In this study, the adsorption of lignin-modified silica gel after association with six different organophenylmercuric compounds in chloroform was investigated. Adsorption reached approximately 90% of the maximum value within 15 min. The adsorption capacity, Fourier transform infrared spectroscopy, and interaction simulation results indicated that the adsorption proportion resulted from the strong dipole-dipole interaction between the lignin and analyte molecules, and was considered to be size- and structure-dependent. However, the π-π complexation interaction arising from the acidic aromatic moiety of the analyte, which was significant in an apolar environment, was not the major force responsible for the resulting adsorption. Additives, such as acid or ether, which competed with the analyte for the binding site on the lignin molecule, were not beneficial to the interaction, and thus not beneficial to the adsorption processes.
In this paper, we investigate the fluorescence quenching of acidic humic-fractionmodified silica gel in the solid state after association with a variety of pesticidal analytes in hexane and acetonitrile. The percentage of fluorescence quenching is found to be dependent on the contact time and linearly on the number of moles of analyte involved in the association process. However, any π-π complexation interaction arising from the acidic aromatic ring on the analyte due to the derivatization of a bulky electron-withdrawing group is not observed. Also, any mechanism leading to adsorption or any quenching process occurring as a result of the steric hindrance obtained by a theoretical interaction simulation is not observed. The Fourier transform infrared (FTIR) data and simulation results, instead, suggest that electron-rich atoms on the analyte, such as oxygen, sulfur, nitrogen, and phosphorus, are responsible for fluorescence quenching, following dipole-dipole interaction with the humic-fraction-modified adsorbent. K E Y W O R D S electron-rich atom, electron-withdrawing group, fluorescence quenching, humicfraction-modified silica gel, theoretical interaction simulation, π-π complexation 1 | INTRODUCTIONThe oxygen molecule is one of the most efficient collisional quenchers because it quenches almost all known fluorophores. [1] Other collisional quenchers, such as aromatic and aliphatic amines, are also efficient for most unsubstituted aromatic hydrocarbons. Other types of collisional quenchers are heavy atoms such as iodine and bromine. However, for larger halogens such as these, in contrast to intersystem crossing to an excited triplet state, a requirement for collisional quenching may be the quenching mechanism rather than molecular contact. For chlorinated hydrocarbons and electron scavengers, such as the proton and divalent ions such as Cu 2+ , the fluorophore is quenched by the withdrawal of an electron. A typical example is the fluorescence quenching of humic acid in the presence of several divalent ions such as Cu 2+ , Al 2+ , Mg 2+ , Mn 2+ , Zn 2+ , and Ni 2+ . [2][3][4][5][6][7][8] The effect of pH on the fluorescence spectra of humic acidlike soil fungal polymers has also been investigated. [9] In this study, we measured the fluorescence quenching of humic-fraction-modified silica gel in the solid state before and after the adsorption of various pesticidal analytes in haxane and acetonitrile. Based on the quenching results, a quantitative analysis was conducted on the percentage of fluorescence quenching, which was dependent on the contact time. The relevance of the number of moles of analyte involved in the quenching process was also considered. Finally, Fourier transform infrared (FTIR) data were collected to clarify the mechanism of solid-state fluorescence quenching.
This paper reports the isocratic resolution of 10 fluoroquinolone-based antibiotics and their precursors on the phenylethyl-bonded phase under the elution of the nonaqueous mobile phase composed of acetonitrile, methanol, acetic acid, and triethylamine. Most of the analytes were baseline resolved within 10 minutes. The interaction simulation and Fourier-transform infrared spectroscopy (FTIR) data indicated that the carbonyl-containing group, a secondary or tertiary amine of an analyte, was heavily involved in the retention, resulting in retention with residual silanol groups on the stationary phase. In some cases, the elution reversal or resolution enhancement of analytes was observed when the volume of acidic or basic additive in the mobile phase was dominant. However, the π-π complexation interaction between the fluorine-attached phenyl group of the analyte and the phenylethyl moiety on the stationary phase was not observed. Consequently, the resolution could not be reproduced either on the other stationary phase modified with C18, phenyl, or phenylhexyl moiety under the same chromatographic conditions or under the aqueous elution.
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