Crown Ether Groups Research Articles

Skeletal Editing of Mechanically Interlocked Molecules: Nitrogen Atom Deletion from Crown Ether-Dibenzylammonium Rotaxanes.

Removing the nitrogen atom from secondary amines while simultaneously linking the remaining fragments is a powerful form of late-stage skeletal editing. Here, we report its use for the deletion of the nitrogen atom of the dibenzylammonium template used to assemble crown ether rotaxanes. The reaction uses an anomeric amide that activates secondary amines to generate a carbon-carbon bond that replaces the amine nitrogen. Despite the potential for dethreading of the intermediate diradical pair, the nitrogen atom was successfully deleted from a series of rotaxane axles as long as the macrocycle could access coconformations that did not inhibit the reaction of the amine group. The skeletally edited interlocked molecules were obtained directly from the parent crown ether-dibenzylammonium rotaxanes in modest yields (23-36%) and characterized by NMR spectroscopy, mass spectrometry, and X-ray crystallography. One skeletally edited rotaxane shows a network of weak CH···O hydrogen bonds between the crown ether and benzylic methylene groups of the axle in the solid state, in place of the crown ether-ammonium binding motif used to assemble the parent, unedited, rotaxane.

Theoretical simulation of ion transport in main-chain poly(arylene piperidinium) anion exchange membranes with crown ether groups

ABSTRACT Experimental studies have confirmed that introduction of the proper content of dibenzo-18-crown-6-ether (DE) into main-chain poly(arylene piperidinium) anion exchange membranes (AEMs) improved the efficiency of OH− transport. In this study, models of the AEMs (PDTP-x) were constructed with varying molar contents of DE groups (x = 0, 0.05, 0.10, 0.15, 0.20 and 0.25). Molecular dynamics simulations were employed to investigate the microscopic effects of the DE groups on OH− transport. The analysis examined the impact of the volume of the overlapping hydration shells around piperidinium groups and the continuities and uniformities of the ion transport channels. Furthermore, the stabilities of the hydrogen bonds between water molecules explained the effect of x on OH− transport. The results showed that the total overlap volume initially increased and then decreased as x increased. When the content of DE groups was appropriate, the hydration shells of the cations exhibited considerable overlap, which facilitated the formation of continuous and uniform ion transport channels. Additionally, the stabilities of the water hydrogen bonds initially decreased and then increased as x increased. The stabilities of the hydrogen bonds were lowest when the DE content was optimal, which facilitated the transport of OH−.

Molecular insight into the separation mechanism of crown Ether-Based channels for lithium Extraction

The shortage of lithium resources can be effectively improved by using membrane separation technology to extract lithium from salt lake brines that contain rich Li. In this study, GO modified with functionalized crown ether group (2)-hydroxymethyl-15-crown-5,15C) was used as a separation membrane for Li+/Mg2+. The effect of 15C and its content on the separation mechanism of Li+/Mg2+ in membrane was designed and studied by molecular dynamics simulation. Improving water permeability of the membrane can be achieved with the appropriate amount of 15Cs, but an excessive amount of 15C will result in channel obstruction, which is not conducive to the transport of water molecules. In addition, the special recognition of Li+ by 15Cs enhances the transmission of Li+ within the channel. Finally, it is found that the dehydration behavior of Li+ is facilitated by the interaction between 15Cs and Li+. As the diameter of Li+ is smaller than the diameter of the 15C cavity, dehydrated Li+ passes through the 15C cavity with ease under pressure. This means that during the separation process, Li+ enters a “dual transport” mode. The membrane gains higher permeability for Li+ while blocking Mg2+. This study clarifies the rapid transport mechanism of Li+ in GO-15C，which provides a feasible strategy for designing highly selective Li+/Mg2+ separation membranes.

Structure affinity of the Langmuir monolayer and the corresponding Langmuir-Blodgett film revealed by X-ray techniques.

The possibility of reproducing the structural organization and functional abilities of a Langmuir monolayer in a film formed from it is one of the fundamental problems of ultrathin film science. This work is devoted to the comparison of monolayer and Langmuir-Blodgett (LB) film characteristics using the example of 2D systems based on the dithia-aza-crown substituted hemicyanine dye HCS. As was shown earlier, the investigated systems are promising for the preparation of selective sensors and extractors for mercury ions in aqueous solutions with a subnanomolar sensitivity threshold. Therefore, the study of the analyte binding mechanism by such a film is of great importance. The study carried out using an ultra-highly brilliant X-ray source (ESRF) allows the application of highly sensitive techniques such as X-ray reflectometry (XRR) and X-ray standing wave (XSW). Comparison of the electron density depth profile of the HCS Langmuir monolayer at the air/water interface and the HCS film transferred to a silicon substrate shows the preservation of the film structure and its functional features. The XSW measurements in turn reveal the similarities in the fine structure of preorganized Langmuir monolayers and Langmuir-Blodgett films of HCS. The integration of X-ray techniques with molecular modeling methods allowed us to show that the crown-ether groups of HCS molecules in the pre-organized monolayer and in the corresponding LB film lie on the surface of water or silicon, and the bound mercury ion is located above the crown-ether, partially binding to the nitrogen atom. The latter loses conjugation to the chromophore group, thereby altering the UV-vis spectrum and providing a response signal. The revealed mechanism of imprinting preorganization allows the proposed approach to be extended to other crown-substituted amphiphilic dyes to significantly enhance the sensory response.

Study on Dynamic Column Behavior and Complexation Mechanism of DBS-Modified Crown Ether-Based Silica to 90Sr.

A crown ether-loaded hybrid adsorbent suitable for the separation and enrichment of strontium from high-level liquid waste was synthesized. 4',4'(5″)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its modifiers dodecyl benzenesulfonic acid (DBS) and 1-dodecanol were impregnated into silica-based polymer support. The hybrid adsorbent exhibited excellent Sr(II) selectivity ability, and effective chromatographic separation and recovery of Sr(II) from simulated high-level liquid waste could be achieved with a (DtBuCH18C6 + DBS + dodec)/SiO2-P packed column. The recovery rate of Sr(II) calculated based on the mass balance was approximately 99% and over 80% for the other coexisting metal ions. An appropriate increase in the concentration of Na-DTPA eluent was favorable to improve the efficiency of the elution process because of the increased complexation capacity of [DTPA]5- to Sr(II). The developed theoretical model can simulate the dynamic breakthrough curves of the material on the basis of short column data, thereby predicting the scale-up column of the practical operation. Density functional theory calculation was used to explore the action mechanism of DBS modifiers on the Sr(II) complexation process of crown ether groups. Two Sr(II) complexation isomeric models of DtBuCH18C6 were established, and the calculation results revealed a similar complexation ability. DtBuCH18C6 could form a stable Sr(II) complexation structure with DBS coordination, which further indicated that DBS could be a ligand to promote the Sr(II) adsorption ability of crown ether materials.

Structural engineering on 6FDA-Durene based polyimide membranes for highly selective gas separation

In this work, four diamine monomers, selected based-on steric hindrance and affinity with gas to be separated, were separately introduced into 6FDA-Durene to prepare co-polyimides. The influences of incorporating diamine monomer geometry on free volume elements (FFV, FAV, cavity size distribution, surface area and cavity connectivity) and gas transport properties (solubility and diffusion) of synthesized co-polyimide membranes were systematically investigated. The introduction of second amino monomer can increase gas selectivity, however leaded to lower gas permeability. Gas solubility and solubility selectivity of membrane remained almost stable with introduction of different amino monomer. While the gas diffusion changed remarkably, and the diffusion selectivity increased by about 170%. The FDDA membrane with crown ether structure displayed the highest gas selectivity (increased by 122%, 121%, 158%, 115% and 115% for H2/N2, H2/CH4, O2/N2, CO2/N2 and CO2/CH4, respectively, compared to 6FDA-Durene membrane), whose selectivity was relatively high among the PI-based membranes. This can be explained that the crown ether group granted the membrane with largest FAV ratio of specific gas pair, as well as the smallest pore size that would cause stronger size sieving effect. These results indicated that gas separation property of polyimide membranes can be effectively adjusted via tuning monomer structure, which is easily synthesized or has been commercialized, to realize the industrial application of membrane-based gas separation.

SELECTIVE SORBENTS BASED ON DIAMINODICYCLOHEXYLCROWN ETHERS

Macromolecules with crown ether groups are a fundamentally new type of sorbents whose active centers are ligands that retain electrical neutrality in the process of simultaneous binding of cations, anions, or organic compounds. The purpose of this work is to create new selective sorbents based on diaminodicyclohexylcrown ethers and to study their complexing properties with respect to alkali metal ions. Methodology. To study the composition and properties of the products of the synthesis of crown ether-containing sorbents, chemical and physicochemical methods of analysis were used: infrared spectroscopy, atomic absorption spectrophotometry. Results and discussion. Chemical grafting of cycloaliphatic crown ethers onto a macroporous chloromethylated copolymer of styrene and divinylbenzene has been carried out. Under the chosen conditions, when using diaminodicyclohexyl-18-crown-6, polycrown ethers were obtained with a content of crown ether grains of 1.42 mmol/g, when using diaminodicyclohexyl-24-crown-8, the content of macrocyclic groups was 1.24 mmol/g. The extraction of alkali metals under static conditions by grafted sorbents based on various macrocycles has been studied. The high values of the distribution coefficients of alkali metals (Na+, K+, Cs+) by the synthesized sorbents in an acidic medium are shown. The following selectivity series were found for the sorbent with diaminodicyclohexyl-18-crown-6 fragments: K+ ˃ Cs + ˃ Na+, and for the sorbent with diaminodicyclohexyl-24-crown-8 fragments: Cs+ ˃ K+ ˃ Na+ metals. Conclusion. The efficiency of extracting metal ions from aqueous solutions containing Crown esters is affected by the presence of amino groups. It is known that the amino group promotes the formation of a polymer that swells in water. It was noted that the use of sorbents based on polymers that swell in water when metal salts are removed from the aqueous medium leads to an increase in the sorption capacity of sorbents by facilitating the access of metal ions in water to the active areas of the immobilized sorbent.

Multistep sequence-controlled supramolecular polymerization by the combination of multiple self-assembly motifs

The precise sequence control of polymer chain is an important research topic of polymer chemistry. Although some methods such as iterative synthesis and supramolecular polymerization have been developed to fabricate sequence-controllable polymer, it is still a great challenge to consecutively prepare multiple supramolecular polymers with different sequence structures. In this work, through the reasonable utilization of assembly motifs, we integrated multiple host-guest recognitions and metal coordination interactions to prepare different sequence-controlled supramolecular polymers by a multistep assembly strategy. This research provides inspiration for the design and preparation of supramolecular polymers with different sequence structures.

Subnanomolar Detection of Mercury Cations in Water by an Interfacial Fluorescent Sensor Achieved by Ultrathin Film Structure Optimization.

The objectives of this work were to develop and extend the previously proposed approaches to control the structure of nanoscale planar systems based on modular fluorophore compounds capable of efficient analyte binding and to optimize the architecture of ultrathin films formed from them to create a thin-film sensor element for mercury cations. The possibility of applying the ratiometric approach to the fluorescence measurements to obtain a quantitative analytical signal was shown. It was found that films with the Langmuir-Schaefer film architecture, in which the receptor crown ether groups of the fluoroionophore are oriented toward the studied solution, allow the quantitative determination of mercury cations in water at concentrations below the threshold limit value and are especially effective in the analyte concentration range of 10-10-10-5 M. High selectivity of the obtained thin-film sensitive elements with respect to mercury cations and the possibility of regeneration of such elements after quantitative determination of mercury cations in aqueous solutions are demonstrated.

Graphene-Based Intrinsically Stretchable 2D-Contact Electrodes for Highly Efficient Organic Light-Emitting Diodes.

Intrinsically stretchable organic light-emitting diodes (ISOLEDs) are becoming essential components of wearable electronics. However, the efficiencies of ISOLEDs have been highly inferior compared with their rigid counterparts, which is due to the lack of ideal stretchable electrode materials that can overcome the poor charge injection at 1D metallic nanowire/organic interfaces. Herein, highly efficient ISOLEDs that use graphene-based 2D-contact stretchable electrodes (TCSEs) that incorporate a graphene layer on top of embedded metallic nanowires are demonstrated. The graphene layer modifies the work function, promotes charge spreading, and impedes inward diffusion of oxygen and moisture. The work function (WF) of 3.57eV is achieved by forming a strong interfacial dipole after deposition of a newly designed conjugated polyelectrolyte with crown ether and anionic sulfonate groups on TCSE; this is the lowest value ever reported among ISOLEDs, which overcomes the existing problem of very poor electron injection in ISOLEDs. Subsequent pressure-controlled lamination yields a highly efficient fluorescent ISOLED with an unprecedently high current efficiency of 20.3cd A-1 , which even exceeds that of an otherwise-identical rigid counterpart. Lastly, a 3 inch five-by-five passive matrix ISOLED is demonstrated using convex stretching. This work can provide a rational protocol for designing intrinsically stretchable high-efficiency optoelectronic devices with favorable interfacial electronic structures.

Directionally Aligned Crown Ethers as Superactive Organocatalysts for Transition-metal Ion-free Arylation of Unactivated Arenes.

When one-dimensionally aligned to the same side, multiple non-covalently associated crown ether groups could act as a whole to yield a higher catalytic activity than an individual poorly active crown ether group, delivering the lowest catalyst loading of 1-2 mol % among all hitherto known organocatalysts for catalyzing direct arylation of unactivated arenes with haloarenes.

Are Highly Stable Covalent Organic Frameworks the Key to Universal Chiral Stationary Phases for Liquid and Gas Chromatographic Separations?

High-performance liquid chromatography (HPLC) and gas chromatography (GC) over chiral stationary phases (CSPs) represent the most popular and highly applicable technology in the field of chiral separation, but there are currently no CSPs that can be used for both liquid and gas chromatography simultaneously. We demonstrate here that two olefin-linked covalent organic frameworks (COFs) featuring chiral crown ether groups can be general CSPs for extensive separation not only in GC but also in normal-phase and reversed-phase HPLC. Both COFs have the same 2D layered porous structure but channels of different sizes and display high stability under different chemical environments including water, organic solvents, acids, and bases. Chiral crown ethers are periodically aligned within the COF channels, allowing for enantioselective recognition of guest molecules through intermolecular interactions. The COF-packed HPLC and GC columns show excellent complementarity and each affords high resolution, selectivity, and durability for the separation of a wide range of racemic compounds, including amino acids, esters, lactones, amides, alcohols, aldehydes, ketones, and drugs. The resolution performances are comparable to and the versatility is superior to those of the most widely used commercial chiral columns, showing promises for practical applications. This work thus advances COFs with high stability as potential universal CSPs for chromatography that are otherwise hard or impossible to produce.

Urea-based covalent organic crown polymers and KI electrostatic synergy in CO2 fixation reaction: A combined experimental and theoretical study

Multifunctional organic polymer materials are supposed to be the most promising catalysts in the utilization of carbon dioxide (CO2) to five-membered cyclic carbonates (5CCs). Herein, functional one dimensional (1D) organic polymer materials (1D-UCP and 1D-UP) were successfully synthesized and their structural features were thoroughly characterized by FT-IR, 13C CP MAS NMR, SEM, TGA and XPS spectroscopy. These materials showed excellent reaction performance in the CO2 cycloaddition reaction. Notably, the 1D-UCP decorated by crown ether group and urea unit simultaneously showed excellent yields of 5CCs under solvent-free conditions and low pressure of CO2. The outstanding performance was attributable to the synergistic effect of activated KI by coordinating with crown ether fragment and urea unit as hydrogen bonding donor facilitating implementation of speed-determined step of this reaction. In combination with density functional theory (DFT) calculations including intermediates structure optimization and transition states free energy profile, a possible catalytic mechanism was proposed that the urea group accelerated the reaction by vicinal dual hydrogen bonding and increasing nucleophilicity of I anion.

Artificial Biomolecular Channels: Enantioselective Transmembrane Transport of Amino Acids Mediated by Homochiral Zirconium Metal-Organic Cages.

Natural transport channels (or carriers), such as aquaporins, are a distinct type of biomacromolecule capable of highly effective transmembrane transport of water or ions. Such behavior is routine for biology but has proved difficult to achieve in synthetic systems. Perhaps most significantly, the enantioselective transmembrane transport of biomolecules is an especially challenging problem both for chemists and for natural systems. Herein, a group of homochiral zirconium metal-organic cages with four triangular opening windows have been proposed as artificial biomolecular channels for enantioselective transmembrane transport of natural amino acids. These structurally well-defined coordination cages are assembled from six synthetically accessible BINOL-derived chiral ligands as spacers and four n-Bu3-Cp3Zr3 clusters as vertices, forming tetrahedral-shaped architectures that feature an intrinsically chiral cavity decorated with an array of specifically positioned binding sites mediated from phenol to phenyl ether to crown ether groups. Fascinatingly, the transformation of single-molecule chirality to global supramolecular chirality within the space-restricted chiral microenvironments accompanies unprecedented chiral amplification, leading to the enantiospecific recognition of amino acids. By virtue of the highly structural stability and excellent biocompatibility, the orientation-independent cages can be molecularly embedded into lipid membranes, biomimetically serving as single-molecular chiral channels for polar-residue amino acids, with the properties that cage-1 featuring hydroxyl groups preferentially transports the l-asparagine, whereas cage-2 attaching crown ether groups spontaneously favor transporting d-arginine. We therefore develop a new type of self-assembled system that can potentially mimic the functions of transmembrane proteins in nature, which is a realistic candidate for further biomedical applications.

Crystal Packing‐Guided Construction of Hetero‐Oligomeric Peptidic Ensembles as Synthetic 3‐in‐1 Transporters

AbstractStrategies to generate heteromeric peptidic ensembles via a social self‐sorting process are limited. Herein, we report a crystal packing‐inspired social self‐sorting strategy broadly applicable to diverse types of H‐bonded peptidic frameworks. Specifically, a crystal structure of H‐bonded alkyl chain‐appended monopeptides reveals an inter‐chain separation distance of 4.8 Å dictated by the H‐bonded amide groups, which is larger than 4.1 Å separation distance desired by the tightly packed straight alkyl chains. This incompatibility results in loosely packed alkyl chains, prompting us to investigate and validate the feasibility of applying bulky tert‐butyl groups, modified with an anion‐binding group, to alternatively interpenetrate the straight alkyl chains, modified with a crown ether group. Structurally, this social self‐sorting approach generates highly stable hetero‐oligomeric ensembles, having alternated anion‐ and cation‐binding units vertically aligned to the same side. Functionally, these hetero‐oligomeric ensembles promote transmembrane transport of cations, anions and more interestingly zwitterionic species such as amino acids.

Crystal Packing‐Guided Construction of Hetero‐Oligomeric Peptidic Ensembles as Synthetic 3‐in‐1 Transporters

Strategies to generate heteromeric peptidic ensembles via a social self-sorting process are limited. Herein, we report a crystal packing-inspired social self-sorting strategy broadly applicable to diverse types of H-bonded peptidic frameworks. Specifically, a crystal structure of H-bonded alkyl chain-appended monopeptides reveals an inter-chain separation distance of 4.8 Å dictated by the H-bonded amide groups, which is larger than 4.1 Å separation distance desired by the tightly packed straight alkyl chains. This incompatibility results in loosely packed alkyl chains, prompting us to investigate and validate the feasibility of applying bulky tert-butyl groups, modified with an anion-binding group, to alternatively interpenetrate the straight alkyl chains, modified with a crown ether group. Structurally, this social self-sorting approach generates highly stable hetero-oligomeric ensembles, having alternated anion- and cation-binding units vertically aligned to the same side. Functionally, these hetero-oligomeric ensembles promote transmembrane transport of cations, anions and more interestingly zwitterionic species such as amino acids.

Helical Fe(II)-Based Metallo-Supramolecular Polymers: Effect of Crown Ether Groups Located outside the Helix on Hydrous Proton Channel Formation

Helical Fe(II)-based metallo-supramolecular polymers with/without crown ether groups (polyFe-C and polyFe-H, respectively) were synthesized by the 1:1 complexation of an Fe(II) salt and chiral bist...

Theoretical design of new macrocycles for nucleophilic fluorination with KF: thiourea-crown-ether is predicted to overcome [2.2.2]-cryptand

A new macrocycle combining thiourea and crown ether groups is able to solubilize KF and promote fluorination via stabilization of the SN2 transition state via four hydrogen bonds.

Hexabenzocoronene Graphitic Nanocoils Appended with Crown Ethers: Supramolecular Chirality Induced by Host-Guest Interaction.

We have designed and synthesized two new achiral hexa-peri-hexabenzocoronene (HBC) derivatives, HBCCE and HBCTEG-CE , which bear the crown ether as the pendant for the amino acid binding site. The HBCCE self-assembled into a racemic mixture of P- and M-handed helical nanocoils, however, in the presence of chiral amino acid guests, it formed helical nanocoils with one-handed screw sense. The effects of the concentration, type and configuration of the guests on the induced circular dichroism (ICD) during the co-assembly of HBCCE with chiral amino acids were also investigated. Additionally, after complete removal of the chiral guests, the optically active nanocoils did not racemize, even in the presence of excess amino acids with the opposite configuration. In contrast, HBCTEG-CE with a long triethylene glycol (TEG) chain between the crown ether group and the HBC unit did not exhibit ICD during the co-assembly with chiral amino acids.

Sub-10 nm Scale Lamellar Structures with a High Degree of Long-Range Order Fabricated by Orthogonal Self-Assembly of Crown Ether/Secondary Dialkylammonium Recognition and Metal···Metal/π-π Interactions.

We here present an orthogonal self-assembly strategy to fabricate a series of metallosupramolecular polymers by coupling planar platinum(II) complexes and starlike poly(ε-caprolactone), through Pt···Pt/π-π interactions and host-guest recognition between secondary dialkylammonium salts and crown ether groups. The solid metallosupramolecular polymers exhibit sub-10 nm scale lamellar structures and one of them occupies an extraordinary degree of long-range order. The platinum(II) complexes can be regarded as an individual supramolecular block to microphase segregate the polymeric segment. Moreover, the metallosupramolecular polymers show intense luminescence and appreciable proton conductivity, originating from these two supramolecular connection modes, respectively. This work paves the way for fabricating metallosupramolecular polymers showing both highly ordered nanostructures and multifunctional properties.