New solid phase extractors for selective separation and preconcentration of mercury (II) based on silica gel immobilized aliphatic amines 2-thiophenecarboxaldehyde Schiff’s bases

2-Thiophenecarboxaldhyde is chemically bonded to silica gel surface immobilized monoamine, ethylenediamine and diethylenetriamine by a simple Schiff’s base reaction to produce three new SP-extractors, phases (I-III). The selectivity properties of these phases toward Hg(II) uptake as well as eight other metal ions: Ca(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) were extensively studied and evaluated as a function of pH of metal ion solution and equilibrium shaking time by the batch equilibrium technique. The data obtained clearly indicate that the new SP-extractors have the highest affinity for retention of Hg(II) ion. Their Hg(II) uptake in mmol g⁻¹ and distribution coefficient as log K_d values are always higher than the uptake of any other metal ion along the range of pH used (pH 1.0-10.0). The uptake of Hg(II) using phase I was 2.0 mmol g⁻¹ (log K_d 6.6) at pH 1.0 and 2.0. 1.8 mmol g⁻¹ (log K_d 4.25), 1.6 mmol g⁻¹ (log K_d 3.90) and 1.08 mmol g⁻¹ (log K_d 3.37) at pH 3.0, 5.0 and 8.0, respectively. Selective separation of Hg(II) from the other eight coexisting metal ions under investigation was achieved successfully using phase I at pH 2.0 either under static or dynamic conditions. Hg(II) was completely retained while Ca(II), Co(II) and Cd(II) ions were not retained. Ni(II), Cu(II), Zn(II), Pb(II) and Fe(III) showed very low percentage retention values to be 0.74, 0.97, 3.5 and 6.3%, respectively. Moreover, the high recovery values (95.5 ± 0.5, 95.8 ± 0.5 and 99.0% ± 1.0) of percolating two liters of doubly distilled water, drinking tap water and Nile river water spiked with 5 ng/l of Hg(II) over 100 mg of phase I packed in a minicolumn and used as a thin layer enrichment bed demonstrate the accuracy and validity of the new SP-extractors for preconcentration of the ultratrace amount of spiked Hg(II) prior to the determination by borohydride generation atomic absorption spectrometry (AAS) with no matrix interference. The detection limit (3σ) for Hg(II) based on enrichment factor 1000 was 4.75 pg/ml. The precision (R.S.D.) obtained for different amounts of mercury was in the range 0.52-1.01% (N = 3) at the 25-100 ng/l level.     

Chelating sorbents based on silica gel and their application in atomic spectrometry

This mini-review covers chelating sorbents anchored to silica gel and their analytical applications for the preconcentration, separation and determination of trace metal ions, focussing mainly on the last 20 years. The article summarizes also the experience gathered by our research group in the synthesis and characterization of new modified silica gels via silanization, and their affinity toward selective extraction and separation of trace elements. The introduction of 1,5-bis(di-2-pyridyl)methylene thiocarbohydrazide silica gel (DPTH-gel) and methylthiosalicylate silica gel (TS-gel) chelating sorbents in trace and ultratrace analysis provide vital breakthroughs in preconcentration methods. These home-made materials allow certain analytes to be selectively extracted from complex matrices without matrix interference and good detection limits. The advantages of these new chelating sorbents in comparison with 8-hydroxyquinoline chelating sorbent immobilized on silica gel are discussed.     

Thin-layer chromatography of 1,2,4-triazoles on silica gel

Summary The TLC behaviour of N-phenyl-1,2,4-triazoles and their derivatives on silica gel plates has been studied using simple solvents. Isomers were very well distinguished, resulting from different activities due to hydrogen bonding. A mixture of seven compounds has been resolved with diethylether-n-butylamine-pyridine (91.4:7.7:0.9).     

Sorption of the peroxocomplex of titanium on silica gel and its analytical use

Summary Sorption of the titanium peroxocomplex on silica gel was studied in dependence on the pH and on the presence of various complexing substances, especially tartaric and citric acids. The distribution coefficients for the titanium peroxocomplex and for some other components were determined. Optimum conditions were established for the separation of small amounts of titanium from a number of accompanying cations and anions on a column and under static conditions.     

Synthesis and characterisation of morin-functionalised silica gel for the enrichment of some precious metal ions

Silica gel was firstly functionalised with aminopropyltrimethoxysilane obtaining the aminopropylsilica gel (APSG). The APSG was reacted subsequently with morin yielding morin-bonded silica gel (morin-APSG). The structure was investigated and confirmed by elemental and thermogravimetric analyses, IR and (13)C NMR spectral studies. Morin-APSG was found to be highly stable in common organic solvents, acidic medium (<2molL(-1) HCl, HNO(3)) or alkaline medium up to pH 8. The separation and preconcentration of Ag(I), Au(III), Pd(II), Pt(II) and Rh(III) from aqueous medium using morin-APSG was studied. The optimum pH values for the separation of Ag(I), Au(III), Pd(II), Pt(II) and Rh(III) on the sorbent are 5.7, 2.2, 3.7, 3.7 and 6.8, giving rise to separation efficiencies of 43.9, 85.9, 97.7, 60.9 and 91.0%, respectively, where the activity was found to be >90% in the presence of acetate ion. The ion sorption capacity of morin-APSG towards Cu(II) at pH 5.5 was found to be 0.249mmolg(-1) where the sorption capacities of Ag(I) and Pd(II) were 0.087 and 0.121mmolg(-1) and 0.222 and 0.241mmolg(-1) at pH 2.2 and 5.7, respectively. This indicates a 1:1 and 1:2 morin/metal ratios at pH 2.2 and 5.7, respectively. Complete elution of the sorbed metal ions was carried out using 10mL (0.5molL(-1) HCl+0.01molL(-1) thiourea) in case of Au(III), Pd(II), Pt(II) and Rh(III) and 10mL 0.5molL(-1) HNO(3) in case of Ag(I). Morin-APSG was successfully employed in the separation and preconcentration of the investigated precious metal ions from some spiking water samples yielding 100-folds concentration factor. The relative standard deviation (R.S.D.) and the T-test (|t|(1)) were calculated.     

Aspects of the synthesis, Characterization and metal–ligand stoichiometry of aminopropyl, nitrobenzamide, and 8-quinolinol silica gels

Surface modification of several silica gels with a number of silanes was studied, as well as further reactions of the modified surfaces. Complete reaction of aminopropylsilane was easily achieved if surface silanols were in excess. Triethoxysilylpropyl-p-nitrobenzamide (TESPN) reacts with difficulty, and complete reaction occured only with long reaction time (at least 12h). The maximum coverage of 100-Å pore silica gel by TESPN was found to be about 1.7 μmol/m², considerably less than the 3–4 /gmmol/m² of available silanol sites, probably due to steric effects of the large silane. Even at this maximum coverage, further reaction of the modified silica with trimethylsilyl capping groups occured, with additional coverage of about 1.0 μmol/m². The maximum amount of silylpropylamido-p-phenylazo-8-quinolinol that could be bound to silica gel was found to be about 1.0 μmol/m², again probably limited by steric effects of the large 8-quinolinol (oxine) moiety. Virtually complete conversion of parent nitrobenzamide silica gel (NBSG) to 8-quinolinol silica gel (QSG) could be achieved if NBSG coverage was less than about 0.7 μmol/m². QSG materials were found to have a 2 oxine to 1 copper(II) stoichiometry, even with surface coverages as low as 0.16 μmol/m².     

The effect of some modifiers on the retention of aromatic hydrocarbons on untreated silica gel

Summary The retention parameters of benzene, naphthalene; anthracene and phenanthrene on untreated silica gel were determined in the presence of four modifiers: 1-methyl-2-pyrrolidone (MP), 4-formyl morpholine (FM), -butyrolactone (BL) and sulfolane (SF). Better column performance was found in the case of FM and MP only.     

Adsorption of di-2-pyridyl ketone salicyloylhydrazone on silica gel: characteristics and isotherms

The adsorption of DPKSH onto silica gel was investigated, at 25±1 °C and pH 1, 4.7 and 12. For the same DPKSH concentration interval, the minimum required time of contact for adsorption maximum at pH 4.7 was smaller than at pH 1 and the maximum amount of DPKSH adsorbed per gram of silica at pH 1 is smaller than at pH 4.7. At pH 12 the DPKSH adsorption onto silica gel was not significant. The adsorption data followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The maximum amount of solute adsorbed (m_ads^max) and the adsorption constant, K_L, were derived from Langmuir isotherm. The Freundlich constants 1/n and K_F related, respectively, to the energetic heterogeneity of adsorption sites and an empirical constant were evaluated. The mean sorption free energy (E) of DPKSH adsorption onto silica gel was calculated from D-R isotherm indicating a physical adsorption mode. Finally, conductimetric titrations showed the silica particle basicity and acidity as 0.002 and 0.3 mmol g⁻¹, respectively.     

Chemoselective synthesis of quinoxalines and benzimidazoles by silica gel catalysis

Treatment of nitroolefins and o-phenylenediamine with silica gel catalyst produced quinoxalines mainly in THF, but gave benzimidazoles efficiently in water. Such a solvent-dependent chemoselective reaction has prominent features of affording two cyclized products selectively with the same substrate, short reaction time, operational simplicity, as well as available starting materials and nontoxic catalysts. In addition, the scope and limitations were explored and a plausible reaction mechanism is proposed.     

Mechanistic investigation of hydrolysis reactions of dithioacetal derivatives grafted on silica gels

Silica gels believed to be grafted with dithioacetal derivatives were recently used for Hg(II) extraction, and were found to selectively remove 94-100% of Hg²⁺ ions from metal ion mixtures. The current studies with one derivative suggest that the functional group in the Hg(II) removal is the mercapto (SH) ligand. The dithioacetal group in (ClCOCH₂S)₂CHPh (2) was hydrolyzed during its reaction with amine (O)₃Si(CH₂)₃NH₂ (3) grafted on silica gel to give the mercapto ligand (O)₃Si(CH₂)₃NHCOCH₂SH (4). The silica gel grafted with the mercapto ligand 4 selectively removed Hg²⁺ ions with reported high capacities.     

Study of silica gel and copper silicate gel solubilities in high performance liquid chromatography

Summary After summarizing published results on silica gel and alkyl-bonded silica gel solubilities, the experimental solubility of unmodified silica and copper silicate gel (used in ligand exchange chromatography) in watermethanol-ammonia and water-acetonitrile-ammonia mixtures are given. These results demonstrate that silica gel solubility, measured by a static method, varies greatly with the water volume fraction of a ternary mixture. Curiously, no influence from the organic nature of the solvent was demonstrated. This observation is inconsistent with the fact that the copper silicate gel used in ligand-exchange chromatography with water-methanol-ammonia as mobile phase is attacked more rapidly than with water-acetonitrile-ammonia.An explanation based upon the variations of acid-base properties of silicic acid versus mobile phase dielectric constant values in conjunction with the methanol protophilic properties is proposed. Finally, it is shown that chromatographic columns filled with copper silicate gel have lifetimes of several months, if they are used with a procolumn (of copper silicate gel) and with acetonitrile as organic solvent with a volume fraction greater than 0.5 in the mobile phase.     

Synthesis and characterization of novel silica gel supported N-pyrazole ligand for selective elimination of Hg(II)

The polar organic molecule N-(2-hydroxyethyl)-3,5-dimethylpyrazole reacted with a 3-glycidoxypropyltrimethoxysilane silylant agent, previously anchored on a silica surface in a heterogeneous way to yield the product SiPz. The epoxide group was opened yielding chelating pendant group bonded to the inorganic surface. The product was characterized through elemental analysis, infrared spectroscopy, ¹³C NMR, surface area and thermogravimetry. The binding and adsorption abilities of SiPz was investigated for Hg²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Zn²⁺, K⁺, Na⁺ and Li⁺ cations and compared to results of classical liquid-liquid extraction with the unbound N-pyrazole compound. The grafting at the surface of silica does not affect complexing properties of the ligand and the SiPz exhibits a high selectivity toward Hg²⁺ ion with no complexation being observed towards Zinc and alkali metals. The extracted and the complexing cation percentage were determined by atomic absorption measurements.     

Separation of trace amounts of titanium by the sorption of the titanium peroxocomplex on silica gel

Summary The possibility of the analytical use of the sorption of titanium peroxocomplex on silica gel for the determination of trace amounts of titanium was studied. The exchange capacity of silica gel in dependence on the time and the composition of the titanium peroxocomplex sorbed were described. A simple and very efficient separation procedure has been developed for the determination of traces of titanium in various waters and water-soluble salts.     

An amperometric sensor based on hemin adsorbed on silica gel modified with titanium oxide for electrocatalytic reduction and quantification of artemisinin

The present work describes the development of an amperometric sensor based on hemin immobilized on a titanium oxide modified silica toward detection of artemisinin (ARN) in neutral medium at an applied potential of −0.5 V vs. Ag/AgCl. The sensor presented its best performance in 0.1 mol L⁻¹ phosphate buffer solution, at pH 7.0. After optimizing the operational conditions, the sensor provided a linear response range for ARN reduction from 50 nmol L⁻¹ to 1000 nmol L⁻¹ with a sensitivity, detection and quantification limits of 24.66 A L mol⁻¹, 15 nmol L⁻¹ and 52 nmol L⁻¹, respectively. The proposed sensor showed a stable response for at least 80 successive determinations. The repeatability of the measurements with the sensor and the preparation of a series of electrodes, evaluated in terms of relative standard deviation, were 4.1% and 5.0%, respectively, for n = 10. The developed sensor was applied for the determination of ARN in the crude extracts of A. vulgaris L and the average recovery for these samples is 101.4 (± 3.1)%.     

Synthesis and characterization of silica gel from siliceous sands of southern Tunisia

The present work aimed to achieve valorization of Albian sands for the preparation of sodium silicates that are commonly used as a precursor to prepare silica gel. A siliceous sand sample was mixed with sodium carbonate and heated at a high temperature (1060 °C) to prepare sodium silicates. The sodium silicates were dissolved in distilled water to obtain high quality sodium silicate solution. Hydrochloric acid was then slowly added to the hydrated sodium silicates to obtain silica gel. The collected raw siliceous sands, as well as the prepared silica gels, were characterized by different techniques, such as X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermal analysis (DSC). XRF confirmed that the detrital sand deposits of southern Tunisia contain high amounts of silica, with content ranging from 88.8% to 97.5%. The internal porosity varied between 17% and 22%, and the specific surface area was less than 5 m²/g. After the treatment described above, it was observed that the porosity of the obtained silica gel reached 57% and the specific surface area exceeded 340 m²/g. Nitrogen adsorption isotherms showed that the prepared silica gels are microporous and mesoporous materials with high adsorption capacities. These results suggest that the obtained silica gels are promising materials for numerous environmental applications.     

Synthesis of a rhodium(I) carbonyl complex with a chiral aminodiphosphine ligand and its immobilization onto aminopropyl functionalized silica gel

The reaction of [Rh(CO)₂(µ-Cl)]₂ with two molar equivalents of a chiral ligand, (R)-N,N-bis(2-diphenylphosphinoethyl)-1-phenylethylamine(PNP*) yield a mono-carbonyl complex, [Rh(CO)Cl(η²-P,P-PNP*)] (1), in which the potentially tridentate PNP* ligand coordinates in a bidentate fashion through P,P bonding. The complex was characterized by elemental analysis, FAB mass, IR, UV-Vis, ¹H- and ³¹P{¹H}-NMR spectroscopy. Variable temperature (223–298 K) ³¹P{¹H}-,NMR spectra of 1 showed a mixture of cis and trans isomers in the solution with the trans predominating at room temperature and the cis at lower temperature. Complex 1 was immobilized on silica through axial coordination of amine from 3-aminopropyltriethoxysilane functionalized silica. The immobilized materials were characterized by elemental analysis (N₂), FTIR, DTA–TGA, N₂-adsorption, XRD, and SEM analysis.     

Production of polyacrylamide gel filled capillaries for capillary gel electrophoresis (CGE): Influence of capillary surface pretreatment on performance and stability

Polyacrylamide gel filled capillaries for electrophoresis can be improved in performance and stability by a specially optimized and reproducible production procedure. After surface pretreatment as described in this contribution, gels polymerized in capillaries are stable for long series of routine separations. Bubbles formation during gel polymerization can be avoided. The procedure is compared with those described by other authors. Separations of different oligonucleotide samples illustrate the quality of the gel capillaries obtained. The peak symmetry achieved proved to be better than that obtained without surface pretreatment.     

硅胶的表面硅烷化处理及其吸附性能研究

为研究改性硅胶对挥发性有机废气的吸附性能,分别采用十六烷基三甲氧基硅烷、辛基三乙氧基硅烷、苯基三甲氧基硅烷、一甲基三乙氧基硅烷对硅胶进行气相改性处理,试验研究了不同改性剂、改性时间对硅胶饱和吸附率的影响,考察了改性硅胶对甲苯、水二组分体系的吸附选择性.结果表明,硅胶对甲苯的吸附主要为物理吸附,长链的硅烷改性剂在60℃、...     

Organically nanoporous silica gel based on carbon paste electrode for potentiometric detection of trace Cr(III)

A new ion-selective electrode (ISE) for the detection of trace chromium(III) was designed by using 2-acetylpyridine and nanoporous silica gel (APNSG)-functionalized carbon paste electrode (CPE). The presence of APNSG acted as not only a paste binder, but also a reactive material. With 7.5 wt% APNSG proportions, the developed electrode exhibited wide dynamic range of 1.0 × 10⁻⁸ to 1.0 × 10⁻³ M toward Cr(III) with a detection limit of 8.0 × 10⁻⁹ M and a Nernstian slope of 19.8 ± 0.2 mV decade⁻¹. The as-prepared electrode displayed rapid response (∼55 s), long-time stability, and high sensitivity. Moreover, the potentiometric responses could be carried out with wide pH range of 1.5-5.0. In addition, the content of Cr(III) in food samples, e.g. coffee and tea leaves, has been assayed by the developed electrode, atomic absorption spectrophotometer (AAS) and atomic emission spectrometer (ICP-AES), respectively, and consistent results were obtained. Importantly, the response mechanism of the proposed electrode was investigated by using AC impedance and UV-vis spectroscopy.     

Influence of silica gel pretreatment and bonding technique on PAH selectivity of octadecyl bonded phases

Summary The effect of silica gel pretreatment and of different bonding techniques, on the chromatographic properties of octadecyl bonded phases is described. The experiments show that a monomeric octadecyl bonded phase, prepared from silica gel that has not been treated before bonding, has a poor selectivity towards polycyclic aromatic hydrocarbons (PAHs) and shows high adsorption of basic components. Silica gel treatment before the bonding of the monofunctional silane does not give a substantial improvement. Polymeric phases on the other hand show a much better PAH selectivity and a lower adsorptivity towards basic components. Further improvement can be achieved with the polymeric modification if silica gel treatment is carried out before bonding.