ABSTRACT
BACKGROUND: Breast cancer (BC), a common malignant tumor originating from the terminal ductal lobular unit of the breast, poses a substantial health risk to women. Previous studies have associated cytochrome b561 (CYB561) with a poor prognosis in BC; however, its underlying mechanism of this association remains unclear. METHODS: We investigated the expression of CYB561 mRNA in BC using databases such as The Cancer Genome Atlas, Gene Expression Omnibus, Tumor-Normal-Metastatic plot, and Kaplan-Meier plotter databases. The prognostic value of CYB561 protein in BC was assessed in relation to its expression levels in tumor tissue samples from 158 patients with BC. The effect of CYB561 on BC progression was confirmed using in vivo and in vitro experiments. The biological functions and related signaling pathways of CYB561 in BC were explored using gene microarray, Innovative Pathway, Gene Ontology enrichment, and Kyoto Encyclopedia of Genes and Genomes enrichment analyses. The correlation between CYB561 and the BC tumor immune microenvironment was evaluated using the CIBERSORT algorithm and single-cell analysis and further validated through immunohistochemistry of serial sections. RESULTS: Our study demonstrated that upregulation of CYB561 expression predicted poor prognosis in patients with BC and that CYB561 knockdown inhibited the proliferation, migration, and invasive ability of BC cells in vitro. CYB561 knockdown inhibited BC tumor formation in vivo.CYB561 was observed to modulate downstream tropomyosin 1 expression. Furthermore, CYB561 expression was associated with macrophage M2 polarization in the BC immune microenvironment. CONCLUSIONS: Elevated CYB561 expression suggests a poor prognosis for patients with BC and is associated with macrophage M2 polarization in the BC microenvironment. Therefore, CYB561 could potentially serve as a therapeutic target for BC treatment.
Subject(s)
Breast Neoplasms , Tumor Microenvironment , Humans , Female , Breast Neoplasms/genetics , Breast Neoplasms/pathology , Breast Neoplasms/metabolism , Breast Neoplasms/immunology , Tumor Microenvironment/immunology , Prognosis , Animals , Mice , Gene Expression Regulation, Neoplastic , Cell Proliferation , Cell Line, Tumor , Biomarkers, Tumor/genetics , Biomarkers, Tumor/metabolism , Cell MovementABSTRACT
The surface quality of milled blade-root grooves in industrial turbine blades significantly influences their mechanical properties. The surface texture reveals the interaction between the tool and the workpiece during the machining process, which plays a key role in determining the surface quality. In addition, there is a significant correlation between acoustic vibration signals and surface texture features. However, current research on surface quality is still relatively limited, and most considers only a single signal. In this paper, 160 sets of industrial field data were collected by multiple sensors to study the surface quality of a blade-root groove. A surface texture feature prediction method based on acoustic vibration signal fusion is proposed to evaluate the surface quality. Fast Fourier transform (FFT) is used to process the signal, and the clean and smooth features are extracted by combining wavelet denoising and multivariate smoothing denoising. At the same time, based on the gray-level co-occurrence matrix, the surface texture image features of different angles of the blade-root groove are extracted to describe the texture features. The fused acoustic vibration signal features are input, and the texture features are output to establish a texture feature prediction model. After predicting the texture features, the surface quality is evaluated by setting a threshold value. The threshold is selected based on all sample data, and the final judgment accuracy is 90%.
ABSTRACT
Breast cancer represents the predominant malignant neoplasm in women, posing significant threats to both life and health. N6-methyladenosine (m6A) methylation, the most prevalent RNA modification, plays a crucial role in cancer development. This study aims to delineate the prognostic implications of m6A-associated long non-coding RNAs (m6AlncRNAs) and identify potential m6AlncRNA candidates as novel therapeutic targets for breast cancer. Through univariate Cox, Least Absolute Shrinkage and Selection Operator and multiple Cox regression analysis, m6AlncRNA was analyzed and a risk-prognosis model was constructed. Kaplan-Meier analysis, principal component analysis and nomogram were used to evaluate the risk model. Finally, we screened candidate lncRNAs and validated them in breast cancer cell lines. m6AlncRNAs were stratified into three subtypes, and their associations with survival outcomes and immune infiltrating capacities were systematically analyzed. Subsequently, breast cancer patients were stratified into high and low-risk groups based on median risk scores, revealing distinct clinical characteristics, tumor immunoinvasive profiles, tumor mutation burden, and survival probabilities. Additionally, a prognostic model was established, highlighting three promising candidate lncRNAs: ECE1-AS1, NDUFA6-DT, and COL4A2-AS1. This study investigated the prognostic implications of m6A-associated long non-coding RNAs (m6AlncRNAs) and developed a prognostic risk model to identify three potential m6AlncRNA candidates. These findings provide valuable insights into the potential application of these m6AlncRNAs in guiding immunotherapeutic strategies for breast cancer.
ABSTRACT
Chiral metasurfaces are capable of generating a huge superchiral field, which has great potential in optoelectronics and biosensing. However, the conventional fabrication process suffers greatly from time consumption, high cost, and difficult multilayer alignment, which hinder its commercial application. Herein, we propose a twisted stacking carbon-based terahertz (THz) chiral metasurface (TCM) based on laser-induced graphene (LIG) technology. By repeating a two-step process of sticking a polyimide film, followed by laser direct writing, the two layers of the TCM are aligned automatically in the fabrication. Laser manufacturing also brings such high processing speed that a TCM with a size of 15 × 15 mm can be prepared in 60 s. In addition, due to the greater dissipation of LIG than that of metals in the THz band, a giant circular dichroism (CD) of +99.5 to -99.6% is experimentally realized. The THz biosensing of bovine serum albumin enhanced by the proposed TCMs is then demonstrated. A wide sensing range (0.5-50 mg mL-1) and a good sensitivity [ΔCD: 2.09% (mg mL-1)-1, Δf: 0.0034 THz (mg mL-1)-1] are proved. This LIG-based TCM provides an environment-friendly platform for chiral research and has great application potential in rapid and low-cost commercial biosensing.
Subject(s)
Carbon , Graphite , Circular Dichroism , Serum Albumin, Bovine , WritingABSTRACT
SMARCA4 encodes one of two mutually exclusive ATPase subunits in the BRG/BRM associated factor (BAF) complex that is recruited by transcription factors (TFs) to drive chromatin accessibility and transcriptional activation. SMARCA4 is among the most recurrently mutated genes in human cancer, including â¼30% of germinal center (GC)-derived Burkitt lymphomas. In mice, GC-specific Smarca4 haploinsufficiency cooperated with MYC over-expression to drive lymphomagenesis. Furthermore, monoallelic Smarca4 deletion drove GC hyperplasia with centroblast polarization via significantly increased rates of centrocyte recycling to the dark zone. Mechanistically, Smarca4 loss reduced the activity of TFs that are activated in centrocytes to drive GC-exit, including SPI1 (PU.1), IRF family, and NF-κB. Loss of activity for these factors phenocopied aberrant BCL6 activity within murine centrocytes and human Burkitt lymphoma cells. SMARCA4 therefore facilitates chromatin accessibility for TFs that shape centrocyte trajectories, and loss of fine-control of these programs biases toward centroblast cell-fate, GC hyperplasia and lymphoma.
Subject(s)
Haploinsufficiency , Lymphoma, B-Cell , Animals , Humans , Mice , Chromatin , DNA Helicases/genetics , Hyperplasia , Lymphoma, B-Cell/genetics , Nuclear Proteins/genetics , Transcription Factors/geneticsABSTRACT
The development of flexible sensors based on laser-induced graphene (LIG) has recently attracted much attention. It was commonly generated by laser-ablating commercial polyimide (PI). However, the weak mechanical extensibility of PI limits the development and diversified applications of LIG-based sensors. In this work, we adopted medical polyurethane (PU) tapes to peel off the LIG generated on PI and developed flexible and wearable sensors based on the proposed LIG/PU composite structure. Compared with other methods for LIG transfer, PU tape has many advantages, including a simplified process and being less time-consuming. We characterized the LIG samples generated under different laser powers and analyzed the property differences introduced by the transfer operation. We then studied the impact of fabrication mode on the strain sensitivity of the LIG/PU and optimized the design of a LIG/PU-based strain sensor, which possessed a gauge factor (GF) of up to 263.6 in the strain range of 75-90%. In addition, we designed a capacitive pressure sensor for tactile sensing, which is composed of two LIG/PU composite structures and a PI space layer. These LIG flexible devices can be used for human motion monitoring and tactile perception in sports events. This work provides a simple, fast, and low-cost way for the preparation of multifunctional sensor systems with good performance, which has a broad application prospect in human motion monitoring.
ABSTRACT
RAB10, a member of the small GTPase family, has complex biological functions, but its role in breast cancer (BC) remains unclear. The aim of this study was to investigate the relationship between RAB10's role in BC, its biological functions, and BC prognosis. An online database was used to analyze the correlation between differential expression of RAB10 in BC and prognosis. The results of immunohistochemical assays in clinical cohorts were combined with the database analysis. The chi-square test and COX regression were employed to analyze the correlation between RAB10 and pathological features of BC. MTT, Transwell, and wound healing assays were conducted to detect BC cell proliferation, invasion, and metastatic ability. Bioinformatics techniques were employed to explore the correlation between RAB10 and BC tumor immune cell infiltration, and to speculate the biological function of RAB10 in BC and related signaling pathways. Our findings suggest that RAB10 expression is elevated in BC and is associated with HER2 status, indicating a poor prognosis for BC patients. RAB10 can promote the proliferation, migration, and invasion ability of BC cells in vitro. RAB10 is also associated with BC immune cell infiltration and interacts with multiple signaling pathways. RAB10 is a potential biomarker or molecular target for BC.
Subject(s)
Breast Neoplasms , Female , Humans , Biological Assay , Breast Neoplasms/genetics , Cell Proliferation , Computational Biology , Neoplastic ProcessesABSTRACT
In this work, we present a network-based technique for chest X-ray image classification to help the diagnosis and prognosis of patients with COVID-19. From visual inspection, we perceive that healthy and COVID-19 chest radiographic images present different levels of geometric complexity. Therefore, we apply fractal dimension and quadtree as feature extractors to characterize such differences. Moreover, real-world datasets often present complex patterns, which are hardly handled by only the physical features of the data (such as similarity, distance, or distribution). This issue is addressed by complex networks, which are suitable tools for characterizing data patterns and capturing spatial, topological, and functional relationships in data. Specifically, we propose a new approach combining complexity measures and complex networks to provide a modified high-level classification technique to be applied to COVID-19 chest radiographic image classification. The computational results on the Kaggle COVID-19 Radiography Database show that the proposed method can obtain high classification accuracy on X-ray images, being competitive with state-of-the-art classification techniques. Lastly, a set of network measures is evaluated according to their potential in distinguishing the network classes, which resulted in the choice of communicability measure. We expect that the present work will make significant contributions to machine learning at the semantic level and to combat COVID-19.
Subject(s)
COVID-19 Testing , COVID-19 , Humans , Databases, Factual , Fractals , Health StatusABSTRACT
Lack of MHC-II is emerging as a causal factor in cancer immune evasion, and the development of small-molecule MHC-II inducers is an unmet clinical need. Here, we identified three MHC-II inducers, including pristane and its two superior derivatives, that potently induce MHC-II expression in breast cancer cells and effectively inhibit the development of breast cancer. Our data suggest that MHC-II is central in promoting the immune detection of cancer to increase the tumor infiltration of T cells and enhance anti-cancer immunity. By discovering the malonyl/acetyltransferase (MAT) domain in fatty acid synthase (FASN) as the direct binding target of MHC-II inducers, we demonstrate that evasion of immune detection and cancer metabolic reprogramming are directly linked by fatty acid-mediated MHC-II silencing. Collectively, we identified three MHC-II inducers and illustrated that lack of MHC-II caused by hyper-activated fatty acid synthesis to limit immune detection is a potentially widespread mechanism underlying the development of cancer.
Subject(s)
Breast Neoplasms , Histocompatibility Antigens Class II , Humans , Female , Histocompatibility Antigens Class II/metabolism , T-Lymphocytes , Fatty AcidsABSTRACT
Oral squamous cell carcinoma (OSCC) in the context of oral submucous fibrosis (OSF) has a high incidence owing to undefined pathogenesis. Identifying key genes and exploring the underlying molecular mechanisms involved in the conversion of OSF into OSCC are in urgent need. Differentially expressed genes (DEGs) between OSCC and OSF were dug from GEO databases and a total of 170 DEGs were acquired. Functional association of DEGs were analyzed by GO and KEGG. Protein-protein interactions (PPIs) analysis was carried out and candidate biomarkers were identified by Gene co-expression analysis and Cox analyses. Hub genes were confirmed by qRT-PCR in tissues and cell lines, of which we found that IRF4 mRNA was successively up-regulated from Normal to OSF and then to OSCC and associated with immune infiltrating levels. In addition, Immunohistochemical (IHC) and Immunofluorescence (IF) assays were conducted to validate the consistent upregulation of IRF4 and the oncogene role of IRF4 in OSF and OSCC at translation level. IRF4 may be indicative biomarker in transformation of OSF into OSCC. High IRF4 expression contribute to increased immune infiltration of OSCC and may provide a novel diagnostic marker for OSCC patients translated from OSF.
Subject(s)
Carcinoma, Squamous Cell , Interferon Regulatory Factors , Mouth Neoplasms , Oral Submucous Fibrosis , Squamous Cell Carcinoma of Head and Neck , Humans , Carcinoma, Squamous Cell/genetics , Carcinoma, Squamous Cell/pathology , Mouth Neoplasms/genetics , Mouth Neoplasms/pathology , Oral Submucous Fibrosis/genetics , Oral Submucous Fibrosis/pathology , Squamous Cell Carcinoma of Head and Neck/genetics , Squamous Cell Carcinoma of Head and Neck/pathologyABSTRACT
The function of the cancer-associated lncRNA Malat1 during aging is as-of-yet uncharacterized. Here, we show that Malat1 interacts with Nucleophosmin (NPM) in young mouse brain, and with Lamin A/C, hnRNP C, and KAP1 with age. RNA-seq and RT-qPCR reveal a persistent expression of Malat1_2 (the 3'isoform of Malat1) in Malat1Δ1 (5'-1.5 kb deletion) mouse retinas and brains at 1/4th level of the full-length Malat1, while Malat1_1 (the 5'isoform) in Malat1Δ2 (deletion of 3'-conserved 5.7 kb) at a much lower level, suggesting an internal promoter driving the 3' isoform. The 1774 and 496 differentially expressed genes in Malat1Δ2 and Malat1Δ1 brains, respectively, suggest the 3' isoform regulates gene expression in trans and the 5' isoform in cis. Consistently, Malat1Δ2 mice show increased age-dependent retinal oxidative stress and corneal opacity, while Malat1Δ1 mice show no obvious phenotype. Collectively, this study reveals a physiological function of the lncRNA Malat1 3'-isoform during the aging process.
ABSTRACT
Macroscopic electric motors continue to have a large impact on almost every aspect of modern society. Consequently, the effort towards developing molecular motors1-3 that can be driven by electricity could not be more timely. Here we describe an electric molecular motor based on a [3]catenane4,5, in which two cyclobis(paraquat-p-phenylene)6 (CBPQT4+) rings are powered by electricity in solution to circumrotate unidirectionally around a 50-membered loop. The constitution of the loop ensures that both rings undergo highly (85%) unidirectional movement under the guidance of a flashing energy ratchet7,8, whereas the interactions between the two rings give rise to a two-dimensional potential energy surface (PES) similar to that shown by FOF1 ATP synthase9. The unidirectionality is powered by an oscillating10 voltage11,12 or external modulation of the redox potential13. Initially, we focused our attention on the homologous [2]catenane, only to find that the kinetic asymmetry was insufficient to support unidirectional movement of the sole ring. Accordingly, we incorporated a second CBPQT4+ ring to provide further symmetry breaking by interactions between the two mobile rings. This demonstration of electrically driven continual circumrotatory motion of two rings around a loop in a [3]catenane is free from the production of waste products and represents an important step towards surface-bound14 electric molecular motors.
ABSTRACT
Brain metastases, including prevalent breast-to-brain metastasis (B2BM), represent an urgent unmet medical need in the care of cancer due to a lack of effective therapies. Immune evasion is essential for cancer cells to metastasize to the brain tissue for brain metastasis. However, the intrinsic genetic circuits that enable cancer cells to avoid immune-mediated killing in the brain microenvironment remain poorly understood. Here, we report that a brain-enriched long noncoding RNA (BMOR) expressed in B2BM cells is required for brain metastasis development and is both necessary and sufficient to drive cancer cells to colonize the brain tissue. Mechanistically, BMOR enables cancer cells to evade immune-mediated killing in the brain microenvironment for the development of brain metastasis by binding and inactivating IRF3. In preclinical brain metastasis murine models, locked nucleic acid-BMOR, a designed silencer targeting BMOR, is effective in suppressing the metastatic colonization of cancer cells in the brain for brain metastasis. Taken together, our study reveals a mechanism underlying B2BM immune evasion during cancer cell metastatic colonization of brain tissue for brain metastasis, where B2BM cells evade immune-mediated killing in the brain microenvironment by acquiring a brain-enriched long noncoding RNA genetic feature.
Subject(s)
Brain Neoplasms , Brain , Breast Neoplasms , Immune Evasion , RNA, Long Noncoding , Animals , Brain/immunology , Brain/metabolism , Brain Neoplasms/genetics , Brain Neoplasms/immunology , Brain Neoplasms/secondary , Breast/pathology , Breast Neoplasms/pathology , Cell Line, Tumor , Female , Humans , Immune Evasion/genetics , Mice , RNA, Long Noncoding/genetics , RNA, Long Noncoding/metabolism , Tumor MicroenvironmentABSTRACT
Molecular recognition1-4 and supramolecular assembly5-8 cover a broad spectrum9-11 of non-covalently orchestrated phenomena between molecules. Catalysis12 of such processes, however, unlike that for the formation of covalent bonds, is limited to approaches13-16 that rely on sophisticated catalyst design. Here we establish a simple and versatile strategy to facilitate molecular recognition by extending electron catalysis17, which is widely applied18-21 in synthetic covalent chemistry, into the realm of supramolecular non-covalent chemistry. As a proof of principle, we show that the formation of a trisradical complex22 between a macrocyclic host and a dumbbell-shaped guest-a molecular recognition process that is kinetically forbidden under ambient conditions-can be accelerated substantially on the addition of catalytic amounts of a chemical electron source. It is, therefore, electrochemically possible to control23 the molecular recognition temporally and produce a nearly arbitrary molar ratio between the substrates and complexes ranging between zero and the equilibrium value. Such kinetically stable supramolecular systems24 are difficult to obtain precisely by other means. The use of the electron as a catalyst in molecular recognition will inspire chemists and biologists to explore strategies that can be used to fine-tune non-covalent events, control assembly at different length scales25-27 and ultimately create new forms of complex matter28-30.
ABSTRACT
BACKGROUND: Breast cancer (BC) is one of the most common cancers and the leading cause of death in women. Previous studies have demonstrated that FAM49B is implicated in several tumor progression, however, the role and mechanism of FAM49B in BC remain to be explored. Therefore, in this study, we aimed to systematically study the role of FAM49B in the proliferation, metastasis, apoptosis, and chemoresistance of BC, as well as the corresponding molecular mechanisms and downstream target. METHODS: The ONCOMINE databases and Kaplan-Meier plotter databases were analyzed to find FAM49B and its prognostic values in BC. FAM49B expression in BC and adjacent non-tumor tissues was detected by western blot and IHC. Kaplan-Meier analysis was used to identify the prognosis of BC patients. After FAM49B knockdown in MCF-7 and MDA-MB-231 cells, a combination of co-immunoprecipitation, MTT, migration, and apoptosis assays, nude mouse xenograft tumor model, in addition to microarray detection and data analysis was used for further mechanistic studies. RESULTS: In BC, the results showed that the expression level of FAM49B was significantly higher than that in normal breast tissue, and highly expression of FAM49B was significantly positively correlated with tumor volume, histological grade, lymph node metastasis rate, and poor prognosis. Knockdown of FAM49B inhibited the proliferation and migration of BC cells in vitro and in vivo. Microarray analysis revealed that the Toll-like receptor signaling pathway was inhibited upon FAM49B knockdown. In addition, the gene interaction network and downstream protein validation of FAM49B revealed that FAM49B positively regulates BC cell proliferation and migration by promoting the Rab10/TLR4 pathway. Furthermore, endogenous FAM49B interacted with ELAVL1 and positively regulated Rab10 and TLR4 expression by stabilizing ELAVL1. Moreover, mechanistic studies indicated that the lack of FAM49B expression in BC cells conferred more sensitivity to anthracycline and increased cell apoptosis by downregulating the ELAVL1/Rab10/TLR4/NF-κB signaling pathway. CONCLUSION: These results demonstrate that FAM49B functions as an oncogene in BC progression, and may provide a promising target for clinical diagnosis and therapy of BC.
ABSTRACT
Breast cancer is the most common cancer, with the highest mortality rate and the most diagnosed cancer type in women worldwide. To identify the effect innate immune checkpoint for breast cancer immunotherapy, the innate immune prognostic biomarkers were selected through the ICI score model and the risk model in breast cancer patients. Moreover, the reliability and accuracy of the ICI score model and the risk model were further examined through the analysis of breast cancer prognosis and immune cell infiltration. The pan cancer analysis further confirmed and selected CXCL9 as the key innate immune checkpoint for breast cancer immunotherapy and identified three small molecular drugs for target CXCL9 through molecular docking analysis. In summary, CXCL9 significantly correlated with the prognostic of breast cancer and immune cell infiltration and could be innate immune checkpoint for breast cancer immunotherapy.
Subject(s)
Biomarkers, Tumor/genetics , Breast Neoplasms/immunology , Gene Expression Profiling , Gene Expression Regulation, Neoplastic , Lymphocytes, Tumor-Infiltrating/immunology , Mutation , Tumor Microenvironment , Breast Neoplasms/genetics , Breast Neoplasms/pathology , Female , Humans , ImmunophenotypingABSTRACT
Graphene-based terahertz (THz) metasurfaces have the advantages of ultra-small thickness, electrical tunability, and fast tuning speed. However, many such structures suffer low efficiency, especially for transmissive devices. Here we propose a hybrid structure for focusing THz waves with tunability and enhanced focusing efficiency, which is composed of a graphene-loaded metallic metasurface sandwiched by two mutually orthogonal gratings. Experimental results show that due to the multi-reflection between the metasurface layer and the grating layer, the focusing efficiency is enhanced by 1.8 times, and the focal length of the metalens is increased by 0.61â mm when the applied gate voltage on the graphene is increased from 0â V to 1.4â V. We hope the proposed structure may open a new avenue for reconfigurable THz metasurfaces with high efficiencies.
ABSTRACT
PURPOSE: Testicular torsion (TT) is a serious surgical emergency. Prompt diagnosis and treatment of TT are essential to improve the incidence of salvaged testes. The aim of this study was to evaluate the historical features, physical examination findings, laboratory tests, and ultrasound examinations in children with TT, as well as to identify the predictors of testicular salvage in children. MATERIALS AND METHODS: We retrospectively reviewed the records of 136 males who presented with TT to our institution. Clinical findings, physical examinations, laboratory data, color Doppler ultrasound findings, operating results, and the results of follow-up were collected and analyzed. Patients with neonatal torsion, negative scrotal exploration, or testicular appendix torsion were excluded. A multivariable logistic regression model was used to identify predictors of testicular salvage. Receiver operator characteristics analyses were performed to determine the probability of a non-salvageable torsed testis based on time and degree of twisting. RESULTS: A total of 136 children with TT were identified. Patients were aged from 1 to 16 years, with a mean age of 9.7 years (median, 12; range, 1-16 years). The peak incidences of TT were found between ages of 12 and 14 years. Acute TT is significantly more common in the winter. Testicular salvage occurred in 49 (36%) cases. Of the 49 cases of testicular salvage, 5 patients developed subsequent testicular atrophy. Cutoff values of 13.5 h and 530 degrees of torsion would provide sensitivities of 96 and 61%, with specificity of 80 and 70%, respectively. Multivariate analysis showed that time to surgery and degree of testicular twist were correlated with the risk of a non-salvageable testis. CONCLUSIONS: Testicular salvage can be predicted by the duration of symptoms along with degree of twisting. Early scrotal exploration based on careful physical examination decreases the risk of misdiagnosis of spermatic cord torsion. A certain percentage of children with TT presenting with lower abdominal pain should have their testicles checked to make sure that they do not have torsion, especially those visitors in cold season.
Subject(s)
Spermatic Cord Torsion/diagnosis , Spermatic Cord Torsion/surgery , Adolescent , Child , Child, Preschool , Humans , Infant , Male , Prognosis , Retrospective StudiesABSTRACT
We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely, an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state coconformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT4+) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF2+ dication, the CBPQT4+ ring is forced toward the molecular rotor, leading to an increased energy barrier for the excited state to rotate the rotor into the state with a high nonradiative rate constant, resulting in an overall 3.4-fold fluorescence enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge-transfer state between the BODIPY rotor and the CBPQT4+ ring, movement of the ring toward the BODIPY rotor produces an unexpectedly strong fluorescence signal decrease as the result of photoinduced electron transfer from the BODIPY rotor to the CBPQT4+ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories, and molecular logic gates.
Subject(s)
Boron Compounds/chemistry , Electrochemical Techniques , Fluorescent Dyes/chemistry , Rotaxanes/chemistry , Molecular Structure , Oxidation-ReductionABSTRACT
Two new highly charged [2]catenanes-namely, mHe[2]C·6PF6 and mHo[2]C·6PF6-were synthesized by exploiting radical host-guest templation between derivatives containing BIPYâ¢+ radical cations and the meta analogue of cyclobis(paraquat-p-phenylene). In contrast to related [2]catenanes that have been isolated as air-stable monoradicals, both mHe[2]C·6PF6 and mHo[2]C·6PF6 exist as air-stable singlet bisradicals, as evidenced by both X-ray crystallography in the solid state and EPR spectroscopy in solution. Electrochemical studies indicate that the first two reduction peaks of these two [2]catenanes are shifted significantly to more positive potentials, a feature which is responsible for their extraordinary stability in air. The mixed-valence nature of the mono- and bisradical states endows them with unique NIR absorption properties, e.g., NIR absorption bands for the mono- and bisradical states observed at â¼1800 and â¼1450 nm, respectively. These [2]catenanes are potentially useful in applications that include NIR photothermal conversion, UV-vis-NIR multiple-state electrochromic materials, and multiple-state memory devices. Our findings highlight the principle of "mechanical-bond-induced stabilization" as an efficient strategy for designing persistent organic radicals.