Solid Lipid Nanoparticle - Functional Template of Meso

Chapter 17

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Solid Lipid Nanoparticle - Functional Template of Meso-Macrostructured Silica Materials Sanghoon Kim, Jonathan Jacoby, Marie-José Stébé, Nadia Canilho, and Andreea Pasc* Université de Lorraine/CNRS, SRSMC, UMR 7565, F-54506, Vandeouvre-lès-Nancy, Cedex, France *E-mail: [email protected].

Solid lipid nanoparticles (SLN) are biocolloidal dispersions able to be loaded with hydrophilic or hydrophobic ingredients, either of low molecular weight drugs or high molecular weight proteins. Their interest is not limited to colloidal science but can be extended to material design, for templating inorganic materials or to afford functional hybrid organic-inorganic materials. Indeed, dispersions of SLN can be used to prepare meso-macroporous materials through a dual templating mechanism combining self-assembling of micelles and imprinting of soft nanoparticles. Moreover, by loading SLN with curcumin, one can obtain responsive carriers, which are of interest in nanomedecine. Finally, supported biocatalysts were obtained by mineralizing green double dispersions W/SLN/W containing a lipase into the aqueous core.

Introduction Hierarchical porous materials combine unique properties of mesostructures, such as high surface area and controllable sized pores, with those of macropores providing high diffusion and throughput rates (1). Typical applications of these materials are separation (2), catalysis (3), sensing (4) or tissue engineering (5). They have also potential applications as reservoirs in drug delivery systems or as inclusion cavities for macromolecules. There are a number of ways to fabricate © 2015 American Chemical Society In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


hierarchical macro–mesostructured silica (6–8), most of them combine soft and hard-templating techniques, for example by using small molecules, surfactants or polymers with hard colloidal spheres (9, 10) such as polystyrene (PS), poly(methyl methacrylate) (PMMA) latexes or silica spheres (9), but also starch gels (11), polyacrylamide-based hydrogels (12), aerogels (13), polyurethane foams (14) or wood tissue (15). Hierarchical porous materials have also been prepared without the use of hard templates, either based on in situ formed polymeric particles (16, 17), bigels (18, 19) or emulsion droplets (20–24), to cite some of them. Our approach to design hierarchical porous silica is inspired by these previously reported examples, but here the originality consists in using a novel soft template, solid lipid nanoparticles (SLN). In recent years, these nanoparticles emerged in the soft matter field as promising drug carriers with target applications in pharmaceutical and biomedical domains (25, 26). Silica is also known to be safe, not only for the environment, but also for the human body within a certain range of administrated dose, approved by US Food and Drug Administration (FDA). Therefore, its application field may be extended to biocompatible materials, such as bone substitutes, cements for bone repair and reconstruction, enzyme and cell immobilization (27), biocatalysts or biosensors (28–33) or for oral drug delivery (34–38). Therefore, combining inorganic silica matter with solid lipid nanoparticles, SLN, appears to be a straightforward approach for the development of novel hybrid organic–inorganic biocompatible materials with high potential applications in drug delivery and food chemistry. SLN not only have a limited toxicity, but also they can be produced in a cost-effective way by different formulation techniques: high-pressure homogenization (industrial method), emulsification–sonication, microemulsion, double emulsion, solvent emulsification–evaporation, solvent diffusion and solvent injection. SLN possess a solid lipid core matrix stabilized by a surfactant shell and are dispersed in an aqueous micellar solution of the same surfactant in excess. Therefore, they could allow the preparation of hierarchical porous materials combining both a cooperative templating mechanism (CTM) and a transcription templating mechanism (39). This paper describes the synthesis of hybrid solid lipid nanoparticle SLN@meso-macroporous silica materials and their uses as novel system for nanomedicine or biocatalysis.

Porous Silica Material Templated by Solid Lipid Nanoparticles SLN-templated porous material was prepared by adding at neutral pH a silica source (tetramethoxylsilane, TMOS) onto SLN dispersions. SLN were prepared form cetyl palmitate (NHP) and Tween 20 by the solvent injection method (40). The mixture was kept in an autoclave at 70 °C to allow the hydrolysis/polycondensation of the silica. The inorganic silica material was obtained after the removal of the organic particles by ethanol/dichloromethane extraction. The designed synthesis strategy is illustrated in Figure 1. 270 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


The macroporous network can be observed by scanning electron microscopy (SEM) analysis. As a matter of fact, silica beads containing spherical macropores of 0.5–1.5 μm in diameter are clearly shown in Figure 1B. The macropore diameters are of the same order of magnitude as the starting SLN. Deeper insights on the morphology of the material were reached by transmission electron microscopy (TEM) (Figure 1C) that clearly showed individual hollow silica spheres.

Figure 1. Schematic illustration of SLN formation and templating of macroporous silica beads. Reproduced with permission from reference (40). Copyright 2011 The Royal Society of Chemistry. 271 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


The morphology and the structure of SLN templated hierarchical meso–macroporous silica could also be tuned (41). By optimizing the reaction conditions such as hydrothermal temperature, TMOS amount or surfactant concentration, silica capsules could be obtained with polyoxyethylene sorbitan (Tween 20 and 40) imprinting of lipid nanoparticles, whereas block silica was obtained with Pluronic P123. Mesopore diameters of about 3 nm were obtained with Tween 20, 5 nm with Tween 40 and 9 nm with Pluronic P123. The size of the mesopores increases with the size of the starting micelles, from Tween 20 to P123. The ordering at the mesoscale also increases with the mesopore size: only wormlike silica was obtained with Tween 20; wormlike silica embedding hexagonally ordered microdomains with Tween 40 and hexagonally ordered silica with circularly ordered mesoporosity were obtained by using P123 as a porogen (Figure 2). Hierarchical meso-macroporous silica material possessing circularly ordered mesoporosity around macropore could offer a highly confined environment for SLN encapsulated drugs (Figure 2C). Indeed, curcumin release from circularly ordered “silicalized” drug- loaded SLN shows a significant decrease of the drug released up to 20 %, as compared to wormlike “silicalized” SLN (data not published). Further details on the curcumin loading and release from various SLN@silica systems will be given in the next section.

Figure 2. (A) Schematic representation of hierarchical porous silica obtained through a dual templating mechanism combining micelles (CTM) and SLN transcription; (B) TEM image of silica capsule obtained using Tween 40 based SLN; (C) TEM image of hexagonally ordered meso-macroporous silica matrix (selected zone shows circularly ordered mesoporosity around macropore). Reproduced with permission from reference (41). Copyright 2012 The Royal Society of Chemistry. 272 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


pH-Controlled Delivery of Curcumin from a Compartmentalized Solid Lipid Nanoparticle@Mesostructured Silica Matrix In recent years, the design of nanocarriers for controlled and sustained delivery of drugs has been extensively studied in order to overcome several problems in conventional drug delivery systems, such as poor solubility, limited stability and lack of selectivity of drugs (42–44). Indeed, CU, a hydrophobic natural polyphenol isolated from Curcuma longa, has been used for centuries in indigenous medicine in the treatment of a variety of inflammatory conditions. It exhibits a wide range of pharmacological capacities, including antitumor, antioxidant, anti-inflammatory, and antimicrobial activities (45–48). However, the main drawback for clinical applications of curcumin are its low water solubility at acidic and physiological pH and its rapid hydrolysis under alkaline conditions to yield ferulic acid, its methyl ester and vanillin (49). These hurdles can be avoided by incorporating CU into nanoparticles, liposomes, micelles, complexing it with cyclodextrins (CD) in aqueous solutions (50) or mesoporous silica (51). Solid lipid nanoparticles (SLNs) loaded with CU for topical administration were also developed and characterized (52). SLNs with a mean size of 450 nm were found to be stable for 6 months and incorporation into SLN strongly reduced the light and oxygen sensitivity of curcuminoids. However, the organic matter based drug carriers could be instable, thus unexpected drug leaking can occur during storage (53). To overcome the disadvantages mentioned above, we recently designed a novel drug delivery system aimed to increase the stability, bioavailability and sustainability of the release of curcumin, through a double encapsulation of the drug into a core–shell nanomatrix combining SLNs and mesostructured silica (54). SLNs act as reservoirs of CU, while mesopores act as pathways to control drug release.

Figure 3. IR spectra (A) and SAXS pattern (B) of CU-SA-SLNs (a), blankSA-SLNs (b), blank-NHP-SLNs (c), CU-NHP-SLNs (d), curcumin (e); SAXS pattern (C) of NHP-Mat (a) and SA-Mat (b) after removal of organic matter. Values in SAXS patterns represent Bragg distances d=2π/q, where q is the scattering vector. Reproduced with permission from reference (54). Copyright 2014 The Royal Society of Chemistry. 273 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 4. TEM image of meso–macroporous silica NHP-Mat (A and B) and SA-Mat (C and D) after removal of organic matter (arrows indicate macropores). Reproduced with permission from reference (54). Copyright 2014 The Royal Society of Chemistry.

The main strategy consists in silicalizing curcumin loaded SLN/micelles dispersion through a dual templating mechanism combining self-assembling of micelles into mesostructured domains (55) and transcription of lipid nanoparticles into macro-structured domains. Indeed, during SLN preparation, one can control the curcumin-partitioning ratio (PR) between SLN core and micelles because curcumin encapsulation amount into SLN core particularly depends on the nature of the solid lipid (cetyl palmitate (NHP) vs. stearic acid (SA)). The interaction between CU and lipid could be the main factor for different partitioning ratio. The interaction can be confirmed using SAXS and FT-IR experiments (Figure 3A and 3B). For instance, cetyl palmitate based curcumin loaded SLN (CU-NHP-SLN), which PR is only 20%, showed no significant peak shift on SAXS and FT-IR spectra, while stearic acid based SLN (CU-SA-SLN) (65% of PR) exhibits strong 274 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


interaction, confirmed by peak shift on SAXS pattern and FT-IR spectra (56). Besides, the size of SLN was also affected by lipid source. According to the size distribution measurement obtained from dynamic DLS, NHP based SLN showed mean particle size as 300 nm in diameter, while 400 nm in diameter was found for SA based SLN. SLN@meso-macroporous silica matrix was obtained by adding silica precursor (tetramethoxysilane, TMOS) into curcumin-loaded solid lipid nanoparticle (SLN)/micelle dispersions, followed by hydrothermal treatment. Silica material shows hexagonally ordered mesopore network (Figure 3C and 4) as well as macropores, resulting from the imprinting of SLN. However, the size of macropores observed by TEM seems to be bigger than the size of SLN obtained by DLS. This might be due to coalescence of lipid nanoparticles, melted at 70°C during hydrothermal treatment. The release experiments of CU-loaded hybrid SLN silica materials were carried out in 3 different receiving media (pH 1.2, 4.5 and 7.4). Figure 5 shows the cumulative release of curcumin from hybrid materials at 25°C at various pH release media. At first, the drug released from NHP-based silica matrix (Figure 5A) quickly reached the plateau within 6 h at any pH. However, the maximum cumulative release percentage was varied with respect to the pH, 100%, 88%, and 16% for pH 1.2, 4.5 and 7.4, respectively. CU release curves from SA-based silica matrix (Figure 5B) show also pH dependence (CU cumulative release: 86, 68 and 18% for pH 1.2, 4.5 and 7.4, respectively). However, the release rate is slower than that of NHP-based silica (12 h vs. 6 h for saturation).

Figure 5. Curcumin cumulative release from (A) NHP-Mat (a) at pH 1.2, (b) at pH 4.5 and (c) at pH 7.4; (B) SA-Mat (a) at pH 1.2, (b) at pH 4.5 and (c) at pH 7.4. Reproduced with permission from reference (54). Copyright 2014 The Royal Society of Chemistry. 275 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 6. Possible interactions between curcumin and silanol on a silica surface (a) at pH 1.2, (b) at pH 4.5 and (c) at pH 7.4. Reproduced with permission from reference (54). Copyright 2014 The Royal Society of Chemistry.

The differences in the curcumin release behaviour might be due to the interaction between curcumin and silanol groups at the surface of silica as described in Figure 6. Moreover, after the release of CU that is encapsulated in mesopores, CU is fed only from the SLN that acts as a drug reservoir. Hence, the release rate becomes mainly dependent on the nature of SLN, which is again, influenced by pH (57). A plausible mechanism of the core–shell nanohybrid vectors described herein is schematized in Figure 7. Finally, cytotoxicity studies showed that the CU-loaded materials have similar IC50 values to free curcumin making the newly designed matrices of potential interest in nanomedicine.

Figure 7. Graphical representation of the release mechanism of curcumin from core–shell SLN@meso-macrostructured silica. Reproduced with permission from reference (54). Copyright 2014 The Royal Society of Chemistry. 276 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


A Meso-Macro Compartmentalized Bioreactor Obtained through Silicalization of “Green” Double Emulsions: W/O/W and W/SLNs/W Though SLN shows various advantages over traditional methods for encapsulation of a guest molecule, loading hydrophilic molecule such as enzymes into SLN has been limited because of hydrophobicity of lipid core of SLN. Several approaches have been attempted in order to increase the loading amount of the hydrophilic molecule. Functionalization (58) or ion pairing (59) of a guest molecule has showed a significant improvement of the guest molecule loading capacity. However, these methods could alter physical-chemical properties of such guest molecules. Our approach consists in using double emulsions in which the inner aqueous droplets contain the enzyme, here Mucor miehei lipase (MmL). This enzyme is known to be a good biocatalyst for the transesterification reaction of vegetable oils in the biodiesel production. Mineralizing this colloidal template pre-loaded with the lipase could afford an one-pot synthesis resulting in a meso-macroporous silica, which supports the enzyme (60). Interestingly, the macroporosity could be tailored herein by templating the silica with double emulsions that have the particularity of being converted into solid lipid nanoparticles (SLNs) by simple removal of the organic solvent (Figure 8).

Figure 8. Illustration of the transformation of a double emulsion containing a solid lipid dissolved in an organic solvent (W/O/W) into solid lipid nanoparticles (W/SLNs/W). (A) Addition of micelles of P123; (B) evaporation of limonene. Reproduced with permission from reference (60). Copyright 2014 The Royal Society of Chemistry. 277 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Briefly, the double emulsion (W/O/W) was prepared by adding a reverse (W/O) emulsion into an aqueous micellar solution of P123 under stirring. Dynamic light scattering measurements show that the size of aqueous droplets of the W/O emulsion is about 200–300 nm, whereas the size of the double emulsions is centered on 2 μm (Figure 9). The compartmentation of the W/O/W emulsion was also confirmed by optical microscopy (Figure 9). W/SLN/W emulsions were prepared by first evaporating 80 wt% of the double emulsion and then, by diluting the resulting highly concentrated emulsion with an aqueous solution of micelles. As determined by DLS, SLNs show a bimodal distribution centered at 130 and 550 nm (Figure 9). By introducing the enzyme (50 mg mL-1), no significant changes in the droplet size were observed. Silica materials were obtained by mineralizing the colloidal template, with or without enzyme, through sol–gel synthesis. Hence, meso-macrostructured silica materials result by a dual templating mechanism that combines the self-assembly of micelles of Pluronic P123 and templating of colloidal lipid spheres of either reverse emulsion (W(MmL)/O/W) or solid nanoparticles (W(MmL)/SLN/W).

Figure 9. Hydrodynamic diameter of O/W emulsion, W/O/W and W/SLNs/W emulsion as determined by DLS and the POM micrograph showing the compartmentalization of the W/O/W emulsion. Reproduced with permission from reference (60). Copyright 2014 The Royal Society of Chemistry.

TEM image of silica materials obtained from W/O/W (Figure 10) and W/SLNs/W (Figure 11) emulsion showed the presence of ordered mesoporosity as well as macropores, which are interconnected through mesopores. Indeed, MSLN sample (Material from SLN) shows macropores with 150 - 600 nm in diameter while MDE (Material from Double Emulsion) have macropores with more than 1μm in diameter. The above results indicate that the transition from MDE to MSLN is accompanied by a decrease of macropore size. These results clearly indicate the hierarchical structure of the silica matrix. The structuring is maintained while adding the lipase into the colloidal template (Figure 11C) 278 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 10. SEM (A) and TEM (B) micrographs of bare silica MDE. Reproduced with permission from reference (60). Copyright 2014 The Royal Society of Chemistry.

Figure 11. TEM micrographs of the bare silica material, MSLN (A and B) and of the enzyme loaded silica material, MmL-MSLN (C). Reproduced with permission from reference (60). Copyright 2014 The Royal Society of Chemistry.

Finally, the resulting materials, MmL-MDE and MmL-MSLN, were used as biocatalysts in the methanolysis of colza oil. The entrapped lipase (0.054 mg MmL per mg of silica) retains its catalytic activity and complete conversion is reached within 50 h (Figure 12, left). For comparison, the reaction was also performed using MmL that was physisorbed onto pre-synthesized mesoporous SBA-15 (0.43 mg MmL per mg of silica) having similar mesopore size, but no macropores. Complete conversion is reached within only 6 h. The difference in behaviour between SBA-15 and MDE or MSLN can be due to higher enzyme loading, almost a factor of 8. The main advantage of the method reported here is that a lower quantity of enzyme is needed. When the Mucor miehei lipase is physisorbed into SBA-15 a higher quantity of enzyme is required. It should be also noted that the encapsulation efficiency is of 100% in the case of entrapment of the enzyme into double dispersions, while of only 25% when the enzyme is physisorbed. 279 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Figure 12 shows that even the catalytic activity of the supported enzyme decreases rapidly, the colloidal-entrapped biocatalysts showed better efficiency than the corresponding physisorbed enzyme, with up to 5 consecutive runs in the case of MmL-MSLN and 4 consecutive runs in the case of MmL-MDE, vs. only 2 consecutive runs for MmL-SBA-15, as reported elsewhere (61).

Figure 12. Variation of the methyl ester (ME) yield as a function of time (left) and variation of methyl ester (ME) yield over the recycling runs obtained using MmL-MDE and MmL-MSLN supported biocatalysts, respectively (right). Reproduced with permission from reference (60). Copyright 2014 The Royal Society of Chemistry. The templating of silica with double emulsions containing an enzyme in the aqueous core of the hydrophobic droplets provides a viable pathway for the synthesis of supported biocatalysts. By using an oily mixture of a green solvent (i.e. limonene) and a solid lipid (i.e. cetylpalmitate), one can easily tune the size of the macrocavities from 5 μm in the case of the emulsion to 600 nm in the case of the solid lipid nanoparticles, by simply reducing the size of the colloidal template by evaporation of the organic solvent. The resulting supported biocatalyst was able to catalyse the methanolysis of colza oil, which is a reaction of interest for the biodiesel production.

Conclusion The present paper highlights the interest of solid lipid nanoparticles to design hierarchical porous materials or compartmentalized and functionalized hybrid materials. Straightforward applications of these novel systems are addressed in nanomedicine and biocatalysis. The morphology and the structure of hierarchical meso–macroporous silica can be easily tuned using a dual templating mechanism with micelles and solid lipid nanoparticles through systematic variations of the reaction parameters and the surfactant nature. 280 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.


Curcumin-loaded meso–macrostructured silica materials were also obtained by mineralizing dispersions of solid lipid nanoparticles in micellar solutions. The release pattern of curcumin highly depends on the pH of the receiving medium and the nature of lipid source. Moreover, a two-step release pattern was observed for stearic acid based hybrid silica matrix, which suggests that SLNs may act as reservoirs of CU, while mesopores act as pathways to control drug release. Lipase loaded-SLN@meso-macroporous silica has been synthesized via silicalization of double emulsion colloidal template. Hydrophobic droplets in of double emulsion can provide a viable pathway to tune the size of the macrocavities from micrometer, in the case of the emulsion, to submicrometer, in the case of the solid lipid nanoparticles, by simply reducing the size of the colloidal template by evaporation of the organic solvent. The resulting supported biocatalyst was able to catalyse the methanolysis of colza oil, a reaction of interest in the biodiesel production. In conclusion, solid lipid nanoparticle(SLN)/micellar dispersion appears as a straightforward way to design novel hybrid-silica system with improved stability and sustainability of guest molecules such as drugs or enzymes.

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283 In Green Polymer Chemistry: Biobased Materials and Biocatalysis; Smith, et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2015.

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