Elsevier

Applied Surface Science

Volume 283, 15 October 2013, Pages 537-545
Applied Surface Science

Solvent optimization for niacinamide adsorption on organo-functionalized SBA-15 mesoporous silica

https://doi.org/10.1016/j.apsusc.2013.06.141Get rights and content

Highlights

  • The ordered SBA-15 mesoporous material was successfully modified with various trialkoxysilanes.

  • The best performance of niacinamide adsorption was observed for sulfopropyl-modified SBA-15.

  • Superior adsorption of niacinamide on SBA-15 was observed in non-polar and aprotic solvents.

Abstract

This work describes the application of organo-modified SBA-15 siliceous materials as the carrier for niacinamide. The surface functionalization of SBA-15 by a grafting strategy with triethoxyphenylsilane, triethoxy(4-methoxyphenyl)silane, triethoxymethylsilane and (3-mercaptopropyl)trimethoxysilane as modifying agents has been successfully achieved. The adsorption process was performed in acetonitrile, methanol, 2-propanol, 1-pentanol and ethyl acetate. The obtained results indicated a promote niacinamide adsorption on sulfopropyl-modified (119 mg/g) and non-modified (78 mg/g) SBA-15 from ethyl acetate. The pure and derivatized SBA-15 products have been characterized by elemental analysis, thermogravimetry, nitrogen adsorption and diffuse reflectance UV spectroscopy. After niacinamide adsorption the textural parameters of mesoporous carriers such as BET surface area, pore volume and microporosity were reduced. The mesoporous matrices loaded with niacinamide exhibited prolonged-release kinetics of this vitamin, especially from sulfopropyl-modified SBA-15 carrier.

Graphical abstract

Simultaneous effect of solvent polarity and adsorbent functionalization on niacinamide adsorption.

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Introduction

Since the discovery of the new class of siliceous mesoporous material of MCM-41 family in 1992 by Kresge et al. [1] new era in materials chemistry has been initiated. The unique physicochemical properties of ordered mesoporous materials such as large specific surface area, uniform pore size distribution and possibility of their surface modification [2] allow preparation of advanced materials for multiple potential applications in chemical and pharmaceutical sciences.

Initially, the mesoporous molecular sieves were used in heterogeneous catalysis [3], [4]. The post-synthetic siliceous surface modification by condensation of free silanol groups with organo-modified trialkoxysilanes [5] and surface functionalization during direct co-condensation synthesis [6] were played a meaningful role in potential application and propagation of mesoporous structures. Presently, the mesoporous materials are widely applied in analytical chemistry as stationary phase in HPLC method [7], biosensors component [8], element of fuel cells [9] and batteries [10], adsorbent for removal of environmental pollutants [11], carriers for enzymes and biomolecules in biocatalysis processes [12].

Since 2001, when Vallet-Regi et al. [13] described the application of MCM-41 ordered mesoporous material as the carrier in drug delivery systems (DDSs), great opportunities for pharmaceutical sciences have been opened. This work has attracted the interest of researchers and initiated the preparation of novel mesoporous materials for drug formulations.

Originally, mesoporous sieves were used as the reservoir for prolonged and controlled drug release. The advantages of these mesostructured materials rely on their large surface area, the presence of micropores (e.g. SBA-15) in the wall structures and tortuos character of mesoporous channels [14]. Following this idea, the application of mesoporous matrices improved the kinetics of release of poorly water-soluble drugs [15]. In the last few years, these types of siliceous mesoporous materials underwent huge development and found application as the carriers for a wide variety of active substances such as cell anti-proliferative agents [16], anti-inflammatory drugs [17], antibiotics [18], corticosteroids [19] smooth muscle relaxants [20] and others [14], [21]. Apart from traditional diffusion drug delivery systems based on mesoporous sieves, magnetic [22], pH-responsive [23], luminescent [24] and enzyme-mediated [25] DDSs were reported.

Considering the above, this paper describes the potential application of organo-functionalized SBA-15 siliceous mesoporous materials as the carrier for niacinamide. The optimization of niacinamide adsorption process is performed in various organic solvents characterized by different polarity. Niacinamide (nicotinamide, PP vitamin) is water-soluble vitamin with anti-pellagra activity [26]. This small active substance exhibits very interesting biological properties. Recently, Mohammad et al. [27] confirmed moisturizing effect of niacinamide in alleviating dry skin condition by reduction of underlying chronic inflammatory process and improvement of stratum corneum barrier function. The clinical studies performed by the group of Bissett and coworkers [28] revealed efficiency of niacinamide and N-acetyl glucosamine-containing formulation in reduction of irregular hyperpigmentation. Moreover, this vitamin is applied as anti-wrinkle cosmetic ingredient [29]. Niacinamide plays also an important role in biochemical processes such as carcinogenesis, DNA repair, genomic stabilization [30], and protection of neurons from nicotinamide-adenine dinucleotide depletion [31].

The aim of this study is to achieve the best performance for a vitamin PP adsorption on mesoporous matrix and to provide niacinamide prolonged release from the carrier. This SBA-15-vitamin complex may be potentially used as niacinamide supplement or cosmetic ingredient.

Section snippets

Chemicals and materials

Niacinamide (≥99.5%), non-ionic surfactant P123 [poly-ethylene-glycol-block-polypropylene-glycol-block-polyethylene-glycol (Mw = 5800)], tetraethyl orthosilicate (≥99.0%), triethoxyphenylsilane (≥98.0%), triethoxy(4-methoxyphenyl)silane (97%), triethoxymethylsilane (99%), (3-mercaptopropyl)trimethoxysilane (95%), 1-pentanol (puriss. p.a., ≥99.0%), 2-propanol (puriss. p.a., ≥99.8%) and perhydrol (purum p.a., ≥30.0%) were purchased from Sigma–Aldrich (St. Louis, MO, USA). Hydrochloric acid (purum

Characterization of organo-functionalized SBA-15 carriers

Fig. 1 represents the small-angle X-ray diffraction (SAXRD) patterns of the five samples. Samples of pure SBA-15 silica and SBA-15 modified with trialkoxysilanes clearly show three well-resolved reflections that may be indexed to the (1 0 0), (1 1 0) and (2 0 0) diffractions at 0.9°, 1.6° and 1.8°, respectively. The presence of these reflections indicates that the ordered hexagonal mesoporous structure of the samples synthesized with trialkoxysilanes via grafting method is preserved [33].

Conclusions

The adsorption of niacinamide on SBA-15 mesoporous material has been the focus of this paper. The modification of SBA-15 surface and properties of the solvents were shown to play an important role in the adsorption process. Different trialkoxysilanes applied in the grafting methods seemed to be an appropriate tool for the change of SBA-15 surface properties. These studies confirmed suitability of liquid–solid chromatography rule in adsorption process of organic compounds on SBA-15 mesoporous

Acknowledgement

The author thank Prof. Marek Łaniecki from Faculty of Chemistry A. Mickiewicz University in Poznan for valuable comments and help in this study realization.

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