Acidity and basicity interplay in amide and imide self-association.
Ontology highlight
ABSTRACT:
SUBMITTER: Vallejo Narvaez WE
PROVIDER: S-EPMC5956980 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:The diamide-imide equilibrium was successfully exploited for the synthesis of dynamic covalent polymer networks in which a dissociative bond exchange mechanism leads to high processibility at temperatures above ≈110 °C. Dynamic covalent networks bridge the gap between thermosets and thermoplastic polymers. At the operating temperature, when the network is fixed, dynamic covalent networks are elastic solids, while at high temperatures, chemical exchange reactions turn the network into a processible viscoelastic material. Upon heating a dissociative network, the viscosity may also decrease due to a shift of the chemical equilibrium; in such materials, the balance between processibility and excessive flow is important. In this study, a network is prepared that upon heating to above ≈110 °C dissociates to a significant extent due to a shift in the amide-imide equilibrium of a bisimide, pyromellitic diimide, in combination with poly(tetrahydrofuran) diamines. At room temperature, the resulting materials are elastic rubbers with a tensile modulus of 2-10 MPa, and they become predominantly viscous above a temperature of approximately 110 °C, which is dependent on the stoichiometry of the components. The diamide-imide equilibrium was studied in model reactions with NMR, and variable temperature infrared (IR) spectroscopy was used to investigate the temperature dependence of the equilibrium in the network. The temperature-dependent mechanical properties of the networks were found to be fully reversible, and the material could be reprocessed several times without loss of properties such as modulus or strain at break. The high processibility of these networks at elevated temperatures creates opportunities in additive manufacturing applications such as selective laser sintering.
| S-EPMC8552437 | biostudies-literature
Project description:The key component currently missing for the next generation of transparent and flexible displays is a high-performance polymer material that is flexible, while showing optical and thermal properties of glass. It must be transparent to visible light and show a low coefficient of thermal expansion (CTE). While specialty plastics such as aromatic polyimides are promising, reducing their CTE and improving transparency simultaneously proved challenging, with increasing coloration the main problem to be resolved. We report a new poly(amide-imide) material that is flexible and displays glass-like behavior with a CTE value of 4 parts per million/°C. This novel polymer was successfully used as a substrate to fabricate transparent and flexible indium-gallium-zinc oxide thin-film transistors.
| S-EPMC6203221 | biostudies-literature
Project description:Mixed chlorometallate ionic liquids (ILs) have been regarded as potential solvents, catalysts, and reagents for many organic processes. The acidity and basicity of these ILs were correlated with theoretically estimated parameters such as electrostatic surface potential maxima and minima, average local surface ionization energy, and Fukui and dual descriptor functions. The introduction of metal chloride into the anions would influence the acidity/basicity of ILs by withdrawing the electron density from the cationic counterpart. For the [C₄mim]-based ILs with the mixed-metal anions, the acidity tends to attenuate while the basicity becomes stronger, as compared to the corresponding chloroaluminate ILs. However, the acidity of [(C₂H₅)₃NH]-based ILs with the mixed-metal anions are greater than that of the net chloroaluminate ILs. The Fukui function values showed that most of the mixed chlorometallate ILs belong to bifunctional distribution. The mixed chlorometallate ILs both have electrophilic and nucleophilic sites, which would be beneficial for their applications.
| S-EPMC6222785 | biostudies-literature
Project description:A series of soluble aromatic poly(amide-imide)s (PAIs) was prepared from a new diamide-diamine monomer having biphenyl units with two CF3 groups. The diamide-diamine monomer was polymerized with 2,2'-bis(trifluoromethyl)benzidine and pyromelltic dianhydride through an imidization reaction to prepare PAIs with a controlled imide/amide bond ratio in the main chains. While the PAIs with the highest imide bond content showed a limited solubility, other PAIs were soluble in polar organic solvents and can be solution-cast into flexible freestanding films. All PAIs exhibited high thermal stability with 5% weight loss temperature (Td5) from 464 to 497 °C in air, and no appearance of glass transition up to 400 °C. Notably, the linear coefficient of thermal expansion (CTE) value of the PAI films was linearly decreased with the imide bond content and varied from 44.8 to 7.8 ppm/°C.
| S-EPMC8840246 | biostudies-literature
Project description:A novel biodegradable poly(amide-imide) (PAI) with good hydrophilicity was synthesized by incorporation of l-glycine into the polymer chain. For comparison purposes, a pure PAI containing no l-glycine was also synthesized with a three-step method. In this study, we evaluated the novel PAI's thermal stability, hydrophilicity, solubility, biodegradability and ability to support bone marrow mesenchymal stem cell (BMSC) adhesion and growth by comparing with the pure PAI. The hydrophilic tests demonstrated that the novel PAI has possible hydrophilicity at a 38° water contact angle on the molecule surface and is about two times more hydrophilic than the pure PAI. Due to an extra unit of l-glycine in the novel PAI, the average degradation rate was about 2.4 times greater than that of the pure PAI. The preliminary biocompatibility studies revealed that all the PAIs are cell compatible, but the pure PAI exhibited much lower cell adhesion than the l-glycine-incorporated novel PAI. The hydrophilic surface of the novel PAI was more suitable for cell adhesion, suggesting that the surface hydrophilicity plays an important role in enhancing cell adhesion and growth.
| S-EPMC6432413 | biostudies-literature
Project description:Catalytic reduction of a representative set of imines, both aldimines and ketimines, to amines has been studied using transfer hydrogenation from 1,4-dicyclohexadiene. Unusually, this has been achieved using s-block pre-catalysts, namely 1-metallo-2-tert-butyl-1,2-dihydropyridines, 2-tBuC5 H5 NM, M(tBuDHP), where M=Li-Cs. Reactions have been monitored in C6 D6 and tetrahydrofuran-d8 (THF-d8 ). A definite trend is observed in catalyst efficiency with the heavier alkali metal tBuDHPs outperforming the lighter congeners. In general, Cs(tBuDHP) is the optimal pre-catalyst with, in the best cases, reactions producing quantitative yields of amines in minutes at room temperature using 5 mol % catalyst. Supporting the experimental study, Density Functional Theory (DFT) calculations have also been carried out which reveal that Cs has a pathway with a significantly lower rate determining step than the Li congener. In the postulated initiation pathways DHP can act as either a base or as a surrogate hydride.
| S-EPMC10952797 | biostudies-literature
Project description:A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB =LAB +LBB allows equilibrium constants, KB , to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB ) and one for Lewis basicity (LBB ). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical-organic descriptors and known thermodynamic data (ΔH BF3 ). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.
| S-EPMC7985883 | biostudies-literature
Project description:In this work, we show that the apparent pKa measured by standard titration experiments is an insufficient measure of acidity or basicity of organic functional groups in multiprotic compounds─a frequent aspect of lead optimization in pharmaceutical research. We show that the use of the apparent pKa in this context may result in costly mistakes. To properly represent the group's true acidity/basicity, we propose pK50─a single-proton midpoint measure derived from a statistical thermodynamics treatment of multiprotic ionization. We show that pK50, which may be directly measured in specialized NMR titration experiments, is superior in tracking the functional group's acidity/basicity across congeneric series of related compounds and converges to the well familiar ionization constant in the monoprotic case.
| S-EPMC10207274 | biostudies-literature
Project description:To fully understand the structure-property relationship of aromatic copoly(amide-imide)s (Co-PAIs) and determine which factors lead to chain rigidity, we prepared two series of Co-PAIs. They were synthesized from two types of amine monomers containing m- and p-isomers and different ratios of 4,4'-(hexafluoroiso-propylidene)diphthalic anhydride (6FDA) and 4,4'-biphthalic anhydride (BPA). m-Substituted and p-substituted N,N'-[2,2'-bis(trifluoromethyl)-4,4'-biphenylene]bis(aminobenzamide) (MPAB) diamine isomers were synthesized from 3- and 4-nitrobenzoyl chloride and 2,2'-bis(trifluoromethyl) benzidine (TFB), respectively. The Co-PAI films were synthesized from poly(amic acid) (PAA), via solution-casting, followed by thermal imidizations. The thermal- and mechanical-properties and optical transparency of the Co-PAI films with different BPA monomer contents were investigated. We also investigated the effects of the different MPAB isomers on the Co-PAI structures. Compared with the m-substituted MPAB Co-PAI films, the p-substituted MPAB Co-PAI films have superior thermo-mechanical properties at the same monomer content. However, the optical transparencies of the m-MPAB Co-PAIs are slightly better than those of the p-MPAB Co-PAIs.
| S-EPMC9041123 | biostudies-literature
Project description:Many functional roles have been attributed to homodimers, the most common mode of protein self-association, notably in the regulation of enzymes, ion channels, transporters and transcription factors. Here we review findings that offer new insights into the different roles conformational flexibility plays in regulating homodimer function. Intertwined homodimers of two-domain proteins and their related family members display significant conformational flexibility, which translates into concerted motion between structural domains. This flexibility enables the corresponding proteins to regulate function across family members by modulating the spatial positions of key recognition surfaces of individual domains, to either maintain subunit interfaces, alter them or break them altogether, leading to a variety of functional consequences. Many proteins may exist as monomers but carry out their biological function as homodimers or higher-order oligomers. We present early evidence that in such systems homodimer formation primes the protein for its functional role. It does so by inducing elevated mobility in protein regions corresponding to the binding epitopes of functionally important ligands. In some systems this process acts as an allosteric response elicited by the self-association reaction itself. Our analysis furthermore suggests that the induced extra mobility likely facilitates ligand binding through the mechanism of conformational selection.This article is part of a discussion meeting issue 'Allostery and molecular machines'.
| S-EPMC5941183 | biostudies-literature