Construction of Hierarchical Porous UiO-66-Br2@PS/DVB-Packed Columns by High Internal Phase Emulsion Strategy for Enhanced Separation of CF4/N2 and SF6/N2.

Recovery and separation of anthropogenic emissions of electronic specialty gases (F-gases, such as CF4 and SF6) from the semiconductor sector are of critical importance. In this work, the hierarchical porous UiO-66-Br2@PS/DVB-packed column was constructed by a high internal phase emulsions strategy. UiO-66-Br2@PS/DVB exhibits a superior selectivity of CF4/N2 (2.67) and SF6/N2 (3.34) predicted by the IAST due to the diffusion limitation in the micropore and the gas-framework affinity. Especially, UiO-66-Br2@PS/DVB showed significant CF4 and SF6 retention and enabled the successful separation of CF4/N2 and SF6/N2 with a resolution of 2.37 and 8.89, respectively, when used as a packed column in gas chromatography. Compared with the Porapak Q column, the HETP of the UiO-66-Br2@PS/DVB-packed column decreased and showed good reproducibility. This research not only offers a convenient method for fabricating a hierarchical porous MOF-packed column but also showcases the prospective utilization of MOFs for the separation of the F-gas/N2 mixture.

Defective UiO-66-NH2 (Zr) for Simultaneous Adsorption of Phosphate and Pb2+ for Hydrogen Peroxide Purification.

Removal of hetero ions from the hydrogen peroxide solution is a crucial step in purifying electronic-grade H2O2. Conventional adsorption materials are challenged to meet the need for the simultaneous adsorption of both anions and cations in solvents. UiO-66 (Zr) modified by acetic acid and amino group for simultaneous adsorption of phosphate and Pb2+ in H2O2 purification was fabricated in this work. The as-prepared defective UiO-66-NH2 (Zr) demonstrated a significant increase in specific surface area and porosity, along with more exposed sites for phosphate and Pb2+ adsorption. The adsorption capacity of De-UiO-66-NH2 for phosphate and Pb2+ in H2O2 solution was 52.28 mg g-1 and 35.4 mg g-1, which is 1.19 times and 1.88 times that of unmodified UiO-66 (Zr), respectively. The trace simultaneous adsorption with both 100 ppb phosphate and Pb2+ showed removal rates of 94.0% and 88.7%, respectively, confirming the practicality of MOF materials in the purification of electronic chemicals. This work highlights the potential of Zr-based MOFs as anionic and cationic simultaneous adsorbents for highly efficient purification of electronic-grade solvents.

Efficient Charge Transport in Inverted Perovskite Solar Cells via 2D/3D Ferroelectric Heterojunction.

While the 2D/3D heterojunction is an effective method to improve the power conversion efficiency (PCE) of perovskite solar cells (PSCs), carriers are often confined in the quantum wells (QWs) due to the unique structure of 2D perovskite, which makes the charge transport along the out-of-plane direction difficult. Here, a 2D/3D ferroelectric heterojunction formed by 4,4-difluoropiperidine hydrochloride (2FPD) in inverted PSCs is reported. The enriched 2D perovskite (2FPD)2PbI4 layer with n = 1 on the perovskite surface exhibits ferroelectric response and has oriented dipoles along the out-of-plane direction. The ferroelectricity of the oriented dipole layer facilitates the enhancement of the built-in electric field (1.06 V) and the delay of the cooling process of hot carriers, reflected in the high carrier temperature (above 1400 K) and the prolonged photobleach recovery time (139.85 fs, measured at bandgap), improving the out-of-plane conductivity. In addition, the alignment of energy levels is optimized and exciton binding energy (32.8 meV) is reduced by changing the dielectric environment of the surface. Finally, the 2FPD-treated PSCs achieve a PCE of 24.82% (certified: 24.38%) with the synergistic effect of ferroelectricity and defect passivation, while maintaining over 90% of their initial efficiency after 1000 h of maximum power point tracking.

One-pot reaction for the preparation of diatom hemostatic particles with effective hemostasis and economic benefits.

Effective hemostatic materials have been in demand for rapid pre-hospital hemostasis in emergency situations, which can significantly reduce accidental deaths. The development of emergency hemostatic materials with rapid hemostasis, biosafety, and economical preparation is a great challenge. In this study, Ca(OH)2-complexed diatom powder hemostatic particles (Ca(OH)2-Php) were prepared based on a one-pot reaction by directly mixing various raw materials and by rotary granulation. High-temperature calcination was able to carbonate and consume the organic matter in the hemostatic particles. The crosslinked hydrogen bonds in those particles were converted to silica-oxygen bonds, the particles became more stable, and the porous structure of diatom biosilica (DBs) was exposed. Ca(OH)2-Php has high porosity, can quickly adsorb the water in blood (water absorption: 75.85 ± 6.93%), and exhibits rapid hemostasis capacity (clotting time was shortened by 43% compared with that of the control group), good biocompatibility (hemolysis rate <7%, no cytotoxicity), and simplicity of handling (conveniently debride, no residues, no tissue inflammation). This study provides a new idea for the preparation of emergency hemostatic materials, and Ca(OH)2-Php prepared by one-pot reaction has various high-quality characteristics including rapid hemostasis, wide applicability, economical preparation, and potential for large-scale production.

Infiltrated 2D/3D Heterojunction with Tunable Electric Field Landscape for Robust Inverted Perovskite Solar Cells with over 24% Efficiency.

In inverted perovskite solar cells, conventional planar 2D/3D perovskite heterojunctions typically exhibit a type-II band alignment, where the electric field tends to drive the electron motion in the opposite direction to the direction of electron transfer. Here, a 2D/3D gradient heterojunction is developed by allowing the 2D perovskite to infiltrate the 3D perovskite surface along the grain boundaries using the interaction between the organic cation of the 2D perovskite and the pseudohalogen thiocyanate ion (SCN- ), which has the ability to diffuse downward. The infiltrated 2D perovskite not only fills the gaps of grain boundaries with improved structural stability, but it also reconstructs the original landscape of the electric field toward the n-doped surface to enable more rapid electron transfer and weaken the adverse type-II band alignment effect. Since 2D perovskite seals the GBs, the nonvolatile SCN- can accumulate at the top and bottom dual interfaces, releasing residual stress and significantly inhibiting nonradiative recombination. The device exhibits an excellent efficiency of 24.76% (certified 24.29%) and long-term stability that is >90% of the original PCE value after 800 h of heating at 85 °C or in high humidity (≈65%).

POSS-based polyionic liquids for efficient CO2 cycloaddition reactions under solvent- and cocatalyst-free conditions at ambient pressure.

The conversion of CO2 into value-added chemicals has become an imminent research topic and the cycloaddition of CO2 with a C1 resource to produce cyclic carbonates is a promising pathway for CO2 utilization. Herein, a series of POSS-based polyionic liquids (PILs) were synthesized by the copolymerization of octavinyl polyhedral oligomeric silsesquioxane (POSS) with an imidazolium ion linker. The prepared PILs have the characteristics of hydrogen bond donors, halogen atom sites, stable pore structures, and thermal stability, and are used as heterogeneous catalysts for the cycloaddition of epoxides with carbon dioxide. The effect of linkers on the cycloaddition is investigated by tuning the ratio of POSS units to imidazolium ions. Under the optimized conditions, the conversion of epichlorohydrin can reach 99.18% at atmospheric pressure with neither co-catalysts nor solvents. It is concluded that the reaction of the cycloaddition of epoxides with carbon dioxide follows pseudo-first-order kinetics. Moreover, the presence of the catalysis of PILs leads to a significant decrease in the activation energy barrier for cycloaddition. The catalyst can be facilely recovered due to its high stability, and only a slight decrease in conversion was observed after five successive runs. In addition, the mechanism of PILs catalyzing the cycloaddition reaction of epoxides with CO2 is proposed. This work not only provides a sustainable and green process for CO2 cycloaddition, but also highlights the potential of using PILs for CO2 utilization.

Ionic Conjugated Polymers as Heterogeneous Catalysts for the Cycloaddition of Carbon Dioxide to Epoxides to Form Carbonates under Solvent- and Cocatalyst-Free Conditions.

The generation of cyclic carbonates by the cycloaddition of CO2 with epoxides is attractive in the industry, by which CO2 is efficiently used as C1 source. Herein, a series of catalysts were developed to efficient mediate the cycloaddition of CO2 with epoxides to generate carbonates. The catalysts were easily synthesized via the amine-formaldehyde condensation of ethidium bromide with a variety of linkers. The newly prepared heterogeneous catalysts have high thermal stability and degradation temperatures. The surface of the catalysts is smooth and spherical in shape. The effect of temperature, pressure, reaction time and catalyst dosage on the cycloaddition of CO2 with epoxide were investigated. The results show that the catalyst with 1,3,5-tris(4-formylphenyl)benzene as the linker can achieve 97.4 % conversion efficiency at the conditions of 100 °C, reaction time of 12 h, and the reaction pressure of 1.2 MPa in a solvent-free environment. Notably, the polymers serve as homogeneous catalysts during the reaction (reaction temperature above Tg ) and can be separated and recovered easily as homogeneous catalysts at room temperature. In addition, the catalyst is not only suitable for a wide range of epoxide substrates, but also can be recycled many times. Furthermore, DFT calculations show that the coordination between the electrophilic center of the catalyst and the epoxide reduces the energy barrier, and the reaction mechanism is proposed based on the reaction kinetic studies and DFT calculations.

Effect of sarcopenia and poor balance on vertebral spinal osteoporotic fracture in female rheumatoid arthritis.

This study investigated the effect of poor balance and sarcopenia on vertebral spinal osteoporotic fracture (VOPF) in female rheumatoid arthritic (RA) patients. A total of 195 female RA and 126 normal subjects were enrolled, and the correlations between sarcopenia, poor balance and VOPF were analyzed. Furthermore, we explored the relationships between sarcopenia or poor balance with disease related indexes of female RA. Binary logistic regression analyses were performed to identify potential risk factors for VOPF in female RA. We found that female RA had an increased risk of sarcopenia, poor balance (Berg balance scale, BBS ≤ 40) and VOPF than controls (P < 0.0001). Female RA with VOPF were more likely to have poor balance and sarcopenia than those without VOPF (P < 0.0001-0.05). Meanwhile, female RA with sarcopenia and poor balance often had higher disease activity, more serious joint damage and worse joint function (P < 0.05) compared with those without sarcopenia and poor balance. Binary logistic regression analysis (LR backwald) revealed that age (OR = 1.112, 95% CI 1.065-1.160, P < 0.0001), OP (OR = 10.137, 95% CI 4.224-24.330, P < 0.0001) and GCs usage (OR = 3.532, 95% CI 1.427-8.741, P = 0.006) were risk factors, while SMI (OR = 0.386, 95% CI 0.243-0.614, P < 0.0001) and BBS (OR = 0.952, 95% CI 0.929-0.976, P < 0.0001) were protective factors for VOPF in female RA. Hence, sarcopenia and poor balance are associated with a higher risk for VOPF and are closely related to disease activity and joint structure damage of female RA.

DMF-Assisted Radical Cyclization of o-Isocyanodiaryl Ethers via 1,5-Aryl Migration: Construction of 2-Arylbenzoxazoles.

A novel DMF-assisted radical cyclization of o-isocyanodiaryl ethers via 1,5-aryl migration has been developed for the synthesis of a series of 2-arylbenzoxazoles by the FeCl3/TBHP/Et3N catalytic system in DMF. However, N,N-dimethylbenzo[d]thiazole-2-carboxamide and N,N-dimethylbenzo[d]selenazole-2-carboxamide were obtained from the corresponding substrate 2-isocyanophenyl p-methoxyphenyl thioether and 2-isocyanodiphenyl selenoether under the same conditions. A possible mechanism may involve aryl 1,5-migration and DMF-assisted radical cyclization of o-isocyanodiaryl ethers.

NiCo-Layered Double Hydroxide-Derived B-Doped CoP/Ni2P Hollow Nanoprisms as High-Efficiency Electrocatalysts for Hydrogen Evolution Reaction.

Rational design and controllable synthesis of multiple metal components according to chemical composition and morphology are essential for obtaining desirable electrochemical performance for efficient hydrogen production because of the morphology and synergistic effects of different components. Herein, we report an approach to facilely fabricate bimetal compounds with a well-defined hollow nanoprism structure using a self-templated strategy to synthesize novel hierarchical NiCo-layered double hydroxide (NiCo-LDH) nanosheets as precursors followed by in situ phosphorization. Among the as-synthesized products of different mole ratios of Ni/Co, the NiCo2-B-P nanoprisms that integrate the advantages of a hollow structure, an optimal Ni-Co synergistic effect, and a unique B-doped CoP/Ni2P bimetallic phosphide derived from NiCo-LDH nanosheets exhibit excellent hydrogen evolution reaction (HER) activity in an alkaline solution at 10 mA cm-2 with the lowest overpotential of 78 mV and long-term stability. This study may offer an appropriate structure and compositional design of bimetallic alkaline HER catalysts.

Cooperation in Cu-MOF-74-Derived Cu-Cu2O-C Nanocomposites To Enable Efficient Visible-Light-Initiated Phenylacetylene Coupling.

Carbon-based metal or metal oxide nanocomposites have played an essential role in many fields. In this work, we reported that graphitic-carbon-layer-supported Cu-Cu2O nanocomposites (denoted as Cu-Cu2O-C) can be obtained via calcination of Cu-MOF-74, which shows superior activity for coupling of phenylacetylene to form 1,4-diphenylbutadiyne under visible light because of the synergistic action of the three components in the as-formed Cu-Cu2O-C. The catalyst is highly efficient and can be facilely recycled. Superior to the already reported phenylacetylene coupling systems, only visible light and a very low amount of copper (1.65 mol %) is required in our system. This study provides a promising strategy for visible-light-induced phenylacetylene coupling and highlights the great potential of using metal-organic frameworks as precursors to obtain carbon-supported metal/metal oxide nanocomposites for heterogeneous cooperative catalysis.

Associations between circulating adipokines and bone mineral density in patients with knee osteoarthritis: a cross-sectional study.

BACKGROUND: Associations between adipokines and bone mineral density (BMD) in knee osteoarthritis (OA) remain indistinct. The aim of this study was to investigate the cross-sectional associations between serum levels of adipokines and BMD in patients with knee OA. METHODS: This study included 164 patients with symptomatic knee OA from the Anhui Osteoarthritis study. Serum levels of leptin, adiponectin, and resistin were measured using an enzyme-linked immunosorbent assay (ELISA). BMD at total body, spine, hip, and femur were measured by dual-energy X-ray absorptiometry (DXA). RESULTS: In multivariable analyses, serum levels of leptin were significantly associated with reduced BMD at total body, hip, total femur, femoral neck, and femoral shaft (ß = - 0.019, 95% CI -0.034 to - 0.005; ß = - 0.018, 95% CI -0.034 to - 0.003; ß = - 0.018, 95% CI -0.034 to - 0.002; ß = - 0.016, 95% CI -0.032 to 0.000; ß = - 0.026, 95% CI -0.046 to - 0.006; respectively). Serum levels of adiponectin were significantly and negatively associated with BMD at total femur and femoral shaft (ß = - 0.007, 95% CI -0.013 to 0.000; ß = - 0.011, 95% CI -0.018 to - 0.003; respectively). However, no significant associations were found between serum levels of resistin and BMD at any site measured. CONCLUSIONS: Serum levels of leptin and adiponectin were significantly and negatively associated with BMD, suggesting potentially detrimental effects of leptin and adiponectin on BMD in knee OA patients.

Associations between systemic bone mineral density, knee cartilage defects and bone marrow lesions in patients with knee osteoarthritis.

AIM: The relationship between bone mineral density (BMD) and osteoarthritis (OA) remains controversial. This study aimed to explore the cross-sectional associations between BMD at the total body, hip and spine and joint structural abnormalities including cartilage defects and bone marrow lesions (BMLs) in patients with knee OA. METHOD: One hundred and eight-five subjects with symptomatic knee OA were included in this study. T2-weighted fast spin echo magnetic resonance imaging was used to assess knee cartilage defects and BMLs. Total body, hip and spine BMD were measured using dual-energy X-ray absorptiometry. RESULTS: After adjustment for potential confounders, total hip BMD was negatively associated with medial tibial cartilage defects, lateral femoral cartilage defects, medial tibial BMLs and lateral tibial BMLs. Spine and total body BMD were negatively associated with lateral femoral cartilage defects, but not with BMLs. CONCLUSION: We concluded that BMD particularly at the hip was negatively associated with knee cartilage defects and BMLs.

Serum levels of resistin and interleukin-17 are associated with increased cartilage defects and bone marrow lesions in patients with knee osteoarthritis.

OBJECTIVES: To investigate cross-sectional associations between serum levels of resistin and interleukin-17 (IL-17) and cartilage defects and bone marrow lesions (BMLs) in patients with knee symptomatic osteoarthritis (OA). METHODS: One hundred and ninety-four consecutively-selected patients with knee symptomatic OA (mean 55.4 years, range 34-74, 87% females) were included in Anhui Osteoarthritis (AHOA) Study. Knee cartilage defects and BMLs were determined at different sites using T2-weighted fat-suppressed fast spin echo MRI. Serum resistin, IL-17, and high-sensitivity C-reactive protein (hs-CRP) levels were measured using ELISA. RESULTS: In multivariable analyses, serum resistin was positively associated with cartilage defects at lateral femoral, lateral tibial, and medial tibial (all p < 0.05) sites. The significant associations were also present with BMLs at lateral femoral and tibial sites (ORs: 1.13-1.19, both p < 0.05). In patients with the highest quartile of hs-CRP (>2.45 pg/ml), IL-17 was positively and significantly associated with cartilage defect score at nearly all sites (ORs: 1.33-1.44, all p < 0.05), and BMLs at lateral and medial femoral sites (ORs: 1.26-1.51, both p < 0.05). CONCLUSIONS: Serum levels of resistin were positively and independently associated with cartilage defects and BMLs in patients with knee OA. Serum IL-17 was significantly associated with cartilage defects and BMLs in patients with an increased inflammatory status. These suggest that metabolic and inflammatory mechanisms may have a role to play in knee OA.

Serum levels of interleukin-17 and adiponectin are associated with infrapatellar fat pad volume and signal intensity alteration in patients with knee osteoarthritis.

BACKGROUND: In the present study, we sought to generate hypotheses regarding the associations of serum levels of interleukin (IL)-17, adiponectin, and resistin with magnetic resonance imaging-measured infrapatellar fat pad (IPFP) size and signal intensity alterations in patients with knee osteoarthritis (OA). METHODS: A total of 170 subjects with symptomatic knee OA (mean age 55.4 years, range 34-74, 88.2 % females) were included. IPFP volume was measured on T1-weighted spoiled gradient-recalled acquisition in the steady state images and was computed by using a software program. IPFP high signal intensity (grades 0-3) was assessed on T2-weighted fast spin echo images. Serum IL-17, adiponectin, and resistin levels were measured using an enzyme-linked immunosorbent assay. RESULTS: In multivariable analyses, serum IL-17 was negatively associated with IPFP volume (ß = -0.185, 95 % CI -0.337 to -0.034) but positively associated with the severity of IPFP signal intensity alteration (OR 1.23, 95 % CI 1.06-1.42) after adjustment for age, sex, weight, and height. Serum adiponectin was positively associated with IPFP volume (ß = 0.016, 95 % CI 0.001-0.032) but negatively associated with IPFP signal intensity alteration (OR 0.99, 95 % CI 0.98-1.00) after adjustment for covariates. Resistin was positively associated with IPFP signal intensity alteration (OR 1.13, 95 % CI 1.04-1.23) but not with IPFP volume. The significant associations of adiponectin or resistin disappeared after further adjustment for IL-17; in contrast, the significant associations of IL-17 remained after further adjustment for adiponectin. CONCLUSIONS: While serum IL-17 and resistin were associated with reduced IPFP volume and/or increased abnormal signal intensity alteration, serum adiponectin had opposite associations that were largely through IL-17. These findings suggest that serum adipocytokines may have a role to play in IPFP changes of knee OA.

Association Between Infrapatellar Fat Pad Volume and Knee Structural Changes in Patients with Knee Osteoarthritis.

OBJECTIVE: The function of the infrapatellar fat pad (IPFP) in knee osteoarthritis (OA) remains uncertain. This study aimed to examine cross-sectional associations between IPFP volume and knee structures in patients with knee OA. METHODS: The study included 174 patients with clinical knee OA (mean age, 55.5 yrs). Fat-suppressed 3-D T1-weighted spoiled gradient recall magnetic resonance imaging (MRI) was used to measure the IPFP and cartilage volume. T2-weighted fast spin echo MRI was used to assess cartilage defects and bone marrow lesions (BML). Radiographic knee osteophytes and joint space narrowing (JSN) were assessed using the Osteoarthritis Research Society International atlas. RESULTS: After adjustment for potential confounders, greater IPFP volume was associated with greater tibial and patellar cartilage volume (all p < 0.05), and fewer cartilage defects at all sites (OR 0.88-0.91, all p < 0.05). IPFP volume was associated with presence of BML at lateral tibial and medial femoral sites (OR 0.88-0.91, all p < 0.05) and osteophytes at lateral tibiofemoral compartment (OR 0.88, p < 0.05). IPFP volume was not significantly associated with JSN. CONCLUSION: Greater IPFP volume was associated with greater knee cartilage volume and fewer structural abnormalities, suggesting a protective role of IPFP size in knee OA.

Real-time ultrasound elastography for differentiation of benign and malignant thyroid nodules: a meta-analysis.

OBJECTIVES: The clinical challenge of managing thyroid nodules nowadays is to diagnose the minority of malignant disease. Real-time ultrasound elastography, which can measure tissue elasticity, is used as a complement to conventional sonography for improving the diagnosis of thyroid tumors. There are 2 common criteria for evaluating an elastogram: the elasticity score and strain ratio. This meta-analysis was performed to expand on a previous meta-analysis to assess the diagnostic power of ultrasound elastography in differentiating benign and malignant thyroid nodules for elasticity score and strain ratio assessment. METHODS: The MEDLINE, EMBASE, PubMed, and Cochrane Library databases up to January 31, 2013, were searched. The pooled sensitivity, specificity, and summary receiver operating characteristic curve were obtained from individual studies with a random-effects model. The extent and sources of heterogeneity were explored. RESULTS: A total of 5481 nodules in 4468 patients for elasticity score studies and 1063 nodules in 983 patients for strain ratio studies were analyzed. The overall mean sensitivity and specificity of ultrasound elastography for differentiation of thyroid nodules were 0.79 (95% confidence interval [CI], 0.77-0.81) and 0.77 (95% CI, 0.76-0.79) for elasticity score assessment and 0.85 (95% CI, 0.81-0.89) and 0.80 (95% CI, 0.77-0.83) for strain ratio assessment, respectively. The areas under the curve for the elasticity score and strain ratio were 0.8941 and 0.9285. CONCLUSIONS: These results confirmed those obtained in the previous meta-analysis. Ultrasound elastography has high sensitivity and specificity for identification of thyroid nodules. It is a promising tool for reducing unnecessary fine-needle-aspiration biopsy.

[Comparison of long bone repair in tibia by vascularized fibular grafting of different sides].

OBJECTIVE: To evaluate the clinical effect of repair of massive bone defect in tibia by vascularized fibula grafting of either sides. METHODS: Twenty-four cases of massive bone defect in tibia, among which 14 case were repaired by vascularized fibula grafting of the other side and another 10 cases were repaired by those of the same side, from 1987 to 1997 were followed up for 3 to 13 years; the functions of the operated limbs were evaluated according to Enneking Score System, and the outcome of the fibula grafts were assessed by radiographic examination with reference to the standard established by International Symposium on Limb Salvage. RESULTS: The average recover rate of the operated limbs in those repaired by the other side grafting was 80.7%, and the average healing period of the fibula graft was 14 weeks with fracture of the graft in one case which made the operated lower limb shorten for about 2.5 cm; the fibula grafts were observed thickened in 43 weeks, on average, and the patients could walk independently without a crutch. While in those repaired by the same side grafting, the average recover rate of the operated limbs was 68.3%, the average healing period of the fibula graft was 17 weeks with fracture of the graft in 3 cases, in 2 of which the lower limbs were shortened for 2 cm and 4 cm respectively, and in the third one infection occurred and amputation was performed finally; the fibula grafts were observed thickened in 49 weeks, on average, which made it available for the patients to walk without a crutch. All of the data showed that there was a significant difference statistically between the differently treated cases. CONCLUSION: It's a good choice to repair massive bone defect in tibia by vascularized fibula grafting, and the vascularized fibula graft from the other side could promote the bone healing and accelerate the recover of the function of the operated lower limb.