Hydrogen Bonds Induced Ultralong Stability of Conductive π-d Conjugated FeCo3(DDA)2 with High OER Activity.

Conductive π-d conjugated metal-organic frameworks (MOFs) have attracted wide concerns in electrocatalysis due to their intrinsic high conductivity. However, the poor electrocatalytic stability is still a major problem that hinders the practical application of MOFs. Herein, a novel approach to enhancing the stability of MOF-based electrocatalyst, namely, the introduction of hydrogen bonds (H-bonds), is reported. Impressively, the π-d conjugated MOF FeCo3(DDA)2 (DDA = 1,5-diamino-4,8-dihydroxy-9,10-anthraceneedione) exhibits ultrahigh oxygen evolution reaction (OER) stability (up to 2000 h). The experimental studies demonstrate that the presence of H-bonds in FeCo3(DDA)2 is responsible for its ultrahigh OER stability. Besides that, FeCo3(DDA)2 also displays a prominent OER activity (an overpotential of 260 mV vs reversible hydrogen electrode (RHE) at a current density of 10 mA cm-2 and a Tafel slope of 46.86 mV dec-1). Density functional theory (DFT) calculations further indicate that the synergistic effect of the Fe and Co sites in FeCo3(DDA)2 contributes to its prominent OER performance. This work provides a new avenue of boosting the electrocatalytic stability of conductive π-d conjugated MOFs.

Clinical Performance of Immunonephelometric Assay and Chemiluminescent Immunoassay for Detection of IgG Subclasses in Chinese.

BACKGROUND: Detection of IgG subclasses (IgGSc) is vital for the diagnosis and management of disease, especially IgG4-related diseases (IgG4-RD). This study aimed to evaluate the performances of the chemiluminescent immunoassay (CLIA) for detecting IgGSc and diagnosing IgG4-RD by IgGSc. METHODS: A total of 40 individuals with IgG4-RD, 40 with primary Sjogren's syndrome (pSS), and 40 healthy controls (HCs) were enrolled. Serum samples were collected for the simultaneous detection of IgG1, IgG2, IgG3, and IgG4 by the Siemens immunonephelometric assay and the CLIA. The correlation analysis was performed, and diagnostic value was analyzed by the receiver operating characteristic (ROC) curve. RESULTS: Patients with IgG4-RD had higher IgG4 (p < 0.001) and lower IgG1 (p < 0.001) than those with pSS, and HC. The results by the Siemens immunonephelometric assay and the CLIA showed a strong correlation in detecting IgG1, IgG2, IgG3, and IgG4 (r = 0.937, r = 0.847, r = 0.871, r = 0.990, all p < 0.001, respectively). The sum of IgG1, IgG2, IgG3, and IgG4 using two assays strongly correlated with total IgG by the IMMAGE 800 (r = 0.866, r = 0.811, both p < 0.001, respectively). For discriminating IgG4-RD from pSS and HC, no significant differences were observed in CLIA IgG4 and Siemens immunonephelometric assay IgG4 (z = 0.138, p = 0.891), which provided the area under the curves (AUCs) of 0.951 (p < 0.001) and 0.950 (p < 0.001), respectively. The AUCs of CLIA IgG1 and Siemens immunonephelometric assay IgG1 in distinguishing pSS from IgG4-RD and HC were 0.761 (p < 0.001) and 0.765 (p < 0.001), respectively, with no significant differences (z = 0.228, p = 0.820). CONCLUSIONS: The CLIA and the Siemens immunonephelometric assay appeared to have good consistency with comparable diagnostic value in detecting IgGSc, especially IgG4, and IgG1 that can accurately identify IgG4-RD or pSS in clinical practice.

Recent Progress on Porous Carbons for Carbon Capture.

High emission of carbon dioxide (CO2) has caused CO2 levels to reach more than 400 ppm in air and led to a serious climate problem. In addition, in confined spaces such as submarines and aircraft, the CO2 concentration increase in the air caused by human respiration also affects human health. In order to protect the environment and human health, the search for high-performance adsorbents for carbon capture from high and low concentration gas is particularly important. Porous carbon materials, possessing the advantages of low cost and renewability, have set off a boom in the research of porous adsorbents, which have the opportunity to be utilized on a large scale for industrial carbon capture in the future. In this review, we summarize the recent research progress of porous carbons for carbon capture from flue gas and directly from air in the last five years, including activated carbon (AC), heteroatom-modified porous carbon, carbon molecular sieves (CMS), and other porous carbon materials, with a focus on the effects of temperature, water content, and gas flow rate of industrial flue gas on the performance of porous carbon adsorbents. We summarize the preparation strategies of various porous carbons and seek environmental friendly porous carbon materials preparation strategies under the premise of improving the CO2 adsorption capacity and selectivity of porous carbon adsorbents. Based on the effects of real industrial flue gas on adsorbents, we provide new ideas and evaluation methods for the development and preparation of porous carbon materials.

Functionalization of a stable AIE-based hydrogen-bonded organic framework for white light-emitting diodes.

Hydrogen-bonded organic frameworks (HOFs) have received tremendous attention in recent years due to the good designability. However, the pure organic nature of HOFs sometimes limits the application development and performance improvement. Functionalizing is an effective strategy to control and modulate material properties, which can achieve properties that cannot be achieved by a pristine material. Herein, a series of HOF-76⊃DSMI were synthesized through functionalizing the stable AIE-based HOF-76 by incorporating a red dye which complements the deficiency of the red component of HOF-76. Then, a single matrix white light-emitting diode (WLED) was fabricated by coating the HOF-76⊃DSMI material on a 460 nm blue LED with CIE chromaticity coordinates of (0.333, 0.329), a correlated colour temperature (CCT) of 5490 K and a colour rendering index (CRI) of 80.

Engineering Supramolecular Binding Sites in a Chemically Stable Metal-Organic Framework for Simultaneous High C2 H2 Storage and Separation.

Developing porous materials to overcome the trade-off between adsorption capacity and selectivity for C2 H2 /CO2 separation remains a challenge. Herein, we report a stable HKUST-1-like MOF (ZJU-50a), featuring large cages decorated with high density of supramolecular binding sites to achieve both high C2 H2 storage and selectivity. ZJU-50a exhibits one of the highest C2 H2 storage capacity (192 cm3 g-1 ) and concurrently high C2 H2 /CO2 selectivity (12) at 298 K and 1 bar. Single-crystal X-ray diffraction studies on gas-loaded ZJU-50a crystal unveil that the incorporated supramolecular binding sites can selectively take up C2 H2 molecule but not CO2 to result in both high C2 H2 storage and selectivity. Breakthrough experiments validated its separation performance for C2 H2 /CO2 mixtures, providing a high C2 H2 recovery capacity of 84.2 L kg-1 with 99.5 % purity. This study suggests a novel strategy of engineering supramolecular binding sites into MOFs to overcome the trade-off for this separation.

Zeolite NPO-Type Azolate Frameworks.

Three-membered rings (3-rings) are an important structural motif in zeolite chemistry, but their formation remains serendipitous in reticular chemistry when designing zeolitic imidazolate frameworks (ZIFs). Herein, we report a design principle for constructing four new ZIFs, termed ZIF-1001 to -1004, from tetrahedral ZnII centers (T), benzotriazolate (bTZ), and different functionalized benzimidazolates (RbIM) that adopt a new zeolite NPO-type topology built from 3-rings. Two factors were critical for this discovery: i) incorporating the bTZ linker within the structures formed 3-rings due to a ∠(T-bTZ-T) angle of 120-130° reminiscent of the ∠(Ge-O-Ge) angle (130°) observed in germanate zeolite-type structures having 3-rings; and ii) RbIM guided the coordination chemistry of bTZ to bind preferentially in an imidazolate-type mode. This series' ability to selectively capture CO2 from high-humidity flue gas and trap ethane from tail gas during shale gas extraction was demonstrated.

Robust and Radiation-Resistant Hofmann-Type Metal-Organic Frameworks for Record Xenon/Krypton Separation.

The discovery of high-performance adsorbents for highly efficient separation of xenon from krypton is an important but challenging task in the chemical industry due to their similar size and inert spherical nature. Herein, we report two robust and radiation-resistant Hofmann-type MOFs, Co(pyz)[Ni(CN)4] and Co(pyz)[Pd(CN)4] (termed as ZJU-74a-Ni and ZJU-74a-Pd), featuring oppositely adjacent open metal sites and perfect pore sizes (4.1 and 3.8 Å) comparable to the kinetic diameter of xenon (4.047 Å), affording the benchmark binding affinity for polarizable Xe gas. These materials thus exhibit both record-high Xe uptake capacities (89.3 and 98.4 cm3 cm-3 at 296 K and 0.2 bar) and Xe/Kr selectivities (74.1 and 103.4) at ambient conditions, all of which are the highest among all the state-of-the-art materials reported so far. The locations of Xe molecules within ZJU-74a-Ni have been visualized by single-crystal X-ray diffraction studies, in which two oppositely adjacent metal centers combined with the right aperture size can construct a unique sandwich-like binding site to offer unprecedented and ultrastrong Ni2+-Xe-Ni2+ interactions with xenon, thus leading to the record Xe capture capacity and selectivity. The excellent separation capacity of ZJU-74a-Pd was verified by breakthrough experiments for Xe/Kr gas mixtures, providing both unprecedentedly high xenon uptake capacity (4.63 mmol cm-3) and krypton productivity (214 cm3 g-1).

Preparation and Bioactivity of Iridium(III) Phenanthroline Complexes with Halide Ions and Pyridine Leaving Groups.

A series of half-sandwich structural iridium(III) phenanthroline (Phen) complexes with halide ions (Cl- , Br- , I- ) and pyridine leaving groups ([(η5 -CpX )Ir(Phen)Z](PF6 )n , Cpx : electron-rich cyclopentadienyl group, Z: leaving group) have been prepared. Target complexes, especially the Cpxbiph (biphenyl-substituted cyclopentadienyl)-based one, showed favourable anticancer activity against human lung cancer (A549) cells; the best one (Ir8) was almost five times that of cisplatin under the same conditions. Compared with complexes involving halide ion leaving groups, the pyridine-based one did not display hydrolysis but effectively caused lysosomal damage, leading to accumulation in the cytosol, inducing an increase in the level of intracellular reactive oxygen species and apoptosis; this indicated an anticancer mechanism of oxidation. Additionally, these complexes could bind to serum albumin through a static quenching mechanism. The data highlight the potential value of half-sandwich iridium(III) phenanthroline complexes as anticancer drugs.

Modulator-Induced Zr-MOFs Diversification and Investigation of Their Properties in Gas Sorption and Fe3+ Ion Sensing.

In this paper, we synthesized three Zr-MOFs (Zr-SXU-1, Zr-SXU-2, and Zr-SXU-3) composed of identical ligands and metal clusters by using tetratopic carboxylic ligand PBPTTBA as the ligand and benzoic acids as modulators. These three Zr-MOFs showed different structures and topologies, and the connectivity of the Zr clusters varied from 8 in Zr-SXU-3, to 10 in Zr-SXU-1, and finally to 12 in Zr-SXU-2 due to the modulators used. Among them, Zr-SXU-1 represents an unusual 6-node network and [6(10)(11)7] transitivity. Besides, Zr-SXU-2 can only be obtained by using ditopic carboxylic acid as a second modulator when using benzoic acid as the main modulator, which is not reported in other Zr-MOFs synthesis. The adsorption and luminescence tests demonstrated their potential as gas reservoirs, separators, and sensors and also showed the importance of structure topologies to the applications.

Engineering of Pore Geometry for Ultrahigh Capacity Methane Storage in Mesoporous Metal-Organic Frameworks.

Mesoporous Zn4O(-COO)6-based metal-organic frameworks (MOFs), including UMCM-1, MOF-205, MUF-7a, and the newly synthesized MOFs, termed ST-1, ST-2, ST-3, and ST-4 (ST = ShanghaiTech University), have been systematically investigated for ultrahigh capacity methane storage. Exceptionally, ST-2 was found to have the highest deliverable capacity of 289 cm3STP/cm3 (567 mg/g) at 298 K and 5-200 bar, which surpasses all previously reported records held by porous materials. We illustrate that the fine-tuned mesoporosity is critical in further improving the deliverable capacities at ultrahigh pressure.

Shape Changes and Interaction Mechanism of Escherichia coli Cells Treated with Sericin and Use of a Sericin-Based Hydrogel for Wound Healing.

UNLABELLED: To verify the interaction mechanism between sericin and Escherichia coli, especially the morphological and structural changes in the bacterial cells, the antimicrobial activity of sericin against E. coli as a model for Gram-negative bacteria was investigated. The antibacterial activity of sericin on E. coli and the interaction mechanism were investigated in this study by analyzing the growth, integrity, and morphology of the bacterial cells following treatment with sericin. The changes in morphology and cellular compositions of bacterial cells treated with sericin were observed by an inverted fluorescence microscope, scanning electron microscopy, and transmission electron microscopy. Changes in electrical conductivity, total sugar concentration of the broth for the bacteria, and protein expression of the bacteria were determined to investigate the permeability of the cell membrane. A sericin-based hydrogel was prepared for an in vivo study of wound dressing. The results showed that the antibacterial activity of the hydrogel increased with the increase in the concentration of sericin from 10 g/liter to 40 g/liter. The introduction of sericin induces membrane blebbing of E. coli cells caused by antibiotic action on the cell membrane. The cytoplasm shrinkage phenomenon was accompanied by blurring of the membrane wall boundaries. When E. coli cells were treated with sericin, release of intracellular components quickly increased. The electrical conductivity assay indicated that the charged ions are reduced after exposure to sericin so that the integrity of the cell membrane is weakened and metabolism is blocked. In addition, sodium dodecyl sulfate-polyacrylamide gel electrophoresis demonstrated that sericin hinders the expression of bacterial protein. Sericin may damage the integrity of the bacterial cell membrane, thereby eventually inhibiting the growth and reproduction of E. coli Compared to sterile gauze, the sericin-based hydrogel promoted fibroblast cell proliferation and accelerated the formation of granulation tissues and neovessels. IMPORTANCE: The specific relationship and interaction mechanism between sericin and E. coli cells were investigated and elucidated. The results show that after 12 h of treatment, sericin molecules induce membrane blebbing of E. coli cells, and the bacteria show decreases in liquidity and permeability of biological membrane, resulting in alterations in the conductivity of the culture medium and the integrity of the outer membrane. The subsequent in vivo results demonstrate that the sericin-poly(N-isopropylacrylamide-N,N'-methylene-bis-acrylamide [NIPAm-MBA]) hydrogel accelerated wound healing compared to that with sterile gauze, which is a beneficial result for future applications in clinical medicine and the textile, food, and coating industries.

Percutaneous first annular pulley release for trigger digits: a systematic review and meta-analysis of current evidence.

PURPOSE: To determine the overall success rate and potential influencing factors within the current evidence for percutaneous first annular pulley release. METHODS: We searched PubMed, EMBASE, and the Cochrane Library for all clinical studies of percutaneous release. The rates of successful procedure and complication were extracted and analyzed. We charted the overall success rate on a forest plot with 95% confidence intervals. Data of success rates were analyzed in 5- and 10-year intervals to determine whether the rate of success had increased chronologically. We then performed 3 subgroup analyses according to instrument type (needles vs knife blades), cortisone use (cortisone vs noncortisone), and sonography guidance (sonography vs non-sonography guidance). Pooled success rates were calculated in the subgroups and compared using chi-square test. RESULTS: A total of 34 studies involving 2,114 percutaneous procedures were included in this systematic review and meta-analysis. The total success rate was 94%. There was a trend toward increasing number of publications in the past 20 years. We found a statistically significant trend showing that overall success rates had increased over time. Chi-square test revealed that percutaneous release with sonography guidance had a significantly higher success rate than non-sonography guidance. There were no significant differences in other subgroup analyses including instrument type and cortisone use. CONCLUSIONS: Percutaneous release is an effective and safe procedure for the treatment of trigger digit. It has become progressively popular in recent years, with a trend toward increased overall success. Sonography might be a helpful tool for maximizing success. The success rates were not affected by instruments and cortisone use. TYPE OF STUDY/LEVEL OF EVIDENCE: Therapeutic IV.

Percutaneous release, open surgery, or corticosteroid injection, which is the best treatment method for trigger digits?

BACKGROUND: Percutaneous A1 pulley release surgery for trigger digit (finger or thumb) has gained popularity in recent decades. Although many studies have reported the failure rate and complications of percutaneous release for trigger digit, the best treatment for trigger digit remains unclear. QUESTIONS/PURPOSES: Our aim was to identify the relative risk of treatment failure, level of satisfaction, and frequency of complications, comparing percutaneous release with open surgery or corticosteroid injections for adult patients with trigger digits. METHODS: We searched PubMed, Embase, and the Cochrane Library for randomized controlled trials (RCTs), comparing percutaneous release with open surgery or corticosteroid injections. Seven RCTs involving 676 patients were identified. Methodologic quality was assessed by the Detsky quality scale. After data extraction, we compared results using a fixed meta-analysis model. RESULTS: There were no differences in the failure rate (risk ratio [RR] = 0.93; 95% CI, 0.14-6.25) and complication frequency (RR = 0.83; 95% CI, 0.15-4.72) between patients undergoing percutaneous release and open surgery. Patients treated with percutaneous release had fewer failures (RR = 0.07; 95% CI, 0.02-0.21) and a greater level of satisfaction (RR = 2.01; 95% CI, 1.62-2.48) compared with the patients treated with corticosteroid injections. We found no difference in complication frequency between percutaneous release and corticosteroid injection (RR = 3.19; 95% CI, 0.51-19.91). CONCLUSIONS: The frequencies of treatment failure and complications were no different between percutaneous release surgery and open surgery for trigger digit in adults. Patients treated with percutaneous releases were less likely to have treatment failure than patients treated with corticosteroid injections.