Unraveling Eumelanin Radical Formation by Nanodiamond Optical Relaxometry in a Living Cell.

Defect centers in a nanodiamond (ND) allow the detection of tiny magnetic fields in their direct surroundings, rendering them as an emerging tool for nanoscale sensing applications. Eumelanin, an abundant pigment, plays an important role in biology and material science. Here, for the first time, we evaluate the comproportionation reaction in eumelanin by detecting and quantifying semiquinone radicals through the nitrogen-vacancy color center. A thin layer of eumelanin is polymerized on the surface of nanodiamonds (NDs), and depending on the environmental conditions, such as the local pH value, near-infrared, and ultraviolet light irradiation, the radicals form and react in situ. By combining experiments and theoretical simulations, we quantify the local number and kinetics of free radicals in the eumelanin layer. Next, the ND sensor enters the cells via endosomal vesicles. We quantify the number of radicals formed within the eumelanin layer in these acidic compartments by applying optical relaxometry measurements. In the future, we believe that the ND quantum sensor could provide valuable insights into the chemistry of eumelanin, which could contribute to the understanding and treatment of eumelanin- and melanin-related diseases.

Self-Assembled Supported Ionic Liquids.

Separation and reuse of the catalytically active metal complexes are persistent issues in homogeneous catalysis. Supported Ionic Liquid Phase (SILP) catalysts, where the catalytic center is dissolved in a thin film of a stable ionic liquid, deposited on a solid support, present a promising alternative. However, the dissolution of the metal center in the film leaves little control over its position and its activity. We present here four novel, task-specific ionic liquids [FPhn ImH R]I (n=1, 2; R=PEG2 , C12 H25 ), designed to self-assemble on a silica surface without any covalent bonding and offering a metal binding site in a controlled distance to the support. Advanced multinuclear solid-state NMR spectroscopic techniques under Magic Angle Spinning, complemented by molecular dynamics (MD) simulations, allow us to determine their molecular conformation when deposited inside SBA-15 as a model silica support. We provide here conceptual proof for a rational design of ionic liquids self-assembling into thin films, opening an avenue for a second, improved generation of SILP catalysts.

Denoising diffusion-based MRI to CT image translation enables automated spinal segmentation.

BACKGROUND: Automated segmentation of spinal magnetic resonance imaging (MRI) plays a vital role both scientifically and clinically. However, accurately delineating posterior spine structures is challenging. METHODS: This retrospective study, approved by the ethical committee, involved translating T1-weighted and T2-weighted images into computed tomography (CT) images in a total of 263 pairs of CT/MR series. Landmark-based registration was performed to align image pairs. We compared two-dimensional (2D) paired - Pix2Pix, denoising diffusion implicit models (DDIM) image mode, DDIM noise mode - and unpaired (SynDiff, contrastive unpaired translation) image-to-image translation using "peak signal-to-noise ratio" as quality measure. A publicly available segmentation network segmented the synthesized CT datasets, and Dice similarity coefficients (DSC) were evaluated on in-house test sets and the "MRSpineSeg Challenge" volumes. The 2D findings were extended to three-dimensional (3D) Pix2Pix and DDIM. RESULTS: 2D paired methods and SynDiff exhibited similar translation performance and DCS on paired data. DDIM image mode achieved the highest image quality. SynDiff, Pix2Pix, and DDIM image mode demonstrated similar DSC (0.77). For craniocaudal axis rotations, at least two landmarks per vertebra were required for registration. The 3D translation outperformed the 2D approach, resulting in improved DSC (0.80) and anatomically accurate segmentations with higher spatial resolution than that of the original MRI series. CONCLUSIONS: Two landmarks per vertebra registration enabled paired image-to-image translation from MRI to CT and outperformed all unpaired approaches. The 3D techniques provided anatomically correct segmentations, avoiding underprediction of small structures like the spinous process. RELEVANCE STATEMENT: This study addresses the unresolved issue of translating spinal MRI to CT, making CT-based tools usable for MRI data. It generates whole spine segmentation, previously unavailable in MRI, a prerequisite for biomechanical modeling and feature extraction for clinical applications. KEY POINTS: • Unpaired image translation lacks in converting spine MRI to CT effectively. • Paired translation needs registration with two landmarks per vertebra at least. • Paired image-to-image enables segmentation transfer to other domains. • 3D translation enables super resolution from MRI to CT. • 3D translation prevents underprediction of small structures.

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility.

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives (1 and 2) as subunits of 8-AGNR, with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR. The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm2  V-1 s-1 for the 8-AGNR.

Elimination of charge-carrier trapping by molecular design.

A common obstacle of many organic semiconductors is that they show highly unipolar charge transport. This unipolarity is caused by trapping of either electrons or holes by extrinsic impurities, such as water or oxygen. For devices that benefit from balanced transport, such as organic light-emitting diodes, organic solar cells and organic ambipolar transistors, the energy levels of the organic semiconductors are ideally situated within an energetic window with a width of 2.5 eV where charge trapping is strongly suppressed. However, for semiconductors with a band gap larger than this window, as used in blue-emitting organic light-emitting diodes, the removal or disabling of charge traps poses a longstanding challenge. Here we demonstrate a molecular strategy where the highest occupied molecular orbital and lowest unoccupied molecular orbital are spatially separated on different parts of the molecules. By tuning their stacking by modification of the chemical structure, the lowest unoccupied molecular orbitals can be spatially protected from impurities that cause electron trapping, increasing the electron current by orders of magnitude. In this way, the trap-free window can be substantially broadened, opening a path towards large band gap organic semiconductors with balanced and trap-free transport.

Saturated Linkers in Two-Dimensional Covalent Organic Frameworks Boost Their Luminescence.

The development of highly luminescent two-dimensional covalent organic frameworks (COFs) for sensing applications remains challenging. To suppress commonly observed photoluminescence quenching of COFs, we propose a strategy involving interrupting the intralayer conjugation and interlayer interactions using cyclohexane as the linker unit. By variation of the building block structures, imine-bonded COFs with various topologies and porosities are obtained. Experimental and theoretical analyses of these COFs disclose high crystallinity and large interlayer distances, demonstrating enhanced emission with record-high photoluminescence quantum yields of up to 57% in the solid state. The resulting cyclohexane-linked COF also exhibits excellent sensing performance for the trace recognition of Fe3+ ions, explosive and toxic picric acid, and phenyl glyoxylic acid as metabolites. These findings inspire a facile and general strategy to develop highly emissive imine-bonded COFs for detecting various molecules.

Attention-based Saliency Maps Improve Interpretability of Pneumothorax Classification.

Purpose: To investigate the chest radiograph classification performance of vision transformers (ViTs) and interpretability of attention-based saliency maps, using the example of pneumothorax classification. Materials and Methods: In this retrospective study, ViTs were fine-tuned for lung disease classification using four public datasets: CheXpert, Chest X-Ray 14, MIMIC CXR, and VinBigData. Saliency maps were generated using transformer multimodal explainability and gradient-weighted class activation mapping (GradCAM). Classification performance was evaluated on the Chest X-Ray 14, VinBigData, and Society for Imaging Informatics in Medicine-American College of Radiology (SIIM-ACR) Pneumothorax Segmentation datasets using the area under the receiver operating characteristic curve (AUC) analysis and compared with convolutional neural networks (CNNs). The explainability methods were evaluated with positive and negative perturbation, sensitivity-n, effective heat ratio, intra-architecture repeatability, and interarchitecture reproducibility. In the user study, three radiologists classified 160 chest radiographs with and without saliency maps for pneumothorax and rated their usefulness. Results: ViTs had comparable chest radiograph classification AUCs compared with state-of-the-art CNNs: 0.95 (95% CI: 0.94, 0.95) versus 0.83 (95%, CI 0.83, 0.84) on Chest X-Ray 14, 0.84 (95% CI: 0.77, 0.91) versus 0.83 (95% CI: 0.76, 0.90) on VinBigData, and 0.85 (95% CI: 0.85, 0.86) versus 0.87 (95% CI: 0.87, 0.88) on SIIM-ACR. Both saliency map methods unveiled a strong bias toward pneumothorax tubes in the models. Radiologists found 47% of the attention-based and 39% of the GradCAM saliency maps useful. The attention-based methods outperformed GradCAM on all metrics. Conclusion: ViTs performed similarly to CNNs in chest radiograph classification, and their attention-based saliency maps were more useful to radiologists and outperformed GradCAM.Keywords: Conventional Radiography, Thorax, Diagnosis, Supervised Learning, Convolutional Neural Network (CNN) Online supplemental material is available for this article. © RSNA, 2023.

Modification of Two-Dimensional Tin-Based Perovskites by Pentanoic Acid for Improved Performance of Field-Effect Transistors.

Understanding and controlling the nucleation and crystallization in solution-processed perovskite thin films are critical to achieving high in-plane charge carrier transport in field-effect transistors (FETs). This work demonstrates a simple and effective additive engineering strategy using pentanoic acid (PA). Here, PA is introduced to both modulate the crystallization process and improve the charge carrier transport in 2D 2-thiopheneethylammonium tin iodide ((TEA)2 SnI4 ) perovskite FETs. It is revealed that the carboxylic group of PA is strongly coordinated to the spacer cation TEAI and [SnI6 ]4- framework in the perovskite precursor solution, inducing heterogeneous nucleation and lowering undesired oxidation of Sn2+ during the film formation. These factors contribute to a reduced defect density and improved film morphology, including lower surface roughness and larger grain size, resulting in overall enhanced transistor performance. The reduced defect density and decreased ion migration lead to a higher p-channel charge carrier mobility of 0.7 cm2 V-1 s-1 , which is more than a threefold increase compared with the control device. Temperature-dependent charge transport studies demonstrate a mobility of 2.3 cm2 V-1 s-1 at 100 K due to the diminished ion mobility at low temperatures. This result illustrates that the additive strategy bears great potential to realize high-performance Sn-based perovskite FETs.

Confining the Sol-Gel Reaction at the Water/Oil Interface: Creating Compartmentalized Enzymatic Nano-Organelles for Artificial Cells.

Living organisms compartmentalize their catalytic reactions in membranes for increased efficiency and selectivity. To mimic the organelles of eukaryotic cells, we develop a mild approach for in situ encapsulating enzymes in aqueous-core silica nanocapsules. In order to confine the sol-gel reaction at the water/oil interface of miniemulsion, we introduce an aminosilane to the silica precursors, which serves as both catalyst and an amphiphilic anchor that electrostatically assembles with negatively charged hydrolyzed alkoxysilanes at the interface. The semi-permeable shell protects enzymes from proteolytic attack, and allows the transport of reactants and products. The enzyme-carrying nanocapsules, as synthetic nano-organelles, are able to perform cascade reactions when enveloped in a polymer vesicle, mimicking the hierarchically compartmentalized reactions in eukaryotic cells. This in situ encapsulation approach provides a versatile platform for the delivery of biomacromolecules.

Hydration, Refinement, and Dissolution of the Crystalline Phase in Polyamide 6 Polymorphs for Ultimate Thermomechanical Properties.

Timescales of polyamide 6 melt-shaping technologies, relative to the dynamics of conformational rearrangements upon crystallization, challenge the formation of the most thermodynamically favorable chain packing and thus optimum performance. In this publication, we make use of the mediation of hydrogen bonding by water molecules in the superheated state of water, i.e., above 100 °C in a closed environment, in the structural refinement of polyamide 6 for enhanced thermomechanical performance. The paper addresses dissolution and (re)crystallization of different polyamide 6 polymorphs in the superheated state of water by time-resolved simultaneous small- and wide-angle X-ray scattering and solid-state 1H NMR spectroscopy and the effect on mechanical properties. The experiments reveal that upon heating in the superheated state of water, the pseudo-hexagonal phase dissolves at relatively low temperature and instantly crystallizes in a defected monoclinic phase that successively refines to a perfected monoclinic structure. The dissolution temperature of the pseudo-hexagonal phase of polyamide 6 is found to be dependent on the degree of crystal perfection originating from conformational disorder and misalignment of hydrogen bonding in the lattice, retrospectively, to the Brill transition temperature. The perfected monoclinic phase below the dissolution temperature can be preserved upon cooling but is plasticized by hydration of the amide moieties in the crystalline phase. The removal of water from the hydrated crystals, in the proximity of Brill transition temperature, strengthening the hydrogen bonding, occurs. Retrospectively, the most thermodynamically stable crystallographic phase is preserved and renders an increase in mechanical properties and dimensional stability of the product. The insight obtained on the influence of superheated water on the structural refinement of imperfected crystallographic states assists in polyamide 6 postprocessing strategies for enhanced performance.

Unexpected Role of Short Chains in Entangled Polymer Networks.

The knowledge of chain entanglement is key to our understanding of the relation between the viscoelastic properties of polymeric material and their microscopic structure and dynamics. This work conducted a detailed study on the role of short chains in the entangled polymer network. A series of poly(ethylene oxide) (PEO) mixtures with bimodal molecular weight distribution were selected for this study. 1H double-quantum (DQ) NMR combined with the rheology measurement was used to investigate the entangled polymer network. We found that short-chain polymers have the potential to significantly alter the entangled polymer network formed by long-chain polymers. Additionally, both the amount of chain ends and the size of the short-chain polymer were found to have clear disentanglement influences on the entangled polymer network. Moreover, adding low molecular weight PEO to the entangle framework formed by the high molecular weight PEO, resulted in the formation of inhomogeneous entangled polymer networks. The effect of low molecular weight polymers on the entangled polymer networks in PEO melts provides a perspective on the molecular level effect of molecular weight distribution (MWD) on entanglement polymer networks.

Association mapping of autumn-seeded rye (Secale cereale L.) reveals genetic linkages between genes controlling winter hardiness and plant development.

Winter field survival (WFS) in autumn-seeded winter cereals is a complex trait associated with low temperature tolerance (LTT), prostrate growth habit (PGH), and final leaf number (FLN). WFS and the three sub-traits were analyzed by a genome-wide association study of 96 rye (Secale cereal L.) genotypes of different origins and winter-hardiness levels. A total of 10,244 single nucleotide polymorphism (SNP) markers were identified by genotyping by sequencing and 259 marker-trait-associations (MTAs; p < 0.01) were revealed by association mapping. The ten most significant SNPs (p < 1.49e-04) associated with WFS corresponded to nine strong candidate genes: Inducer of CBF Expression 1 (ICE1), Cold-regulated 413-Plasma Membrane Protein 1 (COR413-PM1), Ice Recrystallization Inhibition Protein 1 (IRIP1), Jasmonate-resistant 1 (JAR1), BIPP2C1-like protein phosphatase, Chloroplast Unusual Positioning Protein-1 (CHUP1), FRIGIDA-like 4 (FRL4-like) protein, Chalcone Synthase 2 (CHS2), and Phenylalanine Ammonia-lyase 8 (PAL8). Seven of the candidate genes were also significant for one or several of the sub-traits supporting the hypothesis that WFS, LTT, FLN, and PGH are genetically interlinked. The winter-hardy rye genotypes generally carried additional allele variants for the strong candidate genes, which suggested allele diversity was a major contributor to cold acclimation efficiency and consistent high WFS under varying field conditions.

Temperature-Responsive Nanoparticles Enable Specific Binding of Apolipoproteins from Human Plasma.

Apolipoproteins are an important class of proteins because they provide a so-called stealth effect to nanoparticles. The stealth effect on nanocarriers leads to a reduced unspecific uptake into immune cells and thereby to a prolonged blood circulation time. Herein, a novel strategy to bind apolipoproteins specifically on nanoparticles by adjusting the temperature during their incubation in human plasma is presented. This specific binding, in turn, allows a control of the stealth behavior of the nanoparticles. Nanoparticles with a well-defined poly(N-isopropylacrylamide) shell are prepared, displaying a reversible change of hydrophobicity at a temperature around 32 °C. It is shown by label-free quantitative liquid chromatography-mass spectrometry that the nanoparticles are largely enriched with apolipoprotein J (clusterin) at 25 °C while they are enriched with apolipoprotein A1 and apolipoprotein E at 37 °C. The temperature-dependent protein binding is found to significantly influence the uptake of the nanoparticles by RAW264.7 and HeLa cells. The findings imply that the functionalization of nanoparticles with temperature-responsive materials is a suitable method for imparting stealth properties to nanocarriers for drug-delivery.

A Nanographene-Based Two-Dimensional Covalent Organic Framework as a Stable and Efficient Photocatalyst.

Synthesis of covalent organic frameworks (COFs) with desirable organic units furnishes advanced materials with unique functionalities. As an emerging class of two-dimensional (2D) COFs, sp2 -carbon-conjugated COFs provide a facile platform to build highly stable and crystalline porous polymers. Herein, a 2D olefin-linked COF was prepared by employing nanographene, namely, dibenzo[hi,st]ovalene (DBOV), as a building block. The DBOV-COF exhibits unique ABC-stacked lattices, enhanced stability, and charge-carrier mobility of ≈0.6 cm2 V-1 s-1 inferred from ultrafast terahertz photoconductivity measurements. The ABC-stacking structure was revealed by the high-resolution transmission electron microscopy and powder X-ray diffraction. DBOV-COF demonstrated remarkable photocatalytic activity in hydroxylation, which was attributed to the exposure of narrow-energy-gap DBOV cores in the COF pores, in conjunction with efficient charge transport following light absorption.

Mapping pre-harvest sprouting resistance loci in AAC Innova × AAC Tenacious spring wheat population.

BACKGROUND: Pre-harvest sprouting (PHS) is a major problem for wheat production due to its direct detrimental effects on wheat yield, end-use quality and seed viability. Annually, PHS is estimated to cause > 1.0 billion USD in losses worldwide. Therefore, identifying PHS resistance quantitative trait loci (QTLs) is crucial to aid molecular breeding efforts to minimize losses. Thus, a doubled haploid mapping population derived from a cross between white-grained PHS susceptible cv AAC Innova and red-grained resistant cv AAC Tenacious was screened for PHS resistance in four environments and utilized for QTL mapping. RESULTS: Twenty-one PHS resistance QTLs, including seven major loci (on chromosomes 1A, 2B, 3A, 3B, 3D, and 7D), each explaining ≥10% phenotypic variation for PHS resistance, were identified. In every environment, at least one major QTL was identified. PHS resistance at most of these loci was contributed by AAC Tenacious except at two loci on chromosomes 3D and 7D where it was contributed by AAC Innova. Thirteen of the total twenty-one identified loci were located to chromosome positions where at least one QTL have been previously identified in other wheat genotype(s). The remaining eight QTLs are new which have been identified for the first time in this study. Pedigree analysis traced several known donors of PHS resistance in AAC Tenacious genealogy. Comparative analyses of the genetic intervals of identified QTLs with that of already identified and cloned PHS resistance gene intervals using IWGSC RefSeq v2.0 identified MFT-A1b (in QTL interval QPhs.lrdc-3A.1) and AGO802A (in QTL interval QPhs.lrdc-3A.2) on chromosome 3A, MFT-3B-1 (in QTL interval QPhs.lrdc-3B.1) on chromosome 3B, and AGO802D, HUB1, TaVp1-D1 (in QTL interval QPhs.lrdc-3D.1) and TaMyb10-D1 (in QTL interval QPhs.lrdc-3D.2) on chromosome 3D. These candidate genes are involved in embryo- and seed coat-imposed dormancy as well as in epigenetic control of dormancy. CONCLUSIONS: Our results revealed the complex PHS resistance genetics of AAC Tenacious and AAC Innova. AAC Tenacious possesses a great reservoir of important PHS resistance QTLs/genes supposed to be derived from different resources. The tracing of pedigrees of AAC Tenacious and other sources complements the validation of QTL analysis results. Finally, comparing our results with previous PHS studies in wheat, we have confirmed the position of several major PHS resistance QTLs and candidate genes.

The Relationships between Plant Developmental Traits and Winter Field Survival in Rye (Secale cereale L.).

Overwintering cereals accumulate low temperature tolerance (LTT) during cold acclimation in the autumn. Simultaneously, the plants adjust to the colder season by making developmental changes at the shoot apical meristem. These processes lead to higher winter hardiness in winter rye varieties (Secale cereale L.) adapted to Northern latitudes as compared to other cereal crops. To dissect the winter-hardiness trait in rye, a panel of 96 genotypes of different origins and growth habits was assessed for winter field survival (WFS), LTT, and six developmental traits. Best Linear Unbiased Estimates for WFS determined from five field trials correlated strongly with LTT (r = 0.90, p < 0.001); thus, cold acclimation efficiency was the major contributor to WFS. WFS also correlated strongly (p < 0.001) with final leaf number (r = 0.80), prostrate growth habit (r = 0.61), plant height (r = 0.34), but showed weaker associations with top internode length (r = 0.30, p < 0.01) and days to anthesis (r = 0.25, p < 0.05). The heritability estimates (h2) for WFS-associated traits ranged from 0.45 (prostrate growth habit) to 0.81 (final leaf number) and were overall higher than for WFS (h2 = 0.48). All developmental traits associated with WFS and LTT are postulated to be regulated by phytohormone levels at shoot apical meristem.

Effect of different derivatives of paraffin waxes on crystallization of eutectic mixture of cocoa butter-coconut oil.

Paraffin wax is a mixture of numerous unbranched hydrocarbons used frequently for various purposes: to improve the shelf life of products containing lipid system and develop more shiny products. However, because of its complex nature, the effect of such molecular structure on the solid phase behavior of lipids is hardly unstated. Hence in our study, we focus on understanding the impact of derivatives of paraffin wax on the lipid system. In the current work, three unbranched derivatives of paraffin wax: Eicosane C (20), Pentacosane C (25) and Triacontane C (30) were selected as additives. These n-alkanes are specifically added to the eutectic mixture of cocoa butter (CB) and coconut oil (CO) (ECB-CO) to observe the effect on thermal, morphological, rheological properties and crystallization kinetics with respect to the carbon chain length. Results from our study illustrate that melting and crystallization temperature, storage modulus and solid fat content (SFC) increases after the addition of 1 wt% of C (20), C (25). In contrast, there is a phase separation for 1 wt% C (30). Further similar study with addition of n-alkanes to pure CB and CO reveals that the interaction of n-alkanes with ECB-CO is dominated by the interaction of n-alkanes with CO instead of CB. Therefore, our findings provide insight into the effect of addition of n-alkanes having different carbon chain length and their respective concentration on crystallization process of CB and CO. This will definitely help to design the processes for products containing such model systems.

Evaluation of Genomic Prediction for Fusarium Head Blight Resistance with a Multi-Parental Population.

Fusarium head blight (FHB) resistance is quantitatively inherited, controlled by multiple minor effect genes, and highly affected by the interaction of genotype and environment. This makes genomic selection (GS) that uses genome-wide molecular marker data to predict the genetic breeding value as a promising approach to select superior lines with better resistance. However, various factors can affect accuracies of GS and better understanding how these factors affect GS accuracies could ensure the success of applying GS to improve FHB resistance in wheat. In this study, we performed a comprehensive evaluation of factors that affect GS accuracies with a multi-parental population designed for FHB resistance. We found larger sample sizes could get better accuracies. Training population designed by CDmean based optimization algorithms significantly increased accuracies than random sampling approach, while mean of predictor error variance (PEVmean) had the poorest performance. Different genomic selection models performed similarly for accuracies. Including prior known large effect quantitative trait loci (QTL) as fixed effect into the GS model considerably improved the predictability. Multi-traits models had almost no effects, while the multi-environment model outperformed the single environment model for prediction across different environments. By comparing within and across family prediction, better accuracies were obtained with the training population more closely related to the testing population. However, achieving good accuracies for GS prediction across populations is still a challenging issue for GS application.

Dynamic heterogeneity in homogeneous polymer melts.

Chain entanglement behaviors were studied by 1H Hahn echo nuclear magnetic resonance (NMR) and 1H double-quantum (DQ) NMR experiments. Poly(ethylene oxide) (PEO) was chosen to investigate the chain entanglement behaviors. The 1H Hahn echo NMR results demonstrate that the critical molecular weight of PEO is approximately 6 kg mol-1. Above this critical molecular weight, chain entanglements start to occur in the melts resulting in anisotropic motions of polymer chain. The 1H DQ NMR observations establish that PEO melts with molecular weights above the critical value exhibit dynamical entanglements. The entangled networks, formed by PEO with a molecular weight of 480 kg mol-1 (PEO480), present slow mobility and rather homogeneously distributed chain entanglements, while the entangled networks, formed by PEO with a molecular weight of 255 kg mol-1 (PEO255), present fast mobility and obvious dynamic heterogeneity in the distribution of chain entanglement. Short chain PEOs like that with a molecular weight of 2 kg mol-1 are demonstrated to function like solvents when being added in an appropriate concentration to PEO480, and the dilution effect increases the chain mobility of PEO480. Moreover, properly diluted PEO480 networks exhibit dynamic heterogeneity similar to that observed in PEO255.

Molecular Mobility in Oriented and Unoriented Membranes Based on Poly[2-(Aziridin-1-yl)ethanol].

Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of the benzyloxy substituent, the dendritic liquid crystalline group and the clearing transition. The orientation of the mesogenic chain somewhat hindered this molecular motion, especially in the full substituted PAZE. The fragility, free volume and thermal expansion coefficients of these membranes near the glass transition are related to the orientation and the addition of the dendritic groups. PAZE-based membranes combine both order and mobility on a supramolecular and macroscopic level, controlled by the dendritic group and the thermal orientation, and open the possibility of preparing membranes with proper channel mobility that promotes selective ionic transport.