Solid State Sciences 4 (2002) 851858 www.elsevier.

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Metal oxide modication via transition metal complexes: hybrid materials characterizations and potential applications in molecular recognition
Olivier Bordelanne a,b , Marie-Hlne Delville a,
a Institut de Chimie de la Matire Condense de Bordeaux, CNRS, UPR 9048, avenue du Dr. A. Schweitzer, F-33608 Pessac cedex, France b Laboratoire dAnalyse Chimique par Reconnaissance Molculaire, ENSCPB, avenue Pey-Berland, B.P. 108, F-33402 Talence, France

Received 7 January 2002; accepted 14 February 2002

Abstract Transition metal complexes were grafted onto silicon oxide particles and fully characterized by DRIFT, XPS, SEM spectroscopies were used for two tailored purposes: (i) as modiers of inorganic materials for molecular recognition and differentiation and (ii) as potential contrast agents for X-ray mapping in SEM to localize the variation of porosity in materials volume. 2002 ditions scientiques et mdicales Elsevier SAS. All rights reserved.

1. Introduction Inorganic materials based on metal oxides are known to exhibit new relevant properties when modied with organic derivatives leading to hybrid materials [1]. On the other way, transition metals are also known in organometallic chemistry (i) to modify on request the electronic density of aromatic systems to which they are covalently bonded and (ii) to be sensitive to any modication of these -systems. This is particularly true in the case transition metal complexes such as metallocenes and their derivatives and explains why, for nearly fty years, transition metal metallocenes have been extensively studied and applied to a whole host of different elds. Two metallocenes, in particular, ferrocene [2ac] and cobalticinium [2d], have attracted special attention. They were, for example, used for anion recognition [3] and incorporated within complex structures, to serve as versatile building blocks for numerous, specically tailored substrates. These neutral-decient or positively charged abiotic organometallic receptors [4], are able, when used as electrochemical sensors, to non-covalently bind [5], and therefore detect and discriminate between inorganic anions of biochemical, medical and environmental interest placed in solution. In this paper, we show that this capability of recognition can also be used once the complexes are immobilized on
* Correspondence and reprints.

E-mail address: delville@icmcb.u-bordeaux.fr (M.-H. Delville).

solid materials. The use of organometallic complexes to covalently modify the surface of mineral oxides such as silica is a eld of research [6] in which, most often, the transition metal complex is immobilized during the solgel process of the oxide synthesis [7] and/or used as a template [8]. Another process consists in grafting onto the preformed inorganic substrate [9], the desired electron acceptor transition metal complexes [10]. We, therefore, report the synthesis and physical characterizations (DRIFTS, XPS, Auger, SEM) of so-called organometallic/inorganic hybrid materials based on the modication of porous silica particles by metallocenic complexes as chlorocarbonylferrocene and chlorocarbonylcobalticinium. Indeed, these organometallic fragments through their metal ion can act as contrast agents for X-ray mapping in SEM studies and therefore label the topography and areas of low or high density in materials (visualization of channel for example). Besides their ability to recognize ionic species, these materials are also susceptible to induce the detection, the recognition and the separation of non-ionic species such as neutral electron-rich polynuclear -aromatic hydrocarbon (PAH) derivatives, which is the second relevant point of this work. Indeed, as far as molecular recognition is concerned, these sandwich complexes, when neutral, exhibit a -aromatic system able to interact selectively with aromatic molecules via interactions of the two molecules (formation of a charge transfer complex). An additional positive charge as in the case of the Cobalt complex will decrease the charge density on the cyclopentadienyl (5 -C5 H5 ) lig-

1293-2558/02/$ see front matter 2002 ditions scientiques et mdicales Elsevier SAS. All rights reserved. PII: S 1 2 9 3 - 2 5 5 8 ( 0 2 ) 0 1 3 2 3 - 7

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Table 1 Surface densities determination for the three different modied silica phases Silica support Carbon percent (%) Metal percent (%) Grafted amount determined by elemental analysis (mol m2 ) Grafted amount measured by TG TG (mol m2 ) 1 4.50 2.37 2.35 2 13.65 4.55 2.00 2.00 3 10.40 2.60 1.39 1.37

Scheme 1. Organometallic grafting of silica.

and (Scheme 1) and increase the degree of interaction with electron rich -systems.

2. Results and discussion The two metallocenes (ferrocene (FcH) and cobalticinium (CoH+ )) were grafted onto silica particles according to a well-known, two-step procedure (Scheme 1), rst derivatizing silica gel with -aminopropyltriethoxysilane ( -APS) to give -aminopropyl silica 1 which will serve as a reference along the work [11]. The surface modication was carried out in reuxing anhydrous xylene, under argon atmosphere, without any catalyst to prevent -APS homopolycondensation in solution whilst promoting local hydrolysis, followed by condensation onto the silica surface. The second step, involving a reaction between the chlorocarbonyl metallocene and the amino group of the silica gel, took place in the presence of triethyl amine; this traps the HCl formed during the reaction and prevents the deactivation of the NH2 group, producing silica 2 for ferrocene and silica 3 for cobalticinium substituted silica powders [12]. The modied oxides were then washed with dry dichloromethane, THF, pentane, diethylether and acetone and nally dried under vacuum (105 bar) at 50 C for 20 hours. The success of both the silanisation and the organometallic grafting was checked by different techniques, providing some information about the chemical grafting and the spatial distribution of the grafted molecules throughout the silica beads. Elemental analyses were carried out for -aminopropyl silica 1 and, for silica 2 and 3 after their modication by the organometallic halves (Table 1). The coverage densities were obtained from the carbon content given by the elemental analysis. For silica 1, they were calculated using the standard formula [13], which takes into account the fact that the grafting may involve one, two or three vicinal hydroxyl groups present on the oxide surface [11]. For each of the organometallic-bonded phases, 2 and 3, the grafting was determined from the coverage density of silica

Fig. 1. Thermogravimetric evolution of silica 3 particles between room temperature and 1200 C (see text).

1 using the following expression (Eq. (1)): = C mol mm2 , 100 Mc Nc Sp (1)

where C is the difference of content (%) measured carbon between the organometallic phases (2), (3) and the aminopropyl silica (1), Nc the number of carbon atoms of the anchored organometallic complex, Mc the atomic weight of the quantied element (here 12) and Sp the specic surface area of silica (see Table 1). These elemental analyses are conrmed by the loss of mass observed during thermogravimetry experiments. Quantication was calculated from the TG mass loss (Eq. (2)), on the assumption that the thermal degradation proceeds [14] at the SiC bond breaking level between 200 and 650 C (Table 1). TG = m , Mcx Sp m (2)

where m/m is the mass loss between the two concerned temperatures (200 and 650 C) measured, Mcx is the molecular weight of the concerned fragment and Sp the specic surface area of silica. The thermogravimetric evolution of the cobalt silica (3) is illustrated on Fig. 1 as an example with three major losses of matter: (a) physisorbed water up to 160 C, (b) organometallic fragment between 160 and 650 C, (c) nal loss of chemisorbed water between 800 and 1200 C.

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Fig. 2. DRIFT spectra of: (a) pristine silica, (b) silica 1, (c) silica 2, (d) silica 3 beads.

Fig. 3. XPS surveys of silica powders: (a) pristine silica, (b) silica 1, (c) silica 2, (d) silica 3.

Diffuse reectance infrared Fourier transform (DRIFT) spectroscopy is another very useful technique for probing the effectiveness of the chemical grafting [11,15]. The silica powder was systematically predried under vacuum (105 bar) at 180 C for 24 hours to eliminate most of the physisorbed residual water molecules. These bare silica beads present simple infrared spectra (Fig. 2a), with two kinds of hydroxyl groups: (i) the bound SiOH, characterized by a very broad IR absorption band in the 2800 3700 cm1 region; (ii) the so-called free SiOH groups, which provide a narrow IR absorption band at 3740 cm1 , related to the SiOH vibration at 976 cm1 . Despite the thermal treatment, the stretching at 1627 cm1 still shows the presence of residual physisorbed water molecules. The large bands centered on 1875, 1093, 806 and 466 cm1 are assigned to the SiO and SiOSi stretching modes. The subsequent effective silanisation of the mineral oxide is evidenced by the modication of the DRIFT spectrum of the resulting powders. Grafting of the organic -APS is illustrated (Fig. 2b) by: (i) the disappearance of the single Si

OH vibration; (ii) the shape modication of the band around 3500 cm1 , due to the NH vibrations, and the 2969 and 2940 cm1 bands of the grafted alkyl chain; and (iii) the presence of the 1540 (NH) and 1406 (SiCH2 ) cm1 . The chemical grafting of the organometallic units is pointed out by the new stretching bands due to CH vibrations of the cyclopentadienyl ligands (3087 cm1 for ferrocene (Fig. 2c); and 3068 cm1 for cobalticinium cation (Fig. 2d)); and the presence of the amide bands (3328 (NH) and 1635, 1541 (NCO) cm1 for the iron complex (Fig. 2c); 3230 (NH) and 1652, 1558 (NCO) cm1 for the cobalt complex (Fig. 2d)). XPS [16,17] surface analysis (see XPS surveys, Fig. 3) conrmed these results. The unavoidable contaminant carbon peak observed on the bare silica does not appear to make a major contribution to the organic and organometallic subsequent modiers. Indeed, the increase of the C1s peak as well as the presence of N1s peak, [18] on the b, c, and d surveys, and Fe2p3 peak at 707.3 eV (c survey) and Co2p3 at 780 eV, combined with the peaks of P2p (137 eV) and F1s

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O. Bordelanne, M.-H. Delville / Solid State Sciences 4 (2002) 851858

(a)

(b)

(c)

Fig. 4. (a) Back scattered electron image of internal sections of cobalticinium-modied silica 3, (b) silicon and (c) cobalt X-ray maps.

(687 eV) corresponding to the PF counter-anion (d survey) 6 denitely conrm the existence of a chemical bond between SiO2 and the organic and metallocenic groups. On the later, the presence of chloride Cl2p at 199 eV is due to the anion exchange, which occurs between Cl and PF during the 6 amide bond formation. Auger depth proles as well as microprobe X-ray technical analyses for the different elements were carried out to ensure that the penetration depth of the organometallic molecules down to the core of the bead is effective for a pore size of 100 . In fact, the presence of a heavy atom in the organometallic half of the hybrid material, used as a contrast agent, allows a mapping of the desired element throughout

the particles. They were embedded in an epoxy resin, which, after curing, was nely polished to reveal the internal bead sections (Fig. 4 for silica 3). The X-ray mapping of the metallic atom on different section sizes conrms the homogeneous presence throughout the volume of the organometallic fragment. Indeed, although the concentration in cobalt (Fig. 4c) is signicantly lower than that of silicon, (Fig. 4b) it does not show variation of intensity, on the X-ray screening depth (1 m), whatever the diameter sections. Therefore, due to their intrinsic stability, these organometallic synthons can be efciently used in SEM to visualize without ambiguity the repartition of the chemical grafting into the oxide material.

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Fig. 5. HPLC chromatograms for the separation of a mixture of 5 PHAs on silica 1, 2 and 3. Mobile phase: hexane, ow-rate: 1 ml min1 , detection = 254 nm, temperature: 25 C.

This uniformity of the particles modication provides organometallic mineral oxide supports, which may be tested as new stationary phases in chromatographic analyses using high performance liquid chromatography (HPLC) [13,19], a eld in continuous development. These hybrid organometallic/inorganic silica, were therefore used in the case of molecular detection, recognition and separation of -electron rich, organic, pollutant, carcinogen, mutagens derivatives. Such stationary phases operate on separation modes based on various processes: hydrophobic, electron, dipole dipole, and/or electrostatic interactions with the substrate [13]. Among these interactions, the electron mechanism is the most effective for the separation of -electron rich derivatives [20] such as benzene, naphthalene, anthracene, uoranthene and chrysene chosen for their increasing number of -electrons and condensed rings (Fig. 5). The aminopropyl silica (1), which is used for the further surface modication of the appropriate mineral supports by the chemical grafting of the electronpoor sensors also serves as a reference to monitor the electronacceptor behavior of the organometallic materials and to show the contribution of the organometallic moiety to the retention mechanism. The retention times which illustrate the capability of the hybrid material to retain the organic compounds via the organometallic modier, are all alike on the unmodied aminopropyl silica (Fig. 5a) (within a 2 min window) and very short (less than 5 min), showing that the interaction between the PAHs tested and the unmodied silica gel is (i) tiny and (ii) almost the same whatever the PAHs [20]. On the contrary, the organometallic modied materials exhibit

a different behavior and are clearly able to separate PAHs (Fig. 5b,c). They yield a much larger value of the retention time indicating that the formation of interaction between the aromatic cycles of the complexes and the solutes favors the separation of PAHs. The increase in the retention times with increasing ring number of the organic molecules suggests that the larger the number of -electrons of PAHs the stronger the interactions. Moreover, both the retention time and the resolution depend directly on the nature of the organometallic substituent (e.g., chrysene: retention time of 4.54 min on phase 1, 8 min on phase 2, 26 min on phase 3). The chromatographic behavior of these organometallic bonded stationary phases was also investigated while analyzing the retention of 18 PAHs having from 1 up to 5 aromatic rings. The separations were compared to those obtained on the well-known acceptor 3,5-dinitrobenzamido stationary phase (DNB) used as a reference [20,21]. The adimensional retention factors k (k = (tr t0 )/t0 where tr and t0 are, respectively, the retention and dead times) of the PAHs on the different stationary phases are gathered in Table 2. Fig. 6 shows the linear dependence of the retention factor (Ln k) with the -electron number of the 18 solutes. Once again, the most retained solutes are those with a large number of -electrons illustrating the stabilization of the charge transfer complex, by interactions between the solutes and the bonded phases, as the predominant mechanism. The linear relationship observed in each case between Ln(k) and the -electron number of the solutes also conrms that a chargetransfer interaction between the PAHs and the

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Table 2 Retention factors (k) of different PAHs. Mobile phase: hexane, ow-rate: 1 ml min1 , detection = 254 nm, temperature: 25 C Solute -electron Benzene (6) Indene (8) Naphthalene (10) Acenaphthene (10) Biphenyl (12) Fluorene (12) Acenaphthylene (12) Phenanthrene (14) Anthracene (14) Fluoranthene (16) Pyrene (16) Chrysene (18) Benzo(a)anthracene (18) Benzo(a)pyrene (20) Benzo(e)pyrene (20) Perylene (20) Dibenzo(a,h)anthracene (22) Benzo(g,h,i)perylene (22) Silica 1 0.09 0.10 0.18 0.19 0.22 0.25 0.33 0.39 0.49 0.84 0.96 1.41 1.30 1.73 1.78 2.02 2.40 2.21 Silica 2 0.14 0.30 0.45 0.49 0.46 0.70 0.84 1.21 1.18 1.78 1.66 2.99 2.75 3.98 4.20 5.27 6.40 5.82 Silica 3 0.34 0.87 1.25 1.67 1.73 2.56 3.13 4.66 4.85 8.41 6.89 14.01 15.03 19.89 18.73 23.11 59.74 28.22 Silica DNB 0.29 0.87 1.53 2.79 1.36 3.18 4.81 7.22 6.74 16.16 15.93 27.68 23.75 48.85 54.99 73.47 89.76 96.71

(ii) be useful to modify and increase the potentialities of the formed materials, as stationary phases for molecular recognition and differentiation of neutral e -rich derivatives.

3. Experimental section 3.1. General methods DRIFT characterizations were performed using a Bruker IFS Equinox 55FTIR spectrometer (signal averaging 30 scans at a resolution of 4 cm1 in KBr pellets containing ca. 2 mass% of material. X-ray photoelectron spectra were obtained using a VG 220i-XL Escalab spectrometer, employing non-monochromatized Mg K source (h = 1253.6 eV). The X-ray gun was operated at 10 kV and 20 mA (pressure: 108 bar). Powdered samples were pressed onto small indium foils and survey spectra obtained in the constant pass energy mode of 150 eV. The analyzed region corresponds to a 150 m diameter zone. SEM analyses were performed on a JEOL JSM-840A Scanning microscope (acceleration tension of 10 kV and current of 3 1010 A). The stationary phases were packed in stainless steel tubes (150 mm 4.6 mm I.D.) by a slurry method [13]. Packing was carried out at room temperature under a pressure of 400 bars, using a mixture of dichloromethanecyclohexanol (90 : 10, v/v) as the suspension medium and acetone as the pressure uid. Chromatographic studies were performed with a modular HPLC apparatus consisting in a PU-980 Model gradient pump module (Jasco) and a UV-975 UVVis detector (Jasco). Normal phase conditions using hexane (100%) are chosen for chromatographic studies and the typical ow-rate was 1 ml min1 . Detection was carried out at 254 nm. The dead time was obtained with hexane as the nonretained compound. For the analysis, columns were thermostated at 25 C. The silica particles (Kromasil 5 m, 350 m2 g1 , 100 pore size, 7.98 mol m2 of hydroxyl coverage density) were a gift from Eka-Nobel (Bohus, Sweden). All the manipulations were carried out in puried nitrogen or argon atmosphere, using a vacuum line and standard Schlenk tube techniques [22]. Reagent-grade tetrahydrofuranne (THF), pentane and toluene were predried and distilled from sodium benzophenone ketyl under argon just before use. Dichloromethane (CH2 Cl2 ) was distilled from CaH2 just before use. All reagents and HPLC solvents were the best grade commercially available and were used as received. 3.2. Preparation of the amino silica gel [11] Silica was dried under vacuum (105 bar) at 180 C for 24 h. In a round-bottomed ask, the silica (3 g) was suspended and reuxed in 100 ml of dry xylene under stirring. Freshly distilled aminopropyltriethoxysilane (1.86 g, 8.42 mmol) was added dropwise in the suspension

Fig. 6. Dependence of Ln k versus -electron number for the 3 stationary phases and the DNB reference one.

organometallic stationary bonded phases is involved. Furthermore, the slope [20], which depends upon the strength of the interaction, conrms the role of the additional positive charge on the cobalt complex. Comparison with the DNB phase, leads to the conclusion that it is possible to reach (silica 3) the separation properties of conventional phases as the DNB one. It is even possible to improve their potentialities, by increasing the electron withdrawing character of the complex via a more positive charge on the metal, adding electro-withdrawing substituents on the complex or changing the nature of the metal ion. Work is under progress in this direction. We have shown, in this paper, that inorganic materials can be modied using organometallic fragments. These systems present a metallic center which when covalently linked to the support is easily detectable and can (i) act as contrast agent for X-ray mapping in SEM studies and may, for example, be used to visualize internal structures in mesoporous materials (channel imaging),

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and the reaction was reuxed for 20 h. The solution was allowed to cool down to room temperature and the silica was ltered off and washed with 150 ml of successively dry xylene, THF, methanol, water and acetone to give the amino silica. Finally, the material was dried under vacuum (105 bar) at 80 C for 24 h. See Table 1 for elemental analysis. 3.2.1. Synthesis of the chlorocarbonyl ferrocene [23] In a amed Schlenk tube, ferrocene carboxylic acid (2 g, 8.69 mmol) was deaerated under vacuum and dissolved in 40 ml of freshly distilled CH2 Cl2 and cooled down to 0 C. 5 ml (59.65 mmol) oxalyl chloride were then added dropwise using a cannula. The medium was stirred at 0 C under argon for one hour. The solution was then allowed to warm up to room temperature over three hours. The solvent was then evaporated under vacuum, and the residue was dissolved in pentane (50 ml) and ltered. Evaporation of the solvent gave the acid chloride (2.12 g, 98% yield) as dark red crystals, characterized by comparison with literature data (1 H and 13 C NMR spectra, IR spectrum). 3.2.2. Synthesis of the chlorocarbonyl cobalticinium complex [CoIII (5 -C5 H5 )(5 -C5 H4 COCl)]+ PF [2d] 6 In a amed Schlenk tube, the cobalticinium carboxylic acid (1.4 g, 3.70 mmol) was deaerated under vacuum, dissolved in 50 ml of SOCl2 and reuxed under argon for 20 h. SOCl2 was then evaporated under vacuum, and the residue was washed three times with 50 ml pentane. 1.3 g (3.28 mmol, 88% yield) of yellow green powder were obtained and characterized by comparison with literature data [2d] (1 H NMR and IR spectra). 3.2.3. Bonded stationary phases The reaction between the amino silica gel and the organometallic complex is realized according to a classical method [12]. Typically, in a round-bottomed ask the amino silica gel (2.5 g) was suspended under argon in freshly distilled dichloromethane. The adequate organometallic complex (2.8 mmol) was dissolved in dry dichloromethane and added dropwise in the suspension with an excess of 2 eq. of freshly distilled triethylamine (5.6 mmol). The reactive mixture was stirred under argon, at room temperature for 20 h, and for another 20 h at reux temperature. The silica powder was ltered and washed with dry dichloromethane, THF, pentane, diethylether and acetone and dried under vacuum (105 bar) at 50 C for 20 h.

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