You are on page 1of 8

ARTICLE pubs.acs.

org/Langmuir

Hierarchically Mesoporous Silica Nanoparticles: Extraction, Amino-Functionalization, and Their Multipurpose Potentials
Xin Du, and Junhui He*,

Functional Nanomaterials Laboratory and Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry (TIPC), Chinese Academy of Sciences, Zhongguancun Beiyitiao 2, Haidianqu, Beijing 100190, China Graduate University of Chinese Academy of Sciences, Beijing 100864, China
S b Supporting Information

ABSTRACT: Hierarchically mesoporous silica nanoparticles (HMSNs) with uniform morphology and structure and with a diameter of ca. 100-220 nm were facilely fabricated using water, ethanol and ethyl ether as cosolvents. Template extraction and amino-functionalization were performed toward the HMSNs. These hierarchical mesopores are supposed to possess more advantages than conventional monomodal mesopores. Amino-functionalized HMSNs were homogeneously grafted with uorescent molecules and loaded with Au nanoparticles (NPs), respectively. The extracted HMSNs were also successfully used to construct antireection and superhydrophilc coatings. Drug release experiments showed that HMSNs exhibit much quicker rates of drug release compared with conventional mesoporous NPs due to their hierarchically mesoporous structures.

1. INTRODUCTION Design and fabrication of silica nanoparticles (NPs) with hierarchically porous structures are attracting much attention because of novel structures and potential applications. Hierarchically porous structures are those having pores on dierent length scales from micropore (<2 nm) to mesopore (2-50 nm) to macropore (>50 nm). They can be ordered or nonordered. Hierarchically porous systems are supposed to possess more advantages than monomodal porous systems (e.g., MCM-41 and SBA-15) for several reasons.1-9 First, introduction of hierarchical pores may lead to increased surface area and pore volume, which may facilitate functionalization of pore wall and interaction with various species. Second, hierarchical combinations of multiple-scale pores (micropore and mesopore, small and large mesopores, or mesopore and macropore) would allow for accessible mass transport paths within inorganic networks. Thus, small molecules, biomacromolecules, or even NPs could move into or out of the porous matrices through hierarchical pores. Third, the coexistence of multiple-scale pores may enhance and harmonize the diusion of guest molecules of dierent sizes through the porous matrices and allow simultaneous loading of dierent species with varied sizes (such as uorescent molecules, quantum dots, magnetic NPs, and so on). As a result, silica
r 2011 American Chemical Society

nanospheres with hierarchical pores are promising in diverse applications such as catalysis, adsorption, separation, and biomedicine, especially as multifunctional carriers (having uorescent, magnetic, cellular labeling, and/or therapeutic functions) in drug delivery.10-15 Recently, bulk hierarchically porous silica materials have been successfully synthesized using polystyrene nanospheres as macropore template and triblock copolymer Pluronic F127 as mesopore template.16 However, this method is dicult to fabricate nanoparticles with micro or submicrometer sizes instead of bulk materials. Thus, at present, facile and large-scale fabrication of NPs with hierarchically porous structures and submicrometer diameters is still a big challenge due to their more complicated nanostructures of hierarchical pores than those of monomodal pores. Recently, Wu et al. reported that hierarchically nanostructured mesoporous spheres (ca. 1 m) of calcium silicate hydrated were synthesized by a surfactant-free sonochemical method, and a linear relationship was found in the drug-delivery system between the cumulative amount of released drug and the natural logarithm of release time.8 Very recently, Polshettiwar et al. reported a microwave-assisted hydrothermal
Received: November 10, 2010 Revised: January 31, 2011 Published: February 18, 2011
2972
dx.doi.org/10.1021/la200014w | Langmuir 2011, 27, 29722979

Langmuir method to fabricate high specic surface area silica nanospheres with unprecedented brous morphologies, and presumed its widespread applications in drug delivery, hydrogen storage, as a chromatography support, and in nanocomposite materials due to the accessibility of active sites.9 Modication of the interior and/or exterior of mesoporous silica nanometerials with organic groups is particularly interesting because of the possibility to combine the enormous functional variations of organic groups with the advantages of thermally stable and robust silica scaolds.17 Such functionalized mesoporous silica nanometerials are applicable to catalysis, sorption and anity chromatography, separation and decontamination, sensing, and the construction of systems for controlled release of active compounds, as well as molecular switches.18-20 Typical strategies for immobilizing organic functional groups in mesoporous silica nanomaterials via covalent bonds are cocondensation (one-pot synthesis), postsynthesis modication (grafting), and imprint coating method.21 Very recently, we reported easy fabrication of hierarchically mesoporous silica nanoparticles (HMSNs) using water, ethanol, and ethyl ether as cosolvents and CTAB as surfactant.22 The formation of large mesopores (5-50 nm) results from the gasication of ethyl ether in the exothermic hydrolysis and condensation of TEOS. In the current work, we adopted the extraction method to treat the as-prepared HMSNs (as-HMSNs) instead of previous calcination. Excitingly, the extracted HMSNs (ext-HMSNs) achieved more intact and better dened hierarchically mesoporous structure than the calcined HMSNs (calHMSNs). Both postsynthesis modication and co-condensation were employed to functionalize the HMSNs with primary amine groups, respectively. Furthermore, NH2-ext-HMSNs were successfully labeled with uorescein isothiocyanate (FITC) and loaded with Au NPs, respectively. The ext-HMSNs were also used as building block to construct functional coatings by the layer-by-layer (LbL) dip coating method on glass substrate. Finally, HMSNs were used as drug carrier to investigate the drug loading and release behavior in vitro.

ARTICLE

2. EXPERIMENTAL SECTION
2.1. Materials. Cetyltrimethylammonium bromide (CTAB, g99%), aqueous ammonia (NH4OH, 25-28%), hydrochloric acid (HCl, 36-38%), chloroauric acid (HAuCl4 3 4H2O), sodium borohydride (NaBH4), toluene, ethanol, ethyl ether (g99.5%) and fluorescein isothiocyanate (FITC) were obtained from Beijing Chemical Reagent Company. Tetraethoxysilane (TEOS, g98%), sodium poly(4-styrenesulfonate) (PSS, Mw = ca. 70 000), and 3-aminopropyltrimethoxysilane (APMS, g97%) were purchased from Alfa Aesar. Poly(diallyldimethylammonium chloride) (PDDA, Mw = 200 000-350 000, 20 wt %) was purchased from Aldrich. Ibuprofen (IBU, g98%) was purchased from Wuhan Galaxy Chemical Company. All chemicals were analytic grade and used without further purification. Ultrapure water with a resistivity higher than 18.2 M 3 cm was used in all experiments and was obtained from a three-stage Millipore Mill-Q Plus 185 purification system (Academic). 2.2. One Pot Synthesis of Silica Nanoparticles with Hierarchical Mesopores. HMSNs were prepared in basic solution at
room temperature using water, ethanol, and ethyl ether as cosolvents and CTAB as surfactant according to the synthesis procedure of S0.5 in our previous work.22 In a typical procedure, 0.5 g of CTAB was dissolved in an emulsion system composed of 70 mL of H2O, 0.8 mL of aqueous ammonia, 20 mL of ethyl ether, and 10 mL of ethanol. After the mixture was vigorously stirred for 0.5 h at room temperature, 2.5 mL of TEOS

was quickly dripped into the mixture. The resulting mixture was vigorously stirred at room temperature for 4 h. A white precipitate was obtained, filtered, washed with pure water, and dried in air at 60 C for 24 h. Two methods (calcination and template extraction) were performed toward the as-prepared precipitate. Calcination was carried out in air at 550 C for 5 h to eventually remove CTAB and other organic components in the product. The calcined sample was designated as calHMSNs. In order to better maintain the morphology and structure of HMSNs, template extraction was also performed by adding the asprepared precipitate (before calcination) in ethanolic HCl (15 mL of conc. HCl in 120 mL of ethanol) followed by stirring at 70 C for 24 h. Finally, the extracted HMSNs (ext-HMSNs) were filtered, washed with pure water, and dispersed in water or dried in air at 80 C. 2.3. Amino-Functionalization of HMSNs. Two methods including co-condensation and postsynthesis modification were employed to achieve amino-functionalization of HMSNs. Co-condensation was carried out by addition of varied volumes (0.02, 0.05, and 0.2 mL) of APMS as co-condensation precursor after addition of TEOS under otherwise identical conditions of HMSNs. Postsynthesis modification was performed in dry toluene by reaction with APMS, according to a similar procedure that had been applied for grafting mesoporous silicas.23-25 Briefly, the ext-HMSNs, which had been grinded sufficiently, was dehydrated at 120 C to remove adsorbed water molecules. Then, 300 mg of ext-HMSNs were suspended in 80 mL of toluene, and ultrasonicated for 30 min. Finally 0.20 mL of APMS was added, and the mixture was stirred for 6 h at 80 C. The product was recovered by filtration, washed with dry toluene, and dried in air at 120 C. The amino-modified product was designated as NH2-ext-HMSNs. 2.4. Fluorescent Labeling of NH2-ext-HMSNs. The amino groups of NH2-ext-HMSNs were available for attachment of FITC molecules.26 5 g of FITC were suspended in 3 mL of water. After addition of 20 mg of NH2-ext-HMSNs, the suspension was stirred for 8 h. And FITC-labeled NH2-ext-HMSNs (FITC-NH2-ext-HMSNs) were collected, and the residual FITC molecules were removed by repeated water washing/centrifugation/redispersing. 2.5. Loading of Gold NPs. The NH2-ext-HMSNs with hierarchical mesopores were used as carriers for Au NPs by in situ formation.27 Typically, 0.020 g of NH2-ext-HMSNs were dispersed in 20 mL of H2O. After addition of 1 mL aqueous HAuCl4 (3 mM), the color of mixture was yellow. After the mixture was magnetically stirred in a closed conical flask for 2 h at room temperature, a given volume of aqueous NaBH4 (10 mM) was added into the above mixture until the color turned pale red. Finally, the precipitate was centrifuged, washed with water, and redispersed in water.

2.6. Fabrication of Functional Coatings using ext-HMSNs.


ext-HMSNs were used as building blocks to fabricate functional coatings by the LbL dip coating method. The procedure for preparation of functional coatings is divided into three steps and described as follows.28-30 First, commercially available glass or silicon substrates were cleaned with Pirhana solution (98 wt % H2SO4/30 wt % H2O2, 7/ 3, v/v), and then washed with pure water (Caution: the Pirhana solution is highly dangerous and must be used with great care). The cleaned substrates were alternately dipped in a PDDA and a PSS solution for 5 min, and redundant polyelectrolytes were removed by shaking in pure water for 2 min and rinsing for 1 min, followed by drying with N2 flow at room temperature. The concentrations of PDDA and PSS aqueous solutions were 2 mg mL-1. Mutilayers of (PDDA/PSS)5/PDDA were prepared, and were used as a primer in all experiments. Second, the (PDDA/PSS)5/PDDA covered substrates were alternately dipped in an ext-HMSNs aqueous suspension (0.5 wt %, pH 3.46) and a PDDA solution (2 mg mL-1) by the same procedure for an appropriate number of cycles. Finally, the as-prepared coatings were dried with N2 flow, and heated at 80 C overnight. 2.7. Drug Storage and Release by Varied HMSNs. extHMSN, cal-HMSN, and NH2-ext-HMSN were used as drug carrier to
2973
dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

Langmuir
study their drug storage and release behaviors, respectively. Drug storage and in vitro release profiles were obtained according to previously reported methods.31-38 Ibuprofen (IBU) was dissolved in hexane solution, and the IBU concentration was 40 mg/mL. 0.10 g of the HMSN products was added into 20 mL of the IBU hexane solution at room temperature. The vials were sealed to prevent the evaporation of hexane, and then the mixture was stirred for 24 h. The IBU-loaded product (HMSNs@IBU) was separated from this solution by filtration, washed twice with diluted HCl solution (pH 1.0), and dried under vacuum at 60 C. A typical drug release experiment was performed as follows: 0.05 g of HMSNs@IBU powder was grinded, and compacted into a disk (diameter: 1 cm) under a pressure of 3 MPa, and then immersed into 50 mL of phosphate-buered saline (PBS, 137 mM NaCl, 2.7 mM KCl, 5.0 mM Na2HPO4 3 12H2O, 0.7 mM H3PO4 in ultrapure water, pH 7.27.4)35 under magnetic stirring at a rate of ca. 100 rpm at room temperature. One mL of the mixture was extracted with a syringe at given time intervals for analysis. After removal of solid HMSNs@IBU by centrifugation (12 000 rpm, 2 min), the remaining clear solution (1 mL) was diluted to 2 mL, and then analyzed by UV-vis spectroscopy at a wavelength of 264 nm. By measuring the UV absorption spectra of four standard IBU solutions in PBS (Table S1), a calibration curve of IBU concentration (0-1.5 mg mL-1) vs UV-vis absorbance (see Supporting Information, Part 1, Table S1 and Figure S1) was set up as A = 1.6584 C 0.02439, where A is the absorbance at 264 nm and C is the IBU concentration (mg mL-1). IBU release amounts were determined by measuring the absorbance of the above clear solutions, and calculated using the calibration curve. The total IBU release amount for a week was determined as the total storage amount of HMSNs. 2.8. Characterization. Scanning electron microscopy (SEM) observations were carried out on a Hitachi S-4300 field emission scanning electron microscope operated at 10 kV. Specimens were coated with a layer of gold by ion sputtering before SEM observations. For transmission electron microscopy (TEM) observations and selected area electron diffraction (SAED) measurements, powder samples were added on carbon-coated copper grids, and observed on a JEOL JEM2100F transmission electron microscope at an acceleration voltage of 150 kV. The size distributions of partial products were measured by Malvern Zetasizer 3000HS. Small angle X-ray diffraction (SAXRD) patterns of products were recorded on a Bruker D8 Focus X-ray diffractometer using Cu KR radiation ( = 0.154184 nm), and used to identify their phase constitutions and crystallite sizes. Fourier transform infrared (FTIR) spectra were recorded on a Varian Excalibur 3100 spectrometer. UV-vis absorption and transmission spectra were recorded on a TU-1901 spectrophotometer (Beijing Purkinje General Instrument Co.). Reflection spectra were recorded on a Varian Cary 5000 UV-vis-NIR spectrophotometer. For confocal microscope observations, the FITC-NH2-ext-HMSNs suspension was dripped onto the surface of slide glass, dried, and observed on an Olympus BX51 fluorescent microscope. Nitrogen adsorption-desorption measurements were carried out on a QuadraSorb SI automated surface area and pore size analyzer at -196 C using the volumetric method. The products were dried at 200 C before analysis. Brunauer-EmmettTeller (BET) specific surface areas were calculated by using adsorption data in the P/P0 range of 0.04-0.20 (six points collected). Pore size distributions were estimated from desorption branches of the isotherms using the Barrett, Joyner, and Halenda (BJH) method. Pore volumes were determined from the amounts of N2 adsorbed at the single point of P/P0 = 0.98. Water contact angles (WCAs) of surfaces were measured at ambient temperature on a JC2000C contact angle/interface system (Shanghai Zhongchen Digital Technique Apparatus Co.), the angle precision of which is (0.5. Three L of water droplets were dropped carefully onto the sample surfaces. Once a water droplet contacted the sample surface, the machine began to take photos at a speed of 30 photos/s;

ARTICLE

Figure 1. SEM (a, c, and d) and TEM (b, e, and f) images of cal-HMSNs (a and b) and ext-HMSNs (c-f). Inset in panel (b) is a magnied TEM image. that is, the interval between the contact moment and the first image was 33 ms. The measurement was carried out on three different areas of the sample surface.

3. RESULTS AND DISCUSSION


3.1. Morphology and Structure of HMSNs. As shown in Figure S2a and b, as-HMSNs have a size of ca. 100-220 nm. They have large circular mesopores with a diameter of 5-50 nm on their surface (Figure S2b). The dark and pale parts in the interior of nanosphere (Figure S2c and d) reveal the existence of large mesopores on the surface of nanosphere.39,40 After calcination, cal-HMSNs remained nearly unchanged in size, but the large mesopores on the surface had a small shrinkage and their sizes became 5-30 nm (Figure 1a and b). Small mesopores of 2-3 nm were also clearly observed in the interior of cal-HMSNs (inset in Figure 1b). After extraction treatment, unexpectedly and excitingly, ext-HMSNs show uniform structure and morphology, have no aggregation with each other, and have large circular mesopores with a diameter of 5-80 nm on their surface (Figure 1c-f), which are slightly larger and clearer than those of asHMSNs. This may result from that extraction treatment, on one hand, removes the surfactant, and on the other hand, induces further condensation and solidification during the acidic extraction process,
2974
dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

Langmuir

ARTICLE

Figure 3. FT-IR spectra of as-HMSNs (a), cal-HMSNs (b), extHMSNs (c), and NH2-ext-HMSNs (d).

Figure 2. SEM (a and b) and TEM (c and d) images of NH2-extHMSNs. Inset in (a) is a digital image of the product.

thus improving the nanostructure of hierarchical mesopores. The particle size of ext-HMSNs was also measured by dynamic light scattering (DLS), and the results indicate that ext-HMSNs have a Z-average diameter of 229 nm with a polydispersity of 0.22 (Figure S3a). Thus, the extraction treatment can be used to obtain intact and well-defined nanostructures of hierarchical mesopores. 3.2. Amino-Functionalization of HMSNs by Co-condensation. As shown in Figure S4, as-prepared amino-functionalized HMSNs by co-condensation with APMS have better defined spherical morphology and larger mesopores (5-150 nm in size) than those of as-HMSNs. And the diameter of as-prepared amino-functionalized HMSNs has a little increase with increase of added APMS volume (from 0.02 to 0.05 mL). When the added APMS volume increases to 0.20 mL, the diameter of as-prepared amino-functionalized HMSNs has a broad distribution (50700 nm). Unfortunately, however, some unexpected sheets appeared. And it is expected that the sheets can be removed by a simple method (e.g., filtration). FT-IR spectrum (Figure S5a) of extracted NH2-HMSNs fabricated with addition of 0.2 mL of APMS as co-condensation precursor indicates the existence of amino groups. TEM images (Figure S5b and c) of the extracted NH2-HMSNs after loading with Au nanoparticles according to the process of the experimental section show that Au NPs with varied sizes from 0.5 to 15 nm are homogeneously scattered in the pores of HMSNs, indicating the homogeneous modification of amino groups on the pore surface of HMSNs. It can be concluded that APMS as co-condensation precursor plays a regulation role toward the structure of products in the selfassembly process of surfactant and silica species.35 3.3. Amino-Functionalization of HMSNs by Postsynthesis Modification. As shown in Figure 2, the size of large mesopores (5-40 nm) on the surface of NH2-ext-HMSNs becomes slightly smaller than that of ext-HMSNs, but still keeps the clear structure of hierarchical mesopores. The inset in Figure 2a shows that the product is a white powder and on gram-scale. These observations may result from combined effects of grafting of APMS and

structural rearrangement during oil-bath reaction. DLS measurements show that the NH2-ext-HMSNs fabricated by postsynthesis modification have a Z-average diameter of 269 nm with a polydispersity of 0.48 (Figure S3b), and the distribution peak at ca. 600 nm indicates that NH2-ext-HMSNs have a little aggregation. FT-IR spectra of as-HMSNs, cal-HMSNs, ext-HMSNs and NH2-ext-HMSNs are shown in Figure 3. They show typical vibration bands of siliceous materials, such as Si-O-Si asymmetric stretching (SiOSi) at ca. 1085 cm-1, Si-O symmetric stretching (SiO) at ca. 800 cm-1 and Si-O-Si bending vibration (SiOSi) at ca. 470 cm-1. For as-HMSNs, absorption peaks observed at 2920 and 2855 cm-1 and 1494 cm-1 are attributed to C-H stretching vibrations (CH) and C-H bending vibrations (CH) from the CTAB template. After calcination, the corresponding absorption peaks disappeared, indicating complete removal of CTAB. By extraction treatment, the corresponding absorption peaks become very weak, exhibiting eective removal of CTAB. After amino-functionalization, the corresponding absorption peaks have clear increases compared to those of ext-HMSNs, and a new absorption peak appears at 1560 cm-1, which is attributed to typical bending vibration (NH) of amino group. Moreover, the absorption peak at 965 cm-1 disappeared, which belongs to the stretching vibration of Si-OH (SiOH),. This is because the Si-OH groups reacted with APMS, producing the Si-O-Si linkage.38 Figure S6 shows SAXRD patterns of cal-HMSNs, ext-HMSNs, and NH2-ext-HMSNs. cal-HMSNs show a broad peak at 2 = 2.61 with a d spacing of 3.39 nm, indicative of a low degree of long-range order. ext-HMSNs show a broad low-angle reection peak at 2 = 1.00 with a d spacing of 8.84 nm. After aminofunctionalization, however, NH2-ext-HMSNs show no reection peak, suggesting disordered pores. These dierences may result from the change in the pore size and ordering degree of small mesopores, and from the dierence of groups on the mesopore walls of cal-HMSNs, ext-HMSNs and NH2-ext-HMSNs.41 Nitrogen adsorption-desorption isotherms of cal-HMSNs, ext-HMSNs and NH2-ext-HMSNs are shown in Figure S7. The nitrogen adsorption-desorption isotherm of cal-HMSNs shows typical type-IV features, indicative of the presence of mesopores.42 The large H3-type hysteresis loop of ext-HMSNs and NH2-extHMSNs in the P/P0 range of 0.5-1.0 should be normally attributed to slit-like pores, which most probably resulted from the particle packing.42 In addition, pore size distribution curves (Figure S7) of cal-HMSNs, ext-HMSNs, and NH2-ext-HMSNs were determined
2975
dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

Langmuir

ARTICLE

Figure 4. TEM images (a and b) and electron diraction pattern (c) of NH2-ext-HMSNs loaded with Au NPs, and UV-vis absorption spectrum (d) of the suspension of NH2-ext-HMSNs loaded with Au NPs. Inset in (d) is corresponding digital image of the suspension, showing a wine-red color.

Figure 5. SEM images of ext-HMSNs coatings on slide glasses by depositing two (a and b) and four (c and d) cycles of PDDA/extHMSNs.

from the desorption branch of the isotherms. Detailed physicochemical parameters are summarized in Table S2 for comparison. Only one peak appears in the range of 2-4 nm in the pore size distribution curves of cal-HMSNs and ext-HMSNs, and no large mesopores appear, suggesting that small mesopores must be predominant in these two hierarchically porous systems. ext-HMSNs (3.8 nm) have a larger mesopore size than cal-HMSNs (2.5 nm), indicating that calcination caused a small shrinkage of mesopores, and extraction kept the mesopores intact eciently and even expanded the mesopore size. However, there exist two peaks in the pore size distribution curve of NH2-ext-HMSNs. The sharp peak at 3.4 nm and the broad peak at 7.9 nm should be attributed to the existence of small and large mesopores, respectively. The simultaneous appearance of two peaks of small and large mesopores may results from weakening of ordering degree and decrease of small mesopores after amino-functionalization, which is indicated by signicant decrease in y-axis intensity. Moreover, the BET surface area of NH2-ext-HMSNs has a large decrease as compared with those of cal-HMSNs and ext-HMSNs. The appearance of large mesopores and the signicant decrease of BET surface area of NH2-ext-HMSNs indicate that due to the existence of a large number of Si-OH groups on the mesopore wall of extHMSNs, the following amino-functionalization by the reaction of Si-OH with APMS caused the shrinkage and even disappearance of mesopores. 3.3. Fluorescent Labeling of HMSNs. FITC is a popular amine labeling reagent, forming a robust thiourea upon reaction with amine. Absorption spectra of FITC solution and FITCNH2-ext-HMSNs suspension are shown in Figure S8a. After labeling, the absorption maximum of FITC-NH2-ext-HMSNs suspension decreases to ca. 1/4 of the absorption maximum of FITC solution. The nonzero baseline is due to extinction resulting from light scattering.43 The red shift of absorption maximum from 492 to 500 nm results from the interaction

between neighboring FITC molecules labeled on the mesopore walls, which lowers their excited state energy and produces the red shift.43 And the color of FITC solution is pale green (Figure S8b), while the color of FITC-NH2-ext-HMSNs suspension is pale pink after labeling (Figure S8c). Figure S8d shows that FITC-NH2-ext-HMSNs emit strong green fluorescence under excitation by 470-495 nm wavelength light. Thus, FITC-NH2ext-HMSNs may be used to monitor the cellular process of the HMSNs particles. Moreover, due to the existence of amino groups and hierarchically mesoporous structure, it is possible that NH2-ext-HMSNs can be simultaneously loaded with several kinds of species such as drug molecules, protein molecules, magnetic NPs and fluorescent molecules. 3.4. Loading of Au NPs. HMSNs loaded with Au NPs were sonicated, dropped on TEM grid, and observed by TEM (Figure 4a and b). Figure 4a and b show in situ loading results of Au NPs using NH2-ext-HMSNs as carrier. Many Au NPs with a diameter of <5 nm are homogeneously distributed in the mesopores (Figure 4b). It is noted that no free Au nanoparticles are found even after 10 min sonication, indicating that the gold remain stably associated with HMSNs. The strong coordination bonding between Au atom and the amine group would at least partially contribute to the stability of Au labeling. SAED patterns in Figure 4c show four rings, which agree with those indexed to the (111), (200), (220) and (311) planes of face-centered cubic phase of pure Au NPs. The UV-vis absorption spectrum of Au NPs loaded in NH2-ext-HMSNs (Figure 4d) exhibits an absorption band at ca. 524 nm, which is attributed to the surface plasmon resonance absorption of Au NPs.44 The color of Au NPs loaded NH2-ext-HMSNs suspension is wine-red, as shown in the inset of Figure 4d. Apparently, the position of the surfaceplasmon band agrees with the Mie theory and other experimental results reported in the literature. The homogeneous loading of Au NPs confirms the homogeneous functionalization of amino groups in the mesopores of ext-HMSNs. Moreover, Au NPs loaded NH2-ext-HMSNs may exhibit excellent catalytic activity due to the accessibility of active sites.9
2976
dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

Langmuir

ARTICLE

Figure 6. Transmission (a) and reection (b) spectra of blank slide glass and slide glasses coated with two and four cycles of PDDA/extHMSNs. Time-dependent changes (c) in instant contact angle on slide glasses coated with two and four cycles of PDDA/ext-HMSNs. Inset in (c) is a digital image of ca. 3 WCA on a porous PDDA/ext-HMSNs coating of four cycles.

3.5. Functional Coatings. Functional coatings were successfully fabricated on glass substrate using ext-HMSNs as building blocks by the LbL dip coating method. SEM images in Figure 5 show the surface morphologies of ext-HMSNs coatings with two and four cycles of PDDA/ext-HMSNs. Clearly, ext-HMSNs are homogenously distributed on the substrate surface (Figure 5a and c). Magnified SEM images (Figure 5b and d) reveal that the coating surfaces are very rough, and in fact consist of nanometersized islands (ext-HMSNs) and valleys (voids among extHMSNs and large mesopores on the surface of ext-HMSNs). By comparing panels b and d of Figure 5, it can be seen that particle density, coating thickness and surface roughness increase gradually, and the coating presents a three-dimensional network structure more and more clearly with increase of the number of deposition cycles. Clearly, subsequently adsorbed ext-HMSNs

would prefer to fill in or sit on the void spaces among extHMSNs, thus leading to rougher surfaces and thicker coatings. Such morphologies might significantly affect the transmittance, reflectance and wetting property of the coatings. Transmission spectra in Figure 6a show that slide glasses coated with two and four cycles of PDDA/ext-HMSNs have a slightly enhanced transmittance at wavelengths above 533 nm. Meanwhile, reection spectra in Figure 6b exhibit excellent antireection property. And the minimum reectance was estimated to be 4% at the wavelength of ca. 484 nm and 3% at the wavelength of ca. 615 nm, respectively, for the slide glasses coated with two and four cycles of PDDA/ext-HMSNs, thus also exhibiting a red-shift trend with increase of cycle numbers (Figure 6b). Figure S9 directly shows digital images of antireection toward a uorescent lamp of the blank parts and parts coated with two and four cycles of PDDA/ext-HMSNs. Light reection can be suppressed clearly by the coatings with the suppression eect of four deposition cycles more signicant. Moreover, the slide glasses coated with two and four cycles of PDDA/ext-HMSNs also show excellent superhydrophilic property, thus having antifogging behavior.28-30 Time-dependent changes in WCAs on the coating surfaces are shown in Figure 6c. Clearly, the WCAs on the coatings decrease quickly with increase of time from 0 to 1000 ms, indicating fast spreading of water droplets. The time from initial contact to spreading to 5 is ca. 536 and 485 ms, respectively, for the ext-HMSNs coatings with two and four cycles of PDDA/ext-HMSNs. And due to rougher surface and thicker coating, the slide glass coated with four cycles of PDDA/ext-HMSNs has better hydrophilicity than that coated with two cycles of PDDA/ext-HMSNs. The inset in Figure 6c shows the shape of a sheet-like water of ca. 3 WCA after 1000 ms of spreading. In addition, the current coatings with hierarchically porous structure may have potential applications as catalyst supports, chemical sensors, etc. NH2-ext-HMSNs were also used as building blocks. The particulate density after four cycles of deposition is very low (Figure S10a and b) because protonation of NH2-ext-HMSNs in ultrapure water (ca. 0.5 wt %, pH 8.78) results in pH increase from 3.46 (ext-HMSNs) to 8.78 (NH2-ext-HMSNs). WCA is ca. 50 C due to the existence of polyelectrolyte (Figure S10c) and the transmittance is lower than that of blank slide glass (Figure S10d). The properties of coatings fabricated using varied particles (cal-HMSNs,45 ext-HMSNs, and NH2-ext-HMSNs) are summarized in Table 1 and Figure S11 for comparison. The coatings of cal-HMSNs show the best superhydrophilicity due to the removal of polyelectrolytes. The coatings of ext-HMSNs exhibit the best antireective property in the visible wavelength range, and may be due to the relatively intact structure of extHMSNs. 3.6. Drug Storage and Release. Mesoporous silicas are currently widely studied as carrier matrices in drug delivery applications.31-37 Surface functionalization of silica is often employed in order to enhance the interaction between drug and support. However, in many cases the effectiveness of introduced surface functions is much lower than what is expected, and the release rate from surface functionalized silica is often not very different from that of bare silica support, suggesting that the drug-support interactions are weaker than assumed under physiologically relevant conditions.46 The Z average diameter of HMSNs was ca. 200 nm with a narrow size distribution. It has been reported that nonphagocytic eukaryotic cells could internalize particles as large as 500 nm in size and the uptake efficiency
2977
dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

Langmuir Table 1. Properties of Coatings Fabricated Using Varied Particles


particle cal-HMSNs ext-HMSNs NH2-ext-HMSNs cycle numbers two four two four four WCA after 1s spreading (o) 0.2 0 3.3 3 50 maximum transmittance (%) 92.4 at 594 nm 90.2 at 675 nm 92.7 at 667 nm 91.8 at 658 nm 88.0 at 662 nm

ARTICLE

minimum reectance (%) 3.9 at 775 nm 3.8 at 850 nm 4.1 at 484 nm 2.9 at 615 nm 7.0 at 855 nm

curves were plotted based on the sustained releases by using the absorption of the peak at ca. 264 nm. Recently, Vallet-Regi et al. reported that the release rate under similar conditions was very fast during the first day, but decreased with time and reached a maximum value of 80% the third day when using conventional MCM-41 NPs as IBU carriers.36 As shown in Figure 7b, compared with conventional MCM-41 NPs, the current three samples exhibit higher rates of release, i.e., the IBU amounts released from calHMSNs@IBU, ext-HMSNs@IBU and NH2-ext-HMSNs@IBU reach about 80% in 3.4 h, 7.7 and 17.2 h, respectively, indicating that the hierarchically mesoporous nanostructures are favorable for fast molecular diffusion through pore channels. The release rate of ext-HMSNs@IBU is a little lower than that of cal-HMSNs@IBU. This may result from the existence of a large number of Si-OH groups on the mesopore wall of ext-HMSNs, thus producing the interaction between Si-OH and IBU-COOH, despite of the larger size of mesopores. The release rate of NH2-ext-HMSNs@IBU is the lowest, which may be due to the interaction between Si-(CH2)3NH2 groups and IBU-COOH. Generally speaking, slow sustained release of drug is superior to relatively quick release; however, the HMSNs with hierarchically mesoporous nanostructures might be advantageous for some stimulated and quick releases.

Figure 7. UV-vis spectra (a) at dierent times of the aqueous media in which IBU was released from cal-HMSNs@IBU and corresponding controlled release kinetics (b) of cal-HMSNs@IBU, ext-HMSNs@IBU, and NH2-ext-HMSNs@IBU.

was high for particles around 200 nm or smaller,47 so the current fabricated HMSNs would be potentially useful in drug delivery applications. Therefore, ext-HMSNs, cal-HMSNs, and NH2-extHMSNs were used as drug carrier, respectively, to study drug storage capacity and in vitro release behavior. Ibuprofen (IBU), a typical anti-inflammatory drug, was chosen as a probing molecule. The loading capacity of IBU was measured to be 752, 289, and 186 mg per g SiO2 for cal-HMSNs, ext-HMSNs, and NH2ext-HMSNs, respectively. cal-HMSNs have the highest drug loading capacity among the three samples, which is attributed to its high BET specific surface area and the appropriate size of mesopores (2.5 nm) compared with the size of IBU (ca. 1.0 0.6 nm).36 And ext-HMSNs have a much lowered loading capacity, which may be due to their larger mesopore size (3.8 nm), while NH2-ext-HMSNs have the lowest loading capacity, which may be because of their even larger mesopore size (3.4 and 7.9 nm) and low BET specific surface area. Figure 7a shows UV-vis spectra at different times of the aqueous media in which IBU was released from cal-HMSNs@IBU. The IBU concentration gradually increases with prolonging of time, indicating sustained release of IBU molecules. Kinetic release

4. CONCLUSIONS In summary, as-HMSNs with uniform morphology and structure were facilely fabricated by gasication of ethyl ether. Following template extraction gave more intact and better dened nanostructures of hierarchical mesopores than following calcination. Amino-functionalized HMSNs with well spherical structure and larger mesopores were obtained by co-condensation with APMS, though some unexpected silica sheets also appeared. Amino-functionalization on the mesopore wall of extHMSNs was also achieved successfully by postsynthesis modication. FITC molecules and Au NPs of <5 nm were homogeneously grafted/loaded in the mesopores of NH2-ext-HMSNs. ext-HMSNs were successfully used as building blocks to construct antireection and superhydrophilic coatings on glass substrates by the LbL dip coating method. The current coatings with hierarchically porous structures may have other potential applications as catalyst supports, chemical sensors, etc. Due to their hierarchically mesoporous nanostructures, HMSNs exhibited much quicker rates of drug release compared with conventional mesoporous NPs. The current study indicates that the HMSNs are promising as multifunctional and multipurpose carriers in biological, medical, catalytic, and coating applications.
ASSOCIATED CONTENT
S b

Supporting Information. Additional Figures S1-S9 and Table S1 and S2 as described in the text. This material is available free of charge via the Internet at http://pubs.acs.org.
dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

2978

Langmuir

ARTICLE

AUTHOR INFORMATION
Corresponding Author

*Tel.: 86-10-82543535. Fax: 86-10-82543535. E-mail: jhhe@mail.ipc.ac.cn.

ACKNOWLEDGMENT This work was supported by the Knowledge Innovation Program of the Chinese Academy of Sciences (CAS) (Grant No. KGCX2-YW-370), the National Natural Science Foundation of China-NSAF (Grant No. 10776034), the National Natural Science Foundation of China (Grant No. 20871118), Hundred Talents Program of CAS, and Graduate Science and Social Practice Special Funding Innovative Research Program of CAS. REFERENCES
(1) Zhang, H.; Hardy, G. C.; Rosseinsky, M. J.; Cooper, A. I. Adv. Mater. 2003, 15, 78. (2) Karkamkar, A. J.; Kim, S.; Mahanti, S. D.; Pinnavaia, T. J. Adv. Funct. Mater. 2004, 14, 507. (3) Andersson, J.; Johannessen, E.; Areva, S.; Baccile, N.; Azas, T.; Lind, M. J. Mater. Chem. 2007, 17, 463. e (4) Sel, O.; Sallard, S.; Brezesinski, T.; Rathousk, J.; Dunphy, D. R.; y Collord, A.; Smarsly, B. M. Adv. Funct. Mater. 2007, 17, 3241. (5) Ji, Q.; Acharya, S.; Hill, P. J.; Vinu, A.; Yoon, S. B.; Yu, J.; Sakamoto, K.; Ariga, K. Adv. Funct. Mater. 2009, 19, 1792. (6) Li, F.; Wang, Z.; Ergang, N. S.; Fyfe, C. A.; Stein, A. Langmuir 2007, 23, 3996. (7) Ho, W.; Yu, J. C.; Lee, S. Chem. Commun. 2006, 1115. (8) Wu, J.; Zhu, Y. J.; Cao, S. W.; Chen, F. Adv. Mater. 2010, 22, 749. (9) Polshettiwar, V.; Cha, D.; Zhang, X.; Basset, J. M. Angew. Chem., Int. Ed. 2010, 49, 9652. (10) Lim, Y. T.; Kim, J. K.; Noh, Y. W.; Cho, M. Y.; Chung, B. H. Small 2009, 5, 324. (11) Yoon, T. J.; Kim, J. S.; Kim, B. G.; Yu, K. N.; Cho, M. H.; Lee, J. K. Angew. Chem., Int. Ed. 2005, 44, 1068. (12) Fang, C.; Zhang, M. J. Mater. Chem. 2009, 19, 6258. (13) Lin, Y. S.; Haynes, C. L. Chem. Mater. 2009, 21, 3979. (14) Liong, M.; Angelos, S.; Choi, E.; Patel, K.; Stoddart, J. F.; Zink, J. I. J. Mater. Chem. 2009, 19, 6251. (15) Shiomi, T.; Tsunoda, T.; Kawai, A.; Matsuura, S. -I.; Mizukami, F.; Sakaguchi, K. Small 2009, 5, 67. (16) Loiola, A. R.; de Silva, L. R. D.; Cubillas, P.; Anderson, W. J. Mater. Chem. 2008, 18, 49854993. (17) Kruk, M.; Antochshuk, V.; Matos, J. R.; Mercuri, L. P.; Jaroniec, M. J. Am. Chem. Soc. 2002, 124, 768. (18) Du, L.; Liao, S.; Khatib, H. A.; Stoddart, J. F.; Zink, J. I. J. Am. Chem. Soc. 2009, 131, 15136. (19) Liu, N.; Dunphy, D. R.; Atanassov, P.; Bunge, S. D.; Chen, Z.; Lpez, G. P.; Boyle, T. J.; Brinker, C. J. Nano Lett. 2004, 4, 531. o (20) Mal, N. K.; Fujiwara, M.; Tanaka, Y. Nature 2003, 421, 350. (21) Homann, F.; Cornelius, M.; Morell, J.; Frba, M. Angew. o Chem., Int. Ed. 2006, 45, 3216. (22) Du, X.; He, J. Langmuir 2010, 26, 10057. (23) Walcarius, A.; Etienne, M.; Lebeau, B. Chem. Mater. 2003, 15, 2161. (24) Gartman, N.; Schtze, C.; Ritter, H.; Brhwiler, D. J. Phys. u u Chem. Lett. 2010, 1, 379. (25) Yoshitake, H.; Yokoi, T.; Tatsumi, T. Chem. Mater. 2002, 14, 4603. (26) Huang, X.; Teng, X.; Chen, D.; Tang, F.; He, J. Biomaterials 2010, 31, 438. (27) Joseph, T.; Vijay Kumar, K.; Ramaswamy, A. V.; Halligudi, S. B. Catal. Commun. 2007, 8, 629.

(28) Liu, X.; Du, X.; He, J. ChemPhysChem 2008, 9, 305. (29) Liu, X.; He, J. J. Phys. Chem. C 2009, 113, 148. (30) Du, X.; Liu, X.; Chen, H.; He, J. J. Phys. Chem. C 2009, 113, 9063. (31) Zhu, Y.; Shi, J.; Shen, W.; Dong, X.; Feng, J.; Ruan, M.; Li, Y. Angew. Chem., Int. Ed. 2005, 44, 5083. (32) Zhu, Y.; Shi, J.; Shen, W.; Chen, H.; Dong, X.; Ruan, M. Nanotechnology 2005, 16, 2633. (33) Feng, Z.; Li, Y.; Niu, D.; Li, L.; Zhao, W.; Chen, H.; Li, L.; Gao, J.; Ruan, M.; Shi, J. Chem. Commun. 2008, 2629. (34) Zhu, Y.; Shi, J.; Li, Y.; Chen, H.; Shen, W.; Dong, X. Microporous Mesopourous Mater. 2005, 85, 75. (35) Wang, J. G.; Li, F.; Zhou, H. J.; Sun, P. C.; Ding, D. T.; Chen, T. H. Chem. Mater. 2009, 21, 612. (36) Vallet-Reg, M.; Rmila, A.; del Real, R. P.; Prez-Pariente, J. a e Chem. Mater. 2001, 13, 308. (37) Mu~oz, B.; Rmila, A.; Prez-Pariente, J.; Daz, I.; Vallet-Reg, n a e M. Chem. Mater. 2003, 15, 500. (38) Balas, F.; Manzano, M.; Horcajada, P.; Vallet-Reg, M. J. Am. Chem. Soc. 2006, 128, 8116. (39) Guo, X.; Deng, Y.; Tu, B.; Zhao, D. Langmuir 2010, 26, 702. (40) Chen, Y.; Li, Y.; Chen, Y.; Liu, X.; Zhang, M.; Li, B.; Yang, Y. Chem. Commun. 2009, 5177. (41) Hoshikawa, Y.; Yabe, H.; Nomura, A.; Yamaki, T.; Shimojima, A.; Okubo, T. Chem. Mater. 2010, 22, 12. (42) Sing, K. S. W.; Everett, D. H.; Haul, R. A. W.; Moscou, L.; Piertti, R. A.; Rouqurol, J.; Siemieniewska, T. Pure Appl. Chem. 1985, e 57, 603. (43) Imhof, A.; Megens, M.; Engelberts, J. J.; de Lang, D. T. N.; Sprik, R.; Vos, W. L. J. Phys. Chem. B 1999, 103, 1408. (44) Rambaud, F.; Vall, K.; Thibaud, S.; Julin-Lpez, B.; Sanchez, e a o C. Adv. Funct. Mater. 2009, 19, 2896. (45) Du, X.; Li, X.; He, J. ACS Appl. Mater. Interfaces 2010, 2, 23652372. (46) Rosenholm, J. M.; Lindn, M. J. Controlled Release 2008, e 128, 157. (47) Rejman, J.; Oberle, V.; Zuhorn, I. S.; Hoekstra, D. Biochem. J. 2004, 377, 159.

2979

dx.doi.org/10.1021/la200014w |Langmuir 2011, 27, 29722979

You might also like