Sinuhirtins A and B,two uncommon norhumulene-type terpenoids from the South China Sea soft coral Sinularia hirta

Two new uncommon norhumulene-type norsesquiterpenoids, namely sinuhirtins A (1) and B (2), along with two known norcaryophyllene-type norsesquiterpenoids (3 and 4), were isolated from the South China Sea soft coral Sinularia hirta. The structures and absolute configurations of the new compounds were determined by extensive spectroscopic data analyses, and computer-assisted methods including GIAO ¹³C NMR and TDDFT-ECD calculations. A plausible biogenetic relationship of 1–4 was proposed.     

A Polypyridyl‐Based Layered Complex as Dual‐Functional Co‐catalyst for Photo‐Driven Organic Dyes Degradation and Water Splitting

With the ever‐increasing concerns on environmental pollution and energy crisis, it is of great urgency to develop high‐performance photocatalyst to eliminate organic pollutants from wastewater and produce hydrogen via water splitting. Herein, a polypyridyl‐based mixed covalent Cu^I/II complex with triangular {Cu₃} and rhombic {Cu₂Cl₄} subunits alternately extended by mixed SCN^– and Cl^– heterobridges [Cu₄(DNP)(SCN)Cl₄]_n ( 1 ) [DNP = 2,6‐bis(1,8‐naphthyridine‐2‐yl)pyridine] was solvothermally synthesized and employed as a dual‐functional co‐photocatalyst. Resulting from a narrowed band‐gap of 1.07 eV with suitable redox potential and unsaturated Cu^I/II sites, the complex together with H₂O₂ can effectively degrade Rhodamine B and methyl orange up to 87.4 and 88.2 %, respectively. Meanwhile, the complex mixed with H₂PtCl₆ can also accelerate the photocatalytic water splitting in the absence of a photosensitizer with the hydrogen production rate of 27.5 μmol · g^–1 · h^–1. These interesting findings may provide informative hints for the design of the multiple responsive photocatalysts.     

Effect of the Spacer Chain Length of Organic Dicarboxylic Acid on the Supramolecular Assembly of Two Ternary Zinc (II) Coordination Polymers Derived from Mixed Ligands

Two new Zn^II coordination polymers (CPs), [Zn₂(SA)₂(L)₂]_n ( 1 ) and [Zn(AA)(L)]_n ( 2 ) [L = 1,6‐bis(benzimidazol‐1‐yl)hexane, H₂SA = succinic acid, H₂AA = adipic acid], were synthesized via hydrothermal method and characterized by elemental analysis, infrared spectroscopy, and single‐crystal X‐ray diffraction. CP 1 possesses a sql network, which is further extended into a 3D supramolecular skeleton by non‐classical C–H ··· O hydrogen bonding interactions. CP 2 exhibits a 1D linear chain, which is further assembled into a 2D supramolecular layer by π ··· π stacking interactions. The solid state fluorescence properties of two Zn^II CPs were investigated. Both CPs present high photocatalytic activities for the degradation of methylene blue (MB) under UV light irradiation. The photodegradation efficiency using CP 1 as catalyst is 91.3 % and using CP 2 as catalyst is 85.0 %, respectively.     

A Scalable Methylamine Gas Healing Strategy for High‐Efficiency Inorganic Perovskite Solar Cells

An easy and scalable methylamine (MA) gas healing method was realized for inorganic cesium‐based perovskite (CsPbX₃) layers by incorporating a certain amount of MAX (X=I or Br) initiators into the raw film. It was found that the excess MAX accelerated the absorption of the MA gas into the CsPbX₃ film and quickly turned it into a liquid intermediate phase. Through the healing process, a highly uniform and highly crystalline CsPbX₃ film with enhanced photovoltaic performance was obtained. Moreover, the chemical interactions between a series of halides and MA gas molecules were studied, and the results could offer guidance in further optimizations of the healing strategy.     

Directed Evolution of a Bacterial Laccase (CueO) for Enzymatic Biofuel Cells

Escherichia coli's copper efflux oxidase (CueO) has rarely been employed in the cathodic compartment of enzymatic biofuel cells (EBFCs) due to its low redox potential (0.36 V vs. Ag/AgCl, pH 5.5) towards O₂ reduction. Herein, directed evolution of CueO towards a more positive onset potential was performed in an electrochemical screening system. An improved CueO variant (D439T/L502K) was obtained with a significantly increased onset potential (0.54 V), comparable to that of high‐redox‐potential fungal laccases. Upon coupling with an anodic compartment, the EBFC exhibited an open‐circuit voltage (V_oc) of 0.56 V. Directed enzyme evolution by tailoring enzymes to application conditions in EBFCs has been validated and might, in combination with molecular understanding, enable future breakthroughs in EBFC performance     

Platinum/Nickel Bicarbonate Heterostructures towards Accelerated Hydrogen Evolution under Alkaline Conditions

Heterostructured nanomaterials, generally have physicochemical properties that differ from those of the individual components, and thus have potential in a wide range of applications. New platinum (Pt)/nickel bicarbonate (Ni(HCO₃)₂) heterostructures are designed for an efficient alkaline hydrogen evolution reaction (HER). Notably, the specific and mass activity of Pt in Pt/Ni(HCO₃)₂ are substantially improved compared to the bare Pt nanoparticles (NPs). The Ni(HCO₃)₂ provides abundant water adsorption/dissociation sites and modulate the electronic structure of Pt, which determine the elementary reaction kinetics of alkaline HER. The Ni(HCO₃)₂ nanoplates offer a platform for the uniform dispersion of Pt NPs, ensuring the maximum exposure of active sites. The results demonstrate that, Ni(HCO₃)₂ is an effective catalyst promoter for alkaline HER.     

Cleavage of C(aryl)−CH3 Bonds in the Absence of Directing Groups under Transition Metal Free Conditions

Organic chemists now can construct carbon–carbon σ‐bonds selectively and sequentially, whereas methods for the selective cleavage of carbon–carbon σ‐bonds, especially for unreactive hydrocarbons, remain limited. Activation by ring strain, directing groups, or in the presence of a carbonyl or a cyano group is usually required. In this work, by using a sequential strategy site‐selective cleavage and borylation of C(aryl)?CH₃ bonds has been developed under directing group free and transition metal free conditions. Methyl groups of various arenes are selectively cleaved and replaced by boryl groups. Mechanistic analysis suggests that it proceeds by a sequential intermolecular oxidation and coupling of a transient aryl radical, generated by radical decarboxylation, involving a pyridine‐stabilized persistent boryl radical.     

Organic Semiconducting Pro‐nanostimulants for Near‐Infrared Photoactivatable Cancer Immunotherapy

In this study, an organic semiconducting pro‐nanostimulant (OSPS) with a near‐infrared (NIR) photoactivatable immunotherapeutic action for synergetic cancer therapy is presented. OSPS comprises a semiconducting polymer nanoparticle (SPN) core and an immunostimulant conjugated through a singlet oxygen (¹O₂) cleavable linkers. Upon NIR laser irradiation, OSPS generates both heat and ¹O₂ to exert combinational phototherapy not only to ablate tumors but also to produce tumor‐associated antigens. More importantly, NIR irradiation triggers the cleavage of ¹O₂‐cleavable linkers, triggering the remote release of the immunostimulants from OSPS to modulate the immunosuppressive tumor microenvironment. Thus, the released tumor‐associated antigens in conjunction with activated immunostimulants induce a synergistic antitumor immune response after OSPS‐mediated phototherapy, resulting in the inhibited growth of both primary/distant tumors and lung metastasis in a mouse xenograft model, which is not observed for sole phototherapy.     

High Efficiency Electrochemical Nitrogen Fixation Achieved with a Lower Pressure Reaction System by Changing the Chemical Equilibrium

We demonstrate a simple and effective chemical equilibrium regulation strategy to improve the efficiency of electrochemical ammonia synthesis by constructing electrochemical reaction system that works at significantly lower pressure than the Haber–Bosch process. Transferring the nitrogen reduction reaction from ambient conditions to a lightly pressurized environment not only accelerates the activation of the N≡N triple bond but also inhibits the competing reaction of hydrogen evolution while promoting the dissolution and diffusion of nitrogen. The verification experiment of using well‐designed Fe₃Mo₃C/C composite nanosheets as the nitrogen reduction catalyst shows that the lower pressure reaction system can improve the Faradaic current efficiency by one order of magnitude. Moreover, the comparatively low‐pressure reaction system can greatly reduce the cell voltage of the ammonia synthesis reaction (up to 33 %) even at the relatively low pressure of 0.7 MPa, which is of significance for decreasing the energy consumption of electrochemical ammonia synthesis under mild conditions.