Phenylthiol-BODIPY-based supramolecular metallacycles for synergistic tumor chemo-photodynamic therapy.

The development of more effective tumor therapy remains challenging and has received widespread attention. In the past decade, there has been growing interest in synergistic tumor therapy based on supramolecular coordination complexes. Herein, we describe two triangular metallacycles (1 and 2) constructed by the formation of pyridyl boron dipyrromethene (BODIPY)-platinum coordination. Metallacycle 2 had considerable tumor penetration, as evidenced by the phenylthiol-BODIPY ligand imparting red fluorescent emission at ∼660 nm, enabling bioimaging, and transport visualization within the tumor. Based on the therapeutic efficacy of the platinum(II) acceptor and high singlet oxygen (1O2) generation ability of BODIPY, 2 was successfully incorporated into nanoparticles and applied in chemo-photodynamic tumor therapy against malignant human glioma U87 cells, showing excellent synergistic therapeutic efficacy. A half-maximal inhibitory concentration of 0.35 µM was measured for 2 against U87 cancer cells in vitro. In vivo experiments indicated that 2 displayed precise tumor targeting ability and good biocompatibility, along with strong antitumor effects. This work provides a promising approach for treating solid tumors by synergistic chemo-photodynamic therapy of supramolecular coordination complexes.

The Recent Advances of Polymer-POSS Nanocomposites With Low Dielectric Constant.

This study provides a comprehensive overview of the preparation methods for polyhedral oligomeric silsesquioxane (POSS) monomers and polymer/POSS nanocomposites. It focuses on the latest advancements in using POSS to design polymer nanocomposites with reduced dielectric constants. The study emphasizes exploring the potential of POSS, either alone or in combination with other materials, to decrease the dielectric constant and dielectric loss of various polymers, including polyimides, bismaleimide resins, poly(aryl ether)s, polybenzoxazines, benzocyclobutene resins, polyolefins, cyanate ester resins, and epoxy resins. In addition, the research investigates the impact of incorporating POSS on improving the thermal properties, mechanical properties, surface properties, and other aspects of these polymers. The entire study is divided into two parts, discussing systematically the role of POSS in reducing dielectric constants during the preparation of POSS composites using both physical blending and chemical synthesis methods. The goal of this research is to provide valuable strategies for designing a new generation of low dielectric constant materials suitable for large-scale integrated circuits in the semiconductor materials domain.

Eutectic Crystallization Activates Solid-State Zinc-Ion Conduction.

Solid-state zinc (Zn) batteries offer a new candidate for emerging applications sensitive to volume, safety and cost. However, current solid polymeric or ceramic electrolyte structures remain poorly conductive for the divalent Zn2+ , especially at room temperature. Constructing a heterogeneous interface which allows Zn2+ percolation is a viable option, but this is rarely involved in multivalent systems. Herein, we construct a solid Zn2+ -ion conductor by inducing crystallization of tailored eutectic liquids formed by organic Zn salts and bipolar ligands. High-entropy eutectic-networks weaken the ion-association and form interfacial Zn2+ -percolated channels on the nucleator surfaces, resulting in a solid crystal with exceptional selectivity for Zn2+ transport (t Zn 2 + =0.64) and appreciable Zn2+ conductivity (σ Zn 2 + =3.78×10-5  S cm-1 at 30 °C, over 2 orders of magnitude higher than conventional polymers), and finally enabling practical ambient-temperature Zn/V2 O5 metal solid cells. This design principle leveraged by the eutectic solidification affords new insights on the multivalent solid electrochemistry suffering from slow ion migration.

Stable electrically conductive, highly flame-retardant foam composites generated from reduced graphene oxide and silicone resin coatings.

To acheive flexible polyurethane (PU) foam composites with stable electrical conductivity and high flame retardancy involved first coating of graphene oxide (GO) onto PU foam surfaces and then chemically reducing the GO with hydrazine to form reduced GO (RGO). The RGO-coated PU foam is then dipped into a solution containing silicone resin (SiR) and silica nano-particles and cured. The resulting composites (PU-RGO-SiR) show superior flame retardancy, thermal stability and mechanical stability relative to the PU starting materials or PU coated with either RGO or SiR alone. The electrical conductivity of the PU-RGO-SiR composites (as high as 118 S m-1 at room temperature) could almost be retained but with small loss of 9.5% of the original value after 150 cyclic compression. When the samples were subjected to a temperature range from -50 to 400 °C, the electrical conductivity could remain constant at -50 °C, 25 °C, 100 °C, 200 °C, and even at 300 °C and 400 °C; the electrical-conductivity exhibited mild vibration but the vibration range was not beyond 5.6%. Flame retardancy tests show that the limiting oxygen index (LOI) increases from 14.7% for the pure foam to 31.5% for PU-RGO-SiR, and the PU-RGO-SiR composites exhibit a 65% reduction in the peak heat release rate (pHRR) and a 30% reduction in total smoke release (TSR). Thus, stable electrically conductive and highly flame-retardant foam composites have potential applications even in a variety of harsh conditions like high temperature, flame, organic solvents, and external compression.

Polymeric Drug Delivery System Based on Pluronics for Cancer Treatment.

Pluronic polymers (pluronics) are a unique class of synthetic triblock copolymers containing hydrophobic polypropylene oxide (PPO) and hydrophilic polyethylene oxide (PEO) arranged in the PEO-PPO-PEO manner. Due to their excellent biocompatibility and amphiphilic properties, pluronics are an ideal and promising biological material, which is widely used in drug delivery, disease diagnosis, and treatment, among other applications. Through self-assembly or in combination with other materials, pluronics can form nano carriers with different morphologies, representing a kind of multifunctional pharmaceutical excipients. In recent years, the utilization of pluronic-based multi-functional drug carriers in tumor treatment has become widespread, and various responsive drug carriers are designed according to the characteristics of the tumor microenvironment, resulting in major progress in tumor therapy. This review introduces the specific role of pluronic-based polymer drug delivery systems in tumor therapy, focusing on their physical and chemical properties as well as the design aspects of pluronic polymers. Finally, using newer literature reports, this review provides insights into the future potential and challenges posed by different pluronic-based polymer drug delivery systems in tumor therapy.

A Polymer-Reinforced SEI Layer Induced by a Cyclic Carbonate-Based Polymer Electrolyte Boosting 4.45 V LiCoO2 /Li Metal Batteries.

Lithium (Li) metal batteries (LMBs) are enjoying a renaissance due to the high energy densities. However, they still suffer from the problem of uncontrollable Li dendrite and pulverization caused by continuous cracking of solid electrolyte interphase (SEI) layers. To address these issues, developing spontaneously built robust polymer-reinforced SEI layers during electrochemical conditioning can be a simple yet effective solution. Herein, a robust homopolymer of cyclic carbonate urethane methacrylate is presented as the polymer matrix through an in situ polymerization method, in which cyclic carbonate units can participate in building a stable polymer-integrated SEI layer during cycling. The as-investigated gel polymer electrolyte (GPE) assembled LiCoO2 /Li metal batteries exhibit a fantastic cyclability with a capacity retention of 92% after 200 cycles at 0.5 C (1 C = 180 mAh g-1 ), evidently exceeding that of the counterpart using liquid electrolytes. It is noted that the anionic ring-opening polymerization of the cyclic carbonate units on the polymer close to the Li metal anodes enables a mechanically reinforced SEI layer, thus rendering excellent compatibility with Li anodes. The in situ formed polymer-reinforced SEI layers afford a splendid strategy for developing high voltage resistant GPEs compatible with Li metal anodes toward high energy LMBs.

Ketone-Directed Cobalt(III)-Catalyzed Regioselective C2 Amidation of Indoles.

An efficient cobalt(III)-catalyzed method for the direct C-H amidation of unprotected indoles for 2-amino indole scaffold construction has been developed. With dioxazolone as the amidating reagent, a variety of 2-amino indole derivatives were achieved in moderate to excellent yields using an organic acid as the additive and a ketone as the directing group.

Self-Healing Heterometallic Supramolecular Polymers Constructed by Hierarchical Assembly of Triply Orthogonal Interactions with Tunable Photophysical Properties.

Here, we present a method for the building of new bicyclic heterometallic cross-linked supramolecular polymers by hierarchical unification of three types of orthogonal noncovalent interactions, including platinum(II)-pyridine coordination-driven self-assembly, zinc-terpyridine complex, and host-guest interactions. The platinum-pyridine coordination provides the primary driving force to form discrete rhomboidal metallacycles. The assembly does not interfere with the zinc-terpyridine complexes, which link the discrete metallacycles into linear supramolecular polymers, and the conjugation length is extended upon the formation of the zinc-terpyridine complexes, which red-shifts the absorption and emission spectra. Finally, host-guest interactions via bis-ammonium salt binding to the benzo-21-crown-7 (B21C7) groups on the platinum acceptors afford the cross-linked supramolecular polymers. By continuous increase of the concentration of the supramolecular polymer to a relatively high level, supramolecular polymer gel is obtained, which exhibits self-healing properties and reversible gel-sol transitions stimulated by various external stimuli, including temperature, K+, and cyclen. Moreover, the photophysical properties of the supramolecular polymers could be effectively tuned by varying the substituents of the precursor ligands.

Metallacycle-Cored Supramolecular Polymers: Fluorescence Tuning by Variation of Substituents.

Herein, we present a method for the preparation of supramolecular polymers with tunable fluorescence via the combination of metal-ligand coordination and phenanthrene-21-crown-7 (P21C7)-based host-guest interactions. A suite of rhomboidal metallacycles with different substituents were prepared via the coordination-driven self-assembly of a P21C7-based 60° diplatinum(II) acceptor and 120° dipyridyl donors. Upon variation of the substituents on the dipyridyl donors, the metallacycles exhibit emission wavelengths spanning the visible region (λmax = 427-593 nm). Metallacycle-cored supramolecular polymers were obtained via host-guest interactions between bis-ammonium salts and P21C7. The supramolecular polymers exhibit emission wavelengths similar to those of the individual metallacycles and higher fluorescent efficiency in solution and thin films. Utilizing a yellow-emitting supramolecular polymer thin film with high quantum yield (0.22), a white-light-emitting LED was fabricated by painting the thin film onto an ultraviolet LED. This study presents an efficient approach for tuning the properties of fluorescent supramolecular polymers and the potential of the metallacycle-cored supramolecular polymers as a platform for the fabrication of light-emitting materials with good processability and tunability.

Metal Coordination Stoichiometry Controlled Formation of Linear and Hyperbranched Supramolecular Polymers.

Controlling the topologies of polymers is a hot topic in polymer chemistry because the physical and/or chemical properties of polymers are determined (at least partially) by their topologies. This study exploits the host-guest interactions between dibenzo-24-crown-8 and secondary ammonium salts and metal coordination interactions between 2,6-bis(benzimidazolyl)-pyridine units with metal ions (Zn(II) and/or Eu(III) ) as orthogonal non-covalent interactions to prepare supramolecular polymers. By changing the ratios of the metal ion additives (Zn(NO3 )2 and Eu(NO3 )3 ) linkers to join the host-guest dimeric complex, the linear supramolecular polymers (100 mol% Zn(NO3 )2 per ligand) and hyperbranched supramolecular polymers (97 mol% Zn(NO3 )2 and 3 mol% Eu(NO3 )3 per ligand) are separately and successfully constructed. This approach not only expands topological control over polymeric systems, but also paves the way for the functionalization of smart and adaptive materials.

Modulation of aggregation-induced emission and electroluminescence of silole derivatives by a covalent bonding pattern.

The deciphering of structure-property relationships is of high importance to rational design of functional molecules and to explore their potential applications. In this work, a series of silole derivatives substituted with benzo[b]thiophene (BT) at the 2,5-positions of the silole ring are synthesized and characterized. The experimental investigation reveals that the covalent bonding through the 2-position of BT (2-BT) with silole ring allows a better conjugation of the backbone than that achieved though the 5-position of BT (5-BT), and results in totally different emission behaviors. The silole derivatives with 5-BT groups are weakly fluorescent in solutions, but are induced to emit intensely in aggregates, presenting excellent aggregation-induced emission (AIE) characteristics. Those with 2-BT groups can fluoresce more strongly in solutions, but no obvious emission enhancements are found in aggregates, suggesting they are not AIE-active. Theoretical calculations disclose that the good conjugation lowers the rotational motions of BT groups, which enables the molecules to emit more efficiently in solutions. But the well-conjugated planar backbone is prone to form strong intermoelcular interactions in aggregates, which decreases the emission efficiency. Non-doped organic light-emitting diodes (OLEDs) are fabricated by using these siloles as emitters. AIE-active silole derivatives show much better elecroluminescence properties than those without the AIE characterisic, demonstrating the advantage of AIE-active emitters in OLED applications.

Controlled self-assembly of a pyrene-based bolaamphiphile by acetate ions: from nanodisks to nanofibers by fluorescence enhancement.

In this paper, a pyrene moiety is incorporated into a bolaamphiphile to form a novel molecule denoted PRB. Above the critical micelle concentration, PRB forms nanodisks in the aqueous solution. The addition of acetate ions induces a morphological change in self-assembled aggregates, which convert into nanofibers with a diameter of several nanometers. More interestingly, along with the morphological change, the fluorescence of the assemblies was enhanced concomitantly, which can be attributed to the binding effect of acetate ions on pyridinium head groups of PRB.

Copper-catalyzed cascade cyclization reaction of 2-haloaryltriazenes and sodium azide: selective synthesis of 2H-benzotriazoles in water.

A new approach to the synthesis of 2H-benzotriazoles is described. This strategy is based on the copper-catalyzed C-N coupling of 2-haloaryltriazenes or 2-haloazo compounds with sodium azide and the intramolecular addition of nitrene to N=N bonds. This approach allows the synthesis of various N-amino- and N-aryl-2H-benzotriazoles in water, in good to excellent yields. The procedure is simple and the starting materials and catalyst are easily available, offering a practical and convenient synthetic route to 2-substituted benzotriazoles.

A multiple-responsive self-healing supramolecular polymer gel network based on multiple orthogonal interactions.

Supramolecular polymer networks have attracted considerable attention not only due to their topological importance but also because they can show some fantastic properties such as stimuli-responsiveness and self-healing. Although various supramolecular networks are constructed by supramolecular chemists based on different non-covalent interactions, supramolecular polymer networks based on multiple orthogonal interactions are still rare. Here, a supramolecular polymer network is presented on the basis of the host-guest interactions between dibenzo-24-crown-8 (DB24C8) and dibenzylammonium salts (DBAS), the metal-ligand coordination interactions between terpyridine and Zn(OTf)2 , and between 1,2,3-triazole and PdCl2 (PhCN)2 . The topology of the networks can be easily tuned from monomer to main-chain supramolecular polymer and then to the supramolecular networks. This process is well studied by various characterization methods such as (1) H NMR, UV-vis, DOSY, viscosity, and rheological measurements. More importantly, a supramolecular gel is obtained at high concentrations of the supramolecular networks, which demonstrates both stimuli-responsiveness and self-healing properties.

Influence of Chemical Structures on E-Beam Lithography Performance of Polysilsesquioxanes.

Hydrogenated silsesquioxane (HSQ) is a key inorganic electron beam resist, celebrated for its sub-10 nm resolution and etching resistance, but it faces challenges with stability and sensitivity. Our innovative study has comprehensively assessed the lithographic performance of three functionalized polysilsesquioxane (PSQ) resist series─olefins, halogenated alkanes, and alkanes─under electron beam lithography (EBL). We discovered that the addition of olefin groups, such as in the HMP-30 formulation with 30% propyl acrylate, remarkably increased the sensitivity to 0.6 µC/cm2. The inclusion of halogenated aromatic and hydrogen-substituted methyl groups further enhanced sensitivity and contrast, with HClBN-50 achieving a 22.9 nm resolution pattern. At the same time, the storage of PSQ resists was significantly improved compared to commercial HSQ with increasing alkane group content. Crucially, our research has unveiled the lithography reaction mechanism, highlighting how group encapsulation and steric hindrance influence PSQ performance. This insight is groundbreaking, offering a deeper understanding of the molecular structure-performance relationship and laying the groundwork for developing next-generation electron beam resists with superior sensitivity, resolution, and contrast for microelectronics manufacturing.

The Multi-Functional Third Acceptor Realizes the Synergistic Improvement in Photovoltaic Parameters and the High-Ratio Tolerance of Ternary Organic Photovoltaics.

The ternary strategy proves effective for breakthroughs in organic photovoltaics (OPVs). Elevating three photovoltaic parameters synergistically, especially the proportion-insensitive third component, is crucial for efficient ternary devices. This work introduces a molecular design strategy by comprehensively analyzing asymmetric end groups, side-chain engineering, and halogenation to explore the outstanding optoelectronic properties of the proportion-insensitive third component in efficient ternary systems. Three asymmetric non-fullerene acceptors (BTP-SA1, BTP-SA2, and BTP-SA3) are synthesized based on the Y6 framework and incorporated as the third component into the D18:Y6 binary system. BTP-SA3, featuring asymmetric terminal (difluoro-indone and dichloride-cyanoindone terminal), with branched alkyl side chains, exhibited high open-circuit voltage (VOC), balanced crystallinity and compatibility, achieving synergistic enhancements in VOC (0.862 V), short circuit-current density (JSC, 27.52 mA cm-2), fill fact (FF, 81.01%), and power convert efficiency (PCE, 19.19%). Device based on D18/Y6:BTP-SA3 (layer-by-layer processed) reached a high efficiency of 19.36%, demonstrating a high tolerance for BTP-SA3 (10-50%). This work provides novel insights into optimizing OPVs performances in multi-component systems and designing components with enhanced tolerance.

Aggregation-induced emission and efficient solid-state fluorescence from tetraphenylethene-based N,C-chelate four-coordinate organoborons.

In it together: Thermally stable N,C-chelate four-coordinate organoborons were attained by grafting intramolecular B⋅ ⋅ ⋅N coordination into tetraphenylethene-pyridine and -quinoline adducts. They exhibit aggregation-induced emission characteristics (see figure), and high fluorescence quantum yields approaching unity in solid films.

Progress in organic photovoltaics based on green solvents: from solubility enhancement to morphology optimization.

Solution-processed organic photovoltaics (OPVs) is one of the most promising photovoltaic technologies in the energy field, due to their clean and renewable low-cost manufacturing potential. OPV has rapidly developed with the design and synthesis of highly efficient photovoltaic materials and the development of smart device engineering. To date, the majority of advanced OPV devices have been prepared using halogenated solvents, achieving power conversion efficiencies (PCE) exceeding 19% on a laboratory scale. However, for industrial-scale production, less toxic manufacturing processes and environmental sustainability are the key considerations. Therefore, this review summarizes recent advances in green solvent-based approaches for the preparation of OPVs, highlighting material design (including polymer donors and small molecule acceptors) and device engineering (co-solvent methods, additive strategies, post-treatment methods, and regulation of coating method), emphasizing crucial factors for achieving high performance in green solvent-processed OPV devices. This review presents potential future directions for green solvent-based OPVs, which may pave the way for future industrial development.

GSH/pH dual response drug delivery system for photothermal enhanced gene-immunotherapy.

Breast cancer has emerged as a leading cause of mortality among women. Photothermal therapy represents a recent therapeutic modality for eradicating localized tumors, albeit hindered by its limited penetration into tumor tissues. Recognizing the potential of photothermal therapy to induce immunogenic cell death in tumor cells, we explored a gene delivery approach utilizing small interfering RNA targeting programmed death ligand 1 (PD-L1), abbreviated as siPD-L1, to bolster the anti-tumor immune response elicited by this therapy. Nonetheless, the suboptimal release efficiency and inherent instability of RNA molecules have posed challenges to their therapeutic efficacy. In this study, we designed a glutathione (GSH)/pH-responsive micelle system, employing biocompatible and low-toxicity polyethyleneimine in conjunction with structurally robust pluronic P123, to encapsulate both indocyanine green (ICG) and siPD-L1 for precise targeting in breast cancer treatment. The resulting PSP/ICG/siPD-L1 nanocarrier demonstrated admirable biocompatibility and stability. Upon internalization into tumor cells, this nanocarrier exhibited rapid release of both ICG and siPD-L1, responding to the acidic tumor microenvironment and GSH conditions. The inclusion of siPD-L1 effectively downregulated the expression of PD-L1 on the tumor cell surface, thereby impeding tumor growth. Additionally, ICG demonstrated a photothermal effect when exposed to near-infrared light. Both in vitro and in vivo investigations substantiated the nanocarrier's efficacy against tumor cells, culminating in the complete ablation of 4T1 tumors in situ. Consequently, PSP/ICG/siPD-L1 emerges as a promising nanocarrier candidate for augmenting anti-tumor immunity through the synergistic combination of photothermal therapy and gene-based intervention.

Self-Assembled Aza-BODIPY and Iron(III) Nanoparticles for Photothermal-Enhanced Chemodynamic Therapy in the NIR-II Window.

Despite its promising potential in cancer treatment, synergistic photothermal/chemodynamic therapy remains underdeveloped with regard to the utilization of metal-organic materials under second near-infrared (NIR-II) laser excitation. Herein, we report a three-dimensional network constructed via the metal coordination between catechol-functionalized aza-boron dipyrromethenes and iron ions (ABFe), which was further encapsulated by F127 to obtain ABFe nanoparticles (NPs) for combined photothermal/chemodynamic therapy. ABFe NPs exhibited intense absorption in the NIR-II range and negligible fluorescence. Upon 1064 nm laser irradiation, ABFe NPs showed high photothermal conversion efficiency (PCE = 55.0%) and excellent photothermal stability. The results of electron spin resonance spectra and o-phenylenediamine chromaticity spectrophotometry proved that ABFe NPs were capable of generating harmful reactive oxygen species from hydrogen peroxide for chemodynamic therapy, which was promoted by photothermal performance. Notably, in vitro and in vivo experiments demonstrated the great potential of ABFe NPs in photoacoustic imaging and photothermal-enhanced chemodynamic therapy under NIR-II laser irradiation. Therefore, the current work presents a prospective NIR-II excitation therapeutic nanomedicine for combination therapy, offering a novel strategy for simultaneously achieving extended NIR absorption of aza-BODIPY and enhanced chemodynamic therapy with metal-organic materials.