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.

Insight into the Molecular Mechanism for Enhanced Longevity of Supramolecular Vesicular Photocatalysts.

Supramolecular self-assembly is a promising strategy for stabilizing the photo-sensitive components in photocatalysis. However, the underlying correlation between the enhanced photostability and supramolecular structure at the molecular level has not yet been fully understood. Herein, we develop a biomimetic vesicular membrane-based polyporphyrin photocatalyst exhibiting excellent photocatalytic stability with at least activity time of 240 h in hydrogen generation. Time-domain ab initio modelling together with transient absorption spectroscopy, visual frontier orbitals and Gibbs free energy calculation disclose that the ordered aggregation of porphyrin units in the vesicle membrane facilitates "hot" electron relaxation and the rapid dissipation of photo-generated charges, thereby contributing to the longevity. This work deepens the molecular-level understanding on photostability and photocatalytic mechanism of supramolecular photocatalysts.

Imaging Photon-Induced Near-Field Distributions of a Plasmonic, Self-Assembled Vesicle by a Laser-Integrated Electron Microscope.

Plasmonic polymeric nanoassemblies offer valuable opportunities in photoconversion applications. Localized surface plasmon mechanisms behind such nanoassemblies govern their functionalities under light illumination. However, an in-depth investigation at the single nanoparticle (NP) level is still challenging, especially when the buried interface is involved, due to the availability of suitable techniques. Here, we synthesized an anisotropic heterodimer composed of a self-assembled polymer vesicle (THPG) capped with a single gold NP, enabling an 8-fold enhancement in hydrogen generation compared to the nonplasmonic THPG vesicle. We explored the anisotropic heterodimer at the single particle level by employing advanced transmission electron microscopes, including one equipped with a femtosecond pulsed laser, which allows us to visualize the polarization- and frequency-dependent distribution of the enhanced electric near fields at the vicinity of Au cap and Au-polymer interface. These elaborated fundamental findings may guide designing new hybrid nanostructures tailored for plasmon-related applications.

A Janus Au-Polymersome Heterostructure with Near-Field Enhancement Effect for Implant-Associated Infection Phototherapy.

Polymer-inorganic hybrid Janus nanoparticles (PI-JNPs) have attracted extensive attention due to their special structures and functions. However, achieving the synergistic enhancement of photochemical activity between polymer and inorganic moieties in PI-JNPs remains challenging. Herein, the construction of a novel Janus Au-porphyrin polymersome (J-AuPPS) heterostructure by a facile one-step photocatalytic synthesis is reported. The near-field enhancement (NFE) effect between porphyrin polymersome (PPS) and Au nanoparticles in J-AuPPS is achieved to enhance its near-infrared (NIR) light absorption and electric/thermal field intensity at their interface, which improves the energy transfer and energetic charge-carrier generation. Therefore, J-AuPPS shows a higher NIR-activated photothermal conversion efficiency (48.4%) and generates more singlet oxygen compared with non-Janus core-particle Au-PPS nanostructure (28.4%). As a result, J-AuPPS exhibits excellent dual-mode (photothermal/photodynamic) antibacterial and anti-biofilm performance, thereby significantly enhancing the in vivo therapeutic effect in an implant-associated-infection rat model. This work is believed to motivate the rational design of advanced hybrid JNPs with desirable NFE effect and further extend their biological applications.

Regioisomer-Directed Self-Assembly of Alternating Copolymers for Highly Enhanced Photocatalytic H2 Evolution.

Porphyrin-based photocatalytic materials have received great attention, and the effect of the substituents, central ions, and aggregated structure on the catalysis performance has been studied up to now. Herein, we report the effect of porphyrin isomerism on their aggregated structures as well as the photocatalytic activity. Two trans- and cis-porphyrin-based alternating copolymers with the same compositions (P1 and P2) are successfully synthesized. It is found that P1 self-assembles into propeller-like nanoparticles and P2 into multilayer hollow nanospheres. Furthermore, the hydrogen production rate of P1 (5533 µmol g-1 h-1) is 30 times higher than that of P2 (173 µmol g-1 h-1). Mechanism studies reveal that the high photocatalytic properties of P1 originate from the more ordered arrangement of porphyrins than P2, which facilitates the mobility and separation of photoinduced carriers. We believe the covalent and noncovalent polymer self-assembly process as well as the isomerism effect as disclosed here will shed new light on the design of high performance photocatalysts.

Membrane-Bound Inward-Growth of Artificial Cytoskeletons and Their Selective Disassembly.

The cytoskeleton is one of the most important cellular components. Up to now, most of the reported artificial cytoskeletons are based on a gel-in-vesicle strategy. Herein, we report a membrane-bound inward-growth pathway to prepare cytoskeleton-like and radially aligned nanofibers grown from capsule membranes to get membrane-bound artificial cytoskeletons (MACs). The mechanism therein is disclosed through the direct observation of the intermediates in both dried and liquid states. Furthermore, the as-prepared MACs show a selective disassembly behavior in the presence of reductants: both capsule membranes and MACs can be disassembled or only MACs can be disassembled through the selective introduction of dynamic disulfide bonds (DS) into them and by the switch of ultraviolet (UV) irradiation. The present work provides a new hierarchical self-assembly way to construct artificial cytoskeletons with controlled compositions and orientations.

A supramolecular single-site photocatalyst based on multi-to-one Förster resonance energy transfer.

A multi-to-one supramolecular photocatalyst is fabricated by aqueous electrostatic self-assembly of multiple graphene quantum dot (GQD) antennas onto a single-Pt-site porphyrin unimolecular micelle (PtTHPD-UM) catalytic center. Light energy is transferred from GQDs to PtTHPD-UM to catalyze water splitting into hydrogen up to 57 190 µmol g(Pt)-1 h-1 under visible light.

Phase-enabled metal-organic framework homojunction for highly selective CO2 photoreduction.

Conversion of clean solar energy to chemical fuels is one of the promising and up-and-coming applications of metal-organic frameworks. However, fast recombination of photogenerated charge carriers in these frameworks remains the most significant limitation for their photocatalytic application. Although the construction of homojunctions is a promising solution, it remains very challenging to synthesize them. Herein, we report a well-defined hierarchical homojunction based on metal-organic frameworks via a facile one-pot synthesis route directed by hollow transition metal nanoparticles. The homojunction is enabled by two concentric stacked nanoplates with slightly different crystal phases. The enhanced charge separation in the homojunction was visualized by in-situ surface photovoltage microscopy. Moreover, the as-prepared nanostacks displayed a visible-light-driven carbon dioxide reduction with very high carbon monooxide selectivity, and excellent stability. Our work provides a powerful platform to synthesize capable metal-organic framework complexes and sheds light on the hierarchical structure-function relationships of metal-organic frameworks.

Asymmetric Vesicles Self-Assembled by Amphiphilic Sequence-Controlled Polymers.

The asymmetric distribution of lipids on the inner and outer membranes of a cell plays a pivotal role in the physiological and immunological activities of life. It has inspired the elaboration of synthetic asymmetric vesicles for the discovery of advanced materials and functions. The asymmetric vesicles were generally prepared by amphiphilic block copolymers. We herein report on the formation of asymmetric vesicles self-assembled by amphiphilic sequence-controlled polymers with two hydrophilic segments SU and TEO. We also developed an efficient fluorescence titration method with europium(III) ions (Eu3+) to determine the uneven distribution of SU and TEO. SU units are preferentially located on the outer membrane and TEO on the inner membrane of the resulting vesicles, which is facilitated by the electrostatic repulsion of SU and the U-shaped folding of the hydrophobic backbone of the resulting polymers. This work shows that sequence-controlled polymers with alternating monomer sequence provide a powerful toolbox for the elaboration of important yet challenging self-assembled structures for emerging functions and properties.

Ordered Bicontinuous Mesoporous Polymeric Semiconductor Photocatalyst.

Owning triply periodic minimal surfaces and three-dimensional (3D) interconnected pores, bicontinuous porous materials have drawn enormous attention due to their great academic interest and potential applications in many fields including energy and catalysis. However, their synthesis has remained a great challenge. Here, we demonstrate the synthesis of a bicontinuous porous organic semiconductor photocatalyst, which involves the preparation of SiO2 with a shifted double diamond (DD) structure through solvent evaporation-induced self-assembly of a polystyrene-block-poly(ethylene oxide) diblock copolymer and tetraethyl orthosilicate, followed by SiO2-templated self-condensation of melamine monomers in a vacuum. Strikingly, the resultant DD-structured graphitic carbon nitride (g-CN) possesses two sets of 3D continuous mesopores with a mean diameter of 14 nm, which afford a high specific surface area of 131 m2 g-1 and an optical band gap of 2.8 eV. Being a visible-light-driven photocatalyst, the bicontinuous mesoporous g-CN exhibits high catalytic activity for water splitting to generate H2 (6831 µmol g-1 h-1) with excellent cycling stability. This study provides a protocol for the construction of ordered mesoporous materials containing 3D continuous channels, which holds promise for catalysis applications.

In situ supramolecular polymerization-enhanced self-assembly of polymer vesicles for highly efficient photothermal therapy.

Vesicular photothermal therapy agents (PTAs) are highly desirable in photothermal therapy (PTT) for their excellent light-harvesting ability and versatile hollow compartments. However, up to now, the reported vesicular PTAs are generally self-assembled from small molecules like liposomes, and polymer vesicles have seldom been used as PTAs due to the unsatisfactory photothermal conversion efficiency resulting from the irregular packing of chromophores in the vesicle membranes. Here we report a nano-sized polymer vesicle from hyperbranched polyporphyrins with favorable photothermal stability and extraordinarily high photothermal efficiency (44.1%), showing great potential in imaging-guided PTT for tumors through in vitro and in vivo experiments. These excellent properties are attributed to the in situ supramolecular polymerization of porphyrin units inside the vesicle membrane into well-organized 1D monofilaments driven by π-π stacking. We believe the supramolecular polymerization-enhanced self-assembly process reported here will shed a new light on the design of supramolecular materials with new structures and functions.

Porphyrin Alternating Copolymer Vesicles for Photothermal Drug-Resistant Bacterial Ablation and Wound Disinfection.

In the past two decades, polymer vesicles have aroused widespread interest and made significant developments. However, the applications of polymer vesicles in anti-infective therapy are still limited. Here, we construct a polymer vesicle (TPPBV) from a porphyrin alternating copolymer P(TPP-a-BDE) with a high photothermal conversion efficiency (54.1%), which is attributed to the unique chain-folding mechanisms of the alternating copolymer. In particular, TPPBVs exhibit great photothermal antibacterial activity against both Gram-positive methicillin-resistant Staphylococcus aureus (MRSA) and Gram-negative extended-spectrum ß-lactamases Escherichia coli (ESBL E. coli). Moreover, TPPBVs present a specific antibiofilm effect, and they also have remarkable therapeutic effects in vivo on an MRSA-infected mice model. We believe that the porphyrin alternating copolymer vesicles for photothermal bacterial ablation reported here will extend the applications of polymer vesicles.

Endo- and Exo-Functionalized Tetraphenylethylene M12L24 Nanospheres: Fluorescence Emission inside a Confined Space.

The intrinsic relationship between the properties of green fluorescent protein (GFP) and its encapsulated small molecular light machine has spurred many biomimicking studies, aiming at revealing the detailed mechanism and further promoting its wide applications in different disciplines. However, how to build a similar confined microenvironment to mimic the cavity of a ß-barrel and the fluorescence turn-on process is a fundamental challenge for both chemists and biologists. Herein, two distinct exo- and endo-functionalized tetraphenylethylene (TPE)-based M12L24 nanospheres with precise distribution of anchored TPE moieties and unique photophysical properties were constructed by means of a coordination-driven self-assembly strategy. Under dilute conditions, the nanospheres fluoresce more strongly than the corresponding TPE subcomponents. Meanwhile, the endo-functionalized sphere is able to induce a higher local concentration and more restrained motion of the enclosed 24 TPE units compared with exo-functionalized counterpart and thus induces much stronger emission due to the restriction of the rotation of the pendant TPE units. The biomimetic methodology developed here represents a promising way to understand and construct artificial GFP materials on the platforms of supramolecular coordination complexes.

Ultrathin Metal-Organic Framework Nanosheets with Ultrahigh Loading of Single Pt Atoms for Efficient Visible-Light-Driven Photocatalytic H2 Evolution.

A surfactant-stabilized coordination strategy is used to make two-dimensional (2D) single-atom catalysts (SACs) with an ultrahigh Pt loading of 12.0 wt %, by assembly of pre-formed single Pt atom coordinated porphyrin precursors into free-standing metal-organic framework (MOF) nanosheets with an ultrathin thickness of 2.4±0.9 nm. This is the first example of 2D MOF-based SACs. Remarkably, the 2D SACs exhibit a record-high photocatalytic H2 evolution rate of 11 320 µmol g-1 h-1 via water splitting under visible light irradiation (λ>420 nm) compared with those of reported MOF-based photocatalysts. Moreover, the MOF nanosheets can be readily drop-casted onto solid substrates, forming thin films while still retaining their photocatalytic activity, which is highly desirable for practical solar H2 production.

Mesoporous Mo2C/Carbon Hybrid Nanotubes Synthesized by a Dual-Template Self-Assembly Approach for an Efficient Hydrogen Production Electrocatalyst.

Molybdenum carbide-containing nanomaterials have drawn considerable attention in the application of hydrogen production electrocatalysts in light of the high abundance, low cost, and Pt-like electronic structure of molybdenum carbide. In this article, we report the synthesis of one-dimensional (1D) Mo2C/carbon mesoporous nanotubes (Mo2C/C PNTs) through a dual-template self-assembly approach, which employs 1D MoO3 nanobelts as the structure-directing template as well as one of the Mo2C precursors, along with block copolymer (BCP) micelles as the pore-forming template. In aqueous solution, the interface self-assembly of the micelles with pyrrole (Py) molecules absorbed in the PEO domains leads to the tight arrangement of the micelles on the surfaces of the MoO3 nanobelts. The polymerization of Py and the subsequent pyrolysis at 800 °C under a nitrogen atmosphere yield Mo2C/C PNTs with well-defined mesopores. Among the resultant Mo2C/C PNT samples, Mo2C/C PNTs with a specific surface area of 69 m2/g, a N atom percentage of 5.5 atom %, and an optimum Mo2C content of 40 wt % exhibit the highest HER catalytic performance in 0.5 M H2SO4 electrolyte, with a low onset potential of 34 mV, a satisfied overpotential of 140 mV at 10 mA/cm2, and excellent cycling stability. This study not only opens an avenue toward new Mo2C-containing nanomaterials but also provides a new system for the fundamental study on 1D porous nanohybrids with potential applications as hydrogen production electrocatalysts.