Chromophore amphiphile-polyelectrolyte hybrid hydrogels for photocatalytic hydrogen production
Abstract not provided
Sai, Hiroaki↗
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Results for “Amphiphile”
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Dynamics of amphiphilic PEG–PDMS–PEG triblock copolymer assemblies
Here, the size and stability of micelles and vesicles determine the uptake capacity of guest molecules, thereby influencing potential applications in drug/gene delivery, bioreactors, and templates for nanoparticle synthesis. Polyethylene glycol (PEG) and polydimethylsiloxane (PDMS) are commonly used in these applications. We discovered that PEG-PDMS-PEG triblock copolymers can assemble into micelles and vesicles, making them valuable for dynamic studies to derive the bending elasticity, $κ_η$, which governs the stability these objects. We analyzed the structure using cryogenic transmission electron microscopy and small-angle neutron scattering. We investigated the dynamics through dynamic light scattering and neutron spin echo spectroscopy. By varying the number of repeating units in the hydrophilic block, we created micellar (PEG 28 -PDMS 15 -PEG 28 ) and vesicular systems (PEG 14 -PDMS 15 -PEG 14 ). For the vesicle, membrane rigidity was determined from experiments to be $κ_η$ =(16 ± 2) $k_BT$, where $k_BT$ is the thermal energy ($k_B$ Boltzmann’s constant and T is the temperature). According to Zilman and Granek's concept, membrane rigidity reflects height-height fluctuations within the membrane layer. Compared to polymers at the oil-water interface of a microemulsion, the membrane rigidity in polymersomes is over an order of magnitude higher, indicating significantly enhanced stability. This value closely aligns with that of liposomes, suggesting similar stability between polymersomes and liposomes.
Gupta, Sudipta [Louisiana State Univ., Baton Rouge↗
Biomimetic antibiotics based on amphiphilic peptoids and their self-assembly
Bacterial infections pose a serious threat to mankind. Inspired by antimicrobial peptides (AMPs) and their membrane-disruption mechanism, there is immense interest in the design and development of synthetic mimetics for antibacterial applications, overcoming the intrinsic drawbacks of AMPs (e.g. susceptibility to proteolytic degradation). Herein, by exploiting the self-assembly and pore-forming capabilities of sequence-defined peptoids, we discovered a new family of low molecular weight peptoid antibiotics that exhibited excellent broad-spectrum activity and high selectivity toward a panel of clinically significant Gram-positive and Gram-negative bacterial strains. Tuning peptoid sidechain chemistry and structure enabled us to tune the efficacy of antimicrobial activity and study the structure–activity relationship. These findings offer a novel approach to identify new families of antimicrobial peptoids and correlate the pore-forming capability of self-assembling peptoids with their antimicrobial activities. Because peptoids are highly robust and biocompatible, we exhibit these peptoid-based antibiotics will be significant for combating the emerging drug resistance.
59 BASIC BIOLOGICAL SCIENCES↗
Head on Comparison of Self- and Nano-Assemblies of Gamma Peptide Nucleic Acid Amphiphiles
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99 GENERAL AND MISCELLANEOUS↗
Self-assembly of gold nanoparticles grafted with amphiphilic supramolecular block copolymers
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99 GENERAL AND MISCELLANEOUS↗
Acid-Base Equilibrium and Dielectric Environment Regulate Charge in Supramolecular Nanofibers
Peptide amphiphiles are a class of molecules that can self-assemble into a variety of supramolecular structures, including high-aspect-ratio nanofibers. It is challenging to model and predict the charges in these supramolecular nanofibers because the ionization state of the peptides are not fixed but liable to change due to the acid-base equilibrium that is coupled to the structural organization of the peptide amphiphile molecules. Here, we have developed a theoretical model to describe and predict the amount of charge found on self-assembled peptide amphiphiles as a function of pH and ion concentration. In particular, we computed the amount of charge of peptide amphiphiles nanofibers with the sequence C 16 − V 2 A 2 E 2 . In our theoretical formulation, we consider charge regulation of the carboxylic acid groups, which involves the acid-base chemical equilibrium of the glutamic acid residues and the possibility of ion condensation. The charge regulation is coupled with the local dielectric environment by allowing for a varying dielectric constant that also includes a position-dependent electrostatic solvation energy for the charged species. We find that the charges on the glutamic acid residues of the peptide amphiphile nanofiber are much lower than the same functional group in aqueous solution. There is a strong coupling between the charging via the acid-base equilibrium and the local dielectric environment. Our model predicts a much lower degree of deprotonation for a position-dependent relative dielectric constant compared to a constant dielectric background. Furthermore, the shape and size of the electrostatic potential as well as the counterion distribution are quantitatively and qualitatively different. These results indicate that an accurate model of peptide amphiphile self-assembly must take into account charge regulation of acidic groups through acid–base equilibria and ion condensation, as well as coupling to the local dielectric environment.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Molecular-scale origins of solution nanostructure and excess thermodynamic properties in a water/amphiphile mixture
The molecular and nanoscale origins of nonideality in excess thermodynamic properties are essential to understanding cosolvent mixtures, yet they remain challenging to determine. Here, we consider a binary mixture of water and an amphiphile, N,N,N',N'-tetramethylmalonamide (TMMA), which is characterized by strong hydrogen bonding between the two components and no hydrogen bonding between amphiphiles. Using molecular dynamics simulation, validated with excess volume measurements and X-ray scattering, we identify three distinct solution regimes across the composition range of the binary mixture and find that the transition between two of these regimes, marked by the water percolation threshold, is closely correlated with minima in the excess volume and excess enthalpy. Structural analysis of the simulations reveals an interplay between local interactions and solution nanostructure, determined by the relative strength of the water–water and water–amphiphile hydrogen bonding interactions. By comparison with other amphiphiles, such as linear alcohols, the relative strength of like and unlike interactions between water and amphiphile affects the relationship between thermodynamics and structural regimes. This provides insight into how molecular forces of mutual solvation interact across length scales and how they manifest in excess thermodynamic properties.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Implementation of a self-consistent slab model of bilayer structure in the SasView suite
Slab models are simple and useful structural descriptions which have long been used to describe lyotropic lamellar phases, such as lipid bilayers. Typically, slab models assume a midline symmetry and break a bilayer structure into three pieces, a central solvent-free core and two symmetric outer layers composed of the soluble portion of the amphiphile and associated solvent. This breakdown matches reasonably well to the distribution of neutron scattering length density and therefore is a convenient and common approach for the treatment of small-angle scattering data. Here, an implementation of this model within the SasView software suite is reported. The implementation is intended to provide physical consistency through the area per amphiphile molecule and number of solvent molecules included within the solvent-exposed outer layer. The proper use of this model requires knowledge of (or good estimates for) the amphiphile and solvent molecule volume and atomic composition, ultimately providing a self-consistent data treatment with only two free parameters: the lateral area per amphiphile molecule and the number of solvent molecules included in the outer region per amphiphile molecule. Here, the use of this code is demonstrated in the fitting of standard lipid bilayer data sets, obtaining structural parameters consistent with prior literature and illustrating the typical and ideal cases of fitting for neutron scattering data obtained using single or multiple contrast conditions. While demonstrated here for lipid bilayers, this model is intended for general application to block copolymers, surfactants, and other lyotropic lamellar phase structures for which a slab model is able to reasonably estimate the neutron scattering length density/electron-density profile of inner and outer layers of the lamellae.
36 MATERIALS SCIENCE↗
Protein-Mimetic Self-Assembly with Synthetic Macromolecules
Protein-mimetic amphiphiles have significant promise as a platform to access the complex functions of natural biological materials and incorporate the tunability and environmental resilience of synthetic materials. The fields of polymer chemistry and chemical biology have concurrently approached the development of biomimetic amphiphiles with materials ranging from random amphiphilic copolymers to peptide–lipid conjugates. In this Perspective, we incorporate strategies from diverse chemical arenas for controlling assembled morphologies and dynamics of protein-mimetic synthetic macromolecules. An overview of significant advances in peptide amphiphiles and single-chain polymer nanoparticles provides the foundation for comparing recent advances in the implementation of multiple intermolecular interactions and computational strategies to fine-tune the assembled structures. We aim to bridge these fields, combining insights from multiple disciplines to inspire new approaches for the development of protein-mimetic materials, as these assemblies have far-reaching applications including in the development of new sensors, catalysts, and therapeutics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fouling behavior of zwitterionic membranes compared to polyamide membranes
Membrane fouling remains a critical bottleneck for reverse osmosis (RO) desalination, driving energy consumption and reducing membrane lifetime. Here, we employ all-atom molecular dynamics simulations to investigate the antifouling behavior of random zwitterionic amphiphilic copolymer (r-ZAC) membranes composed of sulfobetaine methacrylate (SBMA) and allyl methacrylate (AMA), benchmarked against conventional polyamide (PA) RO membranes. Structural and dynamical analyses—including radial distribution functions, coordination numbers, tetrahedral order parameters, vector orientation, and residence-time correlation functions—reveal that r-ZAC surfaces sustain tightly bound, long-lived hydration layers with preserved tetrahedrality and anisotropic water orientation, in sharp contrast to the weak and disordered hydration of PA. Steered molecular dynamics simulations demonstrate that r-ZAC membranes impose substantial free-energy barriers to foulant approach (alginate ≈ 90 kcal/mol, sucrose ≈ 35 kcal/mol, humic acid ≈ 15 kcal/mol), whereas PA membranes exhibit negligible barriers (< 1 kcal/mol) and thermodynamically favorable adsorption. Detailed foulant–surface interaction analyses show that zwitterionic hydration and electrostatic heterogeneity in r-ZAC suppress adhesion, except in the case of amphiphilic humic acid, which exploits multiple binding modes. Together, these results establish molecular-level design principles for antifouling membranes: the combination of zwitterionic hydration, structured interfacial water, and controlled amphiphilic balance in r-ZAC membranes provides superior resistance to organic fouling relative to PA.
Cross-linked polyamide↗
Decomposition of liquid-liquid extraction organic phase structure into critical and pre-peak contributions
Solution nanostructure induced by amphiphile self-association plays an important role in various chemical and physical processes, including liquid-liquid extraction (LLE). Small angle scattering techniques are an essential means of probing this structure, but, due to non-uniqueness of scattering patterns, their interpretation is not trivial. Here, in this study, we decompose small angle x-ray scattering (SAXS) patterns for a range of binary LLE organic phases into two components: Ornstein-Zernike and pre-peak contributions resulting from, respectively, critical concentration fluctuations and packing of the amphiphilic extractant molecules in the nonpolar aliphatic diluent. While we previously applied Ornstein-Zernike scattering models to similar organic phases, including the pre-peak explicitly in the fit allows us to measure weak fluctuations at high extractant concentration and simultaneously obtain information on the position and intensity of the correlation peak related to amphiphile packing. Scattering patterns and partial structure factors calculated from molecular dynamics simulations support this interpretation. We demonstrate how this minimal scattering model describes nanostructuring for a large number of extractant types over their entire extractant/diluent composition ranges, suggesting simple and universal behavior. The straightforward assignment of these structural contributions facilitates the comparison of these features between different classes of extractant molecules and will enable further studies of organic phase aggregation. Applicability to more complex, process-relevant organic phases is illustrated with post-contact organic phases containing significant quantities of extracted lanthanide nitrate salt, which we find are readily described by this model.
74 ATOMIC AND MOLECULAR PHYSICS↗
Tutorial: Machine-Learning-Based CREASE-2D Analysis of 2D SAXS Profiles to Characterize Anisotropic Nanostructures in Soft Materials
We present a tutorial to guide users on how to extend the Computational Reverse Engineering Analysis of Scattering Experiments-2D (CREASE-2D) framework to interpret their experimental two-dimensional small-angle scattering (SAS) data from soft materials (e.g., polymers, peptide amphiphiles, biomolecular fibrils). Unlike most traditional SAS analysis approaches, which typically rely on azimuthally averaged onedimensional (1D) profiles, CREASE-2D utilizes the complete 2D scattering profile to reveal information about anisotropy in the structure. In past applications, CREASE has provided insights into complex structural features, including the cross-sectional shapes of assembled nanostructures and dispersity in these features, which are difficult to discern with existing analytical models. While (1D- ) CREASE has been applied to SANS and SAXS data, this tutorial shares the steps for implementing CREASE-2D using an example of a dipeptide solution system, for which we have SAXS data. We present details for these steps involved in using CREASE-2D to interpret SAXS profiles: how to preprocess SAXS data, define relevant structural features, generate three-dimensional real-space structures for specific values of these features, train a machine learning (ML) surrogate model to predict scattering profiles for given structural features, and optimize these features using genetic algorithms (GA). Then, we use these steps to interpret complex 2DSAXS data collected from dipeptide solutions that, in microscopy images, exhibit nanoscale structures that could be elliptical tubes/ flat tapes/cylinders or a combination of these cross sections. Open-source codes, computational hardware, and software requirements, as well as the strengths and limitations of this protocol, are also presented. We expect researchers working with (soft) biomaterials, peptide amphiphiles, amphiphilic polymer solutions, polymer nanocomposites, and blends of particles/polymers will find this CREASE-2D method and this tutorial of use.
CREASE↗
Surfactant-like peptide gels are based on cross-β amyloid fibrils
Surfactant-like peptides, in which hydrophilic and hydrophobic residues are encoded within different domains in the peptide sequence, undergo facile self-assembly in aqueous solution to form supramolecular hydrogels. These peptides have been explored extensively as substrates for the creation of functional materials since a wide variety of amphipathic sequences can be prepared from commonly available amino acid precursors. The self-assembly behavior of surfactant-like peptides has been compared to that observed for small molecule amphiphiles in which nanoscale phase separation of the hydrophobic domains drives the self-assembly of supramolecular structures. Here, we investigate the relationship between sequence and supramolecular structure for a pair of bola-amphiphilic peptides, Ac-KLIIIK-NH 2 (L2) and Ac-KIIILK-NH 2 (L5). Despite similar length, composition, and polar sequence pattern, L2 and L5 form morphologically distinct assemblies, nanosheets and nanotubes, respectively. Cryo-EM helical reconstruction was employed to determine the structure of the L5 nanotube at near-atomic resolution. Rather than displaying self-assembly behavior analogous to conventional amphiphiles, the packing arrangement of peptides in the L5 nanotube displayed steric zipper interfaces that resembled those observed in the structures of β-amyloid fibrils. Like amyloids, the supramolecular structures of the L2 and L5 assemblies were sensitive to conservative amino acid substitutions within an otherwise identical amphipathic sequence pattern. This study highlights the need to better understand the relationship between sequence and supramolecular structure to facilitate the development of functional peptide-based materials for biomaterials applications.
Das, Abhinaba [Emory University, Atlanta, GA (Unit↗
Determining population densities in bimodal micellar solutions using contrast-variation small angle neutron scattering
Self-assembly of amphiphilic polymers in water is of fundamental and practical importance. Significant amounts of free unimers and associated micellar aggregates often coexist over a wide range of phase regions. The thermodynamic and kinetic properties of the microphase separation are closely related to the relative population density of unimers and micelles. Although the scattering technique has been employed to identify the structure of micellar aggregates as well as their time-evolution, the determination of the population ratio of micelles to unimers remains a challenging problem due to their difference in scattering power. In this work, using small-angle neutron scattering (SANS), we present a comprehensive structural study of amphiphilic n-dodecyl-PNIPAm polymers, which shows a bimodal size distribution in water. By adjusting the deuterium/hydrogen ratio of water, the intra-micellar polymer and water distributions are obtained from the SANS spectra. The micellar size and number density are further determined, and the population densities of micelles and unimers are calculated to quantitatively address the degree of micellization at different temperatures. Our method can be used to provide an in-depth insight into the solution properties of microphase separation, which are present in many amphiphilic systems.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Imaging Supramolecular Morphogenesis with Confocal Laser Scanning Microscopy at Elevated Temperatures
The morphogenesis of supramolecular assemblies is a highly dynamic process that has only recently been recognized, and our understanding of this phenomenon will require imaging techniques capable of crossing scales. Shape transformations depend both on the complex energy landscapes of supramolecular systems and the kinetically controlled pathways that define their structures and functions. We report here the use of confocal laser scanning microscopy coupled with a custom-designed variable-temperature sample stage that enables in situ observation of such shape changes. The submicrometer resolution of this technique allows for real-time observation of the nanostructures in the native liquid environments in which they transform with thermal energy. We use this technique to study the temperature-dependent morphogenic behavior of peptide amphiphile nanofibers and photocatalytic chromophore amphiphile nanoribbons. Furthermore, the variable-temperature confocal microscopy technique demonstrated in this work can sample a large volume and provides real-time information on thermally induced morphological changes in the solution.
36 MATERIALS SCIENCE↗
Superstructured Biomaterials Formed by Exchange Dynamics and Host–Guest Interactions in Supramolecular Polymers
Dynamic and reversible assembly of molecules is ubiquitous in the hierarchical superstructures of living systems and plays a key role in cellular functions. Recent work from the laboratory reported on the reversible formation of such superstructures in systems of peptide amphiphiles conjugated to oligonucleotides and electrostatically complimentary peptide sequences. Here, a supramolecular system is reported upon where exchange dynamics and host–guest interactions between β-cyclodextrin and adamantane on peptide amphiphiles lead to superstructure formation. Superstructure formation with bundled nanoribbons generates a mechanically robust hydrogel with a highly porous architecture that can be 3D printed. Functionalization of the porous superstructured material with a biological signal results in a matrix with significant in vitro bioactivity toward neurons that could be used as a supramolecular model to design novel biomaterials.
36 MATERIALS SCIENCE↗
Using Aggregation to Chaperone Nanoparticles Across Fluid Interfaces
Abstract Nanoparticles (NPs) transfer is usually induced by adding ligands to modify NP surfaces, but aggregation of NPs oftentimes hampers the transfer. Here, we show that aggregation during NP phase transfer does not necessarily result in transfer failure. Using a model system comprising gold NPs and amphiphilic polymers, we demonstrate an unusual mechanism by which NPs can undergo phase transfer from the aqueous phase to the organic phase via a single‐aggregation‐single pathway. Our discovery challenges the conventional idea that aggregation inhibits NP transfer and provides an unexpected pathway for transferring larger‐sized NPs (>20 nm). The charged amphiphilic polymers effectively act as chaperons for the NP transfer and offer a unique way to manipulate the dispersion and distribution of NPs in two immiscible liquids. Moreover, by intentionally jamming the NP‐polymer assembly at the liquid/liquid interface, the transfer process can be inhibited.
Fu, Yuchen↗
Using Aggregation to Chaperone Nanoparticles Across Fluid Interfaces
Nanoparticles (NPs) transfer is usually induced by adding ligands to modify NP surfaces, but aggregation of NPs oftentimes hampers the transfer. Here, we show that aggregation during NP phase transfer does not necessarily result in transfer failure. Using a model system comprising gold NPs and amphiphilic polymers, we demonstrate an unusual mechanism by which NPs can undergo phase transfer from the aqueous phase to the organic phase via a single-aggregation-single pathway. Our discovery challenges the conventional idea that aggregation inhibits NP transfer and provides an unexpected pathway for transferring larger-sized NPs (>20 nm). The charged amphiphilic polymers effectively act as chaperons for the NP transfer and offer a unique way to manipulate the dispersion and distribution of NPs in two immiscible liquids. Moreover, by intentionally jamming the NP-polymer assembly at the liquid/liquid interface, the transfer process can be inhibited.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗