RESUMO
We present here the high-resolution structure of an antiparallel DNA triplex in which a monomer of para-twisted intercalating nucleic acid (para-TINA: (R)-1-O-[4-(1-pyrenylethynyl)phenylmethyl]glycerol) is covalently inserted as a bulge in the third strand of the triplex. TINA is a potent modulator of the hybridization properties of DNA sequences with extremely useful properties when conjugated in G-rich oligonucleotides. The insertion of para-TINA between two guanines of the triplex imparts a high thermal stabilization (ΔTM = 9ºC) to the structure and enhances the quality of NMR spectra by increasing the chemical shift dispersion of proton signals near the TINA location. The structural determination reveals that TINA intercalates between two consecutive triads, causing only local distortions in the structure. The two aromatic moieties of TINA are nearly coplanar, with the phenyl ring intercalating between the flanking guanine bases in the sequence, and the pyrene moiety situated between the Watson-Crick base pair of the two first strands. The precise position of TINA within the triplex structure reveals key TINA-DNA interactions, which explains the high stabilization observed and will aid in the design of new and more efficient binders to DNA.
Assuntos
DNA , Glicerol , Conformação de Ácido Nucleico , Pirenos , DNA/química , Guanina , Hibridização de Ácido Nucleico , Oligonucleotídeos/química , Pirenos/química , Glicerol/análogos & derivados , Glicerol/químicaRESUMO
Translocation of transfer RNA (tRNA) and messenger RNA (mRNA) through the ribosome is catalyzed by the GTPase elongation factor G (EF-G) in bacteria. Although guanosine-5'-triphosphate (GTP) hydrolysis accelerates translocation and is required for dissociation of EF-G, its fundamental role remains unclear. Here, we used ensemble Förster resonance energy transfer (FRET) to monitor how inhibition of GTP hydrolysis impacts the structural dynamics of the ribosome. We used FRET pairs S12-S19 and S11-S13, which unambiguously report on rotation of the 30S head domain, and the S6-L9 pair, which measures intersubunit rotation. Our results show that, in addition to slowing reverse intersubunit rotation, as shown previously, blocking GTP hydrolysis slows forward head rotation. Surprisingly, blocking GTP hydrolysis completely abolishes reverse head rotation. We find that the S13-L33 FRET pair, which has been used in previous studies to monitor head rotation, appears to report almost exclusively on intersubunit rotation. Furthermore, we find that the signal from quenching of 3'-terminal pyrene-labeled mRNA, which is used extensively to follow mRNA translocation, correlates most closely with reverse intersubunit rotation. To account for our finding that blocking GTP hydrolysis abolishes a rotational event that occurs after the movements of mRNA and tRNAs are essentially complete, we propose that the primary role of GTP hydrolysis is to create an irreversible step in a mechanism that prevents release of EF-G until both the tRNAs and mRNA have moved by one full codon, ensuring productive translocation and maintenance of the translational reading frame.
Assuntos
Fator G para Elongação de Peptídeos , Ribossomos , Fator G para Elongação de Peptídeos/genética , Fator G para Elongação de Peptídeos/química , Guanosina Trifosfato/química , Hidrólise , Ribossomos/metabolismo , RNA de Transferência/química , RNA Mensageiro/química , GTP Fosfo-Hidrolases/genética , Pirenos/análise , GuanosinaRESUMO
Gd-L1 is a macrocyclic Gd-HPDO3A derivative functionalized with a short spacer to a trisulfonated pyrene. When compared to Gd-HPDO3A, the increased relaxivity appears to be determined by both the higher molecular weight and the occurrence of an intramolecularly catalyzed prototropic exchange of the coordinated OH moiety. In water, Gd-L1 displayed a relaxivity of 7.1 mM-1 s-1 (at 298 K and 0.5 T), slightly increasing with the concentration likely due to the onset of intermolecular aggregation. A remarkably high and concentration-dependent relaxivity was measured in human serum (up to 26.5 mM-1 s-1 at the lowest tested concentration of 0.005 mM). The acquisition of 1H-nuclear magnetic relaxation dispersion (NMRD) and 17O-R2 vs T profiles allowed to get an in-depth characterization of the system. In vitro experiments in the presence of human serum albumin, γ-globulins, and polylysine, as well as using media mimicking the extracellular matrix, provided strong support to the view that the trisulfonated pyrene fosters binding interactions with the exposed positive groups on the surface of proteins, responsible for a remarkable in vivo hyperintensity in T1w MR images. The in vivo MR images of the liver, kidneys, and spleen showed a marked contrast enhancement in the first 10 min after the i.v. injection of Gd-L1, which was 2-6-fold higher than that for Gd-HPDO3A, while maintaining a very similar excretion behavior. These findings may pave the way to an improved design of MRI GBCAs, for the first time, based on the setup of weak and dynamic interactions with abundant positive groups on serum and ECM proteins.
Assuntos
Meios de Contraste , Compostos Heterocíclicos , Compostos Organometálicos , Humanos , Meios de Contraste/química , Eletricidade Estática , Imageamento por Ressonância Magnética/métodos , Compostos Organometálicos/química , Pirenos , GadolínioRESUMO
Biomimetic cytochrome P450 for chemical activation of environmental carcinogens is an efficient in vitro model for evaluating their mutagenicity and ultimately acquiring the metabolites that cannot be easily accessed by conventional routes of organic synthesis. Different kinds of mutagen derived from polyaromatic hydrocarbons (PAHs) by metalloporphyrin/oxidant model systems have been reported, but the underlying molecular mechanisms are poorly understood. Herein, we have for the first time demonstrated an effective surface-enhanced Raman scattering (SERS) protocol to study the dynamics and biomimetic metabolic behaviors of pyrene (Pyr) in the presence of various oxygen donors. Quantitative information on the relative concentration of Pyr and its metabolites in the biomimetic system can be extracted from the SERS spectra. On the basis of our results, we conclude that the oxidative metabolism of Pyr is highly influenced by the types and concentrations of oxygen donors, leading to the formation of 1-hydroxypyrene and dioxygenated products. Besides, the addition of an appropriate amount of an organic solvent can promote the formation of secondary oxidation products. These results offer valuable insights into the dynamics of PAHs metabolism and the regulation of their metabolic pathways in biomimetic activation. In comparison to traditional liquid chromatography-mass spectrometry, the present SERS approach is more suitable for high-throughput evaluation of the metabolic process and kinetics of PAHs. We anticipate that this approach will enable a more general and comprehensive tracking of metabolic dynamics and molecular mechanisms involved in the biomimetic activation of other xenobiotics, such as procarcinogens, promutagens, and drugs.
Assuntos
Pirenos , Análise Espectral Raman , Análise Espectral Raman/métodos , Cinética , Pirenos/química , Pirenos/metabolismo , Biomimética , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/química , Materiais Biomiméticos/química , Materiais Biomiméticos/metabolismo , Propriedades de Superfície , Ativação Metabólica , Sistema Enzimático do Citocromo P-450/metabolismo , OxirreduçãoRESUMO
This study presents the synthesis and characterization of two fluorescent norbornadiene (NBD) photoswitches, each incorporating two conjugated pyrene units. Expanding on the limited repertoire of reported photoswitchable fluorescent NBDs, we explore their properties with a focus on applications in bioimaging of amyloid beta (Aß) plaques. While the fluorescence emission of the NBD decreases upon photoisomerization, aligning with what has been previously reported, for the first time we observed luminescence after irradiation of the quadricyclane (QC) isomer. We deduce how the observed emission is induced by photoisomerization to the excited state of the parent isomer (NBD) which is then the emitting species. Thorough characterizations including NMR, UV-Vis, fluorescence, X-ray structural analysis and density functional theory (DFT) calculations provide a comprehensive understanding of these systems. Notably, one NBD-QC system exhibits exceptional durability. Additionally, these molecules serve as effective fluorescent stains targeting Aß plaques inâ situ, with observed NBD/QC switching within the plaques. Molecular docking simulations explore NBD interactions with amyloid, unveiling novel binding modes. These insights mark a crucial advancement in the comprehension and design of future photochromic NBDs for bioimaging applications and beyond, emphasizing their potential in studying and addressing protein aggregates.
Assuntos
Peptídeos beta-Amiloides , Corantes Fluorescentes , Pirenos , Corantes Fluorescentes/química , Pirenos/química , Peptídeos beta-Amiloides/química , Peptídeos beta-Amiloides/metabolismo , Humanos , Simulação de Acoplamento Molecular , Norbornanos/química , Placa Amiloide/química , Placa Amiloide/diagnóstico por imagem , Teoria da Densidade Funcional , Isomerismo , Espectrometria de FluorescênciaRESUMO
Marine hydrocarbonoclastic bacteria can use polycyclic aromatic hydrocarbons as carbon and energy sources, that makes these bacteria highly attractive for bioremediation in oil-polluted waters. However, genomic and metabolic differences between species are still the subject of study to understand the evolution and strategies to degrade PAHs. This study presents Rhodococcus ruber MSA14, an isolated bacterium from marine sediments in Baja California, Mexico, which exhibits adaptability to saline environments, a high level of intrinsic pyrene tolerance (> 5 g L- 1), and efficient degradation of pyrene (0.2 g L- 1) by 30% in 27 days. Additionally, this strain demonstrates versatility by using naphthalene and phenanthrene as individual carbon sources. The genome sequencing of R. ruber MSA14 revealed a genome spanning 5.45 Mbp, a plasmid of 72 kbp, and three putative megaplasmids, lengths between 110 and 470 Kbp. The bioinformatics analysis of the R. ruber MSA14 genome revealed 56 genes that encode enzymes involved in the peripheral and central pathways of aromatic hydrocarbon catabolism, alkane, alkene, and polymer degradation. Within its genome, R. ruber MSA14 possesses genes responsible for salt tolerance and siderophore production. In addition, the genomic analysis of R. ruber MSA14 against 13 reference genomes revealed that all compared strains have at least one gene involved in the alkanes and catechol degradation pathway. Overall, physiological assays and genomic analysis suggest that R. ruber MSA14 is a new haloalkalitolerant and hydrocarbonoclastic strain toward a wide range of hydrocarbons, making it a promising candidate for in-depth characterization studies and bioremediation processes as part of a synthetic microbial consortium, as well as having a better understanding of the catabolic potential and functional diversity among the Rhodococci group.
Assuntos
Biodegradação Ambiental , Genoma Bacteriano , Genômica , Sedimentos Geológicos , Hidrocarbonetos Policíclicos Aromáticos , Rhodococcus , Rhodococcus/genética , Rhodococcus/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Sedimentos Geológicos/microbiologia , Naftalenos/metabolismo , Filogenia , Fenantrenos/metabolismo , Tolerância ao Sal , PirenosRESUMO
Lipid membranes that are separated from the surface of graphene by DNA tethers were prepared by surface functionalization with pyrene coupled to single-stranded DNA (ssDNA), followed by self-assembly of the mixture of ssDNA-functionalized phospholipid and the matrix phospholipids. The formation of uniform membranes was confirmed by fluorescence microscopy, and the structures of the systems before and after hybridization in the direction perpendicular to the global plane of the membranes were investigated using high-energy X-ray reflectivity. The thickness values of the DNA spacers (15 and 37 bp) calculated from the best-fit results were less than the expected thicknesses of the double-stranded DNA (dsDNA) chains taking the upright conformation, indicating that the DNA spacers are tilted with respect to the direction normal to the surface. The Young's moduli of the DNA-tethered membranes obtained by AFM nanoindentation showed higher values than the membranes with no DNA tethers, which suggests that the DNA layer resists against the compression, lifting up the membrane. Intriguingly, the presence of DNA tethers caused no increase in the yield depth. The smaller thickness values as well as the unchanged yield depth suggest that the dsDNA chains can tilt and rotate, which can be attributed to the flexible pyrene-DNA junction.
Assuntos
Grafite , Grafite/química , DNA de Cadeia Simples/química , Propriedades de Superfície , Pirenos/química , DNA/química , Microscopia de Força Atômica , Membranas ArtificiaisRESUMO
Peptide amphiphiles (PAs) are known for their remarkable ability to undergo molecular self-assembly, a process that is highly responsive to the local microenvironment. Herein, we design a pyrene tethered peptide amphiphile Py-VFFAKK, 1 that exhibits pathway-driven self-assembly from metastable nanoparticles to kinetically controlled nanofibers and thermodynamically stable twisted bundles upon modulations in pH, temperature, and chemical cues. The presence of the pyrene moiety ensures donation of the electron to an electron acceptor, namely, 7,7,8,8-tetracyanoquinodimethane (TCNQ), to form a supramolecular charge transfer complex in aqueous solution that was studied in detail with microscopic and spectroscopic techniques. Excitation of the donor species in its excimer state facilitates electron donation to the acceptor moiety, paving away a long-lived charge-separated state that persists for over a nanosecond, as ascertained through transient absorption spectroscopy. Finally, the self-assembled charge transfer complex is explored toward antimicrobial properties with Escherichia coli while maintaining biocompatibility toward L929 mice fibroblast cells.
Assuntos
Sinais (Psicologia) , Nanofibras , Animais , Camundongos , Peptídeos/farmacologia , Peptídeos/química , Análise Espectral , Nanofibras/toxicidade , Nanofibras/química , PirenosRESUMO
This work presents new experimental viscosity and density data for aromatic and polyaromatic compounds in binary and ternary pyrene, 1-methylnaphthalene, and dodecane mixtures. The lack of experimental viscosity data for these mixtures requires the development of a new database, which is vital for understanding the behavior of mixtures in more complex systems, such as asphaltenes and fuels. The mixtures proposed in this work have been measured over a temperature range of (293.15 to 343.15) K at atmospheric pressure. Several mixture compositions have been studied at these conditions: 1.0, 2.5, 5.0, 7.5, 10.0, 12.5, and 15.0% pyrene mass fraction. The concentration of pyrene correlates with an increase in the viscosity and density values. At the lowest temperature in binary mixtures, the corresponding values reach 4.4217 mPa·s for viscosity and 1.0447 × 103 kg·m-3 for density, respectively. In ternary mixtures, the introduction of dodecane leads to the lowest maximum values of 3.5555 mPa·s for viscosity and 1.0112 × 103 kg·m-3 for density at the same temperature. The experimental data have been employed for the specific modification of viscosity models. These modifications could facilitate the prediction of the viscosity of mixtures that are more complex than those presented in this work. Various viscosity models have been employed, such as Linear, Ratcliff and Khan, modified UNIFAC-Visco, and Krieger-Dougherty. The settings in the models used reliably reproduce the experiment reliably. However, the Ratcliff model agrees excellently with the experiment, having a low standard deviation (2.0%) compared to other models. Furthermore, a model based on the equation of state of Guo is proposed to predict the viscosity values by modifying the specific parameters and adjusting them to the mixtures proposed in this work. The results from this study are compared to previous work, where pyrene, toluene, and heptane mixtures were analyzed. In this case, we find that the decrease of aggregation grade in the present systems is predicted by the model fixed in this work.
Assuntos
Alcanos , Naftalenos , Pirenos , Temperatura , Pirenos/química , Viscosidade , Naftalenos/química , Alcanos/química , Modelos Químicos , Hidrocarbonetos Policíclicos Aromáticos/químicaRESUMO
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants of significant public health concern, with several that are highly toxic to humans, including some proven or suspected carcinogens. To account for the high variability of PAH mixtures encountered in occupational settings, adjusting urinary 1-hydroxypyrene (1-OHP) levels by the total airborne pyrene (PyrT)/benzo[a]pyrene (BaP) ratio is essential for human biomonitoring (HBM). Given the complexity and cost of systematically monitoring atmospheric levels, alternative approaches to simultaneous airborne and HBM are required. The aim of this review was to catalog airborne PyrT/BaP ratios measured during different industrial activities and recommend 1-OHP-dedicated biological guidance values (BGV). A literature search was conducted. Seventy-one studies were included, with 5619 samples pertaining to 15 industrial sectors, 79 emission processes, and 213 occupational activities. This review summarized more than 40 years of data from almost 20 countries and highlighted the diversity and evolution of PAH emissions. PyrT/BaP ratios were highly variable, ranging from 0.8 in coke production to nearly 40 in tire and rubber production. A single PyrT/BaP value cannot apply to all occupational contexts, raising the question of the relevance of defining a single biological limit value for 1-OHP in industrial sectors where the PyrT/BaP ratio variability is high. Based upon the inventory, a practical approach is proposed for systematic PAH exposure and risk assessment, with a simple frame to follow based upon specific 1-OHP BGVs depending upon the occupational context and setup of a free PAH HBM interactive tool.
Assuntos
Poluentes Atmosféricos , Benzo(a)pireno , Monitoramento Biológico , Pirenos , Pirenos/análise , Pirenos/urina , Humanos , Benzo(a)pireno/análise , Monitoramento Biológico/métodos , Poluentes Atmosféricos/análise , Monitoramento Ambiental/métodos , Exposição Ocupacional/análise , IndústriasRESUMO
Despite significant advances in understanding the general health impacts of air pollution, the toxic effects of air pollution on cells in the human respiratory tract are still elusive. A robust, biologically relevant in vitro model for recapitulating the physiological response of the human airway is needed to obtain a thorough understanding of the molecular mechanisms of air pollutants. In this study, by using 1-nitropyrene (1-NP) as a proof-of-concept, we demonstrate the effectiveness and reliability of evaluating environmental pollutants in physiologically active human airway organoids. Multimodal imaging tools, including live cell imaging, fluorescence microscopy, and MALDI-mass spectrometry imaging (MSI), were implemented to evaluate the cytotoxicity of 1-NP for airway organoids. In addition, lipidomic alterations upon 1-NP treatment were quantitatively analyzed by nontargeted lipidomics. 1-NP exposure was found to be associated with the overproduction of reactive oxygen species (ROS), and dysregulation of lipid pathways, including the SM-Cer conversion, as well as cardiolipin in our organoids. Compared with that of cell lines, a higher tolerance of 1-NP toxicity was observed in the human airway organoids, which might reflect a more physiologically relevant response in the native airway epithelium. Collectively, we have established a novel system for evaluating and investigating molecular mechanisms of environmental pollutants in the human airways via the combinatory use of human airway organoids, multimodal imaging analysis, and MS-based analyses.
Assuntos
Poluentes Atmosféricos , Pirenos , Sistema Respiratório , Humanos , Reprodutibilidade dos Testes , Organoides , Imagem MultimodalRESUMO
This manuscript introduces a pyrene-based Schiff base L by reacting pyrenecarboxaldehyde with 2-aminothiazole in equimolar ratio. The ligand L was characterized by various spectral data and single crystal. The water sensing ability of L was examined in different organic solvents. The weakly emissive L in DMSO showed a fluorescence enhancement upon the addition of water. The water-induced fluorescence enhancement of L was occurred due to the combined effect of aggregation-induced emission (AIE) phenomenon and suppression of photo-induced electron transfer (PET) process. Using L, the water in DMSO can be detected down to 0.50 wt% with a quantification limit of 1.52 wt%. The analytical novelty of the developed sensor L was validated by detecting moisture in a variety of raw food products.
Assuntos
Corantes Fluorescentes , Água , Água/química , Corantes Fluorescentes/química , Dimetil Sulfóxido , Bases de Schiff/química , Pirenos/químicaRESUMO
A water-soluble polymeric pyrene-based polythioacetal (PTA-Py) with thioacetal units in the main chain is simply synthesized by direct polycondensation of 3, 6-dioxa-1, 8-octanedithiol, 1-pyrene formaldehyde, and mPEG2k-SH. The probe PTA-Py shows a good fluorescence response to Hg2+ ions due to the Hg2+-promoted deprotection reaction of thioacetal groups to regenerate the original 1-pyrene formaldehyde compound. After adding Hg2+ to the PTA-Py solution, the fluorescence intensity (FI) gradually increases with increasing concentrations of Hg2+. Compared with other metal ions, the probe exhibits high sensitivity, good selectivity, and rapid response to Hg2+. The low detection limits are 12.3 nm in ethanol-PBS buffer and 13.3 nm in water, respectively. The results imply that the simply synthesized water-soluble polymeric probe had potential applications in the rapid detection of Hg2+ ions in aqueous solutions. Moreover, the polymeric PTA-Py shows high sensitivity for CH3Hg+ with detection limits of 26.5 nm in ethanol/PBS buffer. In addition, PTA-Py can efficiently detect Hg2+ ions in HeLa cells. The results demonstrate that a valuable method is developed for biocompatible polymeric sensors for Hg2+ ions in biological and environmental samples.
Assuntos
Mercúrio , Humanos , Corantes Fluorescentes , Células HeLa , Água , Pirenos , Polímeros , Íons , Espectrometria de Fluorescência , Etanol , FormaldeídoRESUMO
Organic and polymer fluorescent nanomaterials are a frontier research focus. Here in this work, a series of fluorinated zwitterionic random copolymers end-attached with a quasi-chromophoric group of pyrene or tetraphenylethylene (TPE) are well synthesized via atom transfer radical polymerization with activators regenerated by electron transfer (ARGET ATRP). Those random copolymers with total degree of polymerization 100 or 200 are able to produce fluorescent single-chain nanoparticles (SCNPs) through intra-chain self-folding assembly with quite uniform diameters in the range of 10-20 nm as characterized by dynamic light scattering and transmission electron microscopy. By virtue of the segregation or confinement effect, both SCNPs functionalized with pyrene or TPE group are capable of emitting fluorescence, with pyrene tethered SCNPs exhibiting stronger fluorescence emission reaching the highest quantum yield ≈20%. Moreover, such kind of fluorescent SCNPs manifest low cytotoxicity and good cell imaging performance for Hela cells. The creation of fluorescent SCNPs through covalently attached one quasi-chromophore to the end of one fluorinated zwitterionic random copolymer provides an alternative strategy for preparing polymeric luminescence nanomaterials, promisingly serving as a new type of fluorescent nanoprobes for biological imaging applications.
Assuntos
Corantes Fluorescentes , Nanopartículas , Imagem Óptica , Polímeros , Humanos , Células HeLa , Nanopartículas/química , Polímeros/química , Corantes Fluorescentes/química , Estilbenos/química , Estrutura Molecular , Fluorescência , Halogenação , Pirenos/química , Tamanho da Partícula , Sobrevivência Celular/efeitos dos fármacos , PolimerizaçãoRESUMO
The present work describes the fabrication of the quaternary Zn-Cd-Sn-S nanostructure and its use in photocatalytic remediation of the biological contaminant pyrene from water resources. Nanostructures fabricated were characterized by XRD, UV-DRS, FTIR, DLS, EDX, and SEM. In addition, an agar well diffusion test was conducted to determine the antimicrobial activity. Zn-Cd-Sn-S (ZCSS) nanostructures were evaluated for their photocatalytic degrading potential by using pyrene as a model pollutant and evaluating the effects of parameters like initial pyrene concentration, nanocatalyst dosage, solution pH, and light sources during batch adsorption. Nanostructures had a size of 16.74 nm according to the XRD analysis. With a 300 min time interval, ZCSS nanostructures achieved the highest removal rate of 86.3%. Pyrene degradation metabolites were identified using GC-MS analysis of the degraded samples. A Freundlich isothermal (R2 0.9) and pseudo-first-order (R2 0.952) reaction kinetic path best fit the adsorption results for pyrene by the fabricated ZCSS nanostructure, based on the adsorption and kinetic studies. Zn-Cd-Sn-S exhibited the highest antibacterial activity against Staphylococcusaureus (22.4 mM). Due to the combined synergistic actions of the constituent metals, this quaternary nanostructure exhibited exceptional photocatalytic activity. To our est knowledge, the ZCSS nanostructure was made and used to remove pyrene by photocatalysis and fight microbes. Ultimately, the ZCSS nanostructure was found to be an effective photocatalyst for eradicating pathogenic microbes from water.
Assuntos
Nanoestruturas , Pirenos , Pirenos/química , Nanoestruturas/química , Poluentes Químicos da Água/química , Zinco/química , Cádmio/química , Anti-Infecciosos/farmacologia , Anti-Infecciosos/química , Antibacterianos/farmacologia , Antibacterianos/químicaRESUMO
Polycyclic aromatic hydrocarbons (PAHs) are potentially hazardous compounds that could cause a severe impact on many ecosystems. They are very challenging to remove using conventional methods due to their hydrophobic nature. However, this issue can be resolved by utilizing surface-active molecules to increase their bioavailability. In this study, pyrene was chosen as the PAH compound to explore its degradability by the effect of individual bacterial strains (Pseudomonas stutzeri NA3 and Acinetobacter baumannii MN3) and mixed consortia (MC) along with natural surfactant derived from Sapindus mukorossi and iron oxide nanoparticles (NPs). Additionally, fatty acids esters, dipeptides, and sugar derivative groups were identified as potent bioactive components of natural surfactants. Various techniques, such as XRD, VSM, TEM, and FE-SEM with EDX, were utilized to characterize the pristine and Fenton-treated iron oxide NPs. The analytical results confirmed that the Fe3O4 crystal phase and spherical-shaped NPs exhibited excellent magnetic properties. The impact of natural surfactants and iron oxide NPs has significantly contributed to the biodegradation process, resulting in a prominent decrease in chemical oxygen demand (COD) levels. Gas chromatography-mass spectrometry (GC-MS) analysis showed that biodegradation systems produced primary hydrocarbon intermediates, which underwent oxidative degradation through Fenton treatment. Interestingly, synthesized iron oxide NPs effectively produced hydroxyl radical (â¢OH) during the Fenton reaction, which was confirmed by electron paramagnetic resonance (EPR) spectra, and the pristine iron oxide NPs underwent a material transformation observed. The study demonstrated an integrated approach for biodegradation and the Fenton reaction process to enhance the pyrene degradation efficiency (90%) compared to other systems. Using natural surfactants and iron oxide NPs in aquatic environments serves as a crucial platform at the interface of microorganisms and contaminated oil products. This interaction offers a promising solution for PAHs bioremediation.
Assuntos
Compostos Férricos , Hidrocarbonetos Policíclicos Aromáticos , Poluentes do Solo , Tensoativos/química , Biodegradação Ambiental , Ecossistema , Poluentes do Solo/análise , Pirenos/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Bactérias/metabolismo , Nanopartículas Magnéticas de Óxido de FerroRESUMO
BACKGROUND: Inferior vena cava (IVC) resection is essential for complete (R0) excision of some malignancies. However, the optimal material for IVC reconstruction remains unclear. Our objective is to demonstrate the efficacy, safety, and advantages of using Non-Fascial Autologous Peritoneum (NFAP) for IVC reconstruction. To conduct a literature review of surgical strategies for tumors involving the IVC. METHODS: We reviewed all IVC reconstructions performed at our institution between 2015 and 2023. Preoperative, operative, postoperative, and follow-up data were collected and analyzed. RESULTS: A total of 33 consecutive IVC reconstructions were identified: seven direct sutures, eight venous homografts (VH), and 18 NFAP. With regard to NFAP, eight tubular (mean length, 12.5 cm) and 10 patch (mean length, 7.9 cm) IVC reconstructions were performed. Resection was R0 in 89% of the cases. Two patients had Clavien-Dindo grade I complications, 2 grade II, 2 grade III and 2 grade V complications. The only graft-related complication was a case of early partial thrombosis, which was conservatively treated. At a mean follow-up of 25.9 months, graft patency was 100%. There were seven recurrences and six deaths. Mean overall survival (OS) was 23.4 months and mean disease-free survival (DFS) was 14.4 months. According to our results, no statistically significant differences were found between NFAP and VH. CONCLUSIONS: NFAP is a safe and effective alternative for partial or complete IVC reconstruction and has many advantages over other techniques, including its lack of cost, wide and ready availability, extreme handiness, and versatility. Further comparative studies are required to determine the optimal technique for IVC reconstruction.
Assuntos
Peritônio , Pirenos , Veia Cava Inferior , Humanos , Veia Cava Inferior/cirurgia , Veia Cava Inferior/patologia , Peritônio/cirurgia , Estudos Retrospectivos , Veias , Resultado do TratamentoRESUMO
PURPOSE: Robotic-assisted total knee arthroplasty (r-TKA) facilitates precise bone resection and lower limb alignment, yet accuracy and functional recovery for severe varus/valgus deformity is not well-documented. The aim of study was to investigate whether r-TKA improves implant alignment in the coronal and sagittal view and early functional recovery compared to conventional TKA(c-TKA). METHODS: This comparative study included 86 patients with symptomatic knee arthritis who underwent primary TKA at our institution between 1st May and 31th November 2021. Radiological parameters evaluated included hip-knee-ankle angle (HKAA), femoral varus-valgus angle (FVVA), tibial varus-valgus angle (TVVA), posterior tibial slope angle (PTSA), femoral sagittal angle (FSA), posterior condylar offset ratio, and Insall-Salvati index. Operative time, stay length, and complications were reviewed from patient records. The hospital for special surgery (HSS), Visual Analogue Scale (VAS) and knee joint motion range were evaluated at the six-month follow-up. RESULTS: The c-TKA and r-TKA groups had no significant differences in HKAA (179.73 ± 3.76°, range: 172.10-188.90° vs. 180.53 ± 2.91°, range: 173.30-188.32°, p = 0.277), FVVA (96.13 ± 2.61°, range: 90.27-101.52° vs. 96.38 ± 2.23°, range: 90.98-100.95°, p = 0.636), and TVVA (88.74 ± 2.03°, range: 83.75-92.74° vs. 89.43 ± 1.83°, range: 85.32-94.15°, p = 1.000). Outlier of mechanical alignment incidence (> 3°) was significantly lower in r-TKA compared with c-TKA, 17.50% (7/40) vs. 41.30% (19/46), (p = 0.017). PTSA of r-TKA remained significantly lower than c-TKA (p = 0.009) in mild-deformity patients. For severe varus/valgus deformity, r-TKA had a significantly lesser HKAA-outlier incidence (p = 0.025), PTSA-outlier incidence (p = 0.019), and lower PTSA (p < 0.001) compared with c-TKA. The r-TKA functional outcome was better than c-TKA regarding HSS (93.12 ± 1.97, range: 90-95, 95%CI:92.11-94.13 vs. 91.33 ± 2.50, range: 85-95, 95%CI:90.20-92.69, p = 0.036), and VAS (0.24 ± 0.44, range:0-1 vs. 0.72 ± 0.75, range:0-2, p = 0.026), knee joint flexion (118.53° ± 8.06, range: 105-130°, 95%CI:114.39-122.67° vs. 112.22 ± 8.09°, range: 100-130°, 95%CI:108.20-116.24° ,p = 0.027) for severe varus/valgus deformity. CONCLUSION: r-TKA improved lower-limb coronal alignment, sagittal implant position, and early functional recovery for patients with severe varus/valgus deformity of the knee. r-TKA did not confer substantial advantages over c-TKA in both radiological and clinical outcomes for the mild varus/valgus deformity.
Assuntos
Artroplastia do Joelho , Pirenos , Procedimentos Cirúrgicos Robóticos , Humanos , Artroplastia do Joelho/efeitos adversos , Procedimentos Cirúrgicos Robóticos/efeitos adversos , Articulação do Joelho/diagnóstico por imagem , Articulação do Joelho/cirurgia , Extremidade InferiorRESUMO
Considerable efforts that isolate and characterize degrading bacteria for polycyclic aromatic hydrocarbons (PAHs) have focused on contaminated environments so far. Here we isolated three distinctive pyrene (PYR)-degrading bacteria from a paddy soil that was not contaminated with PAHs. These included a novel Bacillus sp. PyB-9 and efficient degraders, Shigella sp. PyB-6 and Agromyces sp. PyB-10. All three strains could utilize naphthalene, phenanthrene, anthracene, fluoranthene and PYR as sole carbon sources, and degraded PYR in a range of temperatures (27-37 °C) and pH (5-8). Strains PyB-6 and PyB-10 almost completely degraded 50 mg L-1 PYR within 15 days, and 75.5% and 98.9% of 100 mg L-1 PYR in 27 days, respectively. The kinetics of PYR biodegradation was well represented by the Gompertz model. Ten and twelve PYR metabolites were identified in PYR degradation process by strains PyB-6 and PyB-10, respectively. Chemical analyses demonstrated that the degradation mechanisms of PYR were the same for strains PyB-6 and PyB-10 with initial dioxygenation mainly on C-4,5 positions of PYR. The degradation of 4,5-phenanthrenedicarboxylic acid was branched to 4-phenanthrenecarboxylic acid pathway and 5-hydroxy-4-phenanthrenecarboxylic acid pathway, both of which played important roles in PYR degradation by strains PyB-6 and PyB-10. To our knowledge, Shigella sp. and Agromyces sp. were found for the first time to possess the capability for PAHs degradation. These findings contributed to upgrading the bank of microbial resource and knowledge on PAH biodegradation.
Assuntos
Biodegradação Ambiental , Pirenos , Microbiologia do Solo , Poluentes do Solo , Pirenos/metabolismo , Poluentes do Solo/metabolismo , Bactérias/metabolismo , Hidrocarbonetos Policíclicos Aromáticos/metabolismo , Bacillus/metabolismo , Filogenia , Fenantrenos/metabolismo , Shigella/metabolismo , CinéticaRESUMO
The anthropogenic activities toward meeting the energy requirements have resulted in an alarming rise in environmental pollution levels. Among pollutants, polycyclic aromatic hydrocarbons (PAHs) are the most predominant due to their persistent and toxic nature. Amidst the several pollutants depuration methods, bioremediation utilizing biodegradation is the most viable alternative. This study investigated the biodegradation efficacy using developed microbial consortium PBR-21 for 2-4 ringed PAHs named naphthalene (NAP), anthracene (ANT), fluorene (FLU), and pyrene (PYR). The removal efficiency was observed up to 100 ± 0.0%, 70.26 ± 4.2%, 64.23 ± 2.3%, and 61.50 ± 2.6%, respectively, for initial concentrations of 400 mg L-1 for NAP, ANT, FLU, and PYR respectively. Degradation followed first-order kinetics with rate constants of 0.39 d-1, 0.10 d-1, 0.08 d-1, and 0.07 d-1 and half-life t 1 / 2 of 1.8 h, 7.2 h, 8.5 h, and 10 h, respectively. The microbial consortia were found to be efficient towards the co-contaminants with 1 mM concentration. Toxicity examination indicated that microbial-treated PAHs resulted in lesser toxicity in aquatic crustaceans (Artemia salina) than untreated PAHs. Also, the study suggests that indigenous microbial consortia PBR-21 has the potential to be used in the bioremediation of PAH-contaminated environment.