Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of organic liquid crystals containing selectively fluorinated cyclopropanes.

ABSTRACT: This paper describes the synthesis of a series of organic liquid crystals (LCs) containing selectively fluorinated cyclopropanes at their termini. The syntheses used difluorocarbene additions to olefin precursors, an approach which proved straightforward such that these liquid crystal candidates could be efficiently prepared. Their physical and thermodynamic properties were evaluated and depending on individual structures, they either displayed positive or negative dielectric anisotropy. The study gives some guidance into effective structure-property relationships for the design of LCs containing selectively fluorinated cyclopropane motifs.

SUBMITTER: Fang Z

PROVIDER: S-EPMC7176930 | biostudies-literature | 2020

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of organic liquid crystals containing selectively fluorinated cyclopropanes.

Fang Zeguo Z Al-Maharik Nawaf N Kirsch Peer P Bremer Matthias M Slawin Alexandra M Z AMZ O'Hagan David D

Beilstein journal of organic chemistry 20200414

This paper describes the synthesis of a series of organic liquid crystals (LCs) containing selectively fluorinated cyclopropanes at their termini. The syntheses used difluorocarbene additions to olefin precursors, an approach which proved straightforward such that these liquid crystal candidates could be efficiently prepared. Their physical and thermodynamic properties were evaluated and depending on individual structures, they either displayed positive or negative dielectric anisotropy. The stu ...[more]

PMID: 32362945

Similar Datasets

Liquid crystals for organic thin-film transistors.

Project description:Crystalline thin films of organic semiconductors are a good candidate for field effect transistor (FET) materials in printed electronics. However, there are currently two main problems, which are associated with inhomogeneity and poor thermal durability of these films. Here we report that liquid crystalline materials exhibiting a highly ordered liquid crystal phase of smectic E (SmE) can solve both these problems. We design a SmE liquid crystalline material, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), for FETs and synthesize it. This material provides uniform and molecularly flat polycrystalline thin films reproducibly when SmE precursor thin films are crystallized, and also exhibits high durability of films up to 200 °C. In addition, the mobility of FETs is dramatically enhanced by about one order of magnitude (over 10 cm(2) V(-1) s(-1)) after thermal annealing at 120 °C in bottom-gate-bottom-contact FETs. We anticipate the use of SmE liquid crystals in solution-processed FETs may help overcome upcoming difficulties with novel technologies for printed electronics.

| S-EPMC4403349 | biostudies-literature

Chemoenzymatic synthesis and lectin recognition of a selectively fluorinated glycoprotein.

Project description:A chemoenzymatic glycosylation remodeling method for the synthesis of selectively fluorinated glycoproteins is described. The method consists of chemical synthesis of a fluoroglycan oxazoline and its use as donor substrate for endoglycosidase (ENGase)-catalyzed transglycosylation to a GlcNAc-protein to form a homogeneous fluoroglycoprotein. The approach was exemplified by the synthesis of fluorinated glycoforms of ribonuclease B (RNase B). An interesting finding was that fluorination at the C-6 of the 6-branched mannose moiety in the Man3GlcNAc core resulted in significantly enhanced reactivity of the substrate in enzymatic transglycosylation. A structural analysis suggests that the enhancement in reactivity may come from favorable hydrophobic interactions between the fluorine and a tyrosine residue in the catalytic site of the enzyme (Endo-A). SPR analysis of the binding of the fluorinated glycoproteins with lectin concanavalin A (con A) revealed the importance of the 6-hydroxyl group on the α-1,6-branched mannose moiety in con A recognition. The present study establishes a facile method for preparation of selectively fluorinated glycoproteins that can serve as valuable probes for elucidating specific carbohydrate-protein interactions.

| S-EPMC3722283 | biostudies-literature

Bio-inspired synthesis of aqueous nanoapatite liquid crystals.

Project description:The macroscopically ordered structure of rod-like nanoapatites within the collagen matrix is of great significance for the mechanical performance of bones and teeth. However, the synthesis of macroscopically ordered nanoapatite remains a challenge. Inspired by the effect of citrate molecules on apatite crystals in natural bone and the similarities between these ordered rod-like nanoapatites and the nematic phase of inorganic liquid crystals (LCs), we synthesized aqueous liquid crystal from rod-like nanoapatites with the aid of sodium citrate. Following a similar procedure, aqueous Mg(OH)2 and Mg3(PO4)2 LCs were also prepared. These findings lay the foundation for the fabrication of macroscopically assembled nanoapatite-based functional materials for biomedical applications and offer a green chemical synthesis platform for the development of new types of inorganic LCs. This process may reduce the difficulties in synthesizing large quantities of inorganic LCs so that they can be applied to the fabrication of functional materials.

| S-EPMC6345739 | biostudies-literature

Design of Biomolecular Interfaces using Liquid Crystals Containing Oligomeric Ethylene Glycol.

Project description:We report an investigation of nematic LCs formed from miscible mixtures of 4-cyano-4'-pentylbiphenyl (5CB) and 2-(2-[2-{2-(2,3-difluoro-4-{4-(4-trans-pentylcyclohexyl)-phenyl-phenoxy)ethoxy}ethoxy]ethoxy)ethanol (EG4-LC), the latter being a mesogen with a tetra(ethylene glycol) tail. Quantitative characterization of the ordering of this LC mixture at biologically-relevant aqueous interfaces revealed that addition of EG4-LC (1-5% by weight) to 5CB causes a continuous transition in the ordering of the LC from a planar (pure 5CB) to a perpendicular (homeotropic) orientation. The homeotropic ordering is also seen in aqueous dispersions of micrometer-sized droplets of the LC mixture, which exhibit enhanced stability against coalescence. These observations and others, all of which suggest partitioning of the EG4-LC from the bulk of the LC to its aqueous interface, were complemented by measurements of the adsorption of bovine serum albumin (BSA) to the aqueous-LC interface. Whereas adsorption of BSA to the interface of a LC mixture containing 1% wt/wt of EG4-LC triggered an ordering transition, higher concentrations of EG4-LC (>2% wt/wt) prevented this ordering transition, consistent with a decrease in adsorption of BSA. This conclusion is supported by epifluorescence measurements using fluorescently labeled BSA and comparisons to LC interfaces at which EG4-containing lipids are adsorbed. Overall, these results demonstrate a general and facile approach to the design of LCs with interfaces that present biologically relevant chemical functional groups, assume well-defined orientations at aqueous interfaces, and lower non-specific protein adsorption. The bulk of the LC serves as a reservoir of EG4-LC, thus permitting easy preparation of these interfaces and the potential for spontaneous repair of the EG4-decorated interfaces during contact with biological systems.

| S-EPMC3245687 | biostudies-literature

Synthesis of ordered carbonaceous frameworks from organic crystals.

Project description:Despite recent advances in the carbonization of organic crystalline solids like metal-organic frameworks or supramolecular frameworks, it has been challenging to convert crystalline organic solids into ordered carbonaceous frameworks. Herein, we report a route to attaining such ordered frameworks via the carbonization of an organic crystal of a Ni-containing cyclic porphyrin dimer (Ni2-CPDPy). This dimer comprises two Ni-porphyrins linked by two butadiyne (diacetylene) moieties through phenyl groups. The Ni2-CPDPy crystal is thermally converted into a crystalline covalent-organic framework at 581 K and is further converted into ordered carbonaceous frameworks equipped with electrical conductivity by subsequent carbonization at 873-1073 K. In addition, the porphyrin's Ni-N4 unit is also well retained and embedded in the final framework. The resulting ordered carbonaceous frameworks exhibit an intermediate structure, between organic-based frameworks and carbon materials, with advantageous electrocatalysis. This principle enables the chemical molecular-level structural design of three-dimensional carbonaceous frameworks.Carbon-based materials are promising alternatives to noble metal catalysts, but their structures are typically disordered and difficult to control. Here, the authors obtain ordered carbonaceous frameworks with advantageous electrocatalytic properties via the carbonization of nickel-containing porphyrin dimer networks.

| S-EPMC5524644 | biostudies-literature

Triphilic Ionic-Liquid Mixtures: Fluorinated and Non-fluorinated Aprotic Ionic-Liquid Mixtures.

Project description:We present here the possibility of forming triphilic mixtures from alkyl- and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains-polar and nonpolar-three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self-associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long-range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment.

| S-EPMC4641458 | biostudies-literature

Wavelength-tunable and shape-reconfigurable photonic capsule resonators containing cholesteric liquid crystals.

Project description:Cholesteric liquid crystals (CLCs) have a photonic bandgap due to the periodic change of refractive index along their helical axes. The CLCs containing optical gain have served as band-edge lasing resonators. In particular, CLCs in a granular format provide omnidirectional lasing, which are promising as a point light source. However, there is no platform that simultaneously achieves high stability in air and wavelength tunability. We encapsulate CLCs with double shells to design a capsule-type laser resonator. The fluidic CLCs are fully enclosed by an aqueous inner shell that promotes the planar alignment of LC molecules along the interface. The outer shell made of silicone elastomer protects the CLC core and the inner shell from the surroundings. Therefore, the helical axes of the CLCs are radially oriented within the capsules, which provide a stable omnidirectional lasing in the air. At the same time, the fluidic CLCs enable the fine-tuning of lasing wavelength with temperature. The capsules retain their double-shell structure during the dynamic deformation. Therefore, the CLCs in the core maintain the planar alignment along the deformed interface, and a lasing direction can be varied from omnidirectional to bi- or multidirectional, depending on the shape of deformed capsules.

| S-EPMC6014715 | biostudies-literature

Enantiomeric interactions between liquid crystals and organized monolayers of tyrosine-containing dipeptides.

Project description:We have examined the orientational ordering of nematic liquid crystals (LCs) supported on organized monolayers of dipeptides with the goal of understanding how peptide-based interfaces encode intermolecular interactions that are amplified into supramolecular ordering. By characterizing the orientations of nematic LCs (4-cyano-4'-pentylbiphenyl and TL205 (a mixture of mesogens containing cyclohexane-fluorinated biphenyls and fluorinated terphenyls)) on monolayers of l-cysteine-l-tyrosine, l-cysteine-l-phenylalanine, or l-cysteine-l-phosphotyrosine formed on crystallographically textured films of gold, we conclude that patterns of hydrogen bonds generated by the organized monolayers of dipeptides are transduced via macroscopic orientational ordering of the LCs. This conclusion is supported by the observation that the ordering exhibited by the achiral LCs is specific to the enantiomers used to form the dipeptide-based monolayers. The dominant role of the -OH group of tyrosine in dictating the patterns of hydrogen bonds that orient the LCs was also evidenced by the effects of phosphorylation of the tyrosine on the ordering of the LCs. Overall, these results reveal that crystallographic texturing of gold films can direct the formation of monolayers of dipeptides with long-range order, thus unmasking the influence of hydrogen bonding, chirality, and phosphorylation on the macroscopic orientational ordering of LCs supported on these surfaces. These results suggest new approaches based on supramolecular assembly for reporting the chemical functionality and stereochemistry of synthetic and biological peptide-based molecules displayed at surfaces.

| S-EPMC3257416 | biostudies-literature

Biocatalytic Strategy for the Highly Stereoselective Synthesis of CHF<sub>2</sub> -Containing Trisubstituted Cyclopropanes.

Project description:The difluoromethyl (CHF2 ) group has attracted significant attention in drug discovery and development efforts, owing to its ability to serve as fluorinated bioisostere of methyl, hydroxyl, and thiol groups. Herein, we report an efficient biocatalytic method for the highly diastereo- and enantioselective synthesis of CHF2 -containing trisubstituted cyclopropanes. Using engineered myoglobin catalysts, a broad range of α-difluoromethyl alkenes are cyclopropanated in the presence of ethyl diazoacetate to give CHF2 -containing cyclopropanes in high yield (up to >99 %, up to 3000 TON) and with excellent stereoselectivity (up to >99 % de and ee). Enantiodivergent selectivity and extension of the method to the stereoselective cyclopropanation of mono- and trifluoromethylated olefins was also achieved. This methodology represents a powerful strategy for the stereoselective synthesis of high-value fluorinated building blocks for medicinal chemistry, as exemplified by the formal total synthesis of a CHF2 isostere of a TRPV1 inhibitor.

| S-EPMC7969403 | biostudies-literature

A dual growth mode unique for organic crystals relies on mesoscopic liquid precursors.

Project description:Organic solvents host the synthesis of high-value crystals used as pharmaceuticals and optical devices, among other applications. A knowledge gap persists on how replacing the hydrogen bonds and polar attraction that dominate aqueous environments with the weaker van der Waals forces affects the growth mechanism, including its defining feature, whether crystals grow classically or nonclassically. Here we demonstrate a rare dual growth mode of etioporphyrin I crystals, enabled by liquid precursors that associate with crystal surfaces to generate stacks of layers, which then grow laterally by incorporating solute molecules. Our findings reveal the precursors as mesoscopic solute-rich clusters, a unique phase favored by weak bonds such as those between organic solutes. The lateral spreading of the precursor-initiated stacks of layers crucially relies on abundant solute supply directly from the solution, bypassing diffusion along the crystal surface; the direct incorporation pathway may, again, be unique to organic solvents. Clusters that evolve to amorphous particles do not seamlessly integrate into crystal lattices. Crystals growing fast and mostly nonclassically at high supersaturations are not excessively strained. Our findings demonstrate that the weak interactions typical of organic systems promote nonclassical growth modes by supporting liquid precursors and enabling the spreading of multilayer stacks.

| S-EPMC11358147 | 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