Search results for "assembly"
showing 10 items of 768 documents
Porphyrin-Polymer Networks, Worms, and Nanorods: pH-triggerable Hierarchical Self-assembly
2011
In this study, we present a novel, multifaceted pH-triggerable system of self-organized hierarchical nanostructures. The system consists of meso-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and poly(2-vinylpyridine) cylindrical brushes (PVP brushes) and can yield polymer-porphyrin networks, porphyrin loaded polymer brushes and pure porphyrin nanorods. In addition, the polymer influences the pK(a) and the mutual TPPS stacking geometry. Structures were characterized by AFM, dynamic light scattering using an IR laser, UV-Vis spectroscopy and small-angle neutron scattering (SANS). Supramolecular composite porphyrin structures that can be switched through external triggers have potential in photo…
Living Light-Induced Crystallization-Driven Self-Assembly for Rapid Preparation of Semiconducting Nanofibers.
2018
Well-defined nanostructures composed of conjugated polymers have attracted significant attention due to their intriguing electronic and optical properties. However, precise control of the size and uniformity of these semiconducting nanostructures is still rare and challenging, despite recent advances in strategies to obtain self-assembled nanostructures with narrow dispersions. Herein, we demonstrate the preparation of fluorescent conjugated block copolymers by one-shot polymerization and rapid formation of nanofibers in a few minutes via light-induced crystallization-driven self-assembly, driven by facile cis-to- trans photoisomerization of its poly( p-phenylenevinylene) blocks. Furthermor…
From Bowls to Capsules: Assembly of Hexanuclear Ni II Rings Tailored by Alkali Cations
2020
An anionic hexanuclear NiII metallamacrocycle with endo and exo linking sites has been employed as a building block to generate a series of capsules and bowls of nanometric size. The supramolecular arrangement of the {Ni6 } rings was tailored by the size of the alkali cations, showing the transition from {Ni6 -M2 -Ni6 } capsules (M=LiI and NaI ) to {Ni6 -M} bowls (M=KI and CsI ). The alkyl co-cations are determinant to stabilize the assemblies by means of CH⋅⋅⋅π interactions on the exo side of the metallamacrocycles. The effect on the topology of the supramolecular assemblies of the cation size, cation charge, Et3 NH+ or Me4 N+ counter cations has been analyzed. Magnetic measurements reveal…
Macrocyclic (1,3)- and (1,4)-benzena-(1,4)-piperazinacyclophanes
1995
New large, up to 45-membered macrocycles were synthesised from piperazine and m- and p-2,6-bis(bromomethyl)xylene under high dilution conditions. X-ray structures of compounds 3a, 4a, 5a, and 8b were determined. Surprisingly, none of the macrocycles prepared showed any inclusion properties towards small guest molecules. Instead, the compounds were found to self-organize during the packing process into larger structures due to the complementary of the molecular skeletons. In the crystalline state 3a forms nets, where the macrocycles are bound by HCH…N interactions to each other. 4a exits in a dimeric structure, which, in turn, further extends to a sheet structure. The positively charged phan…
Temperature triggered self-assembly of polypeptides into multivalent spherical micelles.
2007
We report herein thermally responsive elastin-like polypeptides (ELPs) in a linear AB diblock architecture with an N-terminal peptide ligand that self-assemble into spherical micelles when heated slightly above body temperature. A series of 10 ELP block copolymers (ELP(BC)'s ) with different molecular weights and hydrophilic-to-hydrophobic block ratios were genetically synthesized by recursive directional ligation. The self-assembly of these polymers from unimers into micelles was investigated by light scattering, fluorescence spectroscopy, and cryo-TEM. These ELP(BC)'s undergo two phase transitions as a function of solution temperature: a unimer-to-spherical micelle transition at an interm…
Topology-Dependent Swichability of Peptide Secondary Structures in Bioconjugates with Complex Architectures
2013
Peptide sequences, which exhibit a reversible pH-responsive coil to α-helix secondary structure transition, are conjugated to polymer precursors to yield linear AB and graft ABA peptide-poly(ethylene oxide) conjugates. While the PEO B-block is comparable, the conjugates differ in topologies of the peptide bearing A-blocks. The influences of topology on the structure transitions in the peptide segments are investigated, comparing linear AB-bioconjugates with graft ABA-bioconjugates having multiple peptide segments combined in star or pom-pom topologies.
Polysarcosine-containing copolymers: Synthesis, characterization, self-assembly, and applications
2018
Although the first polysarcosine (pSar) synthesis by Wesseley et al. was reported almost a century ago, it was only recently that pSar gained broader attention and is considered a potential alternative of poly(ethylene glycol) (PEG). In contrast to polyethers, such as PEG, pSar is a polypeptoid based on the amino acid sarcosine, i.e. N-methylated glycine. As a polymer, pSar combines PEG-like properties, e.g., excellent solubility in water, protein resistance, low cellular toxicity and a non-immunogenic character, while being based on endogenous material. Sarcosine can be obtained in a simple one-step reaction of bromoacetic acid and methylamine, easily transferred into the sarcosine N-(thio…
Liquid-crystalline ordering as a concept in materials science: from semiconductors to stimuli-responsive devices.
2013
While the unique optical properties of liquid crystals (LCs) are already well exploited for flat-panel displays, their intrinsic ability to self-organize into ordered mesophases, which are intermediate states between crystal and liquid, gives rise to a broad variety of additional applications. The high degree of molecular order, the possibility for large scale orientation, and the structural motif of the aromatic subunits recommend liquid-crystalline materials as organic semiconductors, which are solvent-processable and can easily be deposited on a substrate. The anisotropy of liquid crystals can further cause a stimuli-responsive macroscopic shape change of cross-linked polymer networks, w…
Racemic and Optically Pure Heptahelicene-2-carboxylic Acid: Its Synthesis and Self-Assembly into Nanowire-Like Aggregates
2010
Heptahelicene-2-carboxylic acid was effectively synthesised from suitably functionalised naphthalene building blocks. Methoxy-substituted 1,1'-ethyne-1,2-diylbis(2-but-3-yn-1-ylnaphthalene) was cyclised in the presence of CpCo(CO)(2)/PPh(3) to 2-methoxy-7,8,11,12-tetrahydroheptahelicene, which was converted into heptahelicen-2-yl trifluoromethanesulfonate. This reactive intermediate underwent Pd(OAc)(2)/dppp-catalysed methoxycarbonylation reaction to provide, after hydrolysis, heptahelicene-2-carboxylic acid. The racemate was resolved into enantiomers by semipreparative HPLC on a chiral column. The helicity of (+)-(P)-heptahelicene-2-carboxylic acid was assigned by correlating its CD spectr…
Recognition-Directed Supramolecular Assemblies of Metal Complexes of Terpyridine Derived Ligands with Self-Complementary Hydrogen Bonding Sites
2000
The synthesis and X-ray structures of three metal complexes with terpyridine-derived ligands that contain amino-pyrimidine and amino-pyrazine moieties are presented. They have been designed in view of directing their self-assembly into specific supramolecular arrays through molecular recognition interactions. The solid-state structures indeed reveal extensive hydrogen-bonded networks. The Co complex 4a with PF6- counterions builds a two-dimensional infinite interwoven grid through strong double hydrogen bonds (d(N-H-N) =2.918-3.018 A) between the amino groups and the N atoms of the rings, with all H-bonding sites saturated. Changing the anions to BF4- in 4b leads to a similar infinite but p…