Impact of Synthetic Variables on the Structural Diversity of TbIII-Carboxylate Frameworks: Gas Adsorption, Magnetism, and Organocatalysis Investigations.

In this work, three unique TbIII-carboxylate frameworks with the formula {[Tb2(OH)2(H2O)2(abtc)]·2H2O}n (1), {[Tb2(abtc)1.5(H2O)3(DMA)]·H2O}n (2) and {[Tb3(abtc)2.5(H2O)4]·H3O}n (3), each displaying structural variations, have been successfully synthesized by the solvothermal reactions of Tb(NO3)3·6H2O with the azo-containing ligand 3,3',5,5'-azobenzene tetracarboxylic acid (H4abtc) under varying conditions. Detailed single-crystal X-ray diffraction (SC-XRD) analysis manifested a remarkable diversity in these structures, demonstrating various coordination patterns of TbIII-metal nodes with the carboxylate groups of the organic linker, which contributed to the generation of intricate three-dimensional (3D) coordination networks with remarkable chemical resistance. Furthermore, frameworks 2 and 3, characterized by porous networks containing two and three independent TbIII-metal nodes, respectively, were both demonstrated to be efficient heterogeneous catalysts toward the cyanosilylation of imines under mild conditions with excellent reusability. In addition, direct current (Dc) magnetic susceptibility measurements conducted on frameworks 1, 2, and 3 indicated that there were obvious antiferromagnetic interactions among the TbIII-metal nodes, which suggests the involvement of intricate intra- and intertrimer exchange channels, adding another fascinating dimension to their physical properties.

Mechanism and synergistic effect of sulfadiazine (SDZ) and cadmium toxicity in spinach (Spinacia oleracea L.) and its alleviation through zinc fortification.

Cadmium (Cd) and antibiotic's tendency to accumulate in edible plant parts and fertile land is a worldwide issue. The combined effect of antibiotics and heavy metals on crops was analyzed, but not mitigation of their toxicity. This study investigated the potential of zinc oxide nanoparticles (ZnO NPs) to alleviate the SDZ and Cd toxicity (alone/combined) to promote spinach growth. Results revealed that the ZnO 200 mg L-1 spray decreased the malondialdehyde (MDA) 14%, hydrogen peroxide (H2O2) 13%, and electrolyte leakage (EL) 7%, and increased the superoxide dismutase (SOD) 8%, peroxidase (POD) 25%, catalase (CAT) 39% and ascorbate peroxidase (APX) 12% in spinach leaves under combined SDZ+Cd (25 mg Kg-1 +50 mg Kg-1) stress compared to ZnO 100 mg L-1 spray. Likewise, ZnO NPs 200 mg L-1 spray enhanced the zinc (Zn) 97%, iron (Fe) 86%, magnesium (Mg) 35%, manganese (Mn) 8%, and potassium (K) 23% in shoots under combined SDZ+Cd (25 mg Kg-1 +50 mg Kg-1) stress compared to ZnO 100 mg L-1 spray. Further, ZnO 200 mg L-1 spray reduced Cd uptake in roots by 9% and shoots 15% under combined SDZ+Cd (25 mg Kg-1 +50 mg Kg-1) stress compared to ZnO 100 mg L-1. Overall, ZnO NPs alleviated the SDZ and Cd toxicity and enhanced spinach growth in all treatments.

Metal-organic frameworks incorporating azobenzene-based ligands as a heterogeneous Lewis-acid catalyst for cyanosilylation of imines.

In this work, two novel metal-organic frameworks (MOFs) were synthesized by the reaction of azobenzene-based ligands and Zn(NO3)2/CdCO3 under solvothermal conditions with the formula of {[Zn2(abtc)(azpy)(H2O)2]·4H2O} n (1) and {[Cd(abtc)0.5(azpy)0.5(H2O)]·3H2O} n (2) (H4abtc = 3,3',5,5'-azobenzene tetracarboxylic acid, azpy = 4,4'-azobipyridine). According to the single-crystal X-ray diffraction (SC-XRD) analysis, complexes 1 and 2 possessed quite similar structures except for the coordination modes of the central metal nodes attributed to the difference between the cationic radius of Zn(ii) and Cd(ii). The Zn(ii) cations in 1 adopted a distorted seesaw coordination geometry and the coordination between Zn(ii) and organic linkers gave two-dimensional (2D) coordination networks, while the Cd(ii) cations in 2 could also bind with the carboxylate groups from neighboring coordination networks to form a three-dimensional (3D) coordination framework. Furthermore, complexes 1 and 2 showed high catalytic activity as heterogeneous Lewis-acid catalysts towards the cyanosilylation of imines with satisfactory reusability under mild conditions and the similar catalytic performance of 1 and 2 could be attributed to the similarity in their structures. A prudent mechanism has been proposed as well to elucidate the role of complexes 1 and 2 in the catalytic process.

Use of Web-Based Patient Portals in Patients With Atrial Fibrillation Is Associated With Higher Readmissions.

Background: The impact of web-based patient portals on patient outcomes-specifically hospital readmissions in patients with atrial fibrillation (AF)-remains understudied. Methods: This single-center retrospective cohort study investigated the use of an online portal system (MyChart) by patients hospitalized from January 1, 2014 to June 30, 2017 for AF. During the study period, 11,334 unique AF admissions were identified; 50.3% were MyChart users and 49.7% were non-MyChart users. Patients who experienced inpatient mortality were excluded. The study groups were analyzed for demographic variables, comorbidities, readmission rates, and the frequency of MyChart use during the 3.5-year time frame. Results: MyChart users were younger (median age, 74 years, interquartile range [IQR] 66-82 vs 77 years, IQR 68-85; P<0.0001) and more likely to be white (91.9% vs 84.6%; P<0.0001), but the sex distribution was similar between groups, with 51.8% males in the MyChart group vs 53.2% in the non-MyChart group. MyChart users had a significantly higher rate of readmission compared to non-MyChart users at 1 year (43.0% vs 32.0%, respectively; P<0.0001). MyChart users who were readmitted had a higher median number of logins to MyChart (121 [IQR 32-270.5]) than MyChart users who were not readmitted (91 [IQR 26-205]; P<0.0001). Multivariable regression analysis demonstrated that MyChart use was associated with readmission (odds ratio 1.57, 95% CI 1.49-1.70; P<0.0001). Conclusion: Among patients with AF, MyChart use was associated with higher readmissions in this single-center cohort. Use and benefit of bespoke portals require further study.

Development of Cephradine-Loaded Gelatin/Polyvinyl Alcohol Electrospun Nanofibers for Effective Diabetic Wound Healing: In-Vitro and In-Vivo Assessments.

Diabetic wound infections caused by conventional antibiotic-resistant Staphylococcus aureus strains are fast emerging, leading to life-threatening situations (e.g., high costs, morbidity, and mortality) associated with delayed healing and chronic inflammation. Electrospinning is one of the most widely used techniques for the fabrication of nanofibers (NFs), induced by a high voltage applied to a drug-loaded polymer solution. Particular attention is given to electrospun NFs for pharmaceutical applications (e.g., original drug delivery systems) and tissue regeneration (e.g., as tissue scaffolds). However, there is a paucity of reports related to their application in diabetic wound infections. Therefore, we prepared eco-friendly, biodegradable, low-immunogenic, and biocompatible gelatin (GEL)/polyvinyl alcohol (PVA) electrospun NFs (BNFs), in which we loaded the broad-spectrum antibiotic cephradine (Ceph). The resulting drug-loaded NFs (LNFs) were characterized physically using ultraviolet-visible (UV-Vis) spectrophotometry (for drug loading capacity (LC), drug encapsulation efficiency (EE), and drug release kinetics determination), thermogravimetric analysis (TGA) (for thermostability evaluation), scanning electron microscopy (SEM) (for surface morphology analysis), and Fourier-transform infrared spectroscopy (FTIR) (for functional group identification). LNFs were further characterized biologically by in-vitro assessment of their potency against S. aureus clinical strains (N = 16) using the Kirby-Bauer test and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay, by ex-vivo assessment to evaluate their cytotoxicity against primary human epidermal keratinocytes using MTT assay, and by in-vivo assessment to estimate their diabetic chronic wound-healing efficiency using NcZ10 diabetic/obese mice (N = 18). Thin and uniform NFs with a smooth surface and standard size (<400 nm) were observed by SEM at the optimized 5:5 (GEL:PVA) volumetric ratio. FTIR analyses confirmed the drug loading into BNFs. Compared to free Ceph, LNFs were significantly more thermostable and exhibited sustained/controlled Ceph release. LNFs also exerted a significantly stronger antibacterial activity both in-vitro and in-vivo. LNFs were significantly safer and more efficient for bacterial clearance-induced faster chronic wound healing. LNF-based therapy could be employed as a valuable dressing material to heal S. aureus-induced chronic wounds in diabetic subjects.

Synthesis of new boswellic acid derivatives as potential antiproliferative agents.

In the current investigation, a series of heterocyclic derivatives of boswellic acids were prepared along with new monomers of 3-O-acetyl-11-keto-ß-boswellic acid (AKBA, 1) 11-keto-ß-boswellic acid (KBA, 2) and several new bis-AKBA and KBA homodimers and AKBA-KBA heterodimers. The effects of these compounds on the proliferation of different human cancer cell lines, viz., FaDu (pharynx carcinoma), A2780 (ovarian carcinoma), HT29 (colon adenocarcinoma), and A375 (malignant melanoma), have been evaluated. Thus, KBA homodimer 21 effectively inhibited the growth of FaDu, A2780, HT29, and A375 cells with EC50 values below 9 µM. In addition, compounds 7, 8, 11, 12, 15, 16, and 17 also exhibited cytotoxic effects for A2780, HT29, and A375 cancer cells. In particular, the pyrazine analog 8 was highly cytotoxic for A375 cancer cells with an EC50 value of 2.1 µM.

Synthesis of new triterpenic monomers and dimers as potential antiproliferative agents and their molecular docking studies.

In the current investigation, new monomers of myrrhanone B and lupeolic acid were prepared via reaction of triterpenic acids with linkers in the presence of K2CO3. In addition, new bis-myrrhanone B homodimers, myrrhanone B-myrrhanol B heterodimers, and bis-myrrhanone ß-boswellic acids heterodimer were prepared. Evaluation of these compounds on the proliferation of four different human cancer cell lines, viz., FaDu (pharynx carcinoma), A2780 (ovarian carcinoma), HT29 (colon adenocarcinoma) and A375 (malignant melanoma) has been performed. It is worth mentioning that compounds 4, 7, 8, 10, and 11 possess potent antiproliferative effect towards HT29 cancer cells with IC50 values of 8.1 µM, 5.4 µM, 8.8 µM, 6.8 µM, and 8.2 µM, respectively. In addition, these compounds display good to moderate antiproliferative activities towards A2780 and A375 with IC50 values ranging from 10.4 to 24.2 µM. Moreover, the molecular docking studies of most active compounds (4, 7, 8, 10 and 11) with six anti-cancer drug targets DHFR, VEGFR2, HER-2/neu, CDK6, hCA-IX and LOX also carried, in order to know the mode of binding interaction and energy of this class of compounds.