Organic Functionalization and Morphology Control of Mesoporous Silicas via a Co-Condensation Synthesis Method

Huh, Seong; Wiench, Jerzy W.; Yoo, † Ji-Chul; Pruski, and Marek; Lin, Victor S.‐Y.

doi:10.1021/cm0210041

Cited by 759 publications

(689 citation statements)

References 44 publications

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“…It also allows the use of extraction as the only method for surfactant removal, as calcination could destroy organic compounds. After pioneering works of the groups of Mann and co-workers [33] and MacQuarrie [34], many different organically modified mesoporous silicas have been prepared by co-condensation, including those modified with alkyl, thiol, vinyl/allyl [35], amino, cyano/isocyano [36], alkoxy [37], organophosphine, and aromatic groups [38]. Periodic mesoporous organosilicas (PMOs) are materials with modified matrices but preserved organized pore system and narrow pore size distribution.…”

Section: Introductionmentioning

confidence: 99%

Adsorption of hydrogen peroxide on functionalized mesoporous silica surfaces

2014

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MCM-41 and MSU-H mesoporous silicas were successfully functionalized with hydrogen bonds forming organic moieties, which have been proven by elemental analysis. Both moieties, based on oxygen and nitrogen containing groups, were introduced with high efficiencythe amount of carbon in all cases exceeded 10 % and the elemental ratios suggest binding to the surface through two or three Si-O-Si bonds. Hydrogen peroxide adsorption was conducted in its aqueous solutions and the amount adsorbed was determined using the ferric thiocyanate method. Results are presented as a function of hydrogen peroxide concentration in aqueous solution from 5 to 30 %. Both functionalized silicas show increased adsorption capacity when compared with that of their unfunctionalized analogues. The surface modified with nitrogen-based organic moiety revealed better adsorption properties as well as higher resistance against oxidation. MSU-H silica, due to its larger pore diameter, provides more space to bind hydrogen peroxide molecules and thus was found to have higher adsorption capacity: it adsorbed up to four times more hydrogen peroxide than MCM-41.

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Section: Introductionmentioning

confidence: 99%

Adsorption of hydrogen peroxide on functionalized mesoporous silica surfaces

2014

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“…[1][2][3][4][5] The MSN materials with well-ordered cylindrical pore structures, such as MCM-41 and SBA-15, have attracted special interest in the biomedical field. 1 The large surface areas and pore volumes of these materials allow the efficient adsorption of a wide range of molecules, including small drugs, 6-10 therapeutic proteins, [11][12][13] antibiotics, 14,15 and antibodies.…”

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confidence: 99%

Interaction of Mesoporous Silica Nanoparticles with Human Red Blood Cell Membranes: Size and Surface Effects

Zhao¹,

Sun²,

Zhang³

et al. 2011

ACS Nano

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The interactions of mesoporous silica nanoparticles (MSNs) of different particle sizes and surface properties with human red blood cell (RBC) membranes were investigated by membrane filtration, flow cytometry, and various microscopic techniques. Small MCM-41-type MSNs (∼100 nm) were found to adsorb to the surface of RBCs without disturbing the membrane or morphology. In contrast, adsorption of large SBA-15-type MSNs (∼600 nm) to RBCs induced a strong local membrane deformation leading to spiculation of RBCs, internalization of the particles, and eventual hemolysis. In addition, the relationship between the degree of MSN surface functionalization and the degree of its interaction with RBC, as well as the effect of RBC−MSN interaction on cellular deformability, were investigated. The results presented here provide a better understanding of the mechanisms of RBC−MSN interaction and the hemolytic activity of MSNs and will assist in the rational design of hemocompatible MSNs for intravenous drug delivery and in vivo imaging. R ecent advancements in particle size and morphology control of mesoporous materials have led to the creation of nano-and submicrometer-sized mesoporous silica nanoparticles (MSNs). [1][2][3][4][5] The MSN materials with well-ordered cylindrical pore structures, such as MCM-41 and SBA-15, have attracted special interest in the biomedical field. 1 The large surface areas and pore volumes of these materials allow the efficient adsorption of a wide range of molecules, including small drugs, 6-10 therapeutic proteins, 11-13 antibiotics, 14,15 and antibodies. 16 Therefore, these materials have been proposed for use as potential vehicles for biomedical imaging, real-time diagnosis, and controlled delivery of multiple therapeutic agents. [6][7][8]10,[17][18][19][20][21][22][23][24][25] Despite the considerable interest in the biomedical applications of MSNs, relatively few studies have been published on the biocompatibility of the two most common types of MSNs (MCM-41 and SBA-15). [26][27][28][29] Asefa and co-workers reported that the cellular bioenergetics (cellular respiration and ATP levels) were inhibited remarkably by large SBA-15 nanoparticles, but the inhibition was greatly reduced by smaller MCM-41-type nanoparticles. 26 These differences in the disruption of cellular bioenergetics are believed to be caused by the different surface areas, number of surface silanol groups, and/or particle sizes of both types of material. A recent study by Kohane and collaborators on the systemic effects of MCM-41 (particle size ∼150 nm) and SBA-15 (particle size ∼800 nm) MSNs in live animals revealed interesting findings regarding their biocompatibility. 27 While large doses of mesoporous silicas administered subcutaneously to mice appear to be relatively harmless, the same doses given intravenously or intraperitoneally were lethal. 27 A possible reason for the severe systemic toxicity of MSNs when injected intravenously could be the interactions of the nanoparticles with blood cells.Our initial studies...

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“…The interaction between the 3-aminopropyl group and the surfactant micelles during the synthesis of the material tends to favor its localization at the interface between the surfactant and the surface of silica ( Figure 2a). This interface corresponds to the pore surface of the resulting materials (9,10). Powder X-ray diffraction of the material suggests a highly ordered 2D-hexagonal array of mesopores (Figure 2b), as confirmed by transmission electron microscopy (Figure 2c).…”

Section: Synthesis Of Ap-msn and Catalysis Of Self-aldol Condensationmentioning

confidence: 71%

Supported Hybrid Enzyme-Organocatalysts for Upgrading the Carbon Content of Alcohols

Kandel

Althaus

Pruski

et al. 2013

ACS Symposium Series

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A bicatalytic system was prepared by the immobilization of alcohol oxidase enzyme and an alkylamine organocatalyst in distinct locations of mesoporous nanoparticles. The resulting nanocomposites were able to perform a sequence of oxidation and aldol coupling reactions, which transformed short chain alcohols into longer chain molecules. The process takes place at low temperatures, but requires additional enzyme (catalase) to prevent inactivation of the catalyst. This qualitative study introduces a model of a hybrid multicomponent nanomaterial that resembles the behavior of multienzymatic systems within confined spaces. Disciplines Chemistry CommentsReprinted (adapted) with permission from ACS Symposium Series 1132 (2013) A bicatalytic system was prepared by the immobilization of alcohol oxidase enzyme and an alkylamine organocatalyst in distinct locations of mesoporous nanoparticles. The resulting nanocomposites were able to perform a sequence of oxidation and aldol coupling reactions, which transformed short chain alcohols into longer chain molecules. The process takes place at low temperatures, but requires additional enzyme (catalase) to prevent inactivation of the catalyst. This qualitative study introduces a model of a hybrid multicomponent nanomaterial that resembles the behavior of multienzymatic systems within confined spaces.

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Organic Functionalization and Morphology Control of Mesoporous Silicas via a Co-Condensation Synthesis Method

Cited by 759 publications

References 44 publications

Adsorption of hydrogen peroxide on functionalized mesoporous silica surfaces

Adsorption of hydrogen peroxide on functionalized mesoporous silica surfaces

Interaction of Mesoporous Silica Nanoparticles with Human Red Blood Cell Membranes: Size and Surface Effects

Supported Hybrid Enzyme-Organocatalysts for Upgrading the Carbon Content of Alcohols

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