Interpenetrated In(III)-MOF with Multiple Recognition Sites for Single-Step Ethylene Purification.

An interpenetrated indium(III) metal-organic framework (MOF), NTUniv-73, with a rarely reported tetrameric indium cluster is developed for streamlining ethylene purification from C2 gases. At 298 K, the adsorption capacities exhibited a complete reversal sequence of C2H6 > C2H2 > C2H4. Grand canonical Monte Carlo simulation indicated that the corners in a octahedral cage facilitated the C2H2/C2H4 separation, while the pocket-like aperture situated between adjacent octahedral cages allows for full contact of C2H6. Breakthrough experiments illustrated that NTUniv-73 could yield pure C2H4 in a single step with a productivity of 0.42 mmol g-1.

Palladium-Catalyzed Heck Cyclization with P(O)H Compounds to Construct Phosphinonyl-Azaindoline and -Azaoxindole Derivatives.

We report herein a concise method for the construction of phosphinonyl-azaindoline and -azaoxindole derivatives via a palladium-catalyzed cascade cyclization with P(O)H compounds. Various H-phosphonates, H-phosphinates, and aromatic secondary phosphine oxides are all tolerated under the reaction conditions. Furthermore, the phosphinonyl-azaindoline isomer families such as 7-, 5-, and 4-azaindolines could be synthesized in moderate to good yields.

"Two-in-one" core-shell nanozyme probes with double signal amplification for high-performing surface plasmon resonance immunosensing.

Herein, a "two-in-one" Ag@Au core-shell nanozyme probe inducing double-signal amplification has been developed to significantly elevate the sensitivity of SPR sensors via sandwich immunoassay. The Ag@Au core-shell nanozyme with intrinsic peroxide-like activity was demonstrated to catalyze a polymerization reaction leading to formation of polyaniline, allowing further improvement of detection performance of SPR immunosensor. The method demonstrated here offers a universal strategy for enhanced SPR detection and further expands the application of nanozymes.

Formation of a Polar Flow Channel with Embedded Gas Recognition Pockets in a Yttrium-Based MOF for Enhanced C2H2/C2H4 and CO2 Selective Adsorptions.

A polar flow channel with embedded gas recognition pockets was made in a 10-connected hexanuclear yttrium-based metal-organic frameworks (MOF) NTUniv-57 (NTUniv = Nantong University) by lowering the symmetry of the ligand, which showed high chemical stability and obviously enhanced gas adsorption selectivities.

Immunotherapy of targeting MDSCs in tumor microenvironment.

Myeloid-derived suppressor cells (MDSCs) are a group of heterogeneous cells which are abnormally accumulated during the differentiation of myeloid cells. Immunosuppression is the main functional feature of MDSCs, which inhibit T cell activity in the tumor microenvironment (TME) and promote tumoral immune escape. The main principle for immunotherapy is to modulate, restore, and remodel the plasticity and potential of immune system to have an effective anti-tumor response. In the TME, MDSCs are major obstacles to cancer immunotherapy through reducing the anti-tumor efficacy and making tumor cells more resistant to immunotherapy. Therefore, targeting MDSCs treatment becomes the priority of relevant studies and provides new immunotherapeutic strategy for cancer treatment. In this review, we mainly discuss the functions and mechanisms of MDSCs as well as their functional changes in the TME. Further, we review therapeutic effects of immunotherapy against MDSCs and potential breakthroughs regarding immunotherapy targeting MDSCs and immune checkpoint blockade (ICB) immunotherapy.

MOF Pillaring Method: Ligand-to-Ligand and Axial-to-Axial Cross-Linking of "Paddlewheels".

By shortening the previous shortest tetracarboxylate ligand, the first ligand-to-ligand and axial-to-axial pillaring method was realized in the prototype MOF NTUniv-56 (NTUniv = Nantong University), which exhibit a rare (2,4,6)-connected net with a new topology and interesting gas adsorption performance.

Palladium-catalyzed Heck cyclization/carbonylation with formates: synthesis of azaindoline-3-acetates and furoazaindolines.

We report herein a palladium-catalyzed domino cyclization/carbonylation to access ester-functionalized azaindolines, applying formates as a convenient carbonyl source. All four azaindoline isomers were constructed, exhibiting good functional group compatibility. On this basis, modifying the starting tether on the aminopyridine led to furoazaindolines via an intramolecular reductive cyclization after the palladium-catalyzed process.

Structural modification of aluminum oxides for removing fluoride in water: crystal forms and metal ion doping.

In this paper, the effect of different crystal forms of Al2O3 on fluoride removal was studied. All crystal forms of Al2O3 were based on the same boehmite precursor and were obtained using a hydrothermal and calcination method. γ-Al2O3 had higher fluoride removal performance (52.15 mg/g) compared with θ-Al2O3 and α-Al2O3. Density functional theory (DFT) calculations confirmed that fluoride removal was greatest for γ-Al2O3, followed by θ-Al2O3 and α-Al2O3, and γ-Al2O3 possessed the strongest fluoride binding energy (-3.93 eV). The typical adsorption behaviour was consistent with the Langmuir model and pseudo-second-order model, indicating chemical and monolayer adsorption. Different metal ions were used to modify γ-Al2O3, and lanthanum had the best effect. Lanthanum oxide was shown to play an important role in fluoride removal. The best La/Al doping ratio was 20 At%. The adsorption process of the composite was also consistent with chemical and monolayer adsorption. When the La/Al doping rate was 20%, the adsorption capacity reached 94.64 mg/g. Compared with γ-Al2O3 (1.39 × 10-7 m/s), the adsorption rate of 20La-Al2O3 was 3.93 × 10-7 m/s according to the mass transfer model. Furthermore, DFT was used to provide insight into the adsorption mechanism, which was mainly driven by electrostatic attraction and ion exchange.

Finely Tuning Tridentate Carboxylic Acids for the Construction of Rod Scandium Metal-Organic Frameworks with High Chemical Stability and Selective Gas Adsorption.

By systematic ligand tuning for control of the secondary building units, the use of tridentate carboxylic acid to construct the rod scandium metal-organic framework NTUniv-55 (NTUniv = Nantong University) with high chemical stability and interesting selective gas adsorption was reported.

Palladium-Catalyzed Sequential Vinyl C-H Activation/Dual Decarboxylation: Regioselective Synthesis of Phenanthrenes and Cyclohepta[1,2,3-de]naphthalenes.

The application of a C(vinyl), C(aryl)-palladacycle from vinyl-containing substrates is challenging due to the interference of a reactive double bond in palladium catalysis. This Letter describes a [4 + 2] or [4 + 3] cyclization based on a C(vinyl), C(aryl)-palladacycle by employing α-oxocarboxylic acids as the insertion units under a palladium/air system. The reaction proceeded through the key vinyl C-H activation and dual decarboxylation sequence, forming phenanthrenes and cyclohepta[1,2,3-de]naphthalenes regioselectively in good yields. The synthetic versatility of this protocol is highlighted by the gram-scale synthesis and synthesizing functional material molecule.

A Triazole Functionalized txt-Type Metal-Organic Framework with High Performance for CH4 Uptake and Selective CO2 Adsorption.

The metal-organic framework (MOF) NTUniv-54 (NTUniv = Nantong University) was assembled via utilizing click chemistry with densely decorated trizole units and exposed metal sites, which exhibited the best methane working ability (197 cm3·cm-3 from 100 to 5 bar and 177 cm3·cm-3 from 65 to 5 bar at 298 K), and the lowest CO2 Qst of 22.8 kJ·mol-1 in all triazole-MOFs at room temperature.

Vaccination with circulating exosomes in autoimmune uveitis prevents recurrent intraocular inflammation.

BACKGROUND: Exosomes participate in intercellular communication and act as important molecular vehicles in the regulation of numerous physiological and pathological processes, including autoimmune development. The role of circulating exosomes in the development of autoimmune uveitis is unknown. In this study, using the rat model of experimental autoimmune uveitis, which has clinical and histological features of pan uveitis in man, we evaluated the immunoregulatory function of circulating exosomes. METHODS: Experimental autoimmune uveitis was induced in Lewis rats either immunised with interphotoreceptor retinoid-binding protein R16 peptides or injected with activated R16-specific T cells. The disease incidence and severity were examined by indirect fundoscopy and flow cytometry. Circulating exosomes were isolated from peripheral blood of naïve and Day 14 R16 immunised Lewis rats. The effect of exosomes on specific T cells was evaluated by R16-specific T cell proliferation, cytokine production and recurrent uveitis induction. RESULTS: Circulating exosomes derived from active immunised uveitis rats selectively inhibited immune responses of R16-specific T cells in vitro. Vaccination of naïve rats with these exosomes reduced the incidence of recurrent uveitis in an antigen-specific manner. Antigen-specific uveitogenic T cells reduced IFN-γ production and increased IL-10 after vaccination. CONCLUSIONS: Circulating exosomes in autoimmune uveitis have the potential to be a novel treatment for recurrent autoimmune uveitis.

Domino Heck/Hiyama cross-coupling: trapping of the σ-alkylpalladium intermediate with arylsilanes.

A palladium-catalyzed domino Heck cyclization/Hiyama coupling reaction by the trapping of the σ-alkylpalladium intermediate with arylsilanes is described. A wide range of aryl-tethered alkenes and arylsilanes are all compatible with the reaction conditions. This approach shows good yields and excellent functional group tolerance, presenting a more practical and sustainable alternative to the conventional domino Heck cyclization/Suzuki coupling reaction.

Effects of transarterial chemoembolization combined with antiviral therapy on HBV reactivation and liver function in HBV-related hepatocellular carcinoma patients with HBV-DNA negative.

BACKGROUND: The aim of this study was to investigate the reactivation of the hepatitis B virus (HBV) following transarterial chemoembolization (TACE) in primary hepatocellular carcinoma (HCC) patients with HBV-DNA negative and to evaluate the effects of TACE combined with antiviral therapy. METHODS: This prospective study involved 98 patients with HBV-related and HBV-DNA negative HCC (HBV DNA < 10 copies/mL) underwent TACE procedures with serial HBV DNA tests. Patients were divided into the antiviral treatment group and the no-antiviral group. The antiviral group received entecavir antiviral therapy, and the other group received no antiviral therapy. Two groups of patients were compared in rate of HBV reactivation and liver function before and after only 1 session of TACE in average 1-month follow-up after operation. P < .05 indicated differences with a statistical significance. RESULTS: HBV reactivation occurred in 11 patients in the nonantiviral group (11/47, 23.4%) but only 3 patients in the antiviral group (3/51, 5.9%, P < .05). On multivariate analysis, HBeAg-positive status, number of tumors more than 3, and absence of antiviral therapy were the independent risk predictor of HBV reactivation. Liver function indicators did not differ significantly between the antiviral group and the nonantiviral group in 5 days after TACE. However, the level of alanine aminotransferase and bilirubin were raised and albumin was reduced at the HBV reactivation group compared with no HBV reactivation group (P < .05). At 1 month after TACE, liver function indicators did not differ significantly between the HBV reactivation group and without HBV reactivation group. CONCLUSION: HCC patients with HBV DNA negative still remain associated with risk of HBV reactivation after TACE. HBeAg-positive, number of tumors more than 3, and absence of antiviral therapy in HCC patients after TACE have a higher risk of HBV reactivation. Antiviral therapy can reduce the risk of reactivation, helping improve liver function after TACE.

Comparison of CTA and DSA in the diagnosis of superior mesenteric artery dissecting aneurysm.

Objective To compare computed tomography arteriography (CTA) and digital subtraction arteriography (DSA) in the diagnosis of superior mesenteric artery dissecting aneurysm (SMADA). Methods All SMADA patients who underwent CTA and DSA at one of two medical centers between May, 2007 and April, 2017 were identified. The accuracy of CTA and DSA for the depiction of morphologic characteristics of SMADA was analyzed. Results Fourteen patients (12 men; mean age, 55.1 ± 6.4 years) were included in this study. The mean diameter of the dissecting aneurysm was 3.78 ± 1.53 mm on CTA and 3.81 ± 1.54 mm on DSA ( p = 0.96). The luminal stenosis was 0.52 ± 0.27 on CTA and 0.35 ± 0.23 on DSA ( p = 0.09). The thrombosed false lumen was visualized on CTA in 79% (11/14) of patients but in no patients on DSA ( p < 0.001). The entry points of the dissection were visualized on CTA in 64.3% (9/14) of patients and on DSA in 100% (14/14) of patients ( p = 0.041); CTA and DSA did not visualize re-entry points in any patients. The intimal flap was visualized on CTA in 71.4% (10/14) of patients and on DSA in 78.6% (11/14) of patients ( p > 0.05). Branch vessel involvement was visualized in 7.1% (1/14) of patients on CTA but in no patients on DSA ( p > 0.05). Conclusions CTA can be used in place of DSA for the diagnosis of SMADA. Although CTA may exaggerate the degree of luminal stenosis and is weak in depicting the entry points of SMADA, this modality more accurately depicts the thrombosed false lumen and branch vessel involvement.

Chemoembolization for hepatocellular carcinoma fed by right internal thoracic artery.

The purpose of the study was to evaluate the value of transarterial chemoembolization (TACE) via right internal thoracic artery (RITA) for patients with unresectable hepatocellular carcinoma (HCC).From January 2000 to June 2016, a retrospective study was conducted of all patients with unresectable HCC who underwent TACE via RITA across 3 medical centers. The technical success, serum alpha-fetoprotein (AFP) level changes, major complications, disease control rate, and survival were evaluated and analyzed.During the study peroid, in all, 21 patients (men 21; mean age 57.3 ±â€Š7.1 years) were included in this study. Of the 21 patients, all the tumors were located under the capsule of the liver and adjacent to the diaphragm with median tumor diameter of 8.2 cm in 20 patients, and the tumor was located at the surface of the liver due to incisional site metastasis in 1 remaining patient. Lesions fed by the RITA were demonstrated during initial TACE in 2 patients and during repeat TACE therapy in 19 patients. The technical success rate was 100%. The AFP response 1 month after treatment was complete (n = 4) and partial (n = 9) of 13 patients whose AFP was abnormal before the procedure, and the serum levels of AFP reduced significantly 1 month after treatment (1240.1 ±â€Š347.1 vs 175.2 ±â€Š71.8; P < .01). No major complications occurred. The disease control rate was 100% at 3 months after treatment. The median overall survival from the time of TACE therapy via the RITAs was 18.2 months, and 1-year survival after TACE therapy via the RITAs was 76.2%.Chemoembolization via the RITA can improve the therapeutic efficacy of TACE and reduce the presence of residual HCC.

Supplemental conventional transarterial embolization/chemoembolization therapy via extrahepatic arteries for hepatocellular carcinoma.

PURPOSE: To assess the value of conventional transarterial embolization/chemoembolization (cTAE/TACE) therapy via extrahepatic arteries for patients with unresectable hepatocellular carcinoma (HCC). METHODS: Patients with unresectable HCC who underwent cTAE/TACE therapy via extrahepatic arteries between May 2008 and July 2016 across 4 medical centers were identified. The technical success, serum alpha-fetoprotein (AFP) levels changes, tumor response, disease control rate, survival rate, and major complication were analyzed. RESULTS: A total of 185 patients (167 male and 18 female) were included in this study. A total of 401 procedures were performed of the 185 patients, with 2.2 ± 0.4 procedures for each patient. A total of 197 extrahepatic arteries were identified, including inferior phrenic artery (n = 80), omental artery (n = 39), gastric artery (n = 22), right renal capsular artery (n = 21), adrenal artery (n = 13), cystic artery (n = 11), and right internal mammary artery (n = 11). The technical success rate was 96.8% (179/185). The serum AFP levels were significantly reduced at 1 month after treatment in 71 patients whose AFP ≥400 ng/mL preprocedure (P < 0.01). The disease control rate was 93% (172/185) at 3 months after cTAE/TACE, with partial response, stable disease, or progressive disease of 115, 57, and 13 patients, respectively. The cumulative survival rate from the time of cTAE/TACE via extrahepatic arteries was 100% at 6 months. There were no embolization-related major complications. CONCLUSION: cTAE/TACE therapy via the extrahepatic arteries can reduce the incidence of presence of residual HCC, and improve the therapeutic efficacy of cTAE/TACE.