Closed Aromatic Tubes-Capsularenes.

In this study, we describe a synthetic method for incorporating arenes into closed tubes that we name capsularenes. First, we prepared vase-shaped molecular baskets 4-7. The baskets comprise a benzene base fused to three bicycle[2.2.1]heptane rings that extend into phthalimide (4), naphthalimide (6), and anthraceneimide sides (7), each carrying a dimethoxyethane acetal group. In the presence of catalytic trifluoroacetic acid (TFA), the acetals at top of 4, 6 and 7 change into aliphatic aldehydes followed by their intramolecular cyclization into 1,3,5-trioxane (1 H NMR spectroscopy). Such ring closure is nearly a quantitative process that furnishes differently sized capsularenes 1 (0.7×0.9 nm), 8 (0.7×1.1 nm;) and 9 (0.7×1.4 nm;) characterized by X-Ray crystallography, microcrystal electron diffraction, UV/Vis, fluorescence, cyclic voltammetry, and thermogravimetry. With exceptional rigidity, unique topology, great thermal stability, and perhaps tuneable optoelectronic characteristics, capsularenes hold promise for the construction of novel organic electronic devices.

Production of H2S with a Novel Short-Process for the Removal of Heavy Metals in Acidic Effluents from Smelting Flue-Gas Scrubbing Systems.

Direct sulfidation using a high concentration of H2S (HC-H2S) has shown potential for heavy metals removal in various acidic effluents. However, the lack of a smooth method for producing HC-H2S is a critical challenge. Herein, a novel short-process hydrolysis method was developed for the on-site production of HC-H2S. Near-perfect 100% efficiency and selectivity were obtained via CS2 hydrolysis over the ZrO2-based catalyst. Meanwhile, no apparent residual sulfur/sulfate poisoning was detected, which guaranteed long-term operation. The coexistence of CO2 in the products had a negligible effect on the complete hydrolysis of CS2. H2S production followed a sequential hydrolysis pathway, with the reactions for CS2 adsorption and dissociation being the rate-determining steps. The energy balance indicated that HC-H2S production was a mildly exothermic reaction, and the heat energy could be maintained at self-balance with approximately 80% heat recovery. The batch sulfidation efficiencies for As(III), Hg(II), Pb(II), and Cd(II) removal were over 99.9%, following the solubilities (Ksp) of the corresponding metal sulfides. CO2 in the mixed gas produced by CS2 hydrolysis did not affect heavy metals sulfidation due to the presence of abundant H+. Finally, a pilot-scale experiment successfully demonstrated the practical effects. Therefore, this novel on-site HC-H2S production method adequately achieved heavy metals removal requirements in acidic effluents.

High Interleukin-6 Levels Are Associated With Large-Artery Atherosclerotic Stroke.

OBJECTIVES: Interleukins (ILs) play several critical roles in modulating the occurrence and development of atherosclerosis-related diseases. We aimed to investigate the associations between ILs and the diagnosis, progress, and functional outcome in patients with large-artery atherosclerotic (LAA) stroke. METHODS: Plasma levels of IL-2, IL-4, IL-6, and IL-10 were measured within 24 hours after stroke in 181 patients with first-time LAA stroke and on admission in 181 age-matched and sex-matched controls. NIHSS scores were recorded at admission and on Day 1, Day 2, Day 3, Day 4, and Day 5 after the stroke. Functional outcome was measured by the modified Rankin Scale at 3 months after stroke. Subgroup analyses were compared based on short-term progress within 5 days (ΔNIHSS ≥3) and 3-month unfavorable outcome (modified Rankin Scale >2). Logistic regression analysis adjusted for relevant confounders was performed. RESULTS: IL-6 levels were higher in patients with LAA stroke than in controls [AOR (95% CI), 0.701 (95% CI 0.651-0.748, P <0.001], with an area under the receiver operating characteristic curve (AUC) of 0.701. Higher IL-6 levels were associated with short-term progression [AOR (95% CI), 1.070 (1.009, 1.135), P =0.025], with an AUC value of 0.720. Higher IL-6 levels were associated with unfavorable outcomes [AOR (95% CI), 1.075 (1.002, 1.153), P =0.040], with an AUC value of 0.658. No difference in IL-2, IL-4, or IL-10 was found between the groups. CONCLUSIONS: Plasma levels of IL-6 are higher in patients with LAA stroke and are independently associated with short-term progression and 3-month functional outcomes after stroke.

One-pot encapsulation of luminescent quantum dots synthesized in aqueous solution by amphiphilic polymers.

A simple one-pot polymer encapsulation method is developed for group II-VI semiconductor quantum dots (QDs) synthesized in aqueous solution. The micelles of amphiphilic polymers, such as octadecylamine-modified poly(acrylic acid), capture and encapsulate the QDs when the original hydrophilic ligands, namely 3-mercaptopropionic acid (MPA), capped on the CdTe/CdS core/shell QDs are partially or fully exchanged by the hydrophobic ligands, 1-dodecanethiol. The molar ratio of the amphiphilic polymer to QDs plays a crucial role in determining the final morphology of the encapsulated structures, including the number of QDs encapsulated in one polymeric micelle. Importantly, the polymer coating significantly improves the optical properties of the QDs, which enhances the photoluminescence quantum yield by about 50%. Furthermore, the photostability of the amphiphilic polymer-coated QDs is much better than that of the synthesized QDs capped with MPA.

A Ferroptosis-Related Prognostic Signature Based on Antitumor Immunity and Tumor Protein p53 Mutation Exploration for Guiding Treatment in Patients With Head and Neck Squamous Cell Carcinoma.

Background: Due to the lack of accurate guidance of biomarkers, the treatment of head and neck squamous cell carcinoma (HNSCC) has not been ideal. Ferroptosis plays an important role in tumor suppression and treatment of patients. However, tumor protein p53 (TP53) mutation may promote tumor progression through ferroptosis. Therefore, it is particularly important to mine prognostic-related differentially expressed ferroptosis-related genes (PR-DE-FRGs) in HNSCC to construct a prognostic model for accurately guiding clinical treatment. Methods: First, the HNSCC data obtained from The Cancer Genome Atlas (TCGA) was used to identify PR-DE-FRGs for screening candidate genes to construct a prognostic model. We not only used a variety of methods to verify the accuracy of the model for predicting prognosis but also explored the role of ferroptosis in the development of HNSCC from the perspective of the immune microenvironment and mutation. Finally, we explored the correlation between the prognostic model and clinical treatment and drew a high-precision nomogram to predict the prognosis. Results: Seventeen of the 29 PR-DE-FRGs were selected to construct a prognostic model with good predictive performance. Patients in the low-risk group were found to have a greater number of CD8 + T cells, follicular helper T cells, regulatory T cells, mast cells, T-cell costimulations, and type II interferon responses. A higher tumor mutation burden (TMB) was observed in the low-risk group and was associated with a better prognosis. A higher risk score was found in the TP53 mutation group and was associated with a worse prognosis. The risk score is closely related to the expression of immune checkpoint inhibitors (ICIs)-related genes such as PD-L1 and the IC50 of six chemotherapeutic drugs. The nomogram we constructed performs well in predicting prognosis. Conclusion: Ferroptosis may participate in the progression of HNSCC through the immune microenvironment and TP53 mutation. The model we built can be used as an effective predictor of immunotherapy and chemotherapy effects and prognosis of HNSCC patients.

A simple strategy to design 3-layered Au-TiO2 dual nanoparticles immobilized cellulose membranes with enhanced photocatalytic activity.

Cellulose-based photocatalysts of supported nanoparticles feature high photocatalytic activity but their facile construction and photocatalytic mechanism exploration are highly challenging. Herein, a simple structural design principle and synergistic properties of 3-layered porous cellulose-based membranes are used for catalytic degradation of Rhodamine B in an aqua system. The 3-layered Au-TiO2 cellulose membranes were fabricated through the tape method and the suction filtration process. The composite membranes with strong redox ability, high charge-separation efficiency, and wide absorption range could stimulate the solar-driven plasma evaporation of Au nanoparticles and the photocatalytic function of TiO2 nanoparticles simultaneously. As characterized by Scanning Electron Microscopy, well-defined Au nanoparticles with an average size of 18.24 ±â€¯3.17 nm were uniformly distributed on the TiO2-CM surface. Compared with TiO2-CM, TiO2-Au-CM showed better catalytic degradation of organic dye. This work demonstrated that a simple strategy design of Au-TiO2-CM could efficiently enhance the photocatalytic activity for the degradation of dyes in water.

Customized Borosilicate Bioglass Scaffolds With Excellent Biodegradation and Osteogenesis for Mandible Reconstruction.

Graft reconstruction of the mandible is an important approach that aims at improving the appearance and functionality of defected mandibles. The traditional implant materials are generally bioinert, non-degradable, and that they lack favorable pore structures for cell proliferation, which limit their clinical application. In this study, we used boron-containing bioactive glass which was combined with a three-dimensional (3D) printing technology to construct an osteoinductive implant scaffold, according to the imaging instructions of CT scan on bone defects. Here, the boron-containing bioglass scaffold (B-BGs) was prepared through sol-gel processing and a 3D print technique. Different boron content of borosilicate bioglass was prepared by incorporating B2O3 (molar: 19.4 and 38.8%) into 58S bioglass to replace parts of SiO2. For fabricated mandible implants through three-dimensional 3D printing of B-BGs (size: 8 × 2 mm; pore size: 250 µm) modified with borosilicate bioglass powder and sodium alginate. Notably, the compressive strength of the B-BGs was about 3.8 Mpa, which supported mandibular activity. Subsequently, the excellent biocompatibility of B-BGs was confirmed using cytotoxicity in vitro studies. Finally, data from in vivo experiments demonstrated that the B-BGs could promote bone regeneration and they could almost get completely degraded within 4 weeks. Our results showed that the boron-containing bioglass could repair mandibular defects.

Tuning the allosteric sequestration of anticancer drugs for developing cooperative nano-antidotes.

A dual-cavity basket 16-, holding six γ-aminobutyric acids at its termini, encapsulates variously sized aromatics 2-7+, including four anthracyclines (8+-11+), driven by the hydrophobic effect and hydrogen bonding (HB). In particular, the formation of stable (K = 1012 M-2) anthracycline complexes [(8+-11+)2⊂16-], assembled into nanoparticles, occurred with positive homotropic cooperativity (α = 4K2/K1 = 1.1 ± 0.3 × 102-1.3 ± 0.7 × 103) in PBS medium. Importantly, weakening the first binding event (K1, i.e. by removing HBs) turned the second one (K2) more favorable. The finding is of interest for developing cooperative nano-antidotes acting as biodetoxifying agents.

A highly diastereoselective synthesis of deep molecular baskets.

We describe a preparative method for directing Mizoroki-Heck cyclotrimerization of enantioenriched bromonorbornenes into molecular baskets having increasingly deeper and extendable aromatic cavities. Such diastereoselective cyclotrimerizations of the bromo-olefinic substrates resulted from prevalent ß migratory insertions without the formation of palladacycle intermediate(s). The facile access to multigram quantity of a new series of basket-like hosts clears the way for creating novel supramolecular materials for storage, sequestration and catalysis.

X-ray shielding structural and properties design for the porous transparent BaSO4/cellulose nanocomposite membranes.

Since effective shielding of X-rays was required in medical, aviation and nuclear fields, a novel X-ray shielding BaSO4/cellulose nanocomposite membrane (BSCM) material with porous transparent structure has been designed. The effects of carboxylated nano-BaSO4 (BS) addition on the physical and morphological properties of the cellulose membrane (CM) were investigated. Meanwhile, the influence of X-ray shielding capacity was studied by different layers of composite membranes and the shielding mechanism of the X-ray was also discussed. Scanning electron microscopy (SEM) images displayed the aggregations of BS in the cellulose surface. Fourier transform infrared spectroscopy (FTIR) showed that the incorporation of BS into CM caused molecular interactions between CM and BS. Brunauer-Emmett-Teller (BET) indicated that the load of BS contributed little to the specific surface area and pore size. Meanwhile, the water vapor transmission rates (WVTR) also stayed at the same level before and after the binding of BS. The swelling ratios, weight loss ratios and mechanical property were decreased along with the addition of BS. The radiation shielding ability was enhanced. Therefore, this work was regarded as a possible example that the BSCM was designed as X-ray radiation shielding material or sandwich filler material in the implication of radiation shielding glass.

[Preparation and immunogenicity of silk fibroin/chitosan microspheres for DNA vaccine delivery against infectious bursal disease virus].

To evaluate the immunities of biodegradable microsphere as a release delivery system for DNA vaccine against Infectious Bursal Disease Virus, in our study, silk fibroin/chitosan microsphere adjuvant was prepared with a precipitation/coacervation method. Both glutaraldehyde and Na2SO4 solution were used in cross-linking. No immune chicken were intramuscularly inoculated at 14 day-old and boosted 2 weeks later. The results show that glutaraldehyde destroyed the DNA activity of the vaccine whereas Na2SO4 solution did not. Factors of the chitosan concentration 0.5% (pH 5.0), silk fibroin concentration 0.6%, plasmid DNA (500 microg/mL) dissolved in 2% Na2SO4 solution were optimized to produce microsphere, with a loading capacity of 89.14%. The average particle size of SF-CS/pCI-VP2/4/3 microsphere is 1.98 microm, and it can protect the loading DNA vaccine from DNase I digestion. Data from anti IBDV ELISA antibodies in the serum show that immunization activity of the microsphere groups were generally higher than plasmid vaccine group (P < 0.05), and the SF/CS compound microspheres group was better than that of sole CS microsphere group. The developed SF/CS microspheres are a very promising vaccine delivery system.

Reduced graphene oxide/PAMAM-silver nanoparticles nanocomposite modified electrode for direct electrochemistry of glucose oxidase and glucose sensing.

Reduced graphene oxide/PAMAM-silver nanoparticles nanocomposite (RGO-PAMAM-Ag) was synthesized by self-assembly of carboxyl-terminated PAMAM dendrimer (PAMAM-G3.5) on graphene oxide (GO) as growing template, and in-situ reduction of both AgNO(3) and GO under microwave irradiation. The RGO-PAMAM-Ag nanocomposite was used as a novel immobilization matrix for glucose oxidase (GOD) and exhibited excellent direct electron transfer properties for GOD with the rate constant (K(s)) of 8.59 s(-1). The fabricated glucose biosensor based on GOD electrode modified with RGO-PAMAM-Ag nanocomposite displayed satisfactory analytical performance including high sensitivity (75.72 µA mM(-1) cm(-2)), low detection limit (4.5 µM), an acceptable linear range from 0.032 mM to 1.89 mM, and also preventing the interference of some interfering species usually coexisting with glucose in human blood at the work potential of -0.25 V. These results indicated that RGO-PAMAM-Ag nanocomposite is a promising candidate material for high-performance glucose biosensors.