Probing the Association Behavior of Hydrophobic Organic Compounds with Dissolved Humic Materials

The association mechanism between hydrophobic organic compounds (HOC) and dissolved humic materials (DHM) has continued to be one of the interesting areas in environmental applications. The goal of the research reported in this dissertation is to investigate the association behavior of HOC with DHM. The first part of this research involves steady-state fluorescence measurements of these multi-component systems to study the effect of DHM content on the association mechanism of HOC, in particular using pyrene as a model. Results showed that steady-state fluorescence alone may not provide enough information about the quenching mechanism of pyrene with DHM. Lifetime based fluorescence measurements allow for a deeper mechanistic understanding as compared to the traditional steady-state technique. However, photobleaching, dissolved oxygen, and HOC adsorption to cell walls are problems encountered in lifetime measurements. These effects can directly complicate the interpretation of fluorescence lifetime results. Therefore, a new approach to frequency-domain lifetime measurements, based on frequency segmentation and recombination, was developed during the second part of this dissertation research to address these experimental considerations. The frequency segmentation and recombination method was evaluated using a simple two component system consisting of fluorescein and rhodamine B mixture. Comparison of experimental data collected in traditional and segmented fashion with simulated data demonstrated the validity of the technique. The newly developed method was applied to mixtures of pyrene and DHM to further investigate the pyrene quenching mechanism with DHM. Finally, the chemical effect of chiral pesticides (coumachlor, difenacoum, warfarin, and napropamide) in the presence of Leonardite humic acid standard (LHAS) was investigated by use of steady-state fluorescence spectroscopy. In addition, the chiral recognition ability and enantiomeric selectivity of LHAS with pure enantiomers of 1,1\u27-bi-2-naphthol bis (trifluoro - methanesulfonate) and 1-(9-anthryl)-2,2,2-trifluoroethanol, used as probes of the interaction, were investigated using liquid-state 19F NMR spectroscopy. To further study DHM enantioselectivity with chiral compounds, the interaction of R or S-1-(9-anthryl)-2,2,2-trifluoroethanol with LHAS was evaluated for samples monitored in the dark and exposed to light for different time periods by use of high performance liquid chromatography

Study of isotherm and kinetic models of lanthanum adsorption on activated carbon loaded with recently synthesized Schiff’s base

AbstractA new effective adsorbent was developed for a selective extraction and determination of lanthanum from aqueous media by use of inductively coupled plasma-optical emission spectrometry. The new adsorbent was based on activated carbon modified with Schiff’s base derived from diethylenetriamine and 3,4-dihydroxybenzaldehyde (AC-DETADHBA). Isotherm and kinetic models were systematically investigated to evaluate the analytical potential of the AC-DETADHBA phase toward La(III) by employing a batch adsorption technique. Surface properties of AC-DETADHBA were characterized by Fourier transform infrared spectrometry. The maximum static adsorption capacity was determined to be 144.80mgg−1 at pH 6, providing that the adsorption capacity of La(III) was improved by 61.79% with the AC-DETADHBA phase as compared to the carboxylic acid derivative of activated carbon after only 1h contact time. Adsorption isotherm results demonstrated that the adsorption process was mainly monolayer on a homogeneous adsorbent surface, confirming the validity of Langmuir adsorption isotherm model. Data obtained from kinetic models study indicated that the adsorption of La(III) onto the AC-DETADHBA phase obeyed a pseudo second-order kinetic model. In addition, results of thermodynamic investigation also revealed that the adsorption mechanism of AC-DETADHBA toward La(III) is a general spontaneous process and favorable. The effect of several coexisting metal ions displayed that the recovery of La(III) was not affected by the medium composition containing either individual or mixed metals. Finally, the newly proposed method gave satisfactory results for the determination of La(III) in environmental water samples

Kinetic modeling, optimization of biomass and astaxanthin production in Spirogyra sp. under nitrogen and phosphorus deficiency

This study studied the optimum nitrogen (N) and phosphorus (P) concentrations for biomass and astaxanthin production in Spirogyra sp. Spirogyra sp. was cultivated in Blue Green (BG) medium with N/P concentrations adjusted to 1.1/0.01; 1.1/0.03; 1.1/06; 1.1/0.09; 2.2/0.01; 2.2/0.03; 2.2/0.06; 2.2/0.09; 4.4/0.01; 4.4/0.03; 4.4/0.06; 4.4/0.09, 6.6/0.01; 6.6/0.03; 6.6/0.06 and 6.6/0.09 mM. The results showed an increase in biomass accumulation for lower concen‐ trations of N and N:P ratio with the highest accumulation at N/P 1.1/0.03 mM, i.e. 485 mgdryweight and a growth rate of 0.22 d‐1. Astaxanthin accumulation was also found to increase, with the highest at N/P 1.1/0.01 mM, i.e. 0.269 mg/gdryweight, on the 12th day of cultivation. Based on biomass and astaxanthin accumulation, the highest astaxanthin productivity was 0.07 μg/cm2/d at N/P concentration 1.1/0.09 mM. Kinetic models were developed using the Haldane and Luedeking–Piret equations. The growth and astaxanthin production parameters obtained were μmax 0.18±0.02 d‐1, kN 68.2 ± 24.2 mg/L, ki 301.8 ± 78.5 mg/L, YN 0.93 ± 0.68 gbiomass/nitrate, α 0.36 ± 0.69, β ‐0.01 ± 0.02, and kA 0.04 ± 0.03, thus indicating that a lower N concentration is suitable for the cultivation of Spirogyra sp. In conclusion, Spirogyra sp. should be cultivated under nitrogen deficiency for continuous astaxanthin production

Chiral Recognition of Amino Acids by Use of a Fluorescent Resorcinarene

The spectroscopic properties of a chiral boronic acid based resorcinarene macrocycle employed for chiral analysis were investigated. Specifically, the emission and excitation characteristics of tetraarylboronate resorcinarene macrocycle (TBRM) and its quantum yield were evaluated. The chiral selector TBRM was investigated as a chiral reagent for the enantiomeric discrimination of amino acids using steady-state fluorescence spectroscopy. Chiral recognition of amino acids in the presence of the macrocycle was based on diastereomeric complexes. Results demonstrated that TBRM had better chiral discrimination ability for lysine as compared to the other amino acids. Partial least squares regression modeling (PLS-1) of spectral data for macrocycle-lysine guest-host complexes was used to correlate the changes in the fluorescence emission for a set of calibration samples consisting of TBRM in the presence of varying enantiomeric compositions of lysine. In addition, validation studies were performed using an independently prepared set of samples with different enantiomeric compositions of lysine. The results of multivariate regression modeling indicated good prediction ability of lysine, which was confirmed by a root mean square percent relative error (RMS%RE) of 5.8%

Efficient synthesis and characterization of Polyaniline@Aluminium–succinate metal-organic frameworks nanocomposite and its application for Zn(II) ion sensing

A new class of conductive metal-organic framework (MOF), polyaniline- aluminum succinate (PANI@Al-SA) nanocomposite was prepared by oxidative polymerization of aniline monomer using potassium persulfate as an oxidant. Several analytical techniques such as FTIR, FE-SEM, EDX, XRD, XPS and TGA-DTA were utilized to characterize the obtained MOFs nanocomposite. DC electrical conductivity of polymer-MOFs was determined by four probe method. A bare glassy carbon electrode (GCE) was modified by nafion/PANI@Al-SA, and examined for Zn (II) ion detection. Modified electrode showed improved efficiency by 91.9%. The modified electrode (PANI@Al-SA/nafion/GCE) exhibited good catalytic property and highly selectivity towards Zn(II) ion. A linear dynamic range of 2.8–228.6 µM was obtained with detection limit of LOD 0.59 µM and excellent sensitivity of 7.14 µA µM−1 cm−2. The designed procedure for Zn (II) ion detection in real sample exhibited good stability in terms of repeatability, reproducibility and not affected by likely interferents. Therefore, the developed procedure is promising for quantification of Zn(II) ion in real samples

Development of Polymer Based Nanocomposites as a Marker of Cadmium in Complex Matrices

Poly(propylene carbonate)/β-cyclodextrin (PPC-BCD) nanocomposites were developed as effective extractor for a specific extraction and separation of cadmium(II) by use of inductively coupled plasma-optical emission spectrometry. The selectivity of nanocomposites with different wt% of BCD (PPC-BCD 0.5, PPC-BCD 1, PPC-BCD 3, PPC-BCD 5, or PPC-BCD 10) was investigated toward Cd(II). Based on selectivity and pH studies, Cd(II) was the most quantitatively adsorbed on PPC-BCD 5 phase at pH 6, indicating that PPC-BCD 5 was the most selective toward Cd(II) among other nanocomposites. On the basis of adsorption isotherm study, the superior adsorption capacity of PPC-BCD 5 phase for Cd(II) was found to be 149.25 mg·g−1, following the Langmuir adsorption isotherm model. The kinetic of adsorption for Cd(II) has been examined by pseudo-first- and second-order models. The kinetic exploration suggested a pseudo-second-order kinetic model for the adsorption of Cd(II) on the PPC-BCD 5. Additionally, results of thermodynamic investigation demonstrated favorable spontaneous process for the adsorption mechanism of PPC-BCD 5 toward Cd(II)

Efficient synthesis and characterization of Polyaniline@Aluminium–succinate metal-organic frameworks nanocomposite and its application for Zn(II) ion sensing

A new class of conductive metal-organic framework (MOF), polyaniline- aluminum succinate (PANI@Al-SA) nanocomposite was prepared by oxidative polymerization of aniline monomer using potassium persulfate as an oxidant. Several analytical techniques such as FTIR, FE-SEM, EDX, XRD, XPS and TGA-DTA were utilized to characterize the obtained MOFs nanocomposite. DC electrical conductivity of polymer-MOFs was determined by four probe method. A bare glassy carbon electrode (GCE) was modified by nafion/PANI@Al-SA, and examined for Zn (II) ion detection. Modified electrode showed improved efficiency by 91.9%. The modified electrode (PANI@Al-SA/nafion/GCE) exhibited good catalytic property and highly selectivity towards Zn(II) ion. A linear dynamic range of 2.8–228.6 µM was obtained with detection limit of LOD 0.59 µM and excellent sensitivity of 7.14 µA µM−1 cm−2. The designed procedure for Zn (II) ion detection in real sample exhibited good stability in terms of repeatability, reproducibility and not affected by likely interferents. Therefore, the developed procedure is promising for quantification of Zn(II) ion in real samples

Efficient synthesis and characterization of Polyaniline@Aluminium–succinate metal-organic frameworks nanocomposite and its application for Zn(II) ion sensing

A new class of conductive metal-organic framework (MOF), polyaniline- aluminum succinate (PANI@Al-SA) nanocomposite was prepared by oxidative polymerization of aniline monomer using potassium persulfate as an oxidant. Several analytical techniques such as FTIR, FE-SEM, EDX, XRD, XPS and TGA-DTA were utilized to characterize the obtained MOFs nanocomposite. DC electrical conductivity of polymer-MOFs was determined by four probe method. A bare glassy carbon electrode (GCE) was modified by nafion/PANI@Al-SA, and examined for Zn (II) ion detection. Modified electrode showed improved efficiency by 91.9%. The modified electrode (PANI@Al-SA/nafion/GCE) exhibited good catalytic property and highly selectivity towards Zn(II) ion. A linear dynamic range of 2.8–228.6 µM was obtained with detection limit of LOD 0.59 µM and excellent sensitivity of 7.14 µA µM−1 cm−2. The designed procedure for Zn (II) ion detection in real sample exhibited good stability in terms of repeatability, reproducibility and not affected by likely interferents. Therefore, the developed procedure is promising for quantification of Zn(II) ion in real samples

Efficient synthesis and characterization of Polyaniline@Aluminium–succinate metal-organic frameworks nanocomposite and its application for Zn(II) ion sensing

A new class of conductive metal-organic framework (MOF), polyaniline- aluminum succinate (PANI@Al-SA) nanocomposite was prepared by oxidative polymerization of aniline monomer using potassium persulfate as an oxidant. Several analytical techniques such as FTIR, FE-SEM, EDX, XRD, XPS and TGA-DTA were utilized to characterize the obtained MOFs nanocomposite. DC electrical conductivity of polymer-MOFs was determined by four probe method. A bare glassy carbon electrode (GCE) was modified by nafion/PANI@Al-SA, and examined for Zn (II) ion detection. Modified electrode showed improved efficiency by 91.9%. The modified electrode (PANI@Al-SA/nafion/GCE) exhibited good catalytic property and highly selectivity towards Zn(II) ion. A linear dynamic range of 2.8–228.6 µM was obtained with detection limit of LOD 0.59 µM and excellent sensitivity of 7.14 µA µM−1 cm−2. The designed procedure for Zn (II) ion detection in real sample exhibited good stability in terms of repeatability, reproducibility and not affected by likely interferents. Therefore, the developed procedure is promising for quantification of Zn(II) ion in real samples