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Reactive oxygen species (ROS)-mediated emerging treatments exhibit unique advantages in cancer therapy in recent years. While the efficacy of ROS-involved tumor therapy is greatly restricted by complex tumor microenvironment (TME). Herein, a dual-metal CaO2@CDs-Fe (CCF) nanosphere, with TME response and regulation capabilities, are proposed to improve ROS lethal power by a multiple cascade synergistic therapeutic strategy with domino effect. In response to weak acidic TME, CCF will decompose, accompanied with intracellular Ca2+ upregulated and abundant H2O2 and O2 produced to reverse antitherapeutic TME. Then the exposed CF cores can act as both Fenton agent and sonosensitizer to generate excessive ROS in the regulated TME for enhanced synergistic CDT/SDT. In combination with calcium overloading, the augmented ROS induced oxidative stress will cause more severe mitochondrial damage and cellular apoptosis. Furthermore, CCF can also reduce GPX4 expression and enlarge the lipid peroxidation, causing ferroptosis and apoptosis in parallel. These signals of damage will finally initiate damage-associated molecular patterns to activate immune response and to realize excellent antitumor effect. This outstanding domino ROS/calcium loading synergistic effect endows CCF with excellent anticancer effect to efficiently eliminate tumor by apoptosis/ferroptosis/ICD both in vitro and in vivo.
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With the rapid development of electronic industry, it's pressing to develop multifunctional electromagnetic interference (EMI) shielding materials to ensure the stable operation of electronic devices. Herein, multilayered flexible PEG@PAN/MXene (Ti3C2Tx)/PVDF@SiO2 (PMF) composite film has been constructed from the level of microstructure design via coaxial electrospinning, coating spraying, and uniaxial electrospinning strategies. Benefiting from the effective encapsulation for PEG and high conductivity of MXene coating, PEG@PAN/MXene composite film with MXene coating loading density of 0.70 mg cm-2 exhibits high thermal energy storage density of 120.77 J g-1 and great EMI shielding performance (EMI SE of 34.409 dB and SSE of 49.086 dB cm3 g-1) in X-band (8-12 GHz). Therefore, this advanced composite film can not only help electronic devices prevent the influence of electromagnetic pollution in the X-band but also play an important role in electronic device thermal management. Additionally, the deposition of nano PVDF@SiO2 fibers (289 ± 128 nm) endowed the PMF composite film with great hydrophobic properties (water contact angle of 126.5°) to ensure the stable working of hydrophilic MXene coating, thereby breaks the limitation of humid application environments. The finding paves a new way for the development of novel multifunctional EMI shielding composite films for electronic devices.
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All-solid-state sodium batteries (AS3B) emerged as a strong contender in the global electrochemical energy storage market as a replacement for current lithium-ion batteries (LIB) owing to their high abundance, low cost, high safety, high energy density, and long calendar life. Inorganic electrolytes (IEs) are highly preferred over the conventional liquid and solid polymer electrolytes for sodium-ion batteries (SIBs) due to their high ionic conductivity (â¼10-2-10-4 S cm-1), wide potential window (â¼5 V), and overall better battery performances. This review discusses the bird's eye view of the recent progress in inorganic electrolytes such as Na-ß"-alumina, NASICON, sulfides, antipervoskites, borohydride-type electrolytes, etc. for AS3Bs. Current state-of-the-art inorganic electrolytes in correlation with their ionic conduction mechanism present challenges and interfacial characteristics that have been critically reviewed in this review. The current challenges associated with the present battery configuration are overlooked, and also the chemical and electrochemical stabilities are emphasized. The substantial solution based on ongoing electrolyte development and promising modification strategies are also suggested.
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Tetrafluoropropyne (C3F4) is a potential dielectric in various electrical insulating equipment to replace the most potent industrial greenhouse gas, sulfur hexafluoride. Atmospheric oxidation of C3F4 by OH radicals in the presence of molecular O2 has been investigated theoretically in order to clarify the lifetime and degradation products at mechanistic and kinetic aspects. Energetic minimum-energy pathways for the C3F4 + OH/O2 reactions were calculated in detail using various theoretical methods including density functional M06-2X and CCSD for geometries, CBS-QB3, CCSD(T), and multireference RS2 with extrapolation to the complete basis-set limit for energies. It has been demonstrated that the C3F4 + OH reaction takes place via the bifurcated C-O addition/elimination routes leading to CF3C(OH)âCF and CF3CâC(OH)F radical adducts, where the latter is more preferable in view of the difference in barrier heights (1.3 vs 0.3 kcal/mol), followed by H-migration, HF-elimination, and C-C and C-F bond fission. The atmospheric lifetime of C3F4 was estimated to be about 13 days, which is indicative of a very short-lived substance in the atmosphere. Further degradation of the energy-rich C3F4OH* intermediates by O2 takes place spontaneously in view of the successive barrier-free and highly exothermic pathways, producing a variety of fluorinated acids, anhydrides, biacetyls, and regenerating OH radicals. For comparison, the reactions of C3H4, CF3CCH, and CH3CCF with OH radicals were examined to clarify the F-substitution effect. It is revealed that the reactivity of fluoropropynes could be either reduced by CF3 or enhanced by atomic F attached to the acetylenic carbon. The present work provides a fundamental understanding of the reactions of fluoroalkynes with OH/O2. The use of C3F4 as a promising eco-friendly gaseous dielectric alternative to SF6 has been supported.
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Mineral oils and synthetic and natural esters are the predominant insulating liquids in electrical equipment. Structure-activity relationship models to predict the key properties of pure insulating liquids, including pulse breakdown strengths, AC breakdown voltages, dielectric constants, flash points, and kinematic viscosities, have been proposed for the first time. Dependence of the specific properties on the molecular structures has been illustrated quantitatively in terms of surface area, statistical total variance, and average deviation of positive and negative electrostatic potentials, as augmented by molecular weight, volume, and ovality. Moreover, the individual contribution of the functional groups to viscosity has been revealed by an additive approach. The predicted properties are in good agreement with the experimental data. The present theoretical work provides new insights on the development of novel dielectric fluids.
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Eletricidade Estática , Viscosidade , Relação Estrutura-AtividadeRESUMO
The Tripterospermum, comprising 34 species, is a genus of Gentianaceae. Members of Tripterospermum are mostly perennial, entwined herbs with high medicinal value and rich in iridoids, xanthones, flavonoids, and triterpenes. However, our inadequate understanding of the differences in the plastid genome sequences of Tripterospermum species has severely hindered the study of their evolution and phylogeny. Therefore, we first analyzed the 86 Gentianae plastid genomes to explore the phylogenetic relationships within the Gentianae subfamily where Tripterospermum is located. Then, we analyzed six plastid genomes of Tripterospermum, including two newly sequenced plastid genomes and four previously published plastid genomes, to explore the plastid genomes' evolution and phylogenetic relationships in the genus Tripterospermum. The Tripterospermum plastomes have a quadripartite structure and are between 150,929 and 151,350 bp in size. The plastomes of Tripterospermum encoding 134 genes were detected, including 86 protein-coding genes (CDS), 37 transfer RNA (tRNA) genes, eight ribosomal RNA (rRNA) genes, and three pseudogenes (infA, rps19, and ycf1). The result of the comparison shows that the Tripterospermum plastomes are very conserved, with the total plastome GC content ranging from 37.70% to 37.79%. In repeat sequence analysis, the number of single nucleotide repeats (A/T) varies among the six Tripterospermum species, and the identified main long repeat types are forward and palindromic repeats. The degree of conservation is higher at the SC/IR boundary. The regions with the highest divergence in the CDS and the intergenic region (IGS) are psaI and rrn4.5-rrn5, respectively. The average pi of the CDS and the IGS are only 0.071% and 0.232%, respectively, indicating that the Tripterospermum plastomes are highly conserved. Phylogenetic analysis indicated that Gentianinae is divided into two clades, with Tripterospermum as a sister to Sinogeniana. Phylogenetic trees based on CDS and CDS + IGS combined matrices have strong support in Tripterospermum. These findings contribute to the elucidation of the plastid genome evolution of Tripterospermum and provide a foundation for further exploration and resource utilization within this genus.
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Genomas de Plastídeos , Gentianaceae , Filogenia , Evolução MolecularRESUMO
Heptafluoro-iso-butyronitrile (i-C3F7CN) represents a feasible eco-friendly replacement gas for the most potent greenhouse gas sulfur hexafluoride in various high-voltage power transmission equipment. The reaction mechanisms for the in situ synthesis of i-C3F7CN from heptafluoro-iso-butyramide [i-C3F7C(O)NH2] in the presence of trifluoroacetic anhydride (TFAA) and pyridine (Py) in dimethylformamide solution have been studied within density functional theory with M06-2X exchange-correlation functional with the 6-311++G(d,p) basis set and the high-level ab initio complete basis set quadratic CBS-QB3 method. It is revealed that the unimolecular dehydration of i-C3F7C(O)NH2 can be catalyzed efficiently by TFAA in terms of both kinetic and thermodynamic aspects, producing i-C3F7CN and trifluoroacetic acid (TFA). Furthermore, Py is capable of reducing the energy barrier of the rate-determining step through hydrogen abstraction to form pyridinium hydrogen. The synergic effect of the TFAA/Py co-catalyst plays a pivotal role in the production of i-C3F7CN as the Gibbs free energy barrier can be lowered by more than 40 kcal/mol with the ratio of TFAA:2Py, in accordance with the experimental observation. The present theoretical work provides new insights into the rational design on the novel catalysts for large-scale synthesis of the perfluorinated nitriles.
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Due to the increasing global energy demands, scarce fossil fuel supplies, and environmental issues, the pursued goals of energy technologies are being sustainable, more efficient, accessible, and produce near zero greenhouse gas emissions. Electrochemical water splitting is considered as a highly viable and eco-friendly energy technology. Further, electrochemical carbon dioxide (CO2 ) reduction reaction (CO2 RR) is a cleaner strategy for CO2 utilization and conversion to stable energy (fuels). One of the critical issues in these cleaner technologies is the development of efficient and economical electrocatalyst. Among various materials, metal-organic frameworks (MOFs) are becoming increasingly popular because of their structural tunability, such as pre- and post- synthetic modifications, flexibility in ligand design and its functional groups, and incorporation of different metal nodes, that allows for the design of suitable MOFs with desired quality required for each process. In this review, the design of MOF was discussed for specific process together with different synthetic methods and their effects on the MOF properties. The MOFs as electrocatalysts were highlighted with their performances from the aspects of hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and electrochemical CO2 RR. Finally, the challenges and opportunities in this field are discussed.
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Gases for electric insulation are essential for various types of high-voltage power equipment. Sulfur hexafluoride (SF6) has been a dielectric medium commonly used in electrical grids for decades but it is the most potent industrial greenhouse gas. The continuous increase of SF6 emissions in the atmosphere exerts a significant impact on global warming. The identification of suitable drop-in replacements for all SF6-filled apparatuses has been elusive experimentally and theoretically. We claim that tetrafluoropropyne, C3F4, is a breakthrough in chemical alternatives to SF6. The performance of C3F4 was assessed systematically in a 6-dimensional manner, including dielectric strength, liquefaction temperature, global warming potential, thermal stability, toxicity, and arc interruption. On the basis of the extensive ab initio calculations, it has been demonstrated rigorously that C3F4 is an environmentally sustainable solution that may fulfill the complex combination of performance, stability, safety, and environmental properties, namely, the dielectric strength is about 50% higher than that of SF6, the boiling point is -50 °C, the GWP for 100 year time horizons is only 3, the decomposition temperature is above 600 °C, the toxicity is as low as HFOs, and the interruption capability is two-thirds of SF6. Two protocols are suggested for the practical use of C3F4. First, equivalence to 0.5 MPa SF6 could be obtained by filling 0.33 MPa C3F4 pure gas and lead minimum operating temperature down to -21 °C. Second, by taking advantage of synergism effect, the 40% C3F4/60% CO2 mixture is a viable alternative to SF6 with the operating temperature -30 °C without causing any environmental and safety concerns. The present theoretical work sheds new light on the challenging topic of the development of alternative dielectric gases and may stimulate experimental tests on the electrical applications of C3F4 in the future.
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As a potential insulation gas to replace sulfur hexafluoride (SF6) due to environmental concerns, trifluoromethanesulonyl fluoride (CF3SO2F) has attracted great interests in various high-voltage electric applications. Thermal stability of CF3SO2F plays an important role in the rational design of the gas-insulated electric equipment. Unimolecular decomposition of CF3SO2F was investigated using high-level ab initio methods including the explicitly correlated RCCSD(T)-F12, the composite ROCBS-QB3, and the multireference RS2 extrapolated to complete basis set limit on the basis of M06-2X-, B2PLYPD3-, and CCSD-optimized geometrical parameters. Rate coefficients and decomposition temperatures were simulated using master equations. CF3SO2F decomposes predominantly via a simple C-S bond cleavage to form CF3 and SO2F, accompanied by a roaming induced F-abstraction detour to release CF4 and SO2, or isomerizes via CF3 migration to the more stable CF3OSFO followed by the production of CF2O and SOF2. Various characteristic decomposition products (e.g., CF4, C2F6, CF2O, SO2, SOF2, SO2F2, CF3H, and so on.) have been identified theoretically through secondary reactions and hydrolysis of CF3SO2F in the presence of water vapor. Electronic structures and stability of CF3SO2F could be affected significantly by the external electric field orientated along the S-C bond. The field-dependent electron-molecule capture rates support that CF3SO2F is superior to SF6 in dielectric strength. The present computational findings shed light on the practical use of CF3SO2F as the replacement gas for SF6.
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In view of the significant greenhouse effect of sulfur hexafluoride and the potential biotoxic hazard of perfluorinated substances, we proposed that nitryl cyanide (NCNO2), a nearly nonpolar molecule with a unique combination of two strongly electronegative and polarized functional groups, is a novel fluorine-free replacement to be used as the insulating gas in green electrical grids. Atmospheric chemistry of NCNO2 has been investigated theoretically to assess its environmental impact if emitted into the atmosphere. Potential energy surfaces for the reaction of NCNO2 with OH in the presence of O2 were calculated using the restricted open-shell complete basis set quadratic Becke3 and Gaussian-4 methods on the basis of the density functional (M06-2X) and couple-cluster (CCSD) optimized geometrical parameters. The oxidation of NCNO2 takes place via the nearly zero-barrier association of OH with the cyano-C to form energy-rich adducts NC(OH)NO2, followed by C-N bond rupture to the major HOCN + NO2 and the minor HONO + NCO products. Interception of the adduct by O2 can result in OH-regeneration together with further degradation to CO and NOx. Moreover, photolysis of NCNO2 under tropospheric sunlight conditions might compete with OH-oxidation. The atmospheric lifetime and radiative efficiency of NCNO2 were computed to be far less than those of either nitriles or nitro compounds. The global warming potential of NCNO2 was estimated to be in the range of 0-5 for a 100 year time horizon. However, the secondary chemistry of NCNO2 should be treated with caution in view of the production of NOx in the atmosphere.
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As an important cancer therapeutic target, extracellular signal-regulated kinases (ERK) are involved in triggering various cellular responses in tumors. Regulation of the ERK signaling pathway by the small molecular inhibitors is highly desired for the sake of cancer therapy. In contrast to the routine inhibitors targeting ERKs through long-range non-bonding interactions, Ponatinib, a covalent inhibitor to ERK2 with a macrocyclic structure characterized by the α,ß-C=C unsaturated ketone, can form the stable -C(S)-C(H)-type complex via the four-center barrier due to the nucleophilic addition reaction of the thiol group of the Cys166 residue of ERK2 with the C=C double bond of Ponatinib with reaction free-energy barrier of 47.2 kcal/mol. Reaction mechanisms for the covalent binding were calculated using QM/MM methods and molecular dynamics simulations. The interaction modes and the corresponding binding free energies were obtained for the non-covalent and covalent complexation. The binding free energies of the non-covalent and covalent inhibitions are 14.8 kcal/mol and 33.4 kcal/mol, respectively. The mechanistic study stimulated a rational design on the modified Ponatinib structure by substituting the C=C bond with the C=N bond. It was demonstrated that the new compound exhibits better inhibition activity toward ERK2 in term of both thermodynamic and kinetic aspects through the covalent binding with a lower reaction free-energy barrier of 23.1 kcal/mol. The present theoretical work sheds new light on the development of the covalent inhibitors for the regulation of ERKs.
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MAP Quinases Reguladas por Sinal Extracelular , Neoplasias , Humanos , Simulação de Dinâmica Molecular , Imidazóis/farmacologia , TermodinâmicaRESUMO
Oxylipins are important biological regulators that have received extensive research attention. Due to the extremely low concentrations, large concentration variations, and high structural similarity of many oxylipins, the quantitative analysis of oxylipins in biological samples is always a great challenge. Here, we developed a liquid chromatography-tandem mass spectrometry-based method with high sensitivity, wide linearity, and acceptable resolution for quantitative profiling of oxylipins in multiple biological samples. A total of 104 oxylipins, some with a high risk of detection crosstalk, were well separated on a 150 mm column over 20 min. The method showed high sensitivity with lower limits of quantitation for 87 oxylipins, reaching 0.05-0.5 pg. Unexpectedly, we found that the linear range for 16, 18, and 17 oxylipins reached 10,000, 20,000, and 40,000 folds, respectively. Due to the high sensitivity, while reducing sample consumption to below half the volume of previous methods, 74, 78, and 59 low-abundance oxylipins, among which some were difficult to detect like lipoxins and resolvins, were well quantified in the tested mouse plasma, mouse liver, and human plasma samples, respectively. Additionally, we determined that analytes with multifarious concentrations of over a 1,000-fold difference could be well quantified simultaneously due to the wide linearity. In conclusion, most likely due to the instrumental advancement, this method effectively improves the quantitative sensitivity and linear range over existing methods, which will facilitate and advance the study of the physiological and pathophysiological functions of oxylipins.
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Oxilipinas , Espectrometria de Massas em Tandem , Humanos , Animais , Camundongos , Cromatografia Líquida , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida de Alta Pressão/métodos , Ácidos GraxosRESUMO
Hexafluoro-2-butyne (C4F6) is a potential eco-friendly alternative gas in plasma, refrigerants, and electrical insulation applications. Mechanisms for the reactions of C4F6 with OH/O2 have been revealed in detail using various theoretical methods including ROCBS-Q, RCCSD(T), multireference RS2C, and extrapolations to the complete basis-set limit with Aug-cc-pVnZ (n = T, Q, 5) basis sets. Rate coefficients and product branching ratios were predicted for a wide range of temperatures and pressures using the solution of master equations. The vibrationally adiabatic ground-state barrier for the initial C4F6 + OH association was best estimated to be 1.53-2.26 kcal/mol. Energetically preferable decomposition paths for the conformation-dependent C4F6OH adducts include six-center HF elimination, four-center proton migration, and C-C bond cleavage, but the collisional deactivation is dominant under ambient conditions. The subsequent oxidation of C4F6OH by O2 bifurcates in two orientations and proceeds without any well-defined barrier followed by the successive isomerization/elimination steps, forming perfluorobiacetyl to regenerate OH radicals or trifluoroacetic acid with trifluoroacetyl radicals. The OH-recycling path accounts for a branching ratio of 70% under ambient conditions. Theoretical rate coefficients are in good agreement with the available experimental results. The effect of fluorination on the reactivity of alkynes toward OH/O2 is discussed.
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The plant flavonoid dogma proposes that labile plant flavonoid carbocations (PFCs) play vital roles in the biosynthesis of proanthocyanidins (PAs). However, whether PFCs exist in plants and how PFCs function remain unclear. Here, we report the use of an integrative strategy including enzymatic assays, mutant analysis, metabolic engineering, isotope labeling and metabolic profiling to capture PFCs and demonstrate their functions. In anthocyanidin reductase (ANR) assays, an (-)-epicatechin conjugate was captured in protic polar nucleophilic methanol alone or methanol-HCl extracts. Tandem mass spectrum (MS/MS) analysis characterized this compound as an (-)-epicatechin-4-O-methyl (EOM) ether, which resulted from (-)-epicatechin carbocation and the methyl group of methanol. Acid-based catalysis of procyanidin B2 and B3 produced four compounds, which were annotated as two EOM and two (+)-catechin-4-O-methyl (COM) ethers. Metabolic profiling of seven PA pathway mutants showed an absence or reduction of two EOM ether isomers in seeds. Camellia sinensis ANRa (CsANRa), leucoanthocyanidin reductase c (CsLARc), and CsMYB5b (a transcription factor) were independently overexpressed for successful PA engineering in tobacco. The EOM ether was remarkably increased in CsANRa and CsMYB5b transgenic flowers. Further metabolic profiling for eight green tea tissues revealed two EOM and two COM ethers associated with PA biosynthesis. Moreover, an incubation of (-)-epicatechin or (+)-catechin with epicatechin carbocation in CsANRa transgenic flower extracts formed dimeric procyanidin B1 or B2, demonstrating the role of flavan-3-ol carbocation in the formation of PAs. Taken together, these findings indicated that flavan-3-ol carbocations exist in extracts and are involved in the biosynthesis of PAs of plants.
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Flavonoides/metabolismo , Proantocianidinas/biossíntese , Camellia sinensis/genética , Camellia sinensis/metabolismo , Regulação da Expressão Gênica de Plantas/genética , Regulação da Expressão Gênica de Plantas/fisiologia , NADH NADPH Oxirredutases/genética , NADH NADPH Oxirredutases/metabolismo , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismoRESUMO
The efficacy and safety of adjunctive nonconvulsive electrotherapy (NET) for patients with depression are undetermined. This systematic review was conducted to examine the efficacy and safety of adjunctive NET for patients with depression. Chinese (WanFang and Chinese Journal Net) and English (PubMed, EMBASE, PsycINFO and the Cochrane Library) databases were systematically searched from their inception until Jan 27, 2021 by three independent investigators. One randomized controlled trial (RCT) with 3 treatment arms (n = 108) and two observational studies (single-group, before-after design, n = 31) were included. In the RCT, the antidepressant efficacy of NET on depression was similar to that of electroconvulsive therapy (ECT) (P > 0.05) but with significantly fewer neurocognitive impairments as measured by the Repeatable Battery for the Assessment of Neuropsychological Status (RBANS) (P < 0.05). In two observational studies, the 17-item Hamilton Depression Rating Scale (HAMD-17) scores decreased significantly from baseline to post-NET (all Ps < 0.05), without adverse neurocognitive effects. In the RCT, adverse drug reactions (ADRs) were not separately reported among the 3 treatment arms but a similar rate of discontinuation was reported. The currently available limited evidence from 3 studies suggests that NET as an adjunctive treatment may be a safe, well-tolerated, effective therapy for depression without serious neurocognitive impairments.
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Terapia por Estimulação Elétrica , Eletroconvulsoterapia , Antidepressivos , Depressão/terapia , HumanosRESUMO
This study probes the function and mechanism of lymphocyte-specific protein 1 (LSP1) in glioblastoma pathogenesis. According to the data acquired from TCGA, Oncomine and GEO databases, the expression and prognostic value of LSP1 and miR-920 in glioblastoma patients were analyzed. The expression levels of LSP1 in U251 and A172 cell lines were analyzed by qRT-PCR and western blotting. CCK8, colony formation and transwell assays were utilized to test glioblastoma cell malignant abilities. Furthermore, the associations between LSP1 and miR-920 were indentified by bioinformatics analysis and rescue assays. Moreover, the protein expression levels of p-JAK2, JAK2, p-STAT5 and STAT5, as the hallmark of JAK/STAT5 signaling, were detected by western blotting. The observations showed that LSP1 was highly augmented in glioblastoma samples. Additionally, up-regulation of LSP1 was associated with a unfavorable prognosis in glioblastoma patients. Biological experiments revealed that depletion of LSP1 significantly suppressed the proliferation, invasion and migration of U251 and A172 cells. MiR-920, as an upstream regulator of LSP1, negatively modulated LSP1 expression and promoted U251 cells malignant behaviors after miR-920 inhibitor treatment. However, together knockdown LSP1 and miR-920 inhibited these effects. Moreover, the expression levels of p-JAK2 and p-STAT5 were increased or decreased in U251 cells after transfection of miR-920 inhibitor or si-LPS1. Taken together, miR-920 might blocked the malignant development of glioblastoma cells, which is possibly realized by targeting LSP1 and modulation of JAK/STAT5 pathway. These findings implied that miR-920/LSP1 was a potential therapeutic target for glioblastoma treatment.
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Neoplasias Encefálicas/metabolismo , Glioblastoma/metabolismo , Janus Quinase 2/metabolismo , MicroRNAs/metabolismo , Proteínas dos Microfilamentos/metabolismo , Fator de Transcrição STAT5/metabolismo , Proteínas Supressoras de Tumor/metabolismo , Neoplasias Encefálicas/genética , Neoplasias Encefálicas/patologia , Processos de Crescimento Celular/fisiologia , Linhagem Celular Tumoral , Movimento Celular/fisiologia , Glioblastoma/genética , Glioblastoma/patologia , Humanos , MicroRNAs/genética , Proteínas dos Microfilamentos/genética , Transdução de Sinais , TransfecçãoRESUMO
The duplex real-time PCR assay based on SYBR Green Ð was developed for detection of porcine epidemic diarrhea virus (PEDV) and porcine bocavirus (PBoV) 3/4/5 genotypes simultaneously. Two pairs of specific primers were designed targeting the N gene sequence of PEDV and VP1 gene sequence of PBoV3/4/5. PEDV and PBoV3/4/5 could be distinguished by their different melting temperatures (Tm) in one sample. The Tm value of PEDV was 83.5 °C, and the Tm value of PBoV3/4/5 was 78.5 °C, while other swine pathogens showed no specific melting peaks. The detection limits of this assay were 10 copies/µL for both PEDV and PBoV3/4/5. A total of sixty-three intestinal tissue samples were collected from piglets suffering from diarrhea, and the viral nucleic acids detected and identified by the real-time PCR assay and conventional PCR assay. The duplex real-time PCR detection results showed that the prevalence of PEDV and PBoV3/4/5 was 85.7% and 46%, respectively, and the co-infection rate of the two viruses was 28.6%. These results indicated that this duplex real-time PCR assay was a sensitive, specific and reproducible method for differentiating PEDV and PBoV3/4/5 or their co-infection.
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Bocavirus/isolamento & purificação , Infecções por Coronavirus/diagnóstico , Infecções por Coronavirus/virologia , Vírus da Diarreia Epidêmica Suína/isolamento & purificação , Reação em Cadeia da Polimerase em Tempo Real/métodos , Animais , Benzotiazóis/química , Bocavirus/genética , Coinfecção , Primers do DNA , Diaminas/química , Vírus da Diarreia Epidêmica Suína/genética , Quinolinas/química , Sensibilidade e Especificidade , Suínos , Temperatura de TransiçãoRESUMO
Self-healing polymer materials (SHPM) have aroused great interests in recent years. Ideal SHPM should have not only simple operations, but also high elongations at break, tensile strain and self-healing properties at room temperature. Herein, the amidated carbon fibers (CFs) reinforced self-healing polymer composites were designed by hydrogen bonding interaction between functionalized CFs and hyperbranched polymers. The amidated CFs were prepared by transformation of hydroxyl to acylamino through a one-step amidation. By introducing amidated CFs, amidated CFs self-healing polymer composites (called AD-CF) exhibited many desirable characteristics compared to pure polymer composites, such as a better elasticity, lower healing temperatures, and higher self-healing efficiencies. The stress-strain test was selected to carefully study the self-healing property of the AD-CF. The observed same recovery condition, i.e. without any mechanical breakdown after the 10 sequential cycles of cutting and healing indicates no aging of the AD-CF. The ability of AD-CF to exhibit a soft state and rapid self-healing at room temperature makes it possible for much wider applications.
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Heptafluoro-iso-butyronitrile [(CF3)2CFCN, in abbr., C4] with CO2 gas mixture is a promising dielectric candidate to replace sulfur hexafluoride (SF6) for the sake of environmental concern. Detailed mechanisms for the reactions of C4 with atomic oxygen in both triplet and singlet due to dissociation of CO2 were proposed using high-level ab initio methods including density functional theory, quadratic complete basis set, multireference Rayleigh-Schrodinger perturbation theory, and state-averaged multiconfiguration self-consistent field. The reaction of C4 with O(3P) proceeds via the stepwise C-O and N-O addition/elimination and direct displacement mechanisms. The reaction paths are bifurated into cis and trans conformations. The predominant product channel is the C-O association with the barriers 6.1-6.8 kcal/mol to form the C3F7C(O)N intermediates and followed by the C-C bond cleavage to produce C3F7 and NCO radicals. On the singlet surface, the three-center intramolecular conversion to form the C3F7OCN isomer becomes competitive. The singlet-triplet intersystem crossing is favorable due to the significant spin-orbital coupling. Master equation calculations were carried out to obtain the temperature- and pressure-dependent rate coefficients and yields of the O(3P) + C4 reaction and were compared with the analogous reactions of nitriles. It was found that only the NCO + C3F7 product channel is significant. The overall rate coefficients are pressure-independent in the range 1-10 atm and can be expressed by k∞(T/K)=(6.41 ± 0.22) × 10-13(T/298)1.30±0.01e-(3241.5±24.5)/T cm3 molecule-1 s-1. The present theoretical work provides useful insights into the breakdown diagnostic of the C4/CO2 insulation gas.