Cd Column Research Articles

Batch and column modeling of Cd (II) separation from aqueous phase using chitosan nitrogen foam carbon

Beetmolasses resulting from the sugar industry was mixed with keratin solution to prepare nitrogen foam carbon (N-PC) by carbonization. Amino functional groups were introduced to N-PC by coating with a chitosan layer to produce chitosan nitrogen foam carbon (CH- N-PC). The structure of CH- N-PC was characterized and used as an adsorbent in the column and batch sorption system to separate Cd (II) from the aqueous phase. In the column system, the maximum removal was reached 77.30% with a sorption capacity of 133.22 mg/g at optimum pH.5.0. Thomas model indicates a well-fitting with higher R2 > 0.98 than other models. In the batch system indicated a well-fitting with Pseudo-second-order model (R2 > 0.998) with agreement between experimental (qe: 219.45 mg/g) and calculated sorption capacity (qe: 222.64 mg/g) than other models. The batch thermodynamic study showed that the sorption system is an exothermic process. CH-N-PC adsorbent has good regeneration with 2.0 M HCl and recycled up to 5 cycles which indicates the economical use of CH-N-PC in the Cd (II) column sorption system.

Solid-Phase Mediated Methodology To Incorporate Drug into Intermolecular Spaces of Cyclodextrin Columns in Polyethylene Glycol/Cyclodextrin-Polypseudorotaxanes by Cogrinding and Subsequent Heating

In this study, a new preparation method was developed to obtain drug/(polyethylene glycol/cyclodextrin-polypseudorotaxane (PEG/CD-PPRX)) complexes in which drugs were incorporated into the intermolecular spaces of CD columns in PEG/CD-PPRXs. This method was solid-phase mediated and used cogrinding and subsequent heating. Guest drug and CD in PEG/CD-PPRX were amorphized by cogrinding, and then crystallization of CD was promoted by subsequent heating. A previously reported sealed-heating method using the gas phase was not applicable for poorly sublimated and thermally unstable drugs such as piroxicam (PXC) and hydrocortisone, whereas this new method allowed these drugs to be incorporated into the intermolecular spaces of γ-CD columns. Furthermore, salicylic acid (SA) and salicylamide were successfully incorporated into the intermolecular spaces of CD columns using α-CD instead of γ-CD. Powder X-ray diffraction and solution-state 1H nuclear magnetic resonance measurements revealed that complexation followed ...

A fast and direct spectrophotometric method for the sequential determination of nitrate and nitrite at low concentrations in small volumes

The use of vanadium (III) has been proposed recently as a suitable alternative to cadmium for the reduction of NO3− to NO2− during spectrophotometric analysis. However, the methods proposed suffer from decreased sensitivity and additional steps for the measurements of nitrite and nitrate. We have developed an improved fast and sequential protocol that permits the determination of low concentrations of nitrite and nitrate in marine and freshwater samples using small volumes. NO2− concentration is firstly determined by using the common Griess reaction. The subsequent addition of a 2% VCl3 solution in 6N HCl in the same sample and the reaction at 60°C for 25min results in an efficient reduction of the NO3− to NO2− (>95%), which is also detected by the already added Griess reagents. The method has a detection limit <0.05μM, a high precision (ranging from 0.2 to 11%) and accuracy (0.07μM) for the determination of NO3−+NO2− concentrations lower than 30μM. Comparison of the proposed method with the established Cd column method using samples from a variety of environments (fresh water reservoir, sediment freeze lysable pore water, estuarine water samples and samples from an acid mine drainage impacted reservoir) showed good agreement between the two methods, with a difference between methods of 0.073±0.099μM. The analysis can be performed in large batches (~60 samples) by using small sample volumes (≤1mL) for the determination of both NO3− and NO2− in less than 1h.

Core Structures of Dislocations within CdTe Grains

ABSTRACTCdTe is well known as an excellent photovoltaic material for high efficiency solar cell applications because it has a direct band-gap, low fabrication cost and high optical absorption coefficient. However, the nonradiative recombination and low average minority carrier lifetime caused by the defects in CdTe solar cells limit its efficiency. So far, grain boundaries (GB) have been considered to be the major origin of the nonradiative recombination. However, we show that CdTe grains contain many dislocations that could limit device efficiency. Scanning transmission electron microscopy (STEM) was used to determine the atomic structure of intrinsic and extrinsic stacking faults and their terminating partial dislocation cores. Z-contrast images are sensitive to atomic number and are able to distinguish Cd and Te atomic columns. Unpaired Cd and Te atomic columns were found to form the partial dislocation cores, suggesting the presence of dangling bonds. These defects are likely to be electrically active, and may be the origin of the low minority carrier lifetime.

Gasoline Desulfurization with Two Catalytic Distillation Columns

A new approach was proposed to remove sulfuric compounds from fluid catalytic cracking (FCC) gasoline by combining an alkylation desulfurization catalytic distillation (ADCD) column with a hydrodesulfurization catalytic distillation (HDS-CD) column. In the ADCD column, isobutylene (IB) and 3-methylthiophene (3MT) were designated as the model compounds for olefin and sulfide, respectively; NKC-9 cation exchange resin was used as the catalyst. In the HDS-CD column, dibenzothiophene (DBT) was chosen as the model sulfides; Nickel phosphide supported on the TiO2-Al2O3 composite oxide prepared by our laboratory were designated as the HDS catalyst. Simulations for these two CD columns were carried out by RADFRAC module of Aspen Plus. The optimization results revealed that the ADCD column had an alkylation selectivity of 96%, and the sulfur content in the overhead stream was less than 8 μg/g. The simulation results of the HDS-CD process showed that the sulfide in the bottom stream of ADCD column can be removed practically by 100% and the clean oil stream from the bottom of HDS-CD column has hardly any sulfur.

Pressure and temperature transients of a cryogenic distillation system during abnormal operation or accidents

Cryogenic distillation system (CDS) is being employed, among other applications, in tritium separation technologies. CDS in combination with a Liquid Phase Catalytic Exchange (LPCE) process or with a Combined Electrolytic Catalytic Exchange (CECE) process is used for tritium removal/recovery from tritiated water. Large amounts of tritiated water can be produced during long time operation of CANDU reactors or in case of ITER mainly by the Detritiation System (DS). The CDS used to remove/recover tritium consists of a cascade of cryogenic distillation columns and a refrigeration unit which provides the cooling capacity for the condensers of CD columns. The columns, together with the condensers and the process heat-exchangers are accommodated in a vacuum insulated cold box. During abnormal events or accidents, significant amount of liquid hydrogen–deuterium–tritium or helium refrigerant can be spilt inside the cold box or even into the building. The paper analyzes some critical scenarios due to single failure mode or various combinations of failures such as: loss of refrigerant in the columns; loss of vacuum insulation; process liquid spilt into the cold box; refrigerant fails into cryogenic distillation columns.

Separation and identification of flavonoids from complex samples using off-line two-dimensional liquid chromatography tandem mass spectrometry

In this study, a LC-based identification strategy was proposed and off-line two-dimensional liquid chromatography was developed for the separation and identification of flavonoids from complex samples. The highly orthogonal separation system was composed of a CD column, an OEG column and an XTerra C(18) column. The CD column was employed for the first dimensional separation and the OEG column and XTerra C(18) column were used for the second dimensional separation in parallel. A mixture of six traditional Chinese medicines was used as a complex sample in testing this method. Unknown peaks were identified by matching their retention times and accurate mass molecular weights with those of references. The identification efficacy of parallel unidimensional liquid chromatography and off-line two-dimensional liquid chromatography was compared, and the latter was demonstrated to be more efficient for the identification of target compounds-especially co-eluted compounds or minor compounds from complex samples.

A new method for chemical identification based on orthogonal parallel liquid chromatography separation and accurate molecular weight confirmation

Recent advances in the theory and application of orthogonal LC separation have allowed for the establishment of a more effective method for the chemical identification of target compounds in complex samples, especially structurally similar compounds. In this study, a new chemical identification method based on orthogonal parallel separation and accurate molecular weight confirmation was developed. An orthogonal separation system consisting of an XTerra MS C 18 column, a home-made Click OEG column, and a Click CD column was established for separation and identification. In addition, 82 flavonoids were selected as references, to be used for the construction of a library. Retention times of each reference flavonoid on each column and accurate molecular weights were recorded and imported into a searchable library as “tags” for the unknown screening. For the method validation, two complex mixtures, fractions of Dalbergia odorifera T. Chen and Scutellaria baicalensis Georgi, specifically, were separated and identified. In total, nine compounds were unequivocally identified by retention time and confirmation of accurate molecular weight, demonstrating that this method is suitable and efficient for the chemical identification of complex samples.

Characterization of new R-naphthylethyl cyclofructan 6 chiral stationary phase and its comparison with R-naphthylethyl β-cyclodextrin-based column

Derivatized cyclofructans have been recently introduced as a new class of chiral selectors with great application potential. In this study, a R-naphthylethyl-functionalized cyclofructan 6 based chiral stationary phase (RN CF6 CSP) was used for separation of substituted binaphthyl catalysts in the normal phase HPLC mode. Dominant interaction types that play a role in the separation mechanism were revealed by a linear free energy relationship (LFER) method. In order to evaluate the contribution of the substituent on the cyclofructan structure to retention, the R-naphthylethyl-functionalized β-cyclodextrin (RN CD) CSP was chosen for comparison. Retention factors of 46 widely different solutes, with known solvation parameters, were determined on each of the columns under the same mobile phase compositions used for the enantiomeric separations. The LFER results showed that hydrogen bond acidity and polarity/polarizibility have the greatest impact on retention and enantioresolution on the RN CF6 CSP. The equal influence of the naphthylethyl substituent on the both CSPs was also confirmed while the effects of the basic cyclofructan versus cyclodextrin structures were different. The addition of trifluoroacetic acid to the hexane/propane-2-ol mobile phase was negligible on the RN CF6 CSP for the majority of atropoisomers except for one with ionizable functional groups. The RN CF6 column was shown to be more suitable for enantioseparation of the binaphthyl catalysts than the RN CD column. Higher retention offered by the latter CSP had no positive effect on the enantioresolution.

Off‐line 2‐D RPLC/RPLC method for separation of components in Dalbergia odorifera T. Chen

An off-line 2-D RPLC/RPLC system incorporating a beta-CD based column and a BEH C18 column was developed in the separation of components in Dalbergia odorifera T. Chen. (Jiang Xiang). Both orthogonality and van Deemter curves of the two columns were investigated. The orthogonality was about 57%, which was evaluated with 40 standard solutes. Optimized column efficiency could be achieved under optimal linear velocity (0.04 cm/s) on the CD column or under high linear velocity (0.32 cm/s) on the BEH C18 column. With the 2-D LC system, totally 637 peaks were separated in 114 fractions from the extraction of Jiang Xiang. Meanwhile, 19 flavanoids were tentatively identified from 114 fractions with Q-TOF MS. The results demonstrated the separation power of this 2-D LC system and further proved the high orthogonality between CD and C18 columns.

Séparation de molécules pharmaceutiques chirales par les techniques chromatographiques et électrophorétiques

A large number of pharmaceutical drugs possess one or more centers of asymmetry giving rise to enantiomers whose pharmacological properties and toxicity are often different. At successive stages of drug discovery, the enantiomers of any chiral molecule must be isolated and analyzed and their enantiomeric purity determined. The electrophoretic and chromatographic techniques have become the most important tools to routinely determine the enantiomeric purity of pharmaceutical molecules. Liquid chromatography (LC) is the most widely used because of the large number of columns marketed, the variety of selectivities available and the ease at which analytical results can be scaled up to the preparative level. In particular, more than 80% of enantioseparations of pharmaceutical molecules are successful with polysaccharide-derivative stationary phases (cellulose, amylose) for multiple system solvents (normal phase, polar organic phase or reverse phase). Complementary selectivities can be achieved more rapidly with other types of stationary phase (glycopeptides, Pirkle, cyclodextrins) but their application is hindered by problems of stability (proteins) or transfer to the preparative scale (cyclodextrins). At the present time, glycopeptide phases offer very promising prospects for the separation of amino acids (and derivatives) and peptide enantiomers. In addition, because of its faster analysis and environmental benefits, supercritical chromatography (SFC) has given rise to renewed interest. Capillary electrophoresis (CE) is an orthogonal technique complementary to chromatographic methods. Its principle involves the formation of diastereoisomer complexes after addition of anionic (HS-beta-CD, HS-gamma-CD CM-beta-CD) or neutral (TM-beta -CD, HP-beta-CD, DM-beta-CD, HP-gamma-CD) cyclodextrins to the running buffer. Compared to LC, CE analyses are cheaper (no chiral column, no solvent, low consumption of chiral selector) and peak efficiencies are higher by one order of magnitude. Furthermore, the mechanism of separation in CE is much simpler to understand and predict. However, the low capacity of CD column prevents its use at the preparative scale and consequently hampers its development as an analytical technique. Today, the increasing number of new drug candidate molecules produced daily, and for which the determination of enantiomeric purity is required before further development, encourages the pharmaceutical industry to seek fast chiral analysis methods based on simple protocols. The speed of analysis is more important than resolution. Thus, screening strategies are implemented with HPLC, SFC and CE including the selection of a limited number of chiral selectors with strong powers of chiral recognition.

Determinação de nitrato e nitrito em chás de peles de pescados empregados para tratamento de asma brônquica na região sul do Rio Grande do Sul

The objective of this paper was to determine nitrate and nitrite anions in toasted fish skin tea, which the population of southern Rio Grande do Sul believes to have pharmacological properties for trating asthma. Two methods were compared, an official and one described by Guozhen et al., that has the advantage of not needing reduction of nitrate to nitrite on a Cd column. The samples were the skin of the fish species Balistes capriscus (peixe porco) and Menticirrhus littoralis (papa-terra), both crude and toasted, as traditionally used. The method of Guozhen et al. was used due to its performance (detection limit 0.005 µmol/L NO3- and 0.02 µmol/L - NO2- and mean recuperation of 100 and 97% respectively for each anion) and results similar to those of the official methods under conditions used by the population, the estimated daily intake, of the teas is equivalent to 0.03 to 0.05 mg of nitrate and 0.007 to 0.014 mg of nitrite. These values are in accord with safety recommendations and don't represent a health risk.

Competitive transport of cadmium and lead through a natural porous medium: influence of the solid/liquid interface processes

Contaminated groundwater typically contains different metal contaminants which may compete with each other for the same adsorption sites. Understanding the fate of these micro-pollutants is of primary importance for the assessment of the risk associated with their dispersion in the environment and for the evaluation of the most appropriate remediation technology. In this regard, column techniques can be considered as useful tools both to perform transport experiments and to obtain equilibrium adsorption data without any perturbation of the actual solid/liquid interface. Cd and Pb monocomponent step column experiments were used to obtain adsorption isotherms on a natural aquifer material. A General Composite approach was used to define the equilibrium adsorption model characterized by two types of sites (ion-exchange and surface complexation sites). Coupling the adsorption model with the Advection-Dispersion equation (by IMPACT code) allowed us to well represent the monocomponent step experiments. The model was successfully used to predict the competitive Cd and Pb transport behaviour. Cd peaks of concentration due to Pb competition were experimentally observed and simulated by the model. This behaviour can be described only by an accurate modelling of the interaction and cannot be predicted by simple isotherms (such as Langmuir or Freundlich type).

Enantiomeric resolution of fluorous mixture by chiral CD columns: asymmetric reduction of a mixture of fluorous ketones

Asymmetric reduction of a mixture of four fluorous ketone analogues was carried out with ( R)-oxazaborolidine as a catalyst. The fluorous mixture products were resolved by a reverse phase HPLC with chiral β-cyclodextrin column to result in good separation of the enantiomers.

Migration of cadmium through a natural porous medium : Influence of the solid-liquid interface processes

Contaminated groundwater typically contains different metal contaminants which may compete with each other for the same adsorption sites. Understanding the fate of these micro-pollutants is of primary importance for the assessment of the risk associated to their dispersion in the environment and for the evaluation of the most appropriate remediation technology. By this regard, column techniques can be considered as a useful tool both to perform transport experiments and to obtain equilibrium adsorption data without any perturbation of the solid-liquid interface. Cd and Pb mono-component step column experiments were performed to obtain adsorption isotherms with a natural aquifer material. General Composite approach was used to define the equilibrium adsorption model characterised by two types of sites (ion-exchange and surface complexation sites). Coupling the adsorption model to the Advection-Dispersion equation (by IMPACT code) allowed to well represent the mono-component step experiments. The model was successfully used to predict the competitive Cd and Pb transport behaviour.

Chiral high-performance liquid chromatographic analysis of fluoxetine and norfluoxetine in rabbit plasma, urine, and vitreous humor using an acetylated beta-cyclodextrin column.

Fluoxetine (Prozac) is a potent selective serotonin reuptake inhibitor used for the treatment of major depression. Both fluoxetine (F) and its demethylated metabolite, norfluoxetine (NF), are racemic. S-Fluoxetine (SF) and S-norfluoxetine (SNF) are more potent inhibitors of serotonin reuptake than R-fluoxetine (RF) and R-norfluoxetine (RNF). Quantitation of individual enantiomers may provide a greater understanding of pharmacokinetic properties. The objective of this study was to perform a limited chiral selectivity study using rabbit plasma, urine, and vitreous humor analyzed by a solid-phase extraction protocol and a newly developed chiral analysis with an acetylated beta-cyclodextrin (CD) column. Liquid chromatographic parameters for CD were as follows: a mobile phase composition of methanol/0.3% triethylamine buffer, pH 5.6, (30:70), a flow rate of 1 mL/min, detection at 214 nm, and a temperature of 40 degrees C. Elution order was SNF, SF, RNF, and RF with capacity factors of 6, 7, 8, and 9, respectively. The corresponding resolution factors were as follows: R1,2 = 0.8, R2,3 = 1.2, and R3,4 = 0.9. The conditions for solid-phase extraction were optimized for Varian Bond Elut Certify columns. Following sample application, the column was rinsed with water, acetic acid, and then with methanol. Drug enantiomers were eluted with methylene chloride, isopropanol, and ammonium hydroxide (78:20:2). After extract evaporation, the extract residue was reconstituted for high-performance liquid chromatographic analysis. To investigate chiral pharmacology, a biodistribution study was performed by administering 2 mg/kg of F to five rabbits. Blood, urine, and vitreous specimens were collected. Plasma samples collected 45 min postinjection showed nearly equal concentrations of RF and SE After 24 h, the only metabolite detected in plasma was RNF. Drugs were not detectable in vitreous humor. Urine concentrations of SNF, SF, RNF, and RF were 51, 76, 34, and 8 microg/L, respectively. The CD column along with the described extraction protocol may be used for a chiral selectivity study of fluoxetine.

Reverse correlation between urine nitric oxide metabolites and insulin resistance in patients with type 2 diabetes mellitus.

We studied the possible relationship between nitric oxide (NO) production and insulin resistance in patients with type 2 diabetes mellitus. Urine NO metabolites (NOx) were measured as an index for NO production by HPLC combined with a Cd column, Griess reaction and a spectrophotometer in 403 healthy control subjects and 102 hospitalized patients with type 2 diabetes. Glucose infusion rate (GIR) was measured as a reverse index for insulin resistance by euglycemic glucose clamp study using an artificial pancreas in 20 of 102 diabetic patients. Urine NOx was lower in the patients with type 2 diabetes than in healthy control subjects (mean+/-SE: 3.18 +/-0.02 versus 3.25 +/-0.01 log[-micromol/gCr], p<0.01). Urine NOx was correlated with body mass index (BMI) in 102 diabetic patients (r= -0.372, p<0.001), but not related to either age, sex, fasting plasma glucose, HbA1c or blood pressure. Urine NOx was correlated with GIR independent of BMI in 20 diabetic patients (r=0.774, P<0.0001). These findings suggest that NO production is closely related with insulin resistance in patients with type 2 diabetes.

A study of mass transfer behaviour in a catalytic distillation column

AbstractCatalytic distillation (CD) is a process where reaction and separation take place simultaneously in a distillation column. Recently, a new CD process for the aldol condensation of acetone to diacetone alcohol and mesityl oxide was developed in our laboratory. Owing to the unique structure used to support catalysts in the CD column, mass transfer data are needed to model the CD process. The mass transfer behaviour in the CD column has been studied both for the reactive and non‐reactive sections of the column in our laboratory. Based on the experimental results, general correlations for the mass transfer coefficients have been established and the 95% confidence intervals for the associated parameters were obtained. The experimental results indicated that the catalyst bags did not play a significant role for the separation between the vapour and liquid phases. The mass transfer correlations developed in this study have been used successfully to model the CD process for the aldol condensation of acetone carried out in our laboratory.

The analysis of nitrate in highly saline waters

The analysis of nitrate in seawater and hypersaline waters should take account of a significant “salt effect”. Procedures developed for fresh water and marine waters must be applied cautiously to highly saline waters. The most widely used standard method for the determination of nitrate-nitrogen (NO3-N) in fresh and marine waters involves the quantitative reduction of nitrate by the Cd column technique followed by colorimetric procedures. In our study, three approaches to estimate NO3-N in highly saline waters were examined. The first involved dilution. This approach overcame the salt effect but dilution limited the detection of low concentrations of nitrate in highly saline waters. The second involved the use of standard nitrate solutions in saline water. This method is not recommended because of nitrate impurities in AR grade salts. The third- and preferred approach-involved the use of standard additions. “Spikes” of a known volume of NO3-N standard solution were added to natural saline waters. Nitrate values estimated by the stadard addition method were used to calculate an equation for salt error correction at different salinities applicable to waters with the same relative ionic composition as seawater. This could then be used to correct nitrate determinations in highly saline waters where standards made in distilled water were used for calibration. Many previously published data for NO3-N in saline water used methods of analysis which do not take account of salt error and are therefore probably in error.

Preparation and chromatographic characteristics of a chiral-recognizing perphenylated cyclodextrin column

A novel bifunctional chiral recognizing column (PhCD column) was prepared by immobilizing, on silica gel, β-cyclodextrin (CD) which was perphenylated through the reaction of phenyl isocyanate. Using several enantiomeric compounds, chiral recognition by CD was determined to be maintained in a PhCD column. The chromatographic characteristics of a PhCD column were compared with those of a column (CD column) bound with underivatized CD, and the following properties were found. For polyaromatic compounds and alkylbenzene derivatives, hydrophobic interaction is predominant, and for phenylalkyl alcohols and amines whose enatiomers are hard to recognize on a CD column, specific enantioselectivity was exhibited under the effects of the chemical structure around the chiral centre of the solutes. This added function is possibly an induced fit caused by the phenyl cluster on the CD openings. Using these properties, various enantiomeric drugs, in particular β-blockers (amino alcohols), which are hardly separated on conventional chiral separation columns, could be separated.