HPLC Retention Behaviors of Poly-aromatic-hydrocarbones on Cu(II)-octabromotetrakis(4-carboxyphenyl)porphine Derivatives-Immobilized Aminopropyl Silica Gels in Polar and Non-Polar Eluents

Abstract

HPLC is conventionally used for separation and/or analysis of substances such as medicines, mutagens, environmental pollutants, and the like, which are broadly present in the circumstances. [1][2][3][4][5][6] For such a purpose, an octadecylsilyl silica gel column has still been used as a stationary phase for a preparative purpose. [7][8][9] On the other hand, it has been attempted to separate and/or analyze these substances making use of interactions involving p electron because the substances to be separated or analyzed include poly-aromatichydrocarbons (PAHs) and heterocyclic compounds abundantly. As one of approaches, stationary phases having an ability to interact with PAHs through p electron, that is, stationary phases composed of a support carrying a compound with p electron have been developed. 10) Currently, there are commercially available columns in this form, such as a PYE column whose stationary phase comprises a 2-(1-pyrenyl)ethyl group. The applicability to the separation of PAHs and the like has already been reported. 6,10,11) Metal porphyrin analogs such as metal porphyrin or metal phthalocyanine belong to macrocyclic compounds having a wide spread of p electron cloud. Cu-porphyrin-immobilized silica gels have been reported to be useful as an HPLC stationary phase for separation of compounds having p electron such as PAHs. [12][13][14][15] In addition, columns having ability to exert both the p electronic-and electrostatic-interactions such as a pentabromobenzyloxy propylsilyl silica gel column (PBB column) 16) and a nitrophenylethylsilyl silica gel column (NPE column) 17) have been developed and made commercially available to date.In view of the above, we reached the conception that a novel stationary phase for PAHs and its analogous compounds may be obtained by brominating Cu-tetrakis(4-carboxyphenyl)porphine (Cu-TCPP, see Fig. 1) 18) known to show p-p electron interactions with PAHs, because bromination would destroy the planarity of porphyrin ring and change the polarity, thereby providing Cu-TCPP with an ability to exert additional interaction(s), as is the case with PBB column. In the present research, we prepared silica gels immobilizing Cu-octabromotetrakis(4-carboxyphenyl)porphine derivatives to give a prospective stationary phase (Cu-OBTCPP D ), and elucidated their retention property from various aspects. The research revealed that Cu-OBTCPP D has excellent function based on interactions involving p electron, electrostatic force, and the like, as explained in more detail below. ExperimentalChemicals and Reagents Tetrakis-(4-carboxyphenyl)porphine (H 2 -TCPP) was obtained from Tokyo Kasei, Japan. As a support, Develosil NH 2 -5 (hereinafter, referred to as "Dev"), which is spherical aminopropyl-silica gels (particle size, 5 mm; specific surface area, 250 m 2 /g; average pore size, 12 nm, amino-group; 98 mmol/g) was purchased from Nomura Kagaku, Japan. As eluents, purified water by Labo IonPure-12 (Millipore, U.S.A.), methanol and n-hexane for HPLC (Nacalai Tesque, Japan) were mainly...

Aggregation and adsorption of reactive dyes in the presence of an anionic surfactant on mesoporous aminopropyl silica

“…The modification results in products that carry on their surfaces new functional groups capable of interacting with various organic compounds [8]. For example, applications of aminosilanesilica can be found in HPLC retention of polyaromatic hydrocarbons [9], immobilization of electrochemically active Ru complexes [10], and catalytic applications for flavanone syntheses [11]. Aminopropylsilane silica has also been used with increasing frequency as a coupling agent in pigment or organic dye systems [12].…”

Catalytic Activity of Silica Gels Bound Manganese(III)-Porphyrin on Oxidative Reaction of Adrenaline

“…HPLC system was constructed with a JASCO pump (PU-980), a UV/V detector (UV-970) and a Capsellpak packed column (5C 18 ) were prepared by using a similar procedure described in our previous studies for HPLC stationary phase. 13,14) Mn-TSPP resin (20 mmol Mn-TSPP per 1 g of IRA 900) was also prepared as described in the literatures, 12,15) except that the amount of TSPP used for immobilization was two fifths of that used in the previous literatures and was equivalent to that used in the preparation M-TSPP silica . No elution of metal-porphyrins was observed when the M-TSPP resin , M-TCPP silica or M-TCPP glass was shaken with water and/or buffer solutions.…”