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Methicillin-resistant Staphylococcus aureus (MRSA), a drug-resistant human pathogen causes several nosocomial as well as community-acquired infections involving biofilm machinery. Hence, it has gained a wide interest within the scientific community to impede biofilm-induced MRSA-associated health complications. The current study focuses on the utilization of a natural bioactive compound called piperine to control the biofilm development of MRSA. Quantitative assessments like crystal violet, total protein recovery, and fluorescein-di-acetate (FDA) hydrolysis assays, demonstrated that piperine (8 and 16 µg/mL) could effectively compromise the biofilm formation of MRSA. Light and scanning electron microscopic image analysis confirmed the same. Further investigation revealed that piperine could reduce extracellular polysaccharide production by down-regulating the expression of icaA gene. Besides, piperine could reduce the cell-surface hydrophobicity of MRSA, a crucial factor of biofilm formation. Moreover, the introduction of piperine could interfere with microbial motility indicating the interaction of piperine with the quorum-sensing components. A molecular dynamics study showed a stable binding between piperine and AgrA protein (regulator of quorum sensing) suggesting the possible meddling of piperine in quorum-sensing of MRSA. Additionally, the exposure to piperine led to the accumulation of intracellular reactive oxygen species (ROS) and potentially heightened cell membrane permeability in inhibiting microbial biofilm formation. Besides, piperine could reduce the secretion of diverse virulence factors from MRSA. Further exploration revealed that piperine interacted with extracellular DNA (e-DNA), causing disintegration by weakening the biofilm architecture. Conclusively, this study suggests that piperine could be a potential antibiofilm molecule against MRSA-associated biofilm infections.
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Alcaloides , Benzodioxoles , Staphylococcus aureus Resistente a Meticilina , Piperidinas , Alcamidas Poliinsaturadas , Infecciones Estafilocócicas , Humanos , Antibacterianos/farmacología , Antibacterianos/metabolismo , Biopelículas , Fitoquímicos/farmacología , ADN/metabolismo , Pruebas de Sensibilidad MicrobianaRESUMEN
Pseudomonas aeruginosa is widely associated with biofilm-mediated antibiotic resistant chronic and acute infections which constitute a persistent healthcare challenges. Addressing this threat requires exploration of novel therapeutic strategies involving the combination of natural compounds and conventional antibiotics. Hence, our study has focused on two compounds; cuminaldehyde and ciprofloxacin, which were strategically combined to target the biofilm challenge of P. aeruginosa. The minimum inhibitory concentration (MIC) of cuminaldehyde and ciprofloxacin was found to be 400 µg/mL and 0.4 µg/mL, respectively. Moreover, the fractional inhibitory concentration index (FICI = 0.62) indicated an additive interaction prevailed between cuminaldehyde and ciprofloxacin. Subsequently, sub-MIC doses of cuminaldehyde (25 µg/mL) and ciprofloxacin (0.05 µg/mL) were selected for an array of antibiofilm assays which confirmed their biofilm inhibitory potential without exhibiting any antimicrobial activity. Furthermore, selected doses of the mentioned compounds could manage biofilm on catheter surface by inhibiting and disintegrating existing biofilm. Additionally, the test combination of the mentioned compounds reduced virulence factors secretion, accumulated reactive oxygen species and increased cell-membrane permeability. Thus, the combination of cuminaldehyde and ciprofloxacin demonstrates potential in combating biofilm-associated Pseudomonal threats.
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Antibacterianos , Benzaldehídos , Biopelículas , Ciprofloxacina , Pruebas de Sensibilidad Microbiana , Pseudomonas aeruginosa , Especies Reactivas de Oxígeno , Biopelículas/efectos de los fármacos , Ciprofloxacina/farmacología , Pseudomonas aeruginosa/efectos de los fármacos , Pseudomonas aeruginosa/fisiología , Antibacterianos/farmacología , Benzaldehídos/farmacología , Especies Reactivas de Oxígeno/metabolismo , Factores de Virulencia , Cimenos/farmacología , Sinergismo Farmacológico , Permeabilidad de la Membrana Celular/efectos de los fármacos , HumanosRESUMEN
(TaSe_{4})_{2}I is a well-studied quasi-one-dimensional compound long-known to have a charge-density wave (CDW) transition around 263 K. We argue that the critical fluctuations of the pinned CDW order parameter near the transition can be inferred from the resistance noise on account of their coupling to the dissipative normal carriers. Remarkably, the critical fluctuations of the CDW order parameter are slow enough to survive the thermodynamic limit and dominate the low-frequency resistance noise. The noise variance and relaxation time show rapid growth (critical opalescence and critical slowing down) within a temperature window of ϵ≈±0.1, where ϵ is the reduced temperature. This is very wide but consistent with the Ginzburg criterion. We further show that this resistance noise can be quantitatively used to extract the associated critical exponents. Below |ϵ|â²0.02, we observe a crossover from mean-field to a fluctuation-dominated regime with the critical exponents taking anomalously low values. The distribution of fluctuations in the critical transition region is skewed and strongly non-Gaussian. This non-Gaussianity is interpreted as the breakdown of the validity of the central limit theorem as the diverging coherence volume becomes comparable to the macroscopic sample size. The large magnitude critical fluctuations observed over an extended temperature range, as well as the crossover from the mean-field to the fluctuation-dominated regime highlight the role of the quasi-one-dimensional character in controlling the phase transition.
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Staphylococcus aureus causes several nosocomial and community-acquired infections in human host involving biofilm. Thus, strategies need to be explored to curb biofilm threats by either inhibiting the formation of biofilm or disintegrating the pre-existing biofilm. Towards this direction, we had already revealed the biofilm inhibiting properties of 1,4-naphthoquinone against S. aureus. In this study, we have investigated whether this compound can act on pre-existing biofilm. Hence, biofilm of S. aureus was developed first and challenged further with 1,4-naphthoquinone. Experiments such as crystal violet assay, fluorescence microscopy, and estimation of total biofilm protein were performed to confirm the biofilm disintegration properties of 1,4-naphthoquinone. The disintegration of pre-existing biofilm could be attributed to the generation of reactive oxygen species (ROS). To investigate further, we observed that extracellular DNA (eDNA) was found to play an important role in holding the biofilm network as DNaseI treatment could cause an efficient disintegration of the same. To examine the effect of ROS on the eDNA, we exposed pre-existing biofilm to either 1,4-naphthoquinone or a combination of both 1,4-naphthoquinone and ascorbic acid for different length of time. Post-incubation, ROS generation and the amount of eDNA associated with the biofilm were determined wherein an inversely proportional relationship was observed between them. The result indicated that with the increase of ROS generation, the amount of eDNA associated with biofilm got decreased substantially. Thus, the results indicated that the generation of ROS could degrade the eDNA thereby compromising the integrity of biofilm which lead to the disintegration of pre-existing biofilm.
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Infecciones Estafilocócicas , Staphylococcus aureus , Biopelículas , Humanos , Naftoquinonas , Especies Reactivas de Oxígeno , Staphylococcus aureus/genéticaRESUMEN
Staphylococcus aureus causes numerous community-acquired and nosocomial infections in humans by exploiting biofilm. In this context, this study aims to impede the formation of Staphylococcus aureus biofilm by exposing the cells to a plant-based alkaloid, piperine. Our study revealed that piperine exhibited considerable antimicrobial activity against the test organism. However, we had tested the lower concentrations (up to 32 µg/mL) of piperine to observe whether they could show any antibiofilm activity against the same organism. Several experiments, like crystal violet (CV) assay, estimation of total biofilm protein, and fluorescence microscopic observations, established that lower concentrations (up to 16 µg/mL) of piperine showed efficient antibiofilm activity against Staphylococcus aureus. In this connection, we also noticed that the lower concentrations (8 and 16 µg/mL) of piperine showed a considerable reduction in microbial metabolic activity. Besides, it was also observed that the mentioned concentrations of piperine did not compromise the microbial growth of the target organism while exhibiting antibiofilm activity. To understand the underlying mechanism of microbial biofilm inhibition under the influence of piperine, we observed that the compound was found to accumulate reactive oxygen species in the bacterial cells that could play an important role in the inhibition of biofilm formation. Furthermore, the tested concentrations (8 and 16 µg/mL) of piperine were able to inhibit the motility of the test organism that might compromise the development of biofilm. Thus, piperine could be considered as a potential agent for the effective management of biofilm threat caused by Staphylococcus aureus.
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Alcaloides , Staphylococcus aureus , Alcaloides/farmacología , Antibacterianos/farmacología , Benzodioxoles , Biopelículas , Humanos , Pruebas de Sensibilidad Microbiana , Piperidinas , Alcamidas Poliinsaturadas , Especies Reactivas de OxígenoRESUMEN
Water oxidation is a primary step in natural as well as artificial photosynthesis to convert renewable solar energy into chemical energy/fuels. Electrocatalytic water oxidation to evolve O2, utilizing suitable low-cost catalysts and renewable electricity, is of fundamental importance considering contemporary energy and environmental issues, yet it is kinetically challenging owing to the complex multiproton/electron transfer processes. Herein, we report the first cobalt-based pincer catalyst for catalytic water oxidation at neutral pH with high efficiency under electrochemical conditions. Most importantly, ligand (pseudo)aromaticity is identified to play an important role during electrocatalysis. A significant potential jump (â¼300 mV) was achieved toward a lower positive value when the aromatized cobalt complex was transformed into a (pseudo)dearomatized cobalt species. The dearomatized species catalyzes the water oxidation reaction to evolve oxygen at a much lower overpotential (â¼340 mV) on the basis of the onset potential (at a current density of 0.5 mA/cm2) of catalysis at pH 10.5, outperforming other Co-based molecular catalysts reported to date. These observations may provide a new strategy for the judicious design of earth-abundant transition-metal-based water oxidation catalysts.
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BACKGROUND: Imbalance between apoptosis and autophagy in fibroblast-like synoviocytes (FLS) is one of the pathogenic mechanisms responsible for their abnormal proliferation in rheumatoid arthritis (RA). Methotrexate (MTX) demonstrated limited efficacy in amending this imbalance in fluid-derived (fd)-FLS. The active compound of black tea Theaflavin 3,3'-digallate (TF3) may be effective in restoring apoptosis-autophagy imbalance in (fd)-FLS. The combined effect of MTX + TF3 upon the same is yet to be elucidated. OBJECTIVE: To evaluate the effect of MTX + TF3 on fd-FLS to induce apoptosis and inhibit autophagy through Endoplasmic Reticulum (ER) stress-mediated pathways. METHODS: FLS from synovial fluid of 11 RA and 10 osteoarthritis patients were cultured after treatment with MTX/TF3 or a combination of MTX (125 nM) and TF3(10 µM) and the following parameters were evaluated. C-reactive protein, cytokines (TNF-α, IL-6), angiogenic markers were quantified by ELISA. fd-FLS viability was determined by MTT assay and apoptosis by flow cytometry. ER stress markers were estimated by RT-PCR (IRE1A, spliced-XBP-1) and immunoblotting (Grp78, Hsp70, CHOP, HIF-1α). Immunoblot studies were done to evaluate apoptotic (Bcl-2, Bax, Caspases) and autophagic (Beclin1, LC3b, p62) proteins. RESULTS: MTX (IC25) and TF3 (IC50) both in single doses could down-regulate the levels of pro-inflammatory and angiogenic markers. Combinatorial treatment modulated autophagosomal proteins in fd-FLS and induced apoptosis by regulating ER stress response. CONCLUSION: Disruption in homeostasis between apoptosis and autophagy in fd-FLS might be an underlying phenomenon in the progression of pathophysiology in RA. Co-administration of MTX + TF3 successfully restored the homeostasis by inducing apoptosis.
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Antirreumáticos/farmacología , Artritis Reumatoide/tratamiento farmacológico , Biflavonoides/farmacología , Catequina/análogos & derivados , Metotrexato/farmacología , Adulto , Antirreumáticos/administración & dosificación , Apoptosis/efectos de los fármacos , Artritis Reumatoide/fisiopatología , Autofagia/efectos de los fármacos , Biflavonoides/administración & dosificación , Catequina/administración & dosificación , Catequina/farmacología , Células Cultivadas , Progresión de la Enfermedad , Sinergismo Farmacológico , Femenino , Fibroblastos/citología , Fibroblastos/efectos de los fármacos , Humanos , Concentración 50 Inhibidora , Masculino , Metotrexato/administración & dosificación , Persona de Mediana Edad , Osteoartritis/tratamiento farmacológico , Osteoartritis/fisiopatología , Líquido Sinovial/citología , Líquido Sinovial/efectos de los fármacos , Sinoviocitos/citología , Sinoviocitos/efectos de los fármacosRESUMEN
Seventeen Cu complexes with formal oxidation states ranging from CuI to CuIII are investigated through the use of multiedge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations. Analysis reveals that the metal-ligand bonding in high-valent, formally CuIII species is extremely covalent, resulting in Cu K-edge and L2,3-edge spectra whose features have energies that complicate physical oxidation state assignment. Covalency analysis of the Cu L2,3-edge data reveals that all formally CuIII species have significantly diminished Cu d-character in their lowest unoccupied molecular orbitals (LUMOs). DFT calculations provide further validation of the orbital composition analysis, and excellent agreement is found between the calculated and experimental results. The finding that Cu has limited capacity to be oxidized necessitates localization of electron hole character on the supporting ligands; consequently, the physical d8 description for these formally CuIII species is inaccurate. This study provides an alternative explanation for the competence of formally CuIII species in transformations that are traditionally described as metal-centered, 2-electron CuI/CuIII redox processes.
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Complejos de Coordinación/química , Cobre/química , Electrones , Ligandos , Modelos Moleculares , Oxidación-Reducción , Espectroscopía de Absorción de Rayos XRESUMEN
The synthesis and reactivity of a new trimetallic complex Ti(NP)4Ni2 (NP = 2-diphenylphosphinopyrrolide) (3) is reported. Single-crystal X-ray diffraction and X-ray absorption studies point to a unique bonding motif: a d10-d10, Ni0-Ni0 bond stabilized by a proximal d0 TiIV metal center. The coordination chemistry of 3 with a variety of L (L = isocyanide and alkyne) donors has also been explored. In the case of isocyanide coordination, the Ni-Ni bond is broken, while diphenylacetylene binding results in a symmetric butterfly µ2-κ2-alkyne bridge across the Ni-Ni moiety. Finally, complex 3 is capable of the 4-electron cleavage of the NâN double bond in benzo[c]cinnoline, the first example of NâN bond cleavage by Ni. The resulting product, 7, has been characterized structurally and spectroscopically, and the mechanistic implications are discussed in the context of metal-metal cooperativity.
RESUMEN
Previously, we reported the synthesis of Ti[N( o-(NCH2P( iPr)2)C6H4)3] and the Fe-Ti complex, FeTi[N( o-(NCH2P( iPr)2)C6H4)3], abbreviated as TiL (1), and FeTiL (2), respectively. Herein, we describe the synthesis and characterization of the complete redox families of the monometallic Ti and Fe-Ti compounds. Cyclic voltammetry studies on FeTiL reveal both reduction and oxidation processes at -2.16 and -1.36 V (versus Fc/Fc+), respectively. Two isostructural redox members, [FeTiL]+ and [FeTiL]- (2ox and 2red, respectively) were synthesized and characterized, along with BrFeTiL (2-Br) and the monometallic [TiL]+ complex (1ox). The solid-state structures of the [FeTiL]+/0/- series feature short metal-metal bonds, ranging from 1.94-2.38 Å, which are all shorter than the sum of the Ti and Fe single-bond metallic radii (cf. 2.49 Å). To elucidate the bonding and electronic structures, the complexes were characterized with a host of spectroscopic methods, including NMR, EPR, and 57Fe Mössbauer, as well as Ti and Fe K-edge X-ray absorption spectroscopy (XAS). These studies, along with hybrid density functional theory (DFT) and time-dependent DFT calculations, suggest that the redox processes in the isostructural [FeTiL]+,0,- series are primarily Fe-based and that the polarized Fe-Ti π-bonds play a role in delocalizing some of the additional electron density from Fe to Ti (net 13%).
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This review describes some commercially available stimuli-responsive polymers of natural and synthetic origin, and their applications in drug delivery and textiles. The polymers of natural origin such as chitosan, cellulose, albumin, and gelatin are found to show both thermo-responsive and pH-responsive properties and these features of the biopolymers impart sensitivity to act differently under different temperatures and pH conditions. The stimuli-responsive characters of these natural polymers have been discussed in the review, and their respective applications in drug delivery and textile especially for textile-based transdermal therapy have been emphasized. Some practically important thermo-responsive polymers such as pluronic F127 (PF127) and poly(N-isopropylacrylamide) (pNIPAAm) of synthetic origin have been discussed in the review and they are of great importance commercially because of their in situ gel formation capacity. Some pH-responsive synthetic polymers have been discussed depending on their surface charge, and their drug delivery and textile applications have been discussed in this review. The selected stimuli-responsive polymers of synthetic origin are commercially available. Above all, the applications of bio-based or synthetic stimuli-responsive polymers in textile-based transdermal therapy are given special regard apart from their general drug delivery applications. A special insight has been given for stimuli-responsive hydrogel drug delivery systems for textile-based transdermal therapy, which is critical for the treatment of skin disease atopic dermatitis.
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Portadores de Fármacos/química , Sistemas de Liberación de Medicamentos , Polímeros de Estímulo Receptivo/química , Textiles , Humanos , Hidrogeles/química , Concentración de Iones de Hidrógeno , Polímeros de Estímulo Receptivo/síntesis química , Relación Estructura-Actividad , TemperaturaRESUMEN
Reactivity as well as selectivity are crucial in the activation and electrocatalytic reduction of molecular oxygen. Recent developments in the understanding of the mechanism of electrocatalytic O2 reduction by iron porphyrin complexes in situ using surface enhanced resonance Raman spectroscopy coupled to rotating disc electrochemistry (SERRS-RDE) in conjunction with H/D isotope effects on electrocatalytic current reveals that the rate of O2 reduction, â¼104 to 105 M-1 s-1 for simple iron porphyrins, is limited by the rate of O-O bond cleavage of an intermediate ferric peroxide species (FeIII-OOH). SERRS-RDE probes the system in operando when it is under steady state such that any intermediate species that has a greater rate of formation relative to its rate of decay, including the rate determining species, would accumulate and can be identified. This technique is particularly well suited to investigate iron porphyrin electrocatalysts as the intense symmetric ligand vibrations allow determination of the oxidation and spin states of the bound iron with high fidelity. The rate of O2 reduction could be tuned up by 3 orders of magnitude by incorporating residues in the catalyst design that can exert "push" or "pull" effects, that is, axial phenolate and thiolate ligands and distal arginine residues. Similarly the rate of O-O bond cleavage can be enhanced by several orders of magnitude upon incorporating a distal Cu site and installing the active site in a hydrophobic protein environment in synthetic models and biosynthetic protein scaffolds. The selectivity, however, is solely determined by the site of protonation of a ferric peroxide (FeIII-OOH) intermediate and can be governed by installing preorganized second sphere residues in the distal pocket. The 4e-/4H+ reduction of O2 entails protonation of the distal oxygen of the FeIII-OOH species, while 2e-/2H+ reduction requires the proximal oxygen to be protonated. Mechanistic investigations of CO2 reduction by iron porphyrins reveal that the rate-determining step is the C-O bond cleavage of a FeII-COOH species analogous to the O-O bond cleavage step of a FeIII-OOH species in O2 reduction. The selectivity, resulting in either CO or HCOOH, is determined by the site of protonation of this species. These similarities suggests that the chemical principles governing the rate and selectivity of reduction of small molecules like O2, CO2, NOx, and SOx may be quite similar in nature.
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Fish oil microcapsules were successfully prepared from fish oil-in-water emulsions using chitosan as shell material and anionic surfactants sodium dodecyl sulphate (SDS), sodium dodecylbenzenesulfonate (SDBS), sodium cholate (cholate), and sodium deoxycholate (DOC) as emulsifiers. The type of emulsifier influenced the physicochemical characteristics of the prepared microcapsules to different extents. The microcapsules formed with DOC showed the least mean effective diameter (MED) of 500 nm. Emulsion formed with DOC exhibited the smallest MED of 100 nm. The emulsions showed negative zeta potential values which became positive after encapsulation with chitosan. The surfactants showed little influence on thermal stability. Microcapsule suspensions showed creaming over storage. Fish oil at higher loading in SDS microcapsules showed higher primary and secondary oxidation. All microcapsules showed sustained release but the values varied depending upon the surfactants. The emulsion and microcapsules formed with DOC showed better morphology and stability despite its lower loading and encapsulation efficiency.
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Emulsionantes/química , Aceites de Pescado/química , Bencenosulfonatos , Cápsulas , Fenómenos Químicos , Quitosano , Ácido Desoxicólico , Emulsiones , Colato de Sodio , Dodecil Sulfato de SodioRESUMEN
The synthesis, structures, and magnetic properties of two heterometallic Cu(II)-Dy(III) clusters are reported. The first structural motif displays a pentanuclear Cu(II)4Dy(III) core, while the second one reveals a nonanuclear Cu(II)6Dy(III)3 core. We employed o-vanillin-based Schiff base ligands combining o-vanillin with 3-amino-1-propanol, H2vap, (2-[(3-hydroxy-propylimino)-methyl]-6-methoxy-phenol), and 2-aminoethanol, H2vae, (2-[(3-hydroxy-ethylimino)-methyl]-6-methoxy-phenol). The differing nuclearities of the two clusters stem from the choice of imino alcohol arm in the Schiff bases, H2vap and H2vae. This work is aimed at broadening the diversity of Cu(II)-Dy(III) clusters and to perceive the consequence of changing the length of the alcohol arm on the nuclearity of the cluster, providing valuable insight into promising future synthetic directions. The underlying topological entity of the pentanuclear Cu4Dy cluster is reported for the first time. The investigation of magnetic behaviors of 1 and 2 below 2 K reveals slow magnetic relaxation with a significant influence coming from the variation of the alcohol arm affecting the nature of magnetic interactions.
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Heme/porphyrin-based electrocatalysts (both synthetic and natural) have been known to catalyze electrochemical O2, H(+), and CO2 reduction for more than five decades. So far, no direct spectroscopic investigations of intermediates formed on the electrodes during these processes have been reported; and this has limited detailed understanding of the mechanism of these catalysts, which is key to their development. Rotating disk electrochemistry coupled to resonance Raman spectroscopy is reported for iron porphyrin electrocatalysts that reduce O2 in buffered aqueous solutions. Unlike conventional single-turnover intermediate trapping experiments, these experiments probe the system while it is under steady state. A combination of oxidation and spin-state marker bands and metal ligand vibrations (identified using isotopically enriched substrates) allow in situ identification of O2-derived intermediates formed on the electrode surface. This approach, combining dynamic electrochemistry with resonance Raman spectroscopy, may be routinely used to investigate a plethora of metalloporphyrin complexes and heme enzymes used as electrocatalysts for small-molecule activation.
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Técnicas Electroquímicas , Hierro/química , Oxígeno/química , Porfirinas/química , Catálisis , Oxidación-Reducción , Espectrometría RamanRESUMEN
A synthetic heme-Cu CcO model complex shows selective and highly efficient electrocatalytic 4e(-)/4H(+) O2-reduction to H2O with a large catalytic rate (>10(5) M(-1) s(-1)). While the heme-Cu model (FeCu) shows almost exclusive 4e(-)/4H(+) reduction of O2 to H2O (detected using ring disk electrochemistry and rotating ring disk electrochemistry), when imidazole is bound to the heme (Fe(Im)Cu), this same selective O2-reduction to water occurs only under slow electron fluxes. Surface enhanced resonance Raman spectroscopy coupled to dynamic electrochemistry data suggests the formation of a bridging peroxide intermediate during O2-reduction by both complexes under steady state reaction conditions, indicating that O-O bond heterolysis is likely to be the rate-determining step (RDS) at the mass transfer limited region. The O-O vibrational frequencies at 819 cm(-1) in (16)O2 (759 cm(-1) in (18)O2) for the FeCu complex and at 847 cm(-1) (786 cm(-1)) for the Fe(Im)Cu complex, indicate the formation of side-on and end-on bridging Fe-peroxo-Cu intermediates, respectively, during O2-reduction in an aqueous environment. These data suggest that side-on bridging peroxide intermediates are involved in fast and selective O2-reduction in these synthetic complexes. The greater amount of H2O2 production by the imidazole bound complex under fast electron transfer is due to 1e(-)/1H(+) O2-reduction by the distal Cu where O2 binding to the water bound low spin Fe(II) complex is inhibited.
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Complejo IV de Transporte de Electrones/química , Imitación Molecular , Oxígeno/química , Catálisis , Oxidación-ReducciónRESUMEN
The electrochemical O2 reduction by thiolate- and imidazole-bound iron porphyrin complexes and H/D isotope effects on 4e(-) (determined by rotating disc electrochemistry) and 2e(-) (determined by rotating ring disc electrochemistry) O2 reduction rates are investigated. The results indicate that a thiolate axial ligand shows an H/D isotope effect greater than 18 and 47 for the 4e(-) and 2e(-) O2 reductions, respectively. Alternatively, an imidazole axial ligand results in H/D isotope effects of 1.04 and 4.7 for the 4e(-) and 2e(-) O2 reduction, respectively. The catalytic O2 reduction mechanism is investigated in situ with resonance Raman coupled with rotating disc electrochemistry. The data indicate that the rate-determining step changes from O-O bond heterolysis of Fe(III)-OOH species for a thiolate axial ligand to an O-O bond heterolysis of an Fe(II)-OOH for an imidazole axial ligand.
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Técnicas Electroquímicas , Hierro/química , Metaloporfirinas/química , Oxígeno/química , Protones , Catálisis , Medición de Intercambio de Deuterio , Electrones , Ligandos , Estructura Molecular , Oxidación-ReducciónRESUMEN
Vapor sensitive transducer films consisting of chitosan grafted (CNT-CS) and chitosan-co-polycaprolactone grafted (CNT-CS-PCL) multiwalled carbon nanotubes were prepared using a spray layer-by-layer technique. The synthesized materials (CNT-CS and CNT-CS-PCL) were characterized by Fourier transform infrared spectroscopy, 13C CP/MAS solid state nuclear magnetic resonance spectroscopy and thermogravimetric analysis. Both CNT-CS and CNT-CS-PCL transducers were analyzed for the response of volatile organic compounds and toluene vapors. The ranking of the relative resistance (A(r)) for both chitosan based transducers were as follows: toluene < chloroform < ethanol < methanol. The CNT transducer (CNT-CS) was correlated selectively with an exponential law to the inverse of Flory-Huggins interaction parameters, chi12. Dosing the films on the interdigitated electrodes with methanol, ethanol, chloroform and toluene vapors increased the film resistance of CNT-CS but decreased the resistance of CNT-CS-PCL compared to that of the reported transducers.
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Quitosano/química , Nanotubos de Carbono/química , Poliésteres/química , Materiales Biocompatibles/química , Biodegradación Ambiental , Cloroformo/química , Electroquímica , Diseño de Equipo , Etanol/química , Gases , Espectroscopía de Resonancia Magnética , Metanol/química , Microscopía Electrónica de Rastreo , Polímeros/química , Solventes/química , Espectroscopía Infrarroja por Transformada de Fourier , Temperatura , Termogravimetría , Factores de Tiempo , Tolueno/química , TransductoresRESUMEN
Linseed oil which has various biomedical applications was encapsulated by chitosan (Chi)-based microcapsules in the development of a suitable carrier. Oil droplets formed in oil-in-water emulsion using sodium dodecyl sulfate (SDS) as emulsifier was stabilized by Chi, and microcapsules with multilayers were formed by alternate additions of SDS and Chi solutions in an emulsion through electrostatic interaction. No chemical cross-linker was used in the study and the multilayer shell membrane was formed by ionic gelation using Chi and SDS. The rigidification of the shell membrane of microcapsules was achieved by alkali treatment in the presence of a small amount of 1-butanol to reduce aggregation. A trisodium citrate solution was used to stabilize the charge of microcapsules by ionic cross-linking. Effects of butanol during alkali treatment and citrate in post alkali treatment were monitored in terms of morphology and the chemical properties of microcapsules. Various characterization techniques revealed that the aggregation was decreased and surface roughness was increased with layer formation.
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1-Butanol/química , Álcalis/química , Cápsulas/química , Quitosano/química , Citratos/química , Iones/química , Portadores de Fármacos/química , Emulsiones/química , Aceite de Linaza/química , Dodecil Sulfato de Sodio , Soluciones/química , Agua/químicaRESUMEN
Electrocatalytic hydrogen evolution reaction (eHER) is crucial in addressing the growing global energy demand. Although nickel-pincer-based molecular complexes, varying in donor atoms, were studied previously for eHER, the impact of variations in the substituents attached to the donor atoms was not investigated. Herein, three air-stable R1PN3PR2-based NiII-pincer complexes [R1=R2=Ph2 (7); R1=R2=tBu2 (9); R1= tBu2, R2=Ph2 (10)], varying solely in P-substituents, were studied in acetonitrile. While the redox potentials for NiII/I and NiI/0 couples underwent anodic shifts by ~100 mV upon progressively substituting tert-butyl by phenyl groups on each P-atom, the corresponding eHER reactivity with organic acids (acetic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid) of different strengths followed different trends; likely influenced by the pKa of intermediate metal-hydride (M-H) species [pKa(M-H9) > pKa(M-H10) > pKa(M-H7)]. Depending on the acid strength, different oxidation states of the metal were activated to promote eHER. The catalytic rates for 9, 10, and 7 were calculated to be 85 s-1, 77 s-1 and 95 s-1 with Faradaic efficiencies of 88.5 ± 2%, 66.1 ± 1.4%, and 91.7 ± 1.5% respectively, in acetic acid. Electrochemical data supported by theoretical results reinforce a significant electronic influence of the anchoring P-substituents on the activity of these complexes.