Hierarchical superstructure of alkylamine-coated ZnS nanoparticle assemblies

Belman, Nataly; Israelachvili, Jacob N.; Li, Youli; Safinya, Cyrus R.; Ezersky, Vladimir; Rabkin, Alexander; Sima, Olga; Golan, Yuval

doi:10.1039/c0cp00999g

Cited by 19 publications

(22 citation statements)

References 36 publications

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“…Our findings have important implications for the engineering of self-assembled materials, especially in colloidal science, where interactions are generally weak. 40 Understanding how DNA length and end structure affect end-to-end interactions allows us to envision DNA-mediated interactions for self-assembly beyond base-pairing. This is important because the ability to harness a variety of tunable, competing interactions is crucial for developing higher-order self-assemblies (self-assembled on multiple length scales) that are the basis of many materials found in nature.…”

Section: Discussionmentioning

confidence: 99%

Stacking of short DNA induces the gyroid cubic-to-inverted hexagonal phase transition in lipid–DNA complexes

et al. 2013

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Lyotropic phases of amphiphiles are a prototypical example of self-assemblies. Their structure is generally determined by amphiphile shape and their phase transitions are primarily governed by composition. In this paper, we demonstrate a new paradigm for membrane shape control where the electrostatic coupling of charged membranes to short DNA (sDNA), with tunable temperature-dependent end-to-end stacking interactions, enables switching between the inverted gyroid cubic structure (QIIG) and the inverted hexagonal phase (HIIC). We investigated the structural shape transitions induced in the QIIG phase upon complexation with a series of sDNAs (5, 11, 24, and 48 bp) with three types of end structure (“sticky” adenine (A)–thymine (T) (dAdT) overhangs, no overhang (blunt), and “nonsticky” dTdT overhangs) using synchrotron small-angle X-ray scattering. Very short 5 bp sDNA with dAdT overhangs and blunt ends induce coexistence of the QIIG and the HIIC phase, with the fraction of QIIG increasing with temperature. Phase coexistence for blunt 5 bp sDNA is observed from 27 °C to about 65 °C, where the HIIC phase disappears and the temperature dependence of the lattice spacing of the QIIG phase indicates that the sDNA duplexes melt into single strands. The only other sDNA for which melting is observed is 5 bp sDNA with dTdT overhangs, which forms the QIIG phase throughout the studied range of temperature (27 °C to 85.2 °C). The longer 11 bp sDNA forms coexisting QIIG and HIIC phases (with the fraction of QIIG again increasing with temperature) only for “nonsticky” dTdT overhangs, while dAdT overhangs and blunt ends exclusively template the HIIC phase. For 24 and 48 bp sDNAs the HIIC phase replaces the QIIG phase at all investigated temperatures, independent of sDNA end structure. Our work demonstrates how the combined effects of sDNA length and end structure (which determine the temperature-dependent stacking length) tune the phase behavior of the complexes. These findings are consistent with the hypothesis that sDNAs and sDNA stacks with lengths comparable to or larger than the cubic unit cell length disfavor the highly curved channels present in the QIIG phase, thus driving the QIIG-to-HIIC phase transition. As the temperature is increased, the breaking of stacks due to thermal fluctuations restores increasing percentages of the QIIG phase.

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Section: Discussionmentioning

confidence: 99%

Stacking of short DNA induces the gyroid cubic-to-inverted hexagonal phase transition in lipid–DNA complexes

et al. 2013

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“…nanoparticles linked by pure metal constituents). The chemical reduction process usually generates a large amount of effluents during the reaction process, demanding extensive post-processing3738. However, the self-assembly of most metals with nanoparticles into superstructures with controlled architectures remains an unresolved challenge, mainly due to the intrinsic properties of metals.…”

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confidence: 99%

Assembly of metals and nanoparticles into novel nanocomposite superstructures

Chen

Choi

et al. 2013

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Controlled assembly of nanoscale objects into superstructures is of tremendous interests. Many approaches have been developed to fabricate organic-nanoparticle superstructures. However, effective fabrication of inorganic-nanoparticle superstructures (such as nanoparticles linked by metals) remains a difficult challenge. Here we show a novel, general method to assemble metals and nanoparticles rationally into nanocomposite superstructures. Novel metal-nanoparticle superstructures are achieved by self-assembly of liquid metals and nanoparticles in immiscible liquids driven by reduction of free energy. Superstructures with various architectures, such as metal-core/nanoparticle-shell, nanocomposite-core/nanoparticle-shell, network of metal-linked core/shell nanostructures, and network of metal-linked nanoparticles, were successfully fabricated by simply tuning the volume ratio between nanoparticles and liquid metals. Our approach provides a simple, general way for fabrication of numerous metal-nanoparticle superstructures and enables a rational design of these novel superstructures with desired architectures for exciting applications.

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“…Generally, the crystals of organic molecules assemble in response to non‐covalent intermolecular interactions such as metal coordination, van der Waals forces, π–π interactions, and hydrogen bonding . Furthermore, the study of superimposed crystalline structures has been vigorously pursued, with subject areas including ordered supramolecules, metal–organic frameworks (MOFs), coordination complexes with particles and polymers, and covalent organic frameworks (COFs) . However, following the principle of close packing, porous single‐crystals resulting from non‐covalent interactions are rare because most of the molecules in the solid pack efficiently in ways that minimize the crystal volume .…”

Section: Figurementioning

confidence: 99%

Unusually Stable Triazine‐based Organic Superstructures

et al. 2016

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Solid-state reactions have been rapidly gaining popularity in organic chemistry owingt ot heir simplicity, efficiency,a nd selectivity compared to liquid-phase reactions. Herein, we describe the formation of superstructures through the solid-state reaction of an organic single-crystal. The superstructure of 5,5',5''-(1,3,5-triazine-2,4,6-triyl)triisophthalonitrile (TIPN) can be formed by cyclotrimerization of 1,3,5-tricyanobenzene (TCB) single crystals.T he TIPN superstructure was confirmed by single crystal X-ray diffraction and visualizedb yt ransmission electron microscopy. The superstructure has hexagonally packed 1-dimensional (1D) channels along the crystal axis.F urthermore,t he superstructure arises from interdigitated nitrile interactions in the crystal lattice,and thus has electron-beam tolerance and very high thermal stability.

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Hierarchical superstructure of alkylamine-coated ZnS nanoparticle assemblies

Cited by 19 publications

References 36 publications

Stacking of short DNA induces the gyroid cubic-to-inverted hexagonal phase transition in lipid–DNA complexes

Stacking of short DNA induces the gyroid cubic-to-inverted hexagonal phase transition in lipid–DNA complexes

Assembly of metals and nanoparticles into novel nanocomposite superstructures

Unusually Stable Triazine‐based Organic Superstructures

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