Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Homochiral crystallization of microporous framework materials from achiral precursors by chiral catalysis.

ABSTRACT: While it is not uncommon to form chiral crystals during crystallization, the formation of bulk porous homochiral materials from achiral building units is rare. Reported here is the homochiral crystallization of microporous materials through the chirality induction effect of natural alkaloids. The resulting material possesses permanent microporosity and has a uniform pore size of 9.3 A.

SUBMITTER: Zhang J

PROVIDER: S-EPMC2776631 | biostudies-literature | 2008 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Homochiral crystallization of microporous framework materials from achiral precursors by chiral catalysis.

Zhang Jian J Chen Shumei S Wu Tao T Feng Pingyun P Bu Xianhui X

Journal of the American Chemical Society 20080906 39

While it is not uncommon to form chiral crystals during crystallization, the formation of bulk porous homochiral materials from achiral building units is rare. Reported here is the homochiral crystallization of microporous materials through the chirality induction effect of natural alkaloids. The resulting material possesses permanent microporosity and has a uniform pore size of 9.3 A. ...[more]

PMID: 18774816

Similar Datasets

Photothermal conversion triggered thermal asymmetric catalysis within metal nanoparticles loaded homochiral covalent organic framework.

Project description:For seeking high enantiopurity, the previously reported thermal asymmetric catalysis is usually carried out at low temperature sometimes with limited yield, that is, the high enantiomeric excess (ee) usually at the cost of high yield. Thus, the achieving both high stereoselectivity and yield is an enormous challenge. We report herein two metal nanoparticle (M NP)-loaded and porphyrin-containing homochiral covalent organic framework (CCOF)-based composite catalysts, and their application in the thermally-driven asymmetric one-pot Henry and A3-coupling reactions. All the reactions are conducted at elevated temperatures with both excellent stereoselectivity and yield which resulted from the synergy of CCOF confinement effect and M NP catalytic activation. Notably, the needed thermal energy for the asymmetric reactions herein is derived from the photothermal conversion via porphyrin-based CCOF upon irradiation with visible light. Remarkably, the CCOF confinement effect can be effectively maintained up to 100 °C for the asymmetric one-pot Henry and A3-coupling reactions herein.

| S-EPMC6662712 | biostudies-literature

Chiral photochemistry of achiral molecules.

Project description:Chirality is a molecular property governed by the topography of the potential energy surface (PES). Thermally achiral molecules interconvert rapidly when the interconversion barrier between the two enantiomers is comparable to or lower than the thermal energy, in contrast to thermally stable chiral configurations. In principle, a change in the PES topography on the excited electronic state may diminish interconversion, leading to electronically prochiral molecules that can be converted from achiral to chiral by electronic excitation. Here we report that this is the case for two prototypical examples - cis-stilbene and cis-stiff stilbene. Both systems exhibit unidirectional photoisomerization for each enantiomer as a result of their electronic prochirality. We simulate an experiment to demonstrate this effect in cis-stilbene based on its interaction with circularly polarized light. Our results highlight the drastic change in chiral behavior upon electronic excitation, opening up the possibility for asymmetric photochemistry from an effectively nonchiral starting point.

| S-EPMC9019051 | biostudies-literature

An efficient synthesis of achiral and chiral 1,2,4-triazolium salts: bench stable precursors for N-heterocyclic carbenes.

Project description:[reaction: see text] The promising utility of triazolyl N-heterocyclic carbene catalysts in umpolung aldehyde chemistry requires a straightforward reliable synthesis from readily available materials. Herein, we describe the synthesis of a variety of triazolyl N-heterocyclic carbene precursors. The reactions commence from commercially available amino acids and proceed in 44-68% overall yields. The N-heterocyclic salts are air-stable crystalline solids that can be stored with no special precaution and can generate the active catalyst when treated with an appropriate base.

| S-EPMC2527449 | biostudies-literature

Towards homochiral supramolecular entities from achiral molecules by vortex mixing-accompanied self-assembly.

Project description:Achieving homochirality is challenging both at the molecular and the supramolecular levels. While the origin of molecular homochirality still remains mysterious, the fabrication of homochiral assemblies from achiral molecules has attracted considerable interest since it provides many clues to understand the origin of molecular chirality. Here, by using a vortex mixing-accompanied self-assembly strategy, we obtained near-unity homochiral entities with controlled handedness from supramolecular gels that consist of exclusively achiral molecules without any chiral additives. The common supramolecular gelation process via heating and cooling of the achiral molecules only resulted in racemic gels. However, if vortex mixing is applied during the self-assembly, near-unity homochiral assemblies with uncontrolled handedness were obtained. Vortex mixing during the nucleation stage was found to be crucial in this case. On the other hand, if a small amount of the above vortex mixing produced assemblies was added as chiral seeds into the racemic gels, the racemic gels turned into near-unity homochiral suspensions with controlled handedness via a ripening process. Our studies provide an intriguing approach for achieving homochiral supramolecular assemblies from achiral molecules.

| S-EPMC6419933 | biostudies-literature

Homochiral Supramolecular Thin Film from Self-Assembly of Achiral Triarylamine Molecules by Circularly Polarized Light.

Project description:Here, we report the formation of homochiral supramolecular thin film from achiral molecules, by using circularly polarized light (CPL) only as a chiral source, on the condition that irradiation of CPL does not induce a photochemical change of the achiral molecules. Thin films of self-assembled structures consisting of chiral supramolecular fibrils was obtained from the triarylamine derivatives through evaporation of the self-assembled triarylamine solution. The homochiral supramolecular helices with the desired handedness was achieved by irradiation of circularly polarized visible light during the self-assembly process, and the chiral stability of supramolecular self-assembled product was achieved by photopolymerization of the diacetylene moieties at side chains of the building blocks, with irradiation of circularly polarized ultraviolet light. This work provides a novel methodology for the generation of homochiral supramolecular thin film from the corresponding achiral molecules.

| S-EPMC7024168 | biostudies-literature

Chiral structures from achiral liquid crystals in cylindrical capillaries.

Project description:We study chiral symmetry-broken configurations of nematic liquid crystals (LCs) confined to cylindrical capillaries with homeotropic anchoring on the cylinder walls (i.e., perpendicular surface alignment). Interestingly, achiral nematic LCs with comparatively small twist elastic moduli relieve bend and splay deformations by introducing twist deformations. In the resulting twisted and escaped radial (TER) configuration, LC directors are parallel to the cylindrical axis near the center, but to attain radial orientation near the capillary wall, they escape along the radius through bend and twist distortions. Chiral symmetry-breaking experiments in polymer-coated capillaries are carried out using Sunset Yellow FCF, a lyotropic chromonic LC with a small twist elastic constant. Its director configurations are investigated by polarized optical microscopy and explained theoretically with numerical calculations. A rich phenomenology of defects also arises from the degenerate bend/twist deformations of the TER configuration, including a nonsingular domain wall separating domains of opposite twist handedness but the same escape direction and singular point defects (hedgehogs) separating domains of opposite escape direction. We show the energetic preference for singular defects separating domains of opposite twist handedness compared with those of the same handedness, and we report remarkable chiral configurations with a double helix of disclination lines along the cylindrical axis. These findings show archetypally how simple boundary conditions and elastic anisotropy of confined materials lead to multiple symmetry breaking and how these broken symmetries combine to create a variety of defects.

| S-EPMC4403180 | biostudies-literature

Supramolecular Copolymerization of Bichromophoric Chiral and Achiral Perylenediimide Dyes.

Project description:Propagation and amplification of chirality are considered to play an important role in the chemical evolution of biological homochirality. Stereochemical communications have been demonstrated to have a significant effect on the formation of chiral hierarchical structures in helical polymers, surface assemblies and supramolecular polymers. The formation of supramolecular copolymers based on chiral and achiral bichromophoric perylenediimide (PDI) dyes having a binaphtyl- and biphenyl-core-bridging unit, respectively, was investigated in terms of chiral amplification and propagation. The biphenyl-bridged PDI dye was expected to perform as a prochiral component to adopt both right- and left-handed twisting structures with the free rotation over the phenyl-phenyl linkage upon partnered with the chiral binaphtly PDI dye in the coassemblies. The coassemblies between the chiral and achiral PDI dyes with dissimilar core units demonstrated the composition dependent control in the length of supramolecular nanofibers as well as amplification of optical activity.

| S-EPMC8032881 | biostudies-literature

Engineering Achiral Liquid Crystalline Polymers for Chiral Self-Recovery.

Project description:Flexible construction of permanently stored supramolecular chirality with stimulus-responsiveness remains a big challenge. Herein, we describe an efficient method to realize the transfer and storage of chirality in intrinsically achiral films of a side-chain polymeric liquid crystal system by combining chiral doping and cross-linking strategy. Even the helical structure was destroyed by UV light irradiation, the memorized chiral information in the covalent network enabled complete self-recovery of the original chiral superstructure. These results allowed the building of a novel chiroptical switch without any additional chiral source in multiple types of liquid crystal polymers, which may be one of the competitive candidates for use in stimulus-responsive chiro-optical devices.

| S-EPMC8584346 | biostudies-literature

Assembly of planar chiral superlattices from achiral building blocks.

Project description:The spontaneous assembly of chiral structures from building blocks that lack chirality is fundamentally important for colloidal chemistry and has implications for the formation of advanced optical materials. Here, we find that purified achiral gold tetrahedron-shaped nanoparticles assemble into two-dimensional superlattices that exhibit planar chirality under a balance of repulsive electrostatic and attractive van der Waals and depletion forces. A model accounting for these interactions shows that the growth of planar structures is kinetically preferred over similar three-dimensional products, explaining their selective formation. Exploration and mapping of different packing symmetries demonstrates that the hexagonal chiral phase forms exclusively because of geometric constraints imposed by the presence of constituent tetrahedra with sharp tips. A formation mechanism is proposed in which the chiral phase nucleates from within a related 2D achiral phase by clockwise or counterclockwise rotation of tetrahedra about their central axis. These results lay the scientific foundation for the high-throughput assembly of planar chiral metamaterials.

| S-EPMC9304327 | biostudies-literature

Transforming Silver Nanoclusters from Racemic to Homochiral via Seeded Crystallization.

Project description:Chirality has risen as an attractive topic in materials research in recent years, but the attainment of enantiopure materials remains a major challenge. Herein, we obtained homochiral nanoclusters by a recrystallization strategy, without any chiral factors (i.e., chiral ligands, counterions, etc.). Through the rapid flipping of configuration of silver nanoclusters in solution, the initial racemic Ag40 (triclinic) nanoclusters are converted to homochiral (orthorhombic) as revealed by X-ray crystallography. In the seeded crystallization, one homochiral Ag40 crystal is used as a seed to direct the growth of crystals with specific chirality. Furthermore, enantiopure Ag40 nanoclusters can be used as amplifiers for the detection of chiral carboxylic drugs. This work not only provides chiral conversion and amplification strategies to obtain homochiral nanoclusters but also explains the chirality origin of nanoclusters at the molecular level.

| S-EPMC10258841 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data