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Metabolic programs contribute to hematopoietic stem and progenitor cell (HSPC) fate, but it is not known whether the metabolic regulation of protein synthesis controls HSPC differentiation. Here, we show that SLC7A1/cationic amino acid transporter 1-dependent arginine uptake and its catabolism to the polyamine spermidine control human erythroid specification of HSPCs via the activation of the eukaryotic translation initiation factor 5A (eIF5A). eIF5A activity is dependent on its hypusination, a posttranslational modification resulting from the conjugation of the aminobutyl moiety of spermidine to lysine. Notably, attenuation of hypusine synthesis in erythroid progenitors, by the inhibition of deoxyhypusine synthase, abrogates erythropoiesis but not myeloid cell differentiation. Proteomic profiling reveals mitochondrial translation to be a critical target of hypusinated eIF5A, and accordingly, progenitors with decreased hypusine activity exhibit diminished oxidative phosphorylation. This affected pathway is critical for eIF5A-regulated erythropoiesis, as interventions augmenting mitochondrial function partially rescue human erythropoiesis under conditions of attenuated hypusination. Levels of mitochondrial ribosomal proteins (RPs) were especially sensitive to the loss of hypusine, and we find that the ineffective erythropoiesis linked to haploinsufficiency of RPS14 in chromosome 5q deletions in myelodysplastic syndrome is associated with a diminished pool of hypusinated eIF5A. Moreover, patients with RPL11-haploinsufficient Diamond-Blackfan anemia as well as CD34+ progenitors with downregulated RPL11 exhibit a markedly decreased hypusination in erythroid progenitors, concomitant with a loss of mitochondrial metabolism. Thus, eIF5A-dependent protein synthesis regulates human erythropoiesis, and our data reveal a novel role for RPs in controlling eIF5A hypusination in HSPCs, synchronizing mitochondrial metabolism with erythroid differentiation.
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Proteômica , Espermidina , Humanos , Espermidina/metabolismo , Fatores de Iniciação de Peptídeos/genética , Diferenciação Celular , Fator de Iniciação de Tradução Eucariótico 5ARESUMO
Organic cocrystals obtained from multicomponent self-assembly have garnered considerable attention due to their distinct phosphorescence properties and broad applications. Yet, there have been limited reports on cocrystal systems that showcase efficient deep-red to near-infrared (NIR) charge-transfer (CT) phosphorescence. Furthermore, effective strategies to modulate the emission pathways of both fluorescence and phosphorescence remain underexplored. In this work, we dedicated our work to four distinct self-assembled cocrystals called "pyrene box" cages using 1,3,6,8-pyrenetetrasulfonate anions (PTS4-), 4-iodoaniline (1), guanidinium (G+), diaminoguanidinium (A2G+), and hydrated K+ countercations. The binding of such cations to PTS4- platforms adaptively modulates their supramolecular stacking self-assembly with guest molecules 1, allowing to steer the fluorescence and phosphorescence pathways. Notably, the confinement of guest molecule 1 within "pyrene box" PTSK{1} and PTSG{1} cages leads to an efficient deep-red to NIR CT phosphorescence emission. The addition of fuming gases like triethylamine and HCl allows reversible pH modulations of guest binding, which in turn induce a reversible transition of the "pyrene box" cage between fluorescence and phosphorescence states. This capability was further illustrated through a proof-of-concept demonstration in shrimp freshness detection. Our findings not only lay a foundation for future supramolecular designs leveraging weak intermolecular host-guest interactions to engineer excited states in interacting chromophores but also broaden the prospective applications of room-temperature phosphorescence materials in food safety detection.
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Developing nonconjugated materials with large Stokes shifts is highly desired. In this work, three kinds of hyperbranched aggregation-induced emission (AIE) polymers with tunable n/π electronic effects were synthesized. HBPSi-CBD contains alkenyl groups in the backbone and possesses a promoted n-π* transition and red-shifted emission wavelength with a large Stokes shift of 186 nm. Experiments and theoretical simulations confirmed that the planar π electrons in the backbone are responsible for the red-shifted emission due to the strong through-space n···π interactions and restricted backbone motions. Additionally, the designed HBPSi-CBD could be utilized as an ROS scavenger after coupling with l-methionine. The HBPSi-Met exhibits remarkable ROS scavenging properties with a scavenging capacity of 77%. This work not only gains further insight into the structure-property relationship of nonconjugated hyperbranched AIE polymers but also provides a promising ROS-scavenging biomaterial for the treatment of ROS-related diseases.
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Elétrons , Polímeros , Espécies Reativas de Oxigênio , Materiais BiocompatíveisRESUMO
Human erythropoiesis is a complex process leading to the production of 2.5 million red blood cells per second. Following commitment of hematopoietic stem cells to the erythroid lineage, this process can be divided into three distinct stages: erythroid progenitor differentiation, terminal erythropoiesis, and reticulocyte maturation. We recently resolved the heterogeneity of erythroid progenitors into four different subpopulations termed EP1-EP4. Here, we characterized the growth factor(s) responsiveness of these four progenitor populations in terms of proliferation and differentiation. Using mass spectrometry-based proteomics on sorted erythroid progenitors, we quantified the absolute expression of ~5500 proteins from EP1 to EP4. Further functional analyses highlighted dynamic changes in cell cycle in these populations with an acceleration of the cell cycle during erythroid progenitor differentiation. The finding that E2F4 expression was increased from EP1 to EP4 is consistent with the noted changes in cell cycle. Finally, our proteomic data suggest that the protein machinery necessary for both oxidative phosphorylation and glycolysis is present in these progenitor cells. Together, our data provide comprehensive insights into growth factor-dependence of erythroid progenitor proliferation and the proteome of four distinct populations of human erythroid progenitors which will be a useful framework for the study of erythroid disorders.
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Células-Tronco Hematopoéticas , Proteômica , Humanos , Diferenciação Celular , Ciclo Celular , Eritropoese , Redes e Vias Metabólicas , Peptídeos e Proteínas de Sinalização Intercelular/metabolismo , Células Precursoras EritroidesRESUMO
AIM AND OBJECTIVES: The purpose of this study was to describe the number, type and trajectory of symptom clusters during the perioperative period in patients with gastric cancer at four different time points. The study also aimed to identify the changes and consistency of these symptom clusters over time. DESIGN: This was a longitudinal study. METHODS: This study was conducted in a tertiary cancer hospital with 205 patients with gastric cancer. The M.D. Anderson Symptom Inventory Gastrointestinal Cancer Module was used to assess the incidence and severity of symptom clusters. Exploratory factor analysis was used to extract symptom clusters. RESULTS: The study identified four symptom clusters in patients with gastric cancer during the perioperative period: gastrointestinal symptom cluster, physical symptom cluster, psychological symptom cluster, and sleep disturbance symptom cluster. These clusters were observed across two to four time points. CONCLUSION: The findings of this study provide scientific evidence for medical staff and researchers to better understand the symptoms of patients with gastrointestinal cancer during the perioperative period. These findings can help develop individualized interventions for managing symptoms. RELEVANCE TO CLINICAL PRACTICE: Gastric cancer patients suffered from various symptom clusters, which lasted from one day before surgery to one month after surgery. They should be given careful consideration by clinical staff.
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Período Perioperatório , Neoplasias Gástricas , Humanos , Neoplasias Gástricas/cirurgia , Estudos Longitudinais , Masculino , Feminino , Pessoa de Meia-Idade , Idoso , Transtornos do Sono-Vigília/etiologia , Transtornos do Sono-Vigília/epidemiologia , Adulto , Análise Fatorial , Índice de Gravidade de Doença , Idoso de 80 Anos ou maisRESUMO
Objective: Symptom Management Theory has been extensively used in guiding clinical practice to reduce patients' symptom burden, improve their outcomes and quality of life. However, concerning various participants, settings and methods, the effectiveness of practice and research based on the theory was inconsistent, which hindered the further implementation of this theory in clinical practice. Thus, this study aims to systematically evaluate the effectiveness of the Symptom Management Theory in guiding clinical practice. Methods: Systematic review. An online search of Chinese and English databases, including SinoMed, CNKI, WanFang Library, VIP database, MEDLINE, PubMed, Embase, Web of Science database, and Cochrane Library up to December 2023. This systematic review was conducted in accordance with the Joanna Briggs Institute critical appraisal checklist for randomized controlled trials and controlled clinical trials. The literature appraisal and extraction were independently conducted by two researchers. The third person was consulted if there was any disagreement between the two researchers. Results: A total of 20 articles (15 randomized controlled trials and five controlled clinical trials) were finally included. The overall quality of the articles was high. Additionally, the results showed that symptom management measurements based on the Symptom Management Theory could reduce the severity of patient's symptoms, alleviate their distress, relieve patients' anxiety and depression and improve their quality of sleep and quality of life. Conclusion: The Symptom Management Theory positively influenced clinical symptom management. It could provide theory-based symptom management methods in clinical practice to reduce patients' severity and burden of symptoms, level of anxiety, depression and distress. More high-quality original research should be conducted to further explore the theory's influence in guiding clinical practice in the future.
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BACKGROUND: Low-dose ionizing radiation-induced protection and damage are of great significance among radiation workers. We aimed to study the role of glutathione S-transferase Pi (GSTP1) in low-dose ionizing radiation damage and clarify the impact of ionizing radiation on the biological activities of cells. RESULTS: In this study, we collected peripheral blood samples from healthy adults and workers engaged in radiation and radiotherapy and detected the expression of GSTP1 by qPCR. We utilized γ-rays emitted from uranium tailings as a radiation source, with a dose rate of 14 µGy/h. GM12878 cells subjected to this radiation for 7, 14, 21, and 28 days received total doses of 2.4, 4.7, 7.1, and 9.4â¯mGy, respectively. Subsequent analyses, including flow cytometry, MTS, and other assays, were performed to assess the ionizing radiation's effects on cellular biological functions. In peripheral blood samples collected from healthy adults and radiologic technologist working in a hospital, we observed a decreased expression of GSTP1 mRNA in radiation personnel compared to the healthy controls. In cultured GM12878 cells exposed to low-dose ionizing radiation from uranium tailings, we noted significant changes in cell morphology, suppression of proliferation, delay in cell cycle progression, and increased apoptosis. These effects were partially reversed by overexpression of GSTP1. Moreover, low-dose ionizing radiation increased GSTP1 gene methylation and downregulated GSTP1 expression. Furthermore, low-dose ionizing radiation affected the expression of GSTP1-related signaling molecules. CONCLUSIONS: This study shows that low-dose ionizing radiation damages GM12878 cells and affects their proliferation, cell cycle progression, and apoptosis. In addition, GSTP1 plays a modulating role under low-dose ionizing radiation damage conditions. Low-dose ionizing radiation affects the expression of Nrf2, JNK, and other signaling molecules through GSTP1.
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Glutationa S-Transferase pi , Urânio , Adulto , Humanos , Glutationa S-Transferase pi/genética , Radiação Ionizante , Raios gama/efeitos adversos , ApoptoseRESUMO
Tuning the full-color emission of polymers holds significant promise. However, preparing unconventional luminescence polymers with color-tunability in dilute solution and understanding the relationship between non-covalent interactions and luminescent behavior remains a great challenge. We report two emitters (P1 and P2) incorporating tetracoordinate boron. The P1 with non-conjugated D-π-A structure, exhibited red delayed fluorescence at 645 nm with quantum yield of 9.15% in aggregates. Notably, the emission wavelength of P1 can be tuned from 418 to 588 nm at different solvent. Similarly, the emission wavelength of P2 can also be adjusted by manipulating the interactions between the solvent and fluorophore. Experimental characterization and theoretical calculations indicate that the BâN bond and electronic interactions between solvent and fluorophore significantly regulate the equilibrium the electrostatic potential (ESP) and the intramolecular O···O interactions of P1, thereby modulating its emission wavelength. Additionally, these polymers showed excellent potential in fluoride ions detection. This work provides new insights into the complex effects of intermolecular interactions on luminescent properties.
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Nonconventional luminogens with high quantum yield (QY) possess very potential applications in various fields. However, the preparation of such luminogens remains a great challenge. Herein, the first example of piperazine-containing hyperbranched polysiloxane exhibiting blue and green fluorescence is reported under the irradiation of different excitation wavelength and a high QY of 20.9%. The density functional theory (DFT) calculations and experimental results revealed that the through-space conjugation (TSC) within the clusters of N and O atoms is produced via the induction of multiple intermolecular hydrogen bonds and flexible SiO units, which is accountable for the fluorescence. Meanwhile, the introduction of the rigid piperazine units not only rigidifies the conformation, but also enhances the TSC. In addition, the fluorescence of both P1 and P2 shows concentration-, excitation-, and solvent-dependent emission, especially exhibits significant pH-dependent emission and obtains an ultrahigh QY of 82.6% at pH 5. The synthetic luminogens show excellent applications in fluorescence detection for Fe3+ and Co2+ , information encryption, and fluorescent film. This study provides a novel strategy to rationally design high-efficiency nonconventional luminogens.
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The terminal maturation of human erythroblasts requires significant changes in gene expression in the context of dramatic nuclear condensation. Defects in this process are associated with inherited anemias and myelodysplastic syndromes. The progressively dense appearance of the condensing nucleus in maturing erythroblasts led to the assumption that heterochromatin accumulation underlies this process, but despite extensive study, the precise mechanisms underlying this essential biologic process remain elusive. To delineate the epigenetic changes associated with the terminal maturation of human erythroblasts, we performed mass spectrometry of histone posttranslational modifications combined with chromatin immunoprecipitation coupled with high-throughput sequencing, Assay for Transposase Accessible Chromatin, and RNA sequencing. Our studies revealed that the terminal maturation of human erythroblasts is associated with a dramatic decline in histone marks associated with active transcription elongation, without accumulation of heterochromatin. Chromatin structure and gene expression were instead correlated with dynamic changes in occupancy of elongation competent RNA polymerase II, suggesting that terminal erythroid maturation is controlled largely at the level of transcription. We further demonstrate that RNA polymerase II "pausing" is highly correlated with transcriptional repression, with elongation competent RNA polymerase II becoming a scare resource in late-stage erythroblasts, allocated to erythroid-specific genes. Functional studies confirmed an essential role for maturation stage-specific regulation of RNA polymerase II activity during erythroid maturation and demonstrate a critical role for HEXIM1 in the regulation of gene expression and RNA polymerase II activity in maturing erythroblasts. Taken together, our findings reveal important insights into the mechanisms that regulate terminal erythroid maturation and provide a novel paradigm for understanding normal and perturbed erythropoiesis.
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Eritroblastos/metabolismo , Células Eritroides/metabolismo , RNA Polimerase II/metabolismo , Linhagem Celular , Cromatina/genética , Cromatina/metabolismo , Eritroblastos/citologia , Células Eritroides/citologia , Eritropoese , Regulação da Expressão Gênica no Desenvolvimento , Histonas/genética , Histonas/metabolismo , Humanos , RNA Polimerase II/genética , Transcrição GênicaRESUMO
Most organic thermochromic fluorescent materials exhibit thermo-induced hypsochromic emission due to the formation of excimers in ordered molecular solids; however, it is still a challenge to endow them with bathochromic emission despite its significance in making up the field of thermochromism. Here, a thermo-induced bathochromic emission in columnar discotic liquid crystals is reported realized by intramolecular planarization of the mesogenic fluorophores. A three-armed discotic molecule of dialkylamino-tricyanotristyrylbenzene was synthesized, which preferred to twist out of the core plane to accommodate ordered molecular stacking in hexagonal columnar mesophases, giving rise to bright green monomer emission. However, intramolecular planarization of the mesogenic fluorophores occurred in isotropic liquid increasing the conjugation length, and as a result led to thermo-induced bathochromic emission from green to yellow light. This work reports a new concept in the thermochromic field and provides a novel strategy to achieve fluorescence tuning from intramolecular actions.
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BACKGROUNDS: Tigecycline has a broad spectrum of antimicrobial activity and has been approved for the treatment of complicated intra-abdominal infections. However, it is debatable whether tigecycline should be used alone or in combination. This study aimed to investigate whether tigecycline plus ß-lactam antibiotics (combination therapy [CT] group) are superior to tigecycline alone (monotherapy [MT] group) in non-critically ill intra-abdominal infection patients after tumor surgery. METHODS: This was a multicenter, retrospective cohort study. The primary outcome was mortality during the hospital stay. Secondary outcomes were clinical success rate, microbial eradication rate, relapse rate within one week, course of treatment, and adverse effects. Propensity score matching (PSM) was used to adjust the degree of infection before medication between the MT and CT groups. Univariate comparisons were performed using the chi-squared test for qualitative variables and Student's t-test or the Mann-Whitney U-test for continuous variables, as appropriate. Multivariate logistic regression analysis was performed to examine the relationship between antimicrobial treatments and mortality during hospitalization. The paired samples Wilcoxon test was used to compare the parameters before and after medication. RESULTS: In total, 291 patients were included in the final analysis: 128 in MT group and 163 in CT group. Mortality rate was 6.25% in the MT group and 6.13% in the CT group (P = 0.97). Multivariate logistic regression model showed that carbapenem-resistant organisms (OR: 4.35, 95% CI: 2.36 ~ 61.70) and age > 65 (OR: 1.32, 95% CI:1.19 ~ 3.01) were independent risk factors for death. CT group had a shorter defervescence time (P < 0.05), with less likelihood of relapse (P < 0.05) but had a more significant effect on activated partial thromboplastin and prothrombin time. CONCLUSIONS: Tigecycline plus ß-lactam wasn't superior to tigecycline monotherapy for the treatment of non-critically ill patients with intra-abdominal infection. But for advanced age patients with cancer, tigecycline combination therapy maybe a better choice in terms of mortality.
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Anti-Infecciosos , Infecções Intra-Abdominais , Humanos , Tigeciclina/uso terapêutico , Antibacterianos/efeitos adversos , Estudos Retrospectivos , Recidiva Local de Neoplasia/tratamento farmacológico , Infecções Intra-Abdominais/etiologia , Infecções Intra-Abdominais/induzido quimicamente , Carbapenêmicos/uso terapêutico , Monobactamas/uso terapêutico , Anti-Infecciosos/uso terapêutico , Resultado do TratamentoRESUMO
Biocompatible polymers with nontraditional intrinsic luminescence (NTIL) possess the advantages of environmental friendliness and facile structural regulation. To regulate the emission wavelength of polymers with NTIL, the alkane chain lengths of hyperbranched polysiloxane (HBPSi) are adjusted. Optical investigation shows that the emission wavelength of HBPSi is closely related to the alkane chain lengths; namely, short alkane chains will generate relatively long-wavelength emission. Electronic communication among functional groups is responsible for the emission. In a concentrated solution, HBPSi molecules aggregate together due to the strong hydrogen bond and amphiphilicity, and the functional groups in the aggregate are so close that their electron clouds are overlapped and generate spatial electronic delocalizations. HBPSi with shorter alkane chains will generate larger electronic delocalizations and emit longer-wavelength emissions. Moreover, these polymers show excellent applications in the fabrication of fluorescent films and chemical sensing. This work could provide a strategy for regulating the emission wavelengths of unconventional fluorescent polymers.
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The design of tunable luminescent biomaterials with large Stokes shifts is usually pursued by a twisted intramolecular charge transfer (TICT) effect with switchable emission colors in response to various external stimuli. However, such a strategy is usually realized in conjugated molecules containing benzene or its derivatives and consequently suffers from poor biocompatibility. In this work, a hyperbranched polysiloxane (HBPSi)-based non-conjugated fluorescent polymer with TICT and aggregation-induced emission (AIE) features is developed, and its luminescent properties, fluorescence mechanism, and potential applications are investigated. Initially, the non-conjugated HBPSi exhibits remarkable AIE characteristics due to the formation of through-space conjugation. With the introduction of the sulfur atom, a non-conjugated D-A type AIE material, HBPSi-Cys, that exhibits a dual-state emission with a large Stokes shift of 213 nm, is obtained. The correlation of the lower-energy emission band with solvent polarity suggests the existence of the TICT state. TICT and AIE characteristics direct different properties of HBPSi-Cys, with TICT regulating solvatochromic emission wavelengths and AIE manipulating the emission intensity with a compensation effect. Density functional theory calculations reveal that the non-conjugated D-A structure in HBPSi-Cys was formed across the silicon bridge, with auxochromic sulfhydryl groups and adjacent amide groups as acceptor units and amine and hydroxyl groups as donor units. Additionally, the AIE-active HBPSi could be utilized as a fluorescent probe for the analysis of metal ions. After grafting the AS1411 aptamer to HBPSi-Cys as the recognition motif, HBPSi-Apt possesses excellent targeted bioimaging, drug loading, pH/GSH dual-responsive drug release, and visualized drug delivery performance. This work provides a new way to design functional AIE polymers with tunable optical properties, and the synthesized HBPSi-Cys shows great potential as a smart fluorescent biomaterial.
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Polímeros , Silício , Polímeros/química , Liberação Controlada de Fármacos , Sistemas de Liberação de Medicamentos , Corantes Fluorescentes/química , SiloxanasRESUMO
Fine-resolution differentiation trajectories of adult human hematopoietic stem cells (HSCs) involved in the generation of red cells is critical for understanding dynamic developmental changes that accompany human erythropoiesis. Using single-cell RNA sequencing (scRNA-seq) of primary human terminal erythroid cells (CD34-CD235a+) isolated directly from adult bone marrow (BM) and umbilical cord blood (UCB), we documented the transcriptome of terminally differentiated human erythroblasts at unprecedented resolution. The insights enabled us to distinguish polychromatic erythroblasts (PolyEs) at the early and late stages of development as well as the different development stages of orthochromatic erythroblasts (OrthoEs). We further identified a set of putative regulators of terminal erythroid differentiation and functionally validated three of the identified genes, AKAP8L, TERF2IP, and RNF10, by monitoring cell differentiation and apoptosis. We documented that knockdown of AKAP8L suppressed the commitment of HSCs to erythroid lineage and cell proliferation and delayed differentiation of colony-forming unit-erythroid (CFU-E) to the proerythroblast stage (ProE). In contrast, the knockdown of TERF2IP and RNF10 delayed differentiation of PolyE to OrthoE stage. Taken together, the convergence and divergence of the transcriptional continuums at single-cell resolution underscore the transcriptional regulatory networks that underlie human fetal and adult terminal erythroid differentiation.
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Diferenciação Celular/genética , Eritroblastos/fisiologia , Eritropoese/genética , Adulto , Apoptose/genética , Proteínas de Transporte/genética , Proteínas de Transporte/metabolismo , Proteínas de Ligação a DNA/genética , Proteínas de Ligação a DNA/metabolismo , Sangue Fetal/citologia , Técnicas de Silenciamento de Genes , Redes Reguladoras de Genes , Humanos , Recém-Nascido , Peptídeos e Proteínas de Sinalização Intracelular/genética , Peptídeos e Proteínas de Sinalização Intracelular/metabolismo , Masculino , Família Multigênica , Proteínas Nucleares/genética , Proteínas Nucleares/metabolismo , RNA-Seq , Complexo Shelterina , Análise de Célula Única , Proteínas de Ligação a Telômeros/genética , Proteínas de Ligação a Telômeros/metabolismo , Transcrição GênicaRESUMO
Non-traditional fluorescent polymers have attracted significant attention for their excellent biocompatibility and diverse applications. However, designing and preparing non-traditional fluorescent polymers that simultaneously possess long emission wavelengths and long fluorescence lifetime remains challenging. In this study, a series of novel hyperbranched polyborosiloxanes (P1-P4) were synthesized. As the electron density increases on the monomer diol, the optimal emission wavelengths of the P1-P4 polymers gradually red-shift to 510, 570, 575, and 640â nm, respectively. In particular, P4 not only exhibits red emission but also demonstrates delayed fluorescence with a lifetime of 9.73â µs and the lowest critical cluster concentration (1.76â mg/mL). The experimental results and theoretical calculations revealed that the synergistic effect of dual heteroatom-induced electron delocalization and through-space Oâ â â O and Oâ â â N interaction was the key factor contributing to the red-light emission with delayed fluorescence. Additionally, these polymers showed excellent potential in dual-information encryption. This study provides a universal design strategy for the development of unconventional fluorescent polymers with both delayed fluorescence and long-wavelength emission.
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BACKGROUND: In recent years, studies have shown that exposure to environmental pollutants (e.g., radiation, heavy metal substances, air pollutants, organic pollutants) is a leading cause of human non-communicable diseases. The key to disease prevention is to clarify the harmful mechanisms and toxic effects of environmental pollutants on the body. Metabolomics is a high-sensitivity, high-throughput omics technology that can obtain detailed metabolite information of an organism. It is a crucial tool for gaining a comprehensive understanding of the pathway network regulation mechanism of the organism. Its application is widespread in many research fields such as environmental exposure assessment, medicine, systems biology, and biomarker discovery. AIM OF REVIEW: Recent findings show that metabolomics can be used to obtain molecular snapshots of organisms after environmental exposure, to help understand the interaction between environmental exposure and organisms, and to identify potential biomarkers and biological mechanisms. KEY SCIENTIFIC CONCEPTS OF REVIEW: This review focuses on the application of metabolomics to understand the biological effects of radiation, heavy metals, air pollution, and persistent organic pollutants exposure, and examines some potential biomarkers and toxicity mechanisms.
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Poluentes Ambientais , Metabolômica , Biomarcadores , Exposição Ambiental/efeitos adversos , Poluentes Ambientais/toxicidade , HumanosRESUMO
Unconventional fluorescent polymers possess the advantages of excellent biocompatibility, environmental friendliness, and facile structural regulation; however, such polymers usually have low fluorescence intensity and quantum yields in the long-wavelength range. In this work, three kinds of high-efficiency long-wavelength emissive hyperbranched polysiloxanes are obtained by introducing aromatic amino acids. These functionalized hyperbranched polysiloxanes have high fluorescence intensity and quantum yields in green, yellow, and red emission regions. Experimental results and density functional theory calculations reveal that the long-wavelength emission comes from the enhanced electronic communication among the conjugated π bonds, electron-rich atoms, and -Si(O)3 and other functional groups. Especially, the conjugated π bonds efficiently enlarge the spatial electronic delocalizations, resulting in the high-efficiency long-wavelength emission. Moreover, the prepared polymers show excellent applications in information encryption and film preparation. This work could serve as a guide to develop high-efficiency long-wavelength unconventional fluorescent polymers.
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Corantes Fluorescentes , Siloxanas , Fluorescência , Corantes Fluorescentes/química , Polímeros/química , LuzRESUMO
Unconventional fluorescent polymers have attracted increasing attention due to their facile synthesis, excellent biocompatibility, and novel photophysical properties. In this work, a truly multicolor emissive hyperbranched polysiloxane (HBPSi-ß-CD) is obtained through adjusting the distribution of electron-rich atoms and grafting ß-cyclodextrin; the quantum yields of HBPSi-ß-CD after being excited by 360, 420, 450, and 550 nm are 19.36, 31.46, 46.14 and 44.84%, respectively. The density functional theory calculations reveal that the truly multicolor emission is derived from the formed electron delocalization among the hydroxyl, amine, ether, and -Si(O)3 groups due to the strong intermolecular interaction, high density of electron-rich atoms, and low steric hindrance among functional groups. The prepared polymers could serve as a multisensitivity sensor in detecting Fe3+, Cu2+, and Co2+. The HBPSi-ß-CD shows low cytotoxicity and excellent cellular imaging capability. The self-assembly of HBPSi-ß-CD also possesses high drug loading capacity and pH-controlled drug release, especially, the drug delivery system could be applied in the visualization of controlled drug delivery.
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Polímeros , Siloxanas , Sistemas de Liberação de Medicamentos , Liberação Controlada de Fármacos , Preparações FarmacêuticasRESUMO
Large perpendicular magnetic anisotropy energy (MAE) and flexible regulation of the magnitude and direction of MAE have great potential for application in information storage devices. Here, utilizing first-principles calculations, we investigated the magnetic properties of free and MgO(001) supported RumIrn clusters (RumIrn@MgO(m + n = 3)). The results indicate that the MAE of mixed clusters increases with the number of Ir atoms due to Ir having a strong coupling between the non-degenerate dxy and dx2-y2 states. The MAE of free Ir3 is -8.18 meV with the easy magnetization direction parallel to the x-axis, while the MAE of supported Ir3 on the MgO substrate increases by a factor of 2.6, and the easy magnetization axis of the structure is shifted to a direction perpendicular to the substrate surface. This change in MAE is due to the significant enhancement in the coupling between the non-degenerate dyz and dx2-y2 states near the Fermi level of Ir3 atoms. Moreover, Ir3@MgO possesses high thermodynamic stability. These results give a new method for manipulating MAE and the direction of easy magnetization, which has great potential for application in magnetic nanodevices.