Functionalized SBA-15 materials as carriers for controlled drug delivery: influence of surface properties on matrix-drug interactions

Mesoporous SBA-15 materials were functionalized with amine groups through postsynthesis and one-pot synthesis, and the resulting functionalized materials were investigated as matrixes for controlled drug delivery. The materials were characterized by FTIR, N(2) adsorption/desorption analysis, zeta potential measurement, XRD, XPS, and TEM. Ibuprofen (IBU) and bovine serum albumin (BSA) were selected as model drugs and loaded onto the unmodified and functionalized SBA-15. It was revealed that the adsorption capacities and release behaviors of these model drugs were highly dependent on the different surface properties of SBA-15 materials. The release rate of IBU from SBA-15 functionalized by postsynthesis is found to be effectively controlled as compared to that from pure SBA-15 and SBA-15 functionalized by one-pot synthesis due to the ionic interaction between carboxyl groups in IBU and amine groups on the surface of SBA-15. However, SBA-15 functionalized by one-pot synthesis is found to be more favorable for the adsorption and release of BSA due to the balance of electrostatic interaction and hydrophilic interaction between BSA and the functionalized SBA-15 matrix.     

Tailored doxycycline delivery from MCM-41-type silica carriers

Doxycycline, an antibiotic from the tetracycline class with a broad spectrum of activity, was used to prepare drug delivery systems based on pristine and functionalized mesostructured silica supports. MCM-41-type materials with different textural, structural, and surface properties were used to assess their influence on the drug release kinetics. Small- and wide-angle XRD, FTIR spectroscopy and N₂ adsorption/desorption isotherms were used to characterize the carriers before and after doxycycline loading. The drug release experiments were performed in vitro in 0.2 M phosphate buffer solution at 37 °C, and the slowest drug release kinetics was obtained for magnesium-modified MCM-41 carrier. All drug-loaded materials exhibited good antibacterial activity against Klebsiella pneumoniae ATCC 10031 strain, similar to the drug alone.     

有序介孔二氧化硅对正丁醛的吸附性能

合成了一系列具有不同孔结构与性质的有序介孔二氧化硅材料SBA-15、MCM-41、SBA-16、KIT-6, 同时通过改变水热温度制备了不同孔径大小的SBA-15, 并利用小角X射线散射、透射电镜、扫描电镜和氮气吸附-脱附等手段, 对其介孔结构进行了表征. 以正丁醛为探针分子, 考察了其对有机醛的吸附, 并与Y-沸石的吸附性能做了对比. 结果表明, 材料的介孔比表面积与其对正丁醛的吸附量成正比, 吸附等温线符合Langmuir 模型, 属于单层吸附, 具有最大介孔比表面积的MCM-41对正丁醛的吸附量最大(484 mg·g^-1). 最后将SBA-15添加到卷烟滤嘴中, 实验结果表明, SBA-15能显著降低卷烟烟气中巴豆醛的释放量.     

有序介孔二氧化硅对正丁醛的吸附性能

合成了一系列具有不同孔结构与性质的有序介孔二氧化硅材料SBA-15、MCM-41、SBA-16、KIT-6,同时通过改变水热温度制备了不同孔径大小的SBA-15,并利用小角X射线散射、透射电镜、扫描电镜和氮气吸附-脱附等手段,对其介孔结构进行了表征.以正丁醛为探针分子,考察了其对有机醛的吸附,并与Y-沸石的吸附性能做了对比.结果表明,材料的介孔比表面积与其对正丁醛的吸附量成正比,吸附等温线符合Langmuir模型,属于单层吸附,具有最大介孔比表面积的MCM-41对正丁醛的吸附量最大(484 mg·g-1).最后将SBA-15添加到卷烟滤嘴中,实验结果表明,SBA-15能显著降低卷烟烟气中巴豆醛的释放量.     

Effect of amine functionalization of spherical MCM-41 and SBA-15 on controlled drug release

MCM-41 and SBA-15 silica materials with spherical morphology and different particle sizes were synthesized and modified by post-synthesis method with 3-aminopropyltriethoxysilane (APTES). A comparative study of the adsorption and release of a model drug, ibuprofen, were carried out. The modified and drug loaded mesoporous materials were characterized by XRD, TEM, N₂ physisorption, thermal analysis, elemental analysis and FT-IR spectroscopy. Surface modification with amino groups resulted in high degree of ibuprofen loading and slow rate of release for MCM-41, whereas it was the opposite for SBA-15. The adsorbed drug content and the delivery rate can be predetermined by the choice of mesoporous material with the appropriate structural characteristics and surface functionality.     

Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica

A series of Al-containing SBA-15 type materials with different Si/Al ratio, were prepared by post-synthesis modification of a pure highly ordered mesoporous silica SBA-15 obtained by using sodium silicate as silica source, and amphiphilic block copolymer as structure-directing agent. A high level of aluminum incorporation was achieved, reaching an Si/Al ratio of up to 5.5, without any significant loss in the textural properties of SBA-15. These materials were fully characterized by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), ²⁷Al NMR spectroscopy, and N₂ adsorption at 77 K. The acid properties of these materials have been evaluated by NH₃-TPD, adsorption of pyridine and deuterated acetonitrile coupled to FTIR spectroscopy. The effective acidity of these materials was evaluated using two catalytic reactions: 2-propanol dehydrogenation and 1-butene isomerization. The adsorption of basic probe molecules and the catalytic behavior revealed an evolution of the acid properties with the Al content. These studies have shown that the Al-SBA-15 materials contain Brønsted and Lewis acid sites with medium acidity which makes them appropriate to be used as acid catalysts in heterogeneous catalysis, catalytic supports, and adsorbents.     

pH值响应性毒死蜱/铜席夫碱配合物改性SBA-15的制备及缓释性能

以3-氨丙基三乙氧基硅烷(APTES)、水杨醛和铜离子为改性剂,通过后嫁接法制得铜席夫碱配合物改性SBA-15(Cu-SBA-15),并以毒死蜱为模型药物,制备了毒死蜱/铜席夫碱配合物改性SBA-15缓释体系。利用TEM、SEM、XRD、N2吸附-脱附、TG、FTIR和XPS对SBA-15、氨基改性SBA-15(NH_2-SBA-15)、水杨醛希夫碱改性SBA-15(SA-SBA-15)的形貌、结构和Cu-SBA-15的配位情况进行了表征,考察了SBA-15在改性前后对毒死蜱的吸附量和缓释性能,并着重探究了毒死蜱/铜席夫碱配合物改性SBA-15载药体系在不同pH值下的释药行为。结果表明,APTES和水杨醛能够通过后嫁接法修饰于SBA-15,修饰后仍保持十分有序的孔道结构。SBA-15通过改性后,其对毒死蜱的吸附量由100 mg·g~(-1)增加至195 mg·g~(-1),且其对药物的缓释性能也得到改善。毒死蜱/铜席夫碱配合物改性SBA-15缓释体系显示出明显的pH值响应性,pH=3时的释药速率大于pH=11时,而在中性条件下的缓释效果相对最好。载药体系的释药行为可用Riger-Peppas动力学模型来描述,其药物释放由Fick扩散控制。     

Mesoporous silica-magnetite nanocomposite: facile synthesis route for application in hyperthermia

The synthesis of nanostructured magnetic materials has been intensively researched because of their large field of applications as magnetic carriers in drug targeting, hyperthermia in tumor treatment, among others. Much effort has been invested in magnetic nanoparticles for bioapplications. However, as these nanoparticles present high specific surface area, unprotected nanoparticles can easily form aggregates and react with oxygen in the air. They can also rapidly biodegrade when directly exposed to biological systems. In this context, we have explored the possibility of synthesizing a mesoporous SiO₂–Fe₃O₄ nanocomposite and its AC magnetic-field-induced heating properties. The magnetite nanocomposite was obtained by impregnation of an iron precursor into a silica framework. The proposed method involves the preparation of an iron oxide precursor in ethanol and the subsequent impregnation of SBA-15 mesoporous hexagonal silica. Iron oxide was formed inside the porous structure, thus producing the magnetic device. The nanocomposite was characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), N₂ adsorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Measurements of AC magnetic-field-induced heating properties of the obtained nanocomposite, both of the solid form and in aqueous solution, under different applied magnetic fields showed that it is suitable as a hyperthermia agent for biological applications.     

pH值响应性毒死蜱/铜席夫碱配合物改性SBA-15的制备及缓释性能

以3-氨丙基三乙氧基硅烷（APTES）、水杨醛和铜离子为改性剂,通过后嫁接法制得铜席夫碱配合物改性SBA-15（Cu-SBA-15）,并以毒死蜱为模型药物,制备了毒死蜱/铜席夫碱配合物改性SBA-15缓释体系。利用TEM、SEM、XRD、N₂吸附-脱附、TG、FTIR和XPS对SBA-15、氨基改性SBA-15（NH₂-SBA-15）、水杨醛希夫碱改性SBA-15（SA-SBA-15）的形貌、结构和Cu-SBA-15的配位情况进行了表征,考察了SBA-15在改性前后对毒死蜱的吸附量和缓释性能,并着重探究了毒死蜱/铜席夫碱配合物改性SBA-15载药体系在不同pH值下的释药行为。结果表明,APTES和水杨醛能够通过后嫁接法修饰于SBA-15,修饰后仍保持十分有序的孔道结构。SBA-15通过改性后,其对毒死蜱的吸附量由100 mg·g^-1增加至195 mg·g^-1,且其对药物的缓释性能也得到改善。毒死蜱/铜席夫碱配合物改性SBA-15缓释体系显示出明显的pH值响应性,pH=3时的释药速率大于pH=11时,而在中性条件下的缓释效果相对最好。载药体系的释药行为可用Riger-Peppas动力学模型来描述,其药物释放由Fick扩散控制。     

Iron oxide nanoparticles supported on NH2- and COOH-functionalized SBA-15

Iron modified NH₂- or COOH- functionalized SBA-15 is characterized by XRD, N₂-physisorption, TPR-TG, FTIR, M?ssbauer spectroscopy and methanol decomposition. The material obtained from COOH-functionalized silica exhibits the highest catalytic activity.     

Organo-modified mesoporous silica for sorption of carbon dioxide

Abstract  

Organo-modified mesoporous silica SBA-15 has been studied for sorption of carbon dioxide (CO₂). The SBA-15 sample was functionalized with a branched chain polymer, polyethylenimine (PEI), of different molecular weights (1,300 and 2,000 g mol⁻¹). Surface modification was carried out by impregnation of silica by PEI or by grafting with (3-chloropropyl)triethoxysilane, followed by substitution of chlorine atoms by PEI ligands. The prepared modified mesoporous materials were characterized by nitrogen adsorption/desorption at 77 K, high-resolution transmission electron microscopy, small-angle X-ray scattering, and thermal methods. Sorption of CO₂ was studied by gravimetric method at 303 K. The total amount of sorbed CO₂ varied between 0.19–0.67 mmol/g for respective samples. Regeneration of the materials after adsorption was achieved by thermal treatment at 343 K.     

Aqueous mercury adsorption in a fixed bed column of thiol functionalized mesoporous silica

The aim of this work was to investigate the aqueous mercury adsorption in a fixed bed of mesostructured silica SBA-15 functionalized with propylthiol by co-condensation (SBA-15-SH). Powdered synthesized adsorbents were used to prepare pellets with sizes ranging from 0.5 to 1 mm. The physicochemical properties determined from N₂ adsorption and chemical analysis were compared for powder and pellets. Batch static experiments were carried out to obtain the equilibrium mercury adsorption isotherms, resulting that although the maximum adsorption capacity was reduced from powder to pellets, the materials maintained high efficiency for mercury removal even at very low aqueous metal concentration. Dynamic experiments were carried out in a fixed bed column by modifying the volumetric flow rate, bed length, inlet concentration, and amount of propylthiol groups incorporated to the adsorbent, and analyzing the temporal scale and the mercury adsorption capacities. The elution of the fixed bed was carried out chemically by circulating an aqueous 2 M hydrobromic acid stream for 2 h so achieving a complete recovery of the mercury previously adsorbed. Simplified dynamic equations of Bohart–Adams and Wolborska were used for modeling the breakthrough curves.     

氨基功能化短孔道有序介孔材料H_2N-Zr-Ce-SBA-15的合成及吸附性能

以pluronic(P123)为模板剂,正硅酸乙酯(TEOS)为硅源,氯化氧锆和硝酸亚铈为无机前驱盐,N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(AAPTS)为硅烷化试剂,采用后接枝法合成了氨基功能化六方板状短孔道有序介孔材料H2N-Zr-Ce-SBA-15(H2N-ZCS).采用小角X射线衍射(LXRD)、傅里叶变换红外(FTIR)光谱、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热重分析、N2吸附/脱附等手段对H2N-ZCS进行了表征.结果表明AAPTS成功地嫁接到有序介孔材料上,H2N-ZCS仍保持了类似于传统SBA-15高度有序的二维六方相介孔结构,且孔道方向垂直于该六方板面.对阴离子染料酸性品红吸附实验表明,H2N-ZCS比H2N-SBA-15具有较强的吸附能力.这种功能化短孔道、大径轴比的六方板状介孔材料在吸附、分离及催化等领域中能更有效地促进分子的扩散传递.     

Synthesis of carboxyl-modified rod-like SBA-15 by rapid co-condensation

Carboxyl-modified SBA-15 rod-like mesoporous materials have been synthesized by a facile rapid co-condensation of tetraethylorthosilicate (TEOS) and 2-cyanoethyltriethoxysilane (CTES), followed by hydrolysis of cyanide groups in sulfuric acid. The concentration of carboxylic groups was varied by changing the silica source ratio of CTES/TEOS from 0.05 to 0.3. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the uniform ordered mesoporous structure and rod-like morphology of SBA-15 have been preserved even at the high concentration of carboxylic groups employed. Characterization by Fourier transformed infrared spectroscopy (FTIR), solid-state NMR investigation indicated that carboxylic groups have been successfully grafted onto the surface of SBA-15 through siloxane bonds [(O(3))SiCH(2)CH(2)COOH. The negative charges of the modified SBA-15 materials were enhanced by the presence of the carboxylic groups on the surface. The capacity of lysozyme adsorption of the modified SBA-15 materials were found to be significantly improved as compared with pure silica SBA-15. The maximum amount of lysozyme adsorption on carboxyl-modified was increased with the pH of solution increased from 5.5 to 9.0.     

SBA-15负载Pd催化剂的制备及其在Heck反应中的应用研究

利用水热反应制备了表面离子液体功能化的SBA-15介孔材料,在丙酮溶液中与氯化钯反应,然后使用水合肼在乙醇中还原.测试了这种催化剂在Mizoroki-Heck反应中的催化活性.与直接负载在SBA-15上的钯催化剂相比,这种表面修饰的介孔SBA-15负载催化剂表现出更高的催化活性、可回收性和反应稳定性.氮气吸脱附实验和小角XRD衍射实验表明,在合成中,材料的介孔性能并没有被破坏.透视电镜也表征了该材料的表面形貌.最后,Mizoroki-Heck反应表明该催化剂具有很高的催化活性,且循环五次后,其催化活性降低并不明显.     

Submicron particles of SBA-15 modified with MgO as carriers for controlled drug delivery

Submicron particles with modified surface were synthesized by a simple one-pot synthesis approach and used as drug carrier for controlled release. Due to the alkalinity of MgO species on the surface, the amount of a model drug, ibuprofen, adsorbed on the modified surface was increased as compared to pure silica SBA-15 although the surface area was decreased by the surface modification. FTIR investigation indicated that the adsorption state of ibuprofen on MgO modified SBA-15 was different from that on pure silica SBA-15 and pure crystal ibuprofen. The result obtained from in vitro release test exhibited that the surface modification greatly decreased the ibuprofen release rate. In first 6 h in vitro release test, only 63% of the adsorbed ibuprofen was released from the MgO/SBA-15 (Si/Mg=20). In contrast, the release of ibuprofen was complete in 1 h from the pure silica SBA-15 under the same release conditions. The surface modified with MgO created affinity with acidic ibuprofen molecules and retarded the release rate from the mesoporous matrix. In addition, the release rate of ibuprofen could be modulated by varying the content of MgO, and was found to decrease with increasing amount of MgO on surface of SBA-15 submicron particles.     

Combining mesoporous silica–magnetite and thermally-sensitive polymers for applications in hyperthermia

In this work, the synthesis strategy of a multifunctional system of [SBA-16/P(N-iPAAm)/Fe₃O₄] hybrids of interest for magneto-hyperthermia was explored. Magnetite nanoparticles coated by mesoporous silica were prepared by an alternative chemical route using neutral surfactant and without the application of any functionalization method. Monomer adsorption followed by in situ polymerization initiated by a radical was used to incorporate the hydrogel into the pore channels of the silica nanocomposite. Structural and magnetic characterization of the obtained materials was carried out by using thermal analysis, X-ray diffraction, N₂ adsorption desorption isotherms, ⁵⁷Fe Mössbauer spectroscopy, vibrating sample magnetometry and transmission electron microscopy. Measurements of alternating current magnetic-field-induced heating behaviour under different applied magnetic fields showed that the [SBA-16/P(N-iPAAm)/Fe₃O₄] hybrid here synthesized is suitable as a hyperthermia agent for biological applications.     

Synthesis and characterization of surface modified SBA-15 silica materials and their application in chromatography

Hexagonally ordered SBA-15 mesoporous silica spheres with large uniform pore diameters are obtained using the triblock copolymer, Pluronic P123, as template with a cosurfactant cetyltrimethylammonium bromide (CTAB) and the cosolvent ethanol in acidic media. A series of surface modified SBA-15 silica materials is prepared in the present work using mono- and trifunctional alkyl chains of various lengths which improves the hydrothermal and mechanical stability. Several techniques, such as element analysis, nitrogen sorption analysis, small angle X-ray diffraction, scanning electron microscopy (SEM), FTIR, solid-state (29)Si and (13)C NMR spectroscopy are employed to characterize the SBA-15 materials before and after surface modification with the organic components. Nitrogen sorption analysis is performed to calculate specific surface area, pore volume and pore size distribution. By surface modification with organic groups, the mesoporous SBA-15 silica spheres are potential materials for stationary phases in HPLC separation of small aromatic molecules and biomolecules. The HPLC performance of the present SBA-15 samples is therefore tested by means of a suitable test mixture.     

有机胺修饰具有较大孔径介孔材料的二氧化碳吸附性能

以非离子表面活性剂P123为模板剂,正硅酸甲酯为硅源,通过加入不同的扩孔剂制得具有较大孔径的SBA-15类介孔材料,并采用粉末X射线衍射(XRD)、低温氮气吸附-脱附、扫描电镜(SEM)、傅里叶变换红外(FTIR)光谱等手段对所得样品进行了表征.加入扩孔剂可以明显增大介孔材料的孔容和孔径,而异辛烷为扩孔剂的扩孔效果明显优于四氯化碳.经四乙烯五胺(TEPA)镀饰后,这些样品均表现出良好的CO2吸附性能.其中对于除去模板剂后再镀胺的样品,其CO2吸附能力与介孔材料孔道结构关系不大,而对于未除模板剂的原粉镀胺样品,CO2吸附能力则随孔道的变大而增强.此外,通过吸附等温线和CO2-程序升温脱附(TPD)手段比较了温度和压力对CO2吸附的影响,发现在较高温度下吸附时CO2的吸附能力随压力的变化存在显著差别,因而在这类TEPA修饰的介孔材料上可通过变压吸附的途径来实现对环境气流中CO2的吸附和分离.     

Mesoporous SBA-15 materials modified with PW or W active species as catalysts for the epoxidation of olefins with H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Five catalysts containing PW or W active species that anchored onto aminosilylated mesoporous silica SBA-15 by a post-grafting route were prepared and the resulting PW or W/APTES/SBA-15 hybrid materials were characterized by XRD, N₂ adsorption/desorption, surface area analysis, TEM, FT-IR, and ICP (inductively coupled plasma atomic emission spectroscopy). The names of these catalysts have been abbreviated as SBA-15m-a, SBA-15m-b, SBA-15m-c, SBA-15m-d, and SBA-15m-e according to the different active species. The PW or W active species were highly dispersed in the channels of the modified mesoporous materials. The interaction between PW or W species and amino groups grafted on the channel surface of SBA-15 led to the immobilization of PW or W species. Their catalytic activity in the epoxidation of cyclooctene with H₂O₂ as oxidant was investigated. Among them, SBA-15m-a showed the best performance, with 98.9% conversion and 98.4% selectivity. The catalyst could be reused for six times with a little decrease in activity.