Catalytic Atroposelective Synthesis of N-N Axially Chiral Indolylamides.

The catalytic atroposelective synthesis of N-N axially chiral indolylamides was established via dynamic kinetic resolution, which makes use of chiral Lewis base-catalyzed asymmetric acylation of -acylaminoindoles as a new type of platform molecule with anhydrides. By this strategy, a series of N-N axially chiral indolylamides were synthesized in overall good yields (up to 98%) with excellent enantioselectivities (up to 99% ee). Moreover, some of these N-N axially chiral indolylamides display some extent of anticancer activity, which demonstrates their potential application in medicinal chemistry.

Effect of eco-friendly pervious concrete pavement with travertine waste and sand on the heavy metal removal and runoff reduction performance.

To address the negative environmental and economic impact of the large amounts of solid waste generated during travertine mining and to reduce the dependence on natural aggregates and cement for pervious concrete pavement applications, travertine waste, as aggregate and powder, was used for the travertine powder pervious concrete (TPPC) to improve the utilization of solid waste and decrease CO emissions. The experimental results showed that using 25% travertine aggregate and 5% powder results in a compressive strength reduction of only 9.8% to 25.

Oxalic acid-modified activated carbons under hydrothermal condition for the adsorption of the 2-butanone.

Growing volatile organic compound (VOC) emission will cause air pollution and further threaten human health. Activated carbon is widely applied to treatment of VOCs in virtue of lower cost and excellent adsorption ability. In this work, the adsorption capacity of polarity VOCs on activated carbon is improved by oxalic acid (HCO) hydrothermal modification.

Organocatalytic Enantioselective Synthesis of Axially Chiral N,N'-Bisindoles.

This study establishes the first organocatalytic enantioselective synthesis of axially chiral N,N'-bisindoles via chiral phosphoric acid-catalyzed formal (3+2) cycloadditions of indole-based enaminones as novel platform molecules with 2,3-diketoesters, where de novo indole-ring formation is involved. Using this new strategy, various axially chiral N,N'-bisindoles were synthesized in good yields and with excellent enantioselectivities (up to 87 % yield and 96 % ee). More importantly, this class of axially chiral N,N'-bisindoles exhibited some degree of cytotoxicity toward cancer cells and was derived into axially chiral phosphine ligands with high catalytic activity.

In Vitro and In Silico Analyses of New Cinnamid and Rosmarinic Acid-Derived Compounds Biosynthesized in as Arginase Inhibitors.

Arginase is a metalloenzyme that plays a central role in infections. Previously, rosmarinic and caffeic acids were described as antileishmanial agents and as arginase inhibitors. Here, we describe the inhibition of arginase in by rosmarinic acid analogs () and new caffeic acid-derived amides ().

Chemoenzymatic conversion of glycerol to lactic acid and glycolic acid.

Catalytic valorization of raw glycerol derived from biodiesel into high-value chemicals has attracted great attention. Here, we report chemoenzymatic cascade reactions that convert glycerol to lactic acid and glycolic acid. In the enzymatic step, a coenzyme recycling system was developed to convert glycerol into 1,3-dihydroxyacetone (DHA) with a yield of 92.

Regio- and Enantioselective (3+3) Cycloaddition of Nitrones with 2-Indolylmethanols Enabled by Cooperative Organocatalysis.

The regio- and enantioselective (3+3) cycloaddition of nitrones with 2-indolylmethanols was accomplished by the cooperative catalysis of hexafluoroisopropanol (HFIP) and chiral phosphoric acid (CPA). Using this approach, a series of indole-fused six-membered heterocycles were synthesized in high yields (up to 98 %), with excellent enantioselectivities (up to 96 % ee) and exclusive regiospecificity. This approach enabled not only the first organocatalytic asymmetric (3+3) cycloaddition of nitrones but also the first C3-nucleophilic asymmetric (3+3) cycloaddition of 2-indolylmethanols.

Catalytic Asymmetric Construction of Axially Chiral Indole-Based Frameworks: An Emerging Area.

Axially chiral indole-based frameworks have been recognized as a class of important five-membered heterobiaryls and developing catalytic asymmetric approaches for constructing these frameworks in an enantioselective manner is highly desirable. In recent years, synthetic chemists have paid much attention to this research field, and rapid developments have occurred. At this point, a range of axially chiral indole-based scaffolds have been constructed via various catalytic asymmetric reactions based on different strategies.

Organocatalytic [4 + 2] cyclizations of para-quinone methide derivatives with isocyanates.

The first [4 + 2] cyclizations of para-quinone methide derivatives with isocyanates have been established under the catalysis of Brønsted acids or Brønsted bases, which efficiently constructed benzoxazin-2-one frameworks in generally high yields (up to 95%). This reaction will not only enrich the research contents of para-quinone methide-involved cyclization reactions but also provide a useful method for constructing biologically important benzoxazin-2-one frameworks.

Catalytic Asymmetric [4 + 1] Cyclization of Benzofuran-Derived Azadienes with 3-Chlorooxindoles.

A chiral guanidine-catalyzed asymmetric [4 + 1] cyclization of benzofuran-derived azadienes with 3-chlorooxindoles has been established, which constructed chiral spirooxindole frameworks with in situ generation of a five-membered ring with high diastereoselectivities (up to >95:5 dr) and good enantioselectivities (up to 94:6 er). This reaction represents the first catalytic asymmetric [4 + 1] cyclization of benzofuran-derived azadienes, which will enrich the research field of catalytic asymmetric cyclizations of such reactants. In addition, this reaction provides a useful strategy for the enantioselective construction of five-membered ring-based chiral spirooxindole scaffolds.

Brønsted Acid-Catalyzed (4 + 3) Cyclization of N, N'-Cyclic Azomethine Imines with Isatoic Anhydrides.

A Brønsted acid-catalyzed (4 + 3) cyclization of N, N'-cyclic azomethine imines with isatoic anhydrides has been discovered, which constructs seven-membered nitrogenous heterocyclic frameworks with overall high yields (up to 98% yield). This reaction represents a rarely reported (4 + 3) cyclization of N, N'-cyclic azomethine imines, which involves the reassembly of a C-N bond. In addition, this reaction has also accomplished the unprecedented (4 + 3) cyclization of isatoic anhydrides.

Tough protein organohydrogels.

Tough protein organohydrogels were fabricated by applying a solvent displacement-induced toughening (SDIT) strategy. With SDIT, traditionally weak and brittle protein hydrogels were altered to protein organohydrogels with remarkably high performance in anti-freezing, non-drying, topological healing, thermal plasticizing, mechanical toughness and stretchability. The SDIT opens a reliable and straightforward path to develop novel biomimetic materials and artificial devices from abandunt protein-based sources.

Shape morphing of anisotropy-encoded tough hydrogels enabled by asymmetrically-induced swelling and site-specific mechanical strengthening.

This communication reports a dual regulation strategy, i.e., swelling and stiffness mismatch, for the shape morphing of calcium-alginate/polyacrylamide (PAAm) tough hydrogels enabled by site-specific patterning of ferric ions.

Production of caffeoylmalic acid from glucose in engineered Escherichia coli.

Objectives: To achieve biosynthesis of caffeoylmalic acid from glucose in engineered Escherichia coli.

Results: We constructed the biosynthetic pathway of caffeoylmalic acid in E. coli by co-expression of heterologous genes RgTAL, HpaBC, At4CL2 and HCT2.

Softening and Shape Morphing of Stiff Tough Hydrogels by Localized Unlocking of the Trivalent Ionically Cross-Linked Centers.

The mechanical properties (e.g., stiffness, stretchability) of prefabricated hydrogels are of pivotal importance for diverse applications in tissue engineering, soft robotics, and medicine.

Rational Fabrication of Anti-Freezing, Non-Drying Tough Organohydrogels by One-Pot Solvent Displacement.

Tough hydrogels, polymeric network structures with excellent mechanical properties (such as high stretchability and toughness), are emerging soft materials. Despite their remarkably mechanical features, tough hydrogels exhibit two flaws (freezing around the icing temperatures of water and drying under arid conditions). Inspired by cryoprotectants (CPAs) used in the inhibition of the icing of water in biological samples, a versatile and straightforward method is reported to fabricate extreme anti-freezing, non-drying CPA-based organohydrogels with long-term stability by partially displacing water molecules within the pre-fabricated hydrogels.

Mechanochemical Regulated Origami with Tough Hydrogels by Ion Transfer Printing.

Stimuli-responsive hydrogels that undergo programmable shape deformation are of great importance for a wide variety of applications spanning from soft robotics and biomedical devices to tissue engineering and drug delivery. To guide shape morphing, anisotropic elements need to be encoded into the hydrogels during fabrication, which are extremely difficult to alter afterward. This study reports a simple and reliable mechanochemical regulation strategy to postengineer the hydrogels by encoding structures of high stiffness locally into prestretched tough hydrogels through ion transfer printing with a paper-cut.

"Freezing", morphing, and folding of stretchy tough hydrogels.

Highly stretchable and tough Ca-alginate/polyacrylamide hydrogels were "frozen" and folded into program-controlled shapes by exposing them to an Fe ion aqueous solution. The elastic modulus of the as-made tough gels increased either in bulk or locally up to 2.90 MPa, while the toughness remained within the range from 8.

Bioinspired, Mechano-Regulated Interfaces for Rationally Designed, Dynamically Controlled Collection of Oil Spills from Water.

This study describes the fabrication of bioinspired mechano-regulated interfaces (MRI) for the separation and collection of oil spills from water. The MRI consists of 3D-interconnected, microporous structures of sponges made of ultrasoft elastomers (Ecoflex). To validate the MRI strategy, ecoflex sponges are first fabricated with a low-cost sugar-leaching method.