SAXS Research Articles

Optimization of Laser Based-Powder Bed Fusion Parameters for Controlled Porosity in Titanium Alloy Components

Laser based-powder bed fusion (LB-PBF) enables fast, efficient, and cost-effective production of high-performing products. While advanced functionalities are often derived from geometric complexity, the capability to tailor material properties also offers significant opportunities for technical innovation across many fields. This study explores the optimization of the LB-PBF process parameters for producing Ti6Al4V titanium alloy parts with controlled porosity. To this end, cuboid and lamellar samples were fabricated by systematically varying laser power, hatch distance, and layer thickness according to a full factorial Design of Experiments, and the resulting specimens were thoroughly characterized by analyzing envelope porosity, surface roughness and waviness, surface morphology, and surface area. A selection of specimens was further examined using small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) to investigate the atomic structure and nanometric porosity of the material. The results demonstrated the possibility to finely control the porosity and surface characteristics of Ti6Al4V within specific LB-PBF process ranges. The pores were found to be mostly closed even for thin walls, while the surface roughness was recognized as the primary factor impacting the surface area. The lamellar samples obtained by exposing single scan tracks showed nearly an order-of-magnitude increase in both surface area and pore volume, thereby laying the groundwork for the production of parts with optimized porosity.

Adding More Shape to Nanoscale Reference Materials─LiYF4:Yb,Tm Bipyramids as Standards for Sizing Methods and Particle Number Concentration.

The increasing industrial use of nanomaterials calls for the reliable characterization of their physicochemical key properties like size, size distribution, shape, and surface chemistry, and test and reference materials (RMs) with sizes and shapes, closely matching real-world nonspheric nano-objects. An efficient strategy to minimize efforts in producing nanoscale RMs (nanoRMs) for establishing, validating, and standardizing methods for characterizing nanomaterials are multimethod nanoRMs. Ideal candidates are lanthanide-based, multicolor luminescent, and chemically inert nanoparticles (NPs) like upconversion nanoparticles (UCNPs), which can be prepared in different sizes, shapes, and chemical composition with various surface coatings. This makes UCNPs interesting candidates as standards not only for sizing methods, but also for element-analytical methods like laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS), quantitative bioimaging methods like X-ray fluorescence computed tomography (XFCT), and luminescence methods and correlative measurements. Here, we explore the potential of two monodisperse LiYF4:Yb,Tm bipyramids with peak-to-peak distances of (43 ± 2) nm and (29 ± 2) nm as size standards for small-angle X-ray scattering (SAXS) and tools for establishing and validating the sophisticated simulations required for the analysis of SAXS data derived from dispersions of nonspheric nano-objects. These SAXS studies are supplemented by two-dimensional (2D)-transmission electron microscopy measurements of the UCNP bipyramids. Additionally, the particle number concentration of cyclohexane dispersions of these UCNP bipyramids is determined by absolute SAXS measurements, complemented by gravimetry, thermogravimetric analysis (TGA), and inductively coupled plasma optical emission spectrometry (ICP-OES). This approach enables traceable particle number concentration measurements of ligand-capped nonspheric particles with unknown chemical composition.

Modification of Poly(3-Hydroxybutyrate) with a Linear Polyurethane Modifier and Organic Nanofiller—Preparation and Structure–Property Relationship

The growing demand for products made of polymeric materials, including the commonly used polypropylene (PP), is accompanied by the problem of storing and disposing of non-biodegradable waste, increasing greenhouse gas emissions, climate change and the creation of toxic products that constitute a health hazard of all living organisms. Moreover, most of the synthetic polymers used are made from petrochemical feedstocks from non-renewable resources. The use of petrochemical raw materials also causes degradation of the natural environment. A potential solution to these problems is the use of biopolymers. Biopolymers include biodegradable or biosynthesizable polymers, i.e., obtained from renewable sources or produced synthetically but from raw materials of natural origin. One of them is the poly(3-hydroxybutyrate) (P3HB) biopolymer, whose properties are comparable to PP. Unfortunately, it is necessary to modify its properties to improve its processing and operational properties. In the work, hybrid polymer nanobiocomposites based on P3HB, with the addition of chain, uncross-linked polyurethane (PU) and layered aluminosilicate modified with organic salts (Cloisite®30B) were produced by extrusion process. The introduction of PU and Cloisite®30B to the polymer matrix (P3HB) influenced the processing parameters beneficially and resulted in a decrease in the extrusion temperature of more than 10 °C. The influence of the simultaneous addition of a constant amount of PU (10 m/m%) and the different amounts of nanoadditives (1, 2 and 3 m/m%) on the compatibility, morphology and static mechanical properties of the resulted nanobiocomposites were examined. The component interactions by Fourier transformation infrared spectroscopy (FTIR) analysis, nano- and microscale structure studies using small-angle X-ray scattering (SAXS) and morphology by scanning electron microscopy (SEM) were carried out, and the hardness and tensile strength of the obtained polymer nanobiocomposites were determined. FTIR analysis identified the compatibility of the polyester matrix, PU, and organomodified montmorillonite, the greatest being 3 m/m% Cloisite30B content. The addition of PU to the polyester elasticizes the material and decreases the material’s strength and ductility. The presence of nanoclay enhanced the mechanical properties of nanobiocomposites. The resulting nanobiocomposites can be used in the production of short-life materials applied in gardening or agriculture.

Capturing Dynamic Assembly of Nanoscale Proteins During Network Formation.

The structural evolution of hierarchical structures of nanoscale biomolecules is crucial for the construction of functional networks in vivo and in vitro. Despite the ubiquity of these networks, the physical mechanisms behind their formation and self-assembly remains poorly understood. Here, this study uses photochemically cross-linked folded protein hydrogels as a model biopolymer network system, with a combined time-resolved rheology and small-angle x-ray scattering (SAXS) approach to probe both the load-bearing structures and network architectures respectively thereby providing a cross-length scale understanding of the network formation. Combining SAXS, rheology, and kinetic modeling, a dual formation mechanism consisting of a primary formation phase is proposed, where monomeric folded proteins create the preliminary protein network scaffold; and a subsequent secondary formation phase, where both additional intra-network cross-links form and larger oligomers diffuse to join the preliminary network, leading to a denser more mechanically robust structure. Identifying this as the origin of the structural and mechanical properties of protein networks creates future opportunities to understand hierarchical biomechanics in vivo and develop functional, designed-for-purpose, biomaterials.

The Mesoscopic Damage Mechanism of Jointed Sandstone Subjected to the Action of Dry–Wet Alternating Cycles

The effect of the dry–wet cycle, characterized by periodic water level changes in the Three Gorges Reservoir, will severely degrade the bearing performance of rock formations. In order to explore the effect of the dry–wet cycle on the mesoscopic damage mechanism of jointed sandstone, a list of meso-experiments was carried out on sandstone subjected to dry–wet cycles. The pore structure, throat features and mesoscopic damage evolution of jointed sandstone with the action of the dry–wet cycle were analyzed using a-low-field nuclear magnetic resonance (NMR) technique. Subsequently, the impact on the mineral content of dry–wet cycles was studied by small angle X-ray scattering (SAXS). Based on this, the mesoscopic damage mechanism of sandstone subjected to dry–wet cycles was revealed. The results show that the effects of the drying–wetting cycle can promote the development of porous channels within sandstone, resulting in cumulative damage. Besides, with an increase in dry–wet cycles, the proportion of small pores and pore throats decreased, while the proportion of medium and large pores and pore throats increased. The combined effects of extrusion crush, tensile fracture, chemical reaction and dissolution of minerals inside the jointed sandstone contributed to the development of mesoscopic pores, resulting in the increase of porosity and permeability of rock samples under the dry–wet cycles. The results provide an important reference value for the stability evaluation of rock mass engineering under long-term dry–wet alternation.

High-Strength, Self-Healing Copolymers of Acrylamide and Acrylic Acid with Co(II), Ni(II), and Cu(II) Complexes of 4′-Phenyl-2,2′:6′,2″-terpyridine: Preparation, Structure, Properties, and Autonomous and pH-Triggered Healing

The utilization of self-healing polymers is a promising way of solving problems associated with the wear and tear of polymer products, such as those caused by mechanical stress or environmental factors. In this study, a series of novel self-healing, high-strength copolymers of acrylamide, acrylic acid, and novel acrylic complexes of 4′-phenyl-2,2′:6′,2″-terpyridine [Co(II), Ni(II), and Cu(II)] was prepared. A systematic study of the composition and properties of the obtained polymers was carried out using a variety of physicochemical techniques (elemental analysis, gel permeation chromatography (GPC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR), ultraviolet-visible spectroscopy (UV-vis), small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), confocal laser scanning microscopy (CLSM), and tensile testing). All metallopolymer samples exhibit autonomous intrinsic healing along with maintaining high tensile strength values (for some samples, the initial tensile strength exceeded 100 MPa). The best values of healing efficiency are possessed by metallopolymers with a nickel complex (up to 83%), which is most likely due to the highest lability of the metal–heteroatom coordination bonds. The example of this system shows the ability to re-heal with negligible deterioration of the mechanical properties. The possibility of tuning the mechanical properties of self-healing films through the use of different metal ions has been demonstrated.

Liquid Crystal Behavior of Uniform Short Rods Made from Computationally Designed Parallel Coiled Coil Building Blocks.

Parallel, homotetrameric coiled coils were computationally designed using 29 amino acid peptides. These parallel coiled coils, called "bundlemers", have C2 symmetry, with all N-termini displayed from one end of the nanoparticle and all C-termini from the opposite end. This anisotropic display of the peptide termini allowed for the functionalization of two sets of nanoparticles with either maleimide or thiol functionality at the N-terminal region of the constituent peptides. The thiol-Michael conjugation reaction between the N-terminal end of complementary bundlemer nanoparticles formed monodisperse, rigid bundlemer dimer, called "dibundlemer", rods. The constituent, individual bundlemer nanoparticles were characterized with small-angle X-ray scattering (SAXS), Förster resonance energy transfer (FRET), and circular dichroism (CD) spectroscopy to confirm the parallel assembly of the coiled coils, consistent with the computational design. The dibundlemer rods were characterized with SAXS to reveal the uniform dibundlemer nature of the rods. Optical birefringence is observed in concentrated samples of the rods, with polarized optical microscopy (POM) revealing a nematic liquid crystalline behavior.

Exploring Multi-Parameter Effects on Iron Oxide Nanoparticle Synthesis by SAXS Analysis

Iron oxide nanoparticles (IONs) are extensively used in biomedical applications due to their unique magnetic properties. This study optimized ION synthesis via the co-precipitation method, exploring the impact of the reactant concentrations (Fe(II) and Fe(III)), NaOH concentration, temperature (30 °C–80 °C), stirring speed (0–1000 rpm), and dosing rate (10–600 s) on particle size and growth. Using small-angle X-ray scattering (SAXS), we observed, for example, that higher temperatures (e.g., 67 °C compared with 53 °C) led to a 50% increase in particle size, while the stirring speed and NaOH concentration also influenced nucleation and aggregation. These results provide comprehensive insights into optimizing synthetic conditions for targeted applications in biomedical fields, such as drug delivery and magnetic resonance imaging (MRI), where precise control over nanoparticle size and properties is crucial.

Supramolecular arrangements in human amyloid tissues using SAXS

Amyloid diseases are characterized by the accumulation of misfolded protein aggregates in human tissues, pose significant challenges for both diagnosis and treatment. Protein aggregations known as amyloids are linked to several neurodegenerative conditions including Alzheimer's disease, Parkinson's disease, and systemic amyloidosis. The key goal of this research is to employ Small-Angle X-ray Scattering (SAXS) to examine the supramolecular structures of amyloid aggregates in human tissues. We present the structural analysis of amyloid using SAXS, which is employed directly to analyze thin tissue samples without damaging the tissues. This technique provides size and shape information of fibrils, which can be used to generate low-resolution 2D models. The present study investigates the structural changes in amyloid fibril axial d-spacing and scattering intensity in different human tissues, including kidney, heart, thyroid, and others, while also accounting for the presence of triglycerides in these tissues. Tissue structural components were examined at momentum transfer values between q = 0.2 nm−1 and 1.5 nm−1. The d-spacing is a critical parameter in SAXS that provides information about the periodic distances between structures within a sample. From the supramolecular SAXS patterns, the axial d-spacing of fibrils in amyloid tissues is prominent and exists within the 3rd to 10th order, compared to that of healthy tissues which do not have notable peak orders. The axial period of fibrils in amyloid tissues is within the scattering vector range 57.40–64.64 nm−1 while in normal tissues the range is between 60.68 and 61.41 nm−1, which is 3.0 nm−1 smaller than amyloid-containing tissues. Differences in d-spacing are often correlate with distinct pathological mechanisms or stages of disease progression. The application of SAXS to investigate amyloid structures in human tissues has enormous potential to further knowledge of amyloid disorders. This work will open the path for novel diagnostic instruments and therapeutic strategies meant to reduce the burden of amyloid-related diseases by offering a thorough structural examination of amyloid aggregates.

Structural and functional studies of the EGF20-27 region reveal new features of the human Notch receptor important for optimal activation.

The Notch receptor is activated by the Delta/Serrate/Lag-2 (DSL) family of ligands. The organization of the extracellular signaling complex is unknown, although structures of Notch/ligand complexes comprising the ligand-binding region (LBR), and negative regulatory region (NRR) region, have been solved. Here, we investigate the human Notch-1 epidermal growth factor-like (EGF) 20-27 region, located between the LBR and NRR, and incorporating the Abruptex (Ax) region, associated with distinctive Drosophila phenotypes. Our analyses, using crystallography, NMR and small angle X-ray scattering (SAXS), support a rigid, elongated organization for EGF20-27 with the EGF20-21 linkage showing Ca2+-dependent flexibility. In functional assays, Notch-1 variants containing Ax substitutions result in reduced ligand-dependent trans-activation. When cis-JAG1 was expressed, Notch activity differences between WT and Ca2+-binding Ax variants were less marked than seen in the trans-activation assays alone, consistent with disruption of cis-inhibition. These data indicate the importance of Ca2+-stabilized structure and suggest the balance of cis- and trans-interactions explains the effects of Drosophila Ax mutations.

Radiation Resistivity of Ti-5331 Alloy with Different Microstructures

Titanium alloys have promising potential for applications in marine nuclear power systems owing to their exceptional mechanical and corrosion properties. Nevertheless, their radiation resistivity is a determining factor for their extensive use as structural materials in nuclear energy systems. In this study, the radiation resistivity of Ti-5Al-3V-3Zr-Cr (Ti-5331) alloys with three different microstructures was examined using a combination of characterization techniques including positron annihilation Doppler broadening spectroscopy (DBS), Elastic Recoil Detection Analysis (ERDA), Transmission Electron Microscope (TEM), Small-Angle X-ray scattering (SAXS) and nanoindentation. The results reveal that the equiaxed structure, bimodal structure, and Widmanstatten structure of Ti-5331 alloy obtained through different annealing processes exhibit differences in the number of interfaces and the content of the β phase. The α/β interfaces can significantly enhance the radiation resistance of titanium alloys by inhibiting the diffusion of helium atoms after helium ion irradiation. Notably, the alloy with a bimodal structure exhibited the best overall radiation resistivity, showing small defect size, low hardening effect, and low swelling rate of 0.003%. Moreover, the size of helium bubbles of the bimodal structure is half of that in the equiaxed structure and Widmanstatten structure. Thus, the bimodal structure of the Ti-5331 alloy possesses superior radiation resistivity.

Morphology and inter-vesicle distances in condensates of synaptic vesicles and synapsin

Synaptic vesicle clusters or pools are functionally important constituents of chemical synapses. In the so-called reserve and the active pools, neurotransmitter-loaded synaptic vesicles (SVs) are stored and conditioned for fusion with the synaptic membrane and subsequent neurotransmitter release during synaptic activity. Vesicle clusters can be considered as so-called membrane-less compartments, which form by liquid-liquid phase separation (LLPS). Synapsin as one of the most abundant synaptic proteins has been identified as a major driver of pool formation. It has been shown to induce LLPS and form condensates on its own in solution, but also has been shown to integrate vesicles into condensates in vitro. In this process, the intrinsically disordered region of synapsin is believed to play a critical role. Here we first investigate the solution structure of synapsin and SVs separately by small-angle X-ray scattering (SAXS). In the limit of low momentum transfer q, the scattering curve for synapsin gives clear indication for supra-molecular aggregation (condensation). We then study mixtures of SVs and synapsin forming condensates, aiming at the morphology and inter-vesicle distances, i.e the structure of the condensates in solution. To obtain the structure factor S(q) quantifying inter-vesicle correlation, we divide the scattering curve of condensates by that of pure SV suspensions. Analysis of S(q) in combination with numerical simulations of cluster aggregation indicates a non-compact fractal-like vesicular fluid with rather short inter-vesicle distances at the contact sites.

Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin-Based Open Frameworks.

Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo8S8O8(OH)8(guest)]2- complex, formed by the self-condensation of four [MoV 2O2S2]2- fragments around a guest unit (MoVIO6H4 or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids. These new compounds were thoroughly characterized using X-ray diffraction (both powder and single-crystal), N2 adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using 1H NMR titration and small-angle X-ray scattering (SAXS) demonstrated pre-association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.

A microphase-separated structure of polystyrene-b-polyisoprene-b-polystyrene triblock copolymers prepared via shear-press and injection molding methods during uniaxial deformation

The influence of the preparation method on the initial structure and deformation behavior of polystyrene (PS) - polyisoprene (PI) - PS (SIS) triblock copolymer elastomers was investigated using small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). Shear pressing (SP) and injection molding (IM) were used as the preparation methods. The samples exhibited a microphase-separated structure, in which the PS cylinders were packed in a hexagonal lattice for the entire sample. SP-SIS possessed a higher degree of microphase separation (DMPS) and an ordering of a microphase-separated structure (OMPSS), and lower degree of the PS cylinder orientation (DCO) than IM-SIS. Uniaxial tensile testing was performed along the parallel (//) and perpendicular (–|) directions to the PS cylinder orientation combining in situ SAXS/WAXD measurements. Young’s modulus and tensile strength of IM-SIS were lager and smaller than those of SP-SIS. A change in the PS cylinder orientation, which occurs for –| stretching, of IM-SIS occurred at larger strain than SP-SIS, indicating that the orientation of highly ordered PS cylinders are difficult to be changed due to their larger domains. It was found that the DCO relates to Young's modulus, yielding, and change in the PS cylinder orientation, while the OMPSS and DMPS relate to tensile strength.

Tearing properties, crystallization behavior, microstructure, and morphology of LLDPE with different short branched chain distributions

Abstract The length and distribution of comonomers with short-chain branching (SCB) have a significant influence on the crystallization behavior and crystal structure of polymers, as well as the mechanical properties of the material. This study investigates the crystallization behavior and properties of linear low-density polyethylene (LLDPE) samples with similar density, molecular weight, and branching degree but varying SCB distributions. The results show that LLDPE with butene as the comonomer has a stronger ability to suppress crystallization compared to LLDPE with hexene as the comonomer due to its more uniform SCB distribution. Additionally, among LLDPEs with comonomers of octene, hexene, and butene, the LLDPE with the most uniform SCB distribution exhibits the weakest crystallization ability. Small-angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) results indicate that LLDPE with more uniform distribution of SCB has smaller long-period and more regular lamellar structure. Therefore, LLDPE with more uniform SCB distribution exhibits weaker inhibition ability towards crystallization, leading to less agglomerated phases and weaker phase separation, resulting in higher tear strength.

Asymmetric fluctuation of overlapping dinucleosome studied by cryoelectron microscopy and small-angle X-ray scattering.

Nucleosome remodelers modify the local structure of chromatin to release the region from nucleosome-mediated transcriptional suppression. Overlapping dinucleosomes (OLDNs) are nucleoprotein complexes formed around transcription start sites as a result of remodeling, and they consist of two nucleosome moieties: a histone octamer wrapped by DNA (octasome) and a histone hexamer wrapped by DNA (hexasome). While OLDN formation alters chromatin accessibility to proteins, the structural mechanism behind this process is poorly understood. Thus, this study investigated the characteristics of structural fluctuations in OLDNs. First, multiple structures of the OLDN were visualized through cryoelectron microscopy (cryoEM), providing an overview of the tilting motion of the hexasome relative to the octasome at the near-atomistic resolution. Second, small-angle X-ray scattering (SAXS) revealed the presence of OLDN conformations with a larger radius of gyration than cryoEM structures. A more complete description of OLDN fluctuation was proposed by SAXS-based ensemble modeling, which included possible transient structures. The ensemble model supported the tilting motion of the OLDN outlined by the cryoEM models, further suggesting the presence of more diverse conformations. The amplitude of the relative tilting motion of the hexasome was larger, and the nanoscale fluctuation in distance between the octasome and hexasome was also proposed. The cryoEM models were found to be mapped in the energetically stable region of the conformational distribution of the ensemble. Exhaustive complex modeling using all conformations that appeared in the structural ensemble suggested that conformational and motional asymmetries of the OLDN result in asymmetries in the accessibility of OLDN-binding proteins.

Solvent Choice during Flow Assembly of Photocross-Linked Single-Chain Nanoparticles and Micelles Affects Cellular Uptake.

Polymeric micelles have widely been used as drug delivery carriers, and recently, single-chain nanoparticles (SCNPs) emerged as potential, smaller-sized, alternatives. In this work, we are comparing both NPs side by side and evaluate their ability to be internalized by breast cancer cells (MCF-7) and macrophages (RAW 264.7). To be able to generate these NPs on demand, the polymers were assembled by flow, followed by the stabilization of the structures by photocross-linking using blue light. The central aim of this work is to evaluate how the type of solvent affects self-assembly and ultimately the structure of the final NP. Therefore, a library of copolymers with different sequences, including block copolymers (AB, ABA, BAB), and statistical copolymers (rAB and rAC) was synthesized using PET-RAFT with A denoting poly(ethylene glycol) methyl ether acrylate (PEGMEA), B as 2-hydroxyethyl acrylate (HEA), and C as 4-hydroxybutyl acrylate (HBA). The polymers were conjugated with a quinoline derivative to enable the formation of cross-linked structures by photocross-linking during flow assembly. Using water as the dispersant for photocross-linking led to the preassembly of these amphiphilic polymers into compact SCNPs and cross-linked micelles, resulting in a quick photoreaction. In contrast, acetonitrile led to fully dissolved polymers but a low rate of the photoreaction. These intramolecularly cross-linked polymers were then placed in water to result in more dynamic micelles and looser SCNPs. Small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), and size exclusion chromatography (SEC) coupled with a viscosity detector show that cross-linking in acetonitrile results in better-defined NPs with a shell rich in PEGMEA. Cross-linking in acetonitrile led to NPs with significantly higher cellular uptake. Interestingly, passive transport was identified as the main pathway for the delivery of our NPs on MCF-7 cells, confirmed by the uptake of NPs on cells treated with inhibitors and by red blood cells. This work underscored the importance of the polymer precursor's structure and the choice of solvent during intramolecular cross-linking in determining the drug delivery efficiency and biological behavior of SCNPs.

Morphological Characterization and Molecular Dynamics Investigation of In-Situ Silica Nanoparticle-Reinforced Poly(Dimethylsiloxane) as a New Approach to Fouling-Release Coatings

To explore a better understanding of the features of poly(dimethylsiloxane) (PDMS)/silica nanocomposites as fouling-release coatings, a series of PDMS networks filled with silica nanoparticles synthesized in-situ was investigated using small angle x-ray scattering (SAXS) and dynamical mechanical analysis (DMA). Three hydroxyl-terminated (HT) PDMS with different molecular weights, 18,000, 49,000, and 79,000 g/mole, were considered for preparing the nanocomposites at the various weight ratios: 1, 3, and 5:1 of HT-PDMS to tetraethyl orthosilicate (TEOS) as a precursor to the in-situ formation of the nano-silica particles. Two different TEOS were used regarding their degree of polymerization: monomeric type (n∼1) and oligomeric type (n∼5). The small-scale structure of the silica domains was examined using SAXS while scanning electron microscopy (SEM) was used to investigate the large-scale structures of the silica domains. The SAXS data showed a bicontinuous array of aggregates. In addition, the glass transition and molecular dynamics in the nanocomposites were investigated using DMA. The sample including 20 wt% silica, exhibited two tan δ peaks. One was related to the usual polymer glass transition, while the other, occurring at a higher temperature, was attributed to the glass transitions associated with polymer chains in proximity to silica domains. The mobility of these polymer chains was diminished due to their interactions with the surface of the silica particles. This result demonstrated the existence of two types of physical and chemical interactions between the silica aggregates and PDMS chains.

Molecular dynamics and small-angle x-ray scattering: a comparison computational and experimental approaches to studying the structure of biological complexes

The results of studying DNA-protein complexes using two independent structural methods – molecular dynamics (MD) and small-angle X-ray scattering (SAXS) – are compared. MD is a computational method that allows visualization of macromolecule behavior in real environmental conditions based on the laws of physics but suffers from numerous simplifications. SAXS is an X-ray method that allows the reconstruction of the three-dimensional structure of an object in solution based on the one-dimensional profile of small-angle scattering, which presents the problem of ambiguity in solving inverse problems. The use of structural characteristics of complexes obtained by the SAXS method for validating 3D structural models obtained in MD experiments has significantly reduced the ambivalence of theoretical predictions and demonstrated the effectiveness of combining MD and SAXS methods for solving structural biology problems.

Near-Infinite-Chain Polymers with Ge=Ge Double Bonds.

Despite considerable interest in heteroatom-containing conjugated polymers, there are only few examples with heavier p-block elements in the conjugation path. The recently reported heavier acyclic diene metathesis (HADMET) allowed for the synthesis of a polymer containing Ge=Ge double bonds - albeit insoluble and with limited degree of polymerization. By incorporation of long alkyl chains, we now obtained soluble representatives, which exhibit degrees of polymerization near infinity according to diffusion-ordered NMR spectroscopy (DOSY) and dynamic light scattering (DLS). Analyses of the UV/Vis absorption and the NMR spectroscopic data confirm the presence of σ,π-conjugation across the silylene-phenylene linkers between the Ge=Ge double bonds. Favorable intermolecular dispersion interactions lead to ladder-like cylindrical supramolecular assemblies as confirmed by X-ray diffraction (XRD), small angle X-ray scattering (SAXS) and DLS. AFM and TEM images of deposited thin films reveal lamellar ordering of extended polymer bundles.