Anion-assisted amidinium exchange and metathesis.
Ontology highlight
ABSTRACT:
SUBMITTER: Borodin O
PROVIDER: S-EPMC9469691 | biostudies-literature | 2022 Sep
REPOSITORIES: biostudies-literature
Publications
Anion-assisted amidinium exchange and metathesis.
Borodin Oleg O Shchukin Yevhenii Y Schmid Jonas J von Delius Max M
Chemical communications (Cambridge, England) 20220913 73
Dynamic covalent chemistry has become an invaluable tool for the design and preparation of adaptable yet robust molecular systems. Herein we explore the scope of a largely overlooked dynamic covalent reaction - amidinium exchange - and report on conditions that allow formal amidinium metathesis reactions. ...[more]
Similar Datasets
Project description:Advances in supramolecular chemistry are often underpinned by the development of fundamental building blocks and methods enabling their interconversion. In this work, we report the use of an underexplored dynamic covalent reaction for the synthesis of stimuli-responsive [2]rotaxanes. The formamidinium moiety lies at the heart of these mechanically interlocked architectures, because it enables both dynamic covalent exchange and the binding of simple crown ethers. We demonstrated that the rotaxane self-assembly follows a unique reaction pathway and that the complex interplay between crown ether and thread can be controlled in a transient fashion by addition of base and fuel acid. Dynamic combinatorial libraries, when exposed to diverse nucleophiles, revealed a profound stabilizing effect of the mechanical bond as well as intriguing reactivity differences between seemingly similar [2]rotaxanes.
| S-EPMC8517971 | biostudies-literature
Project description:Most phosphoproteomics experiments rely on prefractionation of tryptic digests before online liquid chromatography-mass spectrometry. This study compares the potential and limitations of electrostatic repulsion-hydrophilic interaction chromatography (ERLIC) and anion-exchange chromatography (AEX). At a pH higher than 5, phosphopeptides have two negative charges per residue and are well-retained in AEX. However, peptides with one or two phosphate groups are not separated from peptides with multiple Asp or Glu residues, interfering with the identification of phosphopeptides. At a pH of 2, phosphate residues have just a single negative charge but Asp and Glu are uncharged. This facilitates the separation of phosphopeptides from unmodified acidic peptides. Singly phosphorylated peptides are retained weakly under these conditions, due to electrostatic repulsion, unless hydrophilic interaction is superimposed in the ERLIC mode. Weak anion-exchange (WAX) and strong anion-exchange (SAX) columns were compared, with both peptide standards and a HeLa cell tryptic digest. The SAX column exhibited greater retention at pH 6 than did the WAX column. However, only about 60% as many phosphopeptides were identified with SAX at pH 6 than via ERLIC at pH 2. In one ERLIC run, 12 467 phosphopeptides were identified, including 4233 with more than one phosphate. We conclude that chromatography of phosphopeptides is best performed at low pH in the ERLIC mode. Under those conditions, the performances of the SAX and WAX materials were comparable. The data have been deposited with the ProteomeXchange with identifier PXD001333.
| S-EPMC4423237 | biostudies-literature
Project description:Photoelectric properties of all-inorganic perovskite quantum dots (IPQDs) highly depend on their synthetic route. However, current synthetic processes of IPQDs are widely facing potential unsustainable issues of containing nonreusable and high-cost auxiliary materials. In this work, full-visible-spectrum IPQDs were successfully synthesized by an environmentally friendly ion-exchange approach with a renewable and low-cost anion exchange resin. Introducing anion exchange resin brings the improvement of both optical performance and surface morphology of the prepared IPQDs. The emission wavelength of IPQDs can be precisely controlled without changing their inherent crystal phase, and those IPQD's single crystals with poor morphology and unstable structure are selectively removed. The photoluminescence quantum yield (PLQY) and the fluorescence lifetime of the three-primary-color IPQDs can be dramatically improved to 93.69, 89.99, and 65.03% and 71.3 ns, 22.2 ns, and 13.2 ns, respectively. Notably, the red-emitting PQDs at 622 nm exhibit a record high PLQY. By using the prepared IPQDs for photoluminescent color conversion, the three-primary-color light-emitting diodes (LEDs) provided high brightness and wide color gamut simultaneously. This study provides new ideas for the environmentally friendly and sustainable synthesis route of IPQDs, and it is expected to show great ambitions in the display field.
| S-EPMC11501922 | biostudies-literature
Project description:Anion exchange membrane seawater electrolysis is vital for future large-scale green hydrogen production, however enduring a huge challenge that lacks high-stable oxygen evolution reaction electrocatalysts. Herein, we report a robust OER electrocatalyst for AEMSE by integrating MXene (Ti3C2) with NiFe sulfides ((Ni,Fe)S2@Ti3C2). The strong interaction between (Ni,Fe)S2 and Ti3C2 induces electron distribution to trigger lattice oxygen mechanism, improving the intrinsic activity, and particularly prohibits the dissolution of Fe species during OER process via the Ti-O-Fe bonding effectively, achieving notable stability. Furthermore, the good retention of sulfates and the abundant groups of Ti3C2 provide effective Cl- resistance. Accordingly, (Ni,Fe)S2@Ti3C2 achieves high OER activity (1.598 V@2 A cm-2) and long-term durability (1000 h) in seawater system. Furthermore, AEMSE with industrial current density (0.5 A cm-2) and durability (500 h) is achieved by (Ni,Fe)S2@Ti3C2 anode and Raney Ni cathode with electrolysis efficiency of 70% and energy consumption of 48.4 kWh kg-1 H2.
| S-EPMC11790850 | biostudies-literature
Project description:Anion-exchange membranes (AEMs), known for enabling the high conductivity of hydroxide anions through dense polymeric structures, are pivotal components in fuel cells, electrolyzers, and other important electrochemical systems. This paper unveils an unprecedented utilization of AEMs in an electrochemical oxygen separation process, a new technology able to generate enriched oxygen from an O2/N2 mixture using a small voltage input. We demonstrate a first-of-its-kind AEM-based electrochemical device that operates under mild conditions, is free of liquid electrolytes or sweep gases, and produces oxygen of over 96% purity. Additionally, we develop and apply a one-dimensional time-dependent and isothermal model, which accurately captures the unique operational dynamics of our device, demonstrates good agreement with the experimental data, and allows us to explore the device's potential capabilities. This novel technology has far-reaching applications in many industrial processes, medical oxygen therapy, and other diverse fields while reducing operational complexity and environmental impact, thereby paving the way for sustainable on-site oxygen generation.
| S-EPMC11450738 | biostudies-literature
Project description:This Review provides an overview of the emerging concepts of catalysts, membranes, and membrane electrode assemblies (MEAs) for water electrolyzers with anion-exchange membranes (AEMs), also known as zero-gap alkaline water electrolyzers. Much of the recent progress is due to improvements in materials chemistry, MEA designs, and optimized operation conditions. Research on anion-exchange polymers (AEPs) has focused on the cationic head/backbone/side-chain structures and key properties such as ionic conductivity and alkaline stability. Several approaches, such as cross-linking, microphase, and organic/inorganic composites, have been proposed to improve the anion-exchange performance and the chemical and mechanical stability of AEMs. Numerous AEMs now exceed values of 0.1 S/cm (at 60-80 °C), although the stability specifically at temperatures exceeding 60 °C needs further enhancement. The oxygen evolution reaction (OER) is still a limiting factor. An analysis of thin-layer OER data suggests that NiFe-type catalysts have the highest activity. There is debate on the active-site mechanism of the NiFe catalysts, and their long-term stability needs to be understood. Addition of Co to NiFe increases the conductivity of these catalysts. The same analysis for the hydrogen evolution reaction (HER) shows carbon-supported Pt to be dominating, although PtNi alloys and clusters of Ni(OH)2 on Pt show competitive activities. Recent advances in forming and embedding well-dispersed Ru nanoparticles on functionalized high-surface-area carbon supports show promising HER activities. However, the stability of these catalysts under actual AEMWE operating conditions needs to be proven. The field is advancing rapidly but could benefit through the adaptation of new in situ techniques, standardized evaluation protocols for AEMWE conditions, and innovative catalyst-structure designs. Nevertheless, single AEM water electrolyzer cells have been operated for several thousand hours at temperatures and current densities as high as 60 °C and 1 A/cm2, respectively.
| S-EPMC9284563 | biostudies-literature
Project description:Recently, the development of durable anion-exchange membrane fuel cells (AEMFCs) has increased in intensity due to their potential to use low-cost, sustainable components. However, the decomposition of the quaternary ammonium (QA) cationic groups in the anion-exchange membranes (AEMs) during cell operation is still a major challenge. Many different QA types and functionalized polymers have been proposed that achieve high AEM stabilities in strongly alkaline aqueous solutions. We previously developed an ex situ technique to measure AEM alkaline stabilities in an environment that simulates the low-hydration conditions in an operating AEMFC. However, this method required the AEMs to be soluble in DMSO solvent, so decomposition could be monitored using 1H nuclear magnetic resonance (NMR). We now report the extension of this ex situ protocol to spectroscopically measure the alkaline stability of insoluble AEMs. The stability ofradiation-grafted (RG) poly(ethylene-co-tetrafluoroethylene)-(ETFE)-based poly(vinylbenzyltrimethylammonium) (ETFE-TMA) and poly(vinylbenzyltriethylammonium) (ETFE-TEA) AEMs were studied using Raman spectroscopy alongside changes in their true OH- conductivities and ion-exchange capacities (IEC). A crosslinked polymer made from poly(styrene-co-vinylbenzyl chloride) random copolymer and N,N,N',N'-tetraethyl-1,3-propanediamine (TEPDA) was also studied. The results are consistent with our previous studies based on QA-type model small molecules and soluble poly(2,6-dimethylphenylene oxide) (PPO) polymers. Our work presents a reliable ex situ technique to measure the true alkaline stability of AEMs for fuel cells and water electrolyzers.
| S-EPMC10016746 | biostudies-literature
Project description:In this study, novel crosslinked pore-filling membranes were fabricated by using a centrifugal force from the cylindrical centrifugal machine. For preparing these crosslinked pore-filling membranes, the poly(phenylene oxide) containing long side chains to improve the water management (hydrophilic), porous polyethylene support (hydrophobic) and crosslinker based on the diamine were used. The resulting membranes showed a uniform thickness, flexible and transparent because it is well filled. Among them, PF-XAc-PPO70_25 showed good mechanical properties (56.1 MPa of tensile strength and 781.0 MPa of Young's modulus) and dimensional stability due to the support. In addition, it has a high hydroxide conductivity (87.1 mS/cm at 80 °C) and low area specific resistance (0.040 Ω·cm2), at the same time showing stable alkaline stability. These data outperformed the commercial FAA-3-50 membrane sold by Fumatech in Germany. Based on the optimized properties, membrane electrode assembly using XAc-PPO70_25 revealed excellent cell performance (maximum power density: 239 mW/cm2 at 0.49 V) than those of commercial FAA-3-50 Fumatech anion exchange membrane (maximum power density: 212 mW/cm2 at 0.54 V) under the operating condition of 60 °C and 100% RH as well. It was expected that PF-XAc-PPO70_25 could be an excellent candidate based on the results superior to those of commercial membranes in these essential characteristics of fuel cells.
| S-EPMC7700159 | biostudies-literature
Project description:Designing suitable anion exchange ionomers is critical to improving the performance and in situ durability of anion exchange membrane water electrolyzers (AEMWEs) as one of the promising devices for producing green hydrogen. Herein, highly gas-permeable and dimensionally stable anion exchange ionomers (QC6xBA and QC6xPA) are developed, in which bulky cyclohexyl (C6) groups are introduced into the polymer backbones. QC650BA-2.1 containing 50 mol% C6 composition shows 16.6 times higher H2 permeability and 22.3 times higher O2 permeability than that of QC60BA-2.1 without C6 groups. Through-plane swelling of QC650BA-2.1 decreases to 12.5% from 31.1% (QC60BA-2.1) while OH- conductivity slightly decreases (64.9 and 56.2 mS cm-1 for QC60BA-2.1 and QC650BA-2.1, respectively, at 30 °C). The water electrolysis cell using the highly gas permeable QC650BA-2.1 ionomer and Ni0.8Co0.2O in the anode catalyst layer achieves two times higher performance (2.0 A cm-2 at 1.69 V, IR-included) than those of the previous cell using in-house ionomer (QPAF-4-2.0) (1.0 A cm-2 at 1.69 V, IR-included). During 1000 h operation at 1.0 A cm-2, the QC650BA-2.1 cell exhibits nearly constant cell voltage with a decay rate of 1.1 µV h-1 after the initial increase of the cell voltage, proving the effectiveness of the highly gas permeable and dimensionally stable ionomer in AEMWEs.
| S-EPMC11304252 | biostudies-literature
Project description:Replacing lead in halide perovskites to address the concerns of their toxicity and stability has driven a recent surge in research toward alternative lead-free perovskite materials. Lead-free all inorganic cesium bismuth halide (Cs3Bi2X9) perovskite nanocrystals have attracted attention in recent years due to the air-stability and non-toxic nature of bismuth. Herein, we demonstrate a facile sonication-assisted approach for the preparation of all-inorganic cesium bismuth iodide (Cs3Bi2I9) perovskite nanocrystals (NCs) using propylene carbonate as a green, alternative solvent. The photoluminescence (PL) spectra of the Cs3Bi2X9 NCs have a peak emission that can be tuned from 410 to 550 nm by controlling the composition of the NCs through an anion exchange reaction using tetraalkylammonium halides as a source of halide ions. The rate of this anion exchange reaction is demonstrated to have a significant influence on the dimensions of the NCs obtained from the parent Cs3Bi2I9 NCs. The PL emission of these nanocrystals is predominately due to exciton recombination processes. The NCs also exhibit air-stability for at least 150 days.
| S-EPMC9419692 | biostudies-literature