Core-Shell Spheroidal Hydrogels Produced via Charge-Driven Interfacial Complexation.

Through charge-driven interfacial complexation, we produced millimeter-sized spheroidal hydrogels (SH) with a core-shell structure allowing long-term stability in aqueous media. The SH were fabricated by extruding, dropwise, a cationic cellulose nanofibril (CCNF) dispersion into an oppositely charged poly(acrylic acid) (PAA) bath. The SH have a solid-like CCNF-PAA shell, acting as a semipermeable membrane, and a liquid-like CCNF suspension in the core. Swelling behavior of the SH was dependent on the osmotic pressure of the aging media. Swelling could be suppressed by increasing the ionic strength of the media as this enhanced interfibrillar interactions and thus strengthened the outer gel membrane. We further validated a potential application of SH as reusable matrixes for glucose oxidase (GOx) entrapment, where the SH work as microreactors from which substrate and product are freely able to migrate through the SH shell while avoiding enzyme leakage.

Inorganic and organic characterization of Santa Lucía salt mine peloid for quality evaluations.

Santa Lucía peloid is a sediment used in pelotherapy in Cuban primary health care services. Therefore, in addition to physicochemical regulated parameters, other analyses are required to complement their physicochemical characterization and understand potential element mobility, radiological risk, and toxicity as well as likely bioactive compounds present in Santa Lucía peloid. For these purposes, inorganic and organic elements and compounds were considered to evaluate Santa Lucía peloid's quality. This was accomplished through an integral approach that included (1) determination of physicochemical parameters (pH, electrical conductivity, oxidation-reduction potential, temperature, dissolved oxygen, elemental C, H, and N analyses, organic matter, and hexane removable substances content); (2) determination of total concentration of elements with biological and toxicological importance (i.e., Na, K, Ca, Mg, Fe, Mn, Cr, Cu, Ni, Pb, and Zn), as well as their distribution in operationally defined solid phases, mineralogy, particle size distribution, and total content of radionuclides and radiological dose calculations; and (3) its organic characterization. Results from this study showed that Santa Lucía peloid was non-contaminated and showed low metal mobility and acceptable radiological dose levels, being safe for therapeutic uses. Additionally, these results contribute to the understanding of the organic composition of peloides, provide strong evidences to scientifically explain the therapeutic action of peloids in the treatment of inflammatory diseases, and set a new frame to improve peloid guidelines in Cuba and other countries.

Study of the interaction of flavonoids with 3-mercaptopropionic acid modified CdTe quantum dots mediated by cetyltrimethyl ammonium bromide in aqueous medium.

Flavonoids are polyphenols that help the maintenance of health, aiding the prevention of diseases. In this work, CdTe QDs coated with 3-mercaptopropionic acid (3MPA), with an average size of 2.7nm, were used as photoluminescence probe for flavonoids in different conditions. The interaction between 14 flavonoids and QDs was evaluated in aqueous dispersions in the absence and in the presence of cetyltrimethylammonium bromide (CTAB). To establish a relationship between photoluminescence quenching and the concentration of flavonoids, the Stern-Volmer model was used. In the absence of CTAB, the linear ranges for quercetin, morin and rutin were from 5.0×10-6molL-1 to 6.0×10-5molL-1 and from 1.0×10-5molL-1 to 6.0×10-4molL-1 for kaempferol. The sensibility of the Stern-Volmer curves (Ks) indicated that quercetin interacts more strongly with the probe: Ks quercetin>Ks kaempferol>Ks rutin>Ks morin. The conjugation extension in the 3 rings, and the acidic hydroxyl groups (positions 3'and 4') in the B-ring enhanced the interaction with 3MPA-CdTe QDs. The other flavonoids do not interact with the probe at 10-5molL-1 level. In CTAB organized dispersions, Ks 3-hydroxyflavone>Ks 7-hydroxyflavone>Ks flavona>Ks rutin in the range from 1.0×10-6molL-1 to 1.2×10-5molL-1 for flavones and of 1.0×10-6molL-1 to 1.0×10-5molL-1 for rutin. Dynamic light scattering, conductometric measurements and microenvironment polarity studies were employed to elucidate the QDs-flavonoids interaction in systems containing CTAB. The quenching can be attributed to the preferential solubility of hydrophobic flavonoid in the palisade layer of the CTAB aggregates adsorbed on the surface of the 3MPA CdTe QDs.

Spherical gold nanoparticles and gold nanorods for the determination of gentamicin.

Gentamicin is an antibiotic indicated to treat mastitis in dairy cattle and for the treatment of bacterial resistance in the context of hospital infections. The effect caused by gentamicin on the optical properties of gold nanoparticles aqueous dispersions were used to develop quantitative methods to determine this antibiotic. Two different aqueous dispersions, one containing spherical Au nanoparticles (AuNPs) and the other containing Au nanorods (AuNRs), had their conditions adjusted to enable a stable and sensitive response towards gentamicin. The use of AuNPs, with measurement at 681nm of the rising coupling plasmon band, enabled a limit of detection (LOD) of 0.4ngmL-1 (0.02ng absolute LOD), ten times lower than the one achieved by measuring the decreasing of the longitudinal surface plasmon resonance band (at 662nm). The linear analytical response of AuNPs measured at 681nm did not require rationing of signal values to correct for linearity. Stability of the analytical response resulted in intermediary precision below 2%. No significant interference was imposed by excipients traditionally present in injectable solutions for veterinary use. Percent recoveries obtained in such formulations were between 94.5 and 98.2% regardless the existence of any difference in the proportion of the compounds known as gentamicin (C1, C1a and C2) in standard and in the samples. The method requires no derivatization with toxic reagents as usually is required in other spectroscopic approaches.

Unraveling the binding mechanism of polyoxyethylene sorbitan esters with bovine serum albumin: a novel theoretical model based on molecular dynamic simulations.

To gain a better understanding of the interactions governing the binding mechanism of proteins with non-ionic surfactants, the association processes of Tween 20 and Tween 80 with the bovine serum albumin (BSA) protein were investigated using molecular dynamics (MD) simulations. Protein:surfactant molar ratios were chosen according to the critical micelle concentration (CMC) of each surfactant in the presence of BSA. It was found that both the hydrophilic and the hydrophobic groups of the BSA equally contribute to the surface area of interaction with the non-ionic surfactants. A novel theoretical model for the interactions between BSA and these surfactants at the atomic level is proposed, where both surfactants bind to non-specific domains of the BSA three-dimensional structure mainly through their polyoxyethylene groups, by hydrogen bonds and van der Waals interactions. This is well supported by the strong electrostatic and van der Waals interaction energies obtained in the calculations involving surfactant polyoxyethylene groups and different protein regions. The results obtained from the MD simulations suggest that the formation of surfactant clusters over the BSA structure, due to further cooperative self-assembly of Tween molecules, could increase the protein conformational stability. These results extend the current knowledge on molecular interactions between globular proteins and non-ionic surfactants, and contribute to the fine-tuning design of protein formulations using polysorbates as excipients for minimizing the undesirable effects of protein adsorption and aggregation.

Physico-chemical studies of molecular interactions between non-ionic surfactants and bovine serum albumin.

Surfactants, particularly non-ionic types, are often added to prevent and/or minimize protein aggregation during fermentation, purification, freeze-drying, shipping, and/or storage. In this work we have investigated the interactions between two non-ionic surfactants (Tween 20 and Tween 80) and bovine serum albumin (BSA), as model protein, using surface tension, fluorescence measurements and computational analysis. The results showed that, in both cases, the surface tension profile of the surfactants curve is modified upon addition of the protein, and the CMC values of Tween 20 and Tween 80 in the presence of protein are higher than the CMC values of the pure surfactants. The results indicate that although Tween 20 and Tween 80 do not greatly differ in their chemical structures, their interactions with BSA are of different nature, with distinct binding sites. Measurements at different protein concentrations showed that the interactions are also dependent on the protein aggregation state in solution. It was found from fluorescence studies that changes observed in both the intensity and wavelength of the tryptophan emission are probably caused by modifications of tryptophan environment due to surfactant binding, rather than by direct interaction. Based on a computational analysis of a BSA three-dimensional model, we hypothesize about the binding mechanism of non-ionic surfactant to globular protein, which allowed us to explain surface tension profiles and fluorescence results.

Effect of surfactant structure on the residual fluorescence of micelle-based fluorescent probes.

In the present paper we have investigated some photo-physical characteristics of different micellar-based fluorescent probes containing a fluorophore (pyrene) and a quencher unit (dodecyl-dioxo 2,3,2). The fluorescent response of the probe in the presence of Cu(II) ions was studied using different micellar substrates, and it was found that the pH at which the On-Off jump occurs is not influenced by the chemical structure of surfactant. In addition, the experimental residual fluorescence is not proportionally affected by microviscosity or by the size of the micellar aggregates. The signal of the native fluorescence of pyrene was observed even when the quencher's occupancy number was greater than one. Moreover, we observed discrepancies between experimental values and calculated residual fluorescence using Laplace data. These results were interpreted suggesting that the residual fluorescence has two main components, one that seems to be independent on micellar properties, while the other is directly related to location of molecules inside the surfactant aggregates that serve as substrate.

Mass spectroscopy investigation of the effect of gamma irradiation on the mean value of the number of ethoxy groups in the triton x-100 / Estudio del efecto de la radiación gamma en elvalor medio del número de grupos etoxiLados del surfactante Tritón X-100

El efecto de la radiación gamma proveniente de una fuente de 60Co en la estructura del surfactante no iónico Tritón X-100 fue investigado. Tres regiones principales pueden ser distinguidas en el comportamiento del valor medio del número de grupos etóxidos al aumentar la dosis. Sin embargo, el resultado global encontrado fue una pequeña variación en este valor medio al cambiar la dosis entre 0 y 70 KGy.

The effect of gamma radiation from a 60Co source on the structure of a nonionic surfactant, namely TRITON X-100, was investigated. Three main regions can be distinguished in the behavior of the mean value of ethoxy groups with an increase in the absorbed dose. However just a slightly decrease on this mean value was obtained when the dose range from 0 to 70 kGy.

Interactions and film formation in polyethylenimine-cetyltrimethylammonium bromide aqueous mixtures at low surfactant concentration.

The interactions involved in aqueous mixtures of polyethyleneimine (PEI) and cetyltrimethylammonium bromide (CTAB) were studied under dilute conditions. The phase diagram of this polyelectrolyte-surfactant system of similar charge was constructed by determining the CAC and CMC* values at different PEI concentrations, using surface-tension and conductivity measurements, respectively. Formation of thin films at the air-solution interface was detected at concentrations belonging to the interaction region of the phase diagram, using Brewster angle microscopy. These films were formed at low polymer and surfactant concentrations, 0.01% w/v PEI and 0.1 mmol dm CTAB. Results from SAXS determinations indicate that, under these conditions, mesostructure formation occurs exclusively at the surface. The effect of PEI on surfactant micellisation is determined by the polyelectrolyte nature of the polymer. The presence of the polymer in the aggregate significantly affects free micelle formation, even when hydrophobic interactions are mainly determined by the surfactant structure. The films obtained at low surfactant concentration are mesostructured, composed of five layers, each one 49.7 Å thick, as was determined using specular X-ray reflectometry. These results indicate that mesostructured film formation is achievable under more economical and environmentally friendly conditions, suggesting novel routes for surfactant templating in mixed polyelectrolyte systems of similar charge.

Micelles for the self-assembly of "off-on-off" fluorescent sensors for pH windows.

A micellar approach is proposed to build a series of systems featuring an "off-on-off" fluorescent window response with changes in pH. The solubilizing properties of micelles are used to self-assemble, in water, plain pyrene with lipophilized pyridine and tertiary amine moieties. Since these components are contained in the small volume of the same micelle, pyrene fluorescence is influenced by the basic moieties: protonated pyridines and free tertiary amines behave as quenchers. Accordingly, fluorescence transitions from the "off" to the "on" state, and viceversa, take place when the pH crosses the pK(a) values of the amine and pyridine fragments. To obtain an "off-on-off" fluorescent response in this investigation we use either a set of dibasic lipophilic molecules (containing covalently linked pyridine and tertiary amine groups) or combinations of separate, lipophilic pyridines and tertiary amines. The use of combinations of dibasic and monobasic lipophilic molecules also gives a window-shaped fluorescence response with changes in pH: it is the highest pyridine pK(a) and the lowest tertiary amine pK(a) that determine the window limits. The pK(a) values of all the examined lipophilic molecules were determined in micelles, and compared with the values found for the same molecules in solvent mixtures in which they are molecularly dispersed. The effect of micellization is to significantly lower the observed protonation constants of the lipophilized species. Moreover, the more lipophilic a molecule is, the lower the observed logK value is. Accordingly, changing the substituents on the basic moieties or modifying their structure, tuning the lipophilicity of the mono- or dibases, and choosing among a large set of possible combination of lipophilized mono- and dibases have allowed us to tune, almost at will, both the width and the position along the pH axis of the obtained fluorescent window.