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1.
J Chem Phys ; 158(3): 034901, 2023 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-36681636

RESUMO

In this work, we studied TEMPO-oxidized cellulose nanofibril (OCNF) suspensions in the presence of diverse surfactants. Using a combination of small angle neutron scattering (SANS) and rheology, we compared the physical properties of the suspensions with their structural behavior. Four surfactants were studied, all with the same hydrophobic tail length but different headgroups: hexaethylene glycol mono-n-dodecyl ether (C12EO6, nonionic), sodium dodecyl sulfate (SDS, anionic), cocamidopropyl betaine (CapB, zwitterionic), and dodecyltrimethylammonium bromide (DTAB, cationic). Contrast variation SANS studies using deuterated version of C12EO6 or SDS, or by varying the D2O/H2O ratio of the suspensions (with CapB), allowed focusing only on the structural properties of OCNFs or surfactant micelles. We showed that, in the concentration range studied, for C12EO6, although the nanofibrils are concentrated thanks to an excluded volume effect observed in SANS, the rheological properties of the suspensions are not affected. Addition of SDS or CapB induces gelation for surfactant concentrations superior to the critical micellar concentration (CMC). SANS results show that attractive interactions between OCNFs arise in the presence of these anionic or zwitterionic surfactants, hinting at depletion attraction as the main mechanism of gelation. Finally, addition of small amounts of DTAB (below the CMC) allows formation of a tough gel by adsorbing onto the OCNF surface.


Assuntos
Celulose Oxidada , Tensoativos , Tensoativos/química , Espalhamento a Baixo Ângulo , Dodecilsulfato de Sódio/química
2.
Soft Matter ; 16(13): 3303-3310, 2020 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-32173723

RESUMO

The effect of the filler size on the structural and mechanical properties of an attractive fibrillated network composed of oxidised cellulose nanofibrils (OCNF) in water was investigated. Silica nanoparticles with a diameter of ca. 5 nm (SiNp5) and and ca. 158 nm (SiNp158) were chosen as non-interacting fillers of the OCNF network. These filler sizes were chosen, respectively, to have a particle size which was either similar to that of the network mesh size or much larger than it. Contrast matched small angle neutron scattering (SANS) experiments revealed that the presence of the fillers (SiNp5 and SiNp158) did not perturb the structural properties of the OCNF network at the nanometer scale. However, the filler size difference strongly affected the mechanical properties of the hydrogel upon large amplitude oscillatory shear. The presence of the smaller filler, SiNp5, preserved the mechanical properties of the hydrogels, while the larger filler, SiNp158, allowed a smoother breakage of the network and low network recoverability after breakage. This study showed that the filler-to-mesh size ratio, for non-interacting fillers, is pivotal for tailoring the non-linear mechanical properties of the gel, such as yielding and flow.

3.
Soft Matter ; 16(2): 357-365, 2020 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-31720672

RESUMO

Interfacial gels, obtained by the interaction of water-dispersible oxidised cellulose nanofibrils (OCNF) and oil-soluble oleylamine (OA), were produced across water/oil (W/O) interfaces. Surface rheology experiments showed that the complexation relies on the charge coupling between the negatively-charged OCNF and OA. Complexation across the W/O interface was found to be dependent on the ζ-potential of the OCNF (modulated by electrolyte addition), leading to different interfacial properties. Spontaneous OCNF adsorption at the W/O interface occurred for particles with ζ-potential more negative than -30 mV, resulting in the formation of interfacial gels; whilst for particles with ζ-potential of ca. -30 mV, spontaneous adsorption occurred, coupled with augmented interfibrillar interactions, yielding stronger and tougher interfacial gels. On the contrary, charge neutralisation of OCNF (ζ-potential values more positive than -30 mV) did not allow spontaneous adsorption of OCNF at the W/O interface. In the case of favourable OCNF adsorption, the interfacial gel was found to embed oil-rich droplets - a spontaneous emulsification process.

4.
Soft Matter ; 16(20): 4887-4896, 2020 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-32424387

RESUMO

In this work, we investigated the effect of adding surfactant mixtures on the rheological properties of TEMPO-oxidized cellulose nanofibril (OCNF) saline dispersions. Three surfactant mixtures were studied: cocamidopropyl betaine (CAPB)/sodium dodecyl sulfate (SDS), which forms wormlike micelles (WLMs); cocamidopropylamine oxide (CAPOx)/SDS, which forms long rods; and CAPB/sodium lauroyl sarcosinate (SLS), which forms spherical micelles. The presence of micelles in these surfactant mixtures, independent of their morphology, leads to an increase of tan δ, making the gels less solid-like, therefore acting as a plasticizer. WLMs were able to suppress strain stiffening normally observed in OCNF gels at large strains. OCNF/WLM gels have lower G' values than OCNF gels while the other micellar morphologies have a reduced impact on G'. The presence of unconnected micelles leads to increased dissipative deformation in OCNF gels without affecting the connectivity of the fibrils, while the presence of entangled micelles interferes with the OCNF network.

5.
AAPS PharmSciTech ; 21(4): 125, 2020 Apr 29.
Artigo em Inglês | MEDLINE | ID: mdl-32350635

RESUMO

Sunlight is important to health, but higher exposure to radiation causes early aging of the skin and skin damage that can lead to skin cancers. This study aimed at producing a stable octyl p-methoxycinnamate (OMC)-loaded nanostructured lipid carrier (NLC) sunscreen, which can help in the photoprotective effect. NLC was produced by emulsification-sonication method and these systems were composed of myristyl myristate (MM), caprylic capric triglyceride (CCT), Tween® 80 (TW), and soybean phosphatidylcholine (SP) and characterized by dynamic light scattering (DLS), zeta potential (ZP) measurement, atomic force microscopy (AFM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and in vitro release studies. Pre-formulation studies were performed changing TW concentrations and no differences were found at concentrations of 1.0 and 2.0%. Two selected formulations were designed and showed an average size of 91.5-131.7, polydispersity index > 0.2, and a negative value of ZP. AFM presented a sphere-like morphology and SEM showed ability to form a thin film. DSC exhibited that the incorporation of OMC promoted reduction of enthalpy due to formation of a more amorphous structure. Drug release shows up to 55.74% and 30.57%, and this difference could be related to the presence of SP in this formulation that promoted a more amorphous structure; the release mechanism study indicated Fickian diffusion and relaxation. Sun protection factor (SPF) evaluation was performed using NLC and presented values around 40, considerably higher than those observed in the literature. The developed formulations provide a beneficial alternative to conventional sunscreen formulations.


Assuntos
Cinamatos/síntese química , Portadores de Fármacos/síntese química , Lipídeos/síntese química , Nanoestruturas/química , Fator de Proteção Solar/métodos , Protetores Solares/síntese química , Varredura Diferencial de Calorimetria/métodos , Cinamatos/farmacocinética , Portadores de Fármacos/farmacocinética , Liberação Controlada de Fármacos , Lipídeos/farmacocinética , Microscopia de Força Atômica/métodos , Microscopia Eletrônica de Varredura/métodos , Tamanho da Partícula , Protetores Solares/farmacocinética
6.
Nanotechnology ; 30(27): 275701, 2019 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-30893653

RESUMO

Reduced graphene oxide (rGO) layers are known to be significantly conductive along the basal plane throughout delocalized sp2 domains. Defects present in rGO implies in disordered systems with numerous localized sites, resulting in a charge transport governed mainly by a 2D variable range hopping (VRH) mechanism. These characteristics are observed even in multilayered rGO since the through-plane conduction is expected to be insubstantial. Here, we report on the multilayer assembly of functionalized rGO quantum dots (GQDs) presenting 3D VRH transport that endows elevated charge carrier mobility, ca âˆ¼ 236 cm2 V-1 s-1. Polyelectrolyte-wrapped GQDs were assembled by layer-by-layer technique (LbL), ensuring molecular level thickness control for the formed nanostructures, along with the adjustment of the film transparency (up to 92% in the visible region). The small size and the random distribution of GQDs in the LbL structure are believed to overcome the translational disorder in multilayered films, contributing to a 3D interlayer conduction that enhances the electronic properties. Such high-mobility, transparency-tunable films assembled by a cost-effective method possess interesting features and wide applicability in optoelectronics.

7.
Soft Matter ; 14(45): 9243-9249, 2018 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-30418451

RESUMO

Solvent-induced physical hydrogels of TEMPO-oxidized cellulose nanofibrils (OCNFs) were obtained from aqueous/alcoholic dispersions of fibrils in lower alcohols, namely, methanol, ethanol, 1-propanol and 2-propanol. The sol-gel transition occurs above a critical alcohol concentration of ca. 30 wt% for all alcohols tested. The rheological properties of the hydrogels depend on the nature of the alcohol: for ethanol, 1-propanol and 2-propanol the magnitude of the shear storage modulus follows the alcohol hydrophilicity, whilst methanol produces the weakest gels in the group. Above a second critical concentration, ca. 60 wt% alcohol, phase separation is observed as the gels undergo syneresis. Analysis of small-angle X-ray scattering data shows that the OCNFs may be modelled as rigid rods. In the presence of lower alcohols, attractive interactions between nanofibrils are present and, above the alcohol concentration leading to gelation, an increase of the OCNF cross-section is observed, suggesting alcohol induced aggregation of nanofibrils.

8.
Soft Matter ; 14(38): 7793-7800, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30109338

RESUMO

Zwitterionic cellulose nanofibrils (ZCNFs) with an isoelectric point of 3.4 were obtained by grafting glycidyltrimethylammonium chloride onto TEMPO/NaBr/NaOCl-oxidised cellulose nanofibrils. The ZCNF aqueous dispersions were characterized via transmission electron microscopy, rheology and small angle neutron scattering, revealing a fibril-bundle structure with pronounced aggregation at pH 7. Surfactants were successfully employed to tune the stability of the ZCNF dispersions. Upon addition of the anionic surfactant, sodium dodecyl sulfate, the ZCNF dispersion shows individualized fibrils due to electrostatic stabilization. In contrast, upon addition of the cationic species dodecyltrimethylammonium bromide, the dispersion undergoes charge neutralization, leading to more pronounced flocculation.

9.
Phys Chem Chem Phys ; 20(23): 16012-16020, 2018 Jun 13.
Artigo em Inglês | MEDLINE | ID: mdl-29850680

RESUMO

The structure of dispersions of TEMPO-oxidised cellulose nanofibrils (OCNF), at various concentrations, in water and in NaCl aqueous solutions, was probed using small angle X-ray scattering (SAXS). OCNF are modelled as rod-like particles with an elliptical cross-section of 10 nm and a length greater than 100 nm. As OCNF concentration increases above 1.5 wt%, repulsive interactions between fibrils are evidenced, modelled by the interaction parameter νRPA > 0. This corresponds to gel-like behaviour, where G' > G'' and the storage modulus, G', shows weak frequency dependence. Hydrogels can also be formed at OCNF concentration of 1 wt% in 0.1 M NaCl(aq). SAXS patterns shows an increase of the intensity at low angle that is modelled by attractive interactions (νRPA < 0) between OCNF, arising from the screening of the surface charge of the fibrils. Results are supported by ζ potential and cryo-TEM measurements.

10.
Phys Chem Chem Phys ; 20(41): 26696-26709, 2018 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-30324204

RESUMO

This study reports on investigation of the magnetic properties of layer-by-layer (LbL) assembled nanofilms comprising polyvinyl alcohol (PVA) and citrate-coated magnetite (cit-MAG) nanoparticles deposited onto silicon (SF sample) and glass (GF sample) substrates. DC magnetization measurements were performed over the temperature range of 4 K to 300 K, in the applied magnetic field range of ±60 kOe. The magnetic data of the as-synthesized cit-MAG nanoparticles (F sample) are also collected for comparison. The three as-fabricated samples reveal perfect superparamagnetic (SPM) behavior only around room temperature; at temperatures lower than 200 K the SPM scaling is not observed and all samples behave as interacting superparamagnetic (ISPM) materials. The evolution from the ISPM to the SPM regime is marked by a steady decrease in the hysteretic properties of all samples, with the temperature-dependence of the coercivity decreasing slower than the T1/2 behavior predicted for non-interacting superparamagnetic particles. The modified Bloch's law used to assess information on nanoparticles' surface spins gives the Bloch's exponent close to 2 (for the F and SF samples) and close to 1 (for the GF sample). Interestingly, the surface spin freezing temperature (Tf) is 8 ± 1 K for all samples. The magnetic behavior of all three samples can be described within the model picture of a core-shell structure for the cit-MAG nanoparticles; the core comprising magnetically-ordered spins whereas the shell behaving as a spin-glass-like system. However, the contribution of the shell magnetism to the effective magnetic properties is much more evident in the GF sample in which magnetic dipole-dipole interaction is three-times weaker than in the SF sample and two times weaker than in the F sample. In contrast, the strong magnetic dipole-dipole interaction in the SF sample affects the surface spins, hindering the onset of magnetically-ordered regions in the nanoparticle's shell, making the surface magnetism contribution negligible. The LbL-fabricated nanofilms herein reported and the presented analysis of their magnetic properties we envisage can support the engineering of magnetic nanofilms for multiple applications.

11.
J Nanosci Nanotechnol ; 18(6): 3908-3915, 2018 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-29442726

RESUMO

In this work it was studied the production of nanostructured thin films containing alternating layers of poly(allylamine hydrochloride) (PAH) and bovine serum albumin protein (BSA). It was studied the adsorption processes of these materials onto solid surfaces, which included adsorption kinetics and film growth studies by using UV-Vis spectroscopy. The film morphology, thickness and roughness were studied by using atomic force microscopy (AFM). The AFM results showed that the film presented a globular-like surface morphology and a thickness within the nanoscale, which could be controlled by the number of deposited layers. The roughness and thickness of the film depend on the number of deposited bilayers, where the film roughness increased for films with a number of bilayers up to five, after which the film roughness remained almost constant. This is an indicative that the adsorption and growth processes might occur under two different mechanisms, first under the influence of the substrate (films containing up to five bilayers of PAH/BSA), and second under the influence of the film previously deposited (films containing more than five bilayers of PAH/BSA), respectively.


Assuntos
Nanoestruturas , Poliaminas , Soroalbumina Bovina , Adsorção , Animais , Bovinos , Microscopia de Força Atômica
12.
Biom J ; 60(2): 352-368, 2018 03.
Artigo em Inglês | MEDLINE | ID: mdl-29194715

RESUMO

The deterministic inputs, noisy, "and" gate (DINA) model is a popular cognitive diagnosis model (CDM) in psychology and psychometrics used to identify test takers' profiles with respect to a set of latent attributes or skills. In this work, we propose an estimation method for the DINA model with the No-U-Turn Sampler (NUTS) algorithm, an extension to Hamiltonian Monte Carlo (HMC) method. We conduct a simulation study in order to evaluate the parameter recovery and efficiency of this new Markov chain Monte Carlo method and to compare it with two other Bayesian methods, the Metropolis Hastings and Gibbs sampling algorithms, and with a frequentist method, using the Expectation-Maximization (EM) algorithm. The results indicated that NUTS algorithm employed in the DINA model properly recovers all parameters and is accurate for all simulated scenarios. We apply this methodology in the mental health area in order to develop a new method of classification for respondents to the Beck Depression Inventory. The implementation of this method for the DINA model applied to other psychological tests has the potential to improve the medical diagnostic process.


Assuntos
Biometria/métodos , Cognição , Modelos Estatísticos , Psicometria , Algoritmos , Depressão/fisiopatologia , Depressão/psicologia , Humanos , Método de Monte Carlo
13.
Biomacromolecules ; 18(2): 636-646, 2017 02 13.
Artigo em Inglês | MEDLINE | ID: mdl-28006103

RESUMO

The native states of proteins generally have stable well-defined folded structures endowing these biomolecules with specific functionality and molecular recognition abilities. Here we explore the potential of using folded globular polyproteins as building blocks for hydrogels. Photochemically cross-linked hydrogels were produced from polyproteins containing either five domains of I27 ((I27)5), protein L ((pL)5), or a 1:1 blend of these proteins. SAXS analysis showed that (I27)5 exists as a single rod-like structure, while (pL)5 shows signatures of self-aggregation in solution. SANS measurements showed that both polyprotein hydrogels have a similar nanoscopic structure, with protein L hydrogels being formed from smaller and more compact clusters. The polyprotein hydrogels showed small energy dissipation in a load/unload cycle, which significantly increased when the hydrogels were formed in the unfolded state. This study demonstrates the use of folded proteins as building blocks in hydrogels, and highlights the potential versatility that can be offered in tuning the mechanical, structural, and functional properties of polyproteins.


Assuntos
Hidrogel de Polietilenoglicol-Dimetacrilato/química , Poliproteínas/química , Engenharia de Proteínas , Humanos , Reologia , Espalhamento a Baixo Ângulo , Difração de Raios X
14.
Nanotechnology ; 28(49): 495711, 2017 Dec 08.
Artigo em Inglês | MEDLINE | ID: mdl-28985189

RESUMO

Graphene is a breakthrough 2D material due to its unique mechanical, electrical, and thermal properties, with considerable responsiveness in real applications. However, the coverage of large areas with pristine graphene is a challenge and graphene derivatives have been alternatively exploited to produce hybrid and composite materials that allow for new developments, considering also the handling of large areas using distinct methodologies. For electronic applications there is significant interest in the investigation of the electrical properties of graphene derivatives and related composites to determine whether the characteristic 2D charge transport of pristine graphene is preserved. Here, we report a systematic study of the charge transport mechanisms of reduced graphene oxide chemically functionalized with sodium polystyrene sulfonate (PSS), named as GPSS. GPSS was produced either as quantum dots (QDs) or nanoplatelets (NPLs), being further nanostructured with poly(diallyldimethylammonium chloride) through the layer-by-layer (LbL) assembly to produce graphene nanocomposites with molecular level control. Current-voltage (I-V) measurements indicated a meticulous growth of the LbL nanostructures onto gold interdigitated electrodes (IDEs), with a space-charge-limited current dominated by a Mott-variable range hopping mechanism. A 2D intra-planar conduction within the GPSS nanostructure was observed, which resulted in effective charge carrier mobility (µ) of 4.7 cm2 V-1 s-1 for the QDs and 34.7 cm2 V-1 s-1 for the NPLs. The LbL assemblies together with the dimension of the materials (QDs or NPLs) were favorably used for the fine tuning and control of the charge carrier mobility inside the LbL nanostructures. Such 2D charge conduction mechanism and high µ values inside an interlocked multilayered assembly containing graphene-based nanocomposites are of great interest for organic devices and functionalization of interfaces.

15.
Langmuir ; 32(49): 13174-13186, 2016 12 13.
Artigo em Inglês | MEDLINE | ID: mdl-27951706

RESUMO

Polymeric micelles, in particular PEO-PPO-based Pluronic, have emerged as promising drug carriers, while cyclodextrins (CD), cyclic oligosaccharides with an apolar cavity, have long been used for their capacity to form inclusion complexes with drugs. Dimethylated ß-cyclodextrin (DIMEB) has the capacity to fully breakup F127 Pluronic micelles, while this effect is substantially hindered if drugs are loaded within the micellar aggregates. Four drugs were studied at physiological temperature: lidocaine (LD), pentobarbital sodium salt (PB), sodium naproxen (NP), and sodium salicylate (SAL); higher temperatures shift the equilibrium toward higher drug partitioning and lower drug/CD binding compared to 25 °C ( Valero, M.; Dreiss, C. A. Growth, Shrinking, and Breaking of Pluronic Micelles in the Presence of Drugs and/or ß-Cyclodextrin, a Study by Small-Angle Neutron Scattering and Fluorescence Spectroscopy . Langmuir 2010 , 26 , 10561 - 10571 ). The impact of drugs on micellar structure was characterized by small-angle neutron scattering (SANS), while their solubilization locus was revealed by 2D NOESY NMR. UV and fluorescence spectroscopy, Dynamic and Static Light Scattering were employed to measure a range of micellar properties and drug:CD interactions: binding constant, drug partitioning within the micelles, critical micellar concentration of the loaded micelles, aggregation number (Nagg). Critically, time-resolved SANS (TR-SANS) reveal that micellar breakup in the presence of drugs is substantially slower (100s of seconds) than for the free micelles (<100 ms) ( Valero, M.; Grillo, I.; Dreiss, C. A. Rupture of Pluronic Micelles by Di-Methylated ß-Cyclodextrin Is Not Due to Polypseudorotaxane Formation . J. Phys. Chem. B 2012 , 116 , 1273 - 1281 ). These results combined together give new insights into the mechanisms of protection of the drugs against CD-induced micellar breakup. The outcomes are practical guidelines to improve the design of drug delivery systems as well as a better understanding of competitive assembly mechanisms leading to shape and function modulation.


Assuntos
Ciclodextrinas/química , Micelas , Preparações Farmacêuticas/química , Poloxâmero/química , Lidocaína , Naproxeno , Pentobarbital , Espalhamento a Baixo Ângulo , Salicilato de Sódio
16.
J Nanosci Nanotechnol ; 16(6): 6535-9, 2016 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-27427748

RESUMO

Studies on sonochemical hydrolysis of cellulose have been suggested as an alternative route to obtaining cellulose nanoparticles. In this work, the potential use of acid hydrolysis assisted by sonication to obtain cellulose whiskers was studied. Parameters such as acid concentration, hydrolysis time and temperature were investigated to evaluate their effect on the morphological properties of the nanowhiskers, as compared to the conventional extraction process by acid hydrolysis with mechanical stirring. Morphology and degree of crystallinity of the nanowhiskers were studied by atomic force microscopy (AFM) and X-ray diffraction (XRD). Results indicated that the extraction time was reduced from about 45 min to less than 3 min using the same acid concentration and temperature used in conventional acid hydrolysis treatment. Likewise, it was possible, within the range of 30 min, to extract whiskers at room temperature or using half the concentration of acid by raising the temperature to about 80 degrees C. These are promising results towards a more economically viable and ecologically friendly extraction procedure used to obtain cellulose nanowhiskers, since both extraction time and acid concentration, used in nanowhisker extraction, were significantly reduced by replacing mechanical with sonochemical stirring.


Assuntos
Celulose/química , Celulose/isolamento & purificação , Nanoestruturas , Sonicação , Hidrólise , Cinética
17.
Nanomedicine ; 12(8): 2439-2448, 2016 11.
Artigo em Inglês | MEDLINE | ID: mdl-27431054

RESUMO

Needle-free immunization strategies have been sought for years. Transcutaneous immunization using electroporation has been studied, but the high electrical voltage that must be applied may be painful and cause irreversible cell damage. The application of a weak electric field, such as in iontophoresis, has never been attempted. The aim of this work was to verify the potential of employing iontophoresis for transcutaneous immunization using ovalbumin (OVA) as a model antigen. To target the antigen presenting cells that are located in the viable epidermis, a vaccine formulation composed of OVA-loaded liposomes and silver nanoparticles (NPAg) was developed. In vitro cathodal iontophoresis of the OVA-liposomes associated with NPAg increased OVA penetration into the viable epidermis by 92-fold in comparison to passive delivery. In vivo, transcutaneous immunization with a suitable combination of liposome and iontophoresis induced the production of antibodies, differentiation of immune-competent cells and appeared to present an alternative strategy for needle-free vaccination.


Assuntos
Imunização/métodos , Iontoforese , Nanopartículas , Administração Cutânea , Ovalbumina , Vacinação
18.
Langmuir ; 31(20): 5645-55, 2015 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-25938931

RESUMO

Complexes formed between cyclodextrins (CDs) and polymers - pseudopolyrotaxanes (PPRs) - are the starting point of a multitude of supramolecular structures, which are proposed for a wide range of biomedical and technological applications. In this work, we investigate the complexation of a range of cyclodextrins with Tetronic T1307, a four-arm block copolymer of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) with a pH-responsive central ethylene diamine spacer, and its impact on micellization and the sol-gel transition. At low concentrations, small-angle neutron scattering (SANS) combined with dynamic light scattering (DLS) measurements show the presence of spherical micelles with a highly hydrated shell and a dehydrated core. Increasing the temperature leads to more compact micelles and larger aggregation numbers, whereas acidic conditions induce a shrinking of the micelles, with fewer unimers per micelle and a more hydrated corona. At high concentrations, T1307 undergoes a sol-gel transition, which is suppressed at pH below the pKa,1 (4.6). SANS data analysis reveals that the gels result from a random packing of the micelles, which have an increasing aggregation number and increasingly dehydrated shell and hydrated core with the temperature. Native CDs (α, ß, γ-CD) can complex T1307, resulting in the precipitation of a PPR. Instead, modified CDs compete with micellization to an extent that is critically dependent on the nature of the substitution. (1)H and ROESY NMR combined with SANS demonstrate that dimethylated ß-CD can thread onto the polymer, preferentially binding to the PO units, thus hindering self-aggregation by solubilizing the hydrophobic block. The various CDs are able to modulate the onset of gelation and the extent of the gel phase, and the effect correlates with the ability of the CDs to disrupt the micelles, with the exception of a sulfated sodium salt of ß-CD, which, while not affecting the CMT, is able to fully suppress the gel phase.


Assuntos
Ciclodextrinas/química , Etilenodiaminas/química , Polietilenoglicóis/química , Polímeros/química , Propilenoglicóis/química , Interações Hidrofóbicas e Hidrofílicas
19.
Biomacromolecules ; 16(4): 1401-9, 2015 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-25772227

RESUMO

Small-angle neutron scattering (SANS) was used to characterize the nanoscale structure of enzymatically cross-linked chitosan/gelatin hydrogels obtained from two protocols: a pure chemical cross-linking process (C), which uses the natural enzyme microbial transglutaminase, and a physical-co-chemical (PC) hybrid process, where covalent cross-linking is combined with the temperature-triggered gelation of gelatin, occurring through the formation of triple-helices. SANS measurements on the final and evolving networks provide a correlation length (ξ), which reflects the average size of expanding clusters. Their growth in PC gels is restricted by the triple-helices (ξ ∼ 10s of Å), while ξ in pure chemical gels increases with cross-linker concentration (∼100s of Å). In addition, the shear elastic modulus in PC gels is higher than in pure C gels. Our results thus demonstrate that gelatin triple helices provide a template to guide the cross-linking process; overall, this work provides important structural insight to improve the design of biopolymer-based gels.


Assuntos
Proteínas de Bactérias/química , Quitosana/química , Gelatina/química , Géis/química , Transglutaminases/química , Biocatálise , Reagentes de Ligações Cruzadas/química , Cinética , Polimerização
20.
Sensors (Basel) ; 15(4): 9592-609, 2015 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-25912354

RESUMO

Electronic devices based on organic thin-film transistors (OTFT) have the potential to supply the demand for portable and low-cost gadgets, mainly as sensors for in situ disease diagnosis and environment monitoring. For that reason, poly(3-hexylthiophene) (P3HT) as the active layer in the widely-used bottom-gate/bottom-contact OTFT structure was deposited over highly-doped silicon substrates covered with thermally-grown oxide to detect vapor-phase compounds. A ten-fold organochloride and ammonia sensitivity compared to bare sensors corroborated the application of this semiconducting polymer in sensors. Furthermore, P3HT TFTs presented approximately three-order higher normalized sensitivity than any chemical sensor addressed herein. The results demonstrate that while TFTs respond linearly at the lowest concentration values herein, chemical sensors present such an operating regime mostly above 2000 ppm. Simultaneous alteration of charge carrier mobility and threshold voltage is responsible for pushing the detection limit down to units of ppm of ammonia, as well as tens of ppm of alcohol or ketones. Nevertheless, P3HT transistors and chemical sensors could compose an electronic nose operated at room temperature for a wide range concentration evaluation (1-10,000 ppm) of gaseous analytes. Targeted analytes include not only biomarkers for diseases, such as uremia, cirrhosis, lung cancer and diabetes, but also gases for environment monitoring in food, cosmetic and microelectronics industries.

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