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Anemarrhena asphodeloides is a common medicinal material used in clinical prescriptions and Chinese patent medicine. In this study, the Illumina platform was used to obtain the chloroplast genome sequences of seven kinds of A. asphodeloides from different areas. The specific DNA barcodes were screened by comparative genomics analysis, and the DNA barcodes were used to identify the germplasm resources and analyze the genetic diversity of A. asphodeloides samples from different areas in China. All the seven chloroplast genomes had a ring structure. The total length was 156 801-156 930 bp, and 113 genes were annotated, including 79 protein-coding genes, 30 tRNA genes, and four rRNA genes. The comparative genomics analysis showed that rps16, trnG-GCC, atpF, rpoB, ycf3, rpl16, ndhF, trnS-GCU_trnG-GCC, petN-psbM, and ndhF-rpl32 were potential candidates for specific DNA barcodes of A. asphodeloides. In this study, the second intron of ycf3 and atpF intron sequences with a sequence length of 700-800 bp and easy amplification were selected for polymerase chain reaction(PCR) amplification and sequencing of 594 samples from 26 areas. The sequence analysis showed that six and eight haplotypes of ycf3 and atpF sequences could be identified, respectively, and 17 haplotypes could be identified by combined analysis of the two sequences, which were named Hap1-Hap17. The haplotype diversity(H_d), nucleotide diversity(P_i), and genetic distance of A. asphodeloides in 26 populations were 0.68, 0.93×10~(-3), and 0-0.003 1, respectively, indicating that the genetic diversity within the species of A. asphodeloides is rich. The intermediary adjacent network analysis showed that Hap5 was the oldest haplotype, which was mainly distributed in Yixian county of Baoding, Hebei province, Hequ county of Xinzhou, Shanxi province, and Xiangfen county of Linfen, Shanxi province. This study has important guiding significance for the identification of A. asphodeloides species, the protection and development of germplasm resources, and the identification of production areas, and it provides a research basis for further revealing the genetic evolution law of A. asphodeloides.
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Anemarrhena , Anemarrhena/química , Código de Barras del ADN Taxonómico , Variación Genética , China , FilogeniaRESUMEN
The interaction between catalyst and support plays an important role in electrocatalytic hydrogen evolution (HER), which may explain the improvement in performance by phase transition or structural remodeling. However, the intrinsic behavior of these catalysts (dynamic evolution of the interface under bias, structural/morphological transformation, stability) has not been clearly monitored, while the operando technology does well in capturing the dynamic changes in the reaction process in real time to determine the actual active site. In this paper, nitrogen-doped molybdenum atom-clusters on Ti3 C2 TX (MoACs /N-Ti3 C2 TX ) is used as a model catalyst to reveal the dynamic evolution of MoAcs on Ti3 C2 TX during the HER process. Operando X-ray absorption structure (XAS) theoretical calculation and in situ Raman spectroscopy showed that the Mo cluster structure evolves to a 6-coordinated monatomic Mo structure under working conditions, exposing more active sites and thus improving the catalytic performance. It shows excellent HER performance comparable to that of commercial Pt/C, including an overpotential of 60 mV at 10 mA cm-2 , a small Tafel slope (56 mV dec-1 ), and high activity and durability. This study provides a unique perspective for investigating the evolution of species, interfacial migration mechanisms, and sources of activity-enhancing compounds in the process of electroreduction.
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This case report describes a 6-year-old girl who presented with symmetrical massive keratotic plaques on the palms, soles, and perioral area, as well as hair loss for 4 years.
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Queratodermia Palmoplantar , Humanos , Queratodermia Palmoplantar/diagnóstico , PielRESUMEN
BACKGROUND: The Makorin ring finger protein 1 (MKRN1) gene, also called RNF61, is located on the long arm of chromosome 7 and is a member of the RING finger protein family. The E3 ubiquitin ligase MKRN1 is closely linked to tumour development, but the exact mechanism needs to be elucidated. In this study, we aimed to investigate the specific mechanism and role of MKRN1 in colorectal cancer (CRC) development. METHODS: MKRN1 expression in CRC was analysed using the Cancer Cell Line Encyclopaedia and the Cancer Genome Atlas (TCGA) databases. Rectal tumour tissues were frozen to explore the MKRN1 expression in CRC and its clinical significance. The impact of MKRN1 on CRC cell proliferation and migration was observed using CCK8, colony formation, wound healing, and transwell assays. A combination of MKRN1 quantitative proteomics, ubiquitination modification omics analysis, and a string of in vitro and in vivo experiments revealed the potential mechanisms by which MKRN1 regulates CRC metastasis. RESULTS: MKRN1 expression was significantly elevated in CRC tissues compared to paracancerous tissues and was positively linked with prognosis (P < 0.01). MKRN1 downregulation inhibits CRC cell proliferation, migration, and invasion. Conversely, MKRN1 overexpression promotes the proliferation, migration, and invasion of CRC cells. Mechanistically, MKRN1 induces epithelial-mesenchymal transition (EMT) in CRC cells via ubiquitination and degradation of Smad nuclear-interacting protein 1 (SNIP1). Furthermore, SNIP1 inhibits transforming growth factor-ß (TGF-ß) signalling, and MKRN1 promotes TGF-ß signalling by degrading SNIP1 to induce EMT in CRC cells. Finally, using conditional knockout mice, intestinal lesions and metastatic liver microlesions were greatly reduced in the intestinal knockout MKRN1 group compared to that in the control group. CONCLUSIONS: High MKRN1 levels promote TGF-ß signalling through ubiquitination and degradation of SNIP1, thereby facilitating CRC metastasis, and supporting MKRN1 as a CRC pro-cancer factor. The MKRN1/SNIP1/TGF-ß axis may be a potential therapeutic target in CRC.
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Neoplasias Colorrectales , Proteínas de Unión al ARN , Ribonucleoproteínas , Animales , Ratones , Línea Celular , Proliferación Celular , Neoplasias Colorrectales/genética , Proteolisis , Humanos , Ribonucleoproteínas/metabolismo , Proteínas de Unión al ARN/genética , Factor de Crecimiento Transformador beta/metabolismo , Transducción de SeñalRESUMEN
Objective: To investigate the incidence of complications and types of chemoradiotherepy induces symptom clusters in patients with nasopharyngeal carcinoma (NPC) who were first diagnosed after treatment and discharged from hospital. Methods: After their discharge home, 130 NPC patients who had been treated with chemoradiotherapy were asked to complete a modified Chinese version of the Quality of Life Questionnaire-Head and Neck Module developed by the European Organization for the Research and Treatment of Cancer in the Head and Neck. Symptom clusters in patients were identified through exploratory factor analysis. Results: The most serious symptoms for discharged NPC patients who had received chemoradiotherapy were dental problems, a sense of obstruction while swallowing, embarrassment in physical contact with family members and friends, difficulty in speaking with others, and embarrassment in public. The six symptom clusters identified through exploratory factor analysis were (1) painful eating, (2) social difficulties, (3) psychological disorders, (4) symptomatic shame, (5) teeth/throat injuries, and (6) sensory abnormalities. The total contribution rate of variance was 65.73%. Conclusion: NPC patients who are treated with chemoradiotherapy can experience adverse symptom clusters that continue after discharge. Nurses should evaluate the patients' symptoms before discharge and provide targeted health education services which would reduce the patients' complications and improve the quality of life at home. Besides, medical staff should evaluate the complications in a timely and comprehensive manner and provide individualized health education for the affected patients to help them manage chemoradiotherapy side effects.
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Eleutherococcus senticosus is one of the Dao-di herbs in northeast China. In this study, the chloroplast genomes of three E. senticosus samples from different genuine producing areas were sequenced and then used for the screening of specific DNA barcodes. The germplasm resources and genetic diversity of E. senticosus were analyzed basing on the specific DNA barcodes. The chloroplast genomes of E. senticosus from different genuine producing areas showed the total length of 156 779-156 781 bp and a typical tetrad structure. Each of the chloroplast genomes carried 132 genes, including 87 protein-coding genes, 37 tRNAs, and 8 rRNAs. The chloroplast genomes were relatively conserved. Sequence analysis of the three chloroplast genomes indicated that atpI, ndhA, ycf1, atpB-rbcL, ndhF-rpl32, petA-psbJ, psbM-psbD, and rps16-psbK can be used as specific DNA barcodes of E. senticosus. In this study, we selected atpI and atpB-rbcL which were 700-800 bp and easy to be amplified for the identification of 184 E. senticosus samples from 13 genuine producing areas. The results demonstrated that 9 and 10 genotypes were identified based on atpI and atpB-rbcL sequences, respectively. Furthermore, the two barcodes identified 23 genotypes which were named H1-H23. The haplotype with the highest proportion and widest distribution was H10, followed by H2. The haplotype diversity and nucleotide diversity were 0.94 and 1.82×10~(-3), respectively, suggesting the high genetic diversity of E. senticosus. The results of the median-joining network analysis showed that the 23 genotypes could be classified into 4 categories. H2 was the oldest haplotype, and it served as the center of the network characterized by starlike radiation, which suggested that population expansion of E. senticosus occurred in the genuine producing areas. This study lays a foundation for the research on the genetic quality and chloroplast genetic engineering of E. senticosus and further research on the genetic mechanism of its population, providing new ideas for studying the genetic evolution of E. senticosus.
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Código de Barras del ADN Taxonómico , Eleutherococcus , Eleutherococcus/genética , Secuencia de Bases , Cloroplastos/genética , Variación Genética , FilogeniaRESUMEN
MiR-1283 has been identified as a tumor suppressor in some malignancies. Whereas, the role of miR-1283 in HER2-positive (HER2+) breast cancer, particularly its role in regulating cell proliferation, one of the most significant features of tumor progression, is unclear. The related microRNA screened by the breast cancer sample GSE131599 dataset were detected in HER2+ breast cancer tissues and cell lines. Then, the obtained miR-1283 was overexpressed in SKBR3 and BT-474 cells followed by relevant functional assays concerning cell proliferation and apoptosis. The xenograft mouse model was induced and the effect of miR-1283 on tumor growth and cell proliferation was examined. The target of miR-1283 and the transcription factor regulating miR-1283 were predicted and identified. Finally, the influence of transcription factor KLF14 on cell proliferation and apoptosis was investigated. An integrated analysis confirmed that miR-1283 expression was significantly decreased in HER2+ breast cancer tissues. Also, by q-RT-PCR detection, miR-1283 expression was markedly reduced in HER2+ breast cancer tissues and cell lines. The miR-1283 overexpression prevented the proliferation and enhanced apoptosis of HER2+ breast cancer cells, as well as inhibited tumor growth. Mechanistically, miR-1283 inhibited TFAP2C expression by targeting the 3'-untranslated regions of TFAP2C messenger RNA, and the KLF14 enhanced miR-1283 level via binding to its promoter. The result subsequently confirmed the KLF14/miR-1283 signaling suppressed cell proliferation in HER2+ breast cancer. Our results suggested that the KLF14/miR-1283/TFAP2C axis inhibited HER2+ breast cancer progression, which might provide novel insight into mechanical exploration for this disease.
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Neoplasias de la Mama , MicroARNs , Humanos , Animales , Ratones , Femenino , Línea Celular Tumoral , Neoplasias de la Mama/metabolismo , MicroARNs/metabolismo , Proliferación Celular/genética , Factores de Transcripción/genética , Regulación Neoplásica de la Expresión Génica , Factores de Transcripción de Tipo Kruppel/genética , Factores de Transcripción de Tipo Kruppel/metabolismo , Factor de Transcripción AP-2/genéticaRESUMEN
Introduction: ß-Glucosidase serves as the pivotal rate-limiting enzyme in the cellulose degradation process, facilitating the hydrolysis of cellobiose and cellooligosaccharides into glucose. However, the widespread application of numerous ß-glucosidases is hindered by their limited thermostability and low glucose tolerance, particularly in elevated-temperature and high-glucose environments. Methods: This study presents an analysis of a ß-glucosidase gene belonging to the GH1 family, denoted lqbg8, which was isolated from the metagenomic repository of Hehua hot spring located in Tengchong, China. Subsequently, the gene was cloned and heterologously expressed in Escherichia coli BL21(DE3). Post expression, the recombinant ß-glucosidase (LQBG8) underwent purification through a Ni affinity chromatography column, thereby enabling the in-depth exploration of its enzymatic properties. Results: LQBG8 had an optimal temperature of 70°C and an optimum pH of 5.6. LQBG8 retained 100 and 70% of its maximum activity after 2-h incubation periods at 65°C and 70°C, respectively. Moreover, even following exposure to pH ranges of 3.0-10.0 for 24 h, LQBG8 retained approximately 80% of its initial activity. Notably, the enzymatic prowess of LQBG8 remained substantial at glucose concentrations of up to 3 M, with a retention of over 60% relative activity. The kinetic parameters of LQBG8 were characterized using cellobiose as substrate, with Km and Vmax values of 28 ± 1.9 mg/mL and 55 ± 3.2 µmol/min/mg, respectively. Furthermore, the introduction of LQBG8 (at a concentration of 0.03 mg/mL) into a conventional cellulase reaction system led to an impressive 43.7% augmentation in glucose yield from corn stover over a 24-h period. Molecular dynamics simulations offered valuable insights into LQBG8's thermophilic nature, attributing its robust stability to reduced fluctuations, conformational changes, and heightened structural rigidity in comparison to mesophilic ß-glucosidases. Discussion: In summation, its thermophilic, thermostable, and glucose-tolerant attributes, render LQBG8 ripe for potential applications across diverse domains encompassing food, feed, and the production of lignocellulosic ethanol.
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BACKGROUND: Mediation is increasingly used for medical dispute resolution, and the particularity of such mediation necessitates specialized training. In response to the promotion of compulsory mediation ahead of a legislation in Taiwan, we invited experts with an interdisciplinary team to design a case-based mediator training workshop. Our study aimed to investigate the learning outcomes of trainees and analyze their perspectives. METHODS: We recruited 129 trainees of a non-probability convenience sample who served as mediators or have dealt with medical dispute-related cases to undergo 2.5 h of lectures (introduction; procedure; roles of two mediators; principles and techniques of mediation; dispute arrangement; and issue analysis) and 1.5 h of case-based exercises. An after-class survey was conducted using a 4-point Likert-type scale to evaluate trainees' viewpoints and learning outcomes. A total of 104 questionnaires were collected (response rate: 80.6%). RESULTS: The professions of the participants were medical (56%), law (16%), and administration and others (28%). Males considered the course more helpful (3.79 vs. 3.63, p = 0.053) and more important (3.88 vs. 3.74, p = 0.042) than did females. Participants with a legal background scored the highest in helpfulness (3.84), followed by medical (3.74) and administrative (3.63) professionals. Medical and administrative professionals scored the highest (3.85) and lowest (3.76), respectively, on importance. Respondents with more than 10 years (3.81) and less than 1 year (3.79) of experience produced higher scores in helpfulness. Respondents with 1-5 years of experience (3.68) were found to be less likely to agree with the practical importance of course content compared with other groups of trainees. Administrative professionals obtained the highest scores (89.68) in written examinations. CONCLUSIONS: There are variations in mediators' perspectives based on gender, occupation, and work experience. Our nationwide mediation training workshop can be utilized to cultivate capabilities of mediators for handling medical disputes to achieve the goal of non-litigation in medical disputes.
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Disentimientos y Disputas , Negociación , Masculino , Femenino , Humanos , Taiwán , Programas de Gobierno , GobiernoRESUMEN
The sensitivity and selectivity of electrochemical analysis are challenging due to the materials used for electrode modification as well as electrical conductivity, catalytic activity and recognition ability of the working electrode. In this work, a portable 3D-printed electrochemical electrode clamp was designed and applied in combination with the developed covalent organic framework (COF DQTP)-modified pencil graphite electrode (DQTP/PGE). The ß-ketoenamine-linked COF DQTP synthesized by 1,3,5-triformylphloroglucinol (TP) and 2,6-diaminoanthraquinone (DQ) through solvothermal method is a porous crystalline with excellent conductivity and large periodic π-arrays, coupled with commercial available pencil graphite electrode to fabricate a disposable sensor for simultaneous determination of environmental endocrine disruptors bisphenol A and bisphenol S. The DQTP/PGE sensor exhibited high electrical conductivity and catalytic activity, and a good linearity was obtained in a range of 0.5-30 µM for two bisphenols with a detection limit of 0.15 µM (S/N = 3). Moreover, the sensor showed a reproducible and stable response over one month with negligible interference, and an accepted recovery with real food packaging samples.
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Grafito , Estructuras Metalorgánicas , Compuestos de Bencidrilo , Electrodos , Fenoles , SulfonasRESUMEN
This study was designed to investigate the anti-inflammatory effects of volatile oil of Platycladus orientalis (L.) Franco leaves (VOPF) and the underlying molecular mechanisms by using the non-infectious inflammation rat models and infectious inflammation mouse models. Ear swelling and intraperitoneal capillary permeability in mice, and carrageenan-induced toe swelling and cotton ball-induced granuloma in rats were used to reveal anti-inflammatory effects of VOPF. Moreover, the lipopolysaccharide (LPS)-induced mouse model of acute lung injury was used to explore the anti-inflammatory mechanism of VOPF. The results showed that VOPF could significantly inhibit auricular swelling, intraperitoneal capillary permeability in mice, and reduce granuloma swelling and paw swelling in rats. Furthermore, it significantly alleviated the pathological damage of the lung tissue. In addition, VOPF could reduce the contents of IL-1ß and TNF-α and increase the content of IL-10 in the serum. It had little effect on the expression of p65 but reduced the phosphorylation level of p65 and IκB in NF-κB pathway. In conclusion, VOPF has anti-inflammatory effects and the mechanisms involve the down-regulation of the phosphorylation levels of p65 and IκB and blockage of the NF-κB signaling pathway.
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Antiinflamatorios/uso terapéutico , Proteínas I-kappa B/metabolismo , Aceites Volátiles/uso terapéutico , Aceites de Plantas/uso terapéutico , Factor de Transcripción ReIA/metabolismo , Animales , Antiinflamatorios/farmacología , Permeabilidad Capilar , Carragenina/toxicidad , Enfermedades del Oído/tratamiento farmacológico , Enfermedades del Oído/etiología , Edema/tratamiento farmacológico , Edema/etiología , Granuloma/tratamiento farmacológico , Granuloma/etiología , Proteínas I-kappa B/genética , Interleucinas/genética , Interleucinas/metabolismo , Lipopolisacáridos/toxicidad , Pulmón/efectos de los fármacos , Pulmón/metabolismo , Masculino , Aceites Volátiles/farmacología , Pinales/química , Hojas de la Planta/química , Aceites de Plantas/farmacología , Neumonía/tratamiento farmacológico , Neumonía/etiología , Ratas , Ratas Sprague-Dawley , Transducción de Señal , Factor de Transcripción ReIA/genética , Factor de Necrosis Tumoral alfa/genética , Factor de Necrosis Tumoral alfa/metabolismoRESUMEN
In this work, electro-enhanced solid-phase microextraction (EE-SPME) and covalent organic framework (COF) were adopted to improve the extraction efficiency. A conductive COF synthesized of 2,6-diaminoanthraquinone (DQ) and 1,3,5-triformylphloroglucinol (TP) was in situ bonded to the stainless steel wire via facile solution-phase approach and used as the EE-SPME fiber coating to preconcentrate a typical endocrine disruptor bisphenol A (BPA). Compared with conventional SPME, the DQTP bonded fiber coupled with EE-SPME device exhibited higher extraction efficiency and achieved extraction equilibrium within 10 min. The proposed approach based on EE-SPME and gas chromatography coupled with flame ionization detector gave a linear range of 0.05-10 µg mL-1 and detection limit of 3 µg L-1 (S/N = 3) with good precision (<6.7%) and reproducibility (<7.1%) spiked with 0.1, 0.5, 1.0 µg mL-1 BPA. Quantitative determination of BPA in extracts of food packagings (mineral water bottles, milk boxes and milk tea cups) was achieved with recoveries from 88.6 to 118.0%.
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Estructuras Metalorgánicas , Contaminantes Químicos del Agua , Adsorción , Compuestos de Bencidrilo , Límite de Detección , Fenoles , Reproducibilidad de los Resultados , Microextracción en Fase Sólida , Acero Inoxidable , Contaminantes Químicos del Agua/análisisRESUMEN
As a colorimetric and fluorescent turn-on sensor to Al3+, N'-(2-hydroxybenzylidene)isoquinoline-3-carbohydrazide (HL) has been easily synthesized. The fluorescence intensity increases by 273 times in the presence of Al3+ at 458 nm. Meanwhile, the experiment data indicate that the limit of detection for Al3+ is 1.11 × 10-9 M. Remarkably, the blue fluorescence signal of HL-Al3+ could be specially observed by the naked eye under UV light and is significantly different from those of other metal ions. Fluorescence switch based on the control of Al3+ and EDTA proved HL could act as a reversible chemosensor. According to ESI-MS result and the Job's plots, the 2:1 coordination complex formed by HL and Al3+ could be produced. Density functional theory calculations were performed to illustrate the structures of HL and complex. The cell imaging experiment indicates that HL can be applied for monitoring intracellular Al3+ levels in cells.
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Colorantes Fluorescentes , Bases de Schiff , Iones , Isoquinolinas , Espectrometría de FluorescenciaRESUMEN
A new acylhydrazine-derived Schiff base fluorescence probe DMI based on "ON-OFF-ON" fluorescence strategy was presented in this paper. Probe DMI could detect Cu2+ selectively and sensitively with dramatic fluorescence quenching in CH3OH-PBS (v/v = 3:7) mixed solution. Once the complex DMI-Cu2+ interacted with S2-, 10.67-folds fluorescence increase was induced via a displacement mechanism under the same experimental conditions. The corresponding detection limits for Cu2+ and S2- were calculated to be 1.52 × 10-8 M and 1.79 × 10-8 M, respectively. The structures of DMI and DMI-Cu2+ were systematically characterized by Job's plot analysis, ESI-MS, IR, X-ray diffraction and density functional theory calculations. Furthermore, fluorescence imaging in MCF-7 cells and zebrafish demonstrated the probe DMI could act as a useful tool to monitor and track intracellular Cu2+ and S2-, which was encouraged by remarkable fluorescence performance and low cytotoxicity. Importantly, the complex DMI-Cu2+ could be applied to detect corrupt blood samples, which could estimate the time of death.
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Colorantes Fluorescentes , Pez Cebra , Animales , Cobre , Humanos , Bases de Schiff , Espectrometría de FluorescenciaRESUMEN
Vegetables are easily contaminated by phthalate esters (PAEs) from the environment, agricultural films and fertilizers, affecting human health. In this paper, titanium dioxide (TiO2) nanotube arrays were prepared by electrochemical anodic oxidation on the surface of titanium wire. Covalent organic framework of TpBD was in situ bonded to the titanium wire via TiO2 nanotube arrays using monomers of 1,3,5-trimethylphloroglucinol (Tp) and benzidine (BD). The fabricated TpBD-TiO2 coated titanium wire was used as the solid-phase microextraction fiber to extract 11 PAEs in vegetable samples. Coupled with gas chromatography-tandem mass spectrometry (GC-MS/MS), the limits of detection for PAEs were from 0.001 (di-n-butyl phthalate) to 0.430 (butyl benzyl phthalate) µg/L (S/N = 3) and enrichment factors were between 226 (dimethyl phthalate) and 2154 (di-n-butyl phthalate). Our fabricated TpBD-TiO2 fiber can be used at least 150 times without significant loss of extraction efficiency (<4.8%). Quantitative determination of PAEs in vegetable samples (tomato, lettuce, cucumber) was achieved by standard addition.
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Ésteres/aislamiento & purificación , Contaminación de Alimentos/análisis , Ácidos Ftálicos/aislamiento & purificación , Microextracción en Fase Sólida/métodos , Titanio/análisis , Verduras/química , Ésteres/química , Cromatografía de Gases y Espectrometría de Masas/métodos , Límite de Detección , Estructuras Metalorgánicas/química , Ácidos Ftálicos/química , Microextracción en Fase Sólida/instrumentación , Espectrometría de Masas en Tándem/métodos , Titanio/químicaRESUMEN
The directing effect of coordinating ligands in the formation of uranium molecular complexes has been well established, but the role of counterions in metal-ligand interactions remains ambiguous and requires further investigation. In this work, we describe the targeted isolation, through the choice of alkali-metal ions, of a family of tetravalent uranium sulfates, showing the influence of the overall topology and, unexpectedly, the UIV nuclearity upon the inclusion of such countercations. Analyses of the structures of uranium(IV) oxo/hydroxosulfate oligomeric species isolated from consistent synthetic conditions reveal that the incorporation of Na+ and Rb+ promotes the crystallization of 0D discrete clusters with a hexanuclear [U6O4(OH)4(H2O)4]12+ core, whereas the larger Cs+ ion allows for the isolation of a 2D-layered oligomer with a less condensed trinuclear [U3(O)]10+ center. This finding expands the prevalent view that counterions play an innocent role in molecular complex synthesis, affecting only the overall packing but not the local oligomerization. Interestingly, trends in nuclearity appear to correlate with the hydration enthalpies of alkali-metal cations, such that the alkali-metal cations with larger hydration enthalpies correspond to more hydrated complexes and cluster cores. These findings afford new insights into the mechanism of nucleation of UIV, and they also open a new path for the rational design and synthesis of targeted molecular complexes.
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Three dinuclear lanthanide complexes, [Ln2(L)2(µ3-OAc)4(H2O)2]â 2H2O (Ln = La (1), Eu (2) and Dy (3), HL = N'-(2-hydroxybenzylidene) nicotinohydrazide), have been synthesized and characterized by IR, elemental analysis and X-ray single-crystal diffraction. Crystallographic study revealed that the representative complex 1 displays a discrete dinuclear structure with a distorted tricapped trigonal prismatic geometry around La(III) ion. The interaction of complexes 1-3 with CT-DNA was investigated by absorption spectra, fluorescence quenching and viscosity, which reveals that the complexes bind to CT-DNA with a moderate intercalative mode. The complexes exhibited obvious DNA cleavage activities in the presence of H2O2. All complexes could bind to human serum albumin (HSA) with medium affinity through static mode; thus, HSA could effectively transport complexes. Furthermore, three complexes exhibited specific cytotoxicity to A549 cancer cells in micromole magnitude than other cancer cells tested and less toxicity than cisplatin for normal human cells HUVEC, in which massive cell apoptosis was induced by complexes through producing DNA damage and suppressing DNA synthesis.Communicated by Ramaswamy H. Sarma.
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Antineoplásicos/síntesis química , Antineoplásicos/farmacología , ADN/metabolismo , Hidrazinas/farmacología , Elementos de la Serie de los Lantanoides/síntesis química , Elementos de la Serie de los Lantanoides/farmacología , Bases de Schiff/farmacología , Albúmina Sérica Humana/metabolismo , Animales , Antineoplásicos/química , Apoptosis/efectos de los fármacos , Bovinos , Ciclo Celular/efectos de los fármacos , Línea Celular Tumoral , Cristalografía por Rayos X , División del ADN , Humanos , Hidrazinas/síntesis química , Hidrazinas/química , Concentración 50 Inhibidora , Cinética , Elementos de la Serie de los Lantanoides/química , Conformación Molecular , Unión Proteica , Bases de Schiff/síntesis química , Bases de Schiff/química , Análisis Espectral , Termodinámica , ViscosidadRESUMEN
Phthalate esters (PAEs), a category of widely used plasticizers, are tend to migrate from plastic packaging to drinks. In this paper, we develop a simple and rapid coprecipitation method for synthesis of a magnetic covalent organic framework (COF) adsorbent. The fabricated COF-(TpBD)/Fe3O4 was applied to magnetic solid phase extraction (MSPE) of 15 phthalate esters (PAEs) for subsequent GC-MS/MS determination in beverage samples. The as-synthesized magnetic adsorbent exhibited great potential in PAEs analysis with a limit of detection of 15 PAEs ranged from 0.005 to 2.748⯵gâ¯L-1â¯(S/Nâ¯=â¯3). The intra-day and inter-day relative standard deviations (RSD) value of the PAEs were less than 8.8% and 9.9%, respectively. The adsorbent can be reused after washing with methanol. The developed method was successfully applied for the determination of trace PAEs in eight beverages with recoveries ranging from 79.3% to 121.8% and RSDs were less than 11.9%. This work provides a simple magnetization process, which facilitates the application of COFs for enrichment and separation of PAEs in beverages with different matrices.
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Bebidas/análisis , Ésteres/análisis , Óxido Ferrosoférrico/química , Contaminación de Alimentos/análisis , Estructuras Metalorgánicas/química , Ácidos Ftálicos/análisis , Adsorción , Óxido Ferrosoférrico/síntesis química , Cromatografía de Gases y Espectrometría de Masas/métodos , Límite de Detección , Fenómenos Magnéticos , Estructuras Metalorgánicas/síntesis química , Plastificantes/análisis , Extracción en Fase Sólida/métodos , Espectrometría de Masas en Tándem/métodosRESUMEN
Due to the increasing prevalence of multimorbidity, the percentage of heavy users of health care services increased rapidly. To contain inappropriate outpatient visits and improve better medication management of high utilizers, the National Health Insurance Administration in Taiwan launched a community pharmacist home visit (CPHV) project for high utilizers in 2010. We employed a natural experimental design to evaluate the preliminary effects of the CPHV project. The intervention group consisted of patients enrolled in the CPHV project during 2010 and 2013. Patients in the comparison group were non-enrollees selected via a propensity score matching technique. A difference-in-differences analysis was conducted by using multilevel models to examine the effects of the project. The average number of physician visits decreased from 130.0 to 98.9 visits (23.8%) among the CPHV project enrollees, while the average number decreased from 99.5 to 89.5 visits (10.1%) among the non-enrollees, with a net effect of a 21.0-visit reduction. The CPHV project also led to modest reductions in the number of medication items used per day, the probability of hospital admission and yearly healthcare expenses. The CPHV project seems promising for decreasing health care utilization and costs of the patients with high-needs.