A simple way for targeted delivery of an antibiotic: In vitro evaluation of a nanoclay-based composite.

The sodium-modified form of fluorohectorite nanoclay (NaFh) is introduced as a potential drug carrier, demonstrating its ability for the controlled release of the broad-spectrum antibiotic Ciprofloxacin through in vitro tests. The new clay-drug composite is designed to target the local infections in the large intestine, where it delivers most of the incorporated drug thanks to its pH-sensitive behavior. The composite has been conceived to avoid the use of coating technology and to decrease the side-effects commonly associated to the burst-release of the ciprofloxacin at the stomach level. NaFh was obtained from lithium-fluorohectorite by ion exchange, and its lack of toxicity was demonstrated by in vivo studies. Ciprofloxacin hydrochloride (Cipro) was encapsulated into the clay at different values of the pH, drug initial concentration, temperature and time. Systematic studies by X-ray diffraction (XRD), infrared and visible spectrophotometry (FT-IR and UV-vis), and thermal analysis (TGA) indicated that the NaFh host exhibits a high encapsulation efficiency for Cipro, which reaches a 90% of the initial Cipro in solution at 65 oC, with initial concentration of drug in solution of 1.36 x 10-2 mol L-1 at acid pH. XRD revealed that a true intercalation of Cipro takes place between clay layers. TG showed an increased thermal stability of the drug when intercalated into the clay, as compared to the "free" Cipro. IR suggested a strong clay-Cipro interaction via ketone group, as well as the establishment of hydrogen bonds between the two materials. In vitro drug release tests revealed that NaFh is a potentially efficient carrier to deliver Cipro in the large intestine, where the release process is mediated by more than just one mechanism.

Removal of an Acid Dye from Water Using Calcined and Uncalcined ZnAl-r Anionic Clay.

The present report describes the removal of indigo carmine dye from water via adsorption on ZnAl-r hydrotalcite. Two grades of clay based on Zn/Al molar ratios of 3 and 4, uncalcined and calcined, were used. The adsorbents characterization using X-ray diffraction (XRD), Fourier transform infrared (FTIR), differential thermal and thermogravimetric analysis (DTA and TGA, respectively) revealed a layered structure for the hydrotalcite clays, whereas their calcination favored the formation of ZnO and ZnAl2O4 mixed metal oxides. The calcined materials immobilized much larger amounts of indigo carmine dye than the uncalcined layered double hydroxides (LDHs) specimens. The maximum adsorption capacities obey the order: CZnAl-4 (520.8 mg/g) > CZnAl-3 (358.4 mg/g) > ZnAl-3 (67.25 mg/g) > ZnAl-4 (21.65 mg/g). The adsorption isotherms are best described by Langmuir model. The sorption process is spontaneous in nature and its kinetics data are best described by a pseudo-second-order model. Adsorption tests on re-used calcined clays demonstrate its reusability after three thermal cycles.

Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses.

Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.

Benzalkonium chloride and sulfamethoxazole adsorption onto natural clinoptilolite: effect of time, ionic strength, pH and temperature.

The influence of different physical factors on the adsorption of the cationic surfactant benzalkonium chloride (BC) and the model drug sulfamethoxazole by a purified natural clinoptilolite (NZ) has been studied in order to employ zeolite-surfactant-drug composites as drug deliverer. It has been demonstrated that the adsorption of BC and sulfamethoxazole onto NZ depends of the time, the temperature, the ionic strength and the pH of the aqueous medium. The optimal conditions for the preparation of the zeolite-surfactant and zeolite-surfactant-drug composite materials are established. The results of the composite characterization support the presence of BC and sulfamethoxazole, as well as the structural stability of NZ during the treatments performed. The release experiments in acid medium demonstrate that the adsorption of sulfamethoxazole is reversible. It is also confirmed that the drug release profile corresponds to a diffusion or zero-order mechanism as a function of the compression pressure.

Acid natural clinoptilolite: structural properties against adsorption/separation of n-paraffins.

The employment of an acid natural clinoptilolite (AZH-1) in the adsorption and separation of n-paraffins has been evaluated. Natural clinoptilolite, NZ, was the raw material used to prepare the sodium-exchanged clinoptilolite (AZ) starting from which the AZH-1 sample was obtained by acid treatment. The structural stability of the samples after the applied treatments was demonstrated. The nitrogen adsorption experiments indicated that the acid sample has a homogeneous porous distribution and a considerable increase in the micropore volume with respect to NZ and AZ. The employment of the inverse gas chromatography at infinite dilution (IGCID) allowed studying the adsorption and separation of n-paraffin mixtures on AZH-1. It was also confirmed that the diffusion on AZH-1 took place in an unblocked structure through the A channel of ten members with minimal interactions. The IGCID results demonstrated the capacities of the acid Cuban natural zeolite in the adsorption and separation of n-paraffin mixtures.

Competitive interactions between components in surfactant-cosurfactant-additive systems.

Complex interactions of phenol (PhOH), heptanol (HeOH) and heptanoic acid (HeOIC) with micellar aggregates of hexadecyltrimethylammonium bromide (HTAB) in aqueous solutions at surfactant concentrations close to the CMC, HeOH or HeOIC content of 0.5 mmol kg(-1), and phenol molality of 1, 5, or 10 mmol kg(-1) have been investigated at 303 K by means of (1)H NMR spectroscopy, titration calorimetry and solution conductimetry. The analysis of the composition-dependence of the (1)H chemical shifts assigned to selected protons in the surfactant and additive units revealed the location of PhOH both within the hydrophobic micelle core and in the vicinity of the quaternary ammonium groups, the phenol penetration being somewhat deeper in the presence of HeOIC. The phenomenon was globally more exothermic with increasing extent of PhOH solubilization and it was accompanied by a gradual decrease in the positive entropy of micellization. The solubilization was competitive for high phenol contents in the aqueous phase, with some HeOH and HeOIC units being displaced progressively towards the aqueous phase.

Adsolubilization of drugs onto natural clinoptilolite modified by adsorption of cationic surfactants.

The combined adsorption onto purified natural clinoptilolite (NZ) of the cationic surfactant benzalkonium chloride (BC) and the model drugs metronidazole and sulfamethoxazole has been studied in order to design systems for the storage and release of drugs. The equilibrium adsorption of benzyldimethylalkylammonium chloride surfactants with hydrocarbon chain lengths corresponding to 12, 14 and 16 carbon atoms (BC12, BC14 and BC16) onto NZ from aqueous solutions was compared to that of BC. The effect of exchangeable cations on the NZ structure and that of acid-base pre-treatment of NZ on the adsorption capacity of BC was evaluated. It was shown that the nature of the exchangeable cations had little influence on the adsorption of BC onto NZ, and that acid-base treatments of NZ led to a decrease in the amount of surfactant adsorbed. The results indicated that the adsorption of the less polar drug, sulfamethoxazole, was enhanced by the presence of BC12 at the solid-liquid interface, whereas the uptake of metronidazole was independent of the surfactant adsorption.

Efficiency of succinylated-olive stone biosorbent on the removal of cadmium ions from aqueous solutions.

Chemical functionalization of olive stone wastes with succinate linkers can potentially improve the performance of wastewater treatment technologies via enhanced adsorption and high affinity of the covalently attached succinate groups for heavy metals. In this study, a novel reusable adsorbent material based on agricultural waste has been synthesized by esterifying the lignocellulosic matrix of olive stones with succinic anhydride in toluene under basic conditions. Characterization of the as-prepared material by FTIR and solid-state MAS (13)C NMR spectroscopies and TGA confirmed that the heterogeneous esterification has proceeded very efficiently to yield the succinylated-olive stone (S-OS). Subsequent alkaline treatment of S-OS with saturated NaHCO(3) aqueous solution led to the resulting sodic material (NaS-OS), which was subjected to batch experiments in order to evaluate its cadmium-removing efficiency from aqueous solutions at realistic concentrations of cadmium found in industrial effluents. The results obtained from the sorption characteristics have revealed that NaS-OS material is highly effective in removing cadmium from aqueous solutions, with a maximum uptake capacity of 200 mg g(-1) (1.78 mmol g(-1)). The Langmuir isotherm model was found to fit adequately the equilibrium isotherm data. Cadmium adsorption occurs rapidly and the adsorption mechanism is a chemical sorption via ionic exchange between the adsorbate and adsorbent. Thermodynamic parameters were also evaluated from the effect of temperature studies. Regenerability of NaS-OS material was ascertained by quantitative desorption of cadmium with 1M aqueous NaCl and the reusability of the matrix after five repeated cycles led to nearly no attenuation in its performance (less than 2% in the sorption capacity), indicating that repeated use of NaS-OS is quite feasible. Compared to other low-cost adsorbents utilized for the removal of Cd(II) from water/wastewater, NaS-OS shows higher sorption capacity. These results have important implications for the design of low-cost adsorbents based on agricultural wastes.

Succinate-bonded cellulose: a regenerable and powerful sorbent for cadmium-removal from spiked high-hardness groundwater.

The primary objective of this work was to evaluate a chemically modified cellulose for the sorption efficiency and selectivity to remove cadmium from spiked high-hardness groundwater. Heterogeneous esterification of cellulose with succinic anhydride in toluene under basic conditions has proceeded very efficiently to yield the succinylated cellulose (SC) with fairly high DS value, as confirmed by FTIR and solid-state MAS (13)C NMR spectroscopies. Deprotonation of the free carboxylic acid group was achieved by alkaline treatment of SC with saturated NaHCO(3) aqueous solution. Batch experiments were carried out on the resulting sodic material (NaSC) to examine its cadmium-removing capability in both distilled water (DW) and spiked groundwater (GW). The results obtained from the sorption characteristics (kinetics, isotherms and pH effect) have revealed that NaSC material is particularly effective in removing cadmium from both DW and GW solutions, with a maximum uptake of 185.2 and 178.6 mg g(-1), respectively. These comparable sorption capacities strongly suggest that NaSC sorbent is highly selective to heavy metal over alkaline earth cations (Ca(2+) and Mg(2+)) and therefore less susceptible to interference from background ions, naturally present in groundwater. On the other hand, cadmium sorption is shown to decrease with a decrease in pH which is indubitably inherent to the competing proton during the ion-exchange process. Furthermore, the material has proven to be efficiently regenerable by using a NaCl brine solution. Thus, the use of the sorbent sequentially to the first regeneration led to nearly no attenuation in the material's capacity for cadmium-removal. Finally, the sorption effectiveness of NaSC is compared to those of other low-cost sorbents so far reported in the literature.

Competitive solubilization of phenol by cationic surfactant micelles in the range of low additive and surfactant concentrations.

Competitive interactions of phenol (PhOH) with micellar aggregates of hexadecyltrimethylammonium bromide (HTAB) against 1-butanol (BuOH) in aqueous solutions at surfactant concentrations close to the critical micelle concentration (CMC), BuOH concentration of 0.5 mmol kg(-1), and phenol contents of 1, 5, or 10 mmol kg(-1) have been investigated at 303 K by means of (1)H NMR spectroscopy, titration calorimetry, and solution conductimetry. The solubilization loci for phenol were deduced from the composition-dependence of the (1)H chemical shifts assigned to various protons in the surfactant and additive units. Since in pure HTAB solutions phenol is already in competition with Br(-), addition of 1 mmol kg(-1) NaBr to the system weakens the phenol competitiveness. The presence of butanol in the HTAB micelles causes phenol to penetrate deeper toward the hydrophobic micelle core. For higher phenol contents, the butanol molecules are constrained to remain in the bulk solution and are progressively replaced within the HTAB micelles by the aromatic units. The competitive character of phenol solubilization against butanol is well supported by changes in the thermodynamic parameters of HTAB micellization in the presence of both of the additives.

Contribution of 1H NMR to the investigation of the adsorption of cationic Gemini surfactants with oligooxyethylene spacer group onto silica.

The present study aims to investigate the behavior of a series of cationic Gemini surfactants with a hydrophilic spacer at liquid-gas and solid-liquid interfaces, with particular emphasis on the effect of spacer length. Gemini surfactants containing two quaternary ammonium groups bound by an ethylene oxide spacer chain, referred to as 12-EO(x)-12 with x = 1,3,7 and 12 were synthesized. Surface tension measurements were used to show that the hydrophilic spacer with oxyethylene moieties was not fully extended at the air-water interface. With increasing the spacer group size, it became sufficiently flexible to adopt a particular conformation with a loop at the water side of the interface. A combined study by adsorption isotherm measurements and (1)H NMR spectroscopy allowed a detailed description of the adsorption mechanism of these investigated 12-EO(x)-12 surfactants, with NMR providing more precise information on the conformation of hydrophilic spacer at the solid-liquid interface. Binding to the silica surface involved one cationic headgroup for the surfactants with a short spacer and the two headgroups for the ones with a long spacer. The number of charged surface sites was estimated by considering the dimeric surfactant as a "molecular ruler." The small density of adsorption sites gave rise to the formation of pinned surface micelles.

Chemically modified olive stone: a low-cost sorbent for heavy metals and basic dyes removal from aqueous solutions.

In the present work, we have investigated the sorption efficiency of treated olive stones (TOS) towards cadmium and safranine removal from their respective aqueous solutions. TOS material was prepared by treatment of olive stones with concentrated sulfuric acid at room temperature followed up by a subsequent neutralization with 0.1 M NaOH aqueous solution. The resulting material has been thoroughly characterized by SEM, energy-dispersive X-ray (EDX), MAS (13)C NMR, FTIR and physicochemical parameters were calculated. The sorption study of TOS at the solid-liquid interface was investigated using kinetics, sorption isotherms, pH effect and thermodynamic parameters. The preliminary results indicate that TOS exhibit a better efficiency in terms of sorption capacities toward the two pollutants (128.2 and 526.3 mg/g for cadmium and safranine, respectively) than those reported so far in the literature. Moreover, the sorption process is ascertained to occur fast enough so that the equilibrium is reached in less than 15 min of contact time. The results found in the course of this study suggest that ion exchange mechanism is the most appropriate mechanism involved in cadmium and safranine removal. Finally, the sorption efficiency of TOS is compared to those of other low-cost sorbents materials yet described in the literature.

Sorption study of an acid dye from an aqueous solution on modified Mg-Al layered double hydroxides.

In this paper, experimental methods and results are reported on the removal of the dye Green Bezanyl-F2B (an acid dye) from MgAlCO(3) (HT) and from intercalated anionic surfactant, "sodium dodecylsulfate (SDS)", into the Mg-Al layered double hydroxides by the calcination-rehydration reaction using Mg-Al oxide precursors calcined at 773 K. Dodecylsulfate hydrotalcite was prepared by the calcination-rehydration method. The surfactant intercalation in the interlayer space of hydrotalcite was investigated by XRD and FT-IR spectroscopy where the resulting materials were found to be similar to those reported in the literature and were used to remove an acid dye from an aqueous solution. Equilibrium time and rate-determining step of the dye Green Bezanyl-F2B sorption were determined. Two simplified kinetic models were tested to investigate the sorption. The adsorption capacity data were also fitted to Langmuir and Freundlich equation as well. The sorption data fitted to the Langmuir model gave good values of the determination coefficient.

Interactions of phenol with cationic micelles of hexadecyltrimethylammonium bromide studied by titration calorimetry, conductimetry, and 1H NMR in the range of low additive and surfactant concentrations.

Interactions of phenol (PhOH) with micellar aggregates of hexadecyltrimethylammonium bromide (HTAB) in aqueous solutions at surfactant concentrations close to the CMC and phenol contents of 1, 5, or 10 mmol kg(-1) have been investigated at 303 K by means of titration calorimetry, solution conductimetry, and (1)H NMR spectroscopy. Estimates of the main thermodynamic parameters related to HTAB micellization were made for PhOH/HTAB/H(2)O systems based on the specific conductivity measurements and calorimetric determination of the cumulative enthalpy of dilution as functions of the surfactant concentration at a fixed additive content. The combined analysis of the results obtained in H(2)O solutions pointed to the preferential location of PhOH in the outer micelle parts by an enthalpy-driven mechanism. Additional PhOH molecules were located increasingly deeper within the micelle core. The (1)H NMR study of PhOH solubilization by 1.5 mmol kg(-1) HTAB solutions in D(2)O indicated that the two categories of the solubilization site became saturated with the solubilizate already at the lowest additive content. Dissimilar amounts of the solubilized material in H(2)O and D(2)O solutions were ascribed to the difference in the initial micelle structures formed in the two solvents, as inferred from calorimetry and (1)H NMR studies of the HTAB micellization in D(2)O and H(2)O.

31P chemical shift of adsorbed trialkylphosphine oxides for acidity characterization of solid acids catalysts.

A comprehensive study has been made to predict the adsorption structures and (31)P NMR chemical shifts of various trialkylphosphine oxides (R3PO) probe molecules, viz., trimethylphosphine oxide (TMPO), triethylphosphine oxide (TEPO), tributylphosphine oxide (TBPO), and trioctylphosphine oxide (TOPO), by density functional theory (DFT) calculations based on 8T zeolite cluster models with varied Si-H bond lengths. A linear correlation between the (31)P chemical shifts and proton affinity (PA) was observed for each of the homologous R3PO probe molecules examined. It is found that the differences in (31)P chemical shifts of the R3POH(+) adsorption complexes, when referring to the corresponding chemical shifts in their crystalline phase, may be used not only in identifying Brønsted acid sites with varied acid strengths but also in correlating the (31)P NMR data obtained from various R3PO probes. Such a chemical shift difference therefore can serve as a quantitative measure during acidity characterization of solid acid catalysts when utilizing (31)P NMR of various adsorbed R3PO, as proposed in our earlier report (Zhao; et al. J. Phys. Chem. B 2002, 106, 4462) and also illustrated herein by using a mesoporous H-MCM-41 aluminosilicate (Si/Al = 25) test adsorbent. It is indicative that, with the exception of (TMPO), variations in the alkyl chain length of the R3PO (R = C(n)H(2n+1); n > or = 2) probe molecules have only negligible effect on the (31)P chemical shifts (within experimental error of ca. 1-2 ppm) either in their crystalline bulk or in their corresponding R3POH(+) adsorption complexes. Consequently, an average offset of 8 +/- 2 ppm was observed for (31)P chemical shifts of adsorbed R3PO with n > or = 2 relative to TMPO (n = 1). Moreover, by taking the value of 86 ppm predicted for TMPO adsorbed on 8T cluster models as a threshold for superacidity (Zheng; et al. J. Phys. Chem. B 2008, 112, 4496), a similar threshold (31)P chemical shift of ca. 92-94 ppm was deduced for TEPO, TBPO, and TOPO.

Basic dye removal from aqueous solutions by dodecylsulfate- and dodecyl benzene sulfonate-intercalated hydrotalcite.

Dodecylsulfate- and dodecyl benzene sulfonate-hydrotalcites were prepared by calcination-rehydratation method. The surfactants intercalation in the interlayer space of hydrotalcite were checked by PXRD and FTIR spectroscopy where the resulting materials were found to be similar to those reported in the literature and were used to remove a basic dye (safranine) from aqueous solutions. The sorption kinetics data fitted the pseudo second order model. The isotherms were established and the parameters calculated. The sorption data fitted the Langmuir model with good values of the determination coefficient. The thermodynamic parameters calculated from Van't Hoff plots gave a low value of Delta G degrees (<-20 kJ mol(-1)) indicating a spontaneous physisorption process. Two regeneration cycles were processed by acetone extraction leading to the same removal capacity of the obtained materials as the original surfactant-intercalated hydrotalcites. The UV-vis spectra of the recovered extracts were similar to the spectrum of safranine, which means that the dye was recovered without any modification.