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Covered stent correction of a superior sinus venosus atrial septal defect is increasingly performed as an alternative to surgical repair. While sinus node dysfunction requiring pacemaker implantation may be required after surgical repair, this has not been previously reported after covered stent implantation. We reviewed the experience in two interventional centers. Balloon inflation in the superior vena cava was used to confirm the anomalous pulmonary vein drainage would be unobstructed after stent implantation. During balloon testing in 62 consecutive patients, we assessed gradients across the pulmonary vein to left atrium while monitoring the rhythm. We observed the outcomes after covered stent correction in 51 patients. In a single patient, significant bradycardia and pauses developed on repeat balloon testing and the procedure was abandoned without stent implantation. In another patient, there was no sign of sinus node dysfunction during balloon testing but several hours after stent implantation, the patient became symptomatic from sinus bradycardia and pauses and had a pacemaker implanted 3 days later. Over a year later there are some signs of improvement in sinus node function. While sinus node dysfunction has not been described previously during balloon testing or after stent implantation, this report demonstrates for the first time that it may occur. Larger registries are therefore required to monitor for this uncommon complication.
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A series of new symmetrical highly substituted BODIPYs 6 a-l was synthesized through a prefunctionalization approach in 35 %-89 % yields from the pyrrole core. This strategy allowed modulation of the substituents at the different positions based on the choice of Fischer's alkynyl carbenes, oxazolones and aldehydes used as precursors. The substituent variation at positions 2, 6, 3 and 5 had the greatest effect on the modulation of their photophysical properties such as absorption (λabs ) and emission (λem ) wavelengths, extinction coefficient (ϵ), quantum yields (Ï), Stokes shifts (Δν), fluorescence decay, radiative (krad ) and non-radiative (knr ) constants and the CIE 1931 coordinates. Theoretical calculations allowed to corroborate the effect of the substituents of meso-position on the modification of the dihedral angles. Cyclic voltammetry studies revealed that the BODIPY series presents similar redox potential behavior, being electrochemically active even in successive cycles, which suggests that transport by diffusion is the dominant process.
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We report on the optoelectronic properties of a series of unsymmetrical π-conjugated phenyleneethynylene macromolecules bearing ferrocene (Fc) as the electron-donor group (D), (benzyl) benzoate (Bz) or benzoic acid (Ac) as the electron attractor group (A) and connected through 2,5-di(alcoxy) phenyleneethynylene(s) (nPE) with n = 1, 2, 3 as π-conjugated bridges. In the series, by increasing the distance between the electron-attracting and electron-donor groups, the push-pull effect decreases. The intramolecular charge transfer (D â π â A) was evaluated by static and dynamic spectroscopy, electrochemistry, and density functional theory (DFT) theoretical calculations. The longest oligomer Fc3PEBz formed the best optical quality films. A study at the atomic level by scanning tunneling microscopy (STM) revealed that the molecules self-assemble on highly ordered pyrolytic graphite (HOPG) in domains with a short-range order. Films are mesoporous and the molecules arrange in a lamellar-like pattern, with an edge-on conformation with respect to HOPG, where the conjugated backbones lie parallel to the surface. Two different assemblies were identified in the monoatomic film, which depends on the ferrocene-ferrocene or benzyl-benzyl interactions.
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Two series of 2,5-di(butoxy)phenyleneethynylenes, one halogenated (nPEC4-X; n=2, 3, or 4) and the other boron-dipyrromethene (BODIPY) terminated (nPEC4-By; n=3, 4, or 5; By=BODIPY), were synthesized monodirectionally by the step-by-step approach and the molecular structure was corroborated by NMR spectroscopy (1 H, 13 C-DEPTQ-135, COSY, HSQC, HMBC, 11 B, 19 F) and MALDI-TOF mass spectrometry. The multiplicity and J-coupling constants of 1 H, 11 B, and 19 F/11 Bâ NMR signals revealed, in the nPEC4-By series, that the phenyl in the meso position of BODIPY becomes electronically part of the conjugation of the phenyleneethynylene chain, whereas BODIPY is electronically isolated. The photophysical, electrochemical, and theoretical studies confirm this finding because the properties of nPEC4-By are comparable to those of the nPEC4-X oligomers and BODIPY, indicating negligible electron communication between BODIPY and the nPEC4 moieties. Nevertheless, energy transfer (ET) from nPEC4 to BODIPY was rationalized by spectroscopy and theoretical calculations. Its yield decreases with the nPEC4 conjugation length, according to the increase in distance between the two chromophores, resulting in dual emission for the longest oligomer in which ET is quenched.
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ABSTRACT: Autologous reconstruction for major facial defects is primarily considered for patient's lifetime care. There are situations, however, when autologous reconstruction is not ideal or feasible, and prosthetic reconstruction is necessary to reconstruct missing anatomy or to complement surgical reconstruction. The history of facial prosthetic reconstruction can be traced for millennia. At our craniofacial center, craniomaxillofacial prosthetic rehabilitation has been incorporated in the care provided to our patients since the center's inception, more than 70 years ago.The purpose of this review is to present the evolution of our current thinking based on our long experience since the implementation of computer-assistive technologies over 15 years ago, to further improve our patients' overall rehabilitation.These applications include all stages of prosthetic care from planning, design through device delivery, and for lifetime maintenance. The collaboration among surgeons and anaplastologists is fundamental to achieving optimal patient outcomes and in the success of our technology-based practice. Such collaboration starts with the patient's decision to proceed with prosthetic rehabilitation and continues with postoperative care and lifetime management of the patient's prosthetic device and prosthesis-bearing soft tissue.Although computer-assistive techniques often represent a substantial financial investment, the benefits of using them demonstrate clear advantages to both the clinician and patient. These benefits include: Improved predictability of outcomes, surgeon preparedness, reduction in operating room time, reduction in overall treatment times, improved precision and anatomical accuracy, improved treatment efficiencies, and overall treatment experience, particularly for those patients traveling great distances for access to care.Representative examples will be presented.
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Implantes Dentários , Procedimentos de Cirurgia Plástica , Face/cirurgia , Humanos , Implantação de PróteseRESUMO
The fabrication, molecular structure, and spectroscopy of a stable cholesteric liquid crystal platinum acetylide glass obtained from trans-Pt(PEt3)2(C≡C-C6H5-C≡N)(C≡C-C6H5-COO-Cholesterol), are described and designated as PE1-CN-Chol. Polarized optical microscopy, differential scanning calorimetry, and wide-angle X-ray scattering experiments show room temperature glassy/crystalline texture with crystal formation upon heating to 165 °C. Further heating results in conversion to cholesteric phase. Cooling to room temperature leads to the formation of a cholesteric liquid crystal glass. Scanning tunneling microscopy of a PE1-CN-Chol monolayer reveals self-assembly at the solid-liquid interface with an array of two molecules arranged in pairs, oriented head-to-head through the CN groups, giving rise to a lamella arrangement. The lamella structure obtained from molecular dynamics calculations shows a clear phase separation between the conjugated platinum acetylide and the hydrophobic cholesterol moiety with the lamellae separation distance being 4.0 nm. Ultrafast transient absorption and flash photolysis spectra of the glass show intersystem crossing to the triplet state occurring within 100 ps following excitation. The triplet decay time of the film compared to aerated and deoxygenated solutions is consistent with oxygen quenching at the film surface but not within the film. The high chromophore concentration, high glass thermal stability, and long triplet lifetime in air show that these materials have potential as nonlinear absorbing materials.
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A series of water soluble 8-alcoxypyrene-1,3,6-trisulfonic sodium salts bearing different alcoxy lateral chains and functional end groups was synthesized and the molecular structure was corroborated by nuclear magnetic resonance spectroscopy. The photophysical properties in water analyzed by UV-Vis and static and dynamic fluorescence revealed that all of the pigments emit in the blue region at a maximal wavelength of 436 nm and with fluorescence lifetimes in the range of ns. Among them, sodium 8-((10-carboxydecyl) oxy) pyrene-1,3,6-trisulfonate M1 exhibits a high fluorescence quantum yield (φ = 80%) and a good interaction with B. subtilis LPM1 rhizobacteria; this has been demonstrated through in vitro staining assays. Tomato plants (Solanum lycopersicon cv. Micro-Tom) increased the release of root exudates, mainly malic and fumaric acids, after 12 h of treatment with benzothiadiazole (BTH) as a foliar elicitor. However, the chemotaxis analysis demonstrated that malic acid is the most powerful chemoattractant of the rhizobacteria Bacillus subtilis LPM1: in agar plates, a major growth (60 mm) was found for a concentration of 100 mM, while in capillary tubes, the earliest response was at 30 min with 3.3 × 108 CFU mL-1. The confocal microscopic analysis carried out on the tomato roots of the pyrene stained B. subtilis LPM1 revealed that this bacterium mainly colonizes the epidermal zones, i.e. the junctions to primary roots, lateral roots and root hairs, meaning that these root hair sections are the highest colonisable sites involved in the biosynthesis of exudates. This fluorescent pyrene marker M1 represents a valuable tool to evaluate B. subtilis-plant interactions in an easy and quick test in both in vitro and in vivo tomato crops.
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Bacillus subtilis/química , Fluorescência , Corantes Fluorescentes/química , Raízes de Plantas/química , Pirenos/análise , Solanum lycopersicum/microbiologia , Corantes Fluorescentes/síntese química , Microscopia Confocal , Estrutura Molecular , Espectrometria de FluorescênciaRESUMO
Pharmacological therapies for interrupting biochemical events of the ischaemic cascade and protecting against stroke in humans are as yet unavailable. Up to now, the neuroprotective activity in cerebral ischaemia of phycocyanobilin (PCB), a tetrapyrrolic natural antioxidant, has not been fully examined. Here, we evaluated if PCB protects PC12 neuronal cells against oxygen and glucose deprivation plus reperfusion, and its protective effects in a rat model of endothelin-1-induced focal brain ischaemia. PCB was purified from the cyanobacteria Spirulina platensis and characterized by spectrophotometric, liquid and gas chromatography and mass spectrometry techniques. In Wistar rats, PCB at 50, 100 and 200 µg/kg or phosphate-buffered saline (vehicle) was administered intraperitoneally at equal subdoses in a therapeutic schedule (30 minutes, 1, 3 and 6 hours after the surgery). Brain expression of myelin basic protein (MBP) and the enzyme CNPase was determined by immunoelectron microscopy. PCB was obtained with high purity (>95%) and the absence of solvent contaminants and was able to ameliorate PC12 cell ischaemic injury. PCB treatment significantly decreased brain infarct volume, limited the exploratory behaviour impairment and preserved viable cortical neurons in ischaemic rats in a dose-dependent manner, compared to the vehicle group. Furthermore, PCB at high doses restored the MBP and CNPase expression levels in ischaemic rats. An improved PCB purification method from its natural source is reported, obtaining PCB that is suitable for pharmacological trials showing neuroprotective effects against experimental ischaemic stroke. Therefore, PCB could be a therapeutic pharmacological alternative for ischaemic stroke patients.
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Lesões Encefálicas/induzido quimicamente , Lesões Encefálicas/tratamento farmacológico , Isquemia Encefálica/induzido quimicamente , Isquemia Encefálica/tratamento farmacológico , Endotelina-1/toxicidade , Ficobilinas/uso terapêutico , Ficocianina/uso terapêutico , Animais , Lesões Encefálicas/patologia , Isquemia Encefálica/patologia , Masculino , Células PC12 , Ratos , Ratos WistarRESUMO
A small series of boron-dipyrromethene (BODIPY) dyes, characterized by the presence of multibranched fluorinated residues, were designed and synthesized. The dyes differ in both the position (para-perfluoroalkoxy-substituted phenyl ring or boron functionalization) and number of magnetically equivalent fluorine atoms (27 or 54â fluorine atoms per molecule). Photophysical and crystallographic characterization of the synthesized BODIPYs was carried out to evaluate the effect of the presence of highly fluorinated moieties on the optical and morphological properties of such compounds.
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Fat grafting has become a well-accepted surgical modality to correct soft tissue facial defects and asymmetries with overall good results. Several techniques have been reported over the last few years to assist in improving accurate evaluation of facial defects and in the preoperative planning of the reconstruction. Such techniques include among others, computer tomography, three-dimensional (3D) photogrammetry, high resolution ultrasound, and 3D laser scanning. There are advantages and disadvantages for each technique.With the rapid advance of 3D technologies that have become readily available to clinicians, new clinical applications continually emerge to guide and facilitate reconstructive procedures. The authors explored the possibility of fabricating a 3D printed surgical guide to define volume differences for soft tissue reconstruction in patients with facial asymmetry. The model was developed through the authors' virtual surgical simulation and planning system that consists of computer-assisted design (CAD) and 3D printing (3DP).Three-dimensional volumetric scans of patients' faces were analyzed with computer-aided design to quantify areas of facial asymmetry. Surgical guides with containers defining volumetric differences were fabricated using 3D printing to identify and quantify areas of soft tissue deficiency. The 3D printed patient-specific, guides were sterilized and used by the surgeon intraoperatively to accurately mark the areas of soft deficiency. Thus, facial symmetry was achieved by fat grafting the predetermined volume differences defined in the surgical guides. A postop mask was used by the surgeon at the end of the procedure and during follow-up clinic visit to verify and evaluate accurate fat grafting placement as well as to determine areas where to add volume if needed.This paper details the rational for the authors' approach, outlines the technical planning and fabrication process of these patient-specific custom surgical guides with quantified volumetric containers and their intraoperative use by the surgeon. Despite the authors' limited experience we conclude that the authors' technique offer surgeons a precise means for accurate volumetric reconstruction of facial asymmetry.
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Assimetria Facial/cirurgia , Procedimentos de Cirurgia Plástica/métodos , Cirurgia Assistida por Computador/métodos , Tecido Adiposo/transplante , Adolescente , Desenho Assistido por Computador , Feminino , Humanos , Imageamento Tridimensional , Máscaras , Impressão Tridimensional , Tomografia Computadorizada por Raios X , Adulto JovemRESUMO
Escherichia coli is one the most common bacteria responsible of uropathogenic diseases, which motives the search for rapid and easy methods of detection. By taking advantage of the specific interactions between mannose and type 1 fimbriae, in this work two fluorescent phenyleneethynylene (PE) trimers bearing one or two 4-aminophenyl-α-D-mannopyranoside termini groups were synthesized for the detection of E. coli. Three bacterial strains: ORN 178 (fimbriae I expression), ORN 208 (mutant serotype with no fimbriae expression) and one obtained from a local hospital (SS3) were used. Laser Scanning Confocal Microscopy (LSCM) and Surface Plasmon Resonance (SPR) were applied for the interaction studies following two different approaches: (1) mixing the oligomer solutions with the bacterial suspension, which permitted the observation of stained bacteria and by (2) biosensing as thin films, where bacteria adhered on the surface-functionalized substrate. LSCM allows one to easily visualize that two mannose groups are necessary to have a specific interaction with the fimbriae 1. The sensitivity of SPR assays to E. coli was 104 colony forming unit (CFU)/mL at 50 µL/min flow rate. The combination of PE units with two mannose groups results in a novel molecule that can be used as a specific fluorescent marker as well as a transducer for the detection of E. coli.
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Escherichia coli , Alcinos , Aderência Bacteriana , Éteres , ManoseRESUMO
The supramolecular order of a 2,5-bis(dodecanoxy)phenyleneethynylene-butadiyne series of rod-like oligomers with 2, 4, 6, and 8 phenyleneethynylene moieties was studied in the solid state by differential scanning calorimetry (DSC), temperature-dependent small- and wide-angle X-ray scattering (SWAXS), selected area electron diffraction (SAED), polarized optical microscopy (POM), high-resolution transmission microscopy (HRTEM), and scanning tunneling microscopy (STM). It was found that all of the oligomers self-assemble in blocks of molecules that resemble bricks that are randomly oriented. These oligomers are described as sanidic liquid crystals as a term to classify their mesomorphic behavior because of their brick or board-like structure. The strong π-π interaction that governs the package of conjugated backbones was evidenced by the reiterative distances of 0.36 ± 0.017 nm found by SWAXS and 0.32 ± 0.017 nm found by HRTEM. A STM study of a cast film of the tetramer deposited on highly oriented pyrolitic graphite (HOPG) allowed for the visualization and determination of the conjugated backbone length of 2.48 nm and a phenyl-phenyl distance of 0.34 nm, suggesting that the molecules are stacked in lamellae perpendicularly aligned to the substrate.
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Chitosan (CS) and sodium alginate (SA)-based biocomposites (CSA) were prepared with the in-situ generation of Calcium Carbonate (CSAX_Ca) through a simple, straightforward, economical, and eco-friendly procedure. Different drying conditions (X) were tested to achieve suitable structural and surface characteristics to enhance adsorption capacity: freeze-dried (L), vacuum-dried with methanol (M), and freeze-dried + vacuum-dried with methanol (LM). Temperature and adsorbent dosage effects on the adsorption capacity of Cu2+ or Pb2+ were examined. Results showed that the higher-yielding biocomposite (CSALM_Ca) exhibited rapid adsorption and good diffusion properties, achieving removal above 90â¯% within contaminant initial concentration ranges of 10-100â¯mg/L. At 35⯰C, a pseudo-second-order kinetic and the Langmuir model effectively described kinetics and isotherms, revealing maximum adsorption (qe, max) of 429 mgCu2+/L and 1742 mgPb2+/g. Characterization through FTIR, XRD, and SEM of the as-prepared adsorbents confirmed the presence of CaCO3 in vaterite and calcite forms and the influence of drying conditions on the material morphology. Post-adsorption material characterization, in combination with adsorption findings, revealed chemisorption processes involving Ca2+ ion exchange for Cu2+ or Pb2+, resulting in surface-insoluble compounds. The best-performing material showed that after three reuse cycles, the removal of Cu2+ and Pb2+ decreased to 75â¯% and 62â¯%, respectively.
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Alginatos , Carbonato de Cálcio , Quitosana , Cobre , Chumbo , Poluentes Químicos da Água , Purificação da Água , Quitosana/química , Cobre/química , Alginatos/química , Chumbo/química , Adsorção , Carbonato de Cálcio/química , Poluentes Químicos da Água/química , Cinética , Purificação da Água/métodos , Água/química , Propriedades de Superfície , TemperaturaRESUMO
Fluorescent organotin compounds are useful in sensing, optoelectronic devices, and in vitro bioimaging. Although in vitro fluorescence bioimaging shows low resolution at room temperature, a better resolution is possible at cryotemperatures. Therefore, the search for new cryoluminescent materials with potential application in high-resolution fluorescence bioimaging remains a great challenge. Herein, we report the cryoluminescence properties of two fluorescent bis-organotin compounds, namely, BisNTHySnBu2 (5) and BisNTHySnPh2 (6), synthesized via microwave irradiation. All compounds were fully characterized using 1H, 13C, and 119Sn NMR spectroscopy, Raman spectroscopy, IR spectroscopy, and HR-MS. The 119Sn δ and 3J(1H,119Sn) of 5 and 6 indicate that two Sn-ligands are chemically and electronically equivalent, as confirmed by cyclic voltammetry. The crystal structure of 6 showed pentacoordinate tin atoms with skeleton ligands. The study of self-assembled monolayers of both Sn-complexes via STM microscopy revealed a similar supramolecular packing in lamella-like patterns, adopting a face-on arrangement, where molecules stay flat lying on HOPG in accordance with the height profile of closely packed monolayers on graphite of about 0.33 nm thickness. However, only the Sn complex 6, which bears phenyls, covers large surface areas. The photophysical properties of bis-organotin compounds were also investigated in solution (room and low temperatures) and in the solid state. Good luminescence properties in solutions with fluorescence quantum yields (Φ) of approximately 35% and 50% were found. Despite this, Φ is quenched in the solid state because of aggregation, as supported by solvent/non solvent fluorescence studies, which is in agreement with STM and AFM investigation.
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HeberNasvac, a therapeutic vaccine for chronic hepatitis B, is able to safely stimulate multiple Toll-like receptors, increasing antigen presentation in vitro and in a phase II clinical trial (Profira) in elderly volunteers who were household contacts of respiratory infection patients. Thus, a new indication as a postexposure prophylaxis or early therapy for respiratory infections has been proposed. In this study, we evaluated the expression of several interferon-stimulated genes (ISGs) after mucosal administration of HeberNasvac and compared this effect with the nasal delivery of interferon alpha 2b (Nasalferon). Molecular studies of blood samples of 50 subjects from the Profira clinical trial who were locally treated with HeberNasvac or Nasalferon and concurrent untreated individuals were compared based on their relative mRNA expression of OAS1, ISG15, ISG20, STAT1, STAT3, and DRB1-HLA II genes. In most cases, the gene expression induced by HeberNasvac was similar in profile and intensity to the expression induced by Nasalferon and significantly superior to that observed in untreated controls. The immune stimulatory effect of HeberNasvac on ISGs paved the way for its future use as an innate immunity stimulator in elderly persons and immunocompromised subjects or as part of Mambisa, a nasal vaccine to prevent severe acute respiratory syndrome coronavirus 2 infection.
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Pandemias , Vacinas , Humanos , Idoso , Imunidade Inata/genética , Vacinas/farmacologiaRESUMO
Since the inflammatory response and oxidative stress are involved in the stroke cascade, we evaluated here the effects of Phycocyanobilin (PCB, the C-Phycocyanin linked tetrapyrrole) on PC12 cell survival, the gene expression and the oxidative status of hypoperfused rat brain. After the permanent bilateral common carotid arteries occlusion (BCCAo), the animals were treated with saline or PCB, taking samples 24h post-surgery. Global gene expression was analyzed with GeneChip Rat Gene ST 1.1 from Affymetrix; the expression of particular genes was assessed by the Fast SYBR Green RT-PCR Master Mix and Bioplex methods; and redox markers (MDA, PP, CAT, SOD) were evaluated spectrophotometrically. The PCB treatment prevented the H2O2 and glutamate induced PC12 cell injury assessed by the MTT assay, and modulated 190 genes (93 up- and 97 down-regulated) associated to several immunological and inflammatory processes in BCCAo rats. Furthermore, PCB positively modulated 19 genes mostly related to a detrimental pro-inflammatory environment and counteracted the oxidative imbalance in the treated BCCAo animals. Our results support the view of an effective influence of PCB on major inflammatory mediators in acute cerebral hypoperfusion. These results suggest that PCB has a potential to be a treatment for ischemic stroke for which further studies are needed.
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Sobrevivência Celular/efeitos dos fármacos , Transtornos Cerebrovasculares/tratamento farmacológico , Genes MHC da Classe II/efeitos dos fármacos , Inflamação/genética , Estresse Oxidativo/efeitos dos fármacos , Ficobilinas/farmacologia , Ficocianina/farmacologia , Animais , Biomarcadores/metabolismo , Química Encefálica/efeitos dos fármacos , Química Encefálica/genética , Transtornos Cerebrovasculares/fisiopatologia , Corantes , Citocinas/biossíntese , Ácido Glutâmico/metabolismo , Peróxido de Hidrogênio/farmacologia , Masculino , Análise em Microsséries , Oxirredução , Células PC12 , Ficobilinas/isolamento & purificação , Ficocianina/isolamento & purificação , Ratos , Ratos Wistar , Reação em Cadeia da Polimerase em Tempo Real , Spirulina/química , Sais de Tetrazólio , Tiazóis , Fator A de Crescimento do Endotélio Vascular/metabolismoRESUMO
The morphological, spectroscopic and rheological properties of silver nanoparticles (AgNPs) synthesized in situ within commercial PEDOT:PSS formulations, labeled PP@NPs, were systematically investigated by varying different synthetic parameters (NaBH4/AgNO3 molar ratio, PEDOT:PSS formulation and silver and PEDOT:PSS concentration in the reaction medium), revealing that only the reagent ratio affected the properties of the resulting nanoparticles. Combining the results obtained from the field-emission scanning electron microscopy analysis and UV-Vis characterization, it could be assumed that PP@NPs' stabilization occurs by means of PSS chains, preferably outside of the PEDOT:PSS domains with low silver content. Conversely, with high silver content, the particles also formed in PEDOT-rich domains with the consequent perturbation of the polaron absorption features of the conjugated polymer. Atomic force microscopy was used to characterize the films deposited on glass from the particle-containing PEDOT:PSS suspensions. The film with an optimized morphology, obtained from the suspension sample characterized by the lowest silver and NaBH4 content, was used to fabricate a very initial prototype of a water-processable anode in a solar cell prepared with an active layer constituted by the benchmark blend poly(3-hexylthiophene) and [6,6]-Phenyl C61 butyric acid methyl ester (PC60BM) and a low-temperature, not-evaporated cathode (Field's metal).
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A π-conjugated polymer (PBQT) containing bis-(2-ethylhexyloxy)-benzo [1,2-b'] bithiophene (BDT) units alternated with a quinoline-vinylene trimer was obtained by the Stille reaction. The chemical structure of the polymer was verified by nuclear magnetic resonance (1H NMR), Fourier transform infrared (FT-IR), and mass spectroscopy (MALDI-TOF). The intrinsic photophysical properties of the solution were evaluated by absorption and (static and dynamic) fluorescence. The polymer PBQT exhibits photochromism with a change in absorption from blue (449 nm) to burgundy (545 nm) and a change in fluorescence emission from green (513 nm) to orange (605 nm) due to conformational photoisomerization from the trans to the cis isomer, which was supported by theoretical calculations DFT and TD-DFT. This optical response can be used in optical sensors, security elements, or optical switches. Furthermore, the polymer forms spin-coated films with absorption properties that cover the entire visible range, with a maximum near the solar emission maximum. The frontier molecular orbitals, HOMO and LUMO, were calculated by cyclic voltammetry, and values of -5.29 eV and -3.69, respectively, and a bandgap of 1.6 eV were obtained, making this material a semiconductor with a good energetic match. These properties could suggest its use in photovoltaic applications.
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Introduction: The antinociceptive and pharmacological activities of C-Phycocyanin (C-PC) and Phycocyanobilin (PCB) in the context of inflammatory arthritis remain unexplored so far. In the present study, we aimed to assess the protective actions of these compounds in an experimental mice model that replicates key aspects of human rheumatoid arthritis. Methods: Antigen-induced arthritis (AIA) was established by intradermal injection of methylated bovine serum albumin in C57BL/6 mice, and one hour before the antigen challenge, either C-PC (2, 4, or 8 mg/kg) or PCB (0.1 or 1 mg/kg) were administered intraperitoneally. Proteome profiling was also conducted on glutamate-exposed SH-SY5Y neuronal cells to evaluate the PCB impact on this key signaling pathway associated with nociceptive neuronal sensitization. Results and discussion: C-PC and PCB notably ameliorated hypernociception, synovial neutrophil infiltration, myeloperoxidase activity, and the periarticular cytokine concentration of IFN-γ, TNF-α, IL-17A, and IL-4 dose-dependently in AIA mice. In addition, 1 mg/kg PCB downregulated the gene expression for T-bet, RORγ, and IFN-γ in the popliteal lymph nodes, accompanied by a significant reduction in the pathological arthritic index of AIA mice. Noteworthy, neuronal proteome analysis revealed that PCB modulated biological processes such as pain, inflammation, and glutamatergic transmission, all of which are involved in arthritic pathology. Conclusions: These findings demonstrate the remarkable efficacy of PCB in alleviating the nociception and inflammation in the AIA mice model and shed new light on mechanisms underlying the PCB modulation of the neuronal proteome. This research work opens a new avenue to explore the translational potential of PCB in developing a therapeutic strategy for inflammation and pain in rheumatoid arthritis.
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Artrite Experimental , Artrite Reumatoide , Neuroblastoma , Humanos , Camundongos , Animais , Ficocianina/efeitos adversos , Nociceptividade , Proteoma , Infiltração de Neutrófilos , Camundongos Endogâmicos C57BL , Artrite Reumatoide/tratamento farmacológico , Inflamação/tratamento farmacológico , Expressão Gênica , Citocinas/farmacologia , DorRESUMO
Real-time monitoring of meat quality requires fast, accurate, low-cost, and non-destructive analytical methods that can be used throughout the entire production chain, including the packaged product. The aim of this work was to evaluate the potential of a portable near-infrared (NIR) spectroscopy tool for the on-site detection of freshness of pork loin fillets in modified atmosphere packaging (MAP) stored on display counters. Pork loin slices were sealed in MAP trays under two proportions of O2/CO2/N2: High-Ox-MAP (30/40/30) and Low-Ox-MAP (5/20/75). Changes in pH, color, thiobarbituric acid reactive substances (TBARS), Warner−Bratzler shear force (WBSF), and microbiology (total viable counts, Enteriobacteriaceae, and lactic acid bacteria) were monitored over 15 days post-mortem at 4 °C. VIS-NIR spectra were collected from pork fillets before (through the film cover) and after opening the trays (directly on the meat surface) with a portable LABSPEC 5000 NIR system in diffuse reflectance mode (350−2500 nm). Quantitative NIR models by partial least squares regression (PLSR) showed a promising prediction ability for meat color (L*, a*, C*, and h*) and microbiological variables (R2VAL > 0.72 and RPDVAL > 2). In addition, qualitative models using PLS discriminant analysis obtained good accuracy (over 90%) for classifying pork samples as fresh (acceptable for consumption) or spoiled (not acceptable) based on their microbiological counts. VIS-NIR spectroscopy allows rapid evaluation of product quality and shelf life and could be used for on-site control of pork quality.