 2 ] promoted the exchange of Ca 2+ with Sr 2+ and Cs + , thus improving the selectivity of the composite beads. The highly selective composite bead material can be prepared in batches and easily recycled, providing a new idea for practical engineering applications.

The low efficient transfer of photogenerated electrons to an active catalytic site is a pivotal problem for the photoreduction of highly soluble hexavalent uranium [U(VI)] to low soluble tetravalent uranium [U(IV)]. Herein, we successfully synthesized a TiO 2- x /1T-MoS 2 /reduced graphene oxide heterojunction (T 2- x TMR) with dual charge-transfer channels by exploiting the difference in Fermi levels between the heterojunction interfaces, which induced multilevel separation of photogenerated carriers. Theoretical and experimental results demonstrate that the presence of the electron buffer layer promoted the efficient migration of photogenerated electrons between the dual charge-transfer channels, which achieved effective separation of photogenerated carriers in physical/spatial dimensions and significantly extended the lifetime of photogenerated electrons. The migration of photogenerated electrons to the active catalytic site after multilevel spatial separation enabled the T 2- x TMR dual co-photocatalyst to remove 97.4% of the high concentration of U(VI) from the liquid-phase system within 80 min. This work provides a practical reference for utilizing multiple co-catalysts to accomplish directed spatial separation of photogenerated carriers.

Understanding the growth of nanoclusters and the relationship between structure-activity depends on the precise arrangement of metals on their surface. In this work, we realized the synchronous rearrangement of metal atoms on the equatorial plane of Au-Cu alloy nanoclusters. Upon adsorption of the phosphine ligand, the Cu atoms on the equatorial plane of the Au 52 Cu 72 (SPh) 55 nanocluster are irreversibly rearranged. The whole metal rearrangement process can be understood from a synchronous metal rearrangement mechanism initiated by the adsorption of the phosphine ligand. Furthermore, this metal rearrangement can effectively improve the efficiency of A 3 coupling reactions without increasing the amount of catalyst.

Effective capture of radioactive iodine is highly desirable for decontamination purposes in spent fuel reprocessing. Cu-based adsorbents with a low cost and high chemical affinity for I 2 molecules act as a decent candidate for iodine elimination, but the low utilization and stability remain a significant challenge. Herein, a facile in situ confined synthesis strategy is developed to design and synthesize a copper-encapsulated flaky silicalite-1 (Cu@FSL-1) zeolite with a thickness of ≤300 nm. The maximum iodine uptake capacity of Cu@FSL-1 can reach 625 mg g -1 within 45 min, which is 2 times higher than that of a commercial silver-exchanged zeolite even after nitric acid and NO X treatment. The Cu nanoparticles (NPs) confined within the zeolite exert superior iodine adsorption and immobilization properties as well as high stability and fast adsorption kinetics endowed by the all-silica zeolite matrix. This study provides new insight into the design and controlled synthesis of zeolite-confined metal adsorbents for efficient iodine capture from gaseous radioactive streams.

The immobilization of iodine waste suffers from serious iodine loss during heat treatment. Herein, we reported on the high iodine retention immobilization of simulated radioiodine-contaminated Bi 0 -SiO 2 sorbent in B-Bi-Zn oxide glass using Bi 2 O 3 as a stabilizer under a N 2 atmosphere. The effects of the Bi 2 O 3 content and sintering atmosphere on the iodine immobilization behaviors (iodine retention ratio, phase composition, microstructure, and chemical stability) were investigated. It was found that the decomposition of BiI 3 was prevented by adding Bi 2 O 3 and sintering in a N 2 atmosphere. The iodine retention ratio in the obtained glass waste form was significantly enhanced with increasing Bi 2 O 3 content and sintering in the N 2 atmosphere due to the synergistic effect. The achieved record-high iodine retention (92.22 ± 2.6%) was much higher than that of conventional heat treatment route (18.01 ± 3.5%). The results demonstrated that iodine was effectively immobilized through the formation of stable Bi x O y I (Bi 5 O 7 I and BiOI). Furthermore, the obtained iodine waste form exhibited excellent compactness and chemical stability. Owing to its high iodine retention ratio, this route can be employed to effectively immobilize radioactive iodine.

Meat's freshness is closely related to food safety and human health and has received increasing attention nowadays. To on-site visually screen meat freshness in a fast and non-destructive manner, we rationally constructed a series of fluorescent probes ( JDCN , JDNS , and JDPY ) with distinct electron-withdrawing substitution groups based on julolidine-fused coumarin. These probes underwent an aza-Michael addition followed by an elimination reaction with cadaverine to generate a colorimetric and ratiometric fluorescence response, and their sensing performance was rationally enhanced by improving the electron-withdrawing strength of substitution groups. Particularly, JDCN with a dicyanovinyl group as the reaction site exhibited outstanding sensing performance including rapid response (∼60 s), high selectivity, and low detection limit (14 nM). Furthermore, JDCN was fabricated into test kits to detect cadaverine vapor with a high-contrast fluorescence change from red to green. Based on two-color visualization of cadaverine vapor, on-site non-contact and non-destructive monitoring of meat freshness was successfully achieved. The good sensing performance rendered JDCN test kits a promising real-time fluorescence screening platform for rapid, non-destructive, and accurate evaluation of meat freshness.

Fluorescent polymeric hydrogels are promising soft and wet media for information storage that are desirable for lifelike biomaterials and flexible electronics. Hydrogels based on engineered proteins have attracted considerable interest. However, their potential utility as information storage media has remained largely unexplored. Here, we report a protein-based hydrogel that can serve as an information storage medium. Using LOVTRAP, which consists of protein LOV2 and its binding partner ZDark1, we developed a novel strategy to decorate/release fluorescent proteins onto/from a blank protein hydrogel slate in light-controlled and spatially defined fashions, reversibly generating fluorescent patterns such as quick response codes. To increase the information storage capacity, we further developed grayscale patterning to generate pseudo-colored multi-dimensional fluorescent images. Results of this new method demonstrate a novel reversible information storage approach in soft and wet materials and open a new avenue toward developing next-generation protein-based smart materials for information storage and anti-counterfeit applications.

The development of intercalation anodes with high capacity is key to promote the progress of "rocking-chair" Zn-ion batteries (ZIBs). Here, layered BiOI is considered as a promising electrode in ZIBs due to its large interlayer distance (0.976 nm) and low Zn 2+ diffusion barrier (0.57 eV) obtained by density functional theory, and a free-standing BiOI nanopaper is designed. The process and mechanism of Zn(H 2 O) n 2+ insertion in BiOI are proved by ex situ X-ray diffraction, Raman, and X-ray photoelectron spectroscopy. The suitable potential (0.6 V vs Zn/Zn 2+ ), high reversible capacity (253 mAh g -1 ), good rate performance (171 mAh g -1 at 10 A g -1 ), long cyclic life (113 mAh g -1 after 5000 cycles at 5 A g -1 ), and dendrite-free operation of BiOI nanopaper prove its potential as a superior anode. When it is coupled with Mn 3 O 4 cathode, the quasi-solid-state battery exhibits a high initial capacity of 149 mAh g -1 (for anode) and a good capacity retention of 70 mAh g -1 after 400 cycles. The self-assembled flexible battery also shows stable charge-discharge during the cyclic test. This work shows the feasibility of BiOX anode for dendrite-free ZIBs.

Effective detections of radionuclides including uranium and its predominant fission products, for example, iodine, are highly desired owing to their radiotoxicity and potential threat to human health. However, traditional analytical techniques of radionuclides are instrument-demanding, and chemosensors targeted for sensitization of radionuclides remain limited. In this regard, we report a sensitive and selective sensor of UO 2 2+ and I - based on the unique quenching behavior of a luminescent Zr-based metal-organic framework, Zr 6 O 4 (OH) 4 (OH) 6 (H 2 O) 6 (TCPE) 1.5 ·(H 2 O) 24 (C 3 H 7 NO) 9 ( Zr-TCPE ). Immobilization of the luminescent tetrakis(4-carboxyphenyl)ethylene (TCPE 4- ) linkers by Zr 6 nodes enhances the photoluminescence quantum yield of Zr-TCPE , which facilitates the effective sensing of radionuclides in a "turn-off" manner. Moreover, Zr-TCPE can sensitively and selectively recognize UO 2 2+ and I - ions with the lowest limits of detection of 0.67 and 0.87 μg/kg, respectively, of which the former one is much lower than the permissible value (30 μg/L) defined by the U.S. EPA. In addition, Zr-TCPE features excellent hydrolytic stability and can withstand pH conditions ranging from 3 to 11. To facilitate real-world applications, we have further fabricated polyvinylidene fluoride-integrating Zr-TCPE as luminescence-based sensor membranes for on-site sensing of UO 2 2+ and I - .

Iodine radioisotope, as one of the most important fission products of uranium, may cause severe damage to human health when it is accidentally discharged into the environment. Hence, efficient removal of radioactive iodine is one of the most critical issues for both used nuclear fuel (UNF) reprocessing and environmental remediation. In this work, three metal-organic gels (MOGs) were introduced for iodine removal. The presented zirconium-based MOGs, namely, CWNU , CWNU-NH 2 , and CWNU-2NH 2 , were prepared via moderate solvothermal reactions. These MOGs all exhibit excellent chemical stability and reusability, marked iodine sorption capability, and favorable machinability, which can even rival commercial ones. The sorption capacities are determined to be 3.36, 4.10, and 4.20 g/g, respectively. The increased amount of amino group is considered to be responsible for the elevated iodine sorption capacity and kinetics, as confirmed by combined sorption studies and XPS analysis. The presented work sheds light on the utilization of MOGs for radioiodine capture.

Not only a critical matter in the nuclear fuel cycle but uranium is also a global contaminant with both radioactive and chemical toxicity. Reducing soluble hexavalent uranium [U(VI)] to relatively nonimmigrated tetravalent uranium [U(IV)] by photocatalytic technologies is recognized as a highly promising strategy for avoiding environmental pollution and re-extracting uranium resources from nuclear wastewater. Herein, we have designed a heterojunction photocatalyst constructed from the carbon aerogels (CA) and the CdS nanoflowers with an S-vacancy (CA@CdS-SV). With the S-vacancy and heterojunction being synergized, the U(VI) removal rate exceeded 97% in 40 min without the addition of any sacrificial agents. As impacted by the synergistic effects of the S-vacancy and heterojunction, thermodynamics and kinetics revealed that photogenerated electrons were first captured via shallow traps generated by vacancies on CdS-SV and then transferred to the CA surfaces through the heterojunction to realize the spatial separation of carriers, thereby achieving a satisfactory performance. This work is considered to underpin the improvement of U(VI) immobilization by exploiting the synergistic effect of vacancy engineering and the Schottky heterojunction from the perspective of thermodynamics and kinetics.

The lack of a sizeable band gap has so far prevented graphene from building effective electronic and optoelectronic devices despite its numerous exceptional properties. Intensive theoretical research reveals that a band gap larger than 1 eV can only be achieved in sub-3 nm wide graphene nanoribbons (GNRs), but real fabrication of such ultranarrow GNRs still remains a critical challenge. Herein, we demonstrate an approach for the synthesis of ultranarrow and photoluminescent semiconducting GNRs by longitudinally unzipping single-walled carbon nanotubes. Atomic force microscopy reveals the unzipping process, and the resulting 2.2 nm wide GNRs are found to emit strong and sharp photoluminescence at ∼685 nm, demonstrating a very desirable semiconducting nature. This band gap of 1.8 eV is further confirmed by follow-up photoconductivity measurements, where a considerable photocurrent is generated, as the excitation wavelength becomes shorter than 700 nm. More importantly, our fabricated GNR field-effect transistors (FETs), by employing the hexagonal boron nitride-encapsulated heterostructure to achieve edge-bonded contacts, demonstrate a high current on/off ratio beyond 10 5 and carrier mobility of 840 cm 2 /V s, approaching the theoretical scattering limit in semiconducting GNRs at room temperature. Especially, highly aligned GNR bundles with lengths up to a millimeter are also achieved by prepatterning a template, and the fabricated GNR bundle FETs show a high on/off ratio reaching 10 5 , well-defined saturation currents, and strong light-emitting properties. Therefore, GNRs produced by this method open a door for promising applications in graphene-based electronics and optoelectronics.

Photocatalysts have been extensively used for hydrogen evolution or organic degradation. In this work, two different heterojunction types of composite photocatalysts, 1T-MoS 2 @TiO 2 with Schottky heterojunction and 2H-MoS 2 @TiO 2 with type-II heterojunction, are synthesized via hydrothermal synthesis. These two composite materials exhibit excellent photocatalytic activity toward the degradation of tannic acid, which is a typical organic in nuclear wastewater. At an optimal loading of 16% 1T-MoS 2 , the 1T-MoS 2 @TiO 2 shows the highest degradation capacity of 98%, which is 3.2 times higher than that of pure TiO 2 . The degradation rate of 16% 1T-MoS 2 @TiO 2 is much higher than that of 13% 2H-MoS 2 @TiO 2 . The enhanced photocatalytic activity might be attributed to the improved charge transfer according to the mechanism investigation, supported by the X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) analyses. This work provides new opportunities for constructing highly efficient catalysts for nuclear waste disposal., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Rechargeable aqueous zinc-ion batteries (ZIBs) are promising systems for energy storage due to their operational safety, low cost, and environmental friendliness. However, the development of suitable cathode materials is plagued by the sluggish dynamics of Zn 2+ with strong electrostatic interaction. Herein, an Al 3+ -doped tremella-like layered Al 0.15 V 2 O 5 ·1.01H 2 O (A-VOH) cathode material with a large pore diameter and high specific surface area is demonstrated to greatly boost electrochemical performance as ZIB cathodes. Resultant ZIBs with a 3 M Zn(CF 3 SO 3 ) 2 electrolyte deliver a high specific discharge capacity of 510.5 mAh g -1 (0.05 A g -1 ), and an excellent energy storage performance is well maintained with a specific capacity of 144 mAh g -1 (10 A g -1 ) even after ultralong 10,000 cycles. The decent electrochemical performance roots in the novel tremella-like structure and the interlayer of Al 3+ ions and water molecules, which could improve the electrochemical reaction kinetics and structural long cycle stability. Furthermore, the assembled coin-type cells could power a light-emitting diode (LED) lamp for 2 days. We believed that the design philosophy of unique morphology with abundant active sites for Zn 2+ storage will boost the development of competitive cathodes for high-performance aqueous batteries.

Protein-based hydrogels can mimic many aspects of native extracellular matrices (ECMs) and are promising biomedical materials that find various applications in cell proliferation, drug/cell delivery, and tissue engineering. To be adapted for different tasks, it is important that the mechanical and/or biochemical properties of protein-based hydrogels can be regulated by external stimuli. Light as a regulation stimulus is of advantage because it can be easily applied in demanded spatiotemporal manners. The noncovalent binding between the light-oxygen-voltage-sensing domain 2 (LOV2) and its binding partner ZDark1 (zdk1), named as LOVTRAP, is a light-responsive interaction. The binding affinity of LOVTRAP is much higher in dark than that under blue light irradiation. Taking advantage of these light-responsive interactions, herein we endeavored to use LOVTRAP as a crosslinking mechanism to engineer light-responsive protein hydrogels. Using LOV2-containing and zdk1-containing multifunctional protein building blocks, we successfully engineered a light-responsive protein hydrogel whose viscoelastic properties can change in response to light: in the dark, the hydrogel showed higher storage modulus; under blue light irradiation, the storage modulus decreased. Due to the noncovalent nature of the LOVTRAP, the engineered LOVTRAP protein hydrogels displayed shear-thinning and self-healing properties and served as an excellent injectable protein hydrogel. We anticipated that this new class of light-responsive protein hydrogels will broaden the scope of dynamic protein hydrogels and help develop other light-responsive protein hydrogels for biomedical applications.

The structural determination of alloy hydride nanoclusters with high nuclearity remains challenging. We herein report the synthetic procedure and the structural elucidation of an Au-Ag alloy nanocluster with 12 hydride ligands-[Au 16 Ag 43 H 12 (SPhCl 2 ) 34 ] 5- . The structure of [Au 16 Ag 43 H 12 (SPhCl 2 ) 34 ] 5- comprises an Au 16 Ag 3 kernel that is stabilized by 12 hydride ligands, 8 thiol bridges, and 6 Ag m (SR) n motif units. The 12 hydride ligands in Au 16 Ag 43 have been confirmed by both 2 H NMR and ESI-MS measurements, and their positions have been theoretically evaluated, located at the interlayer between the Au 16 Ag 3 kernel and the Ag-SR shell. The metastable [Au 16 Ag 43 H 12 (SPhCl 2 ) 34 ] 5- can convert to [Au 12 Ag 32 (SPhCl 2 ) 30 ] 4- spontaneously. Structurally, the Au 16 Ag 3 kernel of [Au 16 Ag 43 H 12 (SPhCl 2 ) 34 ] 5- could be regarded as the overlapping of two hollow Au 8 Ag 3 cages via sharing an Ag 3 line, which is in contrast to the solely icosahedral Au 12 kernel of [Au 12 Ag 32 (SPhCl 2 ) 30 ] 4- . Besides, the overall construction of Au 16 Ag 43 or Au 12 Ag 32 follows a complementing or overlapping assembly mode, respectively. Overall, the structural anatomy of Au 16 Ag 43 H 12 (SPhCl 2 ) 34 sheds some new insight into the structural evolution of metal nanoclusters.

U(VI) and Eu(III), as representative elements of the hexavalent actinide and trivalent lanthanides (always as a chemical analogue for trivalent actinide), respectively, have attracted more and more attentions due to the widespread use of nuclear energy. Much effort has been focused on developing versatile materials for their uptake from aqueous solution. For the first time, we report here UiO-66 and its mono- (UiO-66-COOH) and di-carboxyl (UiO-66-2COOH) functional derivatives as robust adsorbents for efficient U(VI) and Eu(III) removal. It is found that the introduction of carboxyl groups greatly reduces the surface charge of UiO-66, thus guaranteeing excellent adsorption capacity at low pH. At pH = 3, for example, the adsorption capacity of UiO-66-2COOH for U(VI) and Eu(III) is more than 100 and 60 mg/g, respectively, while almost no adsorption occurs for pristine UiO-66. At pH = 4, both UiO-66-COOH and UiO-66-2COOH show high performance on U(VI) and Eu(III) removal. UiO-66-COOH has adsorption capacities of 80 and 43 mg/g for U(VI) and Eu(III), respectively, while the values for UiO-66-2COOH reach 150 and 80 mg/g, respectively. Also, all these materials achieve adsorption equilibrium within 100 min. More importantly, combining the needs of practical applications and the characteristics of high stability, high porosity, and excellent adsorption performance of UiO-66-2COOH, dynamic adsorption column experiments were successfully conducted; ∼99% U(VI)/Eu(III) can be efficiently adsorbed, and >90% adsorbed U(VI)/Eu(III) can be re-collected with dilute nitric acid solution, even after four adsorption-desorption cycles. The findings of this work demonstrate the application potential of metal-organic framework materials to remove radionuclides from environmental samples or nuclear waste liquids.

The photocatalysts for hexavalent uranium (U(VI)) reduction suffered from the low uranium uptake capacity and weak long-wavelength light absorption. Herein, we synthesized the CdS x Te 1- x nanobelts capped by ethylenediamine (EDA), which provided amino groups as the adsorption sites. With the increase of the Te content, the amino groups on the CdS x Te 1- x nanobelts decreased because of the variation of the electron density of Cd 2+ , whereas the light adsorption was enhanced due to the narrowed bandgap. In photocatalytic reduction of U(VI), the CdS 0.95 Te 0.05 -EDA nanobelts exhibited a considerable U(VI) removal ratio of 97.4% with a remarkable equilibrium U(VI) extraction amount on per weight unit of the adsorbent ( q e ) of 836 mg/g. The bandgap structure and Fourier transform infrared spectroscopy (FT-IR) spectra analysis revealed that the optimum photocatalytic activity of CdS x Te 1- x nanobelts was achieved at a 5% of Te 2- doping, which balanced the factors of amino groups and bandgap. This adsorption-photoreduction process offers an ultrahigh uranium extraction capacity over wide uranium concentrations.

Dysangiogenesis and chronic inflammation are two critical reasons for diabetic foot ulcers. Desferrioxamine (DFO) was used clinically in the treatment of diabetic foot ulcers by repeated injections because of its capacity to induce vascularization. Biocompatible carriers that release DFO slowly and facilitate healing simultaneously are preferable options to accelerate the healing of diabetic wounds. Here, DFO-laden silk nanofiber hydrogels that provided a sustained release of DFO for more than 40 days were used to treat diabetic wounds. The DFO-laden hydrogels stimulated the healing of diabetic wounds. In vitro cell studies revealed that the DFO-laden hydrogels modulated the migration and gene expression of endothelial cells, and they also tuned the inflammation behavior of macrophages. These results were confirmed in an in vivo diabetic wound model. The DFO-laden hydrogels alleviated dysangiogenesis and chronic inflammation in the diabetic wounds, resulting in a more rapid wound healing and increased collagen deposition. Both in vitro and in vivo studies suggested potential clinical applications of these DFO-laden hydrogels in the treatment of diabetic ulcers.

Fluorination is one of the effective approaches to alter the organic semiconductor properties that impact the performance of the organic solar cells (OSCs). Positive effects of fluorination are also revealed in the application of fused ring electron acceptors (FREAs). However, in comparison with the efforts allocated to the material designs and power conversion efficiency enhancement, understanding on the excitons and charge carriers' behaviors in high-performing OSCs containing FREAs is limited. Herein, the impact of fluorine substituents on the active layer morphology, and therefore exciton dissociation, charge separation, and charge carriers' recombination processes are examined by fabricating OSCs with PTO2 as the donor and two FREAs, O-IDTT-IC and its fluorinated analogue O-IDTT-4FIC, as the acceptors. With the presence of O-IDTT-4FIC in the devices, it is found that the excitons dissociate more efficiently, and the activation energy required to split the excitons to free charge carriers is much lower; the charge carriers live longer and suffer less extent of trap-assisted recombination; the trap density is 1 order of magnitude lower than that of the nonfluorinated counterpart. Overall, these findings provide information about the complex impacts of FREA fluorination on efficiently performed OSCs.

Engineering protein-based hydrogels that can change their physical and mechanical properties in response to environmental stimuli have attracted considerable interest due to their promising applications in biomedical engineering. Among environmental stimuli, temperature is of particular interest. Most thermally responsive protein hydrogels are constructed from thermally responsive elastin-like polypeptides (ELPs), which exhibit a lower critical solution temperature (LCST) transition, or nonstructured elastomeric proteins fused with ELPs. Here we report the engineering of thermally responsive elastomeric protein-based hydrogels by fusing ELPs to elastomeric proteins made of tandemly arranged folded globular proteins. By fusing ELP sequence (VPGVG) n to an elastomeric protein (GR) 4 , which is made of small globular protein GB1 (G) and random coil sequence resilin (R), we engineered a series of protein block copolymers, V n -(GR) 4 . The fusion proteins V n -(GR) 4 exhibit temperature-responsive behaviors in aqueous solution that are different from that of V n -ELPs, as they did not exhibit the macroscopic phase transitions in the turbidity test. Instead, V48-(GR) 4 and V72-(GR) 4 form micelles at temperatures higher than the transition temperature of V48 and V72 at the same concentration. Using the well-developed ruthenium-mediated photochemical cross-linking method, V n -(GR) 4 polymers can be cross-linked into hydrogels, in which V n -ELP serve as side chains of the hydrogel network. These hydrogels exhibited thermoresponsive properties due to the temperature dependent phase transition behaviors of the incorporated V n -ELPs blocks. At elevated temperatures, the V n -ELPs side chains in the hydrogel network underwent aggregation, leading to secondary physical cross-linking. The aggregation of the V n -ELPs resulted in higher Young's modulus and reduced swelling ratio. Furthermore, the amplitude of such property changes can be tuned by side chain length and composition. These results demonstrate that in situ phase behaviors of ELP side chains can regulate thermoresponsiveness of protein-based hydrogels. We anticipate that this method can be applied to other elastomeric proteins for potential biomedical applications.

As the most abundant nonprotein biothiol in living cells, glutathione (GSH) prevents cellular components from oxidative damage and maintains the intracellular redox homeostasis. For further exploring whether GSH can be employed as a bioindicator to discriminate tumor lesion at a cellular level, the highly selective detection and accurate quantification of GSH under pathological conditions are critical. Herein, we design a coumarin derivative-based two-photon fluorescent probe Cou-Br for the detection of GSH in living cells, mice models, and clinical specimens. The prepared probe is capable of sensitively and selectively detecting GSH in complex biological systems. Cou-Br displays a good linear relationship in response to GSH and a low limit of detection. With the fluorescence signal positively associated with intracellular GSH levels, the probe enables real-time imaging of GSH in various cell lines. Under the condition of CS 2 stimulation, Cou-Br can rapidly respond to the fluctuation of intracellular GSH induced by oxidative damage. Furthermore, the in situ and in vivo bioimaging performances of Cou-Br are demonstrated. Typically, relying on the different cellular concentrations of GSH, the probe is successfully employed to identify the human laryngeal cancer lesion with outstanding capabilities of deep tissue imaging and tumor margin recognition. We assume that the abnormal expression level of GSH may be utilized as a potential bioindicator to discriminate tumor tissues from the surrounding disease-free tissues. To conclude, the proposed probe Cou-Br may potentially serve as a powerful chemical tool for the surgical navigation of cancer in clinic.

The efficient and safe capture of radioactive iodine ( 129 I or 131 I) is of great significance in nuclear waste disposal. Here, we report millimeter-scale poly(ether sulfone) composite beads loaded with porous Cu-BTC [Cu 3 (BTC) 2 , BTC = 1,3,5-benzenetricarboxylate] (Cu-BTC@PES), prepared by a phase inversion method for the removal of volatile iodine. Three kinds of Cu-BTC@PES composite beads were obtained with different Cu-BTC contents of 48.6, 60.2, and 71.9%, respectively. While maintaining crystallinity, the composite beads exhibited higher I 2 vapor adsorption capacity (639 mg/g) in the form of iodine molecules. The iodine absorption up to 260 mg/g and the adsorption was followed Langmuir isotherm and pseudo-second-order kinetic model. Furthermore, the composite beads can still absorb more than 85% of iodine after 3 cycles of regeneration with excellent recyclability. The resulting Cu-BTC@PES composite beads show great potential for the sustainable removal of radioactive iodine.

Hydrogels with dynamic mechanical properties are of special interest in the field of tissue engineering and drug delivery. However, it remains challenging to tailor the dynamic mechanical response of hydrogels to simultaneously meet diverse application needs. Here, we report a hetero-coiled-coil complex cross-linked protein hydrogel exhibiting unusual multiple energy dissipation modes and tunable dynamic response. Such unique features confer on the hydrogel responsiveness to mechanical stimuli in a broad range of frequencies. Therefore, the hydrogels are injectable due to their shearing-thinning properties at low shear rates of 0.8 rad s -1 and can fully recover their mechanical properties within a few seconds due to the intrinsic fast dynamics of the cross-linkers. Moreover, the dynamic response of these hydrogels can be fine-tuned by the temperature and the hydrogel network structures. We anticipate that these hydrogels are promising candidates for delivering therapeutic drugs, biological molecules, and cells in a broad spectrum of biomedical applications.

A novel nanospherical hydrous titanium oxide adsorbent (hydrous titanium oxide-immobilized bovine serum albumin nanospheres, HTO-BSA-NSs) was prepared by immobilizing HTOs with a manipulated molecular mass and number of active sites for uranium on the surface of BSA-NSs. The adsorption performances of HTO-BSA-NSs were investigated in spiked natural seawater with extra 8 ppm uranium. The results demonstrated that HTO-BSA-NSs are capable of uranium capture from a complex aqueous matrix with a low uranium concentration. Meanwhile, the microbial stability of HTO-BSA-NSs in sterilized natural seawater with Marinobacter sp. was investigated and observed through an optical microscope and TEM, revealing that the wrapped HTOs could protect the BSA-NSs from the decomposition of microorganisms, and the structure and functional groups of HTO-BSA-NSs remain stable compared with the BSA-NSs. In addition, the uranium adsorption mechanism of HTO-BSA-NSs is mainly recognized as dehydrated complexation, which was concluded from characterization analysis, adsorption model fitting, and theoretical calculations based on density functional theory. The remarkable uranium adsorption performance and microbial stability of HTO-BSA-NSs indicated that they have the potential to be a low-cost and environmentally friendly adsorbent for uranium extraction from complex environments such as seawater or uranium-containing industrial wastewater.

High-quality flexible magnetic oxide thin films have promoted a wide range of potential applications in spintronic devices due to their unique physical properties. To obtain the optimized microwave magnetism for future all-oxide-based spintronic applications, high-quality oxide materials with excellent epitaxial quality as well as specific bending properties related to ferromagnetic resonance are high in demand. Here, (001)-oriented La 0.67 Sr 0.33 MnO 3 epitaxial thin films with different thicknesses have been grown and subsequently transferred onto flexible poly(dimethylsiloxane) substrates. The microwave magnetisms of these film samples have been investigated under various bending states. Under bending, the ferromagnetic resonance lineshape of the film gradually transits from a single mode to a superposition of multimodes, possibly because of the uneven distribution of magnetization in the bending film at X-band. This phenomenon is more apparent when the direction of the applied magnetic field goes close to the out-of-plane of the film. Hence, an integration of invariable and continuous tuning of ferromagnetic resonance field under various mechanical bending can be achieved in one same sample by just tuning the direction of the applied magnetic field, which reveals that the flexible La 0.67 Sr 0.33 MnO 3 thin films have huge potential in the applications in future flexible multifunctional devices.

Clay nanosheets (CNSs) have been widely used in the design of nanocomposite biomaterials. CNSs display a disk-like morphology with strong negatively charged surfaces. It has been shown that guanidinium-containing molecules can bind CNSs through noncovalent salt-bridge interactions and thus serve as "molecular glues" for CNSs. Making use of the guanidinium side chain in arginine, here, we designed novel arginine-rich elastomeric proteins to engineer protein-CNS nanocomposite hydrogels. Our results showed that these arginine-rich proteins can interact with CNSs effectively and can cross-link CNSs into hydrogels. Rheological measurements showed that mechanical properties of the resultant hydrogels depended on the arginine content in the arginine-rich proteins as well as CNS/protein concentration. Compared with hydrogels constructed from CNSs or proteins alone, the novel protein-CNS nanocomposite hydrogels show much improved mechanical properties. Our work opens up a new avenue to engineer functional protein hydrogels for various applications.

Nonfullerene acceptors (NFAs) based on calamitic-shaped small molecules are being developed rapidly to improve the photoelectron conversion efficiencies (PCEs) of organic solar cells. NFAs with light absorption extended to the near-infrared (NIR) region are of interest because they play a pivotal role in both organic tandem cells and semitransparent devices. In this work, two simple acceptor-donor-acceptor-structured NFAs (CPDT-4Cl and CPDT-4F) have been designed and synthesized. Featured with dimerized 4H-cyclopenta[1,2-b:5,4-b']dithiophene (CPDT) as the electron-donating core and Cl- or F-substituted 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile as the electron-accepting unit, the absorption spectra of two NFAs are extended to the NIR region with an absorption edge at approximately 910 nm. In conjunction with the polymer donor material PBDB-T, a PCE of 9.47% was achieved by using a CPDT-4F-based device with a short-circuit current density of up to 20.1 mA/cm 2 , which slightly outperforms its counterpart CPDT-4Cl (PCE = 9.28%) under the same condition. This work broadens the scope of developing new NIR NFAs with both high efficiency and easy accessibility.

We report a visual colorimetric assay for detection of nitramine explosives such as 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) using a smartphone. This assay is based on compartmentalizing incompatible tandem reactions in Pickering emulsions. The alkaline hydrolysis of RDX or HMX in one Pickering emulsion produces nitrite ions, which autodiffuse into the other Pickering emulsion to form nitrous acid. It oxidizes the 3,3',5,5'-tetramethylbenzidine (TMB) to generate yellow TMB diimine. The RGB component change of the optical images is applied to quantitatively determine the RDX and HMX at different reaction temperatures. A distinct color change occurs at RDX and HMX concentrations of 1.2 and 12 μM, respectively. The adjusted intensity increases linearly with the increase of the logarithms of the concentrations of RDX and HMX in the range of 1.2-90 μM and 12-90 μM, respectively. The limits of detection of RDX and HMX are 96 and 110 nM, respectively. Importantly, this assay is employed for the detection of RDX and HMX in real water, proving the applicability of the assay in real-world samples.

The coexistence of radioactive contaminants (e.g., thorium, uranium, and their daughters) in rare earth minerals introduces significant environmental, economic, and technological hurdles in modern rare earth production. Efficient, low cost, and green decontamination strategies are therefore desired to ameliorate this problem. We report here a single-step and quantitative decontamination strategy of thorium from rare earths based on a unique periodic trend in the formation of crystalline selenite compounds across the lanthanide series, where Ce(III) is fully oxidized in situ to Ce(IV). This gives rise to a crystallization system that is highly selective to trap tetravalent f-blocks while all other trivalent lanthanides completely remain in solution when coexist. These results are bolstered by first-principles calculations of lattice energies and an examination of bonding in these compounds. This system is contrasted with typical natural and synthetic systems, where trivalent and tetravalent f-block elements often cocrystallize. The separation factors after one round of crystallization were determined from binary systems of Th(IV)/La(III), Th(IV)/Eu(III), and Th(IV)/Yb(III) to reach 2.1 × 10 5 , 1.2 × 10 5 , and 9 × 10 4 , respectively. Selective crystallization of thorium from a simulated monazite composite yields a separation factor of 1.9 × 10 3 with nearly quantitative removal of thorium.

There have been numerous studies on emission-color regulation by the adjustment of molar amounts of multiple trivalent lanthanide cations, such as Eu 3+ , Tb 3+ , Dy 3+ , and others, in many types of solid host materials. Although uranyl emission originating from charge-transfer transitions has been well-recognized and investigated for many decades, as of now there is no report on tunable 4f/5f bimodal emission based on heterobimetallic lanthanide(III) and uranyl(VI) compounds. In most cases, complete energy transfer between uranyl(VI) and lanthanide(III) centers was observed. In this work, a series of isotypic-europium-incorporated uranyl coordination polymers, Eu@UO 2 L(DMF) (L 2- = 3,5-pyridinedicarboxylate, denoted as 1-10, which represent the different Eu contents in UO 2 L(DMF); DMF = N,N-dimethylformamide), has been synthesized by solvothermal reactions. Crystallographic evidence of this series unveiled one-dimensional chains of UO 2 2+ as pentagonal-bipyramidal units bridged by pyridinedicarboxylate with no defined, crystallographically unique site containing Eu, even for the products with high concentrations of Eu in this series. However, emission bands characteristic of Eu 3+ were clearly observed in every product along with the characteristic uranyl-emission feature when observed with UV-vis fluorescence spectroscopy. Laser-ablation inductively coupled plasma mass spectrometry indicated that europium was concomitant with uranium, corroborating the incorporation of europium into crystals of UO 2 L(DMF). Systematic control of the solvent ratio (V H 2 O /V DMF ) in each reaction gives rise to an enrichment of Eu 3+ in the interior of UO 2 L(DMF). In addition, the color of emission of these compounds changed significantly from bright red to bright green with decreasing Eu content. This phenomenon occurs from the highly efficient energy transfer between the UO 2 2+ and Eu 3+ centers within each sample, providing the first case of a tunable 4f/5f bimodal emission in a mixed 4f/5f-elements-bearing metal-organic-hybrid material.

f-element-bearing iodate compounds are a large family mostly synthesized by hydrothermal reactions starting with actinide/lanthanide ions and iodic acid or iodate salt. In this work, we introduce melting periodic acid flux as a new reaction medium and provide a safe way for single-crystal growth of a series of new f-element iodate compounds including UO 2 (IO 3 ) 2 ·H 2 O (1), UO 2 (IO 3 ) 2 (H 2 O)·HIO 3 (2), α-Th(IO 3 ) 2 (NO 3 )(OH) (3), β-Th(IO 3 ) 2 (NO 3 )(OH) (4), and (H 3 O) 9 Nd 9 (IO 3 ) 36 ·3HIO 3 (5). The structures of these compounds deviate from those afforded from hydrothermal reactions. Specifically, compounds 1 and 2 exhibit pillared structures consisting of uranyl pentagonal bipyramids and iodate trigonal pyramids. Compounds 3 and 4 represent two new thorium iodate compounds that are constructed from subunits of thorium dimers. Compound 5 exhibits a flower-shaped trivalent lanthanide iodate structure with HIO 3 molecules and H 3 O + cations filled in the channels. The aliovalent replacement of f elements in 5 is available from a hydrothermal process, further generating compounds of Th 2 (IO 3 ) 8 (H 2 O) (6) and Ce 2 (IO 3 ) 8 (H 2 O) (7). The distinct absorption features are observed in isotypic compounds 5-7, where 7 shows typical semiconductor behavior with a band gap of 2.43 eV. Remarkably, noncentrosymmetric 1, 6, and 7 exhibit strong second-harmonic-generation efficiencies of 1.3, 3.2, and 9.2 times, respectively, that of the commercial material KH 2 PO 4 . Additionally, the temperature-dependent emission spectra of 1 and 2 were also collected showing typical emission features of uranyl units and a negative correlation between the intensities of the emissions with temperature. Clearly, the presented low-temperature melting inorganic acid flux synthesis would provide a facile and effective strategy to produce a large new family of structurally versatile and multifunctional f-element inorganic compounds.

As one of the materials having a bionic structure, nacrelike layered composites, inspired by their natural hybrid structures, have been studied via a variety of approaches. Graphene oxide (GO), which differed from inert graphene, was used as a new building block because it could be readily chemically functionalized. Rather than natural polymers, synthetic polymers were most commonly used to fabricate nacrelike GO-polymer materials. However, naturally occurring polymers complied more easily with the requirements of biocompatibility, biodegradability, and nontoxicity. Here, a simple solution-casting method was used to mimic natural nacre and fabricate a self-assembled and aging-resistant binary natural polymer, (κ-carrageenan (κ-CAR)-Konjac glucomannan (KGM))-GO nanocomposites, with varying GO concentrations. The investigation results revealed that κ-CAR-KGM and GO mostly self-assemble via the formation of intermolecular hydrogen bonds to form a well-defined layered structure. The mechanical properties of the natural polymer-GO films were improved significantly compared to those of pure natural polymer films. With the addition of 7.5 wt % GO, the tensile strength (TS) and Young's modulus were found to increase by 129.5 and 491.5%, respectively. In addition, the composite films demonstrated high reliability and aging resistance as well as a definite TS after cold and hot shock and ozone aging tests, especially showing a superior ozone resistance. The composite films can potentially be used as biomaterials or packing materials., Competing Interests: The authors declare no competing financial interest.

A copper-catalyzed process for the synthesis of pyrrolo[1,2-a]quinoxalines from readily available α-amino acids and 1-(2-halophenyl)-1H-pyrroles is described. Different functional groups were well tolerated to give the corresponding products.

Two Ru(II) sensitizers TCR-1 and TCR-2 bearing four carboxy anchoring groups were prepared using 4,4',5,5'-tetraethoxycarbonyl-2,2'-bipyridine chelate and 4-(5-hexylthien-2-yl)-2-(3-trifluoromethyl-1H-pyrazol-5-yl)pyridine and 6-t-butyl-1-(3-trifluoromethyl-1H-pyrazol-5-yl)isoquinoline, respectively. Dissolution of these sensitizers in DMF solution afforded a light green solution up to 10(-5) M, for which their color gradually turned red upon further dilution and deposition on the surface of a TiO2 photoanode due to the spontaneous deprotonation of carboxylic acid groups. These sensitizers were characterized using electrochemical means and structural analysis time-dependent density functional theory (TDDFT) simulation and were also subjected to actual device fabrication. The as-fabricated DSC devices showed overall efficiencies η = 6.16% and 6.23% versus their 4,4'-dicarboxy counterparts TFRS-2 and TFRS-52 with higher efficiencies of 7.57% and 8.09%, using electrolyte with 0.2 M LiI additive. Their inferior efficiencies are possibly caused by the combination of blue-shifted absorption on TiO2, inadequate dye loading, and the perpendicularly oriented central carboxy groups.

Here, we report the covalent conjugation of lectin on Fe2O3@Au core@shell nanoparticle (lectin-Fe2O3@Au NP) for T2-weighted magnetic resonance (MR) and X-ray computed tomography (CT) dual-modality imaging. The lectin-Fe2O3@Au NPs are prepared by coupling lectins to the Fe2O3@Au NP surfaces through bifunctional PEG NHS ester disulfide (NHS-PEG-S-S-PEG-NHS) linkers. After the nonspecific adsorption sites on the nanoparticle surface are blocked by thiolated PEG (PEG-SH), the lectin-Fe2O3@Au NPs exhibit excellent stability in biological medium and inappreciable cytotoxicity. A series of in vitro and in vivo experiments were then carried out for evaluating the capabilities of three selected lectin (ConA, RCA and WGA)-Fe2O3@Au NPs. The results revealed that the lectin-Fe2O3@Au NPs had a capacity not only for dual mode MR and CT imaging in vitro but also for MR and CT imaging of colorectal cancer in vivo. The experimental results also suggest that lectin could be used as tumor targeting ligand for synthesizing nanoparticle-based contrast agents.

Because of their thermodynamic instability, their sophisticated formation, and their high reactivity, only three textbook examples of Al(I)/Ga(I) subhalides have been crystallized so far: Al(4)Br(4), Al(4)I(4), and Ga(8)I(8). Here, we present the formation and structural characterization of molecular Ga(8)Br(8) species. The different structures of Ga(8)I(8) and Ga(8)Br(8) are discussed with regard to their different formation conditions and their different thermodynamic stability based on results from DFT calculations. Structural as well as thermodynamic properties of Ga(8)I(8) and Ga(8)Br(8) are strongly related to the low-temperature modifications beta-Ga and gamma-Ga. Therefore, our fruitful hypothesis about the fundamental relation between structure and energy of a number of metalloid clusters and the corresponding element modifications is now supported by two binary Ga(I)-halide compounds.

The treatment of a slurry of an equimolar mixture of [Sn(edt)(2)] (edt = ethane-1,2- dithiolate) and [Et(4)N]Cl.xH(2)O with CuI in the presence of PPh(3) gave a tetranuclear compound, [Sn(edt)(2)Cl(mu-I)(mu(3)-I)(CuPPh(3))(3)] (1), which consists of a rectangular-pyramidal [Sn(edt)(2)Cl](-) moiety ligated by three [Cu(PPh(3))](+) fragments via the sulfur atoms of the edt(2-) ligands. The treatment of a slurry of [Sn(edt)(2)] and excess [Et(4)N]Br with [Cu(MeCN)(4)][PF(6)] in the presence of PPh(3) afforded a pentanuclear compound, [Sn(edt)(2)(mu-Br)(2)(mu(3)-Br)(2)(CuPPh(3))(4)] (2), which comprises two [(CuPPh(3))(2)(mu-Br)](+) fragments symmetrically ligating an octahedral trans-[Sn(edt)(2)Br(2)](2-) moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)(2)] with [Cu(MeCN)(4)][PF(6)] and PPh(3) in a mixed MeCN/CH(2)Cl(2) solution yielded a novel octanuclear compound, [{Sn(edt)(2)}(3)(mu-OH)(3)Cu(5)(PPh(3))(8)][PF(6)](2) (3), which may be described as a triangular [{Sn(edt)(2)}(3)(mu-OH)(3)](3-) core chelated by three [Cu(PPh(3))(2)](+) species and capped by two [Cu(PPh(3))](+) species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH(2)Cl(2) solution at room temperature. Upon excitation at lambda > 360 nm, these compounds are luminescent in CH(2)Cl(2) solution with emissions having maxima at 422, 515, and 494 nm, respectively.