Lithium-sulfur (Li-S) batteries, based on the redox reaction between elemental sulfur and lithium metal, have attracted great interest because of their inherently high theoretical energy density. However, the severe polysulfide shuttle effect and sluggish reaction kinetics in sulfur cathodes, as well as dendrite growth in lithium-metal anodes are great obstacles for their practical application. Herein, a two-in-one approach with superhierarchical cobalt-embedded nitrogen-doped porous carbon nanosheets (Co/N-PCNSs) as stable hosts for both elemental sulfur and metallic lithium to improve their performance simultaneously is reported. Experimental and theoretical results reveal that stable Co nanoparticles, elaborately encapsulated by N-doped graphitic carbon, can work synergistically with N heteroatoms to reserve the soluble polysulfides and promote the redox reaction kinetics of sulfur cathodes. Moreover, the high-surface-area pore structure and the Co-enhanced lithiophilic N heteroatoms in Co/N-PCNSs can regulate metallic lithium plating and successfully suppress lithium dendrite growth in the anodes. As a result, a full lithium-sulfur cell constructed with Co/N-PCNSs as two-in-one hosts demonstrates excellent capacity retention with stable Coulombic efficiency.

Maleic acid-catalyzed hemicellulose hydrolysis reaction in corn stover was analyzed by kinetic modeling. Kinetic constants for Saeman and biphasic hydrolysis models were analyzed by an Arrhenius-type expansion which include activation energy and catalyst concentration factors. The activation energy for hemicellulose hydrolysis by maleic acid was determined to be 83.3 +/- 10.3 kJ/mol, which is significantly lower than the reported E(a) values for sulfuric acid catalyzed hemicellulose hydrolysis reaction. Model analysis suggest that increasing maleic acid concentrations from 0.05 to 0.2 M facilitate improvement in xylose yields from 40% to 85%, while the extent of improvement flattens to near-quantitative by increasing catalyst loading from 0.2 to 1 M. The model was confirmed for the hydrolysis of corn stover at 1 M maleic acid concentrations at 150 degrees C, resulting in a xylose yield of 96% of theoretical. The refined Saeman model was used to evaluate the optimal condition for monomeric xylose yield in the maleic acid-catalyzed reaction: low temperature reaction conditions were suggested, however, experimental results indicated that bi-phasic behavior dominated at low temperatures, which may be due to the insufficient removal of acetyl groups. A combination of experimental data and model analysis suggests that around 80-90% xylose yields can be achieved at reaction temperatures between 100 and 150 degrees C with 0.2 M maleic acid.

The stereochemistry of chiral-at-metal complexes is much more abundant, albeit complicated, than chiral-at-carbon compounds, but how to make use of stereolabile metal-centers remains a formidable challenge due to the highly versatile coordination geometry of metal ions and racemization/epimerization problem. We demonstrate herein a stepwise assembly of configurationally stable [Pd 6 (FeL 3 ) 8 ] 28+ (Δ/Λ-MOCs-42) homochiral octahedral cages from unstable D 3 -symmetry trischelate-Fe type metalloligands via strong face-directed stereochemical coupling and facile chiral-induced resolution processes based on stereodifferentiating host−guest dynamics. Kinetic studies reveal that the dissociation rate of MOC-42 cages is 100-fold slower than that of Femetalloligands and the racemization is effectively inhibited, making the cages retain their chirality over extended periods of time (>5 months) at room temperature. Recyclable enantioseparation of atropisomeric compounds has been successfully achieved, giving up to 88% ee.

An anocage coupling effect from ar edoxR u II -Pd II metal-organic cage is demonstrated for efficient photochemical H 2 production by virtue of redox-guest modulation of the photo-induced electron transfer (PET) process. Through coupling with photoredox cycle of MOC-16, tetrathiafulvalene (TTF) guests act as electron relaym ediator to improve the overall electron transfer efficiency in the hostguest system in al ong-time scale,l eading to significant promotion of visible-light driven H 2 evolution. By contrast, the presence of larger TTF-derivatives in bulk solution without host-guest interactions results in interference with PET process of MOC-16, leading to inefficient H 2 evolution. Suchi nteraction provides an example to understand the interplay between the redox-active nanocage and guest for optimization of redox events and photocatalytic activities in ac onfined chemical nanoenvironment.

Long non-coding RNAs (lncRNAs) were playing critical roles in tumorigenesis. However, in prostate cancer, the roles and mechanisms of lncRNAs especially ANRIL were largely unknown. We investigated the effects of ANRIL on the proliferation and migration of prostate cancer cells using CCK-8 assay and Transwell migration assay. Real-time PCR and western blotting assays were used to analyze the levels of ANRIL, let-7a, TGF-β1, p-Smad2 and p-Smad7. Our results showed that ANRIL was significantly overexpressed in prostate cancer tissues compared with corresponding normal tissues. Knockdown of ANRIL significantly inhibited the proliferation and migration of prostate cancer LNCap, PC3 and DU145 cells. Knockdown of ANRIL significantly decreased the levels of TGF-β1 and p-Smad2, and increased the level of p-Smad7 in prostate cancer LNCap cells. We further found that knockdown of ANRIL significantly enhanced the expression of let-7a, and rescue experiment found that let-7a inhibitor recovered the suppressive effects of ANRIL silencing on the proliferation and migration of prostate cancer LNCap, PC3 and DU145 cells. And let-7a inhibitor recovered the suppressive effects of ANRIL silencing on the activity of TGF-β1/Smad signaling pathway in prostate cancer LNCap cells. Taken together, our findings indicated that overexpression of lncRNA ANRIL promoted the proliferation and migration of prostate cancer cells via regulating let-7a/TGF-β1/Smad signaling pathway.

Efficient and economical hydrolysis of plant cell wall polysaccharides into monomeric sugars is a significant technical hurdle in biomass processing for renewable fuels and chemicals. One possible approach to overcoming this hurdle is a biomimetic approach with dicarboxylic acid catalyst mimicking the catalytic core microenvironment in natural enzymes. This paper reports developments in the use of a dicarboxylic acid catalyst, maleic acid, for hemicellulose hydrolysis in corn stover. Hemicellulose hydrolysis and xylose degradation kinetics in the presence of maleic acid was compared to sulfuric acid. At optimized reaction conditions for each acid, maleic acid hydrolysis results in minimal xylose degradation, whereas sulfuric acid causes 3-10 times more xylose degradation. These results formed the basis for optimizing the hydrolysis of hemicellulose from corn stover using maleic acid. At 40 g/L dry corn stover solid-loading, both acid catalysts can achieve near-quantitative monomeric xylose yield. At higher solids loadings (150-200 g dry stover per liter), sulfuric acid catalyzed hydrolysis results in more than 30% degradation of the xylose, even under the previously reported optimal condition. However, as a result of minimized xylose degradation, optimized biomimetic hydrolysis of hemicellulose by maleic acid can reach approximately 95% monomeric xylose yields with trace amounts of furfural. Fermentation of the resulting unconditioned hydrolysate by recombinant S. cerevisiae results in 87% of theoretical ethanol yield. Enzyme digestibility experiments on the residual corn stover solids show that >90% yields of glucose can be produced in 160 h from the remaining cellulose with cellulases (15 FPU/g-glucan).

Although the photodimerization of acenaphthylene (ACE) has been known for 100 years, the asymmetric cycloaddition of its 1‐substituted derivatives is unknown. Herein, we report a supramolecular photochirogenic approach in which a homochiral and photoactive Δ/Λ‐[Pd6(RuL3)8]28+ metal–organic cage (Δ/Λ‐MOC‐16) is used as a supramolecular reactor for the enantioselective exited‐state photocatalysis of 1‐Br‐ACE. Owing to preorganization of the substrates by the supramolecular cage, stereochemical control of the triplet state, and nanospace transfer of energy and chirality, the cycloaddition of ACE proceeded with high selectivity for the formation of anti over syn stereoisomers, whereas the regio‐, stereo‐, and enantioselective cycloaddition of unsymmetrical 1‐Br‐ACE showed effective enantiodifferentiation of a pair of anti head‐to‐head stereoisomers. The enzyme‐mimicking photocatalysis was verified by catalytic turnover, rate enhancement, and competing‐guest inhibition experiments.

layers has attracted remarkable attention in recent years for surgical challenge and undesirable treatment outcomes. The destruction of the muscular layer is difficult to be sutured and injury of the serosal membrane could induce obvious viscera adhesion. [5,6] In the past few decades, tension-free repair operation is recommended as the standard treatment for soft-tissue defects like abdominal wall defects, in which different types of patches have been widely used. [1,[7][8][9] Traditional synthetic meshes with high strength, light weight, and anti-deformation (e.g., polypropylene (PP) and polyester meshes) have been widely used for tension-free repair of soft-tissue defects. But these meshes could result in severe visceral adhesion and undesirable wound healing, because of an obvious foreign body reaction (Figure 1a). [10][11][12] One of the most common approaches to solve the problem of visceral adhesion is to develop composite patches with anti-adhesion barriers. [9,13] For example, Parietex composite (PCO) mesh has been successfully designed to prevent visceral adhesion by coating an anti-adhesive collagen-based barrier on polyester mesh. [14,15] Nevertheless, these polyester or PP-based composite meshes could cause undesirable wound healing, due to their inherent unsatisfied inflammation response and lack of suitable microstructure for cells to migrate and grow. [16,17] Moreover, the collagen-based barrier would swell and cause deformation of composite meshes in an abdominal wet environment [18] (Figure 1b). Currently, the Implantable meshes used in tension-free repair operations facilitate treatment of internal soft-tissue defects. However, clinical meshes fail to achieve anti-deformation, anti-adhesion, and pro-healing properties simultaneously, leading to undesirable surgery outcomes. Herein, inspired by the peritoneum, a novel biocompatible Janus porous poly(vinyl alcohol) hydrogel (JPVA hydrogel) is developed to achieve efficient repair of internal soft-tissue defects by a facile yet efficient strategy based on top-down solvent exchange. The densely porous and smooth bottom-surface of JPVA hydrogel minimizes adhesion of fibroblasts and does not trigger any visceral adhesion, and its loose extracellular-matrix-like porous and rough top-surface can significantly improve fibroblast adhesion and tissue growth, leading to superior abdominal wall defect treatment to commercially available PP and PCO meshes. With unique anti-swelling property (maximum swelling ratio: 6.4%), JPVA hydrogel has long-lasting anti-deformation performance and maintains high mechanical strength after immersion in phosphate-buffered saline (PBS) for 14 days, enabling tolerance to the maximum abdominal pressure in an internal wet environment. By integrating visceral anti-adhesion and defect pro-healing with anti-deformation, the JPVA hydrogel patch shows great prospects for efficient internal soft-tissue defect repair.