Ultrathin Metal-Organic Framework Nanosheets for Selective Photocatalytic C2 H2 Semihydrogenation in Aqueous Solution.

The selective semihydrogenation of C2 H2 to C2 H4 in crude C2 H4 (with ~1 vol % C2 H2 contamination) is a crucial process in the manufacture of polyethylene. Comparing to conventional thermalcatalytic route with Pd as catalyst under high temperature with H2 as hydrogen source, photocatalytic C2 H2 reduction reaction with H2 O as hydrogen source can achieve high selectivity under milder conditions, but has rarely been reported. Here, we present a kind of ultrathin metal-organic framework nanosheets (Cu-Co-MNSs) that demonstrate excellent catalytic activities in the semihydrogenation of C2 H2 . Employing Ru(bpy)3 2+ as the photosensitizer, this catalyst attains a noteworthy turnover number (TON) of 2124 for C2 H4 , coupled with an impressive selectivity of 99.5 % after 12 h visible light irradiation. This performance is comparable to molecular catalysts and notably surpasses the efficiency of bulk metal-organic framework materials. Furthermore, Cu-Co-MNSs achieve a 99.95 % conversion of C2 H2 under industrial relevant conditions (1.10 % C2 H2 in C2 H4 ) with 90.3 % selectivity for C2 H4 over C2 H6 , demonstrating a great potential for polymer-grade C2 H4 production.

Hierarchical Self-Assembly of Hyperbranched Polymer-Based Topological Supramolecular Amphiphiles.

Supramolecular polymers (SPs) are constructed through non-covalent interactions. The dynamic or reversible nature of SPs endows them unique physical and chemical properties, such as self-adaptive and stimuli-response abilities. The topological structures of SPs play an important role in determining the physicochemical properties and functionality. Hyperbranched polymers (HBPs) are highly branched 3D macromolecules with linear, dendritic, and terminal units, which makes them versatile candidates for the construction of SPs with fascinating architectures. The resultant HBP-based SPs perfectly integrated the dynamic/reversible nature of SPs and the 3D topological features and multifunctionality of HBP polymers. To date, various types of HBP-based SPs and their assemblies have been constructed, and their potential applications have been explored as well. This article overviews the current progress on self-assembly of HBP-based SPs. The strategies for construction of HBP-based SPs and their assemblies are discussed. Typical potential applications of the assemblies of HBP-based SPs are also introduced.

Living Self-Assembly of Monodisperse Micron-Sized Polymer Vesicles.

Artificial vesicles are recognized as powerful platforms for a large body of research across the disciplines of chemistry, physics and biology. Despite the great progress, control of the size distribution to make uniform vesicles remains fundamentally difficult due to the highly uncontrollable growth kinetics, especially for micron-sized vesicles. Here we report a template-free living self-assembly method to prepare monodisperse vesicles around 1 µm from an alternating copolymer. The polymer forms nanodisks (ca. 9 nm) in N,N-dimethylformamide (DMF), acting as seeds for subsequent growth. By adding water, the nanodisks gradually grow into larger circular bilayer nanosheets, which bend to crowns and continue to grow into uniform micron-sized vesicles. The first-order growth kinetics as well as the small size polydispersity index (<0.1) suggests the living self-assembly characteristics. This work paves a new way in both living self-assembly and monodisperse polymer vesicles.

Polymeric Unimolecular CO Dehydrogenase Mimic with both Inner and Outer Spheres for Enhanced Photocatalytic CO2 Reduction in Aqueous Solution.

Inspired by carbon monoxide dehydrogenase (CODH), mimicking its inner and outer spheres is a promising strategy in CO2 reduction catalyst design. However, artificial CODH-like catalysts are generally limited to the inner sphere effect and only applicable in organic solvents or for electrocatalysis. Herein, an aqueous CODH mimic with both inner and outer spheres for photocatalysis is reported. In this polymeric unimolecular catalyst, the inner sphere is composed of cobalt porphyrin with four appended amido groups and the outer sphere consists of four poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) arms. Upon visible light irradiation (λ >420 nm), the as-prepared catalyst exhibits a turnover number (TONCO ) of 1731.2 in the reduction of CO2 into CO, which is comparable to most reported molecular catalysts in aqueous solution. The mechanism studies indicate that, in this water-dispersible and structurally well-defined CODH mimic, the cobalt porphyrin core serves as the catalysis center and the amido groups function as hydrogen-bonding pillars helping to stabilize the CO2 adduct intermediate, whereas the PDMAEMA shell renders both water solubility and a CO2 reservoir through reversibly capturing of CO2 . The present work has clarified the significance of coordination sphere effects for improving the aqueous photocatalytic CO2 reduction performance of CODH mimics.

Self-Assembly of Peapod-like Micrometer Tubes from a Planet-Satellite-type Supramolecular Megamer.

This study presents interesting self-assembly of peapod-like micrometer tubes from a planet-satellite-type supramolecular megamer, which was constructed through the specific host-guest molecular recognition between azobenzene (AZO)-functionalized hyperbranched poly(ethyl-3-oxetanemethanol)-star-poly(ethylene oxide) (HSP-AZO) and ß-cyclodextrin(CD)-based hydrophilic hyperbranched polyglycerol (CD-g-HPG). A peapod-like structure with micrometer-sized tube as the pod and vesicles encapsulated inside as the peas was formed through sequential vesicle entosis, linear association, and fusion processes. Dissipative particle dynamics (DPD) simulations support the structural possibility of the supramolecular peapod formation and its mechanism. UV light irradiation could lead to the disassembly of the peapod-like structure. This study expands the family of supramolecular polymers and opens a new avenue to develop bioinspired complex hierarchical nanoarchitectures at the microscopic level.

pH-Controlled Stereoregular Polymerization of Poly(methyl methacrylate) in Vesicle Membranes.

Here, we report a pH-controlled stereoregular polymerization of methyl methacrylate (MMA) inside the membrane of H20-COOH hyperbranched polymer vesicles using a common radical polymerization process. The vesicle size decreases from 745 to 214 nm with an increase of solution pH from 2.60 to 7.26, and the isotacticity of the obtained polymethyl methacrylates (PMMAs) is accordingly elevated from 9 to 35%. The obtained isotactic-rich PMMAs show a lower glass transition temperature depending on the isotacticity than the commercial random PMMAs. A mechanism study according to the in situ Fourier transform infrared measurements indicates that the control of polymer isotacticity results from the monomer conformation confined effect inside the thin vesicle membranes. The present study provides a new method to realize the preparation of isotactic polymers with the characteristics of facile synthesis, pH controllability, and a green polymerization process in aqueous solution as well as under mild reaction conditions of ambient temperature and pressure.

The Photocatalyst-Free Cross-Dehydrogenative Coupling Reaction Enabled by Visible-Light Direct Excitation of Substrate.

A new photocatalyst-free strategy for the cross-dehydrogenative C-C and C-P coupling reaction has been described. This protocol provides a concise method to synthesize various 1-substituted tetrahydroisoquinoline (THIQ) derivatives enabled by visible-light direct excitation of substrates without using any photocatalyst. Moreover, a wide substrate scope demonstrated good synthetic versatility and practicality.

In Situ Construction of Dye-Sensitized BiOCl/Rutile-TiO2 Nanorod Heterojunctions with Highly Enhanced Photocatalytic Activity for Treating Persistent Organic Pollutants.

The construction of efficient and stable heterojunction photocatalysts with a controllable close contact interface and visible-light response is a challenging research topic in the field of photocatalysis. Herein, a series of BiOCl/rutile-TiO2 (R-TiO2) nanorod heterojunctions were constructed using R-TiO2 nanorods as supporting frameworks followed by selective adsorption of Cl- on R-TiO2(110) facets and in situ growth of BiOCl on the surface of TiO2 nanorods. The strong affinity of rhodamine B (RhB) as a photosensitizer for BiOCl allowed the prepared BiOCl/R-TiO2 heterojunctions to work efficiently under visible-light irradiation. The dye-sensitized BiOCl/R-TiO2 nanorod heterojunctions displayed promising photocatalytic performance for simultaneously treating RhB and the persistent organic pollutant 2-sec-butyl-4,6-dinitrophenol (DNBP). The highly enhanced photodegradation activity of the BiOCl/R-TiO2 system was mainly attributed to the efficient RhB-photosensitization effect, the enhanced heterojunction effect, and the suitable conduction band match between BiOCl and R-TiO2, which facilitated electron transfer from the excited RhB to the catalyst surface and charge separation across the BiOCl/R-TiO2 interface, thus promoting the formation of •O2- and h+ as dominant active species in the reaction system for degradation of pollutants. The results demonstrate that the construction of a dye-sensitized BiOCl/R-TiO2 heterojunction system is an effective strategy for improving the photocatalytic potential.

Quinoxaline and Pyrido[x,y-b]pyrazine-Based Emitters: Tuning Normal Fluorescence to Thermally Activated Delayed Fluorescence and Emitting Color over the Entire Visible-Light Range.

Quinoxaline (Q), pyrido[2,3-b]pyrazine (PP) and pyrido[3,4-b]pyrazine (iPP) are used as electron acceptors (A) to design a series of D-π-A-type light-emitting materials with different donor (D) groups. By adjusting the molecular torsion angles through changing D from carbazole (Cz) to 10-dimethylacridine (DMAC) or 10H-phenoxazine (PXZ) for a fixed A, the luminescence is tuned from normal fluorescence to thermally activated delayed fluorescence (TADF). By gradually enhancing the intramolecular charge-transfer extent through combining different D and A, the emission color is continuously and regularly tuned from pure blue to orange-red. Organic light-emitting diodes (OLEDs) containing these compounds as doped emitters exhibit bright electroluminescence with emission colors covering the entire visible-light range. An external quantum efficiency (ηext ) of 1.2 % with excellent color coordinates of (0.16, 0.07) is obtained for the pure-blue OLED of Q-Cz. High ηext values of 12.9 (35.9) to 16.7 % (51.9 cd A-1 ) are realized in the green, yellow, and orange-red TADF OLEDs. All PP- and iPP-based TADF emitters exhibit superior efficiency stabilities to that of analogues of Q. This provides a practical strategy to tune the emission color of Q, PP, and iPP derivatives with the same molecular skeletons over the entire visible-light range.

Combinatorial synthesis of deuterium-enriched (S)-oxybutynin.

The concept of deuterium enrichment has gained more attention due to its advantages in the studies of clinical pharmacokinetics and metabolic profiles. In addition, it is cost and time efficient to develop deuterium-enriched drugs. Herein we built a combinatorial library of deuterated (S)-oxybutynins which all 8 D-compounds were characterized by MS, [Formula: see text] NMR and [Formula: see text]C NMR.

Combinatorial synthesis of deuterium-enriched atorvastatin.

It becomes more and more difficult to discover a new drug by existing models. The concept of deuteration has gained attention due to its advantages in the study of clinical pharmacokinetics and metabolic profiles. Herein we built a library of deuterated atorvastatins using combinatorial chemistry, and all 16 D-compounds were characterized by 1H NMR, 13C NMR, MS, and elemental analysis.

Hyperbranched polymer vesicles: from self-assembly, characterization, mechanisms, and properties to applications.

Vesicles, including lipid vesicles, surfactant vesicles, as well as polymer vesicles, have been extensively investigated over the past fifty years. Among them, polymer vesicles have attracted more and more attention because of their low permeability, superior stability and toughness, in addition to the numerous possibilities for tailoring physical, chemical and biological properties. Polymer vesicles are generally fabricated through the self-assembly of amphiphilic polymers with a linear architecture. Recently, as representative polymers with a highly branched three-dimensional architecture, hyperbranched polymers have also exhibited great potential for preparing vesicles. The resultant hyperbranched polymer vesicles, defined as branched-polymersomes (BPs), have shown unique properties, such as giant and easily tuned vesicle sizes, facile functionalization, a special formation mechanism, and appealing solution behaviours. In this tutorial review, ten years of advances in BPs have been summarized since their first discovery in the year 2004, including the syntheses of vesicle-forming hyperbranched polymers, self-assembly methods, self-assembly mechanisms, as well as the special properties. In addition, the cytomimetic, biomedical and other initiatory applications of BPs are also included.

Preparation of polydopamine nanocapsules in a miscible tetrahydrofuran-buffer mixture.

A miscible tetrahydrofuran-tris buffer mixture has been used to fabricate polydopamine hollow capsules with a size of 200 nm and with a shell thickness of 40 nm. An unusual non-emulsion soft template mechanism has been disclosed to explain the formation of capsules. The results indicate that the capsule structure is highly dependent on the volume fraction of tetrahydrofuran as well as the solvent, and the shell thickness of capsules can be controlled by adjusting the reaction time and dopamine concentration.

Synthesis and self-assembly of amphiphilic aptamer-functionalized hyperbranched multiarm copolymers for targeted cancer imaging.

A novel targeting cancer imaging platform based on aptamer-functionalized amphiphilic hyperbranched copolymer conjugates, which can self-assemble into nanoscopic micelles with a core-shell structure and a narrow size distribution, has been designed and synthesized. The size, morphology, fluorescence performance, and cytotoxicity of micelles were studied by dynamic light scattering, transmission electron microscopy, fluorescence spectroscopy, and a 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide colorimetric assay. The results indicate that these micelles have low cytotoxicity against MCF-7 cells and can be easily internalized by MCF-7 cells. In addition, they also exhibit enhanced cell uptake, excellent fluorescence properties, and smart targeting capability in vitro, indicating great potential to be promising carriers for bioimaging and cancer specific delivery.

Aza-metallacycles with a heptavalent Re (d0) center.

The oxidation state of the metal center is important for a conjugated metallacycle. Although high valent d0-metallacycles of main groups and early transition metals have been reported, such examples of late transition metals are limited. The reactions of ReOCl3(PPh3)2 with 2-ethynyl anilines produced alkenyl amino Re(V) complexes, which can be further oxidized to Re(VII) aza-metallacycles. The conjugated rhenacycle is nonaromatic, however, with close to zero NICS values and localized currents observed by AICD and GIMIC studies.

Dehydrogenative cyclization of 2-arylbenzoic acid and 2-arylbenzamide with hydrogen evolution in a photoelectrochemical cell.

This paper describes photoelectrochemical dehydrogenative cyclization of 2-arylbenzoic acid and 2-arylbenzamide in a PEC cell consisting of a mesoporous WO3 photoanode and Pt cathode. The cyclization reaction is effectively driven by this PEC system at room temperature with blue LED irradiation under external oxidant- and metal-free conditions, delivering a series of benzolactones and benzolactams in up to 95% isolated yields. Meanwhile, hydrogen is released as the only byproduct of this process.

Synthesis of Helical-Shaped Axially Chiral Bisoxime Ethers via Chiral Phosphoric-Acid-Catalyzed Sequential Enantioselective Condensations.

A successful synthesis of helical-shaped axially chiral bisoxime ethers is reported. This approach utilized symmetric L-shaped diketone scaffolds as carbonyl components for the enantioselective condensation with hydroxylamines, delivering dual axially chiral oxime ethers with up to 99% ee. Additionally, the axially chiral mono-oxime ethers of azabicyclic ketones with high ee's were also successfully produced. Various chiral bicyclic lactams can be readily synthesized via Beckmann rearrangement, demonstrating a potential application in organic synthetic chemistry.

Minisci-Type Dehydrogenative Coupling of C(sp3)-H and N-Heteroaromatics Enabled by Photoelectrochemical Hydrogen Atom Transfer.

Minisci-type dehydrogenative coupling of C(sp3)-H and N-heteroaromatics was performed with N-hydroxysuccinimide as a hydrogen atom transfer catalyst in a photoelectrochemical cell composed of a mesoporous BiVO4 photoanode and a Pt electrode. In the absence of metal catalysts and chemical oxidants, a range of N-heteroarenes (e.g., quinolines, isoquinolines, and quinoxaline) can undergo coupling with various C(sp3)-H partners to form the corresponding products in excellent yields.

Efficacy of outdoor interventions for myopia in children and adolescents: a systematic review and meta-analysis of randomized controlled trials.

Objectives: The objective of this systematic review and meta-analysis was to evaluate the overall efficacy of outdoor interventions for myopia in children and adolescents, and to provide evidence for the prevention and control of myopia. Methods: Randomized controlled trials of outdoor interventions for myopia in children and adolescents were identified using electronic databases and manual searches. The Revised Cochrane risk-of-bias tool for randomized trials (RoB 2) was used to assess risk of bias in randomized controlled trials. A mean difference (MD) and a risk ratio (RR) with a 95% confidence interval (CI) were used to combine effect sizes. A sensitivity analysis was performed for each outcome using a stepwise elimination method to assess whether the pooled results were significantly affected by individual studies. Results: The analysis included seven randomized controlled trials involving a total of 9,437 subjects. The meta-analysis showed marked and statistically significant improvements in spherical equivalent refraction (MD = 0.19; 95% CI 0.14 to 0.25; p < 0.01), axial length (MD = -0.09; 95% CI -0.13 to -0.05; p < 0.01), and myopia incidence (RR = 0.84; 95% CI 0.78 to 0.91; p < 0.01) following outdoor interventions. Conclusion: Outdoor interventions effectively contributed to the prevention and control of myopia in children and adolescents, positively impacting spherical equivalent refraction, axial length, and myopia incidence. Outdoor interventions were characterized by low risk and high therapeutic benefits and could serve as alternative or adjuvant approaches to medication for the treatment of myopia. Considering the advantages in terms of safety and efficacy, outdoor interventions may be considered as a preferred intervention for the treatment of myopia in children and adolescents, while susceptibility to diseases associated with sunlight, particularly UV exposure, must be taken into account. Systematic review registration: https://www.crd.york.ac.uk/prospero/, Identifier CRD42024538695.

Iron-Catalyzed Photoredox Alcohol α-C-H Alkylation and Tandem Intramolecular Cyclization: Facile Access to Multisubstituted 2,3-Dihydrofurans and γ-Butyrolactones.

Multisubstituted furans occupy a pivotal position within the realms of synthetic chemistry and pharmacological science due to their distinctive chemical configurations and inherent properties. We herein introduce a tandem difunctionalization protocol of alcohols for the efficient synthesis of multisubstituted 2,3-dihydrofurans and γ-butyrolactones through the combination of photocatalysis and iron catalysis under mild conditions. Photoredox alcohol α-C(sp3)-H activation and Pinner-type intramolecular cyclization are two key processes. This method features significant convenience, economic benefits, and environmental friendliness.