Fractions collected from humic acids under acidic and basic conditions were immobilized on silica gel and used as adsorbents for a variety of agricultural pesticide compounds bearing a single carboxyl functional group and biogenic amines in acetonitrile. Among these compounds examined under the same conditions, the percentage of adsorption varies considerably from 0 to almost 100%. The percentage is found to be highly related to the structure of the analyte and the type of functional group attached to it. The adsorption, better performed on adsorbent immobilized with the fraction collected under acidic conditions, is believed to result from the reversible interaction between the functional moieties of the analyte and humic acids (e.g., amino or carboxyl group of analyte vs carboxyl group of humic acids, etc.) as no adsorption is observed under the same conditions for analytes that are derivatives of alcohol, amide, and ester. Given the nature of the analyte, the time needed to reach the maximum percent of adsorption decreases as the amount of adsorbent is increased. Also, the longer the time that has elapsed, the higher the percentage of analyte adsorbed, thus indicating that the adsorption process is surface-oriented. Factors such as the acidic or basic origin of the additive in the liquid phase of the matrix also affect the percentage of analyte adsorbed.

Fractions collected from humic acid (HA) under acidic conditions and used as adsorbents for various agricultural organophosphate pesticides in hexane are immobilized on silica gel. For most organophosphate analytes examined in this study under the same conditions, the percentage of adsorption achieved nearly 100 % in 1 h and was found to be highly relevant to the structure of the analyte and the type of interaction that occurred between the functional groups attached to it and HA. The interaction leading to adsorption between the functional moieties of the analyte and HA (e.g., P−O or S bond of analyte vs carboxyl group of HA) is believed to be reversible and dipole−dipole oriented and is significantly enhanced in hexane. The enhancement of π−π interaction, even hydrogen bonding in some cases, was also observed in hexane and contributed to the percentage of adsorption to a certain degree. However, the interaction is subject to the steric hindrance effect caused by the bulky group or element surrounding the phosphorus element. Considering the nature of the analyte, the time required to reach the maximum percentage of adsorption is decreased as the amount of adsorbent is increased. Furthermore, the adsorption process is surface oriented because the longer the time that is elapsed, the higher the percent of the analyte that is adsorbed. Factors such as the type of liquid phase or the acidic or basic origin of the additive in the liquid phase of the matrix also affect the adsorption percentage of analyte.

No abstract

A fraction of humic acid is collected under acidic conditions, then immobilized on silica gel and used as the adsorbent for various symmetrical triazine (s-triazine) derivatives in hexane. The enhanced hydrogen bonding between the analyte and humic fraction molecules, not the complexation interaction, is responsible for the adsorption observed in hexane, based on Fourier transform infrared (FTIR) spectroscopy results. The percentage of adsorption in hexane for all s-triazine derivatives reaches nearly 100% in 1 h, independent of the type, position, and size of the substituent on the aromatic nitrogen heterocyclic ring. Other factors leading to the variation of the percentage of adsorption include the type of liquid phase and the additive of acidic or basic origin present in the matrix.

Humic fraction (HF) collected under acidic conditions and used as an adsorbent for various phosphate-based plasticizers in hexane is immobilized on silica gel. Most plasticizer analytes examined in this study under the same conditions achieved adsorption percentages above 90% in 1 h based on the difference in peak area. The Fourier transform infrared (FTIR) spectroscopy results indicate that the interaction leading to the adsorptions between the functional moieties of the analyte and HF (e.g., the carboxylate group of analyte against the carboxyl group of HF) is specific, reversible, and dipole-dipole-oriented. Moreover, it is significantly enhanced by hexane. However, the π−π interaction (even hydrogen bonding in all cases) was either not as significant or absent in hexane and, therefore, contributed little or nothing to the percentage of adsorption. The interaction is highly affected by the acidic or basic origin of the additive introduced to the liquid phase of the matrix, and it is subject to the steric hindrance effect caused by the bulky alkyl groups attached to ether linkages and the relative position of the two ether bonds on the aromatic moiety of the analyte. The pre-concentration of the analyte and, thus, the recycle of the adsorbent can be achieved by adsorbing and, subsequently, desorbing it in a different solvent, such as acetonitrile. Furthermore, the adsorption process is surface-oriented because of its dependence upon both time and the amount of adsorbent.

A lignin-based adsorbent for metallic ions, nanoparticles and various agricultural organophosphate pesticides in hexane is immobilized on silica gel without further fractional purification. For most organophosphate analytes examined in this study under the same conditions, the percentage of adsorption achieved was well above 90% in 15 min, was found to be highly related to the dipole-dipole attractions that occurred among the oxygen-containing functional groups attached to analyte and lignin molecules and was greatly enhanced in hexane. The adsorption is believed to be reversible and surface oriented; furthermore, the interaction leading to the adsorption is not as significantly subject to the steric hindrance effect caused by the bulky group or elements surrounding the phosphorus element. Other types of interactions enhanced in hexane, such as the p-p interaction, and hydrogen bonding in some cases, were also observed and contributed less to the percentage of adsorption. However, the adsorption of ions and nanoparticles under aqueous conditions is thought to be mainly a result of the complexation of the oxygen-bearing hydrophobic cleft of the lignin molecule. In all cases, the nature of the analyte, the amount of adsorbent and the acidic or basic origin of the additive in matrix also affect the percentage of adsorption.

A variety of compounds containing amines (i.e., amino acids, amino alcohols, etc.) were chemically derivatized with a variety of electrophilic tagging reagents to elucidate the chiral recognition sites on a teicoplanin-bonded chiral stationary phase (CSP) and on R-naphthylethylcarbamate-beta-cyclodextrin (RN-beta-CD)-bonded CSP. Solutes were separated under optimum chromatographic conditions on teicoplanin and RN-beta-CD CSPs for comparison using an acetonitrile-based mobile phase. It was noted that the size of the analyte or tagging reagent exerted a greater influence on compounds separated on teicoplanin than on RN-beta-CD when using the polar organic mode. This suggests that chiral recognition on teicoplanin CSP is more sensitive to size and indicates that the hydrophobic pocket of teicoplanin plays a significant role in chiral recognition in this mode. However, the type of functional groups had a greater impact than the size of analyte on separations obtained from RN-beta-CD phase in the polar-organic mode. Specifically, the pi-pi interaction was enhanced by derivatizing the aromatic ring of the tagging reagent with electron-withdrawing groups and thus altered the resolution substantially. For both phases, chiral recognition is most pronounced when the stereogenic center of the analyte is near the tagging moiety and surrounded by functional groups (e.g., carboxylic, etc.) which are favorable for hydrogen bonding.

A variety of silica-based solid phases, whose surfaces are functionalized with ligands containing sulfur and nitrogen elements, are used as self-supporting adsorbents for environmental remediation evaluation and potential separation application. Each adsorbent is tested for its ability to scavenge five metallic ions: Hg 2+ , Cu 2+ , Cd 2+ , Mn 2+ , Pb 2+ , and two organometallic ions: ethylmercury and phenylmercury, from independent homoionic solutions at both neutral and acidic pH values. The results indicate that the percentage of these ions scavenged by a given adsorbent varies, and is found to be highly related to the structural environment in the vicinity of the sulfur and nitrogen elements on the ligand. It is believed that the scavenging of metallic ions is a result of the complexation formation between the metallic ions and the ligands containing sulfur and nitrogen elements, and is not due to the irreversible association chemistry with the sulfur or nitrogen element itself. In the case of organometallic ions, a p-p interaction is thought to be involved in the adsorption with ligands containing an aromatic moiety in addition to the aforementioned forces. The time needed to reach the maximum percent of adsorption decreases as the amount of adsorbent increases. The longer the adsorption time, the higher percent of ion is removed. Other factors, such as the temperature and the acidity in the liquid phase of the matrix affect the percentage of ions scavenged as well.