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Special Issue "Molecular Self-Assembly 2011"

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Molecular Recognition".

Deadline for manuscript submissions: closed (30 June 2011)

Special Issue Editor

Guest Editor
Prof. Dr. Jurriaan Huskens (Website)

Molecular Nanofabrication Group, MESA+ Institute for Nanotechnology, University of Twente, TNW/MNF, PO Box 217, 7500AE Enschede, The Netherlands
Fax: +31 53 4894645
Interests: host-guest chemistry; cyclodextrins; multivalency; supramolecular surface chemistry; supramolecular materials; nanolithography; soft lithography

Special Issue Information

Dear Colleagues,

Self-assembly provides a unique paradigm to obtain complex and functional molecular architectures in a spontaneous process from small building blocks. These building blocks are designed and preprogrammed with information which ensures the proper thermodynamic and structural properties of the resulting assembly. Essential features are therefore the tuning of inter- (and sometimes intra-) molecular interactions, the collective behavior of multiple interactions (multivalency, cooperativity), reversibility (potentially triggered by external stimuli) which allows error correction, and the expression of a function of the final assembly.

Self-assembly at surfaces can be particularly rewarding since the inherent immobilization and positioning allow characterization by surface analytical, amongst others single molecule, techniques and potential embedding in a device structure. Surfaces and interfaces play an ever larger role in supramolecular chemistry as this establishes the eminent position of supramolecular chemistry as a key enabler in nanotechnology.

The 2011 issue on molecular self-assembly invites the submission of papers on molecular self-assembly in the widest possible sense, ranging from solution systems to the assembly on surfaces and the application-oriented use of assembly in nanotechnology.

Prof. Dr. Jurriaan Huskens
Guest Editor

Keywords

  • self-assembly
  • supramolecular chemistry
  • nanotechnology
  • interfacial assembly
  • cooperativity
  • multivalency
  • dynamics

Related Special Issue

Published Papers (10 papers)

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Research

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Open AccessArticle A Supramolecular Sensing Platform for Phosphate Anions and an Anthrax Biomarker in a Microfluidic Device
Int. J. Mol. Sci. 2011, 12(11), 7335-7351; doi:10.3390/ijms12117335
Received: 24 August 2011 / Revised: 19 October 2011 / Accepted: 20 October 2011 / Published: 26 October 2011
Cited by 9 | PDF Full-text (2514 KB) | HTML Full-text | XML Full-text
Abstract
A supramolecular platform based on self-assembled monolayers (SAMs) has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. [...] Read more.
A supramolecular platform based on self-assembled monolayers (SAMs) has been implemented in a microfluidic device. The system has been applied for the sensing of two different analyte types: biologically relevant phosphate anions and aromatic carboxylic acids, which are important for anthrax detection. A Eu(III)-EDTA complex was bound to β-cyclodextrin monolayers via orthogonal supramolecular host-guest interactions. The self-assembly of the Eu(III)-EDTA conjugate and naphthalene β-diketone as an antenna resulted in the formation of a highly luminescent lanthanide complex on the microchannel surface. Detection of different phosphate anions and aromatic carboxylic acids was demonstrated by monitoring the decrease in red emission following displacement of the antenna by the analyte. Among these analytes, adenosine triphosphate (ATP) and pyrophosphate, as well as dipicolinic acid (DPA) which is a biomarker for anthrax, showed a strong response. Parallel fabrication of five sensing SAMs in a single multichannel chip was performed, as a first demonstration of phosphate and carboxylic acid screening in a multiplexed format that allows a general detection platform for both analyte systems in a single test run with µM and nM detection sensitivity for ATP and DPA, respectively. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Open AccessArticle Recognition-Mediated Assembly of Quantum Dot Polymer Conjugates with Controlled Morphology
Int. J. Mol. Sci. 2011, 12(9), 6357-6366; doi:10.3390/ijms12096357
Received: 28 August 2011 / Revised: 20 September 2011 / Accepted: 20 September 2011 / Published: 23 September 2011
Cited by 3 | PDF Full-text (702 KB) | HTML Full-text | XML Full-text
Abstract
We have demonstrated a polymer mediated “bricks and mortar” method for the self-assembly of quantum dots (QDs). This strategy allows QDs to self-assemble into structured aggregates using complementary three-point hydrogen bonding. The resulting nanocomposites have distinct morphologies and inter-particle distances based on [...] Read more.
We have demonstrated a polymer mediated “bricks and mortar” method for the self-assembly of quantum dots (QDs). This strategy allows QDs to self-assemble into structured aggregates using complementary three-point hydrogen bonding. The resulting nanocomposites have distinct morphologies and inter-particle distances based on the ratio between QDs and polymer. Time resolved photoluminescence measurements showed that the optical properties of the QDs were retained after self-assembly. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Open AccessArticle Ultrasmall Peptides Self-Assemble into Diverse Nanostructures: Morphological Evaluation and Potential Implications
Int. J. Mol. Sci. 2011, 12(9), 5736-5746; doi:10.3390/ijms12095736
Received: 1 July 2011 / Revised: 9 August 2011 / Accepted: 22 August 2011 / Published: 7 September 2011
Cited by 16 | PDF Full-text (1176 KB) | HTML Full-text | XML Full-text
Abstract
In this study, we perform a morphological evaluation of the diverse nanostructures formed by varying concentration and amino acid sequence of a unique class of ultrasmall self-assembling peptides. We modified these peptides by replacing the aliphatic amino acid at the C-aliphatic [...] Read more.
In this study, we perform a morphological evaluation of the diverse nanostructures formed by varying concentration and amino acid sequence of a unique class of ultrasmall self-assembling peptides. We modified these peptides by replacing the aliphatic amino acid at the C-aliphatic terminus with different aromatic amino acids. We tracked the effect of introducing aromatic residues on self-assembly and morphology of resulting nanostructures. Whereas aliphatic peptides formed long, helical fibers that entangle into meshes and entrap >99.9% water, the modified peptides contrastingly formed short, straight fibers with a flat morphology. No helical fibers were observed for the modified peptides. For the aliphatic peptides at low concentrations, different supramolecular assemblies such as hollow nanospheres and membrane blebs were found. Since the ultrasmall peptides are made of simple, aliphatic amino acids, considered to have existed in the primordial soup, study of these supramolecular assemblies could be relevant to understanding chemical evolution leading to the origin of life on Earth. In particular, we propose a variety of potential applications in bioengineering and nanotechnology for the diverse self-assembled nanostructures. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Open AccessArticle Selective Growth of α-Sexithiophene by Using Silicon Oxides Patterns
Int. J. Mol. Sci. 2011, 12(9), 5719-5735; doi:10.3390/ijms12095719
Received: 1 August 2011 / Revised: 25 August 2011 / Accepted: 29 August 2011 / Published: 6 September 2011
Cited by 2 | PDF Full-text (1431 KB) | HTML Full-text | XML Full-text
Abstract
A process for fabricating ordered organic films on large area is presented. The process allows growing sexithiophene ultra-thin films at precise locations on patterned Si/SiOx substrates by driving the orientation of growth. This process combines the parallel local anodic oxidation of [...] Read more.
A process for fabricating ordered organic films on large area is presented. The process allows growing sexithiophene ultra-thin films at precise locations on patterned Si/SiOx substrates by driving the orientation of growth. This process combines the parallel local anodic oxidation of Si/SiOx substrates with the selective arrangement of molecular ultra-thin film. The former is used to fabricate silicon oxide arrays of parallel lines of 400 nm in width over an area of 1 cm2. Selective growth arises from the interplay between kinetic growth parameters and preferential interactions with the patterned surface. The result is an ultra-thin film of organic molecules that is conformal to the features of the fabricated motives. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Figures

Open AccessArticle Functionalization and Self-Assembly of DNA Bidimensional Arrays
Int. J. Mol. Sci. 2011, 12(9), 5641-5651; doi:10.3390/ijms12095641
Received: 23 June 2011 / Revised: 12 August 2011 / Accepted: 23 August 2011 / Published: 2 September 2011
Cited by 4 | PDF Full-text (1205 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract Oligonucleotides carrying amino, thiol groups, as well as fluorescein, c-myc peptide sequence and nanogold at internal positions were prepared and used for the assembly of bidimensional DNA arrays. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Figures

Open AccessArticle Self-Assembly of Protein Monolayers Engineered for Improved Monoclonal Immunoglobulin G Binding
Int. J. Mol. Sci. 2011, 12(8), 5157-5167; doi:10.3390/ijms12085157
Received: 4 July 2011 / Revised: 4 July 2011 / Accepted: 10 August 2011 / Published: 15 August 2011
Cited by 2 | PDF Full-text (467 KB) | HTML Full-text | XML Full-text
Abstract
Bacterial outer membrane proteins, along with a filling lipid molecule can be modified to form stable self-assembled monolayers on gold. The transmembrane domain of Escherichia coli outer membrane protein A has been engineered to create a scaffold protein to which functional motifs [...] Read more.
Bacterial outer membrane proteins, along with a filling lipid molecule can be modified to form stable self-assembled monolayers on gold. The transmembrane domain of Escherichia coli outer membrane protein A has been engineered to create a scaffold protein to which functional motifs can be fused. In earlier work we described the assembly and structure of an antibody-binding array where the Z domain of Staphylococcus aureus protein A was fused to the scaffold protein. Whilst the binding of rabbit polyclonal immunoglobulin G (IgG) to the array is very strong, mouse monoclonal IgG dissociates from the array easily. This is a problem since many immunodiagnostic tests rely upon the use of mouse monoclonal antibodies. Here we describe a strategy to develop an antibody-binding array that will bind mouse monoclonal IgG with lowered dissociation from the array. A novel protein consisting of the scaffold protein fused to two pairs of Z domains separated by a long flexible linker was manufactured. Using surface plasmon resonance the self-assembly of the new protein on gold and the improved binding of mouse monoclonal IgG were demonstrated. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Open AccessArticle Syntheses and Self-assembling Behaviors of Pentagonal Conjugates of Tryptophane Zipper-Forming Peptide
Int. J. Mol. Sci. 2011, 12(8), 5187-5199; doi:10.3390/ijms12085187
Received: 13 June 2011 / Revised: 30 July 2011 / Accepted: 10 August 2011 / Published: 15 August 2011
Cited by 5 | PDF Full-text (1429 KB) | HTML Full-text | XML Full-text
Abstract
Pentagonal conjugates of tryptophane zipper-forming peptide (CKTWTWTE) with a pentaazacyclopentadecane core (Pentagonal-Gly-Trpzip and Pentagonal-Ala-Trpzip) were synthesized and their self-assembling behaviors were investigated in water. Pentagonal-Gly-Trpzip self-assembled into nanofibers with the width of about 5 nm in neutral water (pH 7) via formation [...] Read more.
Pentagonal conjugates of tryptophane zipper-forming peptide (CKTWTWTE) with a pentaazacyclopentadecane core (Pentagonal-Gly-Trpzip and Pentagonal-Ala-Trpzip) were synthesized and their self-assembling behaviors were investigated in water. Pentagonal-Gly-Trpzip self-assembled into nanofibers with the width of about 5 nm in neutral water (pH 7) via formation of tryptophane zipper, which irreversibly converted to nanoribbons by heating. In contrast, Pentagonal-Ala-Trpzip formed irregular aggregates in water. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Figures

Open AccessArticle Enhanced Chiral Recognition by Cyclodextrin Dimers
Int. J. Mol. Sci. 2011, 12(7), 4637-4646; doi:10.3390/ijms12074637
Received: 16 June 2011 / Revised: 7 July 2011 / Accepted: 8 July 2011 / Published: 18 July 2011
Cited by 2 | PDF Full-text (1024 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
In this article we investigate the effect of multivalency in chiral recognition. To this end, we measured the host-guest interaction of a β-cyclodextrin dimer with divalent chiral guests. We report the synthesis of carbohydrate-based water soluble chiral guests functionalized with two borneol, [...] Read more.
In this article we investigate the effect of multivalency in chiral recognition. To this end, we measured the host-guest interaction of a β-cyclodextrin dimer with divalent chiral guests. We report the synthesis of carbohydrate-based water soluble chiral guests functionalized with two borneol, menthol, or isopinocampheol units in either (+) or (–) configuration. We determined the interaction of these divalent guests with a β-cyclodextrin dimer using isothermal titration calorimetry. It was found that—in spite of a highly unfavorable conformation—the cyclodextrin dimer binds to guest dimers with an increased enantioselectivity, which clearly reflects the effect of multivalency. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
Figures

Open AccessArticle One-Dimensional Hydrogen-Bonded Infinite Chain from Nickel(II) Tetraaza Macrocyclic Complex and 1,2-Cyclopentanedicarboxylate Ligand
Int. J. Mol. Sci. 2011, 12(4), 2232-2241; doi:10.3390/ijms12042232
Received: 14 February 2011 / Revised: 24 March 2011 / Accepted: 25 March 2011 / Published: 1 April 2011
Cited by 6 | PDF Full-text (382 KB) | HTML Full-text | XML Full-text
Abstract
The reaction of [Ni(L)]Cl2·2H2O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,01.18,07.12]docosane) with trans-1,2-cyclopentanedicarboxylic acid (H2-cpdc) yields a 1D hydrogen-bonded infinite chain with formula [Ni(L)(H-cpdc-)2] (1). This complex has [...] Read more.
The reaction of [Ni(L)]Cl2·2H2O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,01.18,07.12]docosane) with trans-1,2-cyclopentanedicarboxylic acid (H2-cpdc) yields a 1D hydrogen-bonded infinite chain with formula [Ni(L)(H-cpdc-)2] (1). This complex has been characterized by X-ray crystallography, spectroscopy and cyclic voltammetry. The crystal structure of 1 exhibits a distorted octahedral geometry about Ni atom with four nitrogen atoms of the macrocycle and two oxygen atoms of the H-cpdc- ligand at the axial position. Compound 1 crystallizes in the monoclinic system P21/c with a = 8.7429(17), b = 10.488(2), c = 18.929(4) Å, β = 91.82(2), V = 1734.8(6) Å3, Z = 2. Electronic spectrum of 1 reveals a high-spin octahedral environment. Cyclic voltammetry of 1 undergoes two waves of a one-electron transfer corresponding to NiII/NiIII and NiII/NiI processes. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)

Review

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Open AccessReview Self-Assembly in the Ferritin Nano-Cage Protein Superfamily
Int. J. Mol. Sci. 2011, 12(8), 5406-5421; doi:10.3390/ijms12085406
Received: 20 July 2011 / Revised: 9 August 2011 / Accepted: 15 August 2011 / Published: 22 August 2011
Cited by 26 | PDF Full-text (801 KB) | HTML Full-text | XML Full-text
Abstract
Protein self-assembly, through specific, high affinity, and geometrically constraining protein-protein interactions, can control and lead to complex cellular nano-structures. Establishing an understanding of the underlying principles that govern protein self-assembly is not only essential to appreciate the fundamental biological functions of these [...] Read more.
Protein self-assembly, through specific, high affinity, and geometrically constraining protein-protein interactions, can control and lead to complex cellular nano-structures. Establishing an understanding of the underlying principles that govern protein self-assembly is not only essential to appreciate the fundamental biological functions of these structures, but could also provide a basis for their enhancement for nano-material applications. The ferritins are a superfamily of well studied proteins that self-assemble into hollow cage-like structures which are ubiquitously found in both prokaryotes and eukaryotes. Structural studies have revealed that many members of the ferritin family can self-assemble into nano-cages of two types. Maxi-ferritins form hollow spheres with octahedral symmetry composed of twenty-four monomers. Mini-ferritins, on the other hand, are tetrahedrally symmetric, hollow assemblies composed of twelve monomers. This review will focus on the structure of members of the ferritin superfamily, the mechanism of ferritin self-assembly and the structure-function relations of these proteins. Full article
(This article belongs to the Special Issue Molecular Self-Assembly 2011)
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