Pore Space Partition Synthetic Strategy in Imine-linked Multivariate Covalent Organic Frameworks.

Partitioning the pores of covalent organic frameworks (COFs) is an attractive strategy for introducing microporosity and achieving new functionality, but it is technically challenging to achieve. Herein, we report a simple strategy for partitioning the micropores/mesopores of multivariate COFs. Our approach relies on the predesign and synthesis of multicomponent COFs through imine condensation reactions with aldehyde groups anchored in the COF pores, followed by inserting additional symmetric building blocks (with C2 or C3 symmetries) as pore partition agents. This approach allowed tetragonal or hexagonal pores to be partitioned into two or three smaller micropores, respectively. The synthesized library of pore-partitioned COFs was then applied for the capture of iodine pollutants (i.e., I2 and CH3I). This rich inventory allowed deep exploration of the relationships between the COF adsorbent composition, pore architecture, and adsorption capacity for I2 and CH3I capture under wide-ranging conditions. Notably, one of our developed pore-partitioned COFs (COF 3-2P) exhibited greatly enhanced dynamic I2 and CH3I adsorption performances compared to its parent COF (COF 3) in breakthrough tests, setting a new benchmark for COF-based adsorbents. Results present an effective design strategy toward functional COFs with tunable pore environments, functions, and properties.

Palladium(II) Modulation Enhances the Water Stability and Aqueous 99TcO4-/ReO4- Removal Performance of Metal-Organic Frameworks.

Improving the water stability of metal-organic frameworks (MOFs) is essential for their use in water pollution treatment and environmental remediation, though it remains technically challenging. Herein, we report a novel cationic MOF constructed with [Th6O4(OH)4(COO)12] units and [CoN4·Cl2] units possessing a ftw-type topology (denoted as 1-Th-Co). 1-Th-Co itself exhibited poor water stability but excellent stability following a palladium(II) modulation strategy. Experimental studies reveal that Co(II) ions in 1-Th-Co were replaced by Pd(II) ions through cation exchange in N,N-diethylformamide (yielding 1-Th-Pd). The planar PdN4 units in 1-Th-Pd were responsible for improving the water stability of the framework. As a result, 1-Th-Pd offered excellent stability, fast adsorption kinetics, and high removal ratios for 99TcO4- and ReO4- (as a 99TcO4- surrogate) in contaminated water. When used in packed columns, 1-Th-Pd can dynamically capture ReO4- from groundwater. This work provides a new avenue for improving the water stability of MOFs, offering new vistas for the decontamination of aqueous solutions containing 99TcO4- and ReO4-.

Modulating Anion Nanotraps via Halogenation for High-Efficiency 99TcO4-/ReO4- Removal under Wide-Ranging pH Conditions.

Efficient and sustainable methods for 99TcO4- removal from acidic nuclear waste streams, contaminated water, and highly alkaline tank wastes are highly sought after. Herein, we demonstrate that ionic covalent organic polymers (iCOPs) possessing imidazolium-N+ nanotraps allow the selective adsorption of 99TcO4- under wide-ranging pH conditions. In particular, we show that the binding affinity of the cationic nanotraps toward 99TcO4- can be modulated by tuning the local environment around the nanotraps through a halogenation strategy, thereby enabling universal pH 99TcO4- removal. A parent iCOP-1 possessing imidazolium-N+ nanotraps showed fast kinetics (reaching adsorption equilibrium in 1 min), a high adsorption capacity (up to 1434.1 ± 24.6 mg/g), and exceptional selectivity for 99TcO4- and ReO4- (nonradioactive analogue of 99TcO4-) removal in contaminated water. By introducing F groups near the imidazolium-N+ nanotrap sites (iCOP-2), a ReO4- removal efficiency over 58% was achieved in 60 min in 3 M HNO3 solution. Further, introduction of larger Br groups near the imidazolium-N+ binding sites (iCOP-3) imparted a pronounced steric effect, resulting in exceptional adsorption performance for 99TcO4- under super alkaline conditions and from low-activity waste streams at US legacy Hanford nuclear sites. The halogenation strategy reported herein guides the task-specific design of functional adsorbents for 99TcO4- removal and other applications.

Tuning Local Charge Distribution in Multicomponent Covalent Organic Frameworks for Dramatically Enhanced Photocatalytic Uranium Extraction.

Optimizing the electronic structure of covalent organic framework (COF) photocatalysts is essential for maximizing photocatalytic activity. Herein, we report an isoreticular family of multivariate COFs containing chromenoquinoline rings in the COF structure and electron-donating or withdrawing groups in the pores. Intramolecular donor-acceptor (D-A) interactions in the COFs allowed tuning of local charge distributions and charge carrier separation under visible light irradiation, resulting in enhanced photocatalytic performance. By optimizing the optoelectronic properties of the COFs, a photocatalytic uranium extraction efficiency of 8.02 mg/g/day was achieved using a nitro-functionalized multicomponent COF in natural seawater, exceeding the performance of all COFs reported to date. Results demonstrate an effective design strategy towards high-activity COF photocatalysts with intramolecular D-A structures not easily accessible using traditional synthetic approaches.

Prolyl hydroxylase 2 is dispensable for homeostasis of intestinal epithelium in mice.

Prolyl hydroxylases (PHD1-3) hydroxylate hypoxia inducible factor α (HIFα), leading to HIFα ubiquitination and degradation. Recent studies indicated that administration of generic inhibitors of PHDs improved mice colitis, suggesting that suppression of PHD activity by these inhibitors may be a potential strategy for the treatment of inflammatory bowel diseases. However, the exact role of each member of PHD family in homeostasis of intestinal epithelium remains elusive. The aim of this work is to study the possible role of PHD2 by using mice with genetic ablation of Phd2 in intestinal epithelial cells (IECs). We found that deletion of PHD2 in IECs did not lead to spontaneous enteritis or colitis in mice. Deletion of PHD2 in IECs did not confer upon mice higher susceptibility to dextran sodium sulfate-induced colitis. Furthermore, in a colitis-associated colon cancer model, the PHD2-conditional knockout mice had similar susceptibility to azoxymethane (AOM)-induced colonic tumorigenesis as control mice did. Our results suggest that PHD2 is dispensable for maintenance of intestinal epithelium homeostasis in mice.

Secondary metal ion-induced electrochemical reduction of U(VI) to U(IV) solids.

Recent studies have shown that aqueous U(VI) ions can be transformed into U(VI) precipitates through electrocatalytic redox reactions for uranium recovery. However, there have been no reports of U(IV) solids, such as UO2, using electrochemical methods under ambient conditions since low-valence states of uranium are typically oxidized to U(VI) by O2 or H2O2. Here we developed a secondary metal ion-induced strategy for electrocatalytic production of U(IV) solids from U(VI) solutions using a catalyst consisting of atomically dispersed gallium on hollow nitrogen-doped carbon capsules (Ga-Nx-C). This method relies on the presence of secondary metal ions, e.g., alkaline earth metals, transition metals, lanthanide metals, and actinide metals, which promote the generation of UO2 or bimetallic U(IV)-containing oxides through a two-electron transfer process. No U(IV) solid products were generated in the presence of alkali metal ions. Mechanistic studies revealed that the strong binding affinity between U(IV) and alkaline earth metals (Ca2+/Mg2+/Sr2+/Ba2+), transition metals (Ni2+/Zn2+/Pb2+/Fe3+, etc.) and lanthanide/actinide metals (Ce4+/Eu3+/Th4+/La3+) suppressed re-oxidation of U(IV) to U(VI), leading to the generation of U(IV)O2 and Mx(M = Ce, Eu, Th, La)U(IV)yO2. This work provides fundamental insights into the electrochemical behavior of uranium in aqueous media, whilst guiding uranyl capture from nuclear waste and contaminated water.

Single-Molecule Traps in Covalent Organic Frameworks for Selective Capture of C2H2 from C2H4-Rich Gas Mixtures.

Removing trace amounts of acetylene (C2H2) from ethylene (C2H4)-rich gas mixtures is vital for the supply of high-purity C2H4 to the chemical industry and plastics sector. However, selective removal of C2H2 is challenging due to the similar physical and chemical properties of C2H2 and C2H4. Here, we report a "single-molecule trap" strategy that utilizes electrostatic interactions between the one-dimensional (1D) channel of a covalent organic framework (denoted as COF-1) and C2H2 molecules to massively enhance the adsorption selectivity toward C2H2 over C2H4. C2H2 molecules are immobilized via interactions with the O atom of C=O groups, the N atom of C≡N groups, and the H atom of phenyl groups in 1D channels of COF-1. Due to its exceptionally high affinity for C2H2, COF-1 delivered a remarkable C2H2 uptake of 7.97 cm3/g at 298 K and 0.01 bar, surpassing all reported COFs and many other state-of-the-art adsorbents under similar conditions. Further, COF-1 demonstrated outstanding performance for the separation of C2H2 and C2H4 in breakthrough experiments under dynamic conditions. COF-1 adsorbed C2H2 at a capacity of 0.17 cm3/g at 2,000 s/g when exposed to 0.5 ml/min C2H4-rich gas mixture (99% C2H4) at 298 K, directly producing high-purity C2H4 gas at a rate of 3.95 cm3/g. Computational simulations showed that the strong affinity between C2H2 and the single-molecule traps of COF-1 were responsible for the excellent separation performance. COF-1 is also robust, providing a promising new strategy for the efficient removal of trace amounts of C2H2 in practical C2H4 purification.

A family case report of parathyroid carcinoma associated with CDC73 mutation in hyperparathyroidism-jaw tumor syndrome.

Background: Hereditary primary hyperparathyroidism (PHPT) accounts for 5-10% of all PHPT cases, necessitating genetic testing for diagnosis and management. Among these, hyperparathyroidism-jaw tumor syndrome (HPT-JT) is an autosomal dominant disorder caused by CDC73 mutations with variable clinical presentations and incomplete symptoms. Case summary: The proband, diagnosed with PHPT, underwent parathyroidectomy at the age of 41 with pathological examination of parathyroid carcinoma (PC). Hereditary PHPT was initially suspected due to the early-onset PHPT and family history. Genetic testing identified a heterozygous CDC73 mutation, NM_024529.4: c. 687_688delAG (p. Arg229Serfs*37). Even in the absence of jaw tumors, the diagnosis of HPT-JT was confirmed based on the discovery of renal cysts. A secondary thyroidectomy was performed to reduce the risk of recurrence. Conclusion: Genetic testing is strongly recommended in cases of early-onset PHPT, family history, jaw tumors, renal and uterine involvement, atypical parathyroid tumors, and PC. This testing provides valuable information for personalized management, and counseling is available for affected families.

Engineering the pore environment of antiparallel stacked covalent organic frameworks for capture of iodine pollutants.

Radioiodine capture from nuclear fuel waste and contaminated water sources is of enormous environmental importance, but remains technically challenging. Herein, we demonstrate robust covalent organic frameworks (COFs) with antiparallel stacked structures, excellent radiation resistance, and high binding affinities toward I2, CH3I, and I3- under various conditions. A neutral framework (ACOF-1) achieves a high affinity through the cooperative functions of pyridine-N and hydrazine groups from antiparallel stacking layers, resulting in a high capacity of ~2.16 g/g for I2 and ~0.74 g/g for CH3I at 25 °C under dynamic adsorption conditions. Subsequently, post-synthetic methylation of ACOF-1 converted pyridine-N sites to cationic pyridinium moieties, yielding a cationic framework (namely ACOF-1R) with enhanced capacity for triiodide ion capture from contaminated water. ACOF-1R can rapidly decontaminate iodine polluted groundwater to drinking levels with a high uptake capacity of ~4.46 g/g established through column breakthrough tests. The cooperative functions of specific binding moieties make ACOF-1 and ACOF-1R promising adsorbents for radioiodine pollutants treatment under practical conditions.

Functional Carbon Capsules Supporting Ruthenium Nanoclusters for Efficient Electrocatalytic 99 TcO4 - /ReO4 - Removal from Acidic and Alkaline Nuclear Wastes.

The selective removal of the ß-emitting pertechnetate ion (99 TcO4 - ) from nuclear waste streams is technically challenging. Herein, a practical approach is proposed for the selective removal of 99 TcO4 - (or its surrogate ReO4 - ) under extreme conditions of high acidity, alkalinity, ionic strength, and radiation field. Hollow porous N-doped carbon capsules loaded with ruthenium clusters (Ru@HNCC) are first prepared, then modified with a cationic polymeric network (R) containing imidazolium-N+ units (Ru@HNCC-R) for selective 99 TcO4 - and ReO4 - binding. The Ru@HNCC-R capsules offer high binding affinities for 99 TcO4 - /ReO4 - under wide-ranging conditions. An electrochemical redox process then transforms adsorbed ReO4 - to bulk ReO3 , delivering record-high removal capacities, fast kinetics, and excellent long-term durability for removing ReO4 - (as a proxy for 99 TcO4 - ) in a 3 m HNO3 , simulated nuclear waste-Hanford melter recycle stream and an alkaline high-level waste stream (HLW) at the U.S. Savannah River Site (SRS). In situ Raman and X-ray absorption spectroscopy (XAS) analyses showed that adsorbed Re(VII) is electrocatalytically reduced on Ru sites to a Re(IV)O2 intermediate, which can then be re-oxidized to insoluble Re(VI)O3 for facile collection. This approach overcomes many of the challenges associated with the selective separation and removal of 99 TcO4 - /ReO4 - under extreme conditions, offering new vistas for nuclear waste management and environmental remediation.

Modulating Uranium Extraction Performance of Multivariate Covalent Organic Frameworks through Donor-Acceptor Linkers and Amidoxime Nanotraps.

Covalent organic frameworks (COFs) can be designed to allow uranium extraction from seawater by incorporating photocatalytic linkers. However, often sacrificial reagents are required for separating photogenerated charges which limits their practical applications. Herein, we present a COF-based adsorption-photocatalysis strategy for selective removal of uranyl from seawater in the absence of sacrificial reagents. A series of ternary and quaternary COFs were synthesized containing the electron-rich linker 2,4,6-triformylphloroglucinol as the electron donor, the electron-deficient linker 4,4'-(thiazolo[5,4-d]thiazole-2,5-diyl)dibenzaldehyde as the acceptor, and amidoxime nanotraps for selective uranyl capture (with the quaternary COFs incorporating [2,2'-bipyridine-5,5'-diamine-Ru(Bp)2]Cl2 as a secondary photosensitizer). The ordered porous structure of the quaternary COFs ensured efficient mass transfer during the adsorption-photocatalysis capture of uranium from seawater samples, with photocatalytically generated electrons resulting in the reduction of adsorbed U(VI) to U(IV) in the form of UO2. A quaternary COF, denoted as COF 2-Ru-AO, possessed a high uranium uptake capacity of 2.45 mg/g/day in natural seawater and good anti-biofouling abilities, surpassing most adsorbents thus far. This work shows that multivariate COF adsorption-photocatalysts can be rationally engineered to work efficiently and stably without sacrificial electron donors, thus opening the pathway for the economic and efficient extraction of uranium from the earth's oceans.

Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance.

Covalent organic frameworks (COFs) represent an emerging class of organic photocatalysts. However, their complicated structures lead to indeterminacy about photocatalytic active sites and reaction mechanisms. Herein, we use reticular chemistry to construct a family of isoreticular crystalline hydrazide-based COF photocatalysts, with the optoelectronic properties and local pore characteristics of the COFs modulated using different linkers. The excited state electronic distribution and transport pathways in the COFs are probed using a host of experimental methods and theoretical calculations at a molecular level. One of our developed COFs (denoted as COF-4) exhibits a remarkable excited state electron utilization efficiency and charge transfer properties, achieving a record-high photocatalytic uranium extraction performance of ~6.84 mg/g/day in natural seawater among all techniques reported so far. This study brings a new understanding about the operation of COF-based photocatalysts, guiding the design of improved COF photocatalysts for many applications.

Highly Efficient Electrocatalytic Uranium Extraction from Seawater over an Amidoxime-Functionalized In-N-C Catalyst.

Seawater contains uranium at a concentration of ≈3.3 ppb, thus representing a rich and sustainable nuclear fuel source. Herein, an adsorption-electrocatalytic platform is developed for uranium extraction from seawater, comprising atomically dispersed indium anchored on hollow nitrogen-doped carbon capsules functionalized with flexible amidoxime moieties (In-Nx -C-R, where R denotes amidoxime groups). In-Nx -C-R exhibits excellent uranyl capture properties, enabling a uranium removal rate of 6.35 mg g-1 in 24 h, representing one of the best uranium extractants reported to date. Importantly, In-Nx -C-R demonstrates exceptional selectivity for uranium extraction relative to vanadium in seawater (8.75 times more selective for the former). X-ray absorption spectroscopy (XAS) reveals that the amidoxime groups serve as uranyl chelating sites, thus allowing selective adsorption over other ions. XAS and in situ Raman results directly indicate that the absorbed uranyl can be electrocatalytically reduced to an unstable U(V) intermediate, then re-oxidizes to U(VI) in the form of insoluble Na2 O(UO3 ·H2 O)x for collection, through reversible single electron transfer processes involving InNx sites. These results provide detailed mechanistic understanding of the uranium extraction process at a molecular level. This work provides a roadmap for the adsorption-electrocatalytic extraction of uranium from seawater, adding to the growing suite of technologies for harvesting valuable metals from the earth's oceans.

Surfactant-assisted adsorption of uranyl ions in aqueous solution on TiO2/polythiophene nanocomposite.

In this work, hexadecyltrimethylammonium-bromide (HTAB)-modified polythiophene (PTh)/TiO2 nanocomposite (HTAB/PTh/TiO2) was applied to remove uranyl ions (UO22+). FT-IR, XRD, ζ potential, TGA, SEM, and XPS were utilized to obtain the chemical and physical properties of HTAB/PTh/TiO2. The effects of HTAB content, preparation temperature, and adsorption conditions on UO22+ removal were investigated comprehensively. And the UO22+ adsorption process on HTAB/PTh/TiO2 was fitted to the Sips model with a saturated adsorption capacity of 234.74 mg/g, which was 6 times over TiO2. The results suggested that the surfactant of HTAB can significantly improve the adsorption ability of TiO2 for UO22+ ions. This work provides a strategy of surfactant modification for enhancing the separation and recovery ability of adsorbent toward UO22+ in the radioactive wastewater.

Functionalized Iron-Nitrogen-Carbon Electrocatalyst Provides a Reversible Electron Transfer Platform for Efficient Uranium Extraction from Seawater.

Uranium extraction from seawater provides an opportunity for sustainable fuel supply to nuclear power plants. Herein, an adsorption-electrocatalysis strategy is demonstrated for efficient uranium extraction from seawater using a functionalized iron-nitrogen-carbon (Fe-Nx -C-R) catalyst, comprising N-doped carbon capsules supporting FeNx single-atom sites and surface chelating amidoxime groups (R). The amidoxime groups bring hydrophilicity to the adsorbent and offer surface-specific binding sites for UO2 2+ capture. The site-isolated FeNx centres reduce adsorbed UO2 2+ to UO2 + . Subsequently, through electrochemical reduction of the FeNx sites, unstable U(V) ions are reoxidized to U(VI) in the presence of Na+ resulting in the generation of solid Na2 O(UO3 ·H2 O)x , which can easily be collected. Fe-Nx -C-R reduced the uranium concentration in seawater from ≈3.5 ppb to below 0.5 ppb with a calculated capacity of ≈1.2 mg g-1 within 24 h. To the best of the knowledge, the developed system is the first to use the adsorption of uranyl ions and electrodeposition of solid Na2 O(UO3 .H2 O)x for the extraction of uranium from seawater. The important discoveries guide technology development for the efficient extraction of uranium from seawater.

Knockdown of IRE1ɑ suppresses metastatic potential of colon cancer cells through inhibiting FN1-Src/FAK-GTPases signaling.

The inositol-requiring enzyme 1α (IRE1α) is an endoplasmic reticulum (ER)-resident transmembrane protein and senses cellular unfolded/misfolded proteins. Upon activation, IRE1α removes a 26-bp nucleotide from the mRNA encoding X-box binding protein (XBP) 1 to generate a spliced active form of this transcription factor (XBP1s). Though IRE1α is implicated in development of cancer, the role and underlying mechanism remain unclear. Here, we demonstrate that IRE1α regulates colon cancer cell metastasis through regulating the expression of fibronectin-1 (FN1). We found that knockdown of IRE1α inhibited colon cancer cell migration and invasion in vitro and metastasis in vivo. Knockdown of IRE1α decreased the formation of XBP1s and attenuated the expression of FN1, leading to inhibition of phosphorylation of Src and FAK and inactivation the downstream effector GTPases including RhoA, Rac1 and CDC42. Addition of exogenous FN1 reversed Src/FAK phosphorylation and cell migration inhibited by IRE1α knockdown. We found that XBP1s bound FN1 promoter and acted as a transcription factor to initiate FN1 expression. Our results suggest that IRE1α modulates metastatic potential of colon cancer cells through regulating the expression of FN1.

[A relationship between cyclooxygenase-2 expression and tumor angiogenesis in experimental rat liver carcinogenesis].

OBJECTIVE: To explore the relationship between the expression of cyclooxygenase-2 (COX-2) and angiogenesis in hepatocellular carcinoma. METHODS: Forty Wistar rats were divided into two groups: a model group (30 rats) and a normal group (10 rats). Hepatocellular carcinoma was induced with 0.01% diethylnitrosamine (DEN) in the model group rats. The rats were sacrificed in batches at the 6th, 12th and 18th week of the experiment. Histological sections of liver tissues were made using routine methods. The expressions of COX-2, VEGF, VEGFR-2/KDR, and MMP-2 protein in the liver tissues were evaluated using immunohistochemical methods. RESULTS: In liver sections from the model group there were marked pathological changes (steatosis, cell infiltration, cirrhosis and liver cancer). The expressions of VEGF, VEGFR-2/KDR, and MMP-2 in those liver tissues were remarkably increased during the hepatocellular carcinogenesis. Microvessel density (MVD) was also obviously raised during the process of the cancer development. There was a direct correlation between the MVD and VEGF/KDR/MMP-2 (r=0.858, 0.788, 0.684, respectively; all P less than 0.01). There was also a direct correlation between the COX-2 and VEGF/KDR/MMP-2/MVD (r=0.771, 0.599, 0.690, 0.788, respectively; all P < 0.01). CONCLUSION: COX-2 can promote tumor angiogenesis during rat hepatocellular carcinogenesis. This may be one of the mechanisms in which COX-2 promotes carcinomas.