Biomineralization Nanolithography: Combination of Bottom‐Up and Top‐Down Fabrication To Grow Arrays of Monodisperse Gold Nanoparticles Along Peptide Lines

Nuraje, Nurxat; Mohammed, Samia; Yang, Linglu; Matsui, Hiroshi

doi:10.1002/ange.200805145

Cited by 6 publications

(5 citation statements)

References 33 publications

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“…12,13 Additionally, top-down and bottom-up techniques can be employed together for improved resolution and spatial control. 14 Block copolymers (BCPs) offer high spatial resolution through their self-assembly into periodically ordered, microphase-separated nanoscale morphologies at equilibrium. 15,16 The ability to tune BCPs by their architecture, relative block volumes, and Flory−Huggins interaction parameter to form a variety of morphologies with length scales on the order of tens of nanometers makes them an ideal platform for templating thin films.…”

Section: ■ Introductionmentioning

confidence: 99%

Block Copolymer Directed Nanostructured Surfaces as Templates for Confined Surface Reactions

et al. 2017

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Despite advances in nanomaterials synthesis, the bottom-up preparation of nanopatterned films as templates for spatially confined surface reactions remains a challenge. We report an approach to fabricating nanoscale thin film surface structures with periodicities on the order of 20 nm and with the capacity to localize reactions with small molecules and nanoparticles. A block copolymer (BCP) of polystyrene-block-poly[(allyl glycidyl ether)-co-(ethylene oxide)] (PS-b-P(AGE-co-EO)) is used to prepare periodically ordered, reactive thin films. As proof-of-principle demonstrations of the versatility of the chemical functionalization, a small organic molecule, an amino acid, and ultrasmall silica nanoparticles are selectively attached via thiol−ene click chemistry to the exposed P(AGE-co-EO) domains of the BCP thin film. Our approach employing click chemistry on the spatially confined reactive surfaces of a BCP thin film overcomes solvent incompatibilities typically encountered when synthetic polymers are functionalized with watersoluble molecules. Moreover, this post-assembly functionalization of a reactive thin film surface preserves the original patterning reduces the amount of required reactant, and leads to short reaction times. The demonstrated approach is expected to provide a new materials platform in applications including sensing, catalysis, pattern recognition, or microelectronics.

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Section: ■ Introductionmentioning

confidence: 99%

Block Copolymer Directed Nanostructured Surfaces as Templates for Confined Surface Reactions

et al. 2017

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“…Ligand interactions with nanoparticles (NPs) and NP/NP interactions are implicated in essentially all NP applications including bottom-up device fabrications, biosensing, cancer therapy, and catalysis . Collective oscillations of free electrons in plasmonic NPs under resonance excitations generate strong local electrical fields, which lead to surface-enhanced optical spectroscopic phenomena including surface-enhanced Raman spectroscopy (SERS).…”

Section: Introductionmentioning

confidence: 99%

“…A similar AgNP LSPR change has been observed with aromatic organothiol binding with AgNPs, 11 which was attributed to the organothiol conversion of surface silver atoms into insoluble RS-Ag salts accumulated on the AgNP. 1,19 Consequently, the dielectric constant of the medium surrounding the AgNP is increased, but the metal core size is reduced. Computational modeling showed that such a NP structural change induces red-shift of the AgNP LSPR peak and reduces AgNP LSPR peak absorbance.…”

Section: ■ Introductionmentioning

confidence: 99%

Dispersion Stability, Ligand Structure and Conformation, and SERS Activities of 1-Alkanethiol Functionalized Gold and Silver Nanoparticles

Ansar¹,

Gadogbe²,

Siriwardana³

et al. 2014

J. Phys. Chem. C

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Dispersion stability, ligand structure and conformation, and SERS activities of 1-alkanethiol (C n H 2n+1 SH, n = 2−14) functionalized gold and silver nanoparticles (AuNPs and AgNPs) were studied as a function of alkanethiol carbon chain length and nanoparticle (NP) type and size. The dispersion stability of alkanethiol functionalized NPs in water increases with increasing alkanethiol chain length and NP size, and the stabilities of the alkanethiol-containing AuNPs are higher than their AgNP counterparts. C 3 H 7 SH and longer alkanethiols are highly ordered on AgNPs but disordered on AuNPs. The SERS intensity of the C−S stretch band for the model alkanethiols on AgNPs and AuNPs decays exponentially (I = I 0 exp(−N c /N 0 )) with increasing number of carbon atoms (N c ). The empirical decay length N 0 , in terms of the number of the carbon atoms, is 1.29, 0.53, and 0.10 for AgNPs with diameters of 50, 30, and 10 nm, respectively. This decay length is less than 1 for AuNPs of difference sizes. These results show that changing the NP gap size by a distance equivalent to a single chemical bond can have a significant impact on the NP integrated SERS activities.

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“…Examples include the intricate nano‐ and microcrystalline structures found in mollusk shells,1 coccoliths,2 and eggshells,3 which imbue the shells with important physical properties. Recent work has exploited biomolecules4, 5 and biomimetic processes6, 7 to fabricate new materials, but the scope for this would be greatly enhanced if the mechanism by which the biomolecules effect this control were better understood. Molecular simulation should be an ideal tool for identifying these mechanisms.…”

mentioning

confidence: 99%

Structural Control of Crystal Nuclei by an Eggshell Protein

et al. 2010

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The use of biomolecules in nature to direct crystal growth leads to a degree of polymorph and morphology control that far surpasses anything currently accessible in a laboratory. Examples include the intricate nano-and microcrystalline structures found in mollusk shells, [1] coccoliths, [2] and eggshells, [3] which imbue the shells with important physical properties. Recent work has exploited biomolecules [4,5] and biomimetic processes [6,7] to fabricate new materials, but the scope for this would be greatly enhanced if the mechanism by which the biomolecules effect this control were better understood. Molecular simulation should be an ideal tool for identifying these mechanisms. Methods have been developed to model the clustering of inorganic ions on biomolecules, [8] but simulating the onset of long-range crystalline order in the inorganic deposit due to the biomolecule has not been possible. Crystal nucleation, a crucial step in polymorph selection, occurs on timescales that have hitherto been inaccessible to molecular simulation. Herein, we show that our recent developments to metadynamics, [9,10] coupled with the latest generation of leadership-class computing, have now made it possible to simulate the role of a native protein in controlling the onset of mineral crystallization. We illustrate this process with the first molecular simulation of spontaneous crystallization of amorphous CaCO 3 in the presence of the chicken eggshell protein ovocleidin-17 (OC-17).Eggshells have an intricate structure that consists of two domains attached to an inner membrane. [11] The first domain is an array of small polycrystalline calcite clusters (mammillary caps) attached to the membrane that surrounds the albumin; the second domain (pallisade layer) consists of elongated calcite crystals with partial alignment. Experiments have identified various proteins associated with eggshell formation. One class, C-type lectin-type proteins, is found only within the mineral region and is important in controlling calcite deposition. [12] In vitro studies with OC-17 (chicken) and ansocalcin (goose) have shown that these proteins promote calcite formation and define the crystal morphology. [13][14][15] There is now much experimental evidence that many biominerals, [16] including eggshells, [17] begin as nanoparticle deposits of an amorphous inorganic material. Our recent simulations [10] support this, showing amorphous calcium carbonate (ACC) to be energetically stable, even at larger particle sizes where calcite becomes thermodynamically preferred. The interaction between OC-17 and ACC particles of various sizes is therefore likely to be fundamental to the mechanism by which OC-17 controls calcite growth, and so forms the focus of the work described herein.Simulations [18] were performed using metadynamics (metaD). [19,20] MetaD extends conventional molecular dynamics (MD) to sample the free-energy landscape in terms of collective coordinates (that is, order parameters or reaction coordinates). It is particularly good at finding the rar...

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Biomineralization Nanolithography: Combination of Bottom‐Up and Top‐Down Fabrication To Grow Arrays of Monodisperse Gold Nanoparticles Along Peptide Lines

Cited by 6 publications

References 33 publications

Block Copolymer Directed Nanostructured Surfaces as Templates for Confined Surface Reactions

Block Copolymer Directed Nanostructured Surfaces as Templates for Confined Surface Reactions

Dispersion Stability, Ligand Structure and Conformation, and SERS Activities of 1-Alkanethiol Functionalized Gold and Silver Nanoparticles

Structural Control of Crystal Nuclei by an Eggshell Protein

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