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1.
Environ Pollut ; 347: 123778, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38499171

RESUMO

This study reports the synthesis and characterization of a supramolecular composite comprised of carbon dots (CDots) embedded within net-poly[(α-cyclodextrin)-ν-(citric acid)] (α-CD/CA/CDots) for the removal and detection of toluene and xylene from aqueous media. The remarkable stability of CDots within the composite enables the preservation of photoluminescence properties for prolonged storage and extended UV-light irradiation. As demonstrated, following the adsorption of both organic compounds, the composite detected them in the aqueous medium due to a fluorescence quenching mechanism. Spectroscopic analyses reveal that the accessible Stern-Volmer quenching constants for toluene and xylene are KSVa = 15.4 M-1 and KSVa = 10.3 M-1, respectively. As a result, the α-CD/CA/CDots composite were sensitive to the tested volatile organic compounds (LODtoluene = 3.7 mg/L and LODxylene = 4.9 mg/L). Optimal conditions for toluene and xylene adsorption were found, allowing to achieve noticeable adsorption capabilities (qe(toluene) = 68.9 and qe(xylene) = 48.2 mg/g) and removal efficiencies exceeding 70%. Different characterization techniques confirmed the successful synthesis of the composite and elucidated the interaction mechanisms between the adsorbent and the tested compounds. In summary, the multifunctionality demonstrated by the α-CD/CA/CDots composite ranks it as an efficient and promising adsorbent and detection probe for this class of water contaminants.


Assuntos
Pontos Quânticos , alfa-Ciclodextrinas , Tolueno , Xilenos/química , Carbono/química , Água , Corantes
2.
Nanoscale Adv ; 5(13): 3428-3438, 2023 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-37383075

RESUMO

The energy efficiency of buildings can be significantly improved through the use of renewable energy sources. Luminescent solar concentrators (LSCs) appear to be a solution for integrating photovoltaic (PV) devices into the structure of buildings (windows, for instance) to enable low-voltage devices to be powered. Here, we present transparent planar and cylindrical LSCs based on carbon dots in an aqueous solution and dispersed in organic-inorganic hybrid matrices, which present photoluminescent quantum yield values up to 82%, facilitating an effective solar photon conversion. These LSCs showed the potencial for being incorporated as building windows due to an average light transmittance of up to ∼91% and color rendering index of up to 97, with optical and power conversion efficiency values of 5.4 ± 0.1% and 0.18 ± 0.01%, respectively. In addition, the fabricated devices showed temperature sensing ability enabling the fabrication of an autonomous power mobile temperature sensor. Two independent thermometric parameters were established based on the emission and the electrical power generated by the LSC-PV system, which could both be accessed by a mobile phone, enabling mobile optical sensing through multiparametric thermal reading with relative sensitivity values up to 1.0% °C-1, making real-time mobile temperature sensing accessible to all users.

3.
Polymers (Basel) ; 14(15)2022 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-35956612

RESUMO

Water pollution due to global economic activity is one of the greatest environmental concerns, and many efforts are currently being made toward developing materials capable of selectively and efficiently removing pollutants and contaminants. A series of ß-ketoenamine covalent organic frameworks (COFs) have been synthesized, by reacting 1,3,5-triformylphloroglucinol (TFP) with different C2-functionalized and nonfunctionalized diamines, in order to evaluate the influence of wall functionalization and pore size on the adsorption capacity toward dye and heavy metal pollutants. The obtained COFs were characterized by different techniques. The adsorption of methylene blue (MB), which was used as a model for the adsorption of pharmaceuticals and dyes, was initially evaluated. Adsorption studies showed that -NO2 and -SO3H functional groups were favorable for MB adsorption, with TpBd(SO3H)2-COF [100%], prepared between TFP and 4,4'-diamine- [1,1'-biphenyl]-2,2'-disulfonic acid, achieving the highest adsorption capacity (166 ± 13 mg g-1). The adsorption of anionic pollutants was less effective and decreased, in general, with the increase in -SO3H and -NO2 group content. The effect of ionic interactions on the COF performance was further assessed by carrying out adsorption experiments involving metal ions. Isotherms showed that nonfunctionalized and functionalized COFs were better described by the Langmuir and Freundlich sorption models, respectively, confirming the influence of functionalization on surface heterogeneity. Sorption kinetics experiments were better adjusted according to a second-order rate equation, confirming the existence of surface chemical interactions in the adsorption process. These results confirm the influence of selective COF functionalization on adsorption processes and the role of functional groups on the adsorption selectivity, thus clearly demonstrating the potential of this new class of materials in the efficient and selective capture and removal of pollutants in aqueous solutions.

4.
Front Plant Sci ; 13: 890647, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35860538

RESUMO

Classically, vicariant phenomena have been essentially identified on the basis of biogeographical and ecological data. Here, we report unequivocal evidences that demonstrate that a physical-chemical characterization of the epicuticular waxes of the surface of plant leaves represents a very powerful strategy to get rich insight into vicariant events. We found vicariant similarity between Cercis siliquastrum L. (family Fabaceae, subfamily Cercidoideae) and Ceratonia siliqua L. (family Fabaceae, subfamily Caesalpinoideae). Both taxa converge in the Mediterranean basin (C. siliquastrum on the north and C. siliqua across the south), in similar habitats (sclerophyll communities of maquis) and climatic profiles. These species are the current representation of their subfamilies in the Mediterranean basin, where they overlap. Because of this biogeographic and ecological similarity, the environmental pattern of both taxa was found to be very significant. The physical-chemical analysis performed on the epicuticular waxes of C. siliquastrum and C. siliqua leaves provided relevant data that confirm the functional proximity between them. A striking resemblance was found in the epicuticular waxes of the abaxial surfaces of C. siliquastrum and C. siliqua leaves in terms of the dominant chemical compounds (1-triacontanol (C30) and 1-octacosanol (C28), respectively), morphology (intricate network of randomly organized nanometer-thick and micrometer-long plates), wettability (superhydrophobic character, with water contact angle values of 167.5 ± 0.5° and 162 ± 3°, respectively), and optical properties (in both species the light reflectance/absorptance of the abaxial surface is significantly higher/lower than that of the adaxial surface, but the overall trend in reflectance is qualitatively similar). These results enable us to include for the first time C. siliqua in the vicariant process exhibited by C. canadensis L., C. griffithii L., and C. siliquastrum.

5.
ACS Appl Bio Mater ; 5(6): 2556-2566, 2022 06 20.
Artigo em Inglês | MEDLINE | ID: mdl-35537179

RESUMO

Silk from Bombyx mori is one of the most exciting materials in nature. The apparently simple arrangement of its two major components─two parallel filaments of silk fibroin (SF) coated by a common sericin (SS) sheath─provides a combination of mechanical and surface properties that can protect the moth during its most vulnerable phase, the pupal stage. Here, we recapitulate the topology of native silk fibers but shape them into three-dimensional porous constructs using an unprecedented design strategy. We demonstrate, for the first time, the potential of these macroporous silk foams as dermal patches for wound protection and for the controlled delivery of Rifamycin (Rif), a model antibiotic. The method implies (i) removing SS from silk fibers; (ii) shaping SF solutions into macroporous foams via ice-templating; (iii) stabilizing the SF macroporous foam in a methanolic solution of Rif; and (iv) coating Rif-loaded SF foams with a SS sheath. The resulting SS@SF foams exhibit water wicking capacity and accommodate up to ∼20% deformation without detaching from a skin model. The antibacterial behavior of Rif-loaded SS@SF foams against Staphylococcus aureus on agar plates outperforms that of SF foams (>1 week and 4 days, respectively). The reassembly of natural materials as macroporous foams─illustrated here for the reconstruction of silk-based materials─can be extended to other multicomponent natural materials and may play an important role in applications where controlled release of molecules and fluid transport are pivotal.


Assuntos
Fibroínas , Sericinas , Animais , Antibacterianos/farmacologia , Biomimética , Gelo , Seda
6.
Molecules ; 26(8)2021 Apr 08.
Artigo em Inglês | MEDLINE | ID: mdl-33917730

RESUMO

Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na+)- or lithium (SCa-3-Li+)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na+ and SCa-3-Li+ clays' X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na+ clay presented the highest conductivity of 1.96 × 10-2 S/cm2, and Alg with 10 wt% of SCa-3-Li+ showed conductivity of 1.30 × 10-2 S/cm2, both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples' transmittance and, consequently, an increase of their reflectance.

7.
RSC Adv ; 11(40): 24613-24623, 2021 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-35481055

RESUMO

The development of sensors for pH monitoring is of extreme importance in the monitoring of concrete and reinforced concrete structures. Imidazole derivatives are promising probes for pH sensing due to the amphoteric nature of their heterocyclic ring, which can be protonated/deprotonated upon pH changes. In this work, a triarylimidazole was synthesised and used as a dopant in an organic-inorganic hybrid (OIH) sol-gel matrix to obtain a pH-sensitive membrane for further application in optical fibre sensors (OFS). The triarylimidazole probe shows fluorimetric response in pH between 9 and 13, which is the desired range for monitoring carbonation of concrete. This degradation process lowers the highly alkaline pH of concrete (12.5-13) to values below 9, which creates favourable conditions for corrosion of concrete reinforcement. The OIH membranes used were based on Jeffamine THF170 and 3-glycidoxypropytrimethoxysilane precursors, which had already been shown to be suitable and resistant in contact with cement-based materials. The OIHs were doped with three different contents of the triarylimidazole and the structural, dielectric, thermal and optical properties of the pure and doped OIH materials were evaluated. The structural analysis showed that the presence of the triarylimidazole did not change the structural properties of the OIH material. Electrochemical impedance spectroscopy showed that in the doped samples the conductivity increased with the imidazole concentration. The ε r obtained for the doped samples ranged approximately from 11 to 19 and for the pure matrices was 8. Thermal analysis showed that these materials are stable up to 350 °C and that the presence of the probe did not change that feature. The optical properties showed that the prepared OIH materials have promising properties to be used as pH sensitive fluorimetric probes.

8.
Small ; 16(28): e1907661, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32462808

RESUMO

Non-Newtonian nanofluids present outstanding features in terms of energy transfer and conductivity with high application in numerous areas. In this work, non-Newtonian nanofluids based on carbon dots (Cdots) functionalized with ionic liquids (ILs) are developed. The nanofluids are produced using a simple, single-step method where the raw materials for the Cdots synthesis are glucose and waste biomass (chitin from crab shells). The use of ILs as both reaction media and functionalization molecules allows for the development of a new class of nanofluids, where the ILs on the Cdots surface represent the base-fluid. Here, the well-known benign IL 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) and a novel home-made IL (1-tosylate-3-methyl-imidazolium triflate) [Tmi][Trif] are used. The nanofluids obtained from both substrates show, apart from high conductivity and viscosity, light absorption, and good wettability, an appealing thermal sensitivity behavior. This thermal sensitivity is preserved even when applied as thin films on glass slides and can be boosted using the surface plasmon resonance effect. The results reported demonstrate that the new Cdots/IL-based nanofluids constitute a versatile and cost-effective route for achieving high-performance thermosensitive non-Newtonian sustainable nanofluids with tremendous potential for the energy coatings sector and heat transfer film systems.


Assuntos
Líquidos Iônicos , Carbono , Condutividade Elétrica , Imidazóis , Viscosidade
9.
Biomacromolecules ; 20(11): 4107-4116, 2019 11 11.
Artigo em Inglês | MEDLINE | ID: mdl-31573794

RESUMO

Bombyx mori L. silk fibroin (SF) is widely used in different areas due to its ability to form durable and resilient materials with notable mechanical properties. However, in some of these applications the dissolution of SF is required, and this is not often straightforward due to its inability to be dissolved in the majority of common solvents. This work reports a novel approach to dissolve SF using 40 wt % aqueous tetrabutylammonium hydroxide, TBAOH(aq), at mild temperature. A thorough rheological study combined with small-angle X-ray scattering is presented to correlate the SF state in solution with changes in the rheological parameters. The scattering data suggest that the SF conformation in TBAOH(aq) is close to a random coil, possibly having some compact domains linked with flexible random chains. The radius of gyration (Rg) and the molecular weight (Mw) were estimated to be ca. 17.5 nm and 450 kDa, respectively, which are in good agreement with previous works. Nevertheless, a lower Mw value was deduced from rheometry (i.e., 321 kDa) demonstrating a low degree of depolymerization during dissolution in comparison to other harsh processes. The transition from a dilute to a semidilute regime coincides with the estimated critical concentration and is marked by the presence of a shear-thinning behavior in the flow curves, violation of the empirical Cox-Merz rule, and an upward increase in the activation energy. This work paves the way toward the development of advanced high-tech SF-based materials.


Assuntos
Fibroínas/química , Compostos de Amônio Quaternário/química , Soluções , Solventes/química , Animais , Bombyx/química , Conformação Molecular , Reologia , Solubilidade , Soluções/química , Temperatura , Água/química
10.
ACS Omega ; 3(9): 10811-10822, 2018 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-30320252

RESUMO

New mesoporous silk fibroin (SF)/silica hybrids were processed via a one-pot soft and energy-efficient sol-gel chemistry and self-assembly from a silica precursor, an acidic or basic catalyst, and the ionic liquid 1-butyl-3-methylimidazolium chloride, acting as both solvent and mesoporosity-inducer. The as-prepared materials were obtained as slightly transparent-opaque, amorphous monoliths, easily transformed into powders, and stable up to ca. 300 °C. Structural data suggest the formation of a hexagonal mesostructure with low range order and apparent surface areas, pore volumes, and pore radii of 205-263 m2 g-1, 0.16-0.19 cm3 g-1, and 1.2-1.6 nm, respectively. In all samples, the dominating conformation of the SF chains is the ß-sheet. Cytotoxicity/bioactivity resazurin assays and fluorescence microscopy demonstrate the high viability of MC3T3 pre-osteoblasts to indirect (≥99 ± 9%) and direct (78 ± 2 to 99 ± 13%) contact with the SF/silica materials. Considering their properties and further improvements, these systems are promising candidates to be explored in bone tissue engineering. They also offer excellent prospects as electrolytes for solid-state electrochemical devices, in particular for fuel cells.

11.
ACS Appl Mater Interfaces ; 10(6): 5385-5394, 2018 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-29369609

RESUMO

Battery separators based on silk fibroin (SF) have been prepared aiming at improving the environmental issues of lithium-ion batteries. SF materials with three different morphologies were produced: membrane films (SF-F), sponges prepared by lyophilization (SF-L), and electrospun membranes (SF-E). The latter materials presented a suitable porous three-dimensional microstructure and were soaked with a 1 M LiPF6 electrolyte. The ionic conductivities for SF-L and SF-E were 1.00 and 0.32 mS cm-1 at 20 °C, respectively. A correlation between the fraction of ß-sheet conformations and the ionic conductivity was observed. The electrochemical performance of the SF-based materials was evaluated by incorporating them in cathodic half-cells with C-LiFePO4. The discharge capacities of SF-L and SF-E were 126 and 108 mA h g-1, respectively, at the C/2-rate and 99 and 54 mA h g-1, respectively, at the 2C-rate. Furthermore, the capacity retention and capacity fade of the SF-L membrane after 50 cycles at the 2C-rate were 72 and 5%, respectively. These electrochemical results show that a high percentage of ß-sheet conformations were of prime importance to guarantee excellent cycling performance. This work demonstrates that SF-based membranes are appropriate separators for the production of environmentally friendlier lithium-ion batteries.


Assuntos
Fibroínas/química , Fontes de Energia Elétrica , Eletrodos , Íons , Lítio
12.
Front Chem ; 5: 131, 2017.
Artigo em Inglês | MEDLINE | ID: mdl-29379781

RESUMO

Amine-functionalized bridged silsesquioxanes (BSs) were synthesized from bis[(3-trimethoxysilyl)propyl] amine via a solvent-mediated route. BS-1 and BS-2 were obtained at neutral pH with sub- and stoichiometric amounts of water, respectively, and high tetrahydrofuran content. BS-3 was prepared with hyperstoichiometric water concentration, high tetrahydrofuran content, and hydrochloric acid. BS-4 was synthesized with hyperstoichiometric water concentration, high ethanol content, and sodium hydroxide. BS-1 and BS-2 were produced as transparent films, whereas BS-3 and BS-4 formed white powders. Face-to-face stacking of flat or folded lamellae yielded quasi-hydrophobic platelets with emission quantum yields of 0.05 ± 0.01 (BS-1 and BS-2) or superhydrophilic onion-like nanoparticles with exciting emission quantum yields of 0.38 ± 0.03 (BS-3) and 0.33 ± 0.04 (BS-4), respectively. The latter two values are the largest ever reported for amine-functionalized siloxane-based hybrids lacking aromatic groups. Fast Grotthus proton hopping between = [Formula: see text]/ = NH groups (BS-3) and = N-/ = NH groups (BS-4), promoted by H+ and OH- ions, respectively, and aided by short amine-amine contacts provided by the onion-like morphology, account for this unique optical behavior.

13.
Biomacromolecules ; 15(2): 478-91, 2014 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-24460059

RESUMO

This work aims to shed light on the mechanism of interaction between components of ternary DNA-PEI-Fe(III) complexes, using experimental and theoretical approaches. In the experimental part, the chelation between PEI-Fe(III) was inspected by potentiometry and electrical conductance measurements and the respective importance for the condensation of DNA analyzed. To this end, three different mixing protocols for the components were imposed using different PEIs, branched (bPEI1.2 and bPEI10) and linear (lPEI2.5 and lPEI25). A delay in DNA condensation was observed when PEI and Fe(III) were premixed and then added to DNA. The set of observations was complemented by determination of the amount of Fe(III) included in the polyplexes, which was found to be dependent on the order of mixture and on the type of PEI used, decreasing with intrinsic PEI condensation efficiency. Overall, a coherent picture in which Fe(III) compensates PEI, probably modulating the respective charge, emerges. Some points arisen from the experimental part were rationalized using Monte Carlo simulations. Different architectured polycation (PC) chains were modeled and an interaction between PC and multivalent ions, mimicking the chelation of Fe(III) by the PEI, was imposed. It was found that chelation enhances polyanion (PA) compaction, irrespective of the PC architecture and charge density. The amount of multivalent ions in each polyplex compensates the negative charge unbalanced by the PC. The charge density and the ability of chelation of each PC dictate the disposition of each condensing agent along the PA backbone, and their coexistence strengthens PA compaction. The deep understanding of these ternary mixtures is a step forward in the optimization of such systems for application in gene delivery.


Assuntos
DNA/química , Compostos Férricos/química , Polietilenoimina/química , Método de Monte Carlo
14.
J Colloid Interface Sci ; 414: 66-72, 2014 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-24231086

RESUMO

The interaction of sodium octanoate, decanoate or dodecanoate with lead(II) has been studied in aqueous solutions using potentiometry, electrical conductivity, turbidity and ICP-OES measurements. These show an alkyl chain length dependence on the behavior. At the lead(II) concentration used (1.0 mM), relatively strong interactions are observed with the decanoate and dodecanaote, leading to formation of the lead carboxylates (soaps) as insoluble complexes. All techniques show 1:2 (metal:carboxylate) stoichiometry corresponding to charge neutralization. With sodium octanoate and lead(II), a rather weaker interaction is seen, and complexation is only observed at metal:carboxylate ratios > 0.5. However, in contrast to our previous work on octanoate and calcium(II) in aqueous solutions [1], precipitation does occur at higher concentrations. This difference between the behavior of the metal ions is probably due to the more covalent nature of the bonds of the carboxylate with Pb(2+) than with Ca(2+). Association constants of the complexes have been determined from potentiometric measurements and are consistent with data on solubility products. A comparison is made of the effect of surfactant head group on the interactions with lead(II) using two surfactants with the same chain length: dodecanoate and dodecylsulfate. Differences in their interactions with this metal ion in aqueous solutions are interpreted in terms of greater covalency of the bond between the metal and the carboxylate than with the sulfate group.

15.
Phys Chem Chem Phys ; 14(20): 7517-27, 2012 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-22513819

RESUMO

The interaction of sodium octanoate, decanoate or dodecanoate with calcium(ii) in aqueous solutions has been studied using turbidity, conductivity and potentiometric measurements. These show a marked alkyl chain length dependence on the behaviour. At the calcium concentration used (1.0 mM), there is little interaction with the octanoate, the decanoate shows initially formation of a 1:1 complex, followed by precipitation, while the dodecanoate precipitates at low surfactant concentrations. The solid calcium carboxylates were prepared, and show lamellar, bilayer structures with planes of calcium(II) ions coordinated to carboxylate groups through bidentate chelate linkages. Thermogravimetry and elemental analyses indicate the presence of coordinated water with the calcium decanoate but not with longer chain carboxylates. The results of both the solution and solid state studies suggest that precipitation of long-chain carboxylates depends on a balance between hydration effects and hydrophobic (largely van der Waals') interactions. Electrostatic effects make little energetic contribution but play the important structural role of ordering the carboxylate anions before precipitation. Differences are observed in the interactions between calcium(II) and long chain alkylcarboxylates and alkylsulfates, and are interpreted in terms of stronger binding to the metal of the carboxylate group. A general mechanism is proposed for calcium carboxylate precipitation from aqueous solution based on this and previous studies.

16.
Langmuir ; 28(1): 168-77, 2012 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-22107111

RESUMO

The interaction between sodium octanoate, decanoate, and dodecanoate and aluminum(III) and chromium(III) has been studied in water at natural pH values, starting well below the surfactant critical micelle concentration, using electrical conductivity, turbidity, and potentiometric measurements. With decanoate or dodecanoate, maximum interaction occurs at 3:1 stoichiometry, corresponding to charge neutralization. Although the solutions become turbid with both metal ions, indicating phase separation, differences are observed and attributed to the fact that aluminum(III) is relatively labile to substitution and rapidly replaces its water ligands, whereas chromium(III) is substitution inert. This shows up in well-defined floc formation with Al(3+), whereas Cr(3+) suspensions do not precipitate, probably because that replacement of coordinated water by carboxylate ligands is impeded. This can be overcome by increasing temperature, and differences in the thermal behavior with Al(3+) and Cr(3+) are suggested to be due to increased involvement of substitution reactions in the latter case. The effect of octanoate on the trivalent metal ions is less clear, and with Cr(3+) interaction only occurs when the carboxylate is in excess. Hydrophobic interactions between alkyl chains play a major role in driving phase separation. At high surfactant concentrations, the solid phases do not dissolve, in contrast to what is observed with the corresponding alkylsulfates. This has implications for use of these systems in metal separation through froth flotation. The concentration of metal ions in supernatant solution has been determined for sodium dodecanoate and sodium dodecylsulfate with Al(3+) and Cr(3+) over the whole surfactant concentration range by inductively coupled plasma-mass spectrometry (ICP-MS). From this, association constants have been determined and are found to be larger for the carboxylate than the alkylsulfate, in agreement with the greater Lewis basicity of the -CO(2)(-) group.


Assuntos
Alumínio/química , Ácidos Carboxílicos/química , Cromo/química , Metais/química , Água/química , Espectrometria de Massas , Soluções , Tensoativos/química , Temperatura
17.
J Colloid Interface Sci ; 354(2): 670-6, 2011 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-21084096

RESUMO

The interaction between aqueous solutions of trivalent lanthanide ions (M(3+): La(III) and Gd(III) and Tb (III)) at fixed (1mM) concentrations and various concentrations of sodium dodecyl sulfate (SDS), ranging from pre- to post-micellar, has been investigated by ICP-AES (La(III) and Gd(III)), luminescence spectra (Gd(III)) and lifetimes (Tb(III)) and (139)La NMR spectroscopy. It has been found that at concentration ratios, r=[SDS]/[M(3+)], around the charge neutralization value (ca. 3), dodecyl sulfate (DS(-)) anion interacts with the metal ions to form insoluble aggregates. The metal ion-DS(-) complexes remain flocculated for r values below 5-6 (Gd(III) and La(III), respectively), while at higher r values, re-dissolution takes place. The flocculated aggregates have been characterized by X-ray powder diffraction, and show a lamellar structure. Job plot method indicates that a complex with a 1:3 (M(3+):DS(-)) stoichiometry is formed. From ICP-AES analysis, a model based on a three-step mechanism has been developed and association constants calculated. For all systems the interaction between DS(-) and metal ions follows an associative process with K values ranging between K(1)=10 and K(3)=10(4). These data are discussed on the basis of the physical-chemical characteristics of the metal ions. Re-dissolution with increasing surfactant concentration is attributed to formation of mixed lanthanide/sodium dodecyl sulfate aggregates, with the relative lanthanide fraction in these species decreasing with increasing SDS concentration.


Assuntos
Elementos da Série dos Lantanídeos/química , Dodecilsulfato de Sódio/química , Tensoativos/química , Floculação , Íons/química , Luminescência , Espectroscopia de Ressonância Magnética , Difração de Pó , Solubilidade , Espectrofotometria Atômica , Água/química , Difração de Raios X
18.
J Colloid Interface Sci ; 323(1): 141-5, 2008 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-18440017

RESUMO

Aggregation properties of sodium dodecyl sulfate (SDS) in the presence of cerium(III) chloride, at various temperatures (298.15-323.15 K) have been measured by the electrical conductance technique. The experimental data on aqueous solutions as a function of SDS concentration show the presence of two inflexion points indicating the presence of two distinct interaction mechanisms: the first, occurring at SDS concentrations below the critical micelle concentration of the pure surfactant, which can be explained by the formation of aggregates between dodecyl sulfate (DS-) and Ce(III), while the second one, at SDS concentrations around the critical micelle concentration (cmc) of the pure surfactant which is due to the SDS micellization. The aggregation between DS- and Ce(III) was confirmed by static light scattering. The binding ratio of DS-/Ce(III) changes from 6 to 4, shows a slight dependence on the Ce(III) concentration and is independent of the temperature. The thermodynamic micellization parameters, Gibbs energy, enthalpy and entropy of micellization were calculated on the basis of the experimental data for the aggregation concentration, and the degree of counterion dissociation of the micelles. The SDS micellization is energetically favoured by increasing either the concentration of CeCl3 or the temperature. Such behaviour is clearly dominated by a decrease of the micellization (exothermic) enthalpy. The entropy of micellization approaches zero as the cerium(III) chloride concentration and temperature increase.

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