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The strategy of isomerization is known for its simple yet effective role in optimizing molecular configuration and enhancing the power conversion efficiency (PCE) of organic solar cells (OSCs). However, the impact of isomerization on the design of dimer acceptors has been rarely investigated, and the relationship between the chemical structure and optoelectronic property remains unclear. In this study, we designed and synthesized two dimer acceptor isomers named D-TPh and D-TN, which differ in the positional arrangement of their end capping groups. Compared to D-TN, D-TPh exhibited enhanced backbone planarity, elevated lowest unoccupied molecular orbital energy level, and more ordered molecular stacking. Consequently, the OSC device based on PM6:D-TPh achieved a PCE of 19.05%, higher than that (PCE = 18.42%) of the device based on PM6:D-TN. Large-area PM6:D-TPh devices (1 cm²) yielded a PCE of 18.0%. More importantly, the extrapolated T80 lifetime of the PM6:D-TPh device is over 2800 h with MPP tracking under continuous one-sun illumination. These results suggest that isomerization strategy is an effective way to optimize the molecular configuration of dimer acceptors for the fabrication of high-efficiency and stable OSCs.
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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.
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Photothermal therapy (PTT), which uses the high thermal conversion ability of photothermal agents to ablate tumor cells at high temperatures, has gained significant attention because it has the advantages of high selectivity and specificity, precise targeting of tumor sites, and low invasiveness and trauma. However, PTT guided by the NIR-I has limitations in tissue penetration depth, resulting in limited imaging monitoring and therapeutic effects on deep-seated tumor tissues. Moreover, nanoparticles are easily cleared by the immune system and difficult to passively target tumor sites during the process of treatment. To address these issues, we prepared nanoparticles using NIR-II dyes IR1048 and DSPE-PEG-OH and further encapsulated them in red blood cell membranes derived from mice. These biomimetic nanoparticles, called RDIR1048, showed reduced clearance by the immune system and had long circulation characteristics. They effectively accumulated at tumor sites, and strong fluorescence could still be observed at the tumor site 96 h after administration. Furthermore, through mouse thermal imaging experiments, we found that RDIR1048 exhibited good PTT ability. When used in combination with an immune checkpoint inhibitor, anti-PD-L1 antibodies, it enhanced the immunogenic cell death of tumor cells caused by PTT and improved the therapeutic effect of immunotherapy, which demonstrated good therapeutic efficacy in the treatment of tumor-bearing mice. This study provides a feasible basis for the future development of NIR-II nanoparticles with long circulation properties.
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Membrana Eritrocítica , Imunoterapia , Nanopartículas , Terapia Fototérmica , Animais , Camundongos , Nanopartículas/química , Nanopartículas/uso terapêutico , Imunoterapia/métodos , Membrana Eritrocítica/química , Raios Infravermelhos , Humanos , Linhagem Celular Tumoral , Camundongos Endogâmicos BALB C , Neoplasias/diagnóstico por imagem , Neoplasias/terapia , Feminino , Fototerapia/métodosRESUMO
Supramolecular coordination complexes (SCCs) are popular for their structural diversity and functional adaptability, which make them suitable for a wide range of applications. Photophysical and mechanical performance of SCCs are the most attractive characteristics, yet their ionically conductive behavior and potential in electrical sensing have been rarely investigated. This study reports a well-designed SCC that integrates orthogonal metal coordination and host-guest interactions to achieve sensitive electrical thermal sensing. Owing to the thermodynamic nature of the host-guest interaction, the SCC encounters thermally induced disassembly, leading to significantly enhanced ion mobility and thus allowing for the precise detection of minor temperature variation. The SCC-based thermometer is then fabricated with the assistance of 3D printing and demonstrates good accuracy and reliability in monitoring human skin temperature and real-time temperature changes of mouse during the whole anesthesia and recovery process. Our findings provide an innovative strategy for developing electrical thermometers and expand the current application scope of SCCs in electrical sensing.
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Supramolecular coordination complexes (SCCs) are predictable and size-tunable supramolecular self-assemblies constructed through directional coordination bonds between readily available organic ligands and metallic receptors. Based on planar and 3D structures, SCCs can be mainly divided into two categories: metallacycles (e.g., rhomboidal, triangular, rectangular, and hexagonal) and metallacages (e.g., tetrahedral, hexahedral, and dodecahedral). The directional coordination bonds enable the efficient formation of metallacycles and metallacages with well-defined architectures and geometries. SCCs exhibit several advantages, including good directionality, strong interaction force, tunable modularity, and good solution processability, making them highly attractive for biomedical applications, especially in cellular imaging and cancer therapy. Compared with their molecular precursors, SCCs demonstrate enhanced cellular uptake and a strengthened tumor accumulation effect, owing to their inherently charged structures. These properties and the chemotherapeutic potential inherent to organic platinum complexes have promoted their widespread application in antitumor therapy. Furthermore, the defined structures of SCCs, achieved via the design modification of assembly elements and introduction of different functional groups, enable them to combat malignant tumors through multipronged treatment modalities. Because the development of cancer-treatment methodologies integrated in clinics has evolved from single-modality chemotherapy to synergistic multimodal therapy, the development of functional SCCs for synergistic cancer therapy is crucial. While some pioneering reviews have explored the bioapplications of SCCs, often categorized by a specific function or focusing on the specific metal or ligand types, a comprehensive exploration of their synergistic multifunctionality is a critical gap in the current literature.In this Account, we focus on platinum-based SCCs and their applications in cancer therapy. While other metals, such as Pd-, Rh-, Ru-, and Ir-based SCCs, have been explored for cancer therapy by Therrien and Casini et al., platinum-based SCCs have garnered significant interest, owing to their unique advantages in antitumor therapy. These platinum-based SCCs, which enhance antitumor efficacy, are considered prominent candidates for cancer therapies owing to their desirable properties, such as potent antitumor activity, exceptionally low systemic toxicity, active tumor-targeting ability, and enhanced cellular uptake. Furthermore, diverse diagnostic and therapeutic modalities (e.g., chemotherapy, photothermal therapy, and photodynamic therapy) can be integrated into a single platform based on platinum-based SCCs for cancer therapy. Consequently, herein, we summarize our recent research on platinum-based SCCs for synergistic cancer therapy with particular emphasis on the cooperative interplay between different therapeutic methods. In the Conclusions section, we present the key advancements achieved on the basis of our research findings and propose future directions that may significantly impact the field.
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Complexos de Coordenação , Neoplasias , Humanos , Complexos de Coordenação/farmacologia , Complexos de Coordenação/uso terapêutico , Complexos de Coordenação/química , Neoplasias/tratamento farmacológico , Platina/químicaRESUMO
Owing to their capacity for dynamically linking two or more functional molecules, supramolecular coordination complexes (SCCs), exemplified by two-dimensional (2D) metallacycles and three-dimensional (3D) metallacages, have gained increasing significance in biomedical applications. However, their inherent hydrophobicity and self-assembly driven by heavy metal ions present common challenges in their applications. These challenges can be overcome by enhancing the aqueous solubility and in vivo circulation stability of SCCs, alongside minimizing their side effects during treatment. Addressing these challenges is crucial for advancing the fundamental research of SCCs and their subsequent clinical translation. In this review, drawing on extensive contemporary research, we offer a thorough and systematic analysis of the strategies employed by SCCs to surmount these prevalent yet pivotal obstacles. Additionally, we explore further potential challenges and prospects for the broader application of SCCs in the biomedical field.
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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.
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Nanocompostos , Polímeros , Polímeros/química , Nanocompostos/químicaRESUMO
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.
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Neoplasias da Mama , Hipertermia Induzida , Nanopartículas , Feminino , Humanos , Antígeno B7-H1 , Fototerapia/métodos , Hipertermia Induzida/métodos , Sistemas de Liberação de Medicamentos/métodos , Verde de Indocianina/farmacologia , Verde de Indocianina/química , Neoplasias da Mama/terapia , Imunoterapia , Glutationa , Concentração de Íons de Hidrogênio , Linhagem Celular Tumoral , Nanopartículas/química , Microambiente TumoralRESUMO
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.
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Traditional cancer chemotherapy easily produces serious toxic and side effects due to the lack of specific selection of tumor cells, which restricts its curative effect. Targeted delivery can increase the concentration of drugs in the target site and reduce their toxic and side effects on normal tissues and cells. Biocompatible and surface-modifiable nanocarriers are novel drug delivery systems, which are used to specifically target tumor sites in a controllable way. One of the effective ways to design effective targeting nanocarriers is to decorate with functional ligands, which can bind to specific receptors overexpressed on the surfaces of cancer cells. Various functional ligands, including transferrin, folic acid, polypeptide and hyaluronic acid, have been widely explored to develop tumor-selective drug delivery systems. This review focuses on the research progress of various receptors overexpressed on the surfaces of cancer cells and different nano-delivery systems of anticancer drugs targeted on the surfaces of cancer cells. We believe that through continuous research and development, actively targeted cancer nano-drugs will make a breakthrough and become an indispensable platform for accurate cancer treatment.
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Photodynamic therapy (PDT) has attracted a great deal of attention in the field of cancer treatment due to its non-invasive nature, high repeatability and minimal side effects. Due to the dual effect of organic small molecule donors and platinum receptors, supramolecular coordination complexes (SCCs) exhibit stronger reactive oxygen species (ROS) production capacity and have become a promising class of photosensitizers (PSs). Herein, we report a rhomboid SCC MD-CN based on the D-A structure with aggregation-induced emission (AIE). The results show that the as-prepared nanoparticles (NPs) had excellent photosensitization efficiency and good biocompatibility. Most importantly, they exhibited potential killing effects on cancer cells in vitro under light irradiation.
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Complexos de Coordenação , Nanopartículas , Fotoquimioterapia , Complexos de Coordenação/farmacologia , Complexos de Coordenação/química , Fotoquimioterapia/métodos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/química , Espécies Reativas de Oxigênio , Nanopartículas/químicaRESUMO
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.
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Nanopartículas , Fotoquimioterapia , Ferro , Estudos Prospectivos , Nanopartículas/uso terapêutico , Fotoquimioterapia/métodosRESUMO
Despite the challenges, supramolecular polymers (SPs) have received significant attention. In this study, pH-responsive fluorescent SPs were prepared by a bottom-up strategy. The rhombohedral metallacycle-cored supramolecular coordination complex (SCC) was first prepared by metal-ligand coordination between the 120° pyridinedione boron difluoride and the 60° crown ether-based platinum, which then interacted with ammonium salt-containing covalent polymers to form SP networks. These networks can potentially be used for the detection of organic acid solutions and inorganic acid vapours.
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With the continuous breakthrough of the efficiency of organic photovoltaics (OPVs), their practical applications are on the agenda. However, the thickness tolerance and upscaling in recently reported high-efficiency devices remains challenging. In this work, the multiphase morphology and desired carrier behaviors are realized by utilizing a quaternary strategy. Notably, the exciton separation, carrier mobility, and carrier lifetime are enhanced significantly, the carrier recombination and the energy loss (Eloss ) are reduced, thus beneficial for a higher short-circuit density (JSC ), fill factor (FF), and open-circuit voltage (VOC ) of the quaternary system. Moreover, the intermixing-phase size is optimized, which is favorable for constructing the thick-film and large-area devices. Finally, the device with a 110 nm-thick active layer shows an outstanding power conversion efficiency (PCE) of 19.32% (certified 19.35%). Furthermore, the large-area (1.05 and 72.25 cm2 ) devices with 110 nm thickness present PCEs of 18.25% and 12.20%, and the device with a 305 nm-thick film (0.0473 cm2 ) delivers a PCE of 17.55%, which are among the highest values reported. The work demonstrates the potential of the quaternary strategy for large-area and thick-film OPVs and promotes the practical application of OPVs in the future.
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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 â¼660 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.
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Compostos de Boro , Neoplasias , Fotoquimioterapia , Compostos de Boro/uso terapêutico , Linhagem Celular Tumoral , Complexos de Coordenação/uso terapêutico , Sinergismo Farmacológico , Humanos , Neoplasias/tratamento farmacológico , Platina/uso terapêutico , Porfobilinogênio/análogos & derivadosRESUMO
As one of the major public health concerns, malignant tumors threaten people's lives. With the increasing demand for early accurate diagnosis and the safe treatment of tumors, non-invasive optical imaging (including fluorescence imaging and photoacoustic imaging) and phototherapy (including photothermal therapy and photodynamic therapy) have received much attention. In particular, light in the near-infrared second region (NIR-II) has been attracting research interest, owing to its deep penetration, minimal tissue autofluorescence, and decreased tissue absorption and scattering. Among all biological materials, organic nanomaterials with aggregation-induced emission (AIE) properties have attracted significant attention, owing to various incomparable advantages, such as high brightness, good photostability, tunable photophysical properties, and good biosafety. To modulate the working optical region of AIE molecules to the NIR-II region, many researchers have tried a variety of methods in recent years, and the focus of this review is to summarize the three most common methods from the perspective of molecular design strategies. In addition, this article briefly reviews the recent five-year progress of NIR-II AIE luminophores in tumor imaging and phototherapy applications. The research status is also summarized and prospected, with the hope of contributing to further research.
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Nanopartículas , Neoplasias , Fotoquimioterapia , Humanos , Neoplasias/tratamento farmacológico , Neoplasias/terapia , Imagem Óptica , Fototerapia , Terapia Fototérmica , Nanomedicina Teranóstica/métodosRESUMO
The present work demonstrates a facile hydrothermal approach to synthesize lanthanide-doped carbon quantum dots (CQDs) with europium and/or gadolinium elements. Taking the advantage of broadband adsorption in the ultraviolet-visible region, the doped QDs are directly used as building blocks for photo-electrochemical (PEC)-type photodetectors (PDs) and their performance is systematically investigated under various conditions. The europium (Eu) and gadolinium (Gd) co-doped (C:EuGd) QDs exhibit better photo-response than the single-elemental doped ones and also show outstanding long-term stability. According to the apparent response to light from 350 to 400 nm, the C:EuGd QDs are demonstrated to hold great potential for narrow-band PDs. This work highlights the practical applications of lanthanide-doped CQDs for PDs, and the results are beneficial for the development of elemental-doped CQDs in general.
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Pontos Quânticos , Carbono , GadolínioRESUMO
A triangular metallosalen-based metallacycle was constructed in quantitative yield by the self-assembly of a 180° bis(pyridyl)salen-Al complex and a 60° diplatinum(II) acceptor in a 1 : 1 stoichiometric ratio. This metallacycle was then successfully used to cyanosilylate a wide range of benzaldehydes with trimethylsilyl cyanide.
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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.
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Sistemas de Liberação de Medicamentos/métodos , Polietilenoglicóis/química , Polietilenoglicóis/farmacologia , Propilenoglicóis/química , Propilenoglicóis/farmacologia , Portadores de Fármacos/química , Humanos , Interações Hidrofóbicas e Hidrofílicas , Neoplasias/tratamento farmacológico , Poloxâmero/química , Poloxâmero/metabolismo , Poloxâmero/farmacologia , Polietilenoglicóis/metabolismo , Polímeros/química , Polipropilenos/química , Polipropilenos/farmacologia , Propilenoglicóis/metabolismo , Microambiente Tumoral/efeitos dos fármacosRESUMO
Cancer has become a common disease that seriously endangers human health and life. Up to now, the essential treatment method has been drug therapy, and drug delivery plays an important role in cancer therapy. To improve the efficiency of drug therapy, researchers are committed to improving drug delivery methods to enhance drug pharmacokinetics and cancer accumulation. Supramolecular coordination complexes (SCCs) with well-defined shapes and sizes are formed through the coordination between diverse functional organic ligands and metal ions, and they have emerged as potential components in drug delivery and cancer therapy. In particular, micelles or vesicles with the required biocompatibility and stability are synthesized using SCC-containing polymeric systems to develop novel carriers for drug delivery that possess combined properties and extended system tunability. In this study, the research status of SCC-containing polymeric systems as drug carriers and adjuvants for cancer treatment is reviewed, and a special focus is given to their design and preparation.