Surface modification of biomaterials based on cocoa shell with improved nitrate and Cr(vi) removal.

The present work addresses the development of simple, low-cost and eco-friendly cocoa-shell-based materials for efficient removal of heavy metal hexavalent chromium (Cr(vi)), and toxic nitrate (NO3 -) from aqueous solution. A conventional treatment process was used to purify cocoa shell (CS) into an adsorbent, followed by chemical grafting of dendrimers to promote its surface properties for nitrate and Cr(vi) removal. The morphology, surface charge, structure and stability of the new adsorbent were investigated by scanning electron microscopy, Fourier transform infrared and UV-visible spectroscopies, zeta potential, X-ray photoelectron spectrometry, and differential scanning calorimetry. The successful chemical grafting of the dendrimer (polyethyleneimine, PEI) onto purified CS was confirmed. CS-T-PEI-P proved to be a very efficient candidate for the removal of nitrate and chromium(vi). Removal of the two pollutants at different initial concentrations and pH values was studied and discussed. Sorption of chromium and nitrate was found to obey 2nd-order kinetics and a Freundlich-type isotherm, affording an uptake adsorption of 16.92 mg g-1 for NO3 - and 24.78 mg g-1 for Cr(vi). These results open promising prospects for its potential applications as a low cost catalyst in wastewater treatment.

Silver nanoparticle embedded copper oxide as an efficient core-shell for the catalytic reduction of 4-nitrophenol and antibacterial activity improvement.

A facile and eco-friendly method was developed to prepare a microporous CuO@Ag0 core-shell with high catalytic and antibacterial activities. Scanning and transmission electron microscopy revealed a preponderance of nearly spherical 50 nm particles with slight structure compaction. Comparison of the hysteresis loops confirmed the structure compaction after AgNP incorporation, and a significant decrease of the specific surface area from 55.31 m2 g-1 for CuO to 8.03 m2 g-1 for CuO@Ag0 was noticed. A kinetic study of 4-nitrophenol (4-NP) reduction into 4-aminophenol (4-AP) with sodium borohydride revealed a first order reaction that produces total conversion in less than 18 minutes. CuO@Ag0 also exhibited appreciable antibacterial activity against Staphylococcus aureus. The antibacterial effects were found to strongly depend on the size, contact surface, morphology and chemical composition of the catalyst particles. The addition of Ag0-NPs produced more reactive oxygen species in the bacteria medium. These results open promising prospects for its potential applications as a low cost catalyst in wastewater treatment and antibacterial agent in cosmetics.

A new example of reversal of the order of migration of enantiomers, as a function of cyclodextrin concentration and pH, by cyclodextrin-modified capillary zone electrophoresis: enantioseparation of 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol.

Enantioseparation of 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol (DBBD) by cyclodextrin-modified capillary zone electrophoresis (CD-CZE) was studied using the three native alpha, beta, and gamma cyclodextrins, the three hydroxypropylated cyclodextrins (2-hydroxypropyl-alpha, beta, and gamma), heptakis-2,6-di-O-methyl-beta-CD (DM-beta-CD), and heptakis-2,3,6-tri-O-methyl-beta-cyclodextrin (TM-beta-CD). First, the acidity constants of DBBD were determined using capillary electrophoresis, before performing enantioseparation. The influence of the concentrations of the studied cyclodextrins on the enantioseparation was explored and the experimental optimal concentrations were determined and compared to the theoretical optimal concentrations. Moreover, the apparent complexation constants between each studied cyclodextrin and the two DBBD enantiomers were evaluated using a non-linear curve fitting method and three linear plotting methods (x-reciprocal, y-reciprocal and double reciprocal). For TM-beta-CD, the order of migration of the enantiomers of DBBD reversed as a function of TM-beta-CD concentration. The influence of the nature of methylated cyclodextrin derivatives (methyl-beta-CD (M-beta-CD) and DM-beta-CD) was then studied. Inversion of the order of migration of the enantiomers of DBBD was observed for DM-beta-CD, whereas the S enantiomer of DBBD always migrated first for M-beta-CD.

Enantioseparation of binaphthol and its monoderivatives by cyclodextrin-modified capillary zone electrophoresis: a mathematical approach.

A simple model for the separation of atropisomers of binaphthol and its monoderivatives by means of cyclodextrin-modified capillary zone electrophoresis (CD-CZE) was used to describe the migration behavior of poly charged enantiomers in a chiral separation system. This mathematical approach allowed for the determination of the optimal cyclodextrin concentrations for the enantioseparation of binaphthols by taking into account the influence of the formed complex mobilities. Moreover, using this theoretical approach, the reversal of the enantiomers' migration order as a function of cyclodextrin concentration was predicated. The apparent complexation constants between the cyclodextrins and the binaphthol and its monoderivatives could be calculated using a non-linear curve fitting method and three linear plotting methods (x-reciprocal, y-reciprocal and double reciprocal). Good agreements between the theoretical and experimental cyclodextrin concentrations were obtained.

New ionic liquid for inorganic cations analysis by capillary electrophoresis: 2-hydroxy-N,N,N-trimethyl-1-phenylethanaminium bis(trifluoromethylsulfonyl)imide (phenylcholine NTf2).

The potentialities of new ionic liquids (ILs) based on choline were evaluated as an electrophoretic medium in capillary electrophoresis for the analysis of alkaline and alkaline earth cations (Li(+), K(+), Na(+), Cs(+), Mg(2+), Ba(2+), Ca(2+), and Sr(2+)) with indirect UV detection. Two types of capillaries were tested: an untreated fused silica and fused silica coated with a film of polyvinylalcohol. The coated capillary proved to be the best adapted for the metal ions studied. Moreover, it appeared that the nature of the ionic liquid anion influenced the baseline stability, and the bis(trifluoromethylsulfonyl) imide (NTf(2) (-)) anion seemed to be the most efficient. These preliminary studies led us to synthesize a new ionic liquid, 2-hydroxy-N,N,N-trimethyl-1-phenylethanaminium NTf(2) (phenylcholine NTf(2)). This liquid was able to act as the running electrolyte and probe, generating the background signal in indirect UV light and consequently simplifying the electrophoretic medium. Excellent baseline stability, good reproducibility, as well as good sensitivity of detection were obtained with this new ionic liquid. Thus, 510,000 plates/meter for Li(+) with 40 mM IL were successfully obtained. The optimal concentration of IL was 20 mM with a detection limit ranging from 28 microg L(-1) for Li(+) to 1,000 microg L(-1) for Cs(+). This method (phenylcholine NTf(2) with polyvinylalcohol capillary) was applied to analyze different commercial source and mineral waters. Finally, the potentiality of this ionic liquid in nonaqueous capillary electrophoresis was explored. The use of phenylcholine NTf(2) with a fused silica capillary, in pure methanol medium and in the presence of acetic acid, made it possible to obtain separation selectivity different from that obtained in aqueous medium.

Enantioseparation of binaphthol and its mono derivatives by cyclodextrin-modified capillary zone electrophoresis.

Chiral binaphthols belong to the group of most effective ligands for asymmetrical catalysis. In this context, various binaphthols presenting original substituents have been synthesized. Their study through capillary electrophoresis is the object of this work. The literature dedicated to the separation of atropisomers by capillary electrophoresis, corresponding only to binaphthol, reveals that its enantioseparation is always delicate because of the influence of many factors and the resolutions obtained are weak. Therefore, for a structured optimization, we first successfully evaluated the acidity constants of different binaphthols by means of capillary electrophoresis. With these known physicochemical characteristics, we could successfully carry out enantiomeric separations of the different binaphthols at pH 11.5, practically in completely ionized form, in phosphate medium, and in the presence of cyclodextrin (CD), with analysis times lower than 8min. The nature of CDs (alpha-CD, beta-CD, gamma-CD, hydroxypropyl-alpha-cyclodextrin (HP-alpha-CD), HP-beta-CD, HP-gamma-CD and trimethyl-beta-CD (TM-beta-CD)) and other factors in relation to enantiomeric resolution (applied voltage, nature and concentration of the electrolyte, and concentration of cyclodextrin) were optimized. These studies allowed us to determine the optimal conditions of separation (concentration and nature of CD) for each of the studied binaphthols. It is necessary to mention that, for the 1,1'-binaphthyl-2,2'-diol (Binol) at pH 11.5, the S atropisomer always migrated first, regardless of the nature and concentration of the cyclodextrin used. Moreover, an inversion in elution order of the two atropisomers as a function of pH was observed with gamma-CD (pH range: 10-11.5). The R atropisomer migrated first at pH 10. At pH 10.8 the migration order of the two atropisomers of Binol was reversed as a function of gamma-CD concentration. Finally, the addition of chiral ionic liquids (R(-)-1-hydroxy-N,N,N-trimethylbutan-2-aminium bis(trifluoromethylsulfonyl)imide and S(+)-tetrabutylammonium camphorsulfonate) was conducted. In the case of S(+)-tetrabutylammonium camphorsulfonate, a weak antagonistic effect was observed with modeling the evolution of enantiomeric resolution by means of the experimental design, while in the case of R(-)-1-hydroxy-N,N,N-trimethylbutan-2-aminium bis(trifluoromethylsulfonyl)imide the effect was neutral.

Analysis of neutral surfactants by non-aqueous medium capillary electrophoresis hyphenated to mass spectrometry (ion trap).

Non-derivatized Brij 58 oligomers were analyzed by using non-aqueous capillary electrophoresis (NACE) hyphenated to mass spectrometry (ion trap). The separation of this neutral polyethylene oxide surfactant was based on its complexation with ammonium cation in methanolic medium. Cationic complexes were formed within the capillary and migrated against the anodic electroosmotic flow. The latter was obtained by using a pre-treatment of the capillary with hexadimethrine bromide. By optimizing mass detection and the separation conditions separately, it was demonstrated that two different salts had to be used. Ammonium acetate was used in the sheath liquid to optimize detection sensitivity whereas ammonium iodide was used in the running electrolyte in order to obtain the more appropriate electroosmotic flow for the separation. Despite an aspiration effect due to the hyphenation with MS. that did not allow us to obtain a baseline resolution for the entire mixture, we were able to visualize and characterize more than 25 oligomers of Brij 58. As regards detection sensitivity, the limits of detection (LOD) were estimated at about 7.5 ng for the entire distribution of Brij 58 and 15 pg for C(16)E(5) or C(16)E(6) used as standards.

Determination of acidity constants of enolisable compounds by capillary electrophoresis.

Research on the structure-activity relationships of molecules with acidic carbon atoms led us to undertake a feasibility study on the determination of their acidity constants by capillary electrophoresis (CE). The studied molecules had diverse structures and were tetronic acid, acetylacetone, diethylmalonate, Meldrum's acid, 3-methylrhodanine, nitroacetic acid ethyl ester, pyrimidine-2,4,6-trione, 3-oxo-3-phenylpropionic acid ethyl ester, 1-phenylbutan-1,3-dione, 5,5-dimethylcyclohexan-1,3-dione and homophthalic anhydride. The p Ka range explored by CE was therefore very large (from 3 to 12) and p Ka values near 12 were evaluated by mathematical extrapolations. The analyses were carried out in CZE mode using a fused silica capillary grafted (or not) with hexadimethrine. Owing to the electrophoretic behaviour of these compounds according to the pH, their acidity constants could be evaluated and appeared in perfect agreement with the literature data obtained, a few decades ago, by means of potentiometry, spectrometry or conductimetry. The p Ka of homophthalic anhydride and 3-methylrhodanine were evaluated for the first time.

Utilization of fluorescein sodium salt for the indirect fluorimetric detection in micellar electrokinetic chromatography.

The potential of fluorescein sodium salt to generate a background signal in indirect fluorimetric detection in micellar electrokinetic chromatography (MEKC) has been studied by using a sample test containing various alcohols (methanol, ethanol, propan-1-ol, propan-2-ol, 2-methylpropan-1-ol, pentan-3-ol, 2-methylbutan-1-ol, 3-methylbutan-1-ol), acetaldehyde, acetone and ethyl acetate. In order to optimize sample test resolution and detection sensitivity, we have studied different parameters: sodium dodecyl sulfate concentration, electrolyte ionic strength, applied voltage as well as that of the addition of an organic cosolvent within the running electrolyte. Although the micellar pseudo-phase was not able to be saturated with the fluorophore in order to obtain the maximal detection sensitivity, the detection thresholds were satisfactory. By way of example, the detection threshold reached for 3-methylbutan-1-ol is 0.03% (v/v). The quantitative aspect was approached with ethanol titration in a commercial white wine. Finally the repeatability relating to, on the one hand, the effective electrophoretic mobilities and, on the other hand, the corrected areas has also been studied.