Chiral Imprinting with Amino Acids of Ordered Mesoporous Silica Exhibiting Enantioselectivity after Calcination

Lacasta, Susana; Sebastián, Víctor; Casado, Clara; Mayoral, Álvaro; Romero, Pilar; Larrea, Á.; Vispe, Eugenio; López‐Ram‐de‐Víu, Pilar; Uriel, Santiago; Coronas, Joaquı́n

doi:10.1021/cm1032546

“…[4,5] Although this is a refined process to simultaneously control the morphology and chirality, in conventional chiral mesoporous silica formation, the hydrolytic condensation of alkoxysilane is catalyzed by the added HCl or NaOH solution rather than by micellar template itself. [6][7][8][9] In the design of silica materials, the greatest designer and authority is surely biosilica, such as diatoms and sponges, which have very beautiful, complex, and sophisticated shapes in nano-and microdimensions with silica skeletons. [10][11][12][13] In this sense, diatoms and sponges are eternal texts with a lot of sources of inspiration for the synthesis of silica-based nano/microscale materials, including chiral silica.…”

mentioning

confidence: 99%

High‐Temperature‐Resistant Chiral Silica Generated on Chiral Crystalline Templates at Neutral pH and Ambient Conditions

Matsukizono

¹

,

Jin

²

2012

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In memory of Tadatomi NishikuboChirality is one of the fundamental issues in the related fields of biology, medicine, chemistry, and physics, [1] because components of life, medicine, and display devices are composed of chiral molecules, such as DNA, proteins, cellulose, sugar, amino acids, drugs, and liquid crystalline molecules. However, chirality is not restricted to these molecular regimes. Solid minerals and inorganic materials also have chirality, which arises from the geometric properties and the atomic structure of surfaces. [1][2][3] A difference between molecular and mineral chirality would be in its resilience; the former is temporary at the limited environment, while the latter will be semi-permanent even under the harsh conditions. Therefore, artificial chiral minerals would have great potential for memory, preservation, and development of organic chiral systems.Helical mesoporous silica, which was pioneered by Tatsumi et al, [4] is one of current topics in chiral mineral materials. Its chirality is induced by a templated sol-gel reaction where special micelles self-assembled from chiral molecules serve as templates to direct helical morphology, thereby imprinting the chiral topology in silica. [4,5] Although this is a refined process to simultaneously control the morphology and chirality, in conventional chiral mesoporous silica formation, the hydrolytic condensation of alkoxysilane is catalyzed by the added HCl or NaOH solution rather than by micellar template itself. [6][7][8][9] In the design of silica materials, the greatest designer and authority is surely biosilica, such as diatoms and sponges, which have very beautiful, complex, and sophisticated shapes in nano-and microdimensions with silica skeletons. [10][11][12][13] In this sense, diatoms and sponges are eternal texts with a lot of sources of inspiration for the synthesis of silica-based nano/microscale materials, including chiral silica. It is well known that in the biogenic silica formation, organized organic matrices, such as silaffins (polypeptides), silicateins (proteins), and long-chain polyamines play as catalysts (temporal control) and templates (spatial control) in silica deposition under neutral pH and ambient conditions. [14][15][16][17][18][19][20][21][22][23][24] As mimicking those organic matrices, a lot of organic molecules and polymers having amino groups have been used in the biomimetic silica deposition, and major achievements have been accomplished in this field over the past decade. [25][26][27][28][29][30][31][32][33][34][35][36][37] However, no efforts were put on the construction of chiral silica, although many biomimetic silicas were deposited by co-precipitation with chiral polypeptides. [25][26][27][28] Among biomimetic silica formation, the silicateins particularly attracted our interest because they form axial filaments (fibrils) and act as templates to deposit silica around the surface of the fibrils to give fibrous hybrids consisted of axial filaments and silica shell. [20,22,23] Recently, we have established...

show abstract

“…Its chirality is induced by a templated sol-gel reaction where special micelles self-assembled from chiral molecules serve as templates to direct helical morphology, thereby imprinting the chiral topology in silica. [6][7][8][9] In the design of silica materials, the greatest designer and authority is surely biosilica, such as diatoms and sponges, which have very beautiful, complex, and sophisticated shapes in nano-and microdimensions with silica skeletons. [6][7][8][9] In the design of silica materials, the greatest designer and authority is surely biosilica, such as diatoms and sponges, which have very beautiful, complex, and sophisticated shapes in nano-and microdimensions with silica skeletons.…”

Section: In Memory Of Tadatomi Nishikubomentioning

confidence: 99%

“…[1][2][3] A difference between molecular and mineral chirality would be in its resilience; the former is temporary at the limited environment, while the latter will be semi-permanent even under the harsh conditions. [6][7][8][9] In the design of silica materials, the greatest designer and authority is surely biosilica, such as diatoms and sponges, which have very beautiful, complex, and sophisticated shapes in nano-and microdimensions with silica skeletons. Its chirality is induced by a templated sol-gel reaction where special micelles self-assembled from chiral molecules serve as templates to direct helical morphology, thereby imprinting the chiral topology in silica.…”

mentioning

confidence: 99%

High‐Temperature‐Resistant Chiral Silica Generated on Chiral Crystalline Templates at Neutral pH and Ambient Conditions

Matsukizono

¹

,

Jin

²

2012

View full text Add to dashboard Cite

In memory of Tadatomi NishikuboChirality is one of the fundamental issues in the related fields of biology, medicine, chemistry, and physics, [1] because components of life, medicine, and display devices are composed of chiral molecules, such as DNA, proteins, cellulose, sugar, amino acids, drugs, and liquid crystalline molecules. However, chirality is not restricted to these molecular regimes. Solid minerals and inorganic materials also have chirality, which arises from the geometric properties and the atomic structure of surfaces. [1][2][3] A difference between molecular and mineral chirality would be in its resilience; the former is temporary at the limited environment, while the latter will be semi-permanent even under the harsh conditions. Therefore, artificial chiral minerals would have great potential for memory, preservation, and development of organic chiral systems.Helical mesoporous silica, which was pioneered by Tatsumi et al, [4] is one of current topics in chiral mineral materials. Its chirality is induced by a templated sol-gel reaction where special micelles self-assembled from chiral molecules serve as templates to direct helical morphology, thereby imprinting the chiral topology in silica. [4,5] Although this is a refined process to simultaneously control the morphology and chirality, in conventional chiral mesoporous silica formation, the hydrolytic condensation of alkoxysilane is catalyzed by the added HCl or NaOH solution rather than by micellar template itself. [6][7][8][9] In the design of silica materials, the greatest designer and authority is surely biosilica, such as diatoms and sponges, which have very beautiful, complex, and sophisticated shapes in nano-and microdimensions with silica skeletons. [10][11][12][13] In this sense, diatoms and sponges are eternal texts with a lot of sources of inspiration for the synthesis of silica-based nano/microscale materials, including chiral silica. It is well known that in the biogenic silica formation, organized organic matrices, such as silaffins (polypeptides), silicateins (proteins), and long-chain polyamines play as catalysts (temporal control) and templates (spatial control) in silica deposition under neutral pH and ambient conditions. [14][15][16][17][18][19][20][21][22][23][24] As mimicking those organic matrices, a lot of organic molecules and polymers having amino groups have been used in the biomimetic silica deposition, and major achievements have been accomplished in this field over the past decade. [25][26][27][28][29][30][31][32][33][34][35][36][37] However, no efforts were put on the construction of chiral silica, although many biomimetic silicas were deposited by co-precipitation with chiral polypeptides. [25][26][27][28] Among biomimetic silica formation, the silicateins particularly attracted our interest because they form axial filaments (fibrils) and act as templates to deposit silica around the surface of the fibrils to give fibrous hybrids consisted of axial filaments and silica shell. [20,22,23] Recently, we have established...

show abstract

“…It has been suggested that a minimum of three simultaneous interactions between one of the enantiomers and the chiral selector is required, with at least one of these interactions being stereochemically dependent 10. Alternatively, chiral stationary phases for chromatography can be produced by molecular imprinting of silica 11–13. While often providing high‐quality chiral separations, chromatographic techniques are characterized by high energy consumption, steep costs, low efficiency, and discontinuous operation 4…”

Section: Introductionmentioning

confidence: 99%

Silica Colloidal Membranes with Enantioselective Permeability

Leon

¹

,

Abelow

²

,

Cichelli

³

et al. 2014

Israel Journal of Chemistry

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Dedicated to the memory of Professor Michael Bendikov: a brilliant scientist, a great friend, and a courageous man ties in the range of 1.2-1.8, which were not significantly affected by the structure of the surface-immobilized chiral electors. This selectivity is on par with most reported polymer-based solid membranes and bulk liquid membranes. The enantioselectivity results from the surface-facilitated mechanism of transport of enantiomers through the mesopores.

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Chiral Imprinting with Amino Acids of Ordered Mesoporous Silica Exhibiting Enantioselectivity after Calcination

Cited by 38 publications

References 44 publications

High‐Temperature‐Resistant Chiral Silica Generated on Chiral Crystalline Templates at Neutral pH and Ambient Conditions

High‐Temperature‐Resistant Chiral Silica Generated on Chiral Crystalline Templates at Neutral pH and Ambient Conditions

High‐Temperature‐Resistant Chiral Silica Generated on Chiral Crystalline Templates at Neutral pH and Ambient Conditions

Silica Colloidal Membranes with Enantioselective Permeability

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