Effect Of Side Chain Length Research Articles

Effects of side chain length on the performance of poly(aryl-alkylene) anion exchange membranes for fuel cells

Anion exchange membranes (AEMs) are one of the most critical materials determining the fuel cell (FC) performance. From current reports, there are still many limit factors for AEMs, such as conductivity, mechanical performance, power density and durability, which greatly affect their practicality. Here, we introduce a range of arylfluoroketone monomers with different side chain lengths into the poly (aryl-alkylene) matrix material using a copolymerization strategy to get AEMs. This study aims to investigate the effect of side chain length on the performance of AEMs, such as phase separation, ion conductivity and mechanical properties. Due to the existence of long alkyl side chains, QTPNPC4 shows significant hydrophilic aggregation, outstanding OH− conductivity (158.6 mS cm−1, 80 °C) and excellent flexibility (109.1 %). Meanwhile, QTPNPC4 exhibits remarkable ex-situ durability (96.3 %) and chemical stability (96.6 %) after soaking in a 2 M NaOH solution for 1560 h at 80 °C. In addition, the peak power density (PPD) of a single cell with QTPNPC4 reaches 927 mW cm−2 (80 °C), and the membrane has good in-situ durability (0.689 mV h−1).

Self-assembly of amphiphilic asymmetric comb-like copolymers with responsive rigid side chains.

Amphiphilic asymmetric comb-like copolymers (AACCs) exhibit distinct self-assembly behaviours due to their unique architecture. However, the synthetic difficulties of well-defined AACCs have prohibited a systematic understanding of the architecture-morphology relationship. In this work, we conducted dissipative particle dynamics simulations to investigate the self-assembly behaviours of AACCs with responsive rigid side chains in selective solvents. The effects of side chain length, number of branches, and spacers on the morphology of aggregates were investigated by mapping out morphology diagrams. Besides, the numbers and surface areas of aggregates clearly depicted the morphological transitions during the self-assembly process. Moreover, the rod-to-coil conformation transitions were simulated to explore the stimuli-responsive behaviour of the AACCs with responsive rigid side chains by adjusting the bond angle parameter of the rigid chains. The results indicated that without the support of the rigid chains, the assembly structure collapsed, leading to the tube-to-channelized micelles and one-compartment-to-multicompartment vesicle morphology transformations. The simulation results are consistent with earlier experimental results, which can provide theoretical guidance for assembly toward desired nanostructures.

Cyclic vs Linear Bottlebrush Polymers in Solution: Side-Chain Length Effect

Bottlebrush polymers (BBPs) of different architecture are of considerable interest for a broad range of applications, including nanomedicine, electronics, and self-healing materials. Using atomistic molecular dynamics simulations, we investigate and compare the structural and hydration properties of cyclic and linear poly(vinyl alcohol)-graft-poly(ethylene oxide) (PVA-g-PEONsc) BBPs in aqueous solution as functions of PEO side-chain length, Nsc. We find that overall cyclic BBPs are smaller than the corresponding linear BBPs and their shape changes from donutlike to disklike to starlike with increasing side-chain length, while linear BBPs vary in shape from an expanded coil to a rod/cylinder. The radius of gyration of cyclic BBPs increases with an increase of the side-chain length at a somewhat slower rate than the linear BBPs but follows the same scaling Rg ∼ Nsc0.58 in the limit of long side chains. For short grafts, we determine that the persistence length, lp, for both cyclic and linear BBPs increases in a similar manner following an lp ∼ Nsc0.54 dependence. In the long side-chain limit, the persistence length (lp) of cyclic BBP saturates, while for linear BBPs lp strongly increases following the expected scaling relation lp ∼ Nsc15/8. We propose a scaling model that shows that the fraction of side-chains located inside the cyclic BBPs depends on the radius of the backbone ring and significantly decreases with an increase of graft length. For both cyclic and linear BBPs, the hydrogen bonding between PEO side chains and water is somewhat reduced near the backbone, where local chain stretching is observed, while reaching full hydration on the periphery. Overall, the hydration shell within 1 nm of the cyclic BBP backbone is found to be more dynamically stable compared to linear BBPs.

Effects of Side-Chain Length and Functionality on Polar Poly(dioxythiophene)s for Saline-Based Organic Electrochemical Transistors.

Understanding the impact of side chains on the aqueous redox properties of conjugated polymers is crucial to unlocking their potential in bioelectrochemical devices, such as organic electrochemical transistors (OECTs). Here, we report a series of polar propylenedioxythiophene-based copolymers functionalized with glyme side chains of varying lengths as well as an analogue with short hydroxyl side chains. We show that long polar side chains are not required for achieving high volumetric capacitance (C*), as short hydroxy substituents can afford facile doping and high C* in saline-based electrolytes. Furthermore, we demonstrate that varying the length of the polar glyme chains leads to subtle changes in material properties. Increasing the length of glyme side chain is generally associated with an enhancement in OECT performance, doping kinetics, and stability, with the polymer bearing the longest side chains exhibiting the highest performance ([μC*]OECT = 200 ± 8 F cm-1 V-1 s-1). The origin of this performance enhancement is investigated in different device configurations using in situ techniques (e.g., time-resolved spectroelectrochemistry and chronoamperometry). These studies suggest that the performance improvement is not due to significant changes in C* but rather due to variations in the inferred mobility. Through a thorough comparison of two different architectures, we demonstrate that device geometry can obfuscate the benchmarking of OECT active channel materials, likely due to contact resistance effects. By complementing all electrochemical and spectroscopic experiments with in situ measurements performed within a planar OECT device configuration, this work seeks to unambiguously assign material design principles to fine-tune the properties of poly(dioxythiophene)s relevant for application in OECTs.

Morphological Effect of Side Chain Length in Sulfonated Poly(arylene ether sulfone)s Polymer Electrolyte Membranes via Molecular Dynamics Simulation.

With the recognition of the multiple advantages of sulfonated hydrocarbon-based polymers that possess high chemical and mechanical stability with significant low cost, we employed molecular dynamics simulation to explore the morphological effects of side chain length in sulfonated polystyrene grafted poly(arylene ether sulfone)s (SPAES) proton exchange membranes. The calculated diffusion coefficients of hydronium ions (H3O+) are in range of 0.61-1.15 × 10-7 cm2/s, smaller than that of water molecules, due to the electrical attraction between the oppositely charged sulfonate group and H3O+. The investigation into the radial distribution functions suggests that phase segregation in the SPAES membrane is more probable with longer side chains. As the hydration level of the membranes in this study is relatively low (λ = 3), longer side chains correspond to more water molecules in the amorphous cell, which provides better solvent effects for the distribution of sulfonated side chains. The coordination number of water molecules and hydronium ions around the sulfonate group increases from 1.67 to 2.40 and from 2.45 to 5.66, respectively, with the increase in the side chain length. A significant proportion of the hydronium ions appear to be in bridging configurations coordinated by multiple sulfonate groups. The microscopic conformation of the SPAES membrane is basically unaffected by temperature during the evaluated temperature range. Thus, it can be revealed that the side chain length plays a key role in the configuration of the polymer chain and would contribute to the formation of the microphase separation morphology, which profits proton transport in the hydrophilic domains.

Role of side-chain length on gas transport of CO2/CH4 mixtures in polymers with side-chain porosity

Polymers of intrinsic microporosity (PIMs) are traditionally formed from ladder backbones, but recent synthetic advances have allowed for the formation of non-traditional PIMs using a poly(ladder) motif, whereby rigid PIM-like sidechains are appended onto more flexible backbones. The effect of side-chain length on free volume and gas transport properties was recently evaluated for a methoxy-functionalized poly(ladder) (OMe-ROMP). In this study, we elaborate on the role of side-chain length and its influence on mixed-gas performance and plasticization stability for OMe-ROMP. Pure-gas sorption results are also reported, including hysteresis effects from CO2 conditioning. Taken together, this study reveals the role of side-chain length on gas sorption, diffusion, and plasticization for CO2/CH4 separations. We conclude that the length of a rigid side chain in the poly(ladder) motif is a valuable structural parameter to control sorption, diffusion, and stability towards plasticization for gas separation membrane materials.

Effect of Side Chain Length in Polystyrene POM–POMs on Melt Rheology and Solid Mechanical Fatigue

Effect of Side Chain Length in Polystyrene POM–POMs on Melt Rheology and Solid Mechanical Fatigue

The effect of side chain length on the morphology and transport properties of fluorene-based anion exchange membranes

Poly[(fluorene alkylene)- co(biphenyl alkylene)] (PFBA) compounds with quaternary ammonium (QA) groups (PFBA-nC-QAs) that are linked with side chains of various lengths (n = 1∼6 carbon atoms) are designed and synthesized by a superacid catalysis reaction, which has the advantages of low cost, easy synthesis and mild reaction conditions. The correlative properties of PFBA-nC-QAs, including water uptake, thermal stability, morphology, ion conductivity and alkaline stability, are discussed in detail. The side chain length is vital to the morphology and transport performance of PFBA-nC-QAs. As the side chain length increases, the alkaline stability and hydroxide ion conductivity of the prepared membranes improve with decreasing water uptake. Experimental results indicate that the hydroxide conductivity of PFBA-6C-QA is 154 mS cm−1 at 80 °C. Moreover, no degradation of functional groups of PFBA-6C-QA is observed during 30 days of immersion in 2 M NaOH at 80 °C. The peak power density of PFBA-6C-QA is 278 mW cm−2 at 60 °C with a hydrogen/air single fuel cell. By controlling the length of the polymer side chain, the method is simple and effective for building anion exchange membranes with high performance.

Investigation on n-pentylbenzene combustion at various pressures: Insight into effects of side-chain length on alkylbenzene combustion

This work investigated the flow reactor pyrolysis of n-pentylbenzene using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) at 0.04 and 1 atm, and measured the laminar burning velocities (LBVs) of n-pentylbenzene in a high-pressure constant-volume cylindrical combustion vessel at 473 K, 1–10 atm and equivalence ratios (ϕ) of 0.7–1.5. A kinetic model of n-pentylbenzene combustion was developed from our previous models of n-butylbenzene and validated against the present experimental data. The unimolecular decomposition reactions and H-abstraction reactions are the dominant consumption pathways of n-pentylbenzene under pyrolysis conditions. Aromatic intermediates with unsaturated side-chains play crucial roles in indene and naphthalene formation, while phenyl and benzyl are precursors of unfused polycyclic aromatic hydrocarbons (PAHs) which in turn convert to fused tricyclic PAHs. In the laminar flame propagation, small species reactions are crucial under lean conditions, while chain-termination reactions, especially fuel-specific reactions, show important inhibition effects on the laminar flame propagation under rich conditions. Furthermore, the effects of side-chain length on the pyrolysis and laminar flame propagation of alkylbenzenes were also investigated for toluene, ethylbenzene, n-propylbenzene, n-butylbenzene and n-pentylbenzene. It is concluded that alkylbenzene smaller than n-butylbenzene tends to decompose at low temperature as the side-chain length increases, while n-butylbenzene and n-pentylbenzene have very close decomposition temperature regions. For indene and naphthalene formation, decomposition/cyclization reaction sequences of C9 and C10 alkenylbenzenes have rapidly increasing importance in the pyrolysis of large alkylbenzenes. Benzyl is concluded to play an important role in inhibiting laminar flame propagation of alkylbenzenes, which is an important reason for the observations that toluene and ethylbenzene have the lowest and highest LBVs, respectively.

Effect of side chain length on photovoltaic performance of fused-ring electron acceptors

Effect of side chain length on photovoltaic performance of fused-ring electron acceptors

Experimental and COSMO-RS Simulation Studies on the Effects of Polyatomic Anions on Clay Swelling.

Ionic liquids (ILs) can play a vital role in clay swelling inhibition during hydraulic fracturing. Previous studies highlighted the effect of side-chain length attached to the cationic core and different anions possessing almost the same chemical properties on inhibition performance. However, polyatomic anions have the potential to superiorly inhibit swelling compared to monoatomic anions. In this study, three ILs, namely, 1-butyl-3-methylimidazolium chloride (BMIMCl), 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4), and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF6), were utilized to assess the effects of polyatomic anions on clay swelling inhibition. These performances were compared with the performances of a conventional inhibitor, potassium chloride (KCl). X-ray diffraction (XRD) testing was applied to check the mineral components present in the bentonite clay sample studied in this research. Clay swelling inhibition performance and rheological properties of these ILs were evaluated by the bentonite plate soaking test, linear swelling test, and rheological test. The swelling inhibition mechanisms were investigated through ζ-potential measurement, Fourier transform infrared (FT-IR) spectroscopy, and contact angle measurement. Moreover, COSMO-RS computer simulation was conducted to explain the inhibition mechanisms theoretically. The results demonstrated that BMIMPF6 showed superior inhibition performance and reduced the swelling by 21.55%, while only 9.26% reduction was attained by potassium chloride (KCl). The adsorption ability on the bentonite surface through electrostatic attraction, higher activity coefficient, and less electronegativity of PF6– anion played a vital role in attaining such superior inhibition performance by BMIMPF6.

Molecular dynamics study on water and hydroxide transfer mechanisms in PSU-g-alkyl-TMA membranes at low hydration: Effect of side chain length

Molecular dynamics simulations with anion exchange membranes (alkyl trimethyl ammonium grafted onto polysulfone) are performed to investigate the influence of the spacer length on the transport properties, on the molecular exchange mechanisms between the functional group and the aqueous phase and on the hydrogen bond network. This is especially insightful that in this work the hydration number is small. In this condition the aqueous phase must be thought as an assembly of small clusters. The results show an unexpected dependence of the water and hydroxide (OH) diffusivity on the temperature and the water uptake. The distribution of the cluster size bonded to OH explain partially the OH diffusivity. “Hopping” and “caging” motions are observed with the self-part of the Van Hove functions even at high temperature. The characteristic time of the survival probability correlation function around the functional groups is a decreasing function of the alkyl length.

Effects of side chain length of 10-methyl-aplog-1, a simplified analog of debromoaplysiatoxin, on PKC binding, anti-proliferative, and pro-inflammatory activities.

10-Methyl-aplog-1 (1), a simplified analog of debromoaplysiatoxin, exhibits a high binding affinity for protein kinase C (PKC) isozymes and potent antiproliferative activity against several cancer cells with few adverse effects. A recent study has suggested that its phenol group in the side chain is involved in hydrogen bonding and CH/π interactions with the binding cleft-forming loops in the PKCδ-C1B domain. To clarify the effects of the side chain length on these interactions, four analogs of 1 with various lengths of side chains (2-5) were prepared. The maximal PKC binding affinity and antiproliferative activity were observed in 1. Remarkably, the introduction of a bromine atom into the phenol group of 2 increased not only these activities but also proinflammatory activity. These results indicated that 1 has the optimal side chain length as an anticancer seed. This conclusion was supported by docking simulations of 1-5 to the PKCδ-C1B domain.

Design and synthesis of novel amphipathic ionic liquids for biodiesel production from soapberry oil

Biodiesel produced from non-edible oils has received intensive attention in recent years. Herein, a series of novel amphipathic ionic liquids (ILs) based on the 4-dimethylaminopyridine (DMAP) were prepared for the transesterification of soapberry oil and methanol. The structures of the prepared ILs were systematically characterized by both Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR, 1H NMR and 13C NMR). In addition, the effects of side-chain length of cation and the number of active site (H+) of ILs on the biodiesel yield were investigated, and the results suggested that 1-dodecyl-(4-dimethylammonium)-pyridinium bisulfate ([C12-DMAPH][HSO4]2) exhibited the highest catalytic efficiency. Meanwhile, [C12-DMAPH][HSO4]2 was proven to be amphipathic, and the corresponding catalytic mechanism was proposed. Under the catalysis of [C12-DMAPH][HSO4]2, the optimum operating conditions of transesterification of soapberry oil and methanol were explored via the combination of single factor experiment and response surface methodology, obtaining the high biodiesel yield of (98.02 ± 0.36)% under the optimum operating conditions. Importantly, [C12-DMAPH][HSO4]2 exhibited high stability in the transesterification of soapberry oil and methanol in five consecutive runs. Furthermore, the catalytic activities of [C12-DMAPH][HSO4]2 towards other transesterification of non-edible oils and lower alcohols were also investigated, which indicated a general applicability of the prepared IL.

Influence of Calcium Binding on Conformations and Motions of Anionic Polyamino Acids. Effect of Side Chain Length.

Investigation of the effect of CaCl2 salt on conformations of two anionic poly(amino acids) with different side chain lengths, poly-(α-l glutamic acid) (PGA) and poly-(α-l aspartic acid) (PASA), was performed by atomistic molecular dynamics (MD) simulations. The simulations were performed using both unbiased MD and the Hamiltonian replica exchange (HRE) method. The results show that at low CaCl2 concentration adsorption of Ca2+ ions lead to a significant chain size reduction for both PGA and PASA. With the increase in concentration, the chains sizes partially recover due to electrostatic repulsion between the adsorbed Ca2+ ions. Here, the side chain length becomes important. Due to the longer side chain and its ability to distance the charged groups with adsorbed ions from both each other and the backbone, PGA remains longer in the collapsed state as the CaCl2 concentration is increased. The analysis of the distribution of the mineral ions suggests that both poly(amino acids) should induce the formation of mineral with the same structure of the crystal cell.

Synthesis of spin labeled ethylene glycol based polymers and study of their segmental motion

Understanding segmental dynamics of polymer chains is important to decipher the microscopic behavior in order to modulate the bulk properties of polymers. Study of electron spin resonance (ESR) spectroscopy of polymer chain segments is useful to understand internal dynamics of polymer chains in solution. In this paper, poly(oligoethylene glycol methacrylate-co-2,2,6,6-tetramethyl piperidin-4-yl methacrylate)s, OEG-TMPMs, were synthesized. The synthesized OEG-TMPMs were characterized by nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric (TG) techniques. The TMPM moiety in OEG-TMPMs was oxidized to 2,2,6,6-tetramethyl-1-piperinidyloxy-4-yl methacrylate (TMP) to generate nitroxide radicals. These nitroxide radical-containing OEG-TMPs were analyzed with Fourier transform-infrared (FT-IR) spectroscopy, cyclic voltammetry (CV) and ESR spectroscopy. The effect of side chain length on the segmental mobility of OEG-TMPs was studied. The results showed that the longer pendent chains as in OEG-TMP-4 imparted higher flexibility to the backbone of the polymer and increased rotational freedom of nitroxide radicals as compared to restricted mobility in the case of shorter polymer side chains.

Effect of side chain length change of polycarboxylate-ether based high range water reducing admixture on properties of self-compacting concrete

In this study, the effect of side chain length, molecular weights changes and adsorption amount of polycarboxylate ether-based high range water reducing admixtures having constant main chain length, free non-ionic amount and anionic/non-ionic ratio on fresh properties, early and advanced age compressive strength, water absorption capacity and ultrasonic pulse velocity value of self-compacting concretes (SCC) were investigated. FTIR (Fourier transform infrared) and GPC (Gel Permeation Chromatography) analyzes were carried out to characterize admixtures. According to the test results, all SCC mixtures produced within the scope of the study provided EFNARC criteria. If the admixture side chain length is higher or shorter than a certain value, the admixture requirement is increased for providing the desired target slump-flow value in SCC mixtures. This negative effect is thought to be due to the weakness of the steric hindrance effect for admixture with short side chain, the low adsorption amount and interlacing risk of side chains for admixture with the long side chain. On the other hand, the increase in the side chain length of the admixtures had a positive effect on the time-dependent fresh state performance of the mixtures. This positive effect is thought to be due to the low adsorption amount of the admixture, the increase in the side chain length and the increase of the non-adsorbed free polymer content in the mixture. While side chain length change of the water reducing admixture affected the 1 and 2-day compressive strength values of SCC mixtures, the 3, 7 and 28-day compressive strengths and the 28-day water absorption, ultrasound and dynamic elasticity modulus values did not significantly affect.

Effect of the Side-Chain Length in Perfluorinated Sulfonic and Phosphoric Acid-Based Membranes on Nanophase Segregation and Transport: A Molecular Dynamics Simulation Approach.

The effect of side-chain length on the nanophase-segregated structure and transport in perfluorinated sulfonic acid (PFSA)-based and perfluorinated phosphoric acid (PFPA)-based membranes is investigated at 20 and 5 wt % water content conditions using a molecular dynamics simulation method. It is found using the pair correlation analysis that the longer side chain leads to more developed local water structures in the water phase at 20 wt % water content, observable in both membrane chemistries albeit more distinct in PFPA-based membranes. It is also confirmed from the structure factor analysis that large-scale nanophase segregation is enhanced with increasing side-chain length for PFPA membranes, whereas no significant change is observed at these scales for PFSA membranes. Next, it is revealed that the proton transport is increased by 0.004 S/cm in PFSA-based membranes with increasing side-chain length due to the enhanced vehicular and hopping mechanisms, whereas the proton transport in PFPA-based membranes is decreased by 0.002 S/cm despite improved nanophase segregation. As confirmed by the pair correlation function analysis, the diminished proton transport in PFPA-based membranes is attributed to the molecular association of phosphate groups with hydronium ions via hydrogen bond in the longer side-chain case, which is namely a hydronium-mediated bridge configuration. Such bridge configurations and correspondingly similar trends in proton transport are also observed at 5 wt % water content condition to a lesser extent. Our simulation study demonstrates that the proton transport is affected by the hydrogen-bonding network as well as by the nanophase segregation.

Effect of side-chain length on solute encapsulation by amphiphilic heterografted brush copolymers.

Anisotropic nanomaterials are non-spherical structures that possess unique shape-dependent physicochemical properties and functionalities. Inspired by the abundance of filamentous entities in nature, cylindrical nanostructures have gained significant attention due to their unique performance. Herein, we discuss the effect of side-chain length on the encapsulation properties of amphiphilic heterografted bottlebrushes. We observed that by grafting a long hydrophilic block to the double-brush, we were able to restrict solute-induced conformational changes, thus producing drug-loaded anisotropic carriers. Unimolecular encapsulation in brushes was solute-dependent as shown here for probucol and rose bengal lactone. Stabilization with an amphiphilic diblock copolymer-consisting of the same type of blocks as those comprising the heterografted brush-served to explain the solute-dependent behavior observed for brushes, suggesting that solutes with a higher propensity to nucleation could be more effectively stabilized by the anisotropic carrier in a unimolecular worm-like construct.

A side-chain engineering strategy for constructing fluorescent dyes with direct and ultrafast self-delivery to living cells.

Organic fluorescent dyes with excellent self-delivery to living cells are always difficult to find due to the limitation of the plasma membrane having rigorous selectivity. Herein, in order to improve the permeability of dyes, we utilize a side-chain engineering strategy (SCES): adjusting the side-chain length of dyes to fine-tune the adsorption and desorption processes on the membrane–aqueous phase interfaces of the outer and inner leaflets of the plasma membrane. For this, a family of fluorescent derivatives (SPs) was prepared by functionalizing a styryl-pyridinium fluorophore with alkyl side-chains containing a different carbon number from 1 to 22. Systematic experimental investigations and simulated calculations demonstrate that the self-delivery rate of SPs with a suitable length side-chain is about 22-fold higher in SiHa cells and 76-fold higher in mesenchymal stem cells than that of unmodified SP-1, enabling cell-imaging at an ultralow loading concentration of 1 nM and deep penetration in turbid tissue and in vivo. Moreover, the SCES can even endow a membrane-impermeable fluorescent scaffold with good permeability. Further, quantitative research on the relationship between Clog P and cell permeability shows that when Clog P is in the range of 1.3–2.5, dyes possess optimal permeability. Therefore, this work not only systematically reports the effect of side-chain length on dye delivery for the first time, but also provides some ideal fluorescent probes. At the same time, it gives a suitable Clog P range for efficient cellular delivery, which can serve as a guide for designing cell-permeant dyes. In a word, all the results reveal that the SCES is an effective strategy to dramatically improve dye permeability.