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1.
Skin Res Technol ; 30(5): e13749, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38776128

RESUMO

BACKGROUND: Omalizumab is the only licensed drug that serves as a third-line treatment for chronic idiopathic urticaria (CIU). The optimum doses of omalizumab remain controversial. Therefore, this study aims to estimate the efficacy and safety of different doses of omalizumab in the treatment of CIU patients. MATERIALS AND METHODS: Four databases were searched from the database's creation to April 8, 2023. Several keywords such as omalizumab and urticarias were used to retrieve related studies. The meta-analytical outcomes were analyzed in R 4.2.1 software and Stata 15.1 software. Cochrane risk-of-bias tool Ver. 2 was used to evaluate the risk of bias in randomized controlled trials (RCTs). RESULTS: In total, 2331 patients were included. Five indexes were employed to assess, including weekly Itch Severity Score (ISS7), weekly Hive Severity Score (HSS7), weekly Urticaria Activity Score (UAS7), Dermatology Life Quality Index (DLQI), and adverse events (AE). A 300 mg dose of omalizumab was the optimum dose to treat CIU, followed by the 150 mg dose. Furthermore, 600 mg of omalizumab only showed a significant difference from the placebo in HSS7. No significant statistical difference was observed in AE. Meta-regression analysis revealed that time, as a covariate, was statistically significant in the comparison of omalizumab 150 mg with placebo. CONCLUSION: 300 mg of omalizumab was the optimum dosage to treat CIU patients, with a 150 mg dose also exhibiting good efficacy. Further studies are required to explore the efficacy and safety of different doses of omalizumab in the treatment of CIU patients.


Assuntos
Antialérgicos , Urticária Crônica , Omalizumab , Omalizumab/efeitos adversos , Omalizumab/administração & dosagem , Omalizumab/uso terapêutico , Humanos , Urticária Crônica/tratamento farmacológico , Antialérgicos/administração & dosagem , Antialérgicos/efeitos adversos , Antialérgicos/uso terapêutico , Resultado do Tratamento , Metanálise em Rede , Ensaios Clínicos Controlados Aleatórios como Assunto , Qualidade de Vida , Relação Dose-Resposta a Droga
2.
Spectrochim Acta A Mol Biomol Spectrosc ; 308: 123758, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38091652

RESUMO

Here, a series of dinuclear N-heterocyclic carbene (NHC) copper(I) complexes having 3,3'-(1,4-phenylenebis(methylene))bis(1-(pyridin-2-yl)-1H-imidazolylidene as bis-NHC ligand and bis[(2-diphenylphosphino)phenyl]ether (POP) as auxiliary ligand have been successfully prepared, and their photophysical properites were investigaged experimentally and theocitcally. The resulting complexes all exhibited intense green to yellow emission that originated from the thermally activated delayed fluorescence (TADF) with a high photoluminescence quantum yield of up to 0.67 and longer excited-state lifetimes on the microsecond time scale in the solid state. Green and yellow light-emitting diode (LED) devices based on Cu(I) complexes have successfully achieved good color rendering indices. Moreover, the anti-counterfeiting patterns and QR codes made of Cu(I) complexes have been applied to clothing, banknotes, books and glass plates with excellent anti-counterfeiting effects.

3.
Aging (Albany NY) ; 16(4): 3647-3673, 2024 02 14.
Artigo em Inglês | MEDLINE | ID: mdl-38358909

RESUMO

BACKGROUND: Disulfidptosis, a form of cell death induced by abnormal intracellular accumulation of disulfides, is a newly recognized variety of cell death. Clear cell renal cell carcinoma (ccRCC) is a usual urological tumor that poses serious health risks. There are few studies of disulfidptosis-related genes (DRGs) in ccRCC so far. METHODS: The expression, transcriptional variants, and prognostic role of DRGs were assessed. Based on DRGs, consensus unsupervised clustering analysis was performed to stratify ccRCC patients into various subtypes and constructed a DRG risk scoring model. Patients were stratified into high or low-risk groups by this model. We focused on assessing the discrepancy in prognosis, TME, chemotherapeutic susceptibility, and landscape of immune between the two risk groups. Finally, we validated the expression and explored the biological function of the risk scoring gene FLRT3 through in vitro experiments. RESULTS: The different subtypes had significantly different gene expression, immune, and prognostic landscapes. In the two risk groups, the high-risk group had higher TME scores, more significant immune cell infiltration, and a higher probability of benefiting from immunotherapy, but had a worse prognosis. There were also remarkable differences in chemotherapeutic susceptibility between the two risk groups. In ccRCC cells, the expression of FLRT3 was shown to be lower and its overexpression caused a decrease in cell proliferation and metastatic capacity. CONCLUSIONS: Starting from disulfidptosis, we established a new risk scoring model which can provide new ideas for doctors to forecast patient survival and determine clinical treatment plans.


Assuntos
Carcinoma de Células Renais , Neoplasias Renais , Humanos , Carcinoma de Células Renais/genética , Microambiente Tumoral/genética , Prognóstico , Fatores de Risco , Neoplasias Renais/genética
4.
Toxics ; 11(12)2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-38133425

RESUMO

The potential negative impacts of organochlorine pesticides on the environment and human health continue to receive attention. In order to study the spatial distribution characteristics of organochlorine pesticides in the inland alpine region, researchers collected soil and water samples in the Huangshui River Basin of the Qinghai-Tibetan Plateau and tested them for organochlorine pesticide residues represented by dichlorodiphenyltrichloroethane (DDT) and hexachlorohexane (HCH). The study identified the sources of OCPs by component analysis. We also constructed the LEVEL III model, applicable to the Huangshui River Basin, and used it to study the migration patterns of OCPs in various environmental media. OCPs were detected at low levels in the study area environment. The results of the OCPs source analysis show that there are both historical residuals and new sources in the region. Residual DDTs may originate from the mixture of technical DDTs and dicofol, and HCHs may originate from lindane or technical HCH. DDTs are mainly stored in soil, the input and output pathways are mainly atmospheric advection input and output, and its transport behavior in the environment is mainly air-soil exchange. Carcinogens in the study area pose little threat to people exposed to contaminated soil and contaminated water, but the cancer risk to children is greater than to adults. This study is helpful to managers of regional pesticide management and control.

5.
Sci Rep ; 13(1): 8368, 2023 05 24.
Artigo em Inglês | MEDLINE | ID: mdl-37225919

RESUMO

Cytoskeleton-associated protein 2-like (CKAP2L), a cell cycle-related protein, is correlated to tumor progression in some tumors. But there were no pan-cancer studies on CKAP2L, and its role in cancer immunotherapy is also unclear. The expression levels, expression activity, genomic alterations, DNA methylation and functions of CKAP2L in various tumors, as well as the associations between CKAP2L expression and patient prognosis, chemotherapy sensitivity, and tumor immune microenvironment, were all analyzed in a comprehensive pan-cancer analysis of CKAP2L by various databases, analysis websites, and R software. The experiments were also conducted to verify the analysis results. In the majority of cancers, CKAP2L expression and activity were markedly elevated. Elevated CKAP2L expression led to poor prognostic outcomes in patients, and is an independent risk factor for most tumors. Elevated CKAP2L causes decreased sensitivity to chemotherapeutic agents. Knockdown of CKAP2L significantly inhibited the proliferation and metastasis capacity of the KIRC cell lines and resulted in cell cycle G2/M arrest. In addition, CKAP2L was closely related to immune subtypes, immune cell infiltration, immunomodulators and immunotherapy markers (TMB, MSI), patients with high CKAP2L expression were more sensitive to immunotherapy in the IMvigor210 cohort. The results indicate that CKAP2L is a pro-cancer gene that serves as a potential biomarker for predicting patient outcomes. By inducing cells to transition from the G2 phase to the M phase, CKAP2L may promote cell proliferation and metastasis. Furthermore, CKAP2L is closely related to the tumor immune microenvironment and can be used as a biomarker to predict tumor immunotherapy.


Assuntos
Apoptose , Proteínas do Citoesqueleto , Neoplasias , Humanos , Proteínas de Ciclo Celular , Linhagem Celular Tumoral , Proteínas do Citoesqueleto/genética , Citoesqueleto , Pontos de Checagem da Fase G2 do Ciclo Celular , Neoplasias/genética , Neoplasias/terapia , Prognóstico
6.
Front Oncol ; 13: 1170397, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37388224

RESUMO

Background: CHMP4C is one of the charged multivesicular protein (CHMP), and is involved in the composition of the endosomal sorting complex required for transport III (ESCRT-III), facilitating the necessary separation of daughter cells. CHMP4C has been proposed to be involved in the progression of different carcinomas. However, the value of CHMP4C in prostate cancer has not yet been explored. Prostate cancer is the most frequently occurring malignancy among male and remains a leading cause of deaths in cancers. So far, clinical therapy of prostate cancer is more inclined to molecular classification and specific clinical treatment and research. Our study investigated the expression and clinical prognosis of CHMP4C and explored its potential regulatory mechanism in prostate cancer. The immune status of CHMP4C in prostate cancer and relative immunotherapy were then analyzed in our study. Based on CHMP4C expression, a new subtype of prostate cancer was established for precision treatment. Methods: We studied the expression of CHMP4C and relative clinical outcome using the online databases TIMER, GEPIA2, UALCAN, and multiple R packages. Meanwhile, the biological function, immune microenvironment and immunotherapy value of CHMP4C in prostate cancer were further explored on the R software platform with different R packages. Then we performed qRT-PCR, Western Blotting, transwell, CCK8, wound healing assay, colony formation assay and immunohistochemistry to verify the expression of CHMP4C, carcinogenesis and potential regulatory mechanisms in prostate cancer. Results: We found that the expression of CHMP4C is significant in prostate cancer and the high expression of CHMP4C represents a poor clinical prognosis and malignant progression of prostate cancer. In subsequent vitro validation, CHMP4C promoted the malignant biological behavior of prostate cancer cell lines by adjusting the cell cycle. Based on CHMP4C expression, we established two new subtypes of prostate cancer and found that low CHMP4C expression has a better immune response while high CHMP4C expression was more sensitive to paclitaxel and 5-fluorouracil. Above findings revealed a new diagnostic marker for prostate cancer and facilitated the subsequent precise treatment of prostate cancer.

7.
Aging (Albany NY) ; 15(24): 15134-15160, 2023 12 21.
Artigo em Inglês | MEDLINE | ID: mdl-38147021

RESUMO

BACKGROUND: Type X collagen (COL10) is a homologous trimeric non-fibrillar collagen found in the extracellular matrix of human tissues, and it exhibits a distinctive white appearance. Type X collagen α1 chain (COL10A1) is a specific cleaved fragment of type X collagen. However, the expression, prognostic significance, clinicopathological attributes and immune-related associations of COL10A1 in prostate cancer as well as in pan-cancer contexts remain poorly understood. METHODS: Using bioinformatic analysis of data from the most recent databases (TCGA, GTEx and GEO databases), we have extensively elucidated the role played by COL10A1 in terms of its expression patterns, prognostic implications, and immune efficacy across a pan-cancer spectrum. Subsequently, the biological functions of COL10A1 in prostate cancer were elucidated by experimental validation. RESULTS: Our findings have confirmed that COL10A1 was highly expressed in most cancers and was associated with poorer prognosis in cancer patients. Immune correlation analysis of COL10A1 in various cancers showed its significant correlation with Tumor mutational burden (TMB), microsatellite instability (MSI) and immune cell infiltration. In addition, knockdown of COL10A1 in prostate cancer resulted in a substantial reduction in the proliferation, migration, and invasive potential of prostate cancer cells. CONCLUSION: Our pan-cancer analysis of COL10A1 gene provided novel insights into its pivotal role in cancer initiation, progression, and therapeutic implications, underscoring its potential significance in prognosis and immunotherapeutic interventions for cancer, particularly prostate cancer.


Assuntos
Colágeno Tipo X , Neoplasias da Próstata , Humanos , Masculino , Colágeno Tipo X/genética , Oncogenes/genética , Prognóstico , Próstata , Neoplasias da Próstata/genética , Neoplasias da Próstata/terapia
8.
Front Immunol ; 13: 916800, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35860239

RESUMO

Background: In reference to previous studies, necroptosis played an important role in cancer development. Our team decided to explore the potential prognostic values of long non-coding RNAs (lncRNAs) associated with necroptosis in bladder urothelial carcinoma (BLCA) and their relationship with the tumor microenvironment (TME) and the immunotherapeutic response for accurate dose. Methods: To obtain the required data, bladder urothelial carcinoma transcriptome data were searched from Cancer Genome Atlas (TCGA) (https://portal.gdc.cancer.gov/). We used co-expression analysis, differential expression analysis, and univariate Cox regression to screen out prognostic lncRNAs associated with necroptosis in BLCA. Then the least absolute shrinkage and selection operator (LASSO) was conducted to construct the necroptosis-associated lncRNAs model. Based on this model, we also performed the Kaplan-Meier analysis and time-dependent receiver operating characteristics (ROC) to estimate the prognostic power of risk score. Multivariate and univariate Cox regression analysis were performed to build up a nomogram. Calibration curves, and time-dependent ROC were also conducted to evaluate nomogram. Principal component analysis (PCA) revealed a difference between high- and low-risk groups. In addition, we explored immune analysis, gene set enrichment analyses (GSEA), and evaluation of the half-maximal inhibitory concentration (IC50) in constructed model. Finally, the entire samples were divided into three clusters based on model of necroptosis-associated lncRNAs to further compare immunotherapy in cold and hot tumors. Results: A model was built up based on necroptosis-associated lncRNAs. The model revealed good consistence between calibration plots and prognostic prediction. The area of 1-, 3-, and 5-year OS under the ROC curve (AUC) were 0.707, 0.679, and 0.675. Risk groups could be helpful for systemic therapy due to the markedly diverse IC50 between risk groups. To our delight, clusters could effectively identify cold and hot tumors, which would be beneficial to accurate mediation. Clusters 2 and 3 were considered the hot tumor, which was more sensitive to immunotherapeutic drugs. Conclusions: The outcomes of our study suggested that necroptosis-associated lncRNAs could effectively predict patients with BLCA prognosis, which may be helpful for distinguishing the cold and hot tumors and improving individual treatment of BLCA.


Assuntos
Carcinoma de Células de Transição , RNA Longo não Codificante , Neoplasias da Bexiga Urinária , Biomarcadores Tumorais/genética , Biomarcadores Tumorais/metabolismo , Carcinoma de Células de Transição/genética , Regulação Neoplásica da Expressão Gênica , Humanos , Necroptose/genética , Prognóstico , RNA Longo não Codificante/genética , RNA Longo não Codificante/metabolismo , Microambiente Tumoral/genética , Bexiga Urinária , Neoplasias da Bexiga Urinária/diagnóstico , Neoplasias da Bexiga Urinária/genética , Neoplasias da Bexiga Urinária/terapia
9.
Sci Rep ; 12(1): 21268, 2022 12 08.
Artigo em Inglês | MEDLINE | ID: mdl-36481756

RESUMO

Progestin and adipoQ receptor family member 4 (PAQR4) is a protein-coding gene. Recent studies have shown that PAQR4 is related to the development of multiple cancers. However, there is no systematic pan-cancer analysis of this gene. In this study, the expression of PAQR4, correlations with clinical prognosis, immune situation, and its potential molecular functions and mechanisms in pan-cancer were explored by bioinformatics analysis. The Cancer Genome Atlas was applied to investigate the relations between PAQR4 and clinical features, prognostic effects, and tumor immune microenvironment. R software was used to perform statistical analysis and figure creation. The expression of PAQR4 in BLCA and KIRC was validated by qRT-PCR and immunohistochemistry, and its function was explored by cellular experiments. Bioinformatics analysis revealed that PAQR4 was up-regulated in multiple cancers and related to poor prognosis. The high expression of PAQR4 was closely associated with high tumor stage, immune cell infiltration, tumor mutation burden, and microsatellite instability in different cancer types. In addition, the high expression of PAQR4 also indicated involvement in the immune regulatory pathways. The involvement of PAQR4 in the immune regulation of different tumors was confirmed by GSEA enrichment analysis. Moreover, PAQR4 was highly expressed in bladder cancer and renal clear cell carcinoma tissues and cell lines. Cell proliferation, migration, and invasion of bladder cancer and renal clear cell carcinoma cell lines were significantly decreased after the knockdown of PAQR4. This study elucidated the role of PAQR4 in carcinogenesis as well as tumor immunity. PAQR4 may serve as a potential prognostic biomarker in a variety of cancers.


Assuntos
Carcinoma de Células Renais , Neoplasias Renais , Neoplasias da Bexiga Urinária , Humanos , Prognóstico , Microambiente Tumoral/genética , Neoplasias da Bexiga Urinária/genética
10.
Front Genet ; 13: 938259, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35910212

RESUMO

Background: Clear cell renal cell carcinoma (ccRCC) accounts for 80% of all kidney cancers and has a poor prognosis. Recent studies have shown that copper-dependent, regulated cell death differs from previously known death mechanisms (apoptosis, ferroptosis, and necroptosis) and is dependent on mitochondrial respiration (Tsvetkov et al., Science, 2022, 375 (6586), 1254-1261). Studies also suggested that targeting cuproptosis may be a novel therapeutic strategy for cancer therapy. In ccRCC, both cuproptosis and lncRNA were critical, but the mechanisms were not fully understood. The aim of our study was to construct a prognostic profile based on cuproptosis-associated lncRNAs to predict the prognosis of ccRCC and to study the immune profile of clear cell renal cell carcinoma (ccRCC). Methods: We downloaded the transcriptional profile and clinical information of ccRCC from The Cancer Genome Atlas (TCGA). Co-expression network analysis, Cox regression method, and least absolute shrinkage and selection operator (LASSO) method were used to identify cuproptosis-associated lncRNAs and to construct a risk prognostic model. In addition, the predictive performance of the model was validated and recognized by an integrated approach. We then also constructed a nomogram to predict the prognosis of ccRCC patients. Differences in biological function were investigated by GO, KEGG, and immunoassay. Immunotherapy response was measured using tumor mutational burden (TMB) and tumor immune dysfunction and rejection (TIDE) scores. Results: We constructed a panel of 10 cuproptosis-associated lncRNAs (HHLA3, H1-10-AS1, PICSAR, LINC02027, SNHG15, SNHG8, LINC00471, EIF1B-AS1, LINC02154, and MINCR) to construct a prognostic prediction model. The Kaplan-Meier and ROC curves showed that the feature had acceptable predictive validity in the TCGA training, test, and complete groups. The cuproptosis-associated lncRNA model had higher diagnostic efficiency compared to other clinical features. The analysis of Immune cell infiltration and ssGSEA further confirmed that predictive features were significantly associated with the immune status of ccRCC patients. Notably, the superimposed effect of patients in the high-risk group and high TMB resulted in shorter survival. In addition, the higher TIDE scores in the high-risk group suggested a poorer outcome for immune checkpoint blockade response in these patients. Conclusion: The ten cuproptosis-related risk profiles for lncRNA may help assess the prognosis and molecular profile of ccRCC patients and improve treatment options, which can be further applied in the clinic.

11.
Front Oncol ; 12: 965571, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35978830

RESUMO

Background: Prostate cancer is the most common tumor in men worldwide, seriously threatening the health of older men, and 5-methylcytosine (m5C) RNA modification has been shown to have a significant impact on the development and progression of various tumors. However, as the most critical methyltransferase for m5c RNA modification, the role of the NSUN members (NSUN1-7) in prostate cancer is unclear. Methods: We obtained sequencing data of genes and related clinical data of prostate cancer from The Cancer Genome Atlas (TCGA) database and Gene Expression Omnibus (GEO) database and analyzed the correlation between NSUN members' expression and prognosis. we found that NSUN2 was closely implicated in the prognosis of prostate cancer, then verified the expression of NSUN2 in clinical samples, and obtained the correlation between NSUN2 and immune cell infiltration through CIBERSORT algorithm and ESTIMATE method. The relationship between NSUN2 copy number variation and immune cell infiltration was further analyzed in the TIMER database and identified signaling pathways associated with NSUN2 expression by GO, KEGG, and GSEA analysis. Finally, we verified the expression of NSUN2 in prostate cancer cell lines and confirmed the role of NSUN2 on the biological behavior of prostate cancer cells by proliferation and migration-related assays. Results: NOP2 and NSUN2 were upregulated in prostate tumor tissues. NSUN2 expression is closely associated with tumor prognosis. NSUN2 high expression implies poor clinical features, and the NSUN family is significantly associated with tumor stromal score and immune score. Besides, NSUN2 is associated with a variety of immune infiltrating cells (B cells memory, T cells CD4 memory resting, T cells CD4 memory activated, NK cells resting, and so on). High NSUN2 expression lowers the sensitivity of many chemotherapy drugs, such as docetaxel, doxorubicin, fluorouracil, cisplatin, and etoposide. In prostate cancer, the most common type of mutation in NSUN2 is amplification, and NSUN2 copy number variation is closely associated with NSUN2 expression and immune cell infiltration. GSEA analysis showed that the related genes were mainly enriched in ubiquitin-mediated protein hydrolysis, cell cycle, RNA degradation, endometrial cancer, prostate cancer, p53 signaling pathway, and NSUN2 potentiated the proliferation and migration of prostate cancer cells. Conclusions: NSUN2 is highly expressed in prostate cancer, which contributes to the progression of prostate cancer, and is closely implicated in immune cell infiltration and chemotherapy drugs. NSUN2 is expected to be a prospective marker and a new treatment target for prostate cancer.

12.
Front Cell Dev Biol ; 9: 684125, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34395419

RESUMO

Patients diagnosed with prostate cancer often have a poor prognosis and limited treatment options, as the specific pathogenesis remains to be elucidated. Circular RNA (circRNA) is a type of non-coding RNA that interacts with microRNA (miRNA/miR) and transcription factors to regulate gene expression. However, little is known about specific circRNAs that serve roles in the pathogenesis of prostate cancer. Findings of the present study confirmed that circRNA G protein subunit γ 4 (circGNG4) was upregulated in prostate cancer tissues and cell lines. Knockdown of circGNG4 inhibited the malignant behavior of prostate cancer cells. Furthermore, bioinformatics were used to predict targeting interactions between circGNG4 or miR-223 and EYA transcriptional coactivator and phosphatase 3 (EYA3)/c-Myc mRNA. miR-223 inhibited the malignant behavior of prostate cancer cells, while EYA3/c-Myc had the opposite effect. circGNG4 enhanced the expression of EYA3/c-Myc by sponging miR-223 to promote the growth of prostate cancer tumors in vivo. In conclusion, the circGNG4/miR-223/EYA3/c-Myc regulatory pathway promoted the malignant progression of prostate cancer. The results of the present study may provide potential new targets for the diagnosis or treatment of prostate cancer.

13.
Artigo em Inglês | MEDLINE | ID: mdl-26943490

RESUMO

Two phenanthroline derivatives, 1H-imidazo[4,5-f][1,10]phenanthroline (imPhen) and 2-(9H-fluoren-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline (Flu-imPhen), have been synthesized and characterized and the corresponding absorption and emission spectroscopic properties have been studied in CH2Cl2 solution. The imPhen exhibits the main two absorption bands at 282 nm and 229 nm and these bands are assigned as the typical π→π*(Phen) state. In addition, the weak absorption bands at 313 nm associated with a shoulder near 302 nm were assigned to the π→π*(Phen) state with partial charge transfer (CT) character. A similar absorption spectra are observed in the case of the Flu-imPhen in the region of 200-300 nm, while the region of 300-400 nm of the spectra are dominated by the characteristic π→π* transition of the fluorene moiety. imPhen shows the typical ligand-centered (1)π→π* emission, while Flu-imPhen emits from the mixed (1)π→π*/CT states. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) were employed to rationalize the photophysical properties of these ligands studied. The theoretical data confirm the assignment of the experimental absorption spectra and the nature of the emitting states.

14.
J Mol Model ; 21(12): 313, 2015 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-26589406

RESUMO

Two copper(I) complexes [Cu(Pyz-Phen)2]PF6 (1) and [Cu(POP)(Pyz-Phen)]PF6 (2) (Pyz-Phen = pyrazino[2,3-f] [1, 10]phenanthroline, POP = bis[2-diphenylphosphino]-phenyl]ether) have been synthesized and characterized. The photophysical properties of these complexes in solution have been studied. The electronic absorption spectrum of complexes 1 exhibit the lowest-lying MLCT absorption band at 459 nm and high-energy ligand-based transitions at 275 nm, while that of complex 2 exhibits the MLCT/LLCT band at 400 nm and ligand π-π* band at 262 nm. In addition, both 1 and 2 show similar phosphorescence (3)MLCT/(3)LLCT emissions with maximum emission wavelengths of 569 and 572 nm, respectively. Density functional theory (DFT) and time-dependent density functional theory (TDDFT) were employed to rationalize the photophysical properties of the complexes studied. The theoretical data confirm the assignment of the experimental absorption spectra and the nature of the emitting states. Graphical Abstract Photophysical properties of copper(I) complexes containing pyrazine-fused phenanthroline ligands.


Assuntos
Complexos de Coordenação/química , Cobre/química , Modelos Moleculares , Fenantrolinas/química , Pirazinas/química , Complexos de Coordenação/síntese química , Ligantes , Análise Espectral
15.
J Mol Model ; 21(2): 22, 2015 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-25620419

RESUMO

The accurate prediction for the emission energies of the phosphorescent Ir (III) complexes is very useful for the realizing of full-color displays and large-area solid-state lighting in OLED fields. Quantum chemistry calculations based on TDDFT methods are most widely used to directly compute the triplet vertical excitation energies, yet sometimes the universality of these calculations can be limited because of the lack of experimental data for the relative family of structural analogues. In this letter, 16 literature emission energies at low temperature are linearly correlated with their theoretical values computed by TDDFT using exchange-correlation functionals containing various HF exchange percentage with the relation of E exp (em) = 1.2E calc (em). The relation is proven to be robust across a wide range of structures for Ir (III) complexes. These theoretical studies should be expected to provide some guides for the design and synthesis of efficient emitting materials.


Assuntos
Irídio/química , Modelos Teóricos
16.
J Mol Model ; 20(9): 2416, 2014 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-25123713

RESUMO

The ground electronic states and photophysical properties of three designed Cu(I) complexes [Cu(ImNHC)(POP)](+) (1), [Cu(methyl-ImNHC)(POP)](+) (2), and [Cu(BenzImNHC)(POP)](+) (3); where [ImNHC = 3-methyl-1-(pyridin-2-yl)-1H-imidazol-2-ylidene; methyl-ImNHC = 3-methyl-1-(pyridin-2-ylmethyl)-1H-imidazol-2-ylidene; BenzImNHC = 3-methyl-1-(pyridin-2-yl)-1H-benzimidazol-2-ylidene], have been investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The results reveal that the presence of the methylene spacer in the NHC ligands has a more direct effect on the distribution of frontier molecular orbitals while the elongation of π conjugation provided by the fused imidazole in the NHC ligands has a negligible effect. The UV-vis absorption spectra of all the complexes are well produced by TD-DFT calculations based on the charge transfer amount calculations and the corresponding band assignments are discussed. Importantly, the triplet energy calculations demonstrated that complex 2 would be a highly efficient blue emitter with the deep-blue of 440 nm.


Assuntos
Cor , Cobre/química , Luminescência , Substâncias Luminescentes/química , Metano/análogos & derivados , Simulação por Computador , Elétrons , Transferência de Energia , Ligantes , Metano/química , Modelos Químicos , Modelos Moleculares , Estrutura Molecular , Espectrofotometria Ultravioleta , Relação Estrutura-Atividade
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