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1.
Gels ; 10(4)2024 Mar 26.
Artículo en Inglés | MEDLINE | ID: mdl-38667645

RESUMEN

Gelatin nanofibers are known as wound-healing biomaterials due to their high biocompatible, biodegradable, and non-antigenic properties compared to synthetic-polymer-fabricated nanofibers. The influence of gamma radiation doses on the structure of gelatin nanofiber dressings compared to gelatin of their origin is little known, although it is very important for the production of stable bioactive products. Different-origin gelatins were extracted from bovine and donkey hides, rabbit skins, and fish scales and used for fabrication of nanofibers through electrospinning of gelatin solutions in acetic acid. Nanofibers with sizes ranging from 73.50 nm to 230.46 nm were successfully prepared, thus showing the potential of different-origin gelatin by-products valorization as a lower-cost alternative to native collagen. The gelatin nanofibers together with their origin gelatins were treated with 10, 20, and 25 kGy gamma radiation doses and investigated for their structural stability through chemiluminescence and FTIR spectroscopy. Chemiluminescence analysis showed a stable behavior of gelatin nanofibers and gelatins up to 200 °C and increased chemiluminescent emission intensities for nanofibers treated with gamma radiation, at temperatures above 200 °C, compared to irradiated gelatins and non-irradiated nanofibers and gelatins. The electron paramagnetic (EPR) signals of DMPO adduct allowed for the identification of long-life HO● radicals only for bovine and donkey gelatin nanofibers treated with a 20 kGy gamma radiation dose. Microbial contamination with aerobic microorganisms, yeasts, filamentous fungi, Staphylococcus aureus, Escherichia coli, and Candida albicans of gelatin nanofibers treated with 10 kGy gamma radiation was under the limits required for pharmaceutical and topic formulations. Minor shifts of FTIR bands were observed at irradiation, indicating the preservation of secondary structure and stable properties of different-origin gelatin nanofibers.

2.
Biomolecules ; 13(5)2023 04 29.
Artículo en Inglés | MEDLINE | ID: mdl-37238645

RESUMEN

In this study, the effect of gamma irradiation (10 kGy) on proteins extracted from animal hide, scales, and wool was evidenced by calorimetric (µDSC) and spectroscopic (IR, circular dichroism, and EPR) methods. Keratin was obtained from sheep wool, collagen and bovine gelatin from bovine hide, and fish gelatin from fish scales. The µDSC experiments evidenced that gamma irradiation influences the thermal stability of these proteins differently. The thermal stability of keratin decreases, while a resistance to thermal denaturation was noticed for collagen and gelatins after gamma irradiation. The analysis of the IR spectra demonstrated that gamma irradiation determines changes in the vibrational modes of the amide groups that are associated with protein denaturation, most meaningfully in the case of keratin. As evidenced by circular dichroism for all proteins considered, exposure to gamma radiation produces changes in the secondary structure that are more significant than those produced by UV irradiation. Riboflavin has different effects on the secondary structure of the investigated proteins, a stabilizing effect for keratin and fish gelatin and a destabilizing effect for bovine gelatin, observed in both irradiated and non-irradiated samples. The EPR spectroscopy evidences the presence, in the gamma-irradiated samples, of free radicals centered on oxygen, and the increase in their EPR signals over time due to the presence of riboflavin.


Asunto(s)
Colágeno , Gelatina , Ovinos , Animales , Bovinos , Gelatina/química , Queratinas , Espectroscopía de Resonancia por Spin del Electrón , Dicroismo Circular
3.
Gels ; 9(3)2023 Mar 16.
Artículo en Inglés | MEDLINE | ID: mdl-36975680

RESUMEN

This study analyzes the physico-chemical properties of interpenetrated polymer networks (IPNs) and semi-IPN resulting from cross-linking chitosan with glutaraldehyde and alginate with Ca2+ cations, as a function of the order in which the cross-linking agents are added to the polymer mixture. Three physico-chemical methods were used to assess the differences between systems: rheology, IR spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. While rheology and IR spectroscopy are commonly used to characterize gel materials, EPR spectroscopy is rarely used, but has the advantage of providing local information about the dynamics of a system. The rheological parameters, which describe the global behavior of the samples, show that semi-IPN systems have a weaker gel behavior and the order of introducing the cross-linker in the polymer systems plays a role. The IR spectra of samples resulting by adding only Ca2+ or Ca2+ as the first cross-linker are similar to that of the alginate gel, while the spectra of samples in which glutaraldehyde is firstly added resemble the chitosan gel spectrum. Using spin-labeled alginate and spin-labeled chitosan, we monitored the changes occurring in the dynamic of the spin labels due to the formation of IPN and semi-IPN. The results show that the order of adding the cross-linking agents influences the dynamic of the IPN network, and that the formation of the alginate network determines the characteristics of the entire IPN system. The EPR data were correlated with the rheological parameters and IR spectra of the analyzed samples.

4.
Int J Mol Sci ; 23(23)2022 Nov 25.
Artículo en Inglés | MEDLINE | ID: mdl-36499031

RESUMEN

The properties of newly synthesized Cu2O/CuO-decorated TiO2/graphene oxide (GO) nanocomposites (NC) were analyzed aiming to obtain insight into their photocatalytic behavior and their various applications, including water remediation, self-cleaning surfaces, antibacterial materials, and electrochemical sensors. The physico-chemical methods of research were photoluminescence (PL), electron paramagnetic resonance (EPR) spectroscopy, cyclic voltammetry (CV), and differential pulse voltammetry (DPV). The solid samples evidenced an EPR signal that can be attributed to the oxygen-vacancy defects and copper ions in correlation with PL results. Free radicals generated before and after UV-Vis irradiation of powders and aqueous dispersions of Cu2O/CuO-decorated TiO2/GO nanocomposites were studied by EPR spectroscopy using two spin traps, DMPO (5,5-dimethyl-1-pyrroline-N-oxide) and CPH (1-hydroxy-3-carboxy-2,2,5,5-tetramethylpyrrolidine), to highlight the formation of hydroxyl and superoxide reactive oxygen species, respectively. The electrochemical characterization of the NC modified carbon-paste electrodes (CPE) was carried out by CV and DPV. As such, modified carbon-paste electrodes were prepared by mixing carbon paste with copper oxides-decorated TiO2/GO nanocomposites. We have shown that GO reduces the recombination process in TiO2 by immediate electron transfer from excited TiO2 to GO sheets. The results suggest that differences in the PL, respectively, EPR data and electrochemical behavior, are due to the different copper oxides and GO content, presenting new perspectives of materials functionalization.


Asunto(s)
Grafito , Nanocompuestos , Cobre/química , Grafito/química , Nanocompuestos/química , Carbono/química , Técnicas Electroquímicas/métodos
5.
Polymers (Basel) ; 14(21)2022 Nov 04.
Artículo en Inglés | MEDLINE | ID: mdl-36365713

RESUMEN

In this work, cellulose nanofibers (CNF) were surface treated by plasma and grafted with poly(ethylene glycol)methyl ether methacrylate (PEGMMA) for increasing mechanical strength and hydrophobicity. The surface characteristics of the sponges were studied by scanning electron microscopy, micro-computed tomography, and Fourier transform infrared spectroscopy, which demonstrated successful surface modification. Plasma treatment applied to CNF suspension led to advanced defibrillation, and the resulting sponges (CNFpl) exhibited smaller wall thickness than CNF. The grafting of PEGMMA led to an increase in the wall thickness of the sponges and the number of larger pores when compared with the non-grafted counterparts. Sponges with increased hydrophobicity demonstrated by an almost 4 times increase in the water contact angle and better mechanical strength proved by 2.5 times increase in specific compression strength were obtained after PEGMMA grafting of plasma treated CNF. Cells cultivated on both neat and PEGMMA-grafted CNF sponges showed high viability (>99%). Remarkably, CNF grafted with PEGMMA showed better cell viability as compared with the untreated CNF sample; this difference is statistically significant (p < 0.05). In addition, the obtained sponges do not trigger an inflammatory response in macrophages, with TNF-α secretion by cells in contact with CNFpl, CNF-PEGMMA, and CNFpl-PEGMMA samples being lower than that observed for the CNF sample. All these results support the great potential of cellulose nanofibers surface treated by plasma and grafted with PEGMMA for biomedical applications.

6.
Gels ; 8(7)2022 Jul 08.
Artículo en Inglés | MEDLINE | ID: mdl-35877513

RESUMEN

In this work, we explored by means of electron paramagnetic resonance (EPR) spectroscopy the accessibility of a series of spin probes, covering a scale of molecular weights in the range of 200-60,000 Da, in a variety of hydrogels: covalent network, ionotropic, interpenetrating polymer network (IPN) and semi-IPN. The covalent gel network consists of polyethylene or polypropylene chains linked via isocyanate groups with cyclodextrin, and the ionotropic gel is generated by alginate in the presence of Ca2+ ions, whereas semi-IPN and IPN gel networks are generated in a solution of alginate and chitosan by adding crosslinking agents, Ca2+ for alginate and glutaraldehyde for chitosan. It was observed that the size of the diffusing species determines the ability of the gel to uptake them. Low molecular weight compounds can diffuse into the gel, but when the size of the probes increases, the gel cannot uptake them. Spin-labelled Pluronic F127 cannot be encapsulated by any covalent gel, whereas spin-labelled albumin can diffuse in alginate gels and in most of the IPN networks. The EPR spectra also evidenced the specific interactions of spin probes inside hydrogels. The results suggest that EPR spectroscopy can be an alternate method to evaluate the mesh size of gel systems and to provide information on local interactions inside gels.

7.
Molecules ; 27(1)2021 Dec 29.
Artículo en Inglés | MEDLINE | ID: mdl-35011421

RESUMEN

Riboflavin under UVA radiation generates reactive oxygen species (ROS) that can induce various changes in biological systems. Under controlled conditions, these processes can be used in some treatments for ocular or dermal diseases. For instance, corneal cross-linking (CXL) treatment of keratoconus involves UVA irradiation combined with riboflavin aiming to induce the formation of new collagen fibrils in cornea. To reduce the damaging effect of ROS formed in the presence of riboflavin and UVA, the CXL treatment is performed with the addition of polysaccharides (dextran). Hyaluronic acid is a polysaccharide that can be found in the aqueous layer of the tear film. In many cases, keratoconus patients also present dry eye syndrome that can be reduced by the application of topical solutions containing hyaluronic acid. This study presents physico-chemical evidence on the effect of riboflavin on collagen fibril formation revealed by the following methods: differential scanning microcalorimetry, rheology, and STEM images. The collagen used was extracted from calf skin that contains type I collagen similar to that found in the eye. Spin trapping experiments on collagen/hyaluronic acid/riboflavin solutions evidenced the formation of ROS species by electron paramagnetic resonance measurements.


Asunto(s)
Queratocono/terapia , Fotoquimioterapia , Fármacos Fotosensibilizantes/farmacología , Riboflavina/farmacología , Animales , Bovinos , Colágeno/química , Colágeno/metabolismo , Córnea/efectos de los fármacos , Córnea/metabolismo , Reactivos de Enlaces Cruzados , Humanos , Concentración de Iones de Hidrógeno , Queratocono/diagnóstico , Queratocono/etiología , Queratocono/metabolismo , Piel , Temperatura , Rayos Ultravioleta
8.
Phys Chem Chem Phys ; 22(21): 12154-12165, 2020 Jun 04.
Artículo en Inglés | MEDLINE | ID: mdl-32440670

RESUMEN

Electron paramagnetic resonance (EPR) spectroscopy is the main tool for evidencing the formation of inclusion complexes of cyclodextrins with paramagnetic guests, based on changes in the EPR parameters. In-depth information on complexation can only be obtained by a combination of physico-chemical methods. Herein we report on the interaction of three TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) type radicals with cyclodextrins by collecting and analysing data provided experimentally by EPR and circular dichroism spectroscopies and theoretically by density functional theory and molecular docking. The study focused on the pH influence on the complexation of three paramagnetic probes with cyclodextrins. The EPR spectra revealed that the type and protonation state of the substituent linked to the TEMPO structure influences the affinity of the paramagnetic group for the cyclodextrin cavity. Neutral radical species favour stronger association with cyclodextrins and inclusion of the nitroxide group into the cavity, especially in the case of 4-carboxy-TEMPO. Induced circular dichroism signals of neutral species varied in sign and intensity as a function of substituent and cyclodextrin type. Density functional theory and molecular docking results supported the experimental data regarding the conformational preferences of TEMPO radicals in complexes with cyclodextrins.

9.
Spectrochim Acta A Mol Biomol Spectrosc ; 237: 118413, 2020 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-32380433

RESUMEN

A series of dansyl-based fluorescent probes bearing linear alkyl-1,n-diamine chains of different length (DA1.n, n = 2-8, 10, 12) was characterized in terms of the absorptive and emissive features in solvents of different polarity and hydrogen bond donor/hydrogen bond acceptor character. The probes show solvent-dependent absorption, a feature that is uncommon among dansyl derivatives. The dual emission of DA1.n probes is strong in non-aqueous solvents and is influenced by the chain length and interactions with the solvent. Solvent effects on the spectral parameters were rationalized on the basis of the Kamlet-Taft and Catalán solvatochromic models, in order to quantify the degree of polarity-driven and hydrogen bonding interactions. A comparative discussion of the results predicted by the two models was made. In ground state, the DA1.n probes act as hydrogen bond acceptors. In excited state, hydrogen bonding is less favoured, the solute-solvent interactions being governed by the increasing polarity of the solvent that results in a large bathochromic shift of the emission. A comparison was made with the spectral features previously reported for the corresponding series of bis-dansyl fluorescent probes (2DA1.n).

10.
Molecules ; 24(18)2019 Sep 18.
Artículo en Inglés | MEDLINE | ID: mdl-31540504

RESUMEN

The formation and growth of gold nanoparticles (AuNPs) were investigated in pH 7 buffer solution of bovine serum albumin (BSA) at room temperature. The processes were monitored by UV-Vis, circular dichroism, Raman and electron paramagnetic resonance (EPR) spectroscopies. TEM microscopy and dynamic light scattering (DLS) measurements were used to evidence changes in particle size during nanoparticle formation and growth. The formation of AuNPs at pH 7 in the absence of BSA was not observed, which proves that the albumin is involved in the first step of Au(III) reduction. Changes in the EPR spectral features of two spin probes, CAT16 and DIS3, with affinity for BSA and AuNPs, respectively, allowed us to monitor the particle growth and to demonstrate the protective role of BSA for AuNPs. The size of AuNPs formed in BSA solution increases slowly with time, resulting in nanoparticles of different morphologies, as revealed by TEM. Raman spectra of BSA indicate the interaction of albumin with AuNPs through sulfur-containing amino acid residues. This study shows that albumins act as both reducing agents and protective corona of AuNPs.


Asunto(s)
Oro/química , Nanopartículas del Metal/química , Albúmina Sérica Bovina/química , Animales , Bovinos , Espectroscopía de Resonancia por Spin del Electrón , Nanopartículas del Metal/ultraestructura , Microscopía Electrónica de Transmisión , Espectrometría Raman
11.
Int J Mol Sci ; 20(19)2019 Sep 24.
Artículo en Inglés | MEDLINE | ID: mdl-31554219

RESUMEN

Nitroxide-based radicals, having the advantage of firm chemical stability, are usable as probes in the detection of nanoscale details in the chemical environment of various multi-component systems, based on subtle variations in their electron paramagnetic resonance spectra. We propose a systematic walk through the vast area of problems and inquires that are implied by the rationalization of solvent effects on the spectral parameters, by first-principle methods of structural chemistry. Our approach consists of using state-of-the-art procedures, like Density Functional Theory (DFT), on properly designed systems, kept at the border of idealization and chemical realism. Thus, we investigate the case of real solvent molecules intervening in different configurations between two radical molecules, in comparison with radicals taken in vacuum or having the solvent that is treated by surrogate models, such as polarization continuum approximation. In this work, we selected the dichloromethane as solvent and the prototype radicals abbreviated TEMPO ((2,2,6,6-Tetramethylpiperidin-1-yl) oxyl). In another branch of the work, we check the interaction of radicals with large toroidal molecules, ß-cyclodextrin, and cucurbit[6]uril, modeling the interaction energy profile at encapsulation. The drawn synoptic view offers valuable rationales for understanding spectroscopy and energetics of nitroxide radicals in various environments, which are specific to soft chemistry.


Asunto(s)
Estructura Molecular , Óxidos de Nitrógeno/química , Óxidos N-Cíclicos/química , Teoría Funcional de la Densidad , Espectroscopía de Resonancia por Spin del Electrón , Modelos Moleculares , Conformación Molecular , Solventes/química
12.
Mediators Inflamm ; 2018: 4285268, 2018.
Artículo en Inglés | MEDLINE | ID: mdl-30245588

RESUMEN

Keratoconus is a progressive corneal ectasia that may lead to severe visual impairment due to the irregular astigmatism caused by corneal thinning. In addition to its association with atopy, eye rubbing, or genetic component, late reports suggest the involvement of inflammation in the pathogenesis of the disease. Our aim was to determine the concentration of IL-4, IL-6, IL-10, RANTES, IFN gamma, and TNF alpha in the tear film of patients with keratoconus and their first degree family members. We analyzed forty-eight participants in an observational cross-sectional study. The diagnosis of keratoconus had to be confirmed in addition to a minimum of 47 D corneal refractive power by corneal topography readings provided by a Placido-based topography system and analysis of the pattern: irregular astigmatism with an asymmetric "bow-tie." As for the other groups, the most important diagnosis criteria were a normal topographic pattern with a regular astigmatism. 17 keratoconus patients, 16 relatives, and 15 controls were recruited after clinical assessment as part of the research. The cytokine's mean values were similar in the keratoconus group and the relatives' samples but significantly higher compared to the controls. Important differences were found in IL-4 levels between keratoconus patients and relatives and between relatives and controls (mean difference of 302.42, p < 0.0016 and 219.16, p < 0.033, Tukey's HSD procedure). In the keratoconus group, using the CORR procedure, we found statistically strong correlations of IL-6 lacrimal concentrations with the disease stage (r = 0.56, p < 0.01), keratometry (r = 0.55, p < 0.02), pachymetry (r = -0.64, p < 0.048), and corneal hysteresis (r = -0.53, p < 0.02). Cytokine overexpression may be relevant for the inflammatory etiology of keratoconus. In conclusion, in the case of some first degree family members, the elevated tear biomarkers may represent a supplementary risk factor.


Asunto(s)
Queratocono/metabolismo , Adolescente , Adulto , Quimiocina CCL5/metabolismo , Estudios Transversales , Femenino , Humanos , Interferón gamma/metabolismo , Interleucina-10/metabolismo , Interleucina-4/metabolismo , Interleucina-6/metabolismo , Masculino , Persona de Mediana Edad , Estudios Prospectivos , Factor de Necrosis Tumoral alfa/metabolismo , Adulto Joven
13.
Phys Chem Chem Phys ; 19(40): 27839-27847, 2017 Oct 18.
Artículo en Inglés | MEDLINE | ID: mdl-28990616

RESUMEN

Electron paramagnetic resonance (EPR) and fluorescence spectroscopies provide molecular-level insights on the interaction of paramagnetic and fluorescent species with the microenvironment. A series of dual molecular probes bearing fluorescent and paramagnetic moieties linked by flexible short polyether chains have been synthesized. These new molecular probes open the possibility to investigate various multi-component systems such as host-guest systems, polymeric micelles, gels and protein solutions by using EPR and fluorescence spectroscopies concertedly. The EPR and fluorescence spectra of these compounds show that the dependence of the rotational correlation time and fluorescence quantum yield on the chain length of the linker is not linear, due to the flexibility of the polyether linker. The quenching effect of the nitroxide moiety on the fluorescence intensity of the pyrene group varies with the linker length and flexibility. The interaction of these dual molecular probes with ß-cyclodextrin, in solution and in polymeric gels, was evaluated and demonstrated by analysis of EPR and fluorescence spectra.

14.
Pancreatology ; 17(5): 766-772, 2017.
Artículo en Inglés | MEDLINE | ID: mdl-28811081

RESUMEN

BACKGROUND: The prognostic value of WHO grade in pancreatic neuroendocrine tumors (PanNETs) in patients with Multiple Endocrine Neoplasia Type 1 (MEN1) is unknown. METHODS: We performed a cohort study using the Dutch National MEN1 database, which includes >90% of the Dutch MEN1 population with data collected between 1990 and 2014. Formalin-fixed paraffin embedded tissue blocks from the largest resected PanNET per patient were collected. MIB1 staining was performed and KI67 labeling index (LI) was determined by manual eye-counting under a microscope and by digital image analysis. Mitotic count was evaluated from hematoxylin & eosin stains. Association between WHO grade and (time until) development of liver metastases was calculated. RESULTS: Sixty-nine MEN1 patients who underwent pancreatic surgery were included. Ten patients (14%) developed liver metastases and all had PanNETs ≥3 cm. WHO G1, G2 and G3 PanNETs were seen in 83% (n = 57), 16% (n = 11) and 1% (n = 1) respectively. In non-functioning PanNETs >2 cm, liver metastases occurred in 80% of WHO G2 PanNETs (4/5) compared to 23% (5/22) in WHO G1 PanNETs (p = 0.03) when WHO grade was based on mitotic count only. This significant association was not seen for WHO grade based on Ki67 LI. After five years, liver metastases in non-functioning PanNETs were not seen in tumors ≤2 cm, in 10% of the large WHO G1 (according to mitotic count only) tumors and in 60% of large WHO G2 tumors (p-value 0.000). CONCLUSION: High mitotic count is correlated with poor prognosis in MEN1 patients with large non-functioning PanNETs.


Asunto(s)
Neoplasia Endocrina Múltiple Tipo 1/clasificación , Neoplasias Pancreáticas/clasificación , Organización Mundial de la Salud , Adulto , Anciano , Anciano de 80 o más Años , Femenino , Humanos , Masculino , Persona de Mediana Edad , Neoplasia Endocrina Múltiple Tipo 1/epidemiología , Neoplasia Endocrina Múltiple Tipo 1/cirugía , Países Bajos/epidemiología , Neoplasias Pancreáticas/epidemiología , Neoplasias Pancreáticas/cirugía , Pronóstico
15.
Molecules ; 22(7)2017 Jun 28.
Artículo en Inglés | MEDLINE | ID: mdl-28657593

RESUMEN

The focus of the present work was to investigate the interaction of the anticancer drug mitoxantrone with two bile salts, sodium taurodeoxycholate (NaTDC) and sodium taurocholate (NaTC). Ultraviolet-visible (UV-Vis) absorption and electron paramagnetic resonance (EPR) spectroscopy were used to quantify the interaction and to obtain information on the location of mitoxantrone in bile salt micelles. The presence of submicellar concentrations of both bile salts induces mitoxantrone aggregation and the extent of drug aggregation in NaTDC is higher than in NaTC. For micellar bile salts concentrations, mitoxantrone monomers are entrapped in the micellar core. Binding constants, micelle/water partition coefficients and the corresponding thermodynamic parameters for binding and partitioning processes were estimated using the changes in monomer absorbance in the presence of bile salts. Binding interaction of mitoxantrone is stronger for NaTDC than NaTC micelles, whereas partitioning efficiency is higher for NaTC micelles for all investigated temperatures. Thermodynamic parameters indicate that both binding and partitioning processes are spontaneous and entropy controlled. The spectral behavior and thermodynamic parameters indicate distinct types of mitoxantrone interaction with NaTDC and NaTC micelles supported by the differences in nature and structure of bile salts micelles.


Asunto(s)
Antineoplásicos/química , Ácidos y Sales Biliares/química , Mitoxantrona/química , Ácido Taurocólico/química , Ácido Taurodesoxicólico/química , Espectroscopía de Resonancia por Spin del Electrón , Espectrofotometría Ultravioleta
16.
Ultrason Sonochem ; 36: 326-335, 2017 May.
Artículo en Inglés | MEDLINE | ID: mdl-28069217

RESUMEN

Hierarchical flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method performed in a ordinary ultrasonic bath using an ammonia solution and zinc acetate, in the absence of any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the materials obtained at different ultrasound irradiation times were characterized by infrared, UV-Vis and photoluminescence spectroscopy, X-ray diffraction, scanning and transmission electron microscopy investigations. It was proved that the ultrasound irradiation time manipulates both the defect content (implicit the photoluminescent properties) and morphology of the ZnO materials: shorter irradiation times leads to the synthesis of high-defected ZnO structures of flower morphology with triangular-shaped petals, while higher irradiation times favours the formation of low-defected ZnO structures with tipped rod-like petals. A plausible growth mechanism of the architectures that implies aggregation via oriented attachment followed by an Ostwald ripening is advanced based on these results. The ZnO flower-like structures present high photocatalytic activities, a total phenol mineralization being registered in the case of visible light experiments. Electron-spin resonance measurements demonstrate the generation of reactive oxygen species, namely hydroxyl radicals but also C centred radicals adducts derived most probable from the residual acetate adsorbed on ZnO surface.

17.
Adm Policy Ment Health ; 43(6): 927-944, 2016 11.
Artículo en Inglés | MEDLINE | ID: mdl-27444375

RESUMEN

This manuscript reviews the development and implementation process of the Client Reported Outcome Monitoring Information System in the VA Canada Operational Stress Injury National Network, and reports on outcomes of an evaluation to assess usage, barriers, and facilitators to implementation. The majority of clinicians reported regular use of routine outcomes monitoring, although objective data suggested somewhat lower actual use. In general, clinicians endorsed all barriers and most facilitators as influencing their use of routine outcomes monitoring in a minor way. However, users and non-users differed in their endorsement of facilitators and barriers. Implications for research and implementation efforts are discussed.


Asunto(s)
Sistemas de Información en Salud , Trastornos Mentales/terapia , Servicios de Salud Mental/normas , Enfermedades Profesionales/terapia , Medición de Resultados Informados por el Paciente , Calidad de la Atención de Salud , Salud de los Veteranos , Adulto , Anciano , Actitud del Personal de Salud , Canadá , Retroalimentación , Femenino , Humanos , Masculino , Persona de Mediana Edad , Enfermeras y Enfermeros , Psiquiatría , Psicología , Trabajadores Sociales , Adulto Joven
18.
J Phys Chem B ; 120(18): 4258-67, 2016 05 12.
Artículo en Inglés | MEDLINE | ID: mdl-27065050

RESUMEN

The interaction of human serum albumin (HSA) with amphiphilic block copolymer Pluronic F127 has been investigated by several physical methods. Interest in studying this system stems from a broad range of bioactivities involving both macromolecules. Serum albumins constitute a significant class of proteins in the circulatory system, acting as carriers for a wide spectrum of compounds or assemblies. Pluronic block copolymers have revealed their capacity to ferry a variety of biologically active compounds. Circular dichroism, rheological measurements, and differential scanning microcalorimetry (µDSC) were employed to get insight into the interaction betweeen the two macromolecules. The results reveal that Pluronic F127 induces conformational changes to albumin if it is organized in a micellar form, while albumin influences the self-assembly of Pluronic F127 into micelles or gels. F127 micelles, however, induce smaller conformational changes compared to ionic surfactants. The µDSC thermograms obtained for HSA and/or F127 show that HSA shifts the critical micellar temperature (cmt) to lower values, while concurrently the HSA denaturation behavior is influenced by F127, depending on its concentration. Rheological measurements on solutions of F127 17% have shown that a sol-to-gel transition occurs at higher temperatures in the presence of HSA and the resulting gel is weaker. The global profile on HSA/F127 systems was complemented by local information provided by EPR measurements. A series of X-band EPR experiments was performed with spin probes 4-(N,N'-dimethyl-N-hexadecyl)ammonium-2,2',6,6'-tetramethylpiperidine-1-oxyl iodide (CAT16) and 5-doxyl stearic acid (5-DSA). These spin probes bind to albumin sites and are sensitive to phase transformations in Pluronic block copolymer solutions. For a given F127 concentration, the spin probe binds only to HSA below cmt and migrates to the F127 micelles above cmt. The collective data suggest soft interactions between the macromolecules, with the emerging results projecting potential applications linked to reaching optimal conditions for certain drug formulations.


Asunto(s)
Poloxámero/química , Albúmina Sérica Humana/química , Rastreo Diferencial de Calorimetría , Dicroismo Circular , Espectroscopía de Resonancia por Spin del Electrón , Geles/química , Humanos , Micelas , Poloxámero/metabolismo , Reología , Albúmina Sérica Humana/metabolismo , Temperatura , Termodinámica
19.
J Couns Psychol ; 63(2): 173-182, 2016 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-26651210

RESUMEN

Although integrating progress monitoring (PM) measures into psychotherapy practice can provide numerous benefits, including improved client outcomes, relatively few clinicians use these measures (e.g., Ionita & Fitzpatrick, 2014). To better understand the reasons for clinicians' reluctance, consensual qualitative research methodology was used to examine the challenges faced by clinicians currently using PM measures. Open-ended, semistructured interviews, with 25 clinicians who chose to use PM measures, revealed that clinicians tended to face challenges involving technical concerns, negative responses from others, and personal barriers such as anxiety. The majority of participants discussed ways to overcome the challenges they experienced, including ensuring the fit of the PM measure, explaining measures to others to help engender a positive response, adapting their own perspective, and increasing their own and others' knowledge of the measures. Implications for practicing psychologists and for knowledge translation efforts are discussed.


Asunto(s)
Actitud del Personal de Salud , Trastornos Mentales/terapia , Evaluación de Resultado en la Atención de Salud/métodos , Psicoterapia/estadística & datos numéricos , Adulto , Anciano , Práctica Clínica Basada en la Evidencia , Femenino , Humanos , Entrevistas como Asunto , Masculino , Persona de Mediana Edad , Psicoterapia/métodos , Investigación Cualitativa , Adulto Joven
20.
Soft Matter ; 11(46): 8968-74, 2015 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-26399427

RESUMEN

The formation of alginate gel from low molecular weight alginate and very low molecular weight alginate in the presence of divalent cations was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. The transition from sol to gel in the presence of divalent cations was monitored by the changes in the dynamics of spin labelled alginate. The immobilisation of the spin labelled alginate in the gel reflects the strength of interaction between the cation and alginate chain. Diffusion experiments showed that both the cation and alginate polyanion in the gel fibres can exchange with molecules in solution. In particular, we showed that dissolved alginate polyanions can replace alginates in the gel fibres, which can hence diffuse through the bulk of the gel. This illustrates the surprisingly highly dynamic nature of these gels and opens up the possibility of preparing multicomponent alginate gels via polyanion exchange process.


Asunto(s)
Alginatos/química , Geles/química , Espectroscopía de Resonancia por Spin del Electrón , Ácido Glucurónico/química , Ácidos Hexurónicos/química , Intercambio Iónico , Estructura Molecular , Peso Molecular , Viscosidad
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