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1.
Environ Sci Technol ; 2024 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-38639388

RESUMO

Microbial transformation of per- and polyfluoroalkyl substances (PFAS), including fluorotelomer-derived PFAS, by native microbial communities in the environment has been widely documented. However, few studies have identified the key microorganisms and their roles during the PFAS biotransformation processes. This study was undertaken to gain more insight into the structure and function of soil microbial communities that are relevant to PFAS biotransformation. We collected 16S rRNA gene sequencing data from 8:2 fluorotelomer alcohol and 6:2 fluorotelomer sulfonate biotransformation studies conducted in soil microcosms under various redox conditions. Through co-occurrence network analysis, several genera, including Variovorax, Rhodococcus, and Cupriavidus, were found to likely play important roles in the biotransformation of fluorotelomers. Additionally, a metagenomic prediction approach (PICRUSt2) identified functional genes, including 6-oxocyclohex-1-ene-carbonyl-CoA hydrolase, cyclohexa-1,5-dienecarbonyl-CoA hydratase, and a fluoride-proton antiporter gene, that may be involved in defluorination. This study pioneers the application of these bioinformatics tools in the analysis of PFAS biotransformation-related sequencing data. Our findings serve as a foundational reference for investigating enzymatic mechanisms of microbial defluorination that may facilitate the development of efficient microbial consortia and/or pure microbial strains for PFAS biotransformation.

2.
Sci Total Environ ; 927: 171883, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38531439

RESUMO

Aqueous film-forming foams (AFFFs) have been extensively used for extinguishing hydrocarbon-fuel fires at military sites, airports, and fire-training areas. Despite being a significant source of per- and polyfluoroalkyl substances (PFAS), our understanding of PFAS occurrence in AFFF formulations and AFFF-impacted environments is limited, as is the impact of microbial transformation on the environment fate of AFFF-derived PFAS. This literature review compiles PFAS concentrations in electrochemical fluorination (ECF)- and fluorotelomer (FT)-based AFFFs and provides an overview of PFAS occurrence in AFFF-impacted environments. Our analysis reveals that AFFF use is a predominant point source of PFAS contamination, including primary precursors (polyfluoroalkyl substances as AFFF components), secondary precursors (polyfluoroalkyl transformation products of primary precursors), and perfluoroalkyl acids (PFAAs). Moreover, there are discrepancies between PFAS concentration profiles in AFFFs and those measured in AFFF-impacted media. For example, primary precursors constitute 52.6 % and 99.5 % of PFAS mass in ECF- and FT-based AFFFs, respectively, whereas they represent only 0.7 % total mass in AFFF-impacted groundwater. Conversely, secondary precursors, which constitute <1 % of PFAS in AFFFs, represent 4.0-27.8 % of PFAS in AFFF-impacted environments. The observed differences in PFAS levels between AFFFs and environmental samples are likely due to in-situ biotransformation processes. Biotransformation rates and pathways reported for AFFF-derived primary and secondary precursors varied among different classes of precursors, consistent with the PFAS occurrence in AFFF-impacted environments. For example, readily biodegradable primary precursors, N-dimethyl ammonio propyl perfluoroalkane sulfonamide (AmPr-FASA) and n:2 fluorotelomer thioether amido sulfonate (n:2 FtTAoS), were rarely detected in AFFF-impacted environments. In contrast, key secondary precursors, perfluoroalkane sulfonamides (FASAs) and n:2 fluorotelomer sulfonate (n:2 FTS), were widely detected, which was attributed to their resistance to biotransformation. Key knowledge gaps and future research priorities are presented to better understand the occurrence, fate, and transport of AFFF-derived PFAS in the environment and to design more effective remediation strategies.

3.
Water Res ; 252: 121146, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38306753

RESUMO

Nearly all per- and polyfluoroalkyl substances (PFAS) biotransformation studies reported to date have been limited to laboratory-scale batch reactors. The fate and transport of PFAS in systems that more closely represent field conditions, i.e., in saturated porous media under flowing conditions, remain largely unexplored. This study investigated the biotransformation of 6:2 fluorotelomer sulfonate (6:2 FTS), a representative PFAS of widespread environmental occurrence, in one-dimensional water-saturated flow-through columns packed with soil obtained from a PFAS-contaminated site. The 305-day column experiments demonstrated that 6:2 FTS biotransformation was rate-limited, where a decrease in pore-water velocity from 3.7 to 2.4 cm/day, resulted in a 21.7-26.1 % decrease in effluent concentrations of 6:2 FTS and higher yields (1.0-1.4 mol% vs. 0.3 mol%) of late-stage biotransformation products (C4C7 perfluoroalkyl carboxylates). Flow interruptions (2 and 7 days) were found to enhance 6:2 FTS biotransformation during the 6-7 pore volumes following flow resumption. Model-fitted 6:2 FTS column biotransformation rates (0.039-0.041 cmw3/gs/d) were ∼3.5 times smaller than those observed in microcosms (0.137 cmw3/gs/d). Additionally, during column experiments, planktonic microbial communities remained relatively stable, whereas the composition of the attached microbial communities shifted along the flow path, which may have been attributed to oxygen availability and the toxicity of 6:2 FTS and associated biotransformation products. Genus Pseudomonas dominated in planktonic microbial communities, while in the attached microbial communities, Rhodococcus decreased and Pelotomaculum increased along the flow path, suggesting their potential involvement in early- and late-stage 6:2 FTS biotransformation, respectively. Overall, this study highlights the importance of incorporating realistic environmental conditions into experimental systems to obtain a more representative assessment of in-situ PFAS biotransformation.


Assuntos
Fluorocarbonos , Microbiota , Poluentes Químicos da Água , Fluorocarbonos/análise , Biotransformação , Alcanossulfonatos/metabolismo , Água , Poluentes Químicos da Água/análise
4.
Water Res ; 249: 120941, 2024 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-38070347

RESUMO

Although 6:2 fluorotelomer sulfonate (6:2 FTS) is a common ingredient in aqueous film-forming foam (AFFF) formulations, its environmental fate at AFFF-impacted sites remains poorly understood. This study investigated the biotransformation of 6:2 FTS in microcosms prepared with soils collected from two AFFF-impacted sites; the former Loring Air Force Base (AFB) and Robins AFB. The half-life of 6:2 FTS in Loring soil was 43.3 days; while >60 mol% of initially spiked 6:2 FTS remained in Robins soil microcosms after a 224-day incubation. Differences in initial sulfate concentrations and the depletion of sulfate over the incubation likely contributed to the different 6:2 FTS biotransformation rates between the two soils. At day 224, stable transformation products, i.e., C4C7 perfluoroalkyl carboxylates, were formed with combined molar yields of 13.8 mol% and 1.2 mol% in Loring and Robins soils, respectively. Based on all detected transformation products, the biotransformation pathways of 6:2 FTS in the two soils were proposed. Microbial community analysis suggests that Desulfobacterota microorganisms may promote 6:2 FTS biotransformation via more efficient desulfonation. In addition, species from the genus Sphingomonas, which exhibited higher tolerance to elevated concentrations of 6:2 FTS and its biotransformation products, are likely to have contributed to 6:2 FTS biotransformation. This study demonstrates the potential role of biotransformation processes on the fate of 6:2 FTS at AFFF-impacted sites and highlights the need to characterize site biogeochemical properties for improved assessment of 6:2 FTS biotransformation behavior.


Assuntos
Fluorocarbonos , Poluentes Químicos da Água , Solo/química , Fluorocarbonos/análise , Biotransformação , Alcanossulfonatos/análise , Alcanossulfonatos/metabolismo , Água/análise , Sulfatos , Poluentes Químicos da Água/análise
5.
Am J Cardiol ; 203: 193-202, 2023 09 15.
Artigo em Inglês | MEDLINE | ID: mdl-37499599

RESUMO

Intravascular ultrasound (IVUS)-guided percutaneous coronary intervention (PCI) has been reported to significantly reduce major adverse cardiac events (MACEs) compared with angiography-guided PCI. We aimed to explore whether there were racial differences regarding the beneficial effects of IVUS-guided PCI. Randomized controlled trials for comparison of clinical outcomes between IVUS-guided and angiography-guided PCI were retrieved from PubMed, Web of Science, Embase, and the Cochrane Library from inception to March 15, 2023. The clinical outcomes included MACE, all-cause mortality, myocardial infarction (MI), target vessel revascularization (TVR), target lesion revascularization (TLR), and stent thrombosis (ST). Finally, 18 randomized controlled trials were included in this study (8 in East Asian patients and 10 in Western patients). Results showed that IVUS-guided PCI was associated with a significant reduction of MACE, TVR, TLR, and ST, but not all-cause mortality and MI in both East Asian and Western patients. The reduction of MACE was more significant in East Asian patients (odds ratio [OR] 0.57, 95% confidence interval [CI] 0.46 to 0.70) than that in Western patients (OR 0.83, 95% CI 0.67 to 1.02). Meta-regression analysis revealed that the country the study was performed in (East Asian vs Western countries) was associated with significant heterogeneity between groups, suggesting that racial differences existed (p = 0.033). In conclusion, IVUS-guided PCI was associated with a lower risk of MACE, TLR, TVR, and ST, but not all-cause mortality and MI in both East Asians and Westerners. East Asians benefited more than Westerners upon using IVUS-guided PCI in reducing MACE, suggesting that racial differences do exist between different imaging methods. Larger-sample studies are warranted for further clarification of our findings.


Assuntos
Doença da Artéria Coronariana , Stents Farmacológicos , Infarto do Miocárdio , Intervenção Coronária Percutânea , Trombose , Humanos , Doença da Artéria Coronariana/diagnóstico , Doença da Artéria Coronariana/cirurgia , Doença da Artéria Coronariana/complicações , Intervenção Coronária Percutânea/métodos , Angiografia Coronária/métodos , Fatores Raciais , Stents Farmacológicos/efeitos adversos , Resultado do Tratamento , Ultrassonografia de Intervenção/métodos , Infarto do Miocárdio/cirurgia , Infarto do Miocárdio/etiologia , Trombose/etiologia , Ensaios Clínicos Controlados Aleatórios como Assunto
6.
J Hazard Mater ; 446: 130629, 2023 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-36630879

RESUMO

Production of 8:2 fluorotelomer alcohol (8:2 FTOH) for industrial and consumer products, including aqueous film-forming foams (AFFFs) used for firefighting, has resulted in its widespread occurrence in the environment. However, the fate of 8:2 FTOH at AFFF-impacted sites remains largely unknown. Using AFFF-impacted soils from two United States Air Force Bases, microcosm experiments evaluated the aerobic biotransformation of 8:2 FTOH (extent and byproduct formation) and the dose-response on microbial communities due to 8:2 FTOH exposure. Despite different microbial communities, rapid transformation of 8:2 FTOH was observed during a 90-day incubation in the two soils, and 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were detected as major transformation products. Novel transformation products, including perfluoroalkane-like compounds (1H-perfluoroheptane, 1H-perfluorohexane, and perfluoroheptanal) were identified by liquid chromatography-high resolution mass spectrometry (LC-HRMS) and used to develop aerobic 8:2 FTOH biotransformation pathways. Microbial community analysis suggests that species from genus Sphingomonas are potential 8:2 FTOH degraders based on increased abundance in both soils after exposure, and the genus Afipia may be more tolerant to and/or involved in the transformation of 8:2 FTOH at elevated concentrations. These findings demonstrate the potential role of biological processes on PFAS fate at AFFF-impacted sites through fluorotelomer biotransformation.


Assuntos
Fluorocarbonos , Microbiota , Fluorocarbonos/análise , Biotransformação , Hidrocarbonetos Fluorados/análise , Cromatografia Líquida
7.
Environ Sci Technol ; 56(19): 13728-13739, 2022 10 04.
Artigo em Inglês | MEDLINE | ID: mdl-36127292

RESUMO

The environmental fate of per- and polyfluoroalkyl substances (PFAS) in aqueous film-forming foams (AFFFs) remains largely unknown, especially under the conditions representative of natural subsurface systems. In this study, the biotransformation of 8:2 fluorotelomer alcohol (8:2 FTOH), a component of new-generation AFFF formulations and a byproduct in fluorotelomer-based AFFFs, was investigated under nitrate-, iron-, and sulfate-reducing conditions in microcosms prepared with AFFF-impacted soils. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) and high-resolution mass spectrometry (HRMS) were employed to identify biotransformation products. The biotransformation was much slower under sulfate- and iron-reducing conditions with >60 mol % of initial 8:2 FTOH remaining after ∼400 days compared to a half-life ranging from 12.5 to 36.5 days under nitrate-reducing conditions. Transformation products 8:2 fluorotelomer saturated and unsaturated carboxylic acids (8:2 FTCA and 8:2 FTUA) were detected under all redox conditions, while 7:2 secondary fluorotelomer alcohol (7:2 sFTOH) and perfluorooctanoic acid (PFOA) were only observed as transformation products under nitrate-reducing conditions. In addition, 1H-perfluoroheptane (F(CF2)6CF2H) and 3-F-7:3 acid (F(CF2)7CFHCH2COOH) were identified for the first time during 8:2 FTOH biotransformation. Comprehensive biotransformation pathways for 8:2 FTOH are presented, which highlight the importance of accounting for redox condition and the related microbial community in the assessment of PFAS transformations in natural environments.


Assuntos
Fluorocarbonos , Álcoois/metabolismo , Biotransformação , Cromatografia Líquida , Ferro , Nitratos , Compostos Orgânicos , Solo , Sulfatos , Espectrometria de Massas em Tandem , Água
8.
Bosn J Basic Med Sci ; 19(4): 375-383, 2019 Nov 08.
Artigo em Inglês | MEDLINE | ID: mdl-31202257

RESUMO

We evaluated characteristics and different prognostic factors for survival in age-stratified high-grade glioma in a U.S. cohort. Eligible patients were identified in the Surveillance, Epidemiology, and End Results (SEER) registries and stratified into 3 age groups: 20-39 years old (1,043 patients), 40-59 years old (4,503 patients), and >60 years old (5,045 patients). Overall and cancer-related survival data were obtained. Cox models were built to analyze the outcomes and risk factors. It showed that race was a prognostic factor for survival in patients 40 to 59 years old and in patients ≥60 years old. Partial resection was associated with lower overall survival and cause-specific survival in all age groups (overall survival: 20-39 yr: HR = 6.41; 40-59 yr: HR = 4.84; >60 yr: HR = 5.06; cause-specific survival: 20-39 yr: HR = 5.87; 40-59 yr: HR = 4.01; >60 yr: HR = 3.36). The study highlights that, while some prognostic factors are universal, others are age-dependent. The effectiveness of treatment approaches differs for patients in different age groups. Results of this study may help to develop personalized treatment protocols for glioma patients of different ages.


Assuntos
Neoplasias Encefálicas/diagnóstico , Neoplasias Encefálicas/epidemiologia , Glioma/diagnóstico , Glioma/epidemiologia , Adulto , Fatores Etários , Idoso , Feminino , Geografia , Humanos , Incidência , Masculino , Pessoa de Meia-Idade , Prognóstico , Modelos de Riscos Proporcionais , Sistema de Registros , Estudos Retrospectivos , Fatores de Risco , Programa de SEER , Resultado do Tratamento , Estados Unidos , Adulto Jovem
9.
Dalton Trans ; 48(13): 4324-4332, 2019 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-30860232

RESUMO

A series of dinuclear dysprosium complexes bridged by pyridine-NO ligands with formula [Ln2(BTA)6(pyNO)2] (1Dy, Ln = Dy, 1Y, Ln = Y and 1Gd, Ln = Gd) (BTA = benzoyltrifluoroacetone, pyNO = pyridine-N-oxide) were structurally and magnetically characterized. The X-ray crystallographic analyses of the structures revealed that the NO group serves as the effective bridge to link two Dy(iii) centers and the periphery ß-diketonate (BTA) ligands complete the rest of the coordination sphere. The dynamic magnetic measurements revealed that complex 1Dy displayed significant zero-field single-molecule magnetic (SMM) behaviour with 72 K energy barrier and 2.5 K hysteresis temperature. In order to extend this dinuclear system, double N-oxide bridged ligand 4,4'-bpdo(4,4'-bipyridine-N,N'-dioxide) was used, and consequently, a series of one-dimensional chain complexes possessing repeated [Ln2(BTA)6(pyNO)2] units were synthesized with formula [Ln2(BTA)6(4,4'-bpdo)]n·2EtOH (2Dy, Ln = Dy, 2Y, Ln = Y and 2Gd, Ln = Gd). The AC magnetic susceptibility measurements revealed that complex 2Dy exhibited significant zero-field slow magnetic relaxation behavior with a higher effective energy barrier of 87 K and a hysteresis temperature of 3 K than 1Dy albeit the separation between the repeated units is large.

10.
Environ Sci Pollut Res Int ; 26(1): 577-585, 2019 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-30411288

RESUMO

In response to the shortage of water resources, multiple processes have been applied to turn wastewater secondary effluent (SE) into potable water. However, trace organic contaminants (TOrCs) and high concentrations of organic matter contained in SE pose a significant challenge to the reclamation. In this manuscript, combined UV-based and biofilm processes were used to treat the SE spiked with ibuprofen (IBU) and clofibric acid (CA). The efficiency of these sequential treatments was characterized in terms of changes in dissolved organic carbon (DOC), absorbance at 254 nm (A254), fluorescence excitation-emission matrix (FEEM), the concentration of IBU and CA, and molecular weight of SE. Parallel factor (PARAFAC) was applied as the analysis method for FEEM of the samples and two fluorescent components were successfully identified: humic-like substances (C1) and protein-like matter (C2). Large reductions in A254, C1, C2, IBU, and CA were observed during the UV-based processes, especially with the addition of H2O2. Nearly 50% of A254, 80% of the component C1 were decreased and almost complete removal of the component C2 and TOrCs was achieved by UV/2.0 mM H2O2 after 90-min treatment. During the oxidation processes, the formation of lower molecular weight (LMW) compounds was detected, and the biodegradability of the organic matters was greatly increased. Although no significant DOC reduction was obtained in UV-based processes, an obvious further DOC reduction (30~60%) was achieved by biofilm treatment following UV-based processes, especially after UV/H2O2 treatments. In the meantime, large amounts of LMW were removed in the biofilm treatment process. This manuscript provides an effective advanced treatment of SE for the removal of DOC and TOrCs, facilitating the wastewater reclamation.


Assuntos
Biofilmes , Peróxido de Hidrogênio/química , Eliminação de Resíduos Líquidos/métodos , Biodegradação Ambiental , Água Potável/análise , Peróxido de Hidrogênio/análise , Peso Molecular , Compostos Orgânicos/análise , Oxirredução , Águas Residuárias/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos
11.
Clin Neurol Neurosurg ; 173: 84-90, 2018 10.
Artigo em Inglês | MEDLINE | ID: mdl-30092408

RESUMO

OBJECTIVES: To investigate the diagnostic value of magnetic resonance imaging (MRI)-based 3D texture and shape features in the differentiation of glioblastoma (GBM) and primary central nervous system lymphoma (PCNSL). PATIENTS AND METHODS: A total of eighty-two patients, including sixty patients with GBM and twenty-two patients with PCNSL were followed up retrospectively from January 2012 to September 2017. MRI-based 3D texture and shape analysis were performed to evaluate the detectable differences between the two malignancies. The performance of machine-learning models was assessed. The Mann-Whitney U test and receiver operating characteristic (ROC) analysis were performed, and the corresponding sensitivity, specificity, accuracy, and area under the curve (AUC) were calculated. Ultimately, 60 GBM patients (33 males, 27 females; mean age 51.55 ± 13.58 years, range 8-74 years) and 22 PCNSL patients (14 males, 8 females; mean age 55.18 ± 12.19 years, range 32-78 years) were included in this study. All the PCNSLs were of the diffuse large B-cell type, and all patients were immunocompetent. RESULTS: The variables Firstorder_Skewness, Firstorder_Kurtosis, and Ngtdm_Busyness, representing features extracted from contrast-enhanced T1-weighted images, showed high discriminatory power. Firstorder_ Skewness was the best selected predictor for classification (AUC = 0.86), followed by Ngtdm_Busyness (AUC = 0.83) and Firstorder_Kurtosis (AUC = 0.80). The sensitivities and specificities ranged from 70.0% to 83.3% and from 71.4% to 90.5%, respectively. Among three classification models, the naive Bayes classifier was superior overall, with a high AUC (0.90) and the best specificity (0.91). The support vector machine models provided the best sensitivity and accuracy (0.92 and 0.88, respectively). CONCLUSIONS: MRI-based 3D texture analysis has potential utility for preoperative discrimination of GBM and PCNSL.


Assuntos
Neoplasias do Sistema Nervoso Central/patologia , Glioblastoma/diagnóstico , Glioblastoma/patologia , Linfoma/patologia , Adolescente , Adulto , Idoso , Diferenciação Celular/fisiologia , Neoplasias do Sistema Nervoso Central/diagnóstico , Criança , Diagnóstico Diferencial , Feminino , Humanos , Linfoma/diagnóstico , Imageamento por Ressonância Magnética/métodos , Masculino , Pessoa de Meia-Idade , Sistema Nervoso/diagnóstico por imagem , Curva ROC , Sensibilidade e Especificidade , Adulto Jovem
12.
Huan Jing Ke Xue ; 39(4): 1840-1850, 2018 Apr 08.
Artigo em Chinês | MEDLINE | ID: mdl-29965011

RESUMO

Anthropic activities lead to a high risk of peatland degradation in the alpine regions. Along with the declined plant productivity and the impaired functioning of the soil carbon sink, the diversity and structure of soil microbial communities are also affected in a degraded peatland ecosystem. Tibetan pig herding is a unique peatland management strategy, which can significantly affect the peatland ecosystem, but it has been rarely studied. The changes in the microbial community structure and its responses to disturbances were studied using a 16S rRNA high throughput sequencing technique in an alpine meadow peatland under Tibetan pig herding disturbance and under control (without Tibetan pig herding) in the Northwestern Yunnan province. The results showed that Tibetan pig herding significantly reduced the α diversity of soil microbes, and the soil microbial community structures were significantly changed by pig herding. The soil microbial communities in the peatland soils were dominated by Proteobacteria, Acidobacteria, and Chloroflexi. Compared with those at the phylum level, the changes at the genus level under pig disturbance were more obvious. It was seen that the relative abundances of Sphingomonas and Hymenobacter significantly increased, while the abundances of Nitrospira and Rhodoplanes significantly decreased under pig herding. Venn diagram analysis revealed that there were 71 and 136 core OTUs in the soil under pig herding and in the control group soil, respectively. Burkholderiales, Pseudomonadales, and Sphingomonadales were the main taxa exclusively found under Tibetan pig herding, and could serve as indicators of soil disturbance. CCA ordination further showed that the distribution of Nitrospira and Rhodoplanes were mainly controlled by soil moisture, available phosphorus, and organic matter contents. Our findings provide an insight into the linkages between the soil microbial communities and the degradation of peatlands in alpine regions.


Assuntos
Bactérias/classificação , Pradaria , Microbiologia do Solo , Suínos , Animais , RNA Ribossômico 16S/genética , Solo , Tibet
13.
Inorg Chem ; 57(14): 8065-8077, 2018 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-29965732

RESUMO

A series of Salen-type Zn(II)-Dy(III) complexes [L1Zn(II)ClDy(III)(acac)2]·H2O (1), [L1Zn(II)BrDy(III)(acac)2]·H2O (2), [L1Zn(II)(H2O)Dy(III)(acac)2]·CH2Cl2·PF6 (3), [L2Zn(II)(H2O)Dy(III)(acac)2]·PF6 (4), and Co(III)-Dy(III) complexes [L1Co(III)Br2Dy(III)(acac)2]·CH2Cl2 (5), [L2Co(III)Cl2Dy(III)(acac)Cl(MeO)] (6), [L2Co(III)Cl2Dy(III)(acac)Cl(H2O)] (7), and [L2Co(III)Cl2Dy(III)(NO3)2(MeO)] (8) heterobinuclear single-molecule magnets (SMMs) were synthesized and magnetically characterized. These complexes were constructed by incorporating diamagnetic Zn(II) and Co(III) ions with acetylacetone (acac) and compartmental Schiff-base ligands (H2L1 = N, N'-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine; H2L2 = N, N'-bis(2-oxy-3-methoxybenzylidene)-1,2-diaminocyclohexane). In the Zn(II)-Dy(III) (1-4) system, the coordination environments of the Dy(III) ions are nearly identical, but the apical coordination atom to the Zn(II) ion is different. Complexes 1, 2, and 4 displayed no magnetic relaxation in the absence of external magnetic field, but complex 3 displayed more pronounced SMM behavior with a relaxation energy barrier Ueff/ kB 38 K and magnetic hysteresis at 1.8 K. The SMM performances of 5, 6, and 7 were enhanced significantly by incorporating an octahedral Co(III) instead of square-pyramidal Zn(II) and replacing one of acac- group around Dy(III) ion by a neutral O atom, displaying Ueff of 167, 118, and 75 K as well as magnetic hysteresis up to 3.5 K. These studies indicated that the remote diamagnetic Zn(II) and Co(III) ions played a key role, and the SMM properties were very strongly related to the special coordination atoms configuration around Dy(III) ion. When this coordination configuration around was broken as 8 exhibited, however, it resulted in a dramatically decreased SMM performance. From this work, the key factors that significantly affect the SMM performance of these heteronuclear Zn(II)/Co(III)-Dy(III) SMMs are unambiguously presented.

14.
Ying Yong Sheng Tai Xue Bao ; 29(2): 474-482, 2018 Feb.
Artigo em Chinês | MEDLINE | ID: mdl-29692061

RESUMO

With litter bag methods, we examined mass loss rates and different chemical fractions of litters from two wetland plant species, Zizania caduciflora and Hippuris vulgaris. Those two species examined here varied significantly in their initial litter chemical traits. Experiment was performed under simulated rising temperature (1.5-2.0 ℃), and under three different habitats (air, air-water interface and water-soil interface). The results showed that, during one-year decomposition period, the mass resi-dual rates exhibited distinct seasonal dynamics, and there were strong interactive effects between seasonal dynamics and environmental factors. Different factors contributed differently for the variation of litter decomposition, 28.8% of which being explained by litter quality, 6.3% of which being explained by rising temperature, and 34.9% being explained by habitat. Along with the decomposition, the contents of different chemical fractions (easy or hard to decompose) varied greatly. Among them, nitrogen contents in H. vulgaris decreased by 53.1%, while the lignin contents increased by 45.4%. Overall, habitat was the most important factor driving litter decomposition, the second was litter quality, and rising temperature had minor effect.


Assuntos
Folhas de Planta , Temperatura , Ecossistema , Nitrogênio , Solo
15.
Chem Asian J ; 13(13): 1725-1734, 2018 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-29663704

RESUMO

Crystal structures, single-molecule magnetic behavior, and ab initio calculations of four new phenoxo-bridged dinuclear dysprosium complexes and their gadolinium(III) analogues are explored. Complexes [Dy2 (DMOMP)2 (DBM)4 ]2 ⋅CHCl3 (1; DMOMP=1-methyl-3,5-dimethoxy-4-hydroxybenzene, DBM=1,3-diphenylpropane-1,3-dione); [Dy2 (DMOAP)2 (DBM)4 ]2 ⋅CHCl3 (2; DMOAP=syringaldehyde); Dy2 (DMOEP)2 (DBM)4 (3; DMOEP=methyl syringate); and solvent-free Dy2 (DMOMP)2 (DBM)4 (4), which is obtained by the transformation of single crystal into single crystal from 1, have nearly identical core structures and only differ in the substituents at the para position of the phenol moieties of the bridging ligand. In this system, the electronic effects are efficiently implemented to significantly modify the ligand field strength and exchange coupling by modulating the substituents on the phenol backbone. The effective energy barrier (Ueff ) of magnetization reversal is improved significantly to fivefold magnitude, at most, and the hysteresis temperature up to 3.5 K by deliberately using the electron-withdrawing substituent to replace the electron-donating one. The origin of the two relaxation processes in 1 is mostly attributed to the existence of two molecules in one unit, which is illuminated by means of the transformation of single crystal into single crystal.

16.
J Neurol ; 265(6): 1259-1268, 2018 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-29383514

RESUMO

OBJECTIVE: This systematic review and meta-analysis was performed to investigate the efficacy and safety of transcatheter device closure (TDC) plus anti-thrombotic drugs over medical management alone for patients with cryptogenic stroke and patent foramen oval. METHODS: PubMed, Embase and Cochrane Library database were searched for randomized controlled clinical trials (RCTs). The primary endpoint is the composite of stroke and transient ischemic attack. The secondary endpoints are all-cause mortality, total serious adverse events, atrial fibrillation and bleeding. RESULTS: Five RCTs with a total of 3440 participants were included. TDC significantly decreased the risk of primary endpoint when compared to medical therapy alone (RR 0.54, 95% CI 0.43-0.69). Further subgroup analyses showed that patients with male gender and with substantial shunt size of foramen ovale significantly benefited from TDC as compared to those with female gender and with no substantial shunt size of foramen oval separately. Moreover, TDC was superior to medical therapy with anti-platelet drug alone (not with anti-coagulation). On the other hand, the incidence of atrial fibrillation was higher in TDC group (RR 4.49, 95% CI 2.02-9.97), with the risk of other adverse events equivalent between the two groups. CONCLUSIONS: TDC plus anti-thrombotic drugs is superior than medical therapy alone for secondary prevention of stroke, especially for those with male gender and with substantial shunt size of foramen ovale. Though it may increase the risk of postoperative atrial fibrillation, it would not bring higher risk of all-cause mortality, total adverse events and bleeding.


Assuntos
Fibrinolíticos/uso terapêutico , Forame Oval Patente/complicações , Forame Oval Patente/cirurgia , Acidente Vascular Cerebral/complicações , Acidente Vascular Cerebral/tratamento farmacológico , Forame Oval Patente/tratamento farmacológico , Humanos , Ensaios Clínicos Controlados Aleatórios como Assunto , Prevenção Secundária , Acidente Vascular Cerebral/prevenção & controle , Acidente Vascular Cerebral/cirurgia
17.
Transl Oncol ; 10(4): 570-577, 2017 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-28654820

RESUMO

OBJECT: Preoperative knowledge of meningioma grade is essential for planning treatment and surgery. The purpose of this study was to investigate the diagnostic value of MRI texture and shape analysis in grading meningiomas. METHODS: A surgical database was reviewed to identify meningioma patients who had undergone tumor resection between January 2015 and December 2016. Preoperative MR images were retrieved and analyzed. Texture and shape analysis was conducted to quantitatively evaluate tumor heterogeneity and morphology. Three machine learning classifiers were trained with these features to build classification models. The performance of the features and classification models was assessed. RESULTS: A total of 131 patients were included in this study: 21 with high-grade meningiomas and 110 with low-grade meningiomas. Three texture features were selected: Horzl_RLNonUni, S(2,2)SumOfSqs, and WavEnHL_s-3; three shape features were selected: GeoFv, GeoW4, and GeoW5b. The Mann-Whitney test indicated that all six features were significantly different between high-grade and low-grade meningiomas. AUC values were generally greater than 0.50 (range, 0.73 to 0.88). Sensitivities and specificities ranged from 47.62% to 90.48% and 69.09% to 96.36%, respectively. Among the nine classification models obtained, the one built by training the SVM classifier with all six features achieved the best performance, with a sensitivity, specificity, diagnostic accuracy, and AUC of 0.86, 0.87, 0.87, and 0.87, respectively. CONCLUSIONS: Texture and shape analysis, especially when combined with a SVM classifier, can provide satisfactory performance in the preoperative determination of meningioma grade and is thus potentially useful for clinical application.

18.
Dalton Trans ; 46(25): 8259-8268, 2017 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-28613300

RESUMO

The synthesis, structural characterization and magnetic properties of four heterometallic complexes with formulas Ln2M(OQ)8 [Ln(iii) = Dy, M(ii) = Ca (1), Mg (2); Ln(iii) = Er, M(ii) = Ca (3), Mg (4); HOQ = 8-hydroxyquinoline] are reported. Complexes display a perfectly linear arrangement of three metal ions involving two terminal Ln(iii) ions and one central alkaline earth M(ii) ion, and they are bridged by three phenolato oxygen atoms from three 8-hydroxyquinoline ligands. Direct-current (dc) magnetic susceptibility studies show that there exists a long-range ferromagnetic (FM) interaction between two f-electronic centers in Dy-based complexes 1 and 2 albeit they are separated by diamagnetic alkaline earth ions, and the FM interaction has been successfully reproduced by ab initio calculations. Alternating current (ac) magnetic susceptibility measurements indicate that complexes 1 and 2 exhibit significant single-molecule magnet (SMM) behaviors. This is mostly attributed to the parallel magnetic axes of individual Dy(iii) sites aligning closely to the Dy-M-Dy direction, and the linearly extending magnetic susceptibility tensors of each ion lead to the FM interaction. The dc and ac susceptibility studies of the intramolecularly diluted complexes reveal that the f-f coupling suppresses the QTMs significantly in the absence of the external magnetic field.

19.
Chem Commun (Camb) ; 53(36): 5067-5070, 2017 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-28435959

RESUMO

The white-light emission of a triple-component lanthanide coordination polymer turns to blue and red upon adding Mn2+ and Ag+ ions, respectively.

20.
Int J Surg ; 36(Pt A): 109-117, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-27773598

RESUMO

BACKGROUND: Conventional magnetic resonance imaging (MRI) is considered a valuable tool for preoperative diagnosis of intracranial tumors. We assessed its accuracy in the diagnosis of intracranial tumors in usual clinical practice. MATERIALS AND METHODS: MRI reports of 762 patients who had undergone conventional brain MRI prior to surgery were retrospectively reviewed. A 4-grade scoring system was devised to establish diagnostic agreement. Each tumor type was compared with the corresponding pathological diagnoses by dichotomization. The sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV), and accuracy were calculated for the overall patient population as well as for each tumor type. RESULTS: 664 cases (87.1%) were tumor-positive, and 98 cases (12.9%) were tumor-negative. The most common tumor types were meningiomas, gliomas, pituitary adenomas and schwannomas. These four types together comprised 74.5% of all cases reviewed. Sensitivity and PPV for the overall population were 72.0-90.7% and 91.9-95.4%, respectively. Diagnostic accuracy differed among tumor types. Meningiomas, pituitary adenomas, schwannomas and cholesteatomas were more likely to be diagnosed correctly (sensitivities were 82.6-96.9%, 86.1-96.7%, 88.9-98.2% and 91.3-100.0%, respectively); while some other types like solitary fibrous tumors (SFTs) seemed difficult to identify. Gliomas tended to be confused with metastases, meningiomas with SFTs, and pituitary adenomas with craniopharyngiomas. CONCLUSION: The accuracy of conventional MRI for diagnosing intracranial tumors is generally satisfactory but should not be too heavily relied upon, especially for certain tumor types. In cases of discrepancy, neurosurgeons are encouraged to confer with the reporting neuroradiologists to achieve optimal preoperative diagnoses.


Assuntos
Neoplasias Encefálicas/diagnóstico por imagem , Neoplasias Encefálicas/patologia , Imageamento por Ressonância Magnética , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Neoplasias Encefálicas/cirurgia , Criança , Pré-Escolar , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Reprodutibilidade dos Testes , Estudos Retrospectivos , Sensibilidade e Especificidade , Adulto Jovem
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