Hierarchical Hollow TiO2@Bi2WO6 with Light-Driven Excited Bi(3-x)+ Sites for Efficient Photothermal Catalytic CO2 Reduction.

Converting CO2 into valuable chemicals via sustainable energy sources is indispensable for human development. Photothermal catalysis combines the high selectivity of photocatalysis and the high yield of thermal catalysis, which is promising for CO2 reduction. However, the present photothermal catalysts suffer from low activity due to their poor light absorption ability and fast recombination of photogenerated electrons and holes. Here, a TiO2@Bi2WO6 heterojunction photocatalyst featuring a hierarchical hollow structure was prepared by an in situ growth method. The visible light absorption and photothermal effect of the TiO2@Bi2WO6 photocatalyst is promoted by a hierarchical hollow structure, while the recombination phenomenon is significantly mitigated due to the construction of the heterojunction interface and the existence of excited Bi(3-x)+ sites. Such a catalyst exhibits excellent photothermal performance with a CO yield of 43.7 µmol h-1 g-1, which is 15 and 4.7 times higher than that of pure Bi2WO6 and that of physically mixed TiO2/Bi2WO6, respectively. An in situ study shows that the pathway for the transformation of CO2 into CO over our TiO2@Bi2WO6 proceeds via two important intermediates, including COO- and COOH-. Our work provides a new idea of excited states for the design and synthesis of highly efficient photothermal catalysts for CO2 conversion.

Structurally diverse stilbenes from Gnetum parvifolium and their anti-neuroinflammatory activities.

Phytochemical investigation on the aerial parts of Gnetum parvifolium led to the isolation of 15 new and eight known structurally diverse stilbenes. The isolated compounds comprised (E)- or (Z)-stilbene (1-6, 15-20), dihydrostilbene (21), phenylbenzofuran (7, 8, 22), benzylated stilbene (9-11), benzylated stilbene dimer (12), and nitrogen-containing stilbene (13a, 13b, 14) types. The structures of the new compounds (1-12, 13a, 13b, 14) were established through spectroscopic analyses and experimental and calculated ECD data. Compound 12 is the first stilbene dimer connected through a benzyl group. In the anti-neuroinflammatory activity assay, compounds 4, 5, 9-11, 13b, and 16-21 displayed significant inhibitory effects against LPS-induced NO release in BV-2 microglial cells, with IC50 values of 0.35-16.1 µM. Compound 10 had the most potent activity (IC50 = 0.35 µM), and the further research indicated that it could decrease the mRNA levels of iNOS, IL-1ß, IL-6, and TNF-α in a dose-dependent manner.

N-Doping Coupled with Co-Vacancies Activating Sulfur Atoms and Narrowing Bandgap for CoS Toward Synergistically Accelerating Hydrogen Evolution.

The combination of hetero-elemental doping and vacancy engineering will be developed as one of the most efficient strategies to design excellent electrocatalysts for hydrogen evolution reaction (HER). Herein, a novel strategy for N-doping coupled with Co-vacancies is demonstrated to precisely activate inert S atoms adjacent to Co-vacancies and significantly improve charge transfer for CoS toward accelerating HER. In this strategy, N-doping favors the presence of Co-vacancies, due to greatly decreasing their formation energy. The as-developed strategy realizes the upshift of S 3p orbitals followed by more overlapping between S 3py and H 1s orbitals, which results in the favorable hydrogen atom adsorption free energy change (ΔGH ) to activate inert S atoms as newborn catalytical sites. Besides, this strategy synergistically decreases the bandgap of CoS, thereby achieving satisfactory electrical conductivity and low charge-transfer resistance for the as-obtained electrocatalysts. With an excellent HER activity of -89.0 mV at 10.0 mA cm-2 in alkaline environments, this work provides a new approach to unlocking inert sites and significantly improving charge transfer toward cobalt-based materials for highly efficient HER.

Engineering Rich Active Sites and Efficient Water Dissociation for Ni-Doped MoS2/CoS2 Hierarchical Structures toward Excellent Alkaline Hydrogen Evolution.

Besides improving charge transfer, there are two key factors, such as increasing active sites and promoting water dissociation, to be deeply investigated to realize high-performance MoS2-based electrocatalysts in alkaline hydrogen evolution reaction (HER). Herein, we have demonstrated the synergistic engineering to realize rich unsaturated sulfur atoms and activated O-H bonds toward the water for Ni-doped MoS2/CoS2 hierarchical structures by an approach to Ni doping coupled with in situ sulfurizing for excellent alkaline HER. In this work, the Ni-doped atoms are evolved into Ni(OH)2 during alkaline HER. Interestingly, the extra unsaturated sulfur atoms will be modulated into MoS2 nanosheets by breaking Ni-S bonds during the formation of Ni(OH)2. On the other hand, the higher the mass of the Ni precursor (mNi) for the fabrication of our samples, the more Ni(OH)2 is evolved, indicating a stronger ability for water dissociation of our samples during alkaline HER. Our results further reveal that regulating mNi is crucial to the HER activity of the as-synthesized samples. By regulating mNi to 0.300 g, a balance between increasing active sites and promoting water dissociation is achieved for the Ni-doped MoS2/CoS2 samples to boost alkaline HER. Consequently, the optimal samples present the highest HER activity among all counterparts, accompanied by reliable long-term stability. This work will promise important applications in the field of electrocatalytic hydrogen evolution in alkaline environments.

Single knotless-anchor with two ethicon 2# for Ellman grade III bursal-side partial thickness rotator cuff tears: a cadaveric biomechanical study and short-term clinical evaluation.

BACKGROUND: Several surgical techniques are used to treat bursal-side partial thickness rotator cuff tears (PTRCTs). However, use of single knotless-anchor with two Ethicon 2# repair technique for PTRCTs has not been reported. MATERIALS AND METHODS: Bursal-side PTRCTs (Ellman grade III, 75% thickness of tears) were created in the supraspinatus tendon in 16 fresh-frozen cadaveric shoulders. The specimens were randomly assigned to two equal groups: (1) Group A (Transtendon repair), a single knotless-anchor repair with two Ethicon 2#; (2) Group B, Conversion repair (Double-row, DR). Post-repair, each specimen was subjected to cyclic loading test from 5 to 100 N (50 cycles), followed by an ultimate failure test. The displacement of greater tuberosity (mm) and ultimate (N) were recorded. In the clinical study, 12 patients diagnosed with Ellman grade III Bursal-side PTRCTs (using a single knotless anchor with two Ethicon 2# repair techniques) were operated on and analyzed. Visual analog scale (VAS), American Shoulder and Elbow Surgeons Score (ASES), Constant-Murley Score (CMS), and range of motion (ROM) were assessed before surgery and at final minimum follow-up (>1year). RESULTS: There was no significant between-group difference with respect to load-to-failure test (Group A, 359.25 ± 17.91 N; Group B, 374.38 ± 13.75 N, P > 0.05). There were no significant differences with respect to rotator cuff displacement of 10 mm (Group A, 190.50 ± 8.52 N; Group B, 197.25 ± 6.84 N, P > 0.05) and 15 mm (Group A, 282.25 ± 12.20 N; Group B, 291.13 ± 14.74 N, P > 0.05). However, there was significant between-group difference with respect to displacement of 3 and 5 mm (P < 0.05). In the clinical trial, all patients were followed up for an average of 20.4 months (12-29 months). At the last follow-up after surgery(minimum>1year), the VAS score was 0.50 ± 0.67 (0-2), the ASES score was 86.50 ± 3.96 (79-92), the CMS score was 85.08 ± 5.65 (74-93), the mean Forward flexion ROM was 154.00°± 12.48° (131°-169°), and the abduction ROM was 165.00°±13.26° (138°-173°). There was a statistically significant difference between the results of the preoperative and the last postoperative follow-up. The results of the last postoperative follow-up were statistically different from those of the preoperative follow-up (P < 0.05). Regarding complications, stiffness (2 cases) and shoulder impingement (1 case) occurred in 3 cases (25%). CONCLUSION: A single knotless anchor with two Ethicon 2# may provide a biomechanically and clinically feasible option for the treatment of bursal-side Ellman grade III PTRCTs, particularly in resource-constrained settings. MESH KEYWORDS: Bursal-side Ellman Grade III; Single Knotless-anchor; Double-row repair; Biomechanical study; Short-term clinical evaluation.

Phanerosides A-X, Phenylpropanoid Esters of Sucrose from the Rattans of Phanera championii Benth.

Twenty-four new phenylpropanoid esters of sucrose, phanerosides A-X (1-24), were isolated from an EtOH extract of the rattans of Phanera championii Benth. (Fabaceae). Their structures were elucidated on the basis of comprehensive spectroscopic data analysis. A wide range of structural analogues were presented due to the different numbers and positions of acetyl substituents and the structures of phenylpropanoid moieties. Phenylpropanoid esters of sucrose were isolated from the Fabaceae family for the first time. Biologically, the inhibitory effects of compounds 6 and 21 on NO production in LPS-induced BV-2 microglial cells were better than that of the positive control, with IC50 values of 6.7 and 5.2 µM, respectively. The antioxidant activity assay showed that compounds 5, 15, 17, and 24 displayed moderate DPPH radical scavenging activity, with IC50 values ranging from 34.9 to 43.9 µM.

H2 -free Semi-hydrogenation of Butadiene by the Atomic Sieving Effect of Pd Membrane with Tree-like Pd Dendrites Array.

H2 -free semi-hydrogenation at room temperature shows great advantage for replacing the thermocatalytic process in industry owing to the high energy and resource saving, however, remains great challenges. Herein, a tree-like Pd dendrites array decorated Pd membrane was constructed as the core device in an electrochemistry assisted gas-fed membrane reactor for butadiene semi-hydrogenation. It reveals that hydrogen atomic sieving effect of this Pd-based membrane under electrochemical condition was the key for semi-hydrogenation. The configuration study of Pd nanostructured membrane demonstrates that the penetration of hydrogen atoms through Pd membrane from electrochemical side to chemical side is affected by the consumption of hydrogen atom in semi-hydrogenation step. Such atomic sieving property of nanostructured Pd membrane with 5.1 times increase in catalytic active surface area brings above 14 times higher in butadiene conversion than that of bare Pd foil, with ≈90 % of butenes selectivity at butadiene conversion ≈98 % over 300 h of H2 -free reaction under 15 mA cm-2 .

Ammonium Ion Batteries: Material, Electrochemistry and Strategy.

Ammonium-ion batteries (AIBs) have recently attracted increasing attention in the field of aqueous batteries owing to their high safety and fast diffusion kinetics. The NH4 + storage mechanism is quite different from that of spherical metal ions (e.g. Li+ , Na+ , K+ , Mg2+ , and Zn2+ ) because of the formation of hydrogen bonds between NH4 + and host materials. Although many materials have been proposed as electrode materials for AIBs, their performances hardly meet the requirement of future electrochemical energy storage devices. It is thus urgent to design and exploit advanced materials for AIBs. This review highlights the state-of-the-art research on AIBs. The insights into the basic configuration, operating mechanism and recent progress of electrode materials and corresponding electrolytes for AIBs have been comprehensively outlined. The electrode materials are classified and compared according to different NH4 + storage behaviour in the structure. The challenges, design strategies and perspectives are also discussed for the future development of AIBs.

Phase Conversion Accelerating "Zn-Escape" Effect in ZnSe-CFs Heterostructure for High Performance Sodium-Ion Half/Full Batteries.

Sodium-ion batteries (SIBs) are considered as a promising large-scale energy storage system owing to the abundant and low-cost sodium resources. However, their practical application still needs to overcome some problems like slow redox kinetics and poor capacity retention rate. Here, a high-performance ZnSe/carbon fibers (ZnSe-CFs) anode is demonstrated with high electrons/Na+ transport efficiency for sodium-ion half/full batteries by engineering ZnSe/C heterostructure. The electrochemical behavior of the ZnSe-CFs heterostructure anode is deeply studied via in situ characterizations and theoretical calculations. Phase conversion is revealed to accelerate the "Zn-escape" effect for the formation of robust solid electrolyte interphase (SEI). This leads to the ZnSe-CFs delivering a superior rate performance of 206 mAh g-1 at 1500 mA g-1 for half battery and an initial discharge capacity of 197.4 mAh g-1 at a current density of 1 A g-1 for full battery. The work here heralds a promising strategy to synthesize advanced heterostructured anodes for SIBs, and provides the guidance for a better understanding of phase conversion anodes.

Adsorption-Catalysis-Conversion of Polysulfides in Sandwiched Ultrathin Ni(OH)2 -PANI for Stable Lithium-Sulfur Batteries.

Strong adsorption and catalysis for lithium polysulfides (LiPSs) are critical toward the electrochemical stability of Li-S batteries. Herein, a hollow sandwiched nanoparticle is put forward to enhance the adsorption-catalysis-conversion dynamic of sulfur species. The outer ultrathin Ni(OH)2 nanosheets not only confine LiPSs via both physical encapsulation and chemical adsorption, but also promote redox kinetics and accelerate the conversion of sulfur species, which is revealed by experiments and theoretical calculations. Meanwhile, the inner hollow polyaniline soft core provides a strong chemical bonding to LiPSs after vulcanization, which can chemically adsorpt LiPSs, and synergistically confine the shuttle effect. Moreover, the Ni(OH)2 nanosheets with a large specific area can enhance the wettability of electrolyte, and the flexible hollow sandwiched structure can accommodate the volume expansion, promoting sulfur utilization and structural stability. The obtained cathode exhibits excellent electrochemical performance with an initial discharge capacity of 1173 mAh g-1 and a small capacity decay of 0.08% per cycle even after 500 cycles at 0.2 C, among the best results of Ni(OH)2 -based materials for Li-S batteries. It is believed that the combination of adsorption-catalysis-conversion will shed a light on the development of cathode materials for stable Li-S batteries.

CO2 Electroreduction in Water with a Heterogenized C-Substituted Nickel Cyclam Catalyst.

Molecular catalysis for selective CO2 electroreduction into CO can be achieved with a variety of metal complexes. Their immobilization on cathodes is required for their practical implementation in electrolytic cells and can benefit from the advantages of a solid material such as easy separation of products and catalysts, efficient electron transfer to the catalyst, and high stability. However, this approach remains insufficiently explored up to now. Here, using an appropriate and original modification of the cyclam ligand, we report a novel [Ni(cyclam)]2+ complex which can be immobilized on carbon nanotubes. This material, once deposited on a gas diffusion layer, provides a novel electrode which is remarkably selective for CO2 electroreduction to CO, not only in organic solvents but also, more remarkably, in water, with faradic efficiencies for CO larger than 90% and current densities of 5-10 mA cm-2 during controlled potential electrolysis in H-cells.

Hierarchically Structured Zeolites: From Design to Application.

Hierarchical zeolites combine the intrinsic catalytic properties of microporous zeolites and the enhanced access and transport of the additional meso- and/or macroporous system. These materials are the most desirable catalysts and sorbents for industry and become a highly evolving field of important current interests. In addition to the enhanced mass transfer leading to high activity, selectivity, and cycle time, another essential merit of the hierarchical structure in zeolite materials is that it can significantly improve the utilization effectiveness of zeolite materials resulting in the minimum energy, time, and raw materials consumption. Substantial progress has been made in the synthesis, characterization, and application of hierarchical zeolites. Herein, we provide an overview of recent achievements in the field, highlighting the significant progress in the past decade on the development of novel and remarkable strategies to create an additional pore system in zeolites. The most innovative synthesis approaches are reviewed according to the principle, versatility, effectiveness, and degree of reality while establishing a firm link between the preparation route and the resultant hierarchical pore quality in zeolites. Zeolites with different hierarchically porous structures, i.e., micro-mesoporous structure, micro-macroporous structure, and micro-meso-macroporous structure, are then analyzed in detail with concrete examples to illustrate their benefits and their fabrications. The significantly improved performances in catalytic, environmental, and biological applications resulting from enhanced mass transport properties are discussed through a series of representative cases. In the concluding part, we envision the emergence of "material-properties-by-quantitative and real rational design" based on the "generalized Murray's Law" that enables the predictable and controlled productions of bioinspired hierarchically structured zeolites. This Review is expected to attract important interests from catalysis, separation, environment, advanced materials, and chemical engineering fields as well as biomedicine for artificial organ and drug delivery systems.

New enantiomeric lignans and new meroterpenoids with nitric oxide release inhibitory activity from Piper puberulum.

Six new lignans with various type of linkage between two C6-C3 fragments (1a, 1b, 2a, 2b, 3, 4), two new meroterpenoids (5, 6) and 24 known compounds (7-30) were isolated from an EtOH extract of the stems and leaves of Piper puberulum. The absolute configurations of enantiomers 1a and 1b were determined by single-crystal X-ray diffraction analysis, 2a and 2b were determined by comparing their calculated and experimental ECD spectra. Biogenetically, all the new lignans may come from the polymerization of two molecules of hydroxychavicol (30). In the anti-neuroinflammation activity assay, the IC50 values of fifteen compounds were lower than those of the positive control minocycline, and compound 1a showed good activity, but its enantiomer 1b showed no activity. Compound 1a have notable anti-neuroinflammatory activity, and can significantly decrease mRNA levels of proinflammatory cytokines (IL-1ß, IL-6, TNF-α) in a dose-dependent manner.

Printed aerogels: chemistry, processing, and applications.

As an extraordinarily lightweight and porous functional nanomaterial family, aerogels have attracted considerable interest in academia and industry in recent decades. Despite the application scopes, the modest mechanical durability of aerogels makes their processing and operation challenging, in particular, for situations demanding intricate physical structures. "Bottom-up" additive manufacturing technology has the potential to address this drawback. Indeed, since the first report of 3D printed aerogels in 2015, a new interdisciplinary research area combining aerogel and printing technology has emerged to push the boundaries of structure and performance, further broadening their application scope. This review summarizes the state-of-the-art of printed aerogels and presents a comprehensive view of their developments in the past 5 years, and highlights the key near- and mid-term challenges.

Heterogenised Molecular Catalysts for Sustainable Electrochemical CO2 Reduction.

There has been a rapid rise in interest regarding the advantages of support materials to protect and immobilise molecular catalysts for the carbon dioxide reduction reaction (CO2 RR) in order to overcome the weaknesses of many well-known catalysts in terms of their stability and selectivity. In this Review, the state of the art of different catalyst-support systems for the CO2 RR is discussed with the intention of leading towards standard benchmarking for comparison of such systems across the most relevant supports and immobilisation strategies, taking into account these multiple pertinent metrics, and also enabling clearer consideration of the necessary steps for further progress. The most promising support systems are described, along with a final note on the need for developing more advanced experimental and computational techniques to aid the rational design principles that are prerequisite to prospective industrial upscaling.

Light-Assisted Semi-Hydrogenation of 1,3-Butadiene with Water.

Sustainable processes for semi-hydrogenation of alkynes/alkadienes impurities in alkenes feedstocks are in great demand in industry as the utilization of excessive hydrogen, high temperature and unsatisfactory alkenes selectivity of the current thermo-catalytic route, however, their development is still challenging. Herein, we innovate a light-assisted semi-hydrogenation process in gas-feed fixed bed reactor, with water as hydrogen atom source by in situ photocatalysis. Using Pd/TiO2 as model catalyst, this process shows an excellent catalytic performance for the semi-hydrogenation of 1,3-butadiene, with 100 % of butenes selectivity at ≈99 % of conversion over 180 h of reaction at ambient temperature driven by 66 mW cm-2 of irradiation intensity. This light-driven, H2 -free, ambient temperature semi-hydrogenation process, with superior performance to that of thermocatalytic route, shows attractive to bring an evolution in industrial hydrogenation technology to an economical and safe way.

BN-Doped Metal-Organic Frameworks: Tailoring 2D and 3D Porous Architectures through Molecular Editing of Borazines.

Building on the MOF approach to prepare porous materials, herein we report the engineering of porous BN-doped materials using tricarboxylic hexaarylborazine ligands, which are laterally decorated with functional groups at the full-carbon 'inner shell'. Whilst an open porous 3D entangled structure could be obtained from the double interpenetration of two identical metal frameworks derived from the methyl substituted borazine, the chlorine-functionalised linker undergoes formation of a porous layered 2D honeycomb structure, as shown by single-crystal X-ray diffraction analysis. In this architecture, the borazine cores are rotated by 60° in alternating layers, thus generating large rhombohedral channels running perpendicular to the planes of the networks. An analogous unsubstituted full-carbon metal framework was synthesised for comparison. The resulting MOF revealed a crystalline 3D entangled porous structure, composed by three mutually interpenetrating networks, hence denser than those obtained from the borazine linkers. Their microporosity and CO2 uptake were investigated, with the porous 3D BN-MOF entangled structure exhibiting a large apparent BET specific surface area (1091 m2 g-1 ) and significant CO2 reversible adsorption (3.31 mmol g-1 ) at 1 bar and 273 K.

Piperhancins A and B, Two Pairs of Antineuroinflammatory Cycloneolignane Enantiomers from Piper hancei.

Two pairs of cycloneolignane enantiomers, piperhancins A and B (1 and 2, respectively), along with two enantiomeric pairs of biosynthetic related neolignanes, hancinone C (3) and piperhancin C (4), were isolated from the stems of Piper hancei. Compound 1 is an unprecedented 1',2:1,2'-dicyclo-8,3'-neolignane. Their structures and absolute configurations were elucidated by spectroscopic analyses, X-ray diffraction, and electronic circular dichroism calculations. Among all of the isolates, compounds (+)-1, (-)-1, (+)-2, (-)-2, and (+)-3 could significantly inhibit the production of nitric oxide secreted by lipopolysaccharide (LPS)-induced neuroinflammation in BV-2 microglial cells, with IC50 values of 1.1-26.3 µM. In addition, compound (-)-1 could decrease the mRNA levels of iNOS, IL-6, and TNF-α induced by LPS in BV-2 microglial cells.

New Tyramine- and Aporphine-Type Alkamides with NO Release Inhibitory Activities from Piper puberulum.

Three new tyramine-type alkamides (1-3), three new natural products (4-6), five new N-acylated/formylated aporphine alkamides with different ratios of rotational isomers (7-11), and 20 known alkamides (12-31) were isolated from an EtOH extract of the stems and leaves of Piper puberulum. The absolute configurations of compounds 7, 8, and 10 were determined by single-crystal X-ray diffraction analysis. In the biological activity assay, compounds 3, 5, and 10-23 displayed inhibitory effects against lipopolysaccharide-induced NO release in BV-2 microglial cells, exhibiting IC50 values of 0.93-45 µM.

Chebulic acid derivatives from Balakata baccata and their antineuroinflammatory and antioxidant activities.

Sixteen chebulic acid derivatives, including nine new (1-9) and seven known (10-16) ones, were isolated from an ethanol extract of the branches and leaves of Balakata baccata. The structures of the new compounds were elucidated by their UV, IR, HRESIMS, NMR, electronic circular dichroism (ECD) and single-crystal X-ray diffraction data. The effects of all the isolates on antineuroinflammatory and antioxidant activities were evaluated. Compared with the positive control minocycline (IC50 = 1.21 ± 0.71 µM), compounds 1-16 with IC50 values being greater than 50 µM, displayed almost no effects on the inhibition of NO production in LPS-induced BV-2 microglial cells, however, the results of antioxidant activity for compounds 1-16 showed significant DPPH-radical scavenging abilities with EC50 value ranging from 3.98 to 14.24 µM, while the EC50 value of positive control vitamin C was 14.31 µM. At last, the results of PCR (qRT-PCR) analysis showed that compound 1 could enhance the expression of antioxidases (HO-1, GCLC, and NQO1) at the mRNA levels.