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At least 559 records · Page 31

Microfluidic synthesis of multilayered lipid–polymer hybrid nanoparticles for the formulation of low solubility drugs

Hybrid phospholipid/block copolymer membranes where polymers and lipids are molecularly mixed or phase-separated into polymer-rich and lipid-rich domains are promising drug delivery materials. Harnessing the chemical diversity of polymers and the biocompatability of lipids is a compelling approach to design the next generation of drug carriers. Here, we report on the development of a microfluidics-based strategy analogous to produce lipid nanoparticles (LNPs) for the nanomanufacturing of multilayered hybrid nanoparticles (HNPs). In conclusion, using X-ray scattering, Cryo-electron, and polarized microscopy we show that phosphatidylcholine (PC) and PBD-b-PEO (poly(butadiene-block-ethylene oxide)) hybrid membranes can be nanomanufactured by microfluidics into HNPs with dense and multilayered cores which are ideal carriers of low-solubility drugs of the Biopharmaceutical Classification System (BCS) II and IV such as antimalarial DSM265 and Paclitaxel, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of poly[oligo(ethylene glycol) methyl ether methacrylate] side chain length on the brush swelling behavior in A/B/A–B ternary blends with polystyrene

The phase behavior of ternary blends composed of two homopolymers (A, B) and their corresponding diblock copolymer (A–B) has been widely studied, with emphasis on the volumetrically symmetric isopleth and the formation of bicontinuous microemulsions. However, almost all the previous studies employed linear polymers, and little is known about the impact of polymer architecture on the phase behavior of such ternary blends. Here, in this work, we report the self-assembly of three sets of ternary blends of polystyrene (PS) and poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA n ), with different lengths of oligo(ethylene glycol) side chains n. Small-angle X-ray scattering was used to probe the phase behavior at different compositions and temperatures. The order-to-disorder transition temperature was found to be impacted by the side chain length. It was also observed that longer side chains lead to poorer miscibility of homopolymers in the corresponding block, resulting in a more “dry-brush” like swelling behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Swelling characteristics of DNA polymerization gels

The development of biomolecular stimuli-responsive hydrogels is important for biomimetic structures, soft robots, tissue engineering, and drug delivery. DNA polymerization gels are a new class of soft materials composed of polymer gel backbones with DNA duplex crosslinks that can be swollen by sequential strand displacement using hairpin-shaped DNA strands. The extensive swelling can be tuned using physical parameters such as salt concentration and biomolecule design. Previously, DNA polymerization gels have been used to create shape-changing gel automata with a large design space and high programmability. Here we systematically investigate how the swelling response of DNA polymerization gels can be tuned by adjusting the design and concentration of DNA crosslinks in the hydrogels or DNA hairpin triggers, and the ionic strength of the solution in which swelling takes place. Finally, we also explore the effect hydrogel size and shape have on the swelling response. Tuning these variables can alter the swelling rate and extent across a broad range and provide a quantitative connection between biochemical reactions and macroscopic material behaviour.

59 BASIC BIOLOGICAL SCIENCES↗

Dielectric and Structural Properties of the Hybrid Material Polyvinylidene Fluoride-Bacterial Nanocellulose-Based Composite

In the search for environmentally friendly materials with a wide range of properties, polymer composites have emerged as a promising alternative due to their multifunctional properties. This study focuses on the synthesis of composite materials consisting of four components: bacterial nanocellulose (BNC) modified with magnetic Fe 3 O 4 , and a mixture of BaTiO 3 (BT) and polyvinylidene fluoride (PVDF). The BT powder was mechanically activated prior to mixing with PVDF. The influence of BT mechanical activation and BNC with magnetic particles on the PVDF matrix was investigated. The obtained composite films’ structural characteristics, morphology, and dielectric properties are presented. This research provides insights into the relationship between mechanical activation of the filler and structural and dielectric properties in the PVDF/BT/BNC/Fe 3 O 4 system, creating the way for the development of materials with a wide range of diverse properties that support the concept of green technologies.

36 MATERIALS SCIENCE↗

Control over emergence and alignment of transient blisters in thermo-responsive gels using hierarchically patterned substrates

Surfaces with tunable microscale textures are vital in a large variety of technological applications, including heat transfer, antifouling and adhesion. To facilitate such broad-scale use, there is a need to create surfaces that undergo reconfigurable changes in topology and thus, enable switchable functionality. To date, there is a relative dearth of methods for engineering surfaces that can be actuated to change topography over a range of length scales, and hence, form tunable hierarchically structured layers. Combining modeling and experiments, we design a geometrically patterned, thermo-responsive poly (N-isopropylacrylamide) gel film that undergoes controllable hierarchical changes in topology with changes in temperature. At the bottom, the film is covalently bound to a solid, curved substrate; at the top, the film encompasses longitudinal rectangular ridges that are oriented perpendicular to the underlying cylindrical curves. At temperatures below lower critical solution temperature (LCST), the swollen gel exhibits 3D variations in polymer density and thickness defined by the gel's top and bottom topography. As the temperature rises above LCST, the interplay between the upper ridges and lower curves in the gel drives non-uniform, directional solvent transport, the nucleation and propagation of a phase-separated higher-density skin layer, and the resulting pressure buildup within the film. These different, interacting kinetic processes lead to an instability, which produces transient microscopic blisters in the film. Through simulations, we show how tuning the width of the ridges modifies the propagation of a skin layer and creates localized pressure build-up points, which enables control over the emergence, distribution, and alignment of the microscopic blisters. Futhermore, we provide a simple argument to predict the size of such microscopic features. Experiments confirm our predictions and further highlight how our computational model enables the rational design of topographical transitions in these tunable films. The development of actuatable, hierarchically structured films provides new routes for achieving switchable functionality in actuators, drug release systems and adhesives.

42 ENGINEERING↗

A coarse-grained simulation model for colloidal self-assembly via explicit mobile binders

Colloidal particles with mobile binding molecules constitute a powerful platform for probing the physics of self-assembly. Binding molecules are free to diffuse and rearrange on the surface, giving rise to spontaneous control over the number of droplet–droplet bonds, i.e., valence, as a function of the concentration of binders. This type of valence control has been realized experimentally by tuning the interaction strength between DNA-coated emulsion droplets. Optimizing for valence two yields droplet polymer chains, termed ‘colloidomers’, which have recently been used to probe the physics of folding. To understand the underlying self-assembly mechanisms, here we present a coarse-grained molecular dynamics (CGMD) model to study the self-assembly of this class of systems using explicit representations of mobile binding sites. Further, we explore how valence of assembled structures can be tuned through kinetic control in the strong binding limit. More specifically, we optimize experimental control parameters to obtain the highest yield of long linear colloidomer chains. Subsequently tuning the dynamics of binding and unbinding via a temperature-dependent model allows us to observe a heptamer chain collapse into all possible rigid structures, in good agreement with recent folding experiments. Our CGMD platform and dynamic bonding model (implemented as an open-source custom plugin to HOOMD-Blue) reveal the molecular features governing the binding patch size and valence control, and opens the study of pathways in colloidomer folding. This model can therefore guide programmable design in experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preactivated zeolite nanosheet plate-tiled membrane on porous PVDF film: Synthesis and study of proton-selective ion conduction

Preactivated MFI zeolite nanosheet plates (ZNPs) with large areas (~2.0 × 2.0 μm 2 ) and nanometer thicknesses (~60 nm) were prepared directly in liquid-dispersed state. The individual ZNP was a stack of 4-nm-thick single crystalline zeolite nanosheets (ZNs) interlinked by Si–O–Si bonds between neighboring ZN surfaces. The dispersed open-pore ZNPs allowed formulating suspensions for tiling ZNP membranes on polymer substrates without requiring post-coating activation. A pinhole-free ZNP-tiled (ZNPT) membrane has been achieved on macroporous PVDF film by a self-repairing vacuum-assisted filtration coating method. The resultant ZNPT layer was ~500 nm-thick consisting of about 7 ZNP layers with inter-ZNP width and inter-ZNP entrance porosity around 9 nm and 2%, respectively. The ZNPT-PVDF membrane exhibited high selectivity to proton transport over vanadyl ion and low resistances to proton conduction in aqueous solutions. The membrane also demonstrated to function as an efficient ion separator for the vanadium redox flow battery. The reported synthesis of preactivated ZNP suspension may overcome the major hurdle to realizing polymer-supported ZN membranes, which is the inefficiency of existing methods in obtaining readily dispersible open-pore ZNs. Finally, the ZNPT-PVDF membrane can be a more affordable and sustainable alternative to the Nafion-based ion separation membranes.

36 MATERIALS SCIENCE↗

Vapor Phase Infiltration of Titanium Oxide into P3HT to Create Organic–Inorganic Hybrid Photocatalysts

Herein, we report for the first time the use of vapor phase infiltration (VPI) to infuse conducting polymers with inorganic metal oxide clusters that together form a photocatalytic material. While vapor infiltration has previously been used to electrically dope conjugated polymers, this is the first time, to our knowledge, that the resultant hybrid material has been demonstrated to have photocatalytic properties. The system studied is poly(3-hexylthiophene-2,5-diyl) (P3HT) vapor infiltrated with TiCl 4 and H 2 O to create P3HT-TiO x organic–inorganic hybrid photocatalytic materials. X-ray photoelectron spectroscopy analysis shows that P3HT-TiO x VPI films consist of a partially oxidized P3HT matrix, and the infiltrated titanium inorganic is in a 4+ oxidation state with mostly oxide coordination. Upon visible light illumination, these P3HT-TiO x hybrids degrade methylene blue dye molecules. The P3HT-TiO x hybrids are 4.6× more photocatalytically active than either the P3HT or TiO 2 individually or when sequentially deposited (e.g., P3HT on TiO 2 ). On a per surface area basis, these hybrid photocatalysts are comparable or better than other best in class polymer semiconductor photocatalysts. VPI of TiCl 4 + H 2 O into P3HT makes a unique hybrid structure and idealized photocatalyst architecture by creating nanoscale TiO x clusters concentrated toward the surface achieving extremely high catalytic rates. The mechanism for this enhanced photocatalytic rate is understood using photoluminescence spectroscopy, which shows significant quenching of excitons in P3HT-TiO x as compared to neat P3HT, indicating that P3HT acts as a photosensitizer for the TiO x catalyst sites in the hybrid material. This work introduces a new approach to designing and synthesizing organic–inorganic hybrid photocatalytic materials, with expansive opportunities for further exploration and optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A review of composite polymer-ceramic electrolytes for lithium batteries

All solid-state lithium batteries are garnering attention in both academia and industry. Lithium-ion conductive polymers and lithium-ion conductive ceramics are the two major classes of solid electrolytes that have prevalently been pursued for many years. However, each of them has its own advantages and disadvantages. One approach to overcome the disadvantages and get the best out of each of those materials is a solid composite electrolyte that combines the advantages of inorganic ceramic electrolytes and solid polymer electrolytes. Such composite electrolytes can offer acceptable ionic conductivity, high mechanical strength, and favorable interfacial contact with electrodes, which can greatly improve the electrochemical performance of all-solid-state batteries compared to cells based on a polymer electrolyte alone or a ceramic electrolyte alone. We present in this review the state-of-the-art composite polymer-ceramic electrolytes in view of their electrochemical and physical properties for the applications in lithium batteries. The review mainly encompasses the polymer matrices, various ceramic filler materials, and the polymer/ceramics composite systems. Specifically, the structures, ionic conductivities, electrochemical/chemical stabilities, and fabrications of solid composite electrolytes are discussed in-depth. On the basis of previous work, a perspective on future research directions is highlighted for developing high-performance composite polymer-ceramic electrolytes.

25 ENERGY STORAGE↗

Versailles Project on Advanced Materials and Standards interlaboratory study on intensity calibration for x-ray photoelectron spectroscopy instruments using low-density polyethylene

We report the results of a Versailles Project on Advanced Materials and Standards interlaboratory study on the intensity scale calibration of x-ray photoelectron spectrometers using low-density polyethylene (LDPE) as an alternative material to gold, silver, and copper. An improved set of LDPE reference spectra, corrected for different instrument geometries using a quartz-monochromated Al Kα x-ray source, was developed using data provided by participants in this study. Using these new reference spectra, a transmission function was calculated for each dataset that participants provided. When compared to a similar calibration procedure using the NPL reference spectra for gold, the LDPE intensity calibration method achieves an absolute offset of ~3.0% and a systematic deviation of ±6.5% on average across all participants. For spectra recorded at high pass energies (≥90 eV), values of absolute offset and systematic deviation are ~5.8% and ±5.7%, respectively, whereas for spectra collected at lower pass energies (<90 eV), values of absolute offset and systematic deviation are ~4.9% and ±8.8%, respectively; low pass energy spectra perform worse than the global average, in terms of systematic deviations, due to diminished count rates and signal-to-noise ratio. Differences in absolute offset are attributed to the surface roughness of the LDPE induced by sample preparation. We further assess the usability of LDPE as a secondary reference material and comment on its performance in the presence of issues such as variable dark noise, x-ray warm up times, inaccuracy at low count rates, and underlying spectrometer problems. In response to participant feedback and the results of the study, we provide an updated LDPE intensity calibration protocol to address the issues highlighted in the interlaboratory study. Finally, we also comment on the lack of implementation of a consistent and traceable intensity calibration method across the community of x-ray photoelectron spectroscopy (XPS) users and, therefore, propose a route to achieving this with the assistance of instrument manufacturers, metrology laboratories, and experts leading to an international standard for XPS intensity scale calibration.

36 MATERIALS SCIENCE↗

Second Target Station (STS) Project: Centaur (Technical Report)

CENTAUR will be the flagship general purpose small-angle neutron scattering (SANS) instrument for the Second Target Station of SNS. Based on an optimized and high-performance SANS instrument, it is capable of SANS/wide-angle neutron scattering and diffraction simultaneously filling the capability gap to cover structure scale from atomic scale to hundreds of nanometers for scientific needs ranging from polymers, biology, materials sciences, and quantum condensed matter. Additionally, with a high-speed chopper, it can be used as a direct geometry spectrometer to probe the dynamics in relatively large length-scale structures as an inelastic SANS spectrometer. The technical details of the CENTAUR instrument are presented in this document. As the project progresses, the initial details are subject to change based on feedback.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Up close - Materials division of NASA-Lewis Research Center

The eight branches of the Materials Division of NASA-Lewis Research Center are described. The design and capabilities of the Microgravity Materials Science Laboratory are discussed. Consideration is given to the objectives of the ceramic branch, the advanced metallic branch, the metal science branch, and the polymer branch. Also discussed are the research and development efforts of the surface science branch, the environmental durability branch, and the analytic science branch.

Abel, Phillip↗

Challenges and Vision for Standardization of Biopolymer Data Sets for Machine Learning

Machine learning (ML) is transforming materials research, yet potential for biopolymer discovery remains constrained by fragmented data and nonstandardized reporting. Biopolymers differ significantly from synthetic polymers, requiring specialized approaches to represent their biosynthetic origins, hierarchical structures, and application-specific metrics. In this Perspective, we identify three core challenges limiting biopolymer representation: information encoding, data quality, and data sharing. We describe the most pressing issues and propose commensurate approaches to address each key challenge. Recommendations include the design and adoption of biopolymer-specific fingerprinting and representation frameworks, development of hybrid human-large language model (LLM) data extraction strategies, and expanding Findable, Accessible, Interoperable, Reusable (FAIR)-compliant repositories. We propose a robust foundation to define interoperable, high-quality data sets that capture the full context of biopolymer materials. Standardized metadata, shared ontologies, and community-driven infrastructure would enable scalable, reproducible workflows and accelerate the ML-driven development of biopolymers.

36 MATERIALS SCIENCE↗

Chain dynamics of alternating polymers P(C n EG 4 )

Alternating or sequence defined polymers attract the attention of an increasing number of researchers recently. Due to their different blocks, they are very customizable and material properties can be tuned. In this publication, we present dynamical studies with focus on polymer dynamics, investigated by rheology and fast field cycling (FFC) NMR. The molecular weight dependencies of the relaxation time and zero-shear viscosity could hint to entanglement effects; however, the spectral shape of the viscoelastic data resembles the polymer dynamics of unentangled melts. Furthermore, taking both techniques into account, i.e. rheology and FFC NMR leads to the conclusion that the relaxation spectra of the alternating polymer are similar to those of linear polymers.

36 MATERIALS SCIENCE↗

Dual material fused filament fabrication of composite core‐shell structures with improved impact resistance and interfacial adhesion

The mechanical performance of parts produced by fused filament fabrication (FFF) has been limited due to the presence of voids and poor interlayer welding. Recent advancements in FFF have enabled the fabrication of void-free objects with strong interlayer welding through the use of semicrystalline polymer shells such as high-density polyethylene (HDPE) along with a high viscosity core polymer like acrylonitrile-butadiene-styrene (ABS). Furthermore, the zero-shear viscosity (η0) of ABS is three orders of magnitude higher than HDPE making the ABS-HDPE core-shell configuration preferable. ABS holds the shape by preventing bulk flow and part bending while HDPE promotes full surface contact across the layers. Most polymers, however, are immiscible which causes a weak weld line along the core-shell interface. Herein, maleic anhydride (MAH) is grafted to the butadiene segment of the ABS core thereby compatibilizing the interface with HDPE, improving the interfacial adhesion. Attenuated total reflectance-Fourier transform infrared spectroscopy was employed to confirm successful grafting. Using a custom-made die affording the core-shell structure, the ABS-g-MAH is shown to improve the impact resistance by 253% and 16% compared to neat HDPE and ABS specimens, respectively. Additionally, a 10% increase compared to the unmodified ABS-HDPE core-shell configuration is observed.

36 MATERIALS SCIENCE↗

Anisotropic Resonant X-ray Diffraction of a Conjugated Polymer at the Sulfur K-Edge

The planar, aromatic nature of the backbone of conjugated polymers endows them with anisotropic properties. Here we show that the resonant X-ray diffraction of a sulfur-containing semicrystalline conjugated polymer at the sulfur K-edge is highly anisotropic, with strong modulation of diffracted intensity depending upon the relative orientation of the polarization of the incident beam with respect to the diffracting crystal planes. Through determination of the anisotropic resonant scattering factors, we can spectroscopically reproduce the observed resonant anisotropic scattering effects based on a proposed unit cell geometry for the polymer.

36 MATERIALS SCIENCE↗

Materials Based on Technical Bulk Lignin

Lignin is the second most abundant biopolymer and the main source of aromatic structures on earth. Lignin has long been produced as a byproduct of the pulping process and utilized in low value-added applications like heat. However, lignin has received increased attention in recent years to improve its value through various chemical processes. This Review compiles recent progress in synthesis, properties, and applications of lignin-based materials. The lignin for material applications can often be classified into three categories: technical bulk lignin (TBL), lignin-derived oligomers (LDOs), and lignin-derived phenols (LDPs). Furthermore, this Review focuses on the chemical modifications of TBLs and their applications in novel smart materials like self-healing, stimulus responsive, and shape memory polymers. The conversion of TBL to polymers can be briefly divided into two steps: (1) introduction of polymerizable functional groups into the lignin backbone and (2) polymerization that achieves desired materials. Both lignin functionalization and polymerization approaches are discussed in detail. As such, this work attempts to provide a comprehensive overview that highlights the importance of these approaches for the utilization of the abundant but largely ignored biopolymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗