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Interaction of the lanthanide nitrates M(NO3)3 (M = Gd, Eu) with methylcucurbit[5]uril (Me10Q[5]) in the presence of transition metal chlorides (ZnCl2 and FeCl3) in acidic media resulted in the isolation of the complexes [Me10Q[5]Gd(H2O)2Cl Gd(H2O)6](ZnCl4)2âClâ8.9H2O (1) and [Me10Q[5]Eu(H2O)3Cl(H3O)](FeCl4)3 (2). The molecular structures of 1 and 2 have been determined by single crystal X-ray crystallography, and reveal discrete complexes which are involved in dense stacking with adjacent Me10Q[5]s linked via H-bonding and/or metal anions resulting in a supramolecular assembly.
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A palladium-catalyzed spirocyclopropanation of gem-difluoroalkenes with π-allylpalladium 1,4-dipoles has been successfully developed, which gives a powerful and straightforward synthetic strategy for the construction of novel gem-difluorinated spirocyclic compounds, 6,6-difluoro-5-oxa/azaspiro[2.4]heptanes. The scope of gem-difluoroalkenes can be extended to styrenes, acrylic esters, and acrylamides to realize the installment of various functional groups and different heteroatoms on the spirocyclic skeletons, which could be converted to valuable compounds with potential biological activity. The mechanistic investigations revealed the competition between spirocyclopropanation and ß-F elimination of π-allylpalladium zwitterionic intermediates.
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The simultaneous discrimination and detection of multiple anions in an aqueous solution has been a major challenge due to their structural similarity and low charge radii. In this study, we have constructed a supramolecular fluorescence sensor array based on three host-guest complexes to distinguish five anions (F-, Cl-, Br-, I-, and ClO-) in an aqueous solution using anionic-induced fluorescence quenching combined with linear discriminant analysis. Due to the different affinities of the three host-guest complexes for each anion the anion quenching efficiency for each host-guest complex was likewise different, and the five anions were well recognized. The fluorescence sensor array not only distinguished anions at different concentrations (0.5, 10, and 50 µM) with 100% accuracy but also showed good linearity within a certain concentration range. The limit of detection (LOD) was < 0.5 µM. Our interference study showed that the developed sensor array had good anti-interference ability. The practicability of the developed sensor array was also verified by the identification and differentiation of toothpaste brands with different fluoride content and the prediction of the iodine concentration in urine combined with machine learning.
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Ânions , Iodo , Limite de Detecção , Aprendizado de Máquina , Espectrometria de Fluorescência , Ânions/urina , Ânions/química , Iodo/urina , Iodo/química , Espectrometria de Fluorescência/métodos , Cremes Dentais/química , Corantes Fluorescentes/química , Fluoretos/química , Fluoretos/urina , Análise DiscriminanteRESUMO
A simple fluorescent "on-off" system that can be utilized for the selective identification and determination of paraquat (PQ) is presented herein. 1H NMR spectroscopic data indicated that in aqueous solution the alkaloid palmatine can be partially encapsulated within the cucurbit[7]uril (Q[7]) cavity, whereby a stable 1 : 1 host-guest inclusion complex is formed. Other characterization techniques including mass spectrometry, UV-Vis and fluorescence spectroscopy also provided further evidence, and the host-guest inclusion complex was found to exhibit reasonable fluorescence intensity. It is noteworthy that the addition of PQ resulted in quenching the fluorescence of the host-guest inclusion complex, whereas the presence of 12 other pesticides did not significantly affect the fluorescence intensity. Given the linear relationship between the intensity of the fluorescence and the PQ concentration, the PQ concentration in aqueous solution was easily detected. Thus, a new method for identifying and determining the fluorescence quenching of PQ has been developed in this work.
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For metastatic prostate cancer, androgen deprivation therapy (ADT) is the key strategy to control the disease. However, after 18-24 months of treatment, most patients will progress from metastatic hormone-sensitive prostate cancer (mHSPC) to metastatic castration-resistant prostate cancer (mCRPC) even with ADT. Once patients enter into mCRPC, they face with significant declines in quality of life and a dramatically reduced survival period. Thus, doublet therapy, which combines ADT with new hormone therapy (NHT) or ADT with docetaxel chemotherapy, substitutes ADT alone and has become the "gold standard" for the treatment of mHSPC. In recent years, triplet therapy, which combines ADT with NHT and docetaxel chemotherapy, has also achieved impressive effects in mHSPC. This article provides a comprehensive review of the recent applications of the triplet therapy in the field of mHSPC.
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ETHNOPHARMACOLOGICAL RELEVANCE: Ginkgo biloba leaf and seed have been traditionally used in ancient China for the treatment of cough and asthma. However, there is limited literature available on the anti-COPD effects and mechanisms of Ginkgo biloba. AIMS OF THE STUDY: The aim of this study was to comprehensively investigate the therapeutic potential of ginkgo extracts in COPD through a combination of in vivo and in vitro functional experiments. Transcriptomic analyses were also employed to uncover novel molecular mechanisms underlying the therapeutic effects of ginkgetin in COPD. MATERIALS AND METHODS: The therapeutic efficacy of ginkgo extracts was assessed in a COPD model. The anti-inflammatory effects of ginkgetin and its underlying molecular mechanisms were examined in A549 cells treated with cigarette smoke extract (CSE). Additionally, transcriptomic analyses were conducted to identify novel molecular pathways influenced by ginkgetin. These findings were further validated using quantitative real-time polymerase chain reaction (qPCR) and Western blot techniques. RESULTS: The ethyl acetate extract of Ginkgo biloba L. seeds and ginkgetin treatment significantly reduced cytokine production in COPD mice. Following drug administration, lung function improved in different groups. The transcriptome data strongly supports the inhibitory effect of ginkgetin on CSE-induced inflammation through the downregulation of the c/EBPß signaling pathway and subsequent inhibition of CCL2 expression. CONCLUSION: Our results demonstrate that ginkgetin, one of the biflavones found in Ginkgo biloba, exhibits inhibitory effects on smoke-induced airway inflammation. This effect is achieved through the downregulation of the c/EBPß signaling pathway and the reduction of CCL2 expression.
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Biflavonoides , Quimiocina CCL2 , Regulação para Baixo , Ginkgo biloba , Doença Pulmonar Obstrutiva Crônica , Transdução de Sinais , Animais , Doença Pulmonar Obstrutiva Crônica/tratamento farmacológico , Biflavonoides/farmacologia , Biflavonoides/uso terapêutico , Humanos , Transdução de Sinais/efeitos dos fármacos , Ginkgo biloba/química , Regulação para Baixo/efeitos dos fármacos , Quimiocina CCL2/genética , Quimiocina CCL2/metabolismo , Camundongos , Masculino , Extratos Vegetais/farmacologia , Extratos Vegetais/uso terapêutico , Fumaça/efeitos adversos , Anti-Inflamatórios/farmacologia , Anti-Inflamatórios/uso terapêutico , Células A549 , Camundongos Endogâmicos C57BL , Modelos Animais de Doenças , Pulmão/efeitos dos fármacos , Pulmão/metabolismo , Pulmão/patologia , Extrato de GinkgoRESUMO
A supramolecular assembly was constructed based on the tetraphenylethylene derivatives (TPEs) and nor-seco-cucurbit[10]uril (ns-Q[10]). Upon introduction of the dye Rhodamine B (RB) into the TPEs@ns-Q[10] assembly, an energy transfer process can occur from the TPEs@ns-Q[10] assembly to RB. Moreover, after the addition of Nile Red (NiR), a two-step sequential energy transfer process from the TPEs@ns-Q[10] assembly to RB and then to NiR can occur. Additionally, the dye Eosin Y (ESY) was introduced into the TPEs@ns-Q[10] assembly and an energy transfer process can take place from the TPEs@ns-Q[10] assembly to ESY. To utilize the harvested energy from the TPEs@ns-Q[10]-RB-NiR and TPEs@ns-Q[10]-ESY system, we applied the TPEs@ns-Q[10] assembly-based light-harvesting systems (LHSs) as a catalyst for the advancement of the photocatalytic dehalogenation reaction in aqueous solution. When promoted with 0.5 mol % catalyst, the reaction yield reached 78 and 68%, demonstrating the promising potential of TPEs@ns-Q[10] assembly-based LHSs in the promotion of the photocatalytic dehalogenation reaction.
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Double-cavity Q[n]s are relatively new members of the Q[n] family and have garnered significant interest due to their distinctive structures and novel properties. While they incorporate n glycoluril units, akin to their single-cavity counterparts, their geometry can best be described as resembling a figure-of-eight or a handcuff, distinguishing them from single-cavity Q[n]s. Despite retaining the core molecular recognition traits of single-cavity Q[n]s, these double-cavity variants introduce fascinating new attributes rooted in their distinct configurations. This overview delves into the synthesis, structural attributes, properties, and intriguing applications of double-cavity Q[n]s. Some of the applications explored include their role in supramolecular polymers, molecular machinery, supra-amphiphiles, sensors, artificial light-harvesting systems, and adsorptive separation materials. Upon concluding this review, we discuss potential challenges and avenues for future development and offer valuable insights for other scholars working in this area with the aim of stimulating further exploration and interest.
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Tyrosine kinase inhibitors (TKIs) are commonly used in tumor targeting therapy. However, the rapid analysis of TKIs remains a significant challenge, especially in complex biological fluid environments. In this work, we have constructed a supramolecular fluorescence sensor array based on a cucurbituril-dye host-guest complex. The binding affinity between the three complexes and each TKI is different, resulting in different cross-response signals of the complexes to the fluorescence of each TKI. Combined with linear discriminant analysis(LDA), five kinds of TKIs can be well identified. The supramolecular fluorescence sensor array could accurately identify and distinguish the five TKIs in water and could classify mixtures containing different concentrations of TKIs in serum. The concentration and Factor 1 exhibited a good linear relationship and the detection limit (LOD) was as low as 10-7 mol L-1. The method has good reproducibility and stability. In addition, the differentiation of four clinical concentrations of first-generation TKIs further validated the potential application of arrays in drug monitoring. Finally, our proposed array enabled drug imaging in living cells. Our array platform provided the foundation for the rapid and easy monitoring of 4-anilinoquinazoline TKIs.
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Monitoramento de Medicamentos , Reprodutibilidade dos Testes , Diferenciação Celular , Análise DiscriminanteRESUMO
The safe and efficient management of hazardous radioactive iodine is significant for nuclear waste reprocessing and environmental industries. A novel supramolecular framework compound based on cucurbit[8]uril (Q[8]) and 4-aminopyridine (4-AP) is reported in this paper. In the single crystal structure of Q[8]-(4-AP), two 4-AP molecules interact with the outer surface of Q[8] and the two other 4-AP molecules are encapsulated into the Q[8] cavity to form the self-assembly Q[8]-(4-AP). Iodine adsorption experiments show that the as-prepared Q[8]-(4-AP) not only has a high adsorption capacity (1.74 g· g-1) for iodine vapor but also can remove the iodine in the organic solvent and the aqueous solution with the removal efficiencies of 95% and 91%, respectively. The presence of a large number of hydrogen bonds between the iodine molecule and the absorbent, as seen in the single crystal structure of iodine-loaded Q[8]-(4-AP) (I2@Q[8]-(4-AP)), is thought to be responsible for the exceptional iodine adsorption capacity of the material. In addition, the adsorption-desorption tests reveal that the self-assembly material has no significant loss of iodine capture capacity after five cycles, indicating that it has sufficient reusability.
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The etiology of short stature is multifaceted and influenced by various potential factors including genetics,nutrition,endocrine and psychology. Research has shown that psychological factors can contribute to growth disorders,impacting the behavioral,emotional,and neuropsychological well-being of children with short stature. These growth disorders may lead to language problems,social disorders,etc. Additionally,physical limitations and environmental barriers can pose practical challenges in the daily lives of children with short stature,potentially leading to a decrease in their health-related quality of life(HrQoL). Moreover,growth disorders can increase parental care burden,further impacting their HrQoL. This article offers a literature review on the challenges faced by children with short stature and the neuropsychological implications of various types of short stature.
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Objective To investigate the efficacy and safety of Tubridge flow diverter(TFD)in the treatment of ruptured intracranial aneurysms.Methods The clinical data of 13 patients with aneurysmal subarachnoid hemorrhage,who received TFD treatment at the First Affiliated Hospital of Zhengzhou University between March 2019 and Jul 2022,were retrospectively collected.The perioperative materials and follow-up results were summarized and analyzed.Results Successful operation was accomplished in all the 13 patients(13 aneurysms in total).TFD and coil embolization were simultaneously performed in 10 patients(simultaneous treatment),spring coil filling followed by selective staged TFD placement was adopted in 2 patients(staged treatment),and pure TFD placement was employed in one patient.The incidence of perioperative complications was 15.4%(2/13),including asymptomatic ischemic event in one patient and extra-ventricular drainage-related postoperative bleeding in another patient,which caused death of the patient.The median follow-up time was 6.5 months,and 83.3%of patients(10/12)completed cerebral angiography reexamination with DSA.OKM grade D(complete occlusion of the aneurysm)was obtained in 8 patients(80%),and OKM grade C(residual aneurysm neck)in 2 patients.Conclusion For ruptured intracranial aneurysms,TFD implantation is a clinically feasible treatment with favorable safety and efficacy.
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AIM: To investigate the clinical features of acute exacerbation chronic obstructive pulmonary disease (AECOPD) of complicated with type 2 diabetes mellitus (T2DM), and analyze the related clinical features and risk factors. METHODS: This was a single-center cross-sectional study. From March 2020 to January 2023, 479 hospitalized patients with AECOPD in the department of respiratory and critical care medicine, Suining Central Hospital were included. There were 215 patients in AECOPD group and 60 patients in AECOPD with T2DM group. The collected variables included demographic data, complications, blood routine, infection index, random blood glucose, blood gas analysis and lung function. The adoption rate and constituent ratio of the basic description classification data were expressed as mean standard deviation for the normal distribution measurement data and median interquartile range for the skew distribution measurement data. T-test was used for normal distribution and non - parameter test was used for non-normal distribution. The categorical variables were tested by chi-square test. Rank sum test was used for rank variable data. Binary logistic regression model was used to investigate the independent factors associated with T2DM in patients with AECOPD. Finally, the results of logistic regression were verified and visualized by nomogram, validation curve, ROC curve and DCA curve. P0.05). The results of logistic regression were verified and visualized by Nomogram and its-associated ccurves. The MAE and AUC curves were 0.021 and 0.847 respectively, indicating that the model had good prediction consistency and accuracy. The DCA curve showed that Nomogram's risk threshold ranged from 0.01 to 0.99, suggesting that nomogram's model had better clinical predictive value. CONCLUSION: Our results showed that increased BMI, PaCO2 and random glucose, decreased blood lymphocyte, and atrial fibrillation is an independent clinical feature of AECOPD with T2DM. These results suggest that the immune function of patients with AECOPD and T2DM are more severely impaired and more likely to be accompanied by atrial fibrillation, which is a potential cause of poor prognosis in these patients. Meanwhile, this conclusion needs to be further verified in multicenter study with large sample size.
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Objective: Our previous studies have demonstrated that Plasmodium immunotherapy (infection) has antitumor effects in mice. However, as a new form of immunotherapy, this therapy has a weakness: its specific killing effect on tumor cells is relatively weak. Therefore, we tested whether Plasmodium immunotherapy combined with gemcitabine (Gem), a representative chemotherapy drug, has synergistic antitumor effects. Methods: We designed subcutaneously and intravenously implanted murine Lewis lung cancer (LLC) models to test the antitumor effect of Plasmodium chabaudi ASS (Pc) infection in combination with Gem treatment and explored its underlying mechanisms. Results: We found that both Pc infection alone and Gem treatment alone significantly inhibited tumor growth in the subcutaneous model, and combination therapy was more effective than either monotherapy. Monotherapy only tended to prolong the survival of tumor-bearing mice, while the combination therapy significantly extended the survival of mice, indicating a significant synergistic effect of the combination. In the mechanistic experiments, we found that the combination therapy significantly upregulated E-cadherin and downregulated Snail protein expression levels, thus inhibiting epithelial-mesenchymal transition (EMT) of tumor cells, which may be due to the blockade of CXCR2/TGF-ß-mediated PI3K/Akt/GSK-3ß signaling pathway. Conclusion: The combination of Pc and Gem plays a synergistic role in inhibiting tumor growth and metastasis, and prolonging mice survival in murine lung cancer models. These effects are partially attributed to the inhibition of EMT of tumor cells, which is potentially due to the blockade of CXCR2/TGF-ß-mediated PI3K/Akt/GSK-3ß/Snail signaling pathway. The clinical transformation of Plasmodium immunotherapy combined with Gem for lung cancer is worthy of expectation.
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Fluorescent carbon quantum dots (CQDs) were synthesized from cucurbit[7]uril (Q[7]) and 2,2-bis(hydroxymethyl)propionic (DMPA) by a hydrothermal method. The Q[7]-DMPA complex was confirmed by X-ray crystallography. The CQDs showed blue fluorescence, photostability, and ionic strength stability. They were used to detect histamine with a low limit of 2.33 × 10-6 M.
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Histamina , Pontos Quânticos , Carbono/química , Pontos Quânticos/química , Corantes Fluorescentes/químicaRESUMO
A white-light-emitting supramolecular complex through supramolecular interactions has been assembled; the white luminescent supramolecular complex exhibits two emission spectra. Based on this, a dual-channel white-light array sensor was constructed. The results show that it can quickly identify and detect nitroaniline isomer pollutants (p-nitroaniline, m-nitroaniline, o-nitroaniline). When these three nitroaniline isomers were added to the supramolecular white-light array sensor, the fluorescence intensity of the white-light complex decreased to varying degrees. Linear discriminant analysis (LDA) showed that the supramolecular white-light array sensor could recognize and distinguish three nitroaniline isomers and could classify mixtures containing different concentrations. Factor 1 of the array had a good linear relationship with the concentration of pollutants, and the detection limit (LOD) was as low as 0.7 µM. The method has good reproducibility and stability. In addition, it can also qualitatively detect the nitroaniline isomers in river water and contaminated rice seedling extract. It provides an ideal platform for constructing multiresponse sensors.
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The noble metal-based electrochemical sensor design for efficient and stable formaldehyde(FA) detection is important ongoing research. In this paper, PtPd/Nafion/GCE is prepared by electrochemical cyclic voltammetry deposition method based on electrodepositing nanostructured platinum (Pt)-palladium (Pd) nanoparticles in Nafion film-coated glassy carbon electrode (GCE). The influence of deposition parameters and chemical composition (atomic ratio of Pt and Pd) on the electrochemical behaviour of PtPd/Nafion/GCE has been investigated. PtPd/Nafion/GCE displays a remarked electrocatalytic activity for the oxidation of FA and exhibits a linear relationship in the range of 10-5000µM, with a detection limit of 3.3µM in 0.1 M H2SO4solution. It is proved that the detection performance of PtPd/Nafion/GCE electrode is valuable for further application with low detection limit, wide linear range, favourable selectivity and high response.
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The separation of phenylenediamine (PDA) isomers is crucial in the field of chemical manufacturing. Herein, we presented a strategy for the separation of PDA isomers (para-phenylenediamine, p-PDA; meta-phenylenediamine, m-PDA; ortho-phenylenediamine, o-PDA) using four supramolecular framework materials of ns-cucurbit[10]uril (ns-Q[10]), (1) ns-Q[10](Cd), (2) ns-Q[10](Mn), (3) ns-Q[10](Cu), (4) ns-Q[10](Pb). Our findings indicated that these supramolecular framework materials of ns-Q[10] showed remarkable selectivity for para-phenylenediamine (p-PDA) in p-PDA, m-PDA, and o-PDA mixtures, respectively. The variations in selectivity observed in these four single-crystal structures arose from variations in the thermodynamic stabilities and binding modes of the host-guest complexes. Importantly, the supramolecular framework based on ns-Q[10] exhibited selective accommodation of p-PDA over its isomers. This study highlighted the practical application of ns-Q[10] in effectively separating PDA isomers and demonstrated the potential utility of ns-Q[10] in isolating other organic molecules.
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BACKGROUND: For children with abdominal Henoch-Schonlein purpura presenting abdominal pain as an initial symptom and severe clinical manifestations, but without purpura appearance on the skin, the diagnosis and treatment are relatively difficult. This study summarized the characteristics of this group of patients by literature review and provided additional references for further refinement of glucocorticoid therapy in this vasculitis. CASE SUMMARY: A 6-year-old girl presented mainly with repeated abdominal pain and had received short-term out-of-hospital treatment with hydrocortisone. On day 7 after onset, gastroscopy revealed chronic non-atrophic gastritis and erosive duodenitis without purpuric rash, and no obvious resolution of the abdominal pain was found after treatment against infection and for protection of gastric mucosa. On day 14 the inflammatory indices continued to rise and the pain was relieved after enhanced anti-infective therapy, but without complete resolution. On day 19, the patient presented with aggravated abdominal pain with purplish-red dots on the lower limbs, by which Henoch-Schonlein purpura was confirmed. After 5 d of sequential treatment with methylprednisolone and prednisone, abdominal pain disappeared and she was discharged. CONCLUSION: Henoch-Schonlein purpura-related rash may appear after long-term abdominal pain, and should be distinguished from acute and chronic gastrointestinal diseases at the early stage without typical rash. For bacterial infection-induced Henoch-Schonlein purpura, glucocorticoid therapy alone without clearing the infection may not relieve symptoms.
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White light emitting materials have broad application prospects in fields such as displays, lighting devices, etc., but developing such materials faces considerable challenges. In this study, 1,3,5-tris[4-(pyridine-4-butyl)phenyl]benzene derivative (BTPY) was synthesized and a supramolecular assembly with AIE properties named BTPY@Q[7] was prepared with cucurbit[7]uril (Q[7]). Furthermore, by adding rhodamine 6G (R6G) to it, and controlling its ratio with R6G, a dual-emission white light system (0.33, 0.33) was synthesized and used for white light emitting materials as well as anti-counterfeiting fields. In addition, based on the BTPY@Q[7]-R6G system, a light harvesting system in aqueous phase was constructed, with an energy transfer efficiency (ΦET) of 26.19 % and an antenna effect (AE) of 10.21. Interestingly, the supramolecular self-assembly can also be used as a fluorescent probe, specifically recognize Fe(CN)63- ions in water, with a detection limit of 2.5 × 10-8 M.