Effect Of Chain Length Research Articles

High performance mixed-dimensional assembled MXene composite membranes for molecular sieving

Two-dimensional (2D) separation membranes have proved their superiorities in addressing global water scarcity and recycling resources. However, current 2D membranes usually suffer from swelling and irregular stacking issues, which result in poor separation performance. Herein, we developed novel mix-dimensional assembled MXene composite membranes with high permeability and selectivity by intercalating 1D carboxylated cellulose nanofibers (CNFs) into 2D lamellar MXene nanosheets. The effects of chain length of CNFs and MXene/CNFs mass ratios on the morphologies, physicochemical properties, and separation performances of composite membranes were systematically investigated. The optimized MXC-3-L membrane exhibited superior rejection to Congo red (CR, >99%) and remarkable separation efficiency of dye/salt. The separation factors for the CR/NaCl and CR/Na2SO4 mixtures were 512.0 and 517.2, respectively. Moreover, the MXC-3-L membrane showed distinct rejections to perfluoroalkyl substances (PFAS) (>95%) with a nearly 8-fold increase of permeance in comparison with the commercial polyamide membrane. The 2D X-ray diffraction analysis verified that the intercalation of 1D CNFs into 2D MXene nanosheets via strong hydrogen bonding can regulate the nanochannel into more stable and regularly stacking lamellar structures, which plays a key role in high permeance and excellent molecular separation efficiency. In addition, 1D CNFs play an essential role as “threading” and “stitching”, shielding the defects between adjacent MXene nanosheets and improving the separation efficiencies. Our work provides new insights into design of defect-free and highly selective 2D materials-based membranes for enhanced wastewater treatment and molecular sieving.

Exploring alkyl-diamine chain length effects on electrochemical behavior of AuNPs fabricated electrodes: Influence of linkers on the sensitive detection of hydrazine

In this electrochemical exploration, we scrutinized the influence of alkyl-diamine (AD) chain length as crucial linkers between glassy carbon electrodes (GCE) and citrate-capped gold nanoparticles (Cit-AuNPs), focusing on their conductive behavior and sensing proficiency, particularly in hydrazine detection. Meticulous examination of self-assembled monolayers (SAMs) formed by three distinct ADs, namely 1,6-hexanediamine (HDA), 1,8-octanediamine (ODA) and 1,10-decanediamine (DDA) unfolded over GC surfaces revealed a precise adherence to Langmuir adsorption kinetics during the SAM formation process. Utilizing cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the electrochemical activity of the [Ru(NH₃)₆]³⁺/²⁺ redox pair at electrodes modified with ADs was investigated. The proposed mechanism involves a Michael-like nucleophilic addition process at the GC surface/diamine solution interface during the SAM formation. Analysis across various techniques underscored the compact nature of the DDA-formed SAM in comparison to HDA and ODA. Exploiting the free amine functional groups on the SAMs, the as-synthesized Cit-AuNPs were attached on the electrode surface and investigated comprehensively through CV, EIS, attenuated total reflection Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. Remarkably, Cit-AuNPs attached DDA-SAM/GC electrode offered superior electro active surface area, establishing an advanced electrochemical platform for carcinogenic hydrazine determination. The DDA/Cit-AuNPs electrode demonstrated a linear determination range of 0.003–1 mM, limits of detection at 11 nM, and sensitivity of 1080 µA mM−1 cm−2. This study gives a complete picture of how AD chain lengths, SAM formation, Cit-AuNPs attachment, and electrocatalytic performance work together to make an advanced electrochemical sensing scaffold for environmental pollutants determination.

Elucidating adsorption mechanisms of benzalkonium chlorides (BACs) on polypropylene and polyethylene terephthalate microplastics (MPs): Effects of BACs alkyl chain length and MPs characteristics

Since the onset of the COVID-19 pandemic, there has been an increase in the use of disposable plastics and disinfectants. This study systematically investigated the adsorption behavior and mechanisms of benzalkonium chlorides (BACs), commonly used disinfectants, on polypropylene (PP) and polyethylene terephthalate (PET) microplastics (MPs), considering various factors, such as characteristics of MPs, alkyl chain length of BACs, and environmental conditions. Our results demonstrated a higher adsorption capacity for PP-MPs with relatively hydrophobic properties compared to PET-MPs, where longer alkyl chains in BACs (i.e., higher octanol-water partition coefficients, Kow) significantly enhanced adsorption through hydrophobic interactions. The inverse relationship between particle size of MPs and adsorption was evident. While changes in pH minimally affected adsorption on PP-MPs, adsorption on PET-MPs increased with rising pH, highlighting the influence of pH on electrostatic interactions. Moreover, MP aging with UV/H2O2 amplified BAC adsorption on PP-MPs due to surface oxidation and fragmentation, whereas the properties of PET-MPs remained unaltered, resulting in unchanged adsorption capacities. Spectroscopy studies and density functional theory (DFT) calculations confirmed hydrophobic and electrostatic interactions as the primary adsorption mechanisms. These findings improve our understanding of MPs and BACs behavior in the environment, providing insights for environmental risk assessments related to combined pollution.

Wettability-modulated behavior of polymers under varying degrees of nano-confinement

Extreme confinement in nanochannels results in unconventional equilibrium and flow behavior of polymers. The underlying flow physics dictating such paradigms remains far from being understood and more so if the confining substrate is composed of two-dimensional materials, such as graphene. In this study, we conducted systematic molecular dynamics simulations to explore the effect of wettability, confinement, and chain length on polymer flow through graphene-like nanochannels. Altering the wetting properties of these membranes that structurally represent graphene results in substantial changes in the behavior of polymers of disparate chain lengths. Longer hydrocarbon chains (n-dodecane) exhibit negligible wettability-dependent structuring in narrower nanochannels compared to shorter chains (n-hexane) culminating in higher average velocities and interfacial slippage of n-dodecane under less wettable conditions. We demonstrate that the wettability compensation comes from chain entanglement attributed to entropic factors. This study reveals a delicate balance between wettability-dependent enthalpy and chain-length-dependent entropy, resulting in a unique nanoscale flow paradigm, thus not only having far-reaching implications in the superior discernment of polymeric flow in sub-micrometer regimes but also potentially revolutionizing various applications in the oil industry, including innovative oil transport, oil extraction, ion transport polymers, and separation membranes.

Short-chain fatty acids of various lengths differentially inhibit Klebsiella pneumoniae and Enterobacteriaceae species.

The gut microbiota is inextricably linked to human health and disease. It can confer colonization resistance against invading pathogens either through niche occupation and nutrient competition or via its secreted metabolites. Short-chain fatty acids (SCFA) are the primary metabolites in the gut as a result of dietary fiber fermentation by the gut microbiota. In this work, we demonstrate that the interaction of single-species gut commensals on solid media is insufficient for pathogen inhibition, but supernatants from monocultures of these commensal bacteria enriched in acetate confer inhibition against anaerobic growth of the enteric pathogen Klebsiella pneumoniae. The three primary SCFAs (acetate, propionate, and butyrate) strongly inhibit the intestinal commensal Escherichia coli Nissle as well as a panel of enteric pathogens besides K. pneumoniae at physiological pH of the cecum and ascending colon. This inhibition was significantly milder on anaerobic gut commensals Bacteroides thetaiotaomicron and Bifidobacterium adolescentis previously demonstrated to be associated with microbiota recovery after antibiotic-induced dysbiosis. We describe a general suppression of bacterial membrane potential by these SCFAs at physiological cecum and ascending colonic pH. Furthermore, the strength of bacterial inhibition increases with increasing alkyl chain length. Overall, the insights gained in this study shed light on the potential therapeutic use of SCFAs for conferring colonization resistance against invading pathogens in a dysbiotic gut.IMPORTANCERising antimicrobial resistance has made treatment of bacterial infections increasingly difficult. According to the World Health Organization, it has become a burgeoning threat to hospital and public health systems worldwide. This threat is largely attributed to the global rise of carbapenem-resistant Enterobacteriaceae in recent years, with common hospital-acquired pathogens growing increasingly resistant to last-line antibiotics. Antibiotics disrupt the homeostatic balance of the gut microbiota, resulting in the loss of colonization resistance against enteric pathogens. This work describes the ability of short-chain fatty acids (SCFAs) produced by gut microbiota to be effective against a wide panel of enteric pathogens without major impact on common gut commensal species. We also demonstrate a previously undescribed link between alkyl chain length and antibacterial effects of SCFAs. SCFAs, thus, hold promise as an alternative therapeutic option leveraging on the antimicrobial activity of these endogenously produced gut metabolites without disrupting gut microbiota homeostasis.

Effect of alkyl chain length of alcohols on the physicochemical properties of their binary mixtures with diethylmethylammonium trifluoroacetate,

Effect of alkyl chain length of alcohols on the physicochemical properties of their binary mixtures with diethylmethylammonium trifluoroacetate,

Pyridine catalyzed acylation of electrospun chitosan membranes by C6-C12 acyl chlorides: Effect of reaction time and chain length

Chitosan nanofiber membranes manufactured via electrospinning are attractive for drug delivery applications due to their increased surface area. The as-spun fibers contain trifluoroacetate (TFA)-salts that cause swelling and loss of nanofiber structure in physiological solutions and are cytotoxic. Here, a post-electrospinning treatment has been reported using fatty acyl chlorides and pyridine to O-acylate the membranes with different acyl chain-length (C6, C8, C10, and C12). The O-acylation reactions were carried out with acyl chlorides in a basic environment for 2 hr, 3 hr, 4 hr and, 5 hr. The effects of the acyl chain length and the reaction time were assessed using various physio-chemical characterization techniques including FTIR, NMR, Contact Angle, XPS, and SEM. The acylated nanofibers displayed hydrophobic properties and allowed the removal of the cytotoxic TFA salts without compromising the nanofibrous structure. The fiber diameter increased with the increasing length of the substituted acyl chain. The degree of substitution of the acyl chains did not change significantly when reacted for a longer period indicating the completion of the reaction within 2 hr. This could allow the faster modification of the membranes for potential application in the delivery of hydrophobic drugs.

Computational insight into the effect of alkyl chain length in tetraalkylammonium-based deep eutectic solvents

The effect of the increase in the alkyl chain length of cation on the properties of deep eutectic solvents based on ethylene glycol has been investigated employing classical molecular dynamics simulations. The change in the structural and dynamic properties in both the bulk and liquid–vapor interface is explored through various analyses. The interaction between the anion and the ethylene glycol increases with an increase in the alkyl chain length of the cation, as observed in the increase of the lifetime of the hydrogen bond formed between the two. The terminal carbon atoms are found to be closer to each other when the cation changes from tetraethylammonium to tetrabutylammonium. The cations are located closer to the interface, and the association of the alkyl chains becomes more significant with increased alkyl chain length, decreasing the surface tension values.

Effect of ionic liquids on structure and electromechanical properties of plasticized polyvinyl chloride (PVC) gels

Polyvinyl chloride (PVC) gels, as electroactive polymers, have various applications in the fields of soft actuators and sensors. The relationship between the structure and electromechanical properties of PVC gels, however, has not been fully understood so far. In this work, the effect of different alkyl chain length of 1-allyl- imidazolium cations of tetrafluoroborate (BF4)-based ionic liquid (IL) on structure, mechanical and dielectric properties, bending actuation, sensing and electroadhesion properties of plasticized polyvinyl chloride/dibutyl adipate (PVC/DBA) gel were investigated. The interaction between DBA and ILs in PVC/DBA/IL gels leads to the disruption of interactions between inter-DBA molecules and subsequent formation of DBA-rich phases with DBA/IL complexes. The number of DBA-rich phases in PVC/DBA/IL gels increases as the alkyl chain length of the cation in IL increases, due to an enhanced interaction between DBA and ILs with an increase in the alkyl chain length of the cation in IL. The Young's modulus of the PVC/DBA gel was slightly reduced, while the dielectric constant significantly increased when IL was added. Additionally, the bending actuation properties and capacitance pressure sensing sensitivity of the PVC/DBA/IL gel increased with an increase in the alkyl chain length of the cation of IL. However, there was an opposite trend observed for electroadhesion peel strength. Among the studied PVC/DBA/IL gels, the bending displacement, pressure sensing sensitivity, and electroadhesion peel strength of PVC/DBA/IL gel with 3.2 wt% of 1-allyl-3-butylimidazolium tetrafluoroborate ([ABIM]BF4) increased by 2.6 times, 7.5 times, and 1.7 times compared to PVC/DBA gel, respectively. These results provide new insights into understanding the relationship between structure and electromechanical properties of PVC gels for their application in actuation, sensing, and electroadhesion integrated soft grippers.

Impact of the Hydrocarbon Chain Length of Biodegradable Ester-Bonded Cationic Gemini Surfactants on Self-Assembly, In Vitro Gene Transfection, Cytotoxicity, and Antimicrobial Activity.

Gemini surfactants, due to their unique structural features and enhanced properties compared to conventional surfactants, are becoming more popular in the domain of colloid and interface science, drug delivery, and gene delivery science. This distinct class of surfactants forms a wide range of self-assembled aggregates depending on their chemical structure and environmental conditions. The present work aims to develop Gemini with three distinct chain lengths linked through the ester group and quaternary nitrogen head groups that can bind DNA molecules and ultimately serve as vectors for DNA transfection. Thus, we synthesized three distinct cationic Gemini with 12, 14, and 16 carbons in their tails and studied the effect of the hydrocarbon chain length on their physicochemical properties and biological applications. The self-assembly of these Geminis in aqueous solution was investigated by a number of techniques, including surface tension, electrical conductivity, fluorescence probe, calorimetry, dynamic light scattering, and atomic force microscopy. All three Gemini were extremely surface active and self-assembled above a very low critical micelle concentration. Calorimetric studies suggested the formation of thermodynamically favorable aggregates in an aqueous medium. Chain length dependence was observed in the size as well as the morphology of the aggregates. These Gemini ions were found to bind DNA strongly, as indicated by the high binding constant values. In vitro gene transfection studies using the RAW 264.7 cell line suggested that all three cationic Gemini had transfection efficiencies comparable to that of commercial standard turbofectamine. MTT assay was also performed for concentration selection while using these Gemini as transfection vectors. Overall, it was observed that Gemini had very little cytotoxicity within the investigated concentration range, highlighting the significance of the ester link within the structure. When compared with known antimicrobials such as kanamycin and ampicillin, all three Gemini furnished excellent antimicrobial activity in both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) microorganisms.

Structure-dynamics correlations in composite PF127-PEG-based hydrogels; cohesive/hydrophobic interactions determine phase and rheology and identify the role of micelle concentration in controlling 3D extrusion printability

A library of composite polymer networks (CPNs) were formed by combining Pluronic F127, as the primary gelator, with a range of di-acrylate functionalised PEG polymers, which tune the rheological properties and provide UV crosslinkability. A coarse-grained sol–gel room temperature phase diagram was constructed for the CPN library, which identifies PEG-dependent disruption of micelles as leading to liquefication. Small angle X-ray scattering and rheological measurements provide detailed insight into; (i) micelle-micelle ordering; (ii) micelle-micelle disruption, and; (iii) acrylate-micelle disruption; with contributions that depend on composition, including weak PEG chain length and end group effects. The influence of composition on 3D extrusion printability through modulation of the cohesive/hydrophobic interactions was assessed. It was found that only micelle content provides consistent changes in printing fidelity, controlled largely by printing conditions (pressure and feed rate). Finally, the hydrogels were shown to be UV photo-crosslinkable, which further improves fidelity and structural integrity, and usefully reduces the mesh size. Our results provide a guide for design of 3D-printable CPN inks for future biomedical applications.

Synthesis of Biobased Furan Polyamides with Excellent Mechanical Properties: Effect of Diamine Chain Length

Synthesis of Biobased Furan Polyamides with Excellent Mechanical Properties: Effect of Diamine Chain Length

Effect of Chain Length on Swelling Transitions of Brodie Graphite Oxide in Liquid 1‐Alcohols (Adv. Mater. Interfaces 1/2024)

Effect of Chain Length on Swelling Transitions of Brodie Graphite Oxide in Liquid 1‐Alcohols (Adv. Mater. Interfaces 1/2024)

Tunable mechanochromic luminescence of benzofuran-fused pyrazine: effects of alkyl chain length and branching pattern

Tuning the alkyl chains of bisbenzofuropyrazines allowed control over the on/off switching of mechanochromic luminescence and self-recovery rates.

Effect of chain length, electrolyte composition and aerosolization on the removal of per- and polyfluoroalkyl substances during electrochemical oxidation

We utilized a BDD anode in a two-electrode system to investigate the degradation of a suite of PFASs in aqueous matrices.

Effects of chain lengths and backbone chirality on the bone-targeting ability of poly(glutamic acid)s.

Anionic synthetic polypeptides are promising candidates as standalone bone-targeting drug carriers. Nevertheless, the structure-property relationship of the bone-targeting ability of polypeptides remains largely unexplored. Herein we report the optimization of the in vitro and in vivo bone-targeting ability of poly(glutamic acid)s (PGAs) by altering their chain lengths and backbone chirality. PGA 100-mers exhibited higher hydroxyapatite affinity in vitro, but their rapid macrophage clearance limited their targeting ability. Shorter PGA was therefore favored in terms of in vivo bone targeting. Meanwhile, the backbone chirality showed less significant impact on the in vitro and in vivo targeting behavior. This study highlights the modulation of structural parameters on the bone-targeting performance of anionic polypeptides, shedding light on the future design of polypeptide-based carriers.

Tailoring the molecular size of alkylamine modifiers for fabricating efficient and stable inverted CsPbI3 perovskite solar cells

Three alkylamine modifiers with different molecular sizes were incorporated to post-treat CsPbI3 films to systematically investigate the effect of alkyl chain length on device performance.

Azaylide-based gemini amphiphiles displaying unique self-assembling behavior via an even-odd effect of alkyl linker chain length.

Herein, we report a straightforward synthesis of azaylide-based gemini amphiphiles using bis(diphenylphosphino)alkanes via the Staudinger reaction. The prepared gemini amphiphiles exhibited an even-odd effect in their self-assembly behavior depending on the length of the alkyl linkers. Furthermore, the assembled micelles had high host capability toward hydrophobic guests in water.

Effect of graphene nanoplatelets relative size and polyethylene chain length on the enhancement of thermal conductivity of their composite

Effect of graphene nanoplatelets relative size and polyethylene chain length on the enhancement of thermal conductivity of their composite

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.