Asymmetric and Sustainable Synthesis of Cyclic Sulfoxides with Low Loading of Bisguanidinium Peroxomolybdate Ion-Pairing Catalyst

Chiral cyclic sulfoxides are valuable heterocyclic building blocks in natural products and pharmaceutically active molecules as well as optoelectronics materials. In view of their manifold applications but limited number of available synthetic methodologies to obtain them, highly enantioselective catalytic approaches to access chiral cyclic sulfoxides are therefore desired. Here, a sustainable and enantioselective oxidation of cyclic sulfides has been developed by employing in situ-generated bisguanidinium peroxomolybdate ion-pairing catalysis. Chiral cyclic sulfoxides bearing different ring sizes and functional groups have been achieved under mild and green conditions with low catalyst loading (0.05–0.5 mol %). The synthetic potentials based on chiral cyclic sulfoxide products have also been demonstrated in preparation of medicinally relevant molecules such as BI 1015550, a candidate drug for the treatment of idiopathic pulmonary fibrosis

Enantioselective Reaction of α-Lithiated Dithioacetals Using Chiral Bis(oxazoline)s: New Chiral Formyl Anion Equivalents

The enantioselective reaction of various α-lithiated dithioacetals with aldehydes or a ketone in the presence of bis(oxazoline)s was examined. Among them, unsymmetrical dithioacetals were found to be the best choice for attaining high enantioselectivity. The reaction of lithiated tert-butylthio(2-pyridylthio)methane with aldehydes proceeded with good diastereoselectivity as well as with good enantioselectivity. The enantioselective reaction was shown to proceed through dynamic thermodynamic resolution. Mercury(II) chloride effected hydrolysis of the dithioacetal moiety of the products to 2-hydroxyaldehydes, which were directly reduced to give the optically active 1,2-diols

Persistence of immune tolerance to asthma antigens in the adult stage.

<p>Saline and OVA represented mice treated, sensitized and challenged by saline and OVA respectively. OVA+rAdV-CTLA4Ig and OVA+rAdV-GFP represented mice treated with OVA+rAdV-CTLA4Ig and OVA+rAdV-GFP in the neonatal period sensitized and challenged by OVA at 3 and 7 months old. Each group contains 10 mice. A, regimen of sensitization, challenge, and treatment. B, representative histopathological characteristics of mice lung: upper, lungs of 3-month-old mice; lower, lungs of 7-month-old mice. C, airway reactivity testing in 3-month-old mice. * indicates significantly low airway reactivity of OVA+rAdV-CTLA4Ig treated mice versus the asthma mice (OVA group). D. airway reactivity testing in 7-month-old mice. * indicates significantly low airway reactivity of OVA+rAdV-CTLA4Ig treated mice versus the asthma mice (OVA group).</p

<i>In vitro</i> evaluation of the function of DCs modified by rAdV-CTLA4Ig.

<p>A, IL-10 (left Y-axis) and IL-12 (right Y-axis) secretion of modified DCs. B, characteristics of T cell stimulation of modified DCs evaluated by MLR. MLR, mixed lymphocyte reaction.</p

Additional file 1 of Efficacy and safety of vedolizumab for pediatrics with inflammatory bowel disease: a systematic review

Additional file 1: Table S1. Search strategy in databases. Table S2. Methodological quality of case series

Selective ethylene oligomerization bearing hyperbranched bispyridylamine chromium catalyst

Two new hyperbranched bispyridylamine ligands and multinuclear chromium complexes were synthesized with 1.0 G hyperbranched macromolecules, 2-chloropyridine, 2-chloro-4-methylpyridine and CrCl3(THF)3 as raw materials. The structures of hyperbranched ligands and chromium complexes were characterized by UV, FT-IR, 1H NMR, ESI-MS, and elemental analysis. These hyperbranched chromium complexes were evaluated as catalyst precursors by using MAO as activator in the oligomerization of ethylene. Effects of reaction temperature, reaction pressure, Al/Cr molar ratio, concentration of catalyst, solvent, and the structure of catalysts on the catalytic activity and product selectivity were investigated. The oligomerization results showed that with increase of reaction temperature, reaction pressure, and Al/Cr molar ratio, the catalytic activity increased and then decreased; the catalytic activity continuously decreased as the amount of catalyst increased. The products were mainly based on C6 and C8. Under optimized conditions, the catalytic system of hyperbranched NNN/Cr(III)/MAO led to activity of 1.26 × 105 g/(mol·Cr·h) and 63.34% selectivity for C6 and C8.</p

Humoral immunological changes in the specificity assessment.

<p>For easy comparisons, the rates of change in IL-4, IL-10, IFN-γ, and IgE in both BALF and sera were adjusted by the values of the control (sensitized and challenged by saline). * indicates statistical significance of each comparison. A, the increasing rates of IL-4 in the regimens of sensitization, challenge, and treatment. B, IFN-γ decreasing rates in the regimens of sensitization, challenge, and treatment. C, IL-10 changes in the regimens of sensitization, challenge, and treatment. D, the increasing rates of IgE in the regimens of sensitization, challenge, and treatment.</p

Cell classification and changes in cytokine levels 3 and 7 months after sensitization.

<p>BALF, bronchoalveolar lavage fluid; IL, interleukin; IFN, interferon; CTLA4Ig, cytotoxic T lymphocyte antigen 4-immunoglobulin; GFP, green fluorescent protein; IgE, immunoglobulin E. The mice sensitized and challenged by saline were used as controls; the mice sensitized and challenged by OVA were defined as the asthma group; the mice transplanted with DCs modified by treatment with OVA+rAdV-CTLA4lg before being sensitized to OVA were defined as OVA+rAdV-CTLA4Ig; the mice transplanted with DCs modified by treatment with OVA+rAdV-GFP before being sensitized to OVA were difined as OVA+rAdV-GFP.</p><p>*, P<0.05 compared to controls;</p><p>▲, P<0.05 compared to the asthma group.</p><p>Cell classification and changes in cytokine levels 3 and 7 months after sensitization.</p

Supplement_Figure – Supplemental material for Nickel complexes based on hyperbranched bispyridylamine ligands as catalyst precursors for ethylene oligomerization

Supplemental material, Supplement_Figure for Nickel complexes based on hyperbranched bispyridylamine ligands as catalyst precursors for ethylene oligomerization by Jun Wang, Jinyi Liu, Liduo Chen, Tianyu Lan and Libo Wang in Journal of Chemical Research</p

Specificity assessment.

<p>To evaluate whether the persistent immune tolerance was allergen-specific, the neonatal mice were treated with OVA+rAdV-CTLA4Ig-modified DCs or Derp+rAdV-CTLA4Ig-modified DCs, 3 months later, the specificity of the therapeutic strategy was assessed by allergen cross challenge. Each group contains 10 mice. Saline, OVA and Derp represented mice treated, sensitized and challenged by saline, OVA and Derp respectively. OVA+rAdV-CTLA4Ig+OVA represented mice treated with rAdV-CTLA4Ig, sensitized by OVA and challenged by OVA. Derp+rAdV-CTLA4Ig+OVA represented mice treated with rAdV-CTLA4Ig, sensitized by Derp and challenged by OVA. Derp+rAdV-CTLA4Ig+Derp represented mice treated with rAdV-CTLA4Ig, sensitized by Derp and challenged by Derp. OVA+rAdV-CTLA4Ig+Derp represented mice treated with rAdV-CTLA4Ig, sensitized by OVA and challenged by Derp. A, the regimen of sensitization, challenge, and treatment in specificity assessment. B, airway reactivity testing of OVA-sensitized mice challenged by OVA or Derp. C, airway reactivity testing of Derp-sensitized mice challenged with Derp or OVA.</p