Exclusive and Switchable Superoxide Radical Generation by O2-Capture-Based Electron Transfer and Supramolecular Assembly.

Type-I photosensitizers (PSs) can generate free radical anions with a broad diffusion range and powerful damage effect, rendering them highly desirable in various areas. However, it still remains a recognized challenge to develop pure Type-I PSs due to the inefficiency in producing oxygen radical anions through the collision of PSs with nearby substrates. In addition, regulating the generation of oxygen radical anions is also of great importance toward the control of photosensitizer (PS) activities on demand. Herein, a piperazine-based cationic Type-I PS (PPE-DPI) that exhibits efficient intersystem crossing and subsequently captures oxygen molecules through binding O2 to the lone pair of nitrogen in piperazine is reported. The close spatial vicinity between O2 and PPE-DPI strongly promotes the electron transfer reaction, ensuring the exclusive superoxide radical (O2 •-) generation via Type-I process. Particularly, PPE-DPI with cationic pyridine groups is able to associate with cucurbit[7]uril (CB[7]) through host-guest interactions. Thus, supramolecular assembly and disassembly are easily utilized to realize switchable O2 •- generation. This switchable Type-I PS is successfully employed in photodynamic antibacterial control.

Passivating Oxygen Evolution Activity of NiFe-LDH through Heterostructure Engineering to Realize High-Efficiency Electrocatalytic Formate and Hydrogen Co-Production.

An electrocatalytic methanol oxidation reaction (MOR) is proposed to replace oxygen evolution reaction (OER) in water electrolysis owing to the favorable thermodynamics of MOR than OER. However, there is still a competition between the MOR and the OER when the applied potential is in the conventional OER zone. How to inhibit OER while maintaining efficient MOR is an open and challenging question, and there are few reports focusing on this thus far. Herein, by taking NiFe layered double hydroxide (LDH) as a model catalyst due to its intrinsically high catalytic activity for the OER, the perspective of inhibiting OER is shown and thus promoting MOR through a heterogenous engineering of NiFe-LDH. The engineered heterostructure comprising NiFe-LDH and in situ formed NiFe-hexylaminobenzene (NiFe-HAB) coordination polymer exhibits outstanding electrocatalytic capability for methanol oxidation to formic acid (e.g., the Faradaic efficiencies (FEs) of formate product are close to 100% at various current densities, all of which are much larger than those (53-65%) on unmodified NiFe-LDH). Mechanism studies unlock the modification of NiFe-HAB passivates the OER activity of NiFe-LDH through tailoring the free energies for element reaction steps of the OER and increasing the free energy of the rate-determining step, consequently leading to efficient MOR.

Nitrogen-Doped Graphene-Encapsulated Nickel-Copper Alloy Nanoflower for Highly Efficient Electrochemical Hydrogen Evolution Reaction.

Development of high-performance and low-cost nonprecious metal electrocatalysts is critical for eco-friendly hydrogen production through electrolysis. Herein, a novel nanoflower-like electrocatalyst comprising few-layer nitrogen-doped graphene-encapsulated nickel-copper alloy directly on a porous nitrogen-doped graphic carbon framework (denoted as Nix Cuy @ NG-NC) is successfully synthesized using a facile and scalable method through calcinating the carbon, copper, and nickel hydroxy carbonate composite under inert atmosphere. The introduction of Cu can effectively modulate the morphologies and hydrogen evolution reaction (HER) performance. Moreover, the calcination temperature is an important factor to tune the thickness of graphene layers of the Nix Cuy @ NG-NC composites and the associated electrocatalytic performance. Due to the collective effects including unique porous flowered architecture and the synergetic effect between the bimetallic alloy core and graphene shell, the Ni3 Cu1 @ NG-NC electrocatalyst obtained under optimized conditions exhibits highly efficient and ultrastable activity toward HER in harsh environments, i.e., a low overpotential of 122 mV to achieve a current density of 10 mA cm-2 with a low Tafel slope of 84.2 mV dec-1 in alkaline media, and a low overpotential of 95 mV to achieve a current density of 10 mA cm-2 with a low Tafel slope of 77.1 mV dec-1 in acidic electrolyte.

Dramatic Differences in Aggregation-Induced Emission and Supramolecular Polymerizability of Tetraphenylethene-Based Stereoisomers.

Geometric (Z)- and (E)-isomers play important but different roles in life and material science. The design of new (Z)-/(E)- isomers and study of their properties, behaviors, and interactions are crucially important in molecular engineering. However, difficulties with their separation and structure confirmation limit their structural diversity and functionality in scope. In the work described herein, we successfully synthesized pure isomers of ureidopyrimidinone-functionalized tetraphenylethenes ((Z)-TPE-UPy and (E)-TPE-UPy), featuring both the aggregation-induced emission characteristic of tetraphenylethene and the supramolecular polymerizability of ureidopyrimidinone. Their structures were confirmed by 2D COSY and NOESY NMR spectroscopies. The two isomers show distinct fluorescence in the aggregate state: (Z)-TPE-UPy exhibits green emission, while its (E)-counterpart is blue-emitting. The cavity formed by the two ureidopyrimidinone groups of (Z)-TPE-UPy makes it suitable for Hg2+ detection, and the high-molecular-weight polymers prepared from (E)-TPE-UPy can be used to fabricate highly fluorescent fibers and 2D/3D photopatterns from their chloroform solutions.

Mesoporous Nanosheet Networked Hybrids of Cobalt Oxide and Cobalt Phosphate for Efficient Electrochemical and Photoelectrochemical Oxygen Evolution.

A novel mesoporous nanosheet networked hybrid comprising Co3 O4 and Co3 (PO4 )2 is successfully synthesized using a facile and scalable method through calcinating the carbon, cobalt hydroxy carbonate, and cobalt phosphate composite precursor. Electron transfer from Co3 O4 to Co3 (PO4 )2 , together with the special networked structure and the porous nature of the nanosheets enable the Co3 (PO4 )2 -Co3 O4 hybrid to have a high oxygen evolution reaction (OER) activity and outstanding stability in alkaline electrolyte, e.g., an overpotential of 270 mV at current density of 10 mA cm-2 , and a Tafel slope of 39 mV dec-1 , which are superior to most non-noble metal-based OER electrocatalysts reported thus far and as well the commercial RuO2 electrocatalyst. Furthermore, Co3 (PO4 )2 -Co3 O4 hybrid is demonstrated to be used as an efficient cocatalyst to enhance the photoelectrochemical OER performance of BiVO4 photoanode. A significantly increased photocurrent density of 3.0 mA cm-2 at 1.23 V (vs reversible hydrogen electrode, RHE), and a potential reduction of 530 mV with respect to that of bare BiVO4 at the photocurrent density of 0.5 mA cm-2 are achieved. The electron transfer-induced enhancement of OER by a hybrid structure may pave the new routes for the design and synthesis of low-cost catalysts for electrochemical and photoelectrochemical oxygen evolution.

Convenient synthesis of functionalized bis-ureidopyrimidinones based on thiol-yne reaction.

The preparation of functionalized bis-ureidopyrimidinones (Bis-UPy) through the thiol-yne reaction is described. Various Bis-UPys with different functional groups were synthesized by using the readily available functionalized alkynes and UPy-thiol to affirm the simplicity and versatility of the methodology.

Recent Developments in Nickel-Based Layered Double Hydroxides for Photo(-/)electrocatalytic Water Oxidation.

Layered double hydroxides (LDHs), especially those containing nickel (Ni), are increasingly recognized for their potential in photo(-/)electrocatalytic water oxidation due to the abundant availability of Ni, their corrosion resistance, and their minimal toxicity. This review provides a comprehensive examination of Ni-based LDHs in electrocatalytic (EC), photocatalytic (PC), and photoelectrocatalytic (PEC) water oxidation processes. The review delves into the operational principles, highlighting similarities and distinctions as well as the benefits and limitations associated with each method of water oxidation. It includes a detailed discussion on the synthesis of monolayer, ultrathin, and bulk Ni-based LDHs, focusing on the merits and drawbacks inherent to each synthesis approach. Regarding the EC oxygen evolution reaction (OER), strategies to improve catalytic performance and insights into the structural evolution of Ni-based LDHs during the electrocatalytic process are summarized. Furthermore, the review extensively covers the advancements in Ni-based LDHs for PEC OER, including an analysis of semiconductors paired with Ni-based LDHs to form photoanodes, with a focus on their enhanced activity, stability, and underlying mechanisms facilitated by LDHs. The review concludes by addressing the challenges and prospects in the development of innovative Ni-based LDH catalysts for practical applications. The comprehensive insights provided in this paper will not only stimulate further research but also engage the scientific community, thus driving the field of photo(-/)electrocatalytic water oxidation forward.

Aggregation-induced emission photosensitizer microneedles for enhanced melanoma photodynamic therapy.

The incidence and mortality rates of skin melanoma have been increasing annually. Photodynamic therapy (PDT) enables effective destruction of tumor cells while minimizing harm to normal cells. However, traditional photosensitizers (PSs) suffer from photobleaching, photodegradation and the aggregation-caused quenching (ACQ) effect, and it is challenging for light to reach the deep layers of the skin to maximize the efficacy of PSs. Herein, we developed dissolving microneedles (MNs) loaded with PSs of TPE-EPy@CB[7] through supramolecular assembly. The PSs effectively enhanced the type-I reactive oxygen species (ROS) generation capacity, with a concentration of 2 µM possessing nearly half of the tumor cell-killing ability under 10 min white light irradiation. The MNs were successfully pierced into the targeted site for precise drug delivery. Additionally, the conical structure of the MNs, as well as the lens-like structure after dissolution, facilitated the transmission of light in the subcutaneous tissue, achieving significant inhibition of tumor growth with a tumor suppression rate of 97.8% and no systemic toxicity or side effects in melanoma mice. The results demonstrated the potent melanoma inhibition and biosafety of this treatment approach, exhibiting a new and promising strategy to conquer malignant melanoma.

Tailoring the Activity of Electrocatalytic Methanol Oxidation on Cobalt Hydroxide by the Incorporation of Catalytically Inactive Zinc Ions.

Catalytically inactive Zn2+ is incorporated into cobalt hydroxide to synthesize hierarchical ZnCo-layered double hydroxide nanosheet networks supported on carbon fiber (ZnCo-LDH/CF). The incorporation of Zn2+ is revealed to endow ZnCo-LDH/CF with significantly superior performance in the aspects of the activity and selectivity for methanol electrooxidation to formic acid and the boosting effect for cathodic hydrogen production compared with the counterpart without Zn2+. Density functional theory (DFT) calculation reveals that the incorporation of nonactive Zn2+ can increase the density of states near the Fermi level of LDH (i.e., elevate electrical conductivity to form favorable charge transportation during electrocatalysis) and promote the adsorption and subsequent cleavage of methanol, thus leading to the enhanced methanol electrooxidation performance.

Stereoisomeric engineering of aggregation-induced emission photosensitizers towards fungal killing.

Fungal infection poses and increased risk to human health. Photodynamic therapy (PDT) as an alternative antifungal approach garners much interest due to its minimal side effects and negligible antifungal drug resistance. Herein, we develop stereoisomeric photosensitizers ((Z)- and (E)-TPE-EPy) by harnessing different spatial configurations of one molecule. They possess aggregation-induced emission characteristics and ROS, viz. 1O2 and O2-• generation capabilities that enable image-guided PDT. Also, the cationization of the photosensitizers realizes the targeting of fungal mitochondria for antifungal PDT killing. Particularly, stereoisomeric engineering assisted by supramolecular assembly leads to enhanced fluorescence intensity and ROS generation efficiency of the stereoisomers due to the excited state energy flow from nonradiative decay to the fluorescence pathway and intersystem (ISC) process. As a result, the supramolecular assemblies based on (Z)- and (E)-TPE-EPy show dramatically lowered dark toxicity without sacrificing their significant phototoxicity in the photodynamic antifungal experiments. This study is a demonstration of stereoisomeric engineering of aggregation-induced emission photosensitizers based on (Z)- and (E)-configurations.

Triple-Phase Interface Engineering over an In2O3 Electrode to Boost Carbon Dioxide Electroreduction.

The electrocatalytic reduction of CO2 is deemed to be a promising method to ease environmental and energy issues. However, achieving high efficiency and selectivity of CO2 electroreduction remains a bottleneck due to huge limitation of CO2 mass transfer and competition of hydrogen evolution reaction (HER) in aqueous solution. In this work, we propose to utilize triple-phase interface engineering over an In2O3 electrode to enhance its CO2 reduction reaction (CO2RR) performance. Notably, distinguishing from other research studies (doping, defect introduction, and heterojunction construction) that regulate the nature of In2O3-based catalysts themselves, we herein tune interfacial wettability of In2O3 using facile fluoropolymer coating for the first time. In contrast to the hydrophilic In2O3 electrode [Faraday efficiency (FE)HCOOH ∼ 62.7% and FEH2 ∼ 24.1% at -0.67 V versus RHE], the hydrophobic fluoropolymer (taking polyvinylidene fluoride as an example)-coated In2O3 electrode delivers a significantly enhanced FEHCOOH of 82.3% and a decreased FEH2 of 5.7% at the same potential. Upon combining contact angle measurements, density functional theory calculation, and ab initio molecular dynamics simulation, the enhanced CO2RR performance is revealed to be attributed to the rich triple-phase interfaces formed after fluoropolymer coating as an "aerophilic sponge", which increases the local concentration of CO2 near In2O3 active sites to improve CO2 reduction and meanwhile reduces the accessible water molecules to suppress competitive HER. This work presents a feasible approach for the enhanced selectivity of HCOOH yield over In2O3 by triple-phase interface engineering, which also provides a convenient and effective method for developing other materials used in gas-consumption reactions.

Modulation of Aggregation-Induced Emission by Excitation Energy Transfer: Design and Application.

Excitation energy transfer (EET) as a fundamental photophysical process is well-explored for developing functional materials with tunable photophysical properties. Compared to traditional fluorophores, aggregation-induced emission luminogens (AIEgens) exhibit unique advantages for building EET systems, especially serving as energy donors, due to their outstanding photophysical properties such as bright fluorescence in aggregation state, broad absorption and emission spectra, large Stokes shift, and high photobleaching resistance. In addition, the photophysical properties of AIEgens can be modulated by energy transfer for improved luminescence performance. Therefore, a variety of EET systems based on AIEgens have been constructed and their applications in different areas have been explored. In this review, we summarize recent progress in the design strategy of AIE-based energy transfer systems for light-harvesting, fluorescent probes and theranostic systems, with an emphasis on design strategies to achieve desirable properties. The limitations, challenges and future opportunities of AIE-EET systems are briefly outlined. Design strategies and applications (light-harvesting, fluorescent probe and theranostics) of AIEgen-based excitation energy systems are discussed in this review.

Simultaneously boosting the conjugation, brightness and solubility of organic fluorophores by using AIEgens.

Organic near-infrared (NIR) emitters hold great promise for biomedical applications. Yet, most organic NIR fluorophores face the limitations of short emission wavelengths, low brightness, unsatisfactory processability, and the aggregation-caused quenching effect. Therefore, development of effective molecular design strategies to improve these important properties at the same time is a highly pursued topic, but very challenging. Herein, aggregation-induced emission luminogens (AIEgens) are employed as substituents to simultaneously extend the conjugation length, boost the fluorescence quantum yield, and increase the solubility of organic NIR fluorophores, being favourable for biological applications. A series of donor-acceptor type compounds with different substituent groups (i.e., hydrogen, phenyl, and tetraphenylethene (TPE)) are synthesized and investigated. Compared to the other two analogs, MTPE-TP3 with TPE substituents exhibits the reddest fluorescence, highest brightness, and best solubility. Both the conjugated structure and twisted conformation of TPE groups endow the resulting compounds with improved fluorescence properties and processability for biomedical applications. The in vitro and in vivo applications reveal that the NIR nanoparticles function as a potent probe for tumour imaging. This study would provide new insights into the development of efficient building blocks for improving the performance of organic NIR emitters.

Bioinspired Simultaneous Changes in Fluorescence Color, Brightness, and Shape of Hydrogels Enabled by AIEgens.

Development of stimuli-responsive materials with complex practical functions is significant for achieving bioinspired artificial intelligence. It is challenging to fabricate stimuli-responsive hydrogels showing simultaneous changes in fluorescence color, brightness, and shape in response to a single stimulus. Herein, a bilayer hydrogel strategy is designed by utilizing an aggregation-induced emission luminogen, tetra-(4-pyridylphenyl)ethylene (TPE-4Py), to fabricate hydrogels with the above capabilities. Bilayer hydrogel actuators with the ionomer of poly(acrylamide-r-sodium 4-styrenesulfonate) (PAS) as a matrix of both active and passive layers and TPE-4Py as the core function element in the active layer are prepared. At acidic pH, the protonation of TPE-4Py leads to fluorescence color and brightness changes of the actuators and the electrostatic interactions between the protonated TPE-4Py and benzenesulfonate groups of the PAS chains in the active layer cause the actuators to deform. The proposed TPE-4Py/PAS-based bilayer hydrogel actuators with such responsiveness to stimulus provide insights in the design of intelligent systems and are highly attractive material candidates in the fields of 3D/4D printing, soft robots, and smart wearable devices.

Aggregation-Induced Nonlinear Optical Effects of AIEgen Nanocrystals for Ultradeep In Vivo Bioimaging.

Nonlinear optical microscopy has become a powerful tool in bioimaging research due to its unique capabilities of deep optical sectioning, high-spatial-resolution imaging, and 3D reconstruction of biological specimens. Developing organic fluorescent probes with strong nonlinear optical effects, in particular third-harmonic generation (THG), is promising for exploiting nonlinear microscopic imaging for biomedical applications. Herein, a simple method for preparing organic nanocrystals based on an aggregation-induced emission (AIE) luminogen (DCCN) with bright near-infrared emission is successfully demonstrated. Aggregation-induced nonlinear optical effects, including two-photon fluorescence (2PF), three-photon fluorescence (3PF), and THG, of DCCN are observed in nanoparticles, especially for crystalline nanoparticles. The nanocrystals of DCCN are successfully applied for 2PF microscopy at 1040 nm NIR-II excitation and THG microscopy at 1560 nm NIR-II excitation, respectively, to reconstruct the 3D vasculature of the mouse cerebral vasculature. Impressively, the THG microscopy provides much higher spatial resolution and brightness than the 2PF microscopy and can visualize small vessels with diameters of ≈2.7 µm at the deepest depth of 800 µm in a mouse brain. Thus, this is expected to inspire new insights into the development of advanced AIE materials with multiple nonlinearity, in particular THG, for multimodal nonlinear optical microscopy.

A Functioning Macroscopic "Rubik's Cube" Assembled via Controllable Dynamic Covalent Interactions.

The dynamic behavior of a macroscopic adhered hydrogel stabilized through controllable dynamic covalent interactions is reported. These interactions, involving the cross-linked formation of a hydrogel through reaction of a diacylhydrazine precursor with a tetraformyl partner, increase as a function of time. By using a contact time of 24 h and different compounds with recognized aggregation-induced emission features (AIEgens), it proves possible to create six laminated acylhydrazone hydrogels displaying different fluorescent colors. Blocks of these hydrogels are then adhered into a structure resembling a Rubik's Cube, a trademark of Rubik's Brand Limited, (RC) and allowed to anneal for 1 h. This produces a 3 × 3 × 3 block (RC) wherein the individual fluorescent gel blocks are loosely adhered to one another. As a consequence, the 1 × 3 × 3 layers making up the RC can be rotated either horizontally or vertically to produce new patterns. Ex situ modification of the RC or application of a chemical stimulus can be used to produce new color arrangements. The present RC structure highlights how the temporal features, strong versus weak adhesion, may be exploited to create smart macroscopic structures.

Visualizing the Initial Step of Self-Assembly and the Phase Transition by Stereogenic Amphiphiles with Aggregation-Induced Emission.

Many highly ordered structures with smart functions are generated by self-assembly with stimuli responsiveness. Despite that electron microscopes enable us to directly observe the end products, it is hard to visualize the initial step and the kinetic stimuli-responsive behavior of self-assembly. Here, we report the design and synthesis of stereogenic amphiphiles, namely, ( Z)-TPE-OEG and ( E)-TPE-OEG, with aggregation-induced emission (AIE) characteristics from the hydrophobic tetraphenylethene core and thermoresponsive behavior from the hydrophilic oligoethylene glycol monomethyl ether chain. The two isomers can be easily isolated by high-performance liquid chromatography and characterized by 2D NMR spectroscopy. While ( Z)-TPE-OEG self-assembles into vesicles, its ( E)-cousin forms micelles in water. The initial step of their self-assembly processes can be visualized based on AIE characteristics, with a sensitivity much higher than the method based on transmittance measurement. The entrapment and release capabilities of the ( Z)-stereogenic amphiphile are demonstrated by employing pyrene as a guest. The thermoresponsive behavior of the ( Z)-amphiphile results in its continuous phase transition from microscopic self-assembly to macroscopic aggregation, which is successfully visualized in situ by confocal laser scanning microscopy accompanied by the AIE technique. Such a kinetic process shows different stages according to the microscopic visualization, and these stages have never been monitored through roughly observing the appearance of precipitates. It is anticipated that this study can deepen the understanding of the self-assembly processes for better monitoring and controlling them in different systems.

"Seeing" and Controlling Photoisomerization by (Z)-/(E)-Isomers with Aggregation-Induced Emission Characteristics.

Efficient photoisomerization of chromophores is important in living systems, and structural constraints of protein pocket on chromophores are the probable reason for moving their dynamic reaction equilibrium forward. On the other hand, photochemical reaction to switch a molecule from one isomer to the other with different geometry and property in a high yield will continue to play a vital role in the synthetic chemistry and material science. Because of the important role of efficient photoisomerization, a biomimetic approach for "seeing" and controlling the photoisomerization is developed by using the technology of aggregation-induced emission (AIE) with supramolecular chemistry. It is revealed that a (Z)-isomer of a 2-ureido-4[1H]-pyrimidinone-containing tetraphenylethene (TPE-UPy) can be photoisomerized into supramolecular polymer form of its (E)-counterpart in chloroform in a high reaction yield of 68.1%. The yield is further enhanced to 100% in THF as aggregates of supramolecular polymers of (E)-TPE-UPy are formed, which completely inhibits the reverse photoreaction to form (Z)-TPE-UPy. In chloroform with organic acid, a mixture of equal amounts of (E)- and (Z)-isomers was obtained due to the disruption of the formation of intermolecular hydrogen bonds. The AIE characteristics of the isomers allow us to directly "see" the "turn-on" photoisomerization process by distinct fluorescence color changes, and the photoisomerization observed here may enable the development of a promising generation of optical power limiting materials.

Ethyl 4-nitro-phenyl-acetate.

In the asymmetric unit of the title compound, C(10)H(11)NO(4), there are two crystallographically independent mol-ecules, which are connected via a C-H⋯O hydrogen bond. The crystal structure is stabilized by this hydrogen bond together with an N-O⋯π contact [O⋯Cg 3.297 (5) Å; Cg is the centroid of one of the benzene rings].