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 CO2 emissions. The experimental results showed that using 25% travertine aggregate and 5% powder results in a compressive strength reduction of only 9.8% to 25.92 MPa but a significant improvement in water permeability of 57.1% from 3.89 to 6.11 mm/s. To improve the performance of TPPC, further research was done on the effect of sand addition rate (SAR) on TPPC's density, compressive strength, porosity, water permeability, freeze-thaw resistance and heavy metal removal capacity to obtain an optimal incorporation ratio. As SAR rises, the compressive strength of TPPC with sand (STPC) initially increases and then decreases, while permeability behaves inversely. At 3% SAR, the compressive strength reached a maximum of 26.51 MPa, primarily due to the sand added to fill in some of the pores and stabilize the gradation. After 25 cycles, the strength loss rate of STPC varies from 11.39 to 17.93% and the freeze-thaw resistance is most excellent when SAR is 3%. The removal rate of heavy metals using the immersion method was found to be significantly higher (83.4-100%) compared to the rapid method (11.7-28.1%). Therefore, the 3% SAR was recommended for the mixture design of STPC. A laboratory-scale version of the pavement was constructed to assess the efficacy of STPC pavement (STPCP) in reducing runoff and removing heavy metals. The results showed that STPCP could remove more than 94% of runoff with varying intensities after 1 h. The STPCP exhibited removal rates ranging from 42.0 to 99.4% for Cd2+ and 79.5-95.4% for Cu2+. STPCP also attained a removal rate above 98% for Pb2+ after 30 min, demonstrating its environmental friendliness.

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field.

With the rapid development of asymmetric catalysis, the demand for the enantioselective synthesis of complex and diverse molecules with different chiral elements is increasing. Owing to the unique features of atropisomerism, the catalytic asymmetric synthesis of atropisomers has attracted a considerable interest from the chemical science community. In particular, introducing additional chiral elements, such as carbon centered chirality, heteroatomic chirality, planar chirality, and helical chirality, into atropisomers provides an opportunity to incorporate new properties into axially chiral compounds, thus expanding the potential applications of atropisomers. Thus, it is important to perform catalytic asymmetric transformations to synthesize atropisomers bearing multiple chiral elements. In spite of challenges in such transformations, in recent years, chemists have devised powerful strategies under asymmetric organocatalysis or metal catalysis, synthesizing a wide range of enantioenriched atropisomers bearing multiple chiral elements. Therefore, the catalytic asymmetric synthesis of atropisomers bearing multiple chiral elements has become an emerging field. This review summarizes the rapid progress in this field and indicates challenges, thereby promoting this field to a new horizon.

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 (H2C2O4) hydrothermal modification. After 2 M H2C2O4 modification, the adsorption capacity of 2-butanone rose from 312.60 to 345.98 mg/g, and the time reaching saturation adsorption became shorter. BET results showed that both the specific surface area and total pore volume of 2 M H2C2O4-modified activated carbon increased by 3.32% and 3.9%, respectively. Both FTIR and XPS characterization confirmed variation of the surface oxygen-containing functional groups (SOFGs), while quantitative analysis via Boehm titration showed the significant increase of total acidity (61.36%), particularly the carboxyl content increased by 96.28%. The results indicated modification process can not only change the pore structure but also the SOFGs of activated carbons. The dynamic adsorption curves conform to the Bangham kinetics model, indicating that the adsorption of 2-butanone on both activated carbon is controlled by the diffusion in the pore channel. The adsorption data was also modeled by the internal particle diffusion model, and the internal diffusion adsorption stage is the rate-controlling step. The stability before and after adsorption and the cycling performance were studied.

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. This study provides a new strategy for enantioselective synthesis of axially chiral N,N'-bisindoles using asymmetric organocatalysis and is the first to realize the applications of such scaffolds in medicinal chemistry and asymmetric catalysis.

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

Arginase is a metalloenzyme that plays a central role in Leishmania infections. Previously, rosmarinic and caffeic acids were described as antileishmanial agents and as Leishmania amazonensis arginase inhibitors. Here, we describe the inhibition of arginase in L. amazonensis by rosmarinic acid analogs (1-7) and new caffeic acid-derived amides (8-10). Caffeic acid esters and amides were produced by means of an engineered synthesis in E. coli and tested against L. amazonensis arginase. New amides (8-10) were biosynthesized in E. coli cultured with 2 mM of different combinations of feeding substrates. The most potent arginase inhibitors showed Ki(s) ranging from 2 to 5.7 µM. Compounds 2-4 and 7 inhibited L. amazonensis arginase (L-ARG) through a noncompetitive mechanism whilst compound 9 showed a competitive inhibition. By applying an in silico protocol, we determined the binding mode of compound 9. The competitive inhibitor of L-ARG targeted the key residues within the binding site of the enzyme, establishing a metal coordination bond with the metal ions and a series of hydrophobic and polar contacts supporting its micromolar inhibition of L-ARG. These results highlight that dihydroxycinnamic-derived compounds can be used as the basis for developing new drugs using a powerful tool based on the biosynthesis of arginase inhibitors.

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 92.3% in potassium phosphate buffer (300 mM, pH 7.1) containing 100 mM glycerol, 2 mM NAD+, 242 U/mL glycerol dehydrogenase-GldA and NADH oxidase-SpNoxK184R at 30 °C. Subsequently, NaOH or NaClO2 catalyzes the formation of lactic acid and glycolic acid from DHA. The high yield of lactic acid (72.3%) and glycolic acid (78.2%) verify the benefit of the chemoenzymatic approaches.

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. More importantly, theoretical calculations elucidated the role of the cocatalyst HFIP in helping CPA control the reactivity and enantioselectivity of the reaction, demonstrating a new mode of cooperative catalysis.

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. Thus, the catalytic asymmetric construction of axially chiral indole-based frameworks has become an emerging area. This minireview summarizes the rapid advances in this field and gives some insights into future developments, which will help this research field to thrive.

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.

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. This study reports a feasible method to fabricate ultrasoft and highly stretchable structures from stiff and tough hydrogels of low stretchability and the application of these switchable hydrogels in programmable shape-morphing systems. Stiff and tough hydrogel structures are first fabricated by the mechanical strengthening of Ca2+ -alginate/polyacrylamide tough hydrogels by addition of Fe3+ ions, which introduces Fe3+ ionically cross-linked centers into the Ca2+ divalent cross-linked hydrogel, forming an additional and much less flexible trivalent ionically cross-linked network. The resulting stiff and tough hydrogels are exposed to an L-ascorbic acid (vitamin C, VC) solution to rapidly reduce Fe3+ to Fe2+ . As a result, flexible divalent ionically cross-linked networks are formed, leading to swift softening of the stiff and tough hydrogels. Moreover, localized stiffness variation of the tough hydrogels can be realized by precise patterning of the VC solution. To validate this concept, sequential steps of VC patterning are carried out for local tuning of the stiffness of the hydrogels. With this strategy, localized softening, unfolding, and sequential folding of the tough hydrogels into complex 3D structures is demonstrated.

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. To enhance the production of caffeoylmalic acid, we optimized the tyrosine metabolic pathway of E. coli to increase the supply of the substrate caffeic acid. Consequently, an E. coli-E. coli co-culture system was used for the efficient production of caffeoylmalic acid. The final titer of caffeoylmalic acid reached 570.1 mg/L. CONCLUSIONS: Microbial production of caffeoylmalic acid using glucose has application potential. In addition, microbial co-culture is an efficient tool for producing caffeic acid esters.

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. CPA-based Ca-alginate/polyacrylamide (PAAm) tough hydrogels were successfully fabricated with glycerol, glycol, and sorbitol. The CPA-based organohydrogels remain unfrozen and mechanically flexible even up to -70 °C and are stable under ambient conditions or even vacuum.

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. During printing, trivalent ions (Fe3+) were patterned and diffused into the prestretched tough gels, which dramatically increased the local stiffness by forming the second trivalent ionically cross-linked network. By removing the applied stretching force, the stiff anisotropy-encoded prestretched tough hydrogels underwent programmable shape morphing into complex three-dimensional origami structures due to the stiffness mismatch.

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. Complex 3D or even 4D folding of tough hydrogels is achieved by sequentially applying the dual regulation.

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.

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. This study then systematically investigates the absorption capacity (up to 1280% for chloroform) of the sponges to different oils and organic solvents. More importantly, the oil flux through the as-made sponges is controlled by mechanical deformation, which increases up to ≈33-fold by tensile strain applied to the sponge from 0 to 400%. On the basis of MRI, this study further demonstrates the application of ecoflex sponges in oil skimmers for selective collecting oil from water with high efficiency and durable recyclability. The as-developed MRI strategy has opened a new path to allow rational design and dynamical control toward developing high performance devices for oil permeation and selective collection of oil spills from water.

"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 Fe3+ 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 8.18 to 4.41 kJ m-2.

[Effects of polychlorinated biphenyl on bcl-2 and TGFbeta1 expression in rat testes].

OBJECTIVE: To study the effects of polychlorinated biphenyl (PCB) on bcl-2 and TGFbeta1 expression in rat testes. METHODS: Forty male Wistar rats were divided into 4 groups at random: Group A (normal control), Group B (fed on 10(-8) mol/L PBC), Group C (feb on 10(-7) mol/L) and Group D (feb on 10(-6) mol/L). After three months, all the rats were killed, the animal model established, and observations made on the expression of bcl2 and TGFbeta1 in the rat testis using the optical microscope and immunohistochemical techniques. RESULTS: The damage to the structure of the testis was related to the dosage of PCB: the higher the dodage, the more serious the damage. PCB induced the expression of bcl-2 and TGFbeta1. The TGFbeta1 expression was significantly higher in the highest dosage group than in others (P < 0.01 ), and the bcl-2 expression was dramatically higher in Group C than in other groups (P < 0.01). CONCLUSION: PCB can cause injury in rat testes.