A Novel Two-Component Physical Gel Based on Interaction Between Poly(acrylic acid) and 6-Deoxy-6-amino-b-cyclodextrin

Song Sun, Xi Chen, Jing Liu, Junlin Yan, Yu Fang Key Laboratory of Applied Surface and Colloid Chemistry (Shaanxi Normal University), Ministry of Education, School of Chemistry and Materials Science, Shaanxi Normal University, Xian 710062, Peoples Republic of China

A two-component physical organogel was produced by interactions of 6-deoxy-6-amino-b-cyclodextrin (bCDNH2) and poly(acrylic acid). The microstructure and morphology of the gels were characterized by scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. It was revealed that the intermolecular hydrogen bonds between the molecules of b-CDNH2 and the electrostatic interaction between the carboxyl groups of PAA and amino group of b-CDNH2 were the main driving forces for the formation and maintenance of the network structures of the gel. POLYM. ENG.
SCI., 49:99103, 2009. 2008 Society of Plastics Engineers

INTRODUCTION In the past 10 years, supramolecular hydrogels resulting from the inclusion complexation of cyclodextrins (CDs) with other polymers have attracted much attention because of their potential applications in materials science and biological science [18]. CDs are cyclic oligomers of a-D-glucose, which are linked together by a-(1,4) bonds. In aqueous solution, CDs can form stable inclusion complexes with less polar molecules (guests) that t tightly inside the CD cavity. The guest molecules, however, are not necessarily small molecules. They could be polymers. Based upon hostguest interaction and hydrogen bonding, polymers can interact with one or more CDs, forming supramolecular complexes including supramolecular networks [9, 1017]. Yui and coworkers [1012] fabricated a pH- and heat-sensitive supramolecular hydrogel by mixing poly (e-lysine), which brought CDs on its side chains, and a specic guest, 3-(trimethylsilyl) propionic acid. Harada and coworkers [13] prepared a photoresposive hydrogel by utilizing the inclusion complexation of a-CD with dodecyl-modied poly(acrylic acid) (PAA).
Correspondence to: Yu Fang; e-mail: yfang@snnu.edu.cn Contract grant sponsor: Natural Science Foundation of China; contract grant number: 20773083. DOI 10.1002/pen.21225 Published online in Wiley InterScience (www.interscience.wiley.com). C 2008 Society of Plastics Engineers V

Another interesting supramolecular hydrogel based on CDs was also reported. The gel was prepared by crosslinking poly(ethylene glycol) (PEG) or poly(propylene glycol), containing CDs as their side chains, with polypseudorotaxanes, which functioned as a crosslinker in aqueous solution [1417]. These hydrogels can also be prepared by utilizing CDs and linear hydrophilic polymers of high molecular mass. In the gels, the CDs can function as hoops, the polymer chains penetrate through them, and in this way, the gel networks are formed. For example, Haradas [14] and Lis [15] group prepared such hydrogels by mixing PEG, which is of high molecular mass, and a-CD or b-CD. Similar hydrogels were also prepared by Huh et al. [16, 17]. It is to be noted, however, that of most of the gels containing CDs, the concentrations of the gelators are high. Furthermore, most of them are hydrogels, and organogels with CDs are rarely reported. One of the exceptions is a mixed gel of b-CD-pyridinewater, which was created by Rango et al. [18]. Therefore, it is necessary to make more effort to nd new gel systems with better performances. Based on the earlier discussions, it is interesting to construct novel organogels with CDs and polymers as main components. Thus, as a continuation of our previous work [19, 20], a known compound, 6-deoxy-6-amino-bcyclodextrin (b-CDNH2), and a polymer in common use, PAA, were prepared, and the supramolecular interactions between them in N-methyl pyrrolidone (NMP) and at solid state were studied. It was found that a physical organogel was formed by mixing PAA with b-CDNH2. The details of the studies are reported in this article.

EXPERIMENTAL Materials and Instruments b-Cyclodextrin (b-CD, AR) and p-toluenesulfonyl chloride (tosyl chloride, CR) were puried by recrystallization

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from water and petroleum ether, respectively. Acrylic acid (CR) was puried by standard procedures. The used solvents except water were puried by standard procedures. Water used throughout was deionized and then double distilled. Bruker AV 300 NMR spectrometer, Elementar Analysensysteme GmbH VarioEL elemental analyzer, Brucher Equinox 55 FTIR spectrometer, Quanta 200 scanning electron microscopy spectrometer (Philips-FEI) (SEM), Rigaku/MSC D/Max-2550/PC X-ray diffraction system (XRD), and Christ Alpha1-2 instrument were employed for the characterization of the samples and for the studies of supramolecular interactions. Synthesis of b-CDNH2 and PAA The activation of b-CD to 6-o-tosyl-b-CD (b-CDOTs) was performed by using a literature method [21]. bCDNH2 was prepared by aminolysis of b-CDOTs according to a slightly modied literature method [22]. The details of the preparation are as follows: b-CDOTs (4 g, 3 mmol) was dissolved in 100 mL of ammonium solution (u 25%) and stirred at 508C overnight. After evaporation of the solvent under reduced pressure, the reaction mixture was poured into cold acetone. The precipitate was collected and dried in vacuum, and then puried through a Sephadex C-25 column using the aqueous solution of NH4HCO3 (0.1 M) as eluant. The puried bCDNH2 was obtained as a white solid. Anal. calcd for b-CDNH24H2O: C 41.79, H 6.55, N 1.16; Found: C 41.60, H 6.44, N 1.01. FTIR (KBr) m/ cm21: 3414 (O H), 2929 (C H), 1156 (C N). 1H NMR (D2O, 300 MHz) d/ppm: 4.98 (s, 7H, H-1), 3.90 3.49 (m, H-2, H-3, H-4, H-5, H-6), 3.36 (t, 1H, H-40 ), 3.20 (dd, 1H, CH2 NH2), 2.802.71 (dd, 1H, CH2 NH2). PAA was prepared by free radical copolymerization, using azodiisobutyronitrile as an initiator in 1,4-dioxane at 608C [23]. Polymerization was conducted in a threenecked round bottom ask equipped with a magnetic stirrer, condenser, and nitrogen purge. Purication was accomplished by multiple reprecipitations from methanol into ether. Sample Preparation and Measurements Gelation Test. A known weight of PAA (0.03 g, 83 mM for monomer unit) and a measured aliquot of puried NMP (1 mL) were placed into a sealed glass tube (d 13 mm, v 5 mL) and stirred in an oil or water bath at 608C, until all solid materials were dissolved. Then, to the solution, b-CDNH2 (0.0621 g, 55 mM) was added. The solution was stirred continuously for 1 h, and a transparent gel was formed. SEM Measurements. The xerogel was prepared by freezing the gel in liquid nitrogen and was then freeze100 POLYMER ENGINEERING AND SCIENCE -2009

dried. The dried sample thus obtained was attached to a mica slice or by conductive adhesive tape and shielded by gold. The accelerating voltage was 15 kV, and the emission was 10 mA. XRD Measurements. The xerogel was directly loaded onto a rectangular glass sample holder, and then it was scanned. The XRD patterns were obtained using Cu Ka radiation with an incident wavelength of 0.1542 nm under a voltage of 40 kV and a current of 50 mA. The scan rate was 0.58/min. FTIR Measurements. The solution of b-CDNH2 or PAA and the semigel samples for measurement were coated in a thin lm form on a potassium bromide (KBr) slice. Then, the samples were measured in an attenuated total reectance (ATR) mode by a Brucher EQUINX55 infrared spectrometer. Salt Effect Studies. Tetrabutylammonium bromide (Bu4NBr, 0.6716 g) was added to NMP (5 mL), and the mixture was stirred for 1 h at room temperature, and then the suspension was ltered. The resulting solution was used as a solvent for the test of the gelling ability of bCDNH2 and PAA in a way as that shown in the section of gelation test. Acid Effect Studies Dried HCl gas was introduced into a gel system for several minutes to see if the gel is stable or not.

RESULTS AND DISCUSSION XRD Studies The XRD patterns of the b-CD (a), PAA(b), and xerogel (c) are shown in Fig. 1. With reference to the gure, it can be seen that the XRD pattern of b-CD is characterized by a group of sharp reections, indicating that the compound is in a crystalline state. In contrast, the XRD pattern of PAA is a typical one for amorphous polymers. The curve for the xerogel (Fig. 1c), however, is characterized by two obtuse reections appearing at 2y values of 5.588 and 11.088, respectively, which correspond to d spacings and 7.98 A , respectively. The latter value is of 15.84 A close to the characteristic value of the height of b-CD, indicating that the basic structure of the host was well maintained in the supramolecular structure containing PAA. Considering the general formation mechanism of supramolecular complexes based on CDs with other molecules [118, 24, 2529], it may be supposed that the larger ) which is approximately twice as large d value (15.84 A should be the repeat distance of as the d spacing of 7.98 A the aggregate. Considering that the polymer PAA is a polyacid and b-CDNH2 is a base, mixing of these compounds must result in neutralization of the acids, and forms
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FTIR Measurements FTIR measurements can provide useful information for conrming formation of electrostatic interaction and hydrogen bonds [3640]. Compared with the spectra of bCDNH2 (Fig. 3a) and PAA (Fig. 3b), the new stretching vibration (1554 cm21) that is observed in Fig. 3c can be attributed to the carboxylate ( COO2) asymmetric stretching vibration. At the same time, other new peaks also appeared in Fig. 3c (2562, 2416, and 2148 cm21), indicating the formation of ammonium salt and conrming neutralization of PAA by b-CDNH2 [41]. Moreover, the absorption band around 3475 cm21 of the gel (Fig. 3c) is much more broad and intense when compared with those of the corresponding components, suggesting hydrogen-bond formation between CDs [42, 43]. Similar results have also been obtained by recording the spectra in an ATR mode (Fig. 4).

FIG. 1. X-ray diffraction patterns of powder b-CDNH2 (a), PAA (b), and the xerogel (c).

a polyelectrolyte with b-CDNH2 on its side chains (cf. Fig. 2). Furthermore, hydrogen-bond formation between CDs is possible due to the coexistence of CDs in the systems, which may be the reason why the repeat distance is twice the radius of the b-CDs (cf. Fig. 2). Similar combination and interactions have been reported by others [29, 30 35]. The hypothesis of hydrogen-bond formation between b-CDs was further conrmed by FTIR spectroscopy studies.

Salt Effect and Acid Effect Studies It can be imagined that the gel should be sensitive to the presence of salt if the nature of the interaction between PAA and b-CDNH2 is electrostatic. Salt effect study revealed that NMP cannot be gelled by PAA and bCDNH2 in the presence of Bu4NBr even if the solution is stirred overnight, in support of the hypothesis of exist of

FIG. 2. Schematic representation of the physical gel-formation process.

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FIG. 5. Tuning the gel formation by salt effect and acid effect. FIG. 3. FTIR transmission spectra of b-CDNH2 (a), PAA (b), and the semigel (c).

electrostatic interaction between b-CDNH2 and PAA in the gel [44]. There is no doubt that protonation of the amino group in b-CDNH2 will block out the association between PAA and b-CDNH2, because in this case the polymer will exist in a neutral form. This tentative predication was conrmed by the result from a specially designed experiment, in which predried HCl was introduced into the gel system, and it was found that the gel was destroyed and changed into a turbid solution within a few minutes. The results are shown in Fig. 5. In addition to PAA and b-CDNH2, the solvent NMP also plays an important rule for the formation of the gel. This is because the gel formation is very much dependent on the properties of solvents. For more than 10 solvents studied, only NMP can be gelled, suggesting that the solvent participated in the gel-formation process, and not just simply presented in the gel. In fact, it is well known that a gel state is a balance of several interactions, including

gelatorgelator interaction, gelatorsolvent interaction, and solventsolvent interaction [45]. As a normal practice, the molecules of NMP existing in the gel can be divided into three types according to their mobility. The rst type is the molecules in binding state, the second is those in semibinding state, and the third in free state, suggesting that NMP may have played its rule in the formation of the gel by stabilizing the aggregates of the gelators, which are the bases of the gel. This statement has been evidenced by the collapse of the gel network structures in the preparation of the xerogels for SEM measurements (cf. SEM imagine shown in Fig. 2). CONCLUSIONS In summary, a novel two-component physical gel based on the interaction of PAA and b-CDNH2 has been prepared and characterized. SEM and XRD measurements revealed that the gel takes a lamella structure, with a repeat distance of about two b-CDs. FTIR, salt effect, and acid effect studies revealed that the intermolecular hydrogen bonds between the molecules of b-CDNH2, and the electrostatic interaction between the carboxyl groups of PAA and the amino group of b-CDNH2 are the main driving forces for the formation and maintenance of the gel networks in NMP. On the basis of the studies, a gelation model was proposed to describe how the system was gelled. REFERENCES
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FIG. 4. Partial ATR-FTIR spectra of b-CDNH2 (a), PAA (b), and the semigel (c).

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