Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Thermoresponsive Molecular Brushes with a Rigid-Chain Aromatic Polyester Backbone and Poly-2-alkyl-2-oxazoline Side Chains.

ABSTRACT: A new polycondensation aromatic rigid-chain polyester macroinitiator was synthesized and used to graft linear poly-2-ethyl-2-oxazoline as well as poly-2-isopropyl-2-oxazoline by cationic polymerization. The prepared copolymers and the macroinitiator were characterized by NMR, GPC, AFM, turbidimetry, static, and dynamic light scattering. The molar masses of the polyester main chain and the grafted copolymers with poly-2-ethyl-2-oxazoline and poly-2-isopropyl-2-oxazoline side chains were 26,500, 208,000, and 67,900, respectively. The molar masses of the side chains of poly-2-ethyl-2-oxazoline and poly-2-isopropyl-2-oxazoline and their grafting densities were 7400 and 3400 and 0.53 and 0.27, respectively. In chloroform, the copolymers conformation can be considered as a cylinder wormlike chain, the diameter of which depends on the side chain length. In water at low temperatures, the macromolecules of the poly-2-ethyl-2-oxazoline copolymer assume a wormlike conformation because their backbones are well shielded by side chains, whereas the copolymer with short side chains and low grafting density strongly aggregates, which was visualized by AFM. The phase separation temperatures of the copolymers were lower than those of linear analogs of the side chains and decreased with the concentration for both samples. The LCST were estimated to be around 45 °C for the poly-2-ethyl-2-oxazoline graft copolymer, and below 20 °C for the poly-2-isopropyl-2-oxazoline graft copolymer.

SUBMITTER: Tarabukina E

PROVIDER: S-EPMC8622345 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Synthesis, Structure, Hydrodynamics and Thermoresponsiveness of Graft Copolymer with Aromatic Polyester Backbone at Poly(2-isopropyl-2-oxazoline) Side Chains.

Project description:New thermoresponsive graft copolymers with an aromatic polyester backbone and poly(2-isopropyl-2-oxazoline) (PiPrOx) side chains are synthesized and characterized by NMR and GPC. The grafting density of side chains is 0.49. The molar masses of the graft-copolymer, its backbone, side chains, and the modeling poly-2-isopropyl-2-oxaziline are 74,000, 19,000, 4300, and 16,600 g·mol-1, respectively. Their conformational properties in nitropropane as well as thermoresponsiveness in aqueous solutions are studied and compared with that of free side chains, i.e., linear PiPrOx with a hydrophobic terminal group. In nitropropane, the graft-copolymer adopts conformation of a 13-arm star with a core of a collapsed main chain and a PiPrOx corona. Similarly, a linear PiPrOx chain protects its bulky terminal group by wrapping around it in a selective solvent. In aqueous solutions at low temperatures, graft copolymers form aggregates due to interaction of hydrophobic backbones, which contrasts to molecular solutions of the model linear PiPrOx. The lower critical solution temperature (LCST) for the graft copolymer is around 20 °C. The phase separation temperatures of the copolymer solution were lower than that of the linear chain counterpart, decreasing with concentration for both polymers.

| S-EPMC7698206 | biostudies-literature

Self-Assembly of Molecular Brushes with Polyimide Backbone and Amphiphilic Block Copolymer Side Chains in Selective Solvents.

Project description:Three-component molecular brushes with a polyimide backbone and amphiphilic block copolymer side chains with different contents of the "inner" hydrophilic (poly(methacrylic acid)) and "outer" hydrophobic (poly(methyl methacrylate)) blocks were synthesized and characterized by molecular hydrodynamics and optics methods in solutions of chloroform, dimethylformamide, tetrahydrofuran and ethanol. The peculiarity of the studied polymers is the amphiphilic structure of the grafted chains. The molar masses of the molecular brushes were determined by static and dynamic light scattering in chloroform in which polymers form molecularly disperse solutions. Spontaneous self-assembly of macromolecules was detected in dimethylformamide, tetrahydrofuran and ethanol. The aggregates size depended on the thermodynamic quality of the solvent as well as on the macromolecular architectural parameters. In dimethylformamide and tetrahydrofuran, the distribution of hydrodynamic radii of aggregates was bimodal, while in ethanol, it was unimodal. Moreover, in ethanol, an increase in the poly(methyl methacrylate) content caused a decrease in the hydrodynamic radius of aggregates. A significant difference in the nature of the blocks included in the brushes determines the selectivity of the used solvents, since their thermodynamic quality with respect to the blocks is different. The macromolecules of the studied graft copolymers tend to self-organization in selective solvents with formation of a core-shell structure with an insoluble solvophobic core surrounded by the solvophilic shell of side chains.

| S-EPMC7762168 | biostudies-literature

Novel poly(2-oxazoline) block copolymer with aromatic heterocyclic side chains as a drug delivery platform.

Project description:Here we report a novel poly(2-oxazoline)-based block copolymer with the aromatic heterocyclic side chains in one block, poly(2-methyl-2-oxazoline)-b-poly(2-N,N-dimethyl-1,3,5-triazine-2,4-diamine-6-ethyl-2-oxazoline) (PMeOx-PcBOx), and demonstrate its potential application as a drug delivery platform. The copolymer was synthesized via the condensation of N,N-dimethylbiguanide with the methyl ester side chain in poly(2-methoxycarboxyethyl-2-oxazoline) block (PMestOx) of the PMeOx-PMestOx diblock copolymer. We confirmed the N,N-dimethylbiguanide condensation with PMestOx and the complete conversion of the side chain to the N,N-dimethyl-1,3,5-triazine-2,4-diamine-6-ethyl moiety by NMR spectroscopy, MALDI-TOF mass spectroscopy, UV-Vis spectroscopy, and titration analysis. The PMeOx-PcBOx copolymer self-assemble into polymeric micelles in aqueous solution. Successful encapsulation into these micelles has been demonstrated for 1) several poorly soluble drugs, such as bruceantin and LY2109761, and 2) dichloro(1,2-diaminocyclohexane)platinum(II) (DachPt). The first class of drugs is incorporated possibly via hydrogen bonding and pi-pi interactions with the PcBOx side groups, while the second one is likely forms coordination bonds with the same side groups. The capability of this new copolymer to solubilize a uniquely diverse set of active pharmaceutical ingredients suggests potential applications in drug delivery.

| S-EPMC7482421 | biostudies-literature

Role of aromatic side chains in amyloid β-protein aggregation.

Project description:Aggregation of the amyloid β-protein (Aβ) is believed to be involved in Alzheimer's disease pathogenesis. Here we have investigated the importance of the aromatic rings at positions 19 and 20 for the aggregation rate and mechanism by substituting phenylalanine with leucine. Aggregation kinetics were monitored as a function of time and peptide concentration by thioflavin T (ThT) fluorescence, the aggregation equilibrium by sedimentation assay, structural changes using circular dichroism spectroscopy and the presence of fibrillar material was detected with cryo-transmission electron microscopy. All peptides convert from monomer to amyloid fibrils in a concentration-dependent manner. Substituting F19 with leucine results in a peptide that aggregates significantly slower than the wild type, while substitution of F20 produces a peptide that aggregates faster. The effects of the two substitutions are additive, since simultaneous substitution of F19 and F20 produces a peptide with aggregation kinetics intermediate between F19L and F20L. Our results suggest that the aromatic side-chain of F19 favors nucleation of the aggregation process and may be an important target for therapeutic intervention.

| S-EPMC3526965 | biostudies-literature

Can 5-methylcytosine analogues with extended alkyl side chains guide DNA methylation?

Project description:5-Methylcytosine (MeC) is an endogenous modification of DNA that plays a crucial role in DNA-protein interactions, chromatin structure, epigenetic regulation, and DNA repair. MeC is produced via enzymatic methylation of the C-5 position of cytosine by DNA-methyltransferases (DNMT) which use S-adenosylmethionine (SAM) as a cofactor. Hemimethylated CG dinucleotides generated as a result of DNA replication are specifically recognized and methylated by maintenance DNA methyltransferase 1 (DNMT1). The accuracy of DNMT1-mediated methylation is essential for preserving tissue-specific DNA methylation and thus gene expression patterns. In the present study, we synthesized DNA duplexes containing MeC analogues with modified C-5 side chains and examined their ability to guide cytosine methylation by the human DNMT1 protein. We found that the ability of 5-alkylcytosines to direct cytosine methylation decreased with increased alkyl chain length and rigidity (methyl > ethyl > propyl ∼ vinyl). Molecular modeling studies indicated that this loss of activity may be caused by the distorted geometry of the DNA-protein complex in the presence of unnatural alkylcytosines.

| S-EPMC5805131 | biostudies-literature

Thermo-Responsive Polymer Brushes with Side Graft Chains: Relationship Between Molecular Architecture and Underwater Adherence.

Project description:During the last few decades, wet adhesives have been developed for applications in various fields. Nonetheless, key questions such as the most suitable polymer architecture as well as the most suitable chemical composition remain open. In this article, we investigate the underwater adhesion properties of novel responsive polymer brushes with side graft chain architecture prepared using "grafting through" approach on flat surfaces. The incorporation in the backbone of thermo-responsive poly(N-isopropylacrylamide) (PNIPAm) allowed us to obtain LCST behavior in the final layers. PNIPAm is co-polymerized with poly(methyl ethylene phosphate) (PMEP), a poloyphosphoester. The final materials are characterized studying the surface-grafted polymer as well as the polymer from the bulk solution, and pure PNIPAm brush is used as reference. PNIPAm-g-PMEP copolymers retain the responsive behavior of PNIPAm: when T > LCST, a clear switching of properties is observed. More specifically, all layers above the critical temperature show collapse of the chains, increased hydrophobicity and variation of the surface charge even if no ionizable groups are present. Secondly, effect of adhesion parameters such as debonding rate and contact time is studied. Thirdly, the reversibility of the adhesive properties is confirmed by performing adhesion cycles. Finally, the adhesive properties of the layers are studied below and above the LCST against hydrophilic and hydrophobic substrates.

| S-EPMC6941113 | biostudies-literature

Degradable terpolymers with alkyl side chains demonstrate enhanced gene delivery potency and nanoparticle stability.

Project description:Degradable, cationic poly(?-amino ester)s (PBAEs) with alkyl side chains are developed for non-viral gene delivery. Nanoparticles formed from these PBAE terpolymers exhibit significantly enhanced DNA transfection potency and resistance to aggregation. These hydrophobic PBAE terpolymers, but not PBAEs lacking alkyl side chains, support interaction with PEG-lipid conjugates, facilitating their functionalization with shielding and targeting moieties and accelerating the in vivo translation of these materials.

| S-EPMC3824380 | biostudies-literature

Monte Carlo refinement of rigid-body protein docking structures with backbone displacement and side-chain optimization.

Project description:Structures of hitherto unknown protein complexes can be predicted by docking the solved protein monomers. Here, we present a method to refine initial docking estimates of protein complex structures by a Monte Carlo approach including rigid-body moves and side-chain optimization. The energy function used is comprised of van der Waals, Coulomb, and atomic contact energy terms. During the simulation, we gradually shift from a novel smoothed van der Waals potential, which prevents trapping in local energy minima, to the standard Lennard-Jones potential. Following the simulation, the conformations are clustered to obtain the final predictions. Using only the first 100 decoys generated by a fast Fourier transform (FFT)-based rigid-body docking method, our refinement procedure is able to generate near-native structures (interface RMSD <2.5 A) as first model in 14 of 59 cases in a benchmark set. In most cases, clear binding funnels around the native structure can be observed. The results show the potential of Monte Carlo refinement methods and emphasize their applicability for protein-protein docking.

| S-EPMC2222816 | biostudies-literature

Ultrafast energy transfer from rigid, branched side-chains into a conjugated, alternating copolymer.

Project description:We present the synthesis and characterization of a benzodithiophene/thiophene alternating copolymer decorated with rigid, singly branched pendant side chains. We characterize exciton migration and recombination dynamics in these molecules in tetrahydrofuran solution, using a combination of static and time-resolved spectroscopies. As control experiments, we also measure electronic relaxation dynamics in isolated molecular analogues of both the side chain and polymer moieties. We employ semi-empirical and time-dependent density functional theory calculations to show that photoexcitation of the decorated copolymer using 395 nm laser pulses results in excited states primarily localized on the pendant side chains. We use ultrafast transient absorption spectroscopy to show that excitations are transferred to the polymer backbone faster than the instrumental response function, ∼250 fs.

| S-EPMC3977892 | biostudies-other

Poly(alkyl-biphenyl pyridinium)-Based Anion Exchange Membranes with Alkyl Side Chains Enable High Anion Permselectivity and Monovalent Ion Flux.

Project description:Poly(alkyl-biphenyl pyridinium)-based anion exchange membranes with alkyl side chains were synthesized for permselective anion separation. By altering the length of the grafted side chain, the hydrophilicity and other attributes of the membranes could be controlled. The QDPAB-C5 membrane with the best comprehensive performance exhibited a Cl- ion flux of 3.72 mol m-2 h-1 and a Cl-/SO42- permselectivity of 15, which are significantly better than the commercial Neosepta ACS membrane. The QDPAB-C5 membranes with distinct microscopic phase separation structures formed interconnected hydrophilic/hydrophobic ion channels and exhibited excellent ion flux and permselectivity for other anionic systems (NO3-/SO42-, Br-/SO42-, F-/SO42-, NO3-/Cl-, Br-/Cl-, and F-/Cl-) as well. Furthermore, the influence of alkyl side chain length on the membranes' ion flux and permselectivity in electrodialysis was investigated, which may be attributed to the alterations in ion channels and hydrophobic regions of the membranes. This work provides an effective strategy for the development of monovalent anion permselective membranes.

| S-EPMC9967815 | 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