Dual Temperature- and pH-Dependent Self-Assembly of Cellulose-Based Copolymer with a Pair of Complementary Grafts

Thermo- and pH-responsive micellization of HEC-g-(PNiPAAm&PAA) (CNiPAa) was studied. This binary graft copolymer CNipAa was synthesized via successive radical polymerization of N-isopropylacrylamide (NiPAAm) and acrylic acid (AA) from hydroxyethyl cellulose (HEC) as the backbone. The copolymers are able to self-assembly into a trinity of micelles of different structures by combined pH and temperature stimuli:  (1) at 30 °C and a low pH range (<4.6), forming the micelles with a core of PAA/PNiPAAm due to hydrogen-bonding interaction between the two grafts; (2) in basic solution and at a temperature above the LCST of PNipAAm, hydrophobic aggregation of PNiPAAm grafts leading to PNiPAAm-core micelles with a compound shell of PAA/HEC; (3) forming a three-layer micellar structure due to the further response of the PNipAAm-core micelles to pH change. These three forms of micelles were examined by TEM, AFM, and DLS/SLS, and the corresponding forming mechanisms were clarified. As far as we know, it is the first report on so diverse micellization behavior of graft copolymers

Dihydrogen Phosphate Clusters: Trapping H₂PO₄^– Tetramers and Hexamers in Urea-Functionalized Molecular Crystals

Co-crystallization of two urea-functionalized ligands with tetrabutylammonium (TBA) dihydrogen phosphate resulted in the isolation of discrete (H₂PO₄^–)₄ and (H₂PO₄^–)₆ clusters stabilized in the crystalline state by multiple urea hydrogen bonds. Structural analysis by single-crystal X-ray diffraction, combined with a Cambridge Structural Database survey of (H₂PO₄^–)_<i>n</i> aggregates, established that these clusters display unique topologies and hydrogen-bonding connectivities

One-Pot Preparation of Arylalkynes by a Tandem Catalytic Iodination of Arenes and Palladium-Catalyzed Coupling of Iodoarenes with Terminal Alkynes

Iodination of activated arenes by air-oxidation is carried out in the presence of catalytic bismuth salts at room temperature. Subsequently, the formed iodoarenes react with terminal alkynes to give arylalkynes under a selected palladium-catalyzed coupling condition in the same pot

Dihydrogen Phosphate Clusters: Trapping H₂PO₄^– Tetramers and Hexamers in Urea-Functionalized Molecular Crystals

Co-crystallization of two urea-functionalized ligands with tetrabutylammonium (TBA) dihydrogen phosphate resulted in the isolation of discrete (H₂PO₄^–)₄ and (H₂PO₄^–)₆ clusters stabilized in the crystalline state by multiple urea hydrogen bonds. Structural analysis by single-crystal X-ray diffraction, combined with a Cambridge Structural Database survey of (H₂PO₄^–)_<i>n</i> aggregates, established that these clusters display unique topologies and hydrogen-bonding connectivities

Desymmetrized Vertex Design for the Synthesis of Covalent Organic Frameworks with Periodically Heterogeneous Pore Structures

Two novel porous 2D covalent organic frameworks (COFs) with periodically heterogeneous pore structures were successfully synthesized through desymmetrized vertex design strategy. Condensation of <i>C</i>_2<i>v</i> symmetric 5-(4-formylphenyl)­isophthalaldehyde or 5-((4-formylphenyl)­ethylene)­isophthalaldehyde with linear hydrazine linker under the solvothermal or microwave heating conditions yields crystalline 2D COFs, <b>HP-COF-1</b> and <b>HP-COF-2</b>, with high specific surface areas and dual pore structures. PXRD patterns and computer modeling study, together with pore size distribution analysis confirm that each of the resulting COFs exhibits two distinctively different hexagonal pores. The structures were characterized by FT-IR, solid state ¹³C NMR, gas adsorption, SEM, TEM, and theoretical simulations. Such rational design and synthetic strategy provide new possibilities for preparing highly ordered porous polymers with heterogeneous pore structures

Sodium Sulfate Separation from Aqueous Alkaline Solutions via Crystalline Urea-Functionalized Capsules: Thermodynamics and Kinetics of Crystallization

The thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions have been measured in the 15–55 °C temperature range for a fundamental understanding of the elementary steps involved in this sulfate separation method. The use of radiolabeled Na₂³⁵SO₄ provided a practical way to monitor the sulfate concentration in solution by β liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na₂SO₄(L1)₂­(H₂O)₄ capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. This corresponds to 77–91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 °C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 °C, 63% and 75% of sulfate was removed from solution within 8 and 24 h, respectively. These results indicate the capsule crystallization method is a viable approach to sulfate separation from nuclear wastes

DataSheet1_A novel signature based on pyroptosis-related genes for predicting prognosis and treatment response in prostate cancer patients.docx

Background: Pyroptosis is a form of programmed cell death accompanied by specific inflammatory and immune responses, and it is closely related to the occurrence and progression of various cancers. However, the roles of pyroptosis-related genes (PRGs) in the prognosis, treatment response, and tumor microenvironment (TME) of prostate cancer (PCa) remain to be investigated.Methods: The mRNA expression data and clinical information of PCa patients were obtained from the Cancer Genome Atlas database (TCGA) and the cBioPortal for Cancer Genomics website, and the 52 PRGs were obtained from the published papers. The univariate, multivariate, and LASSO Cox regression algorithms were used to obtain prognostic hub PRGs. Meanwhile, qRT-PCR was used to validate the expression of hub genes between PCa lines and normal prostate epithelial cell lines. We then constructed and validated a risk model associated with the patient’s disease-free survival (DFS). Finally, the relationships between risk score and clinicopathological characteristics, tumor immune microenvironment, and drug treatment response of PCa were systematically analyzed.Results: A prognostic risk model was constructed with 6 hub PRGs (CHMP4C, GSDMB, NOD2, PLCG1, CYCS, GPX4), and patients were divided into high and low-risk groups by median risk score. The risk score was confirmed to be an independent prognostic factor for PCa in both the training and external validation sets. Patients in the high-risk group had a worse prognosis than those in the low-risk group, and they had more increased somatic mutations, higher immune cell infiltration and higher expression of immune checkpoint-related genes. Moreover, they were more sensitive to cell cycle-related chemotherapeutic drugs and might be more responsive to immunotherapy.Conclusion: In our study, pyroptosis played a significant role in the management of the prognosis and tumor microenvironment of PCa. Meanwhile, the established model might help to develop more effective individual treatment strategies.</p

DataSheet_1_Overexpression of CDCA8 Predicts Poor Prognosis and Promotes Tumor Cell Growth in Prostate Cancer.zip

Human cell division cycle-related protein 8 (CDCA8) is an essential component of the vertebrate chromosomal passenger complex (CPC). CDCA8 was confirmed to play a role in promoting malignant tumor progression. However, the exact function of CDCA8 in the development and progression of prostate cancer (PCa) remains unclear. In this study, the database GSE69223 was downloaded by the gene expression omnibus (GEO) database, as well as CDCA8 expression differences in multiple tumor tissues and normal tissues were detected by The Cancer Genome Atlas (TCGA), TIMER, Oncomine, and Ualcan databases. Kaplan-Meier and Cox regression methods were used to analyze the correlation between CDCA8 expression and prognosis in PCa. We confirmed the expression of CDCA8 in PCa tissues by HPA. We also analyzed the association of CDCA8 expression with PCa clinical characteristics in the TCGA database. To further understand the role of CDCA8 in PCa, we assessed the effects of CDCA8 on PCa cell growth, proliferation, and migration in vitro studies. As a result, CDCA8 was significantly overexpressed in PCa cells compared with normal prostate cells. High CDCA8 expression predicts poor prognosis in PCa patients, and CDCA8 expression was higher in high-grade PCa. In addition, silencing of CDCA8 significantly inhibited PCa cell proliferation and migration. In summary, CDCA8 promoted the proliferation and migration of PCa cells.</p

Pressure-Quenched Superconductivity in Weyl Semimetal NbP Induced by Electronic Phase Transitions under Pressure

The TaAs family (NbAs, TaAs, NbP, TaP) are kinds of Weyl semimetals with lots of novel properties, thus attracting considerable attention in recent years. Here, we systematically studied the Weyl semimetal NbP up to 72 GPa through the resistivity, Raman spectra, X-ray diffraction measurements, and first-principles density functional theory (DFT) calculations. A pressure-induced semimetal–metal transition was observed at ∼36 GPa, which was further confirmed by the DFT calculations. With further compression up to 52 GPa, a superconducting state was observed. Interestingly, the Tc increases significantly upon decompression and shows a dome-shaped trend as a function of pressure. Surprisingly, the pressure-induced superconductivity can be quenched to ambient pressure, and all transitions under pressure do not involve any structural change. Our work not only depicts a phase diagram of the NbP system under high pressure but also provides a new experimental insight for superconductivity in Weyl semimetals