Simultaneous recovery of cadmium and lead from aqueous effluents by a semi-continuous laboratory-scale polymer enhanced ultrafiltration process

Performance of a semi-continuous polymer enhanced ultrafiltration (PEUF) process has been investigated for the simultaneous recovery of cadmium and lead from binary mixtures. This method uses poly(acrylic acid) as water-soluble polymer to bind these metals. Experiments have taken place in a laboratory-scale system. Loading ratio (mg total metal ions/g polymer) and pH values for separation of cadmium and lead have been studied by means of preliminary experiments, analyzing their influence on permeate flux, metal rejection coefficients and separation factor.The proposed process includes three different stages: total retention of metal ions, selective separation and polymer regeneration. Operating pH values for total retention of metal ions and polymer regeneration processes are 5 and 2, respectively. Selective separation has been investigated working at an intermediate pH value. In this way, if a stream containing 12.5 ppm of each metal ion (1:1 in weight) is treated in the first stage, two different streams enriched in each metal ion are obtained in the second stage. Permeate stream is enriched in cadmium with a proportion near 5:1 in weight, and retentate is enriched in lead with a similar proportion.Finally, the three stages have been modelled successfully with a mathematical model based on conservation equations and chemical reactions taking place in solution.     

Effect of operating parameters on selective separation of heavy metals from binary mixtures via polymer enhanced ultrafiltration

Performance of continuous polymer enhanced ultrafiltration (PEUF) method was investigated for removal of mercury and cadmium from binary mixtures. This method includes the addition of polyethyleneimine (PEI) as a water soluble polymer to bind the metals, which was followed by ultrafiltration operation performed on both laboratory and pilot scale systems. The influence of various operating parameters such as temperature, metal/polymer ratio, presence of calcium ions and pH on retention of metals and permeate flux was investigated. To investigate the possibility of selective separation of mercury and cadmium, experiments were conducted for binary solutions at different pH and loading ratios. It was seen that the retention of mercury decreased and permeate flux increased when the temperature increased. The increased pH and decreased metal/polymer ratio, loading (L), resulted in higher retention of both metals. Shapes of retention vs. pH or L curves were very similar for both metals. Retentions stay almost constant at a value very close to unity until a critical L or pH value was reached, then, R decreases almost linearly with L or pH. However, retention of cadmium was affected more than that of mercury as the pH decreased and L increased. This leads to the selective separation of mercury and cadmium. At low pH values (about 5) and at high L values (about 0.3), mercury was removed by ultrafiltration operation while almost all cadmium passed through the membrane. At pH 5.5 and cadmium/polymer ratio about 0.35 and mercury/polymer ratio about 0.39, the highest separation factor was obtained as 49.     

Determination of heavy metal concentration in feed and permeate streams of polymer enhanced ultrafiltration process

Polymer enhanced ultrafiltration (PEUF) is a newly developed method for the removal of heavy metals from aqueous solutions. This method was applied for the removal of mercury and cadmium with the presence of polyethyleneimine (PEI) as a water soluble polymer. After ultrafiltration experiments for metal–polymer mixtures, two separate streams, namely, retentate and permeate, former of which contains mainly metal–polymer complex and free polymer molecules while latter of which mainly contains free metal ions, were obtained. At the end of PEUF experiments, performance of operation was determined by concentration analyses which was achieved by atomic absorption spectroscopy (AAS) applied in a different way for permeate and retentate streams considering the effect of presence of polymer. For mercury analysis, cold vapor AAS was applied. It was observed that the presence of PEI did not affect the atomic absorption signal when 10% HCl was added to the sample solutions. For calcium and cadmium, flame AAS was used. It was observed that change in PEI concentration results in change in measured concentration of calcium and cadmium. Therefore, two new approaches were developed for accurate measurement of concentrations of calcium and cadmium. It was also observed that presence of other metals did not affect the accuracy of the measurement of a particular metal in the concentration range studied.     

Enantioseparations of hydrobenzoin and structurally related compounds in capillary zone electrophoresis using heptakis(2,3-dihydroxy-6-O-sulfo)-beta-cyclodextrin as chiral selector and enantiomer migration reversal of hydrobenzoin with a dual cyclodextrin system in the presence of borate complexation

We investigated the enantioseparations of racemic hydrobenzoin, together with benzoin and benzoin methyl ether, in capillary electrophoresis (CE) using the single-isomer heptakis(2,3-dihydroxy-6-O-sulfo)-beta-cyclodextrin (SI-S-beta-CD) as a chiral selector in the presence and absence of borate complexation and enantiomer migration reversal of hydrobenzoin with a dual CD system consisting of SI-S-beta-CD and beta-CD in the presence of borate complexation at pH 9.0 in a borate buffer. The enantioselectivity of hydrobenzoin increased remarkably with increasing SI-S-beta-CD concentration and the enantioseparation depended on CD complexation between hydrobenzoin-borate and SI-S-beta-CD. The (S,S)-enantiomer of hydrobenzoin-borate complexes interacted more strongly than the (R,R)-enantiomer with SI-S-beta-CD. The enantiomers of hydrobenzoin could be baseline-resolved in the presence of SI-S-beta-CD at a concentration as low as 0.1% w/v, whereas the three test analytes were simultaneously enantioseparated with addition of 0.3% w/v SI-S-beta-CD or at concentrations >2.0% w/v in a borate buffer and 0.5% w/v in a phosphate background electrolyte at pH 9.0. Compared with the results obtained previously using randomly sulfated beta-CD (MI-S-beta-CD) in a borate buffer, enantioseparation of these three benzoin compounds is more advantageously aided by SI-S-beta-CD as the chiral selector. The enantioselectivity of hydrobenzoin depended greatly on the degree of substitution of sulfated beta-CD. Moreover, binding constants of the enantiomers of benzoin compounds to SI-S-beta-CD and those of hydrobenzoin-borate complexes to SI-S-beta-CD were evaluated for a better understanding of the role of CD complexation in the enantioseparation and chiral recognition. Enantiomer migration reversal of hydrobenzoin could be observed by varying the concentration of beta-CD, while keeping SI-S-beta-CD at a relatively low concentration. SI-S-beta-CD and beta-CD showed the same chiral recognition pattern but they exhibited opposite effects on the mobility of the enantiomers.     

Copper recovery by polymer enhanced ultrafiltration (PEUF) and electrochemical regeneration

In this work, the removal of Cu²⁺ from a synthetic effluent has been tested by means of polymer enhanced ultrafiltration (PEUF), using partially ethoxylated polyethylenimine (PEPEI) as water-soluble polymer. Overall, the two necessary steps of a hypothetical continuous process, metal retention (in total recirculation and discontinuous mode) and polymer regeneration (in discontinuous mode), have been confronted individually. On the one hand, the values of temperature (T), transmembrane pressure (ΔP), metal–polymer ratio and pH that maximize both, permeate fluxes and rejection coefficients, have been obtained by ultrafiltration tests, reaching Cu²⁺ retention coefficients higher than 97%. On the other hand, the polymer regeneration step has been carried out by the electrochemical technique, which consists in the metal electrodeposition on the cathode of an electrochemical cell. In a first step, cyclic voltammetries have been carried out to assure the polymer does not suffer any oxidation or reduction process. From these tests, a cathodic working potential has been selected to minimize hydrogen evolution reaction (−0.7 V vs. Ag/AgCl). Working at this voltage in deposition tests, a pH of 3.3 has been selected from experiments at different pH values. This pH is less extreme than the pH necessary if this step was carried out chemically (pH 2).     

Protein type effects on steady-state crossflow membrane ultrafiltration fluxes and protein transmission

The permeate fluxes and percent protein transmission were evaluated for steady-state crossflow ultrafiltration of two proteins of different composition: bovine serum albumin (BSA), containing fatty acid, and “fatty-acid-poor” BSA, from which most of the fatty acids had been removed (BSA/FAP). The influences of protein concentration up to 6.5 percent w/v, transmembrane pressure, ionic environment and membrane type (i.e. nominal molecular weight cut-off) were investigated. For both BSA and BSA/FAP, the fluxes and the protein transmission were dependent on the amount of salt present. The higher fatty acid content in the BSA apparently enhanced protein-protein interaction, resulting in a more cohesive and resistant fouling layer; permeate fluxes were lower with BSA/FAP than with BSA at otherwise corresponding operating conditions. A hysteresis behaviour of the flux (J)-transmembrane pressure (TMP) relationship was observed whenever the ultrafiltration unit was operated at a TMP less than some higher value to which the membrane previously had been exposed.     

Economic feasibility study of polyelectrolyte-enhanced ultrafiltration (PEUF) for water softening

In polyelectrolyte-enhanced ultrafiltration (PEUF), a water-soluble anionic polyelectrolyte (in this study sodium polystyrene sulfonate or PSS) is added to hard water. The calcium and magnesium bind to the polymer which has a high enough molecular weight to be rejected by an ultrafiltration membrane. The permeate is softened water. Economically, the PSS needs to be recovered from the retentate for reuse. Three methods of recovery developed in this study were addition of NaCl, Na₂CO₃ or HCl to PEUF to regenerate PSS. Of the three PEUF processes considered, NaCl/PEUF as compared to Na₂CO₃/PEUF and HCl/PEUF provided the best scheme for the water softening process. PEUF is shown in this study to be competitive with lime softening at low flow rates. The PEUF process is more expensive than ion exchange for a stream containing only hardness ions. However, PEUF becomes nearly comparable with ion exchange for a stream containing hardness ions as well as bacteria, viruses and pyrogen. The cost comparisons are based on fully continuous operations and include treatment of waste streams from each process.     

Enantioselective total synthesis of (S)-(+)-lennoxamine through asymmetric hydrogenation mediated by l-proline-tetrazole ruthenium catalyst

A novel asymmetric synthetic strategy to prepare isoindolobenzazepine based lennoxamine alkaloid has been achieved in high ee% starting from 2-(benzo[d][1,3]dioxol-5-yl)ethanamine and 1-(chloromethyl)-2,3-dimethoxybenzene in 5 steps and with a 34% overall yield. The potentiality of this route involved the Bischler-Napieralsky cyclization that leads to tetracyclic indolinium skeleton, generation of chiral center through asymmetric hydrogen-transfer reaction employing l-proline-tetrazole as chiral ligand with Ru/Ir/Rh, and anodic oxidation as the key steps in the synthesis.     

A hydrodynamic study of the retention of polyethylene glycols by cellulose acetate membranes in the absence and presence of proteins

The ultrafiltration behaviour of polyethylene glycols has been investigated with respect to their partial retention by YM5 and YM10 membranes. Retention coefficients were found to follow a log-normal distribution except at low molecular weights, which exhibited higher than expected values. Increasing the applied pressure resulted in increased retention of PEG, although linear flux-pressure relationships were observed in all cases. Increasing hydrodynamic activity by applying higher stirrer speeds led to reduced permeate concentrations. The mean molecular weights of the permeates were higher under hydrodynamic conditions resulting in lower retention coefficients, which suggests increased permeabilities for the larger PEG component molecules.

The retention behaviour of solutions of PEG with varying concentration of bovine serum albumin (BSA) as the flux rate was altered paralleled the results for pure PEG solutions. However, when the flux rate was kept constant and the concentration varied, there was an initial increase of retention at a BSA concentration of 0.2% w/v and thereafter a reduction up to a tested bulk concentration of 10%. Various proposals were made to explain this behaviour.     

Achiral and chiral separations using MEKC,polyelectrolyte multilayer coatings,and mixed mode separation techniques with molecular micelles

Mixed mode (MM) separation using a combination of MEKC and polyelectrolyte multilayer (PEM) coatings is herein reported for the separation of achiral and chiral analytes. Many analytes are difficult to separate by MEKC and PEM coatings alone. Therefore, the implementation of a MM separation provides several advantages for overcoming the limitations of these well‐established methods. In this study, it was observed that achiral separations using MEKC and PEM coatings individually resulted in partial resolution of eight very similar aryl ketones when the molecular micelle (sodium poly(N‐undecanoyl‐L ‐glycinate)) concentration was varied from 0.25 to 1.00% w/v and the bilayer number varied from 2 to 4. However, when MM separation was introduced, baseline resolution was achieved for all eight analytes. In the case of chiral separations, temazepam, aminoglutethimide, benzoin, benzoin methyl ether, and coumachlor were separated using the three separation techniques. For chiral separations, the chiral molecular micelle, sodium poly(N‐undecanoyl‐L ‐leucylvalinate), was employed at concentrations of 0.25–1.50% w/v for both MEKC and PEM coatings. Overall, the results revealed partial separation with MEKC and PEM coatings individually. However, MM separation enabled baseline separation of each chiral mixture. The separation of achiral and chiral compounds from different compound classes demonstrates the versatility of this MM approach.     

正反相模式下键合纤维素手性固定相对手性化合物的拆分

在自行合成的键合型纤维素-(3,5-二甲基苯基氨基甲酸酯)(CDMPC-CSP)手性固定相上,在正相模式下对苯偶姻和甲霜灵外消旋体进行了拆分,考察了流动相中醇以及温度在手性识别中对手性分离的影响。同时考察了反相模式下外消旋体的拆分。     

The Use of Poly(Vinyl Alcohol) to Cross‐link Penicillinase for the Fabrication of a Penicillin Potentiometric Biosensor

Chemically cross‐linked PVA films are permeable matrices for the fabrication of biosensors. PVA provides an attractive immobilisation method as it preserves the enzymatic activity. Penicillinase (P’nase) was cross‐linked with poly(vinyl alcohol) (PVA) and bovine serum albumin (BSA). The optimum conditions for the of BSA‐PVA‐P’nase film were: 2.5 % w/v PVA, 0.006 % w/v BSA, 2.4 mM penicillin (Pen) and 16 U/mL P’nase. The minimum detectable concentration was 1.7 µM. The linear concentration range obtained for the BSA‐PVA film was 7.5–283 µM. The BSA‐PVA P’nase biosensor detected penicillin in amoxycillin with an average percentage recovery of 97±12 %. Higher penicillin concentrations (10–20 ppm) were detected more successfully than lower concentrations (≤5 ppm). These results indicate that further work is required to enable the successful detection of lower penicillin concentrations such as 5 ppm.     

Chiral separation of ephedrine isomers by capillary electrophoresis using bovine serum albumin as a buffer additive

A method utilizing bovine serum albumin (BSA) as buffer additive for chiral separation by means of capillary electrophoresis is described. Parameters that affect chiral separation, such as buffer pH, buffer concentration, BSA concentration, and organic modifier, are investigated. Baseline resolution of ephedrine-pseudoephedrine and norephedrine-norpseudoephedrine isomers are achieved in an uncoated capillary with a 20 mmol/L phosphate buffer at pH 9.0 in the presence of 10 micromol/L BSA and 15% (v/v) 2-propanol at 25 degrees C. The developed method can be applied for the analysis of ephedra plant extracts that contain the four test drugs.     

Polyacrylamide-based monolithic capillary column with coating of cellulose tris(3,5-dimethylphenyl-carbamate) for enantiomer separation in capillary electrochromatography

A hydrophilic chiral capillary monolithic column for enantiomer separation in CEC was prepared by coating cellulose tris(3,5-dimethylphenyl-carbamate) (CDMPC) on porous hydrophilic poly(acrylamide-co-N,N'-methylene-bisacrylamide) (poly(AA-co-MBA)) monolithic matrix with confine of a fused-silica capillary. The coating conditions were optimized to obtain a stable and reproducible chiral stationary phase for CEC. The effect of organic modifier of ACN in aqueous mobile phase for the enantiomer separation by CEC was investigated, and the significant influence of ACN on the enantioresolution and electrochromatographic retention was observed. Twelve pairs of enantiomers including acidic, neutral, and basic analytes were tested and nine pairs of them were baseline-enantioresolved with acidic and basic aqueous mobile phases. A good within-column repeatability in retention time (RSD = 2.4%) and resolution (RSD = 3.2%) was obtained by consecutive injections of a neutral compound, benzoin, on a prepared chiral monolithic column, while the between-column repeatability in retention time (RSD = 6.4%) and resolution (RSD = 9.6%) was observed by column-to-column examination. The prepared monolithic stationary phase showed good stability in either acidic or basic mobile phase.     

金纳米粒子修饰的手性毛细管电色谱固定相的制备及性能表征

制备了粒径为15 nm的金纳米粒子(GNPs)并将其修饰到氨基衍生化的硅胶整体柱内,通过化学键合法将牛血清白蛋白(BSA)固载到GNPs的表面作为手性固定相。通过透射电子显微镜、扫描电子显微镜等方法进行表征,结果表明,GNPs分散性良好,并被成功地修饰到毛细管柱内,含量高达17.18%。优化了BSA手性柱的制备条件,最终确定了体积分数为10%的3-氨丙基三乙氧基硅烷(APTES)和15 g/L BSA为最佳反应条件。在毛细管电色谱分离模式下,对缓冲液pH值、电压等分离条件进行了考察,最终选择了10 mmol/L pH 7.4的磷酸缓冲液和15 kV运行电压作为最佳分离条件。手性柱对3种手性化合物(色氨酸、阿替洛尔和麻黄碱)有拆分效果,对色氨酸能实现基线分离。与物理吸附法相比,化学键合法制备的手性柱拆分效果好,分析物无需柱前衍生化,且色谱柱稳定性良好。该文的制备方法也为其他类型手性选择剂的引入提供了良好的思路。     

Determination of enantiomeric compositions of DOPA by tandem mass spectrometry using the kinetic method with fixed ligands

A fixed ligand (FL) version of the kinetic method was applied to rapid, simple, and accurate chiral analysis of DOPA, which is an important drug used for treatment of Parkinson's disease. Singly charged clusters containing the transition metal ion Cu(II), pyridyl ligands which serve as a fixed ligand, some amino acid as a reference, and the analyte DOPA were generated by electrospray ionization. The cluster ion of interest was mass-selected, and the kinetics of its competitive unimolecular dissociations was investigated in an ion trap mass spectrometer. The chiral selectivity (R(chiral)), the ratio of the two fragment ion abundances when the cluster contains one pure enantiomer of the analyte expressed relative to that for the other enantiomer, varies with fixed ligands, references, and transition metals. Chiral discrimination was optimized in 1,10-phenanthroline as a FL, L-Phe and L-Pro as a reference, and Cu(II) as a central metal ion. Quantitative determinations of the enantiomeric composition of DOPA were achieved using two-point calibration curves. The linear relationship between the logarithm of the fragment ion abundance ratio (ln R) and enantiomeric compositions (ee%) of the DOPA allows the determination of the chiral purity of enantiomeric mixtures.     

Asymmetric Palladium-Assisted Alkylation of Alkenes

Palladium-promoted alkylation of alkenes using chiral sulfoxide-containing carbanions and chiral lithiated oxazolines results in asymmetric induction (AI) ranging from 3–5% (1,5 induction), 20–40% (1,3 induction) to 44–52% (1,4 induction). No general trend allowing predictions of results was found. With 1-hexene, attack at C(1) is almost exclusive but propene gives a mixture of attack at C(1) and C(2). The use of a chiral ligand together with malonate anion also leads to some asymmetric induction (ca. 20%).     

吸附蛋白质固定相电色谱手性分离的研究

 将牛血清白蛋白 (BSA)吸附于强阴离子交换固定相 (SAX)上用于电色谱手性分离。当SAX吸附BSA后 ,电渗淌度仅仅下降 2 6 3% ,而电渗流的方向没有改变。在该系统中电渗流的方向和阴离子的电泳方向一致 ,因而克服了一般蛋白质固定相不能分离酸性对映体的缺点。 1种中性对映体安息香和 4种阴离子性对映体色氨酸、华法令、非诺洛芬、酮基布洛芬获得了成功分离。当流动相含体积分数为 7%的乙腈时 ,死时间和D 色氨酸、L 色氨酸的迁移时间的相对标准偏差分别为 0 90 % ,0 87%和 0 96 % (n =2 1) ,说明该体系有很好的重现性。     

Fractionation of BSA and lysozyme using ultrafiltration: effect of pH and membrane pretreatment

Selective transmission of a solute through membranes proves to be a challenge in ultrafiltration processes. This is because the transport of a solute through an ultrafiltration membrane does not depend on size alone, but on several other factors such as solute-solute and solute-membrane interactions. By manipulating physicochemical parameters and process variables (eg. pH, ionic strength, concentration of solute, etc.) and by membrane modification, it is possible to enhance the transmission of a particular solute and thus enhance fractionation of solutes. In this paper, the effect of pH on fractionation of BSA and lysozyme by ultrafiltration through 50 kDa MWCO (molecular weight cut off) polysulfone membrane has been examined. It was found that the selectivity of solute separation for dilute mixtures of BSA and lysozyme was very much pH dependent and varied from 3.3 at pH 5.2 to 220.0 at pH 8.8. However, at a higher feed concentration, the transmission of lysozyme through polysulfone membrane decreases quite dramatically resulting in lower throughput of product. An attempt has been made to enhance the transmission of lysozyme through the polysulfone ultrafiltration membrane by pretreating the surface of the membrane by adsorption of another protein, myoglobin. An increase in lysozyme transmission of up to 63% with respect to native membrane was observed. The stability of this pretreatment and its effect on permeate flux have been examined. The pretreated membrane was used to fractionate BSA/lysozyme mixtures. Even at higher feed concentration, enhanced fractionation with respect to native membrane was observed due to highly enhanced transmission of lysozyme through the pretreated membrane.     

Preparation and characterization of polyethyleneimine modified ion-exchanger based on poly(methacrylate-co-ethylene dimethacrylate) monolith

A polyethyleneimine (PEI) modified ion-exchanger was prepared based on poly(methacrylate-co-ethylene dimethacrylate) monolith cast in 100 mm x 4.6 mm I.D. stainless steel tube with heptane as the porogenic solvent at 65 degrees C for 12 h. The pores larger than 500 nm presented 85% of total pore volume of PEI monolith and provided the better permeability for separation. Bovine serum albumin (BSA) binding capacity on the column was enhanced with increasing the molecular weight of PEI, indicated that the brush ligand emanated from the surface and captured more protein by multiple binding sites. Titration experiment as well as BSA retention versus the pH of mobile phase showed that the monolith exhibited weak ion-exchange property, and recovered BSA on the monolith reached 97% when NaCl content in mobile phase was higher than 0.5 M. Frontal analysis and gradient elution of BSA indicated that PEI monolith provided the rapid mass transfer in chromatographic procedure, which made the dynamic binding capacities as well as column efficiency keep as constants at high operating flow rate. Fast separation of three mode proteins mixture (lysozyme, hemoglobin and BSA) on the monolith was achieved within 3 min at velocity of 1445 cm/h. This demonstrated the potential of PEI monolith for the rapid analysis and separation of proteins.