Near-Infrared Emission Beyond 900†nm from Stable Radicals in Nonconjugated Poly(diphenylmethane).

Organic radicals with narrow energy gaps are highly sought-after for the production of near-infrared (NIR) fluorophores. However, the current repertoire of developed organic radicals is notably limited, facing challenges related to stability and low fluorescence efficiency. This study addresses these limitations by achieving stable radicals in nonconjugated poly(diphenylmethane) (PDPM). Notably, PDPM exhibits a well-balanced structural flexibility and rigidity, resulting in a robust intra-/inter-chain through-space conjugation (TSC). The stable radicals within PDPM, coupled with strong TSC, yield a remarkable full-spectrum emission spanning from blue to NIR beyond 900 nm. This extensive tunability is achieved through careful adjustments of concentration and excitation wavelength. The findings highlight the efficacy of polymerization in stabilizing radicals and introduce a novel approach for developing nonconjugated NIR emitters based on triphenylmethane subunits.

Phosphine-Capped Effects Enable Full-Color Clusteroluminescence in Nonconjugated Polyesters.

Full-color luminophores have advanced applications in materials and engineering, but constructing color-tunable clusteroluminescence (CL) from nonconjugated polymers based on through-space interactions remains a huge challenge. Herein, we develop phosphine-capped nonconjugated polyesters exhibiting blue-to-red CL (400-700 nm) based on phosphine-initiated copolymerization of epoxides and cyclic anhydrides, especially P1-0.5TPP, which exhibits red CL (610 nm) with a high quantum yield of 32%. Experiments and theoretical calculations disclose that the phosphine-capped effect in polyesters brings about conformational changes and induces phosphine-ester clusters by through-space (n,π*) interactions. Moreover, CL colors and efficiencies can be easily tailored by types of phosphines, compositions and structures of polyesters, and concentration. Significantly, the role of polymer motions (group, segmental, and chain motions) on CL originating from microregions inside polyesters is revealed. Further, phosphine-capped nonconjugated polyesters are demonstrated to be nonconjugated dyes and fluorescent fibers and are also used for multicolor light-emitting diodes including white light. This work not only provides an engineering strategy based on the end-group effect to prepare full-color clusteroluminogens but also broadens the prospects for material applications.

Adipocyte­rich microenvironment promotes chemoresistance via upregulation of peroxisome proliferator­activated receptor gamma/ABCG2 in epithelial ovarian cancer.

The effects of adipocyte­rich microenvironment (ARM) on chemoresistance have garnered increasing interest. Ovarian cancer (OVCA) is a representative adipocyte­rich associated cancer. In the present study, epithelial OVCA (EOC) was used to investigate the influence of ARM on chemoresistance with the aim of identifying novel targets and developing novel strategies to reduce chemoresistance. Bioinformatics analysis was used to explore the effects of ARM­associated mechanisms contributing to chemoresistance and treated EOC cells, primarily OVCAR3 cells, with human adipose tissue extracts (HATES) from the peritumoral adipose tissue of patients were used to mimic ARM in vitro. Specifically, the peroxisome proliferator­activated receptor Î³ (PPARγ) antagonist GW9662 and the ABC transporter G family member 2 (ABCG2) inhibitor KO143, were used to determine the underlying mechanisms. Next, the effect of HATES on the expression of PPARγ and ABCG2 in OVCAR3 cells treated with cisplatin (DDP) and paclitaxel (PTX) was determined. Additionally, the association between PPARγ, ABCG2 and chemoresistance in EOC specimens was assessed. To evaluate the effect of inhibiting PPARγ, using DDP, a nude mouse model injected with OVCAR3­shPPARγ cells and a C57BL/6 model injected with ID8 cells treated with GW9662 were established. Finally, the factors within ARM that contributed to the mechanism were determined. It was found that HATES promoted chemoresistance by increasing ABCG2 expression via PPARγ. Expression of PPARγ/ABCG2 was related to chemoresistance in EOC clinical specimens. GW9662 or knockdown of PPARγ improved the efficacy of chemotherapy in mice. Finally, angiogenin and oleic acid played key roles in HATES in the upregulation of PPARγ. The present study showed that the introduction of ARM­educated PPARγ attenuated chemoresistance in EOC, highlighting a potentially novel therapeutic adjuvant to chemotherapy and shedding light on a means of improving the efficacy of chemotherapy from the perspective of ARM.

How the Length of Through-Space Conjugation Influences the Clusteroluminescence of Oligo(Phenylene Methylene)s.

The length and mode of conjugation directly affect the molecular electronic structure, which has been extensively studied in through-bond conjugation (TBC) systems. Corresponding research greatly promotes the development of TBC-based luminophores. However, how the length and mode of through-space conjugation (TSC), one kind of weak interaction, influence the photophysical properties of non-conjugated luminophores remains a relatively unexplored field. Here, we unveil a non-linear relationship between TSC length and emission characteristics in non-conjugated systems, in contrast to the reported proportional correlation in TBC systems. More specifically, oligo(phenylene methylene)s (OPM[4]-OPM[7]) exhibit stronger TSC and prominent blue clusteroluminescence (CL) (≈440 nm) compared to shorter counterparts (OPM[2] and OPM[3]). OPM[6] demonstrates the highest solid-state quantum yield (40 %), emphasizing the importance of balancing flexibility and rigidity. Further theoretical calculations confirmed that CL of these oligo(phenylene methylene)s was determined by stable TSC derived from the inner rigid Diphenylmethane (DPM) segments within the oligomers instead of the outer ones. This discovery challenges previous assumptions and adds a new dimension to the understanding of TSC-based luminophores in non-conjugated systems.

Heteroatom-facilitated blue to near-infrared emission of nonconjugated polyesters.

Making nonconjugated polymers to emit visible light remains a formidable challenge, let alone near-infrared (NIR) light, although NIR luminophores have many advanced applications. Herein, we propose an electron-bridging strategy of using heteroatoms (O, N, and S) to achieve tunable emission from blue to NIR regions (440-800 nm) in nonconjugated polyesters. Especially, sulfur-containing polyester P4 exhibits NIR clusteroluminescence (CL) on changing either the concentration or excitation wavelength. Experimental characterization and theoretical calculation demonstrate that the introduction of heteroatoms significantly enhances the through-space interactions (TSIs) via the electron-bridging effect between heteroatoms and carbonyls. The strength of the electron-bridging effect follows the order of S > N > O, based on two synergistic effects: electronic structure and van der Waals radius of heteroatoms. This work provides a low-cost, scalable platform to produce new-generation nonconjugated luminophores with deeper insight into the photophysical mechanism.

Enabling nonconjugated polyesters emit full-spectrum fluorescence from blue to near-infrared.

Near-infrared luminophores have many advantages in advanced applications, especially for structures without π-conjugation aromatic rings. However, the fabrication of red clusteroluminogens from nonconjugated polymers is still a big challenge, let alone the near-infrared clusteroluminogens. Here, we develop nonconjugated luminophores with full-spectrum from blue to near-infrared light (470 ~ 780 nm), based on color phenomenon of nonconjugated polyesters synthesized from the amine-initiated copolymerization of epoxides and cyclic anhydrides. We reveal that amines act as initiators attached to polymer chain ends. The formation of various amine-ester complexes in polyesters induces red to near-infrared light, conceptually, amine-ester complexed clusteroluminescence via intra/inter-chain charge transfer. Significantly, emission colors can be easily tuned by the contents and types of amines, microstructures of polyesters, and their concentration. This work provides a low-cost, scalable platform and strategy for the production of high-efficiency, multicolor luminescent materials.

Luminescent polypeptides.

Polypeptides, as biomacromolecules, hold immense potential in various biological applications such as tissue engineering, immunomodulating agents, and target binding. Among these applications, the attention towards luminescent polypeptides has grown significantly, due to their ability to visualize biological processes effectively. In this perspective, we have compiled information on three distinct types of luminescent polypeptides: natural fluorescent proteins, luminophores-bioconjugated polypeptides, and synthesized polypeptides with clusteroluminescence. Last, we shed light on the significance and prospects of clusteroluminescent polypeptides, which are expected to emerge as crucial new-generation bioluminophores, offering high emission efficiency and tunable emission wavelengths.

Differential fluorescent response to amino acids based on metal-organic framework Zn-PBC.

A novel metal-organic framework (MOF) Zn-PBC (H2PBC = pyridine-3,5-bis(phenyl-4-carboxylic acid)) was designed and synthesized via a solvothermal reaction with the H2PBC ligand, and produced a strong fluorescence. The material exhibited good stability and an ideal luminescent property in water. In addition, it was found that Zn-PBC displayed a different fluorescent response to different types of amino acids, and the mechanism was investigated. This research might give insight to the interaction between MOFs and amino acids, which would provide a strategy to fabricate MOF-based sensors for biomolecules in future.

177 Lu Radiolabelled AIE Dots for Multimodal Imaging Guided Photothermal/Radiopharmaceutical Tumor Therapy.

Aggregation-induced emission luminogens (AIEgens) in the second near-infrared region (NIR-II,1000-1700 nm) have shown tremendous potential as theragnostic probe for tumor multimodal diagnostic imaging and combined treatment owing to their programmable optical, structural and functional properties. Herein, we presented a radionuclide 177 Lu-labeled AIEgen, 177 Lu-2TT-oC6B dots, for NIR-II fluorescence and SPECT/CT imaging-guided tumor photothermal and radiopharmaceutical therapy. Intriguingly, 177 Lu-2TT-oC6B self-assembled into 10 nm dots, exhibited high NIR-II fluorescence quantum yield (QY, 1.34 %) and unprecedented photothermal conversion efficiency (PCE, 70.3 %) in vitro, furtherly performed extremely long blood circulation (T1/2 =52.4 h), persistent tumor accumulation and retention in tumor (NIR-II SNR=5.56; SPECT SNR=36.59) via intravenous administration in vivo. Furthermore, upon NIR light activation and 177 Lu irradiation, 177 Lu-2TT-oC6B demonstrated great application potential in synergistic photothermal/radiopharmaceutical tumor therapy.

Excited-State Odd-Even Effect in Through-Space Interactions.

The odd-even effect is a fantastic phenomenon in nature, which has been applied in diverse fields such as organic self-assembled monolayers and liquid crystals. Currently, the origin of each odd-even effect remains elusive, and all of the reported odd-even effects are related to the ground-state properties. Here, we discover an excited-state odd-even effect in the through-space interaction (TSI) of nonconjugated tetraphenylalkanes (TPAs). The TPAs with an even number of alkyl carbon atoms (C2-TPA, C4-TPA, and C6-TPA) show strong TSI, long-wavelength emission, and high QY. However, the odd ones (C1-TPA, C3-TPA, C5-TPA, and C7-TPA) are almost nonexistent with negligible QY. Systematically experimental and theoretical results reveal that the excited-state odd-even effect is synthetically determined by three factors: alkyl geometry, molecular movability, and intermolecular packing. Moreover, these flexible luminescent TPAs possess tremendous advantages in fluorescent information encryptions. This work extends the odd-even effect to photophysics, demonstrating its substantial importance and universality in nature.

A Mitochondria-Targeted NIR-II AIEgen Induced Pyroptosis for Enhanced Tumor Immunotherapy.

Cancer immunotherapy is a favorable strategy for facilitating anti-tumor immunity, but it shows limited benefits in clinical practice owing to the immunosuppressive tumor microenvironment. Pyroptosis shows great immunostimulatory effect on tumor, whereas the lack of pyroptotic inducer with imaging property has restricted its progress in tumor theranostics. Herein, a mitochondria-targeted aggregation-induced emission (AIE) luminogen (TPA-2TIN) with NIR-II emission is designed for highly efficient induction of tumor cell pyroptosis. The fabricated TPA-2TIN nanoparticles can be efficiently taken up by tumor cells and selectively accumulated in tumor for a long term observed by NIR-II fluorescence imaging. More importantly, the TPA-2TIN nanoparticles can effectively stimulate immune responses both in vitro and in vivo mediated by the mitochondrial dysfunctions and the subsequent activation of the pyroptotic pathway. Ultimately, the reversal of the immunosuppressive tumor microenvironment significantly enhances the immune checkpoint therapy. This study paves a new avenue for adjuvant immunotherapy of cancer.

Regulating the proximity effect of heterocycle-containing AIEgens.

Proximity effect, which refers to the low-lying (n,π*) and (π,π*) states with close energy levels, usually plays a negative role in the luminescent behaviors of heterocyclic luminogens. However, no systematic study attempts to reveal and manipulate proximity effect on luminescent properties. Here, we report a series of methylquinoxaline derivatives with different electron-donating groups, which show different photophysical properties and aggregation-induced emission behaviors. Experimental results and theoretical calculation reveal the gradually changed energy levels and different coupling effects of the closely related (n,π*) and (π,π*) states, which intrinsically regulate proximity effect and aggregation-induced emission behaviors of these luminogens. With the intrinsic nature of heterocycle-containing compounds, they are utilized for sensors and information encryption with dynamic responses to acid/base stimuli. This work reveals both positive and negative impacts of proximity effect in heterocyclic aggregation-induced emission systems and provides a perspective to develop functional and responsive luminogens with aggregation-induced emission properties.

Substrate-Responsive Pillar[5]arene-Based Organic Room-Temperature Phosphorescence.

Room-temperature phosphorescence (RTP) is a photophysical phenomenon typically associated with a long-lived emission that can be detected by the unaided eye. Several natural proteins display RTP, as do certain artificial polymers. In both cases, the RTP is ascribed to effective intramolecular through-space electronic communication. However, small molecules with internal electronic communication that enable RTP are relatively rare. Herein, we describe an alkyl halide-responsive RTP system consisting of a meta-formylphenyl-bearing pillar[5]arene derivative that supports effective through-space charge transfer (TSCT) within the pillararene cavity. Treatment with bromoethane, a heavy atom-containing guest for the pillar[5]arene host, serves to enhance the emission. An isomeric para-formylphenyl-bearing pillar[5]arene system proved ineffective in producing an RTP effect. Quantum chemical calculations based on single-crystal X-ray diffraction analyses provided insights into the structural determinants governing TSCT between the 1,4-dimethoxybenzene donor units and the formylphenyl groups of the pillar[5]arene, as well as the associated energy gaps and intersystem crossing channels. We believe that the present system and the associated mechanistic analysis provide the foundation for design of new small molecule with tunable RTP features.

NIR Clusteroluminescence of Non-conjugated Phenolic Resins Enabled by Through-Space Interactions.

Clusteroluminescence (CL) and through-space interactions (TSIs) of non-conjugated molecules have drawn more attention due to their unique photophysical behaviors that are different from largely conjugated luminogens. However, achieving red and even near-infrared (NIR) emission from such systems is still challenging due to the intrinsic drawbacks of non-conjugated molecules and the lack of theories for structure-property relationships. In this work, six phenolic resins are designed and synthesized based on two molecule-engineering strategies: increasing the number of TSIs units and introducing electron-donating/-withdrawing groups. All phenolic resins are verified as luminogens with CL property (CLgens), and the first example of CLgens with NIR emission (maximum emission wavelength ≥680 nm) and high absolute quantum yield (47 %) is reported. Experiments and theoretical analysis reveal that two TSIs types, through-space locally excited state and through-space charge transfer state, play essential roles in achieving CL from these non-conjugated polymers, which could be manipulated via changing structural conformation and electron density or altering electron transition behaviors. This work not only provides an approach to manipulate TSIs and CL of non-conjugated polymers but also endows commercially available phenolic resins with high practical value as luminescence materials.

Radiolabeled AIE Probes as Dual-modality Imaging Agents for PET/NIR-II Fluorescence-Guided Photothermal Therapy.

Breast cancer has become a huge burden with continued rise of incidence and death rate worldwide. Various methods for diagnosis and therapy of breast cancer have met the challenges of lack of complete information about the tumor location and limited therapy efficacy. Although aggregation-induced emission luminogens (AIEgens) have shown great promise for various cancer treatment applications, they may be incompetent for deep-seated tumor diagnosis due to the limited penetration depth. Herein, we designed and prepared a radiolabeled AIEgen-based organic photothermal agent for bimodal PET/fluorescence imaging-guided breast tumor photothermal therapy. The prepared multifunctional nanoparticles (68 Ga-TPA-TTINC NPs) with NIR-II fluorescence, gamma irradiation and photothermal conversion property could be efficiently taken up by tumor cells and induce reactive oxygen species burst in vitro, further boosting the photothermal treatment of tumor in vivo. More importantly, the nanoprobe could target and clearly visualize 4T1 tumor xenografts through PET and NIR-II fluorescence imaging with high tumor/muscle ratio up to 4.8, which provides a promising tool and solution for breast tumor theranostics.

Applications of Polyacetylene Derivatives in Gas and Liquid Separation.

As a low energy consumption, simple operation and environmentally friendly separation method, membrane separation has attracted extensive attention. Therefore, researchers have designed and synthesized various types of separation membrane, such as metal organic framework (MOF), covalent organic framework (COF), polymer of intrinsic micro-porosity (PIM) and mixed matrix membranes. Some substituted polyacetylenes have distorted structures and formed micropores due to the existence of rigid main chains and substituted side groups, which can be applied to the field of membrane separation. This article mainly introduces the development and application of substituted polyacetylenes in gas separation and liquid separation based on membrane technology.

Polymerization-Induced Crystallization of Dopant Molecules: An Efficient Strategy for Room-Temperature Phosphorescence of Hydrogels.

Conventional hydrogels such as polyacrylamide and polyacrylic acid ones seldom exhibit phosphorescences at ambient conditions, which limit their applications as optical materials. We propose and demonstrate here a facile strategy to afford these hydrogels with room-temperature phosphorescence by polymerization-induced crystallization of dopant molecules that results in segregation and confinement of the gel matrix with carbonyl groups and thus clusterization-induced phosphorescence. As a model system, crown ethers (CEs) are dissolved in an aqueous solution of concentrated acrylamide that greatly increases the solubility of CEs. During the polymerization process, CEs crystallize to form large spherulites in the polyacrylamide hydrogel. The crystallization arises from the drastically reduced solubility of CEs after the conversion of monomers to polymers during the gel synthesis. The resultant composite hydrogel with a water content of 67 wt % exhibits extraordinary phosphorescence behavior yet maintains good stretchability and resilience. We found that the partial gel matrix is squeezed and confined by in situ-formed crystals, leading to carbonyl clusters and thus phosphorescence emission. The composite gel shows green phosphorescence with an emission peak at 512 nm and a lifetime of 342 ms. The afterglow emission is detectable by the naked eye for several seconds. This strategy has good universality, as validated in other hydrogels with different polymeric matrices and dopant molecules. The development of hydrogels with good mechanical and phosphorescent properties should merit the design of multifunctional soft machines with applications in biomedical and engineering fields.

Molecular characteristics, oncogenic roles, and relevant immune and pharmacogenomic features of NEK2 in gastric cancer.

Gastric cancer (GC) is the most common form of gastrointestinal cancer, with a high mortality rate and limited treatment options. High levels of NEK2 are associated with malignant progression and a poor prognosis in several tumors; however, the role of NEK2 in GC remains unclear. We aimed to explore the potential role of NEK2 in the oncogenesis of GC and in the shaping of the tumor microenvironment (TME). The expression levels of NEK2 were analyzed using immunohistochemistry and real-time quantitative polymerase chain reaction. We found that NEK2 expression was upregulated in GC and was a predictor of a poor prognosis. Based on Kyoto Encyclopedia of Genes and Genomes pathway enrichment and gene set enrichment analyses, multiple tumor pathways were hyperactivated in patients with high NEK2 mRNA expression. Immunological characteristics indicated that NEK2 upregulation might lead to decreased immune cell infiltration and weakened immune activity in the cancer immunity cycle. Additionally, higher frequencies of amplifications and deletions were observed in the high NEK2 expression subpopulation. Based on the TME classification, patients with high expression of NEK2 were more susceptible to targeted therapy with drugs targeting the cell cycle and DNA replication. Following verification, a NEK2-derived genomic model reliably predicted the patient prognosis; A nomogram (radiation therapy, tumor/node/metastasis staging, and the NEK2-derived risk score) was used to better estimate an individual's survival probability. In summary, our findings indicate that NEK2 plays a vital role in the tumorigenesis of GC.

Intrinsic Anti-Freezing and Unique Phosphorescence of Glassy Hydrogels with Ultrahigh Stiffness and Toughness at Low Temperatures.

Most hydrogels become frozen at subzero temperatures, leading to degraded properties and limited applications. Cryoprotectants are massively employed to improve anti-freezing property of hydrogels; however, there are accompanied disadvantages, such as varied networks, reduced mechanical properties, and the risk of cryoprotectant leakage in aqueous conditions. Reported here is the glassy hydrogel having intrinsic anti-freezing capacity and excellent optical and mechanical properties at ultra-low temperatures. Supramolecular hydrogel of poly(acrylamide-co-methacrylic acid) with moderate water content (≈50 wt.%) and dense hydrogen-bond associations is in a glassy state at room temperature. Since hydrogen bonds become strengthened as the temperature decreases, this gel becomes stronger and stiffer, yet still ductile, with Young's modulus of 900 MPa, tensile strength of 30 MPa, and breaking strain of 35% at -45 °C. This gel retains high transparency even in liquid nitrogen. It also exhibits unique phosphorescence due to presence of carbonyl clusters, which is further enhanced at subzero temperatures. Further investigations elucidate that the intrinsic anti-freezing property is related to a fact that most water molecules are tightly bound and confined in the glassy matrix and become non-freezable. This correlation, as validated in several systems, provides a roadmap to develop intrinsic anti-freezing hydrogels for widespread applications at extreme conditions.

Highly Emissive Organic Cage in Single-Molecule and Aggregate States by Anchoring Multiple Aggregation-Caused Quenching Dyes.

It remains a great challenge to design and synthesize organic luminescent molecules with strong emission in both dilute solution and aggregate state. Herein, an organic cage with dodecadansyl groups (D-RCC1) from an easy sulfonation reaction displays strong emissive behavior in dilute organic solution with a quantum yield of 42%. Moreover, D-RCC1 exhibits an ultrahigh quantum yield of 92% in the solid state, which is more than 3 times that of 27% for the model compound D-DEA. The results of the experiment and theoretical calculation show that the three-dimensional symmetrical skeleton of the organic cage anchored evenly by multiple dye molecules effectively satisfies both high local density and a symmetrical distribution of chromophores, which prevents the interaction of dye molecules and ensures that dye molecules have strong emission in both single-molecule and aggregate states.