Photo-assisted Bottom-up Synthesis of Orange Phosphorus.

A tubular strand of phosphorus composed of vectorially aligned pentagons has been theoretically predicted as a new allotrope of phosphorus with a polar structure, expecting potential applications. However, it has not been successfully synthesized yet due to the difficulty of creating isolated strands to avoid interchain bonding. Here, such an allotrope named "orange phosphorus" was successfully produced using a photo-assisted synthesis from an amorphous film of solution-processable Na2P16 precursors.

Correction: Enhanced catalytic activity of solubilised species obtained by counter-cation exchange of K{Co [Fe(CN)]} for water oxidation.

[This corrects the article DOI: 10.1039/D4SC04390A.].

Electronic regulation of single-atomic Ti sites on metal hydroxide for boosting photocatalytic CO reduction.

Photocatalytic CO reduction is considered a sustainable method to address energy and environmental issues by converting CO into fuels and chemicals, yet the performance is still unsatisfactory. Single atom catalysts hold promising potential in photocatalysis, but the selection of metal species is still limited, especially in early transition metals. Herein, inspired by the structure of anatase TiO, single Ti sites were successfully incorporated into a metal hydroxide support for the first time cationic defects, significantly enhancing the photocatalytic performance by more than 30 times (from 0.

Mechanically induced polyamorphism in a one-dimensional coordination polymer.

We created different amorphous structures of a coordination polymer by applying mechanical shear forces. One-dimensional Cu(TfN)(bip) (1, TfN = bis(trifluoromethanesulfonyl)imide, bip = 1,3-bis(1-imidazolyl)propane) melted at 245 °C and underwent a glass transition at -10 °C by a static cooling process. 1 formed another amorphous state with a distinct glass transition point of 70 °C under oscillatory shear stress.

Second-shell modulation on porphyrin-like Pt single atom catalysts for boosting oxygen reduction reaction.

The first coordination shell is considered crucial in determining the performance of single atom catalysts (SACs), but the significance of the second coordination shell has been overlooked. In this study, we developed a post-doping strategy to realize predictable and controlled modulation on the second coordination shell. By incorporating a P atom into the second coordination shell of a porphyrin-like Pt SAC, the charge density at the Fermi level of Pt single atom increases, enhancing its intrinsic activity.

Systematic design and functionalisation of amorphous zirconium metal-organic frameworks.

Controlling the structure and functionality of crystalline metal-organic frameworks (MOFs) using molecular building units and post-synthetic functionalisation presents challenges when extending this approach to their amorphous counterparts (aMOFs). Here, we present a new bottom-up approach for synthesising a series of Zr-based aMOFs, which involves linking metal-organic clusters with specific ligands to regulate local connectivity. In addition, we overcome the limitations of post-synthetic modifications in amorphous systems, demonstrating that homogeneous functionalisation is achievable even without regular internal voids.

Enhanced catalytic activity of solubilised species obtained by counter-cation exchange of K{Co [Fe(CN)]} for water oxidation.

A cyano-bridged coordination polymer, K{Co [Fe(CN)]} {(K)Co-Fe}, reported as a highly active heterogeneous catalyst for water oxidation was solubilised by a conventional counter-cation exchange of K with MeN ions to provide the homogeneous catalyst of (MeN){Co [Fe(CN)]} {(MeN)Co-Fe}. (MeN)Co-Fe exhibited enhanced catalytic activity for photocatalytic water oxidation using [Ru(2,2'-bipyridine)] and SO as a photosensitiser and a sacrificial electron acceptor, respectively, in terms of the initial reaction rate (1.26 μmol min), which is about twice that of (K)Co-Fe (0.

Temporal dynamics of N-hydroxypipecolic acid and salicylic acid pathways in the disease response to powdery mildew in wheat.

Wheat (Triticum aestivum) is a major staple crop worldwide, and its yields are significantly threatened by wheat powdery mildew (Blumeria graminis f. sp. tritici).

Pyrolytic Depolymerization of Polyolefins Catalysed by Zirconium-based UiO-66 Metal-Organic Frameworks.

Polyolefins such as polyethylenes and polypropylenes are the most-produced plastic waste globally, yet are difficult to convert into useful products due to their unreactivity. Pyrolysis is a practical method for large-scale treatment of mixed, contaminated plastic, allowing for their conversion into industrially-relevant petrochemicals. Metal-organic frameworks (MOFs), despite their tremendous utility in heterogeneous catalysis, have been overlooked for polyolefin depolymerization due to their perceived thermal instabilities and inability of polyethylenes and polypropylenes to penetrate their pores.

Crystalline organic monoliths with bicontinuous porosity.

Organic crystals are a promising class of materials for various optical applications. However, it has been challenging to make macroscopic organic crystals with bicontinuous porosity that are applicable to flow chemistry. In this study, a new class of porous materials, cm-scale crystalline organic monoliths (COMs) with bicontinuous porosity, are synthesized by replicating the porous structure of silica monolith templates.

Furan and benzene ring formation in cellulose char: the roles of 5-HMF and reducing ends.

The authors previously proposed that 5-hydroxymethylfurfural (5-HMF) can be produced from the reducing ends of cellulose as a key intermediate during carbonization. The present work investigated the mechanisms by which furan and benzene rings are formed in cellulose char based on carbonization at 280 °C using C-labeled 5-HMF together with C-labeled glucose (as a model for the cellulose reducing ends). Glycerol was added to the 5-HMF to prevent the formation of stable glassy polymers.

Fractionation of beech wood cell walls into digestible cellulose-rich residues and photoluminescent lignin-rich precipitates semi-flow hot-compressed water treatment with 2-naphthol.

Utilization of cell wall components of woody biomass has attracted attention as alternatives for fossil fuels towards a sustainable society. A semi-flow hydrothermal treatment was used to fractionate the beech () wood into cellulose-rich residues and lignin-rich precipitates. The enzymatic saccharification of the cellulose component in the residue was enhanced significantly because the preferential delignification from the secondary wall increased enzyme accessibility.

Increased CO/N selectivity by stepwise fluorination in isoreticular ultramicroporous metal-organic frameworks.

Exploration of porous adsorbents with high CO/N selectivity is of great significance for reducing CO content in the atmosphere. In this study, a series of isoreticular ultramicroporous fluorinated metal-organic frameworks (MOFs) were prepared to explore the benefits of fluorinated ultramicropores in improving CO/N selectivity. Gas adsorption measurements revealed that the increase in the number of fluorine atoms in a ligand molecule leads to the increased CO uptakes and CO/N selectivity.

Functional metal-organic liquids.

For decades, the study of coordination polymers (CPs) and metal-organic frameworks (MOFs) has been limited primarily to their behavior as crystalline solids. In recent years, there has been increasing evidence that they can undergo reversible crystal-to-liquid transitions. However, their "liquid" states have primarily been considered intermediate states, and their diverse properties and applications of the liquid itself have been overlooked.

Modular Design of Highly Stable Semiconducting Porous Coordination Polymer for Efficient Electrosynthesis of Ammonia.

Developing highly stable porous coordination polymers (PCPs) with integrated electrical conductivity is crucial for advancing our understanding of electrocatalytic mechanisms and the structure-activity relationship of electrocatalysts. However, achieving this goal remains a formidable challenge because of the electrochemical instability observed in most PCPs. Herein, we develop a "modular design" strategy to construct electrochemically stable semiconducting PCP, namely, Fe-pyNDI, which incorporates a chain-type Fe-pyrazole metal cluster and π-stacking column with effective synergistic effects.

Improving the gas sorption capacity in lantern-type metal-organic polyhedra by a scrambled cage method.

The synthesis of multivariate metal-organic frameworks (MOFs) is a well-known method for increasing the complexity of porous frameworks. In these materials, the structural differences of the ligands used in the synthesis are sufficiently subtle that they can each occupy the same site in the framework. However, multivariate or ligand scrambling approaches are rarely used in the synthesis of porous metal-organic polyhedra (MOPs) - the molecular equivalent of MOFs - despite the potential to retain a unique intrinsic pore from the individual cage while varying the extrinsic porosity of the material.

Pseudomorphic amorphization of three-dimensional superlattices through morphological transformation of nanocrystal building blocks.

Nanocrystal (NC) superlattices (SLs) have been widely studied as a new class of functional mesoscopic materials with collective physical properties. The arrangement of NCs in SLs governs the collective properties of SLs, and thus investigations of phenomena that can change the assembly of NC constituents are important. In this study, we investigated the dynamic evolution of NC arrangements in three-dimensional (3D) SLs, specifically the morphological transformation of NC constituents during the direct liquid-phase synthesis of 3D NC SLs.

Synthesis of mesoionic triazolones a formal [3+2] cycloaddition between 4-phenyl-1,2,4-triazoline-3,5-dione and alkynes.

1,2,4-Triazoline-3,5-diones (TADs) are versatile reagents and have found widespread adoption in chemical science. Despite their remarkable reactivity toward a wide array of unsaturated hydrocarbons, the chemical reaction between TADs and alkynes has remained largely unexplored. Herein, we demonstrate that 1,1,1,3,3,3-hexafluoro-2-propanol facilitates the unusual [3+2] cycloaddition between 4-phenyl-1,2,4-triazoline-3,5-dione and alkynes, resulting in the formation of unprecedented mesoionic triazolones.

Impact of multiple H/D replacements on the physicochemical properties of flurbiprofen.

Although deuterium incorporation into pharmaceutical drugs is an attractive way to expand drug modalities, their physicochemical properties have not been sufficiently examined. This study focuses on examining the changes in physicochemical properties between flurbiprofen (FP) and flurbiprofen- (FP-), which was successfully prepared by direct and multiple H/D exchange reactions at the eight aromatic C-H bonds of FP. Although the effect of deuterium incorporation was not observed between the crystal structures of FP and FP-, the melting point and heat of fusion of FP- were lower than those of FP.

Study of assessment of knowledge and understanding for coping with sick days among patients with diabetes in community pharmacy: a cluster randomized controlled trial (SAKURA trial).

Background: Awareness regarding coping with sick days among patients with diabetes is limited. Thus, we evaluated the effectiveness of sick-day education by community pharmacists among patients with type 2 diabetes (T2D) using sick-day educational materials (sick-day cards).

Methods: A cluster randomized controlled trial was conducted.

Porous supramolecular gels produced by reversible self-gelation of ruthenium-based metal-organic polyhedra.

Supramolecular gels based on metal-organic polyhedra (MOPs) represent a versatile platform to access processable soft materials with controlled porosity. Herein, we report a self-gelation approach that allows the reversible assembly of a novel Ru-based MOP in the form of colloidal gels. The presence of cationic mixed-valence [Ru(COO)] paddlewheel units allows for modification of the MOP charge acid/base treatment, and therefore, its solubility.

An Aqueous Redox Flow Battery Using CO as an Active Material with a Homogeneous Ir Catalyst.

For the application of CO as an energy storage material, a H storage system has been proposed based on the interconversion of CO and formic acid (or formate). However, energy losses are inevitable in the conversion of electrical energy to H as chemical energy (≈70 % electrical efficiency) and H to electrical energy (≈40 % electrical efficiency). To overcome these significant energy losses, we developed a system based on the interconversion of CO and formate for the direct storage and generation of electricity.

A Nitro-Modified Luminescent Hydrogen-Bonded Organic Framework for Non-Contact and High-Contrast Sensing of Aromatic Amines.

The global demand for intelligent sensing of aromatic amines has consistently increased due to concerns about health and the environment. Efforts to improve material design and understand mechanisms have been made, but highly efficient non-contact sensing with host-guest structures remains a challenge. Herein, we report the first example of non-contact, high-contrast sensing of aromatic amines in a hydrogen-bonded organic framework (HOF) based on a nitro-modified stereo building block.

Crossover Sorption of C H /CO and C H /C H in Soft Porous Coordination Networks.

Porous sorbents are materials that are used for various applications, including storage and separation. Typically, the uptake of a single gas by a sorbent decreases with temperature, but the relative affinity for two similar gases does not change. However, in this study, we report a rare example of "crossover sorption," in which the uptake capacity and apparent affinity for two similar gases reverse at different temperatures.