Phenyl Selenosulfides as Cathode Materials for Rechargeable Lithium Batteries

The Se? Se bond in an organo‐diselenide (RSeSeR, R is an organic group) can break in a 2e^? reduction reaction, but it has limited capacity as a cathode material for rechargeable lithium‐ion batteries. To increase its capacity, redox active species (e.g., sulfur) can be added in the middle of the selenium atoms. Herein, phenyl diselenide (PDSe, PhSeSePh) is mixed with sulfur to form two hybrid compounds with 1:1 and 1:2 molar ratios, which almost double and triple the capacity of PDSe, respectively. Theoretical calculations suggest that phenyl selenosulfide (PDSe‐S, PhSe‐S‐SePh) and phenyl selenodisulfide (PDSe‐S₂, PhSe‐SS‐SePh) can form via addition reactions, which is supported by mass spectrometry analysis. The hybrid materials exhibit three highly reversible redox plateaus and enhanced cycling stability due to the reduced solubility of the discharge products. PDSe‐S and PDSe‐S₂ show initial capacities of 252 and 330 mAh g^?1, respectively, followed by stable cycling performance with a capacity retention of >73% after 200 cycles at C/5 rate. In addition, they show steady rate capabilities. This study reports a novel strategy to increase the electrochemical performance of organo‐diselenide by addition of sulfur.     

Bimolecular Crystals of Fullerenes in Conjugated Polymers and the Implications of Molecular Mixing for Solar Cells

The performance of polymer:fullerene bulk heterojunction solar cells is heavily influenced by the interpenetrating nanostructure formed by the two semiconductors because the size of the phases, the nature of the interface, and molecular packing affect exciton dissociation, recombination, and charge transport. Here, X‐ray diffraction is used to demonstrate the formation of stable, well‐ordered bimolecular crystals of fullerene intercalated between the side‐chains of the semiconducting polymer poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene. It is shown that fullerene intercalation is general and is likely to occur in blends with both amorphous and semicrystalline polymers when there is enough free volume between the side‐chains to accommodate the fullerene molecule. These findings offer explanations for why luminescence is completely quenched in crystals much larger than exciton diffusion lengths, how the hole mobility of poly(2‐methoxy‐5‐(3′,7′‐dimethyloxy)‐p‐phylene vinylene) increases by over 2 orders of magnitude when blended with fullerene derivatives, and why large‐scale phase separation occurs in some polymer:fullerene blend ratios while thermodynamically stable mixing on the molecular scale occurs for others. Furthermore, it is shown that intercalation of fullerenes between side chains mostly determines the optimum polymer:fullerene blending ratios. These discoveries suggest a method of intentionally designing bimolecular crystals and tuning their properties to create novel materials for photovoltaic and other applications.     

Antimicrobial Gallium‐Doped Phosphate‐Based Glasses

Novel quaternary gallium‐doped phosphate‐based glasses (1, 3, and 5 mol % Ga₂O₃) were synthesized using a conventional melt quenching technique. The bactericidal activities of the glasses were tested against both Gram‐negative (Escherichia coli and Pseudomonas aeruginosa) and Gram‐positive (Staphylococcus aureus, methicillin‐resistant Staphylococcus aureus, and Clostridium difficile) bacteria. Results of the solubility and ion release studies showed that these glass systems are unique for controlled delivery of Ga³⁺. ⁷¹Ga NMR measurements showed that the gallium is mostly octahedrally coordinated by oxygen atoms, whilst FTIR spectroscopy provided evidence for the presence of a small proportion of tetrahedral gallium in the samples with the highest gallium content. FTIR and Raman spectra also afford an insight into the correlation between the structure and the observed dissolution behavior via an understanding of the atomic‐scale network bonding characteristics. The results confirmed that the net bactericidal effect was due to Ga³⁺, and a concentration as low as 1 mol % Ga₂O₃ was sufficient to mount a potent antibacterial effect. The dearth of new antibiotics in development makes Ga³⁺ a potentially promising new therapeutic agent for pathogenic bacteria including MRSA and C. difficile.     

Design of an ultra fast pipelined wavelength scheduler for optical burst switching

Optical Burst Switching (OBS) is an emerging technology that allows variable size data bursts to be transported directly over DWDM links without encountering O/E/O conversion. In OBS, before the transmission of a data burst, a burst header is transmitted through an electronic control path, setting up and tearing down optical paths on-the-fly. Data bursts can remain in the optical domain and pass through the OBS network transparently. Unfortunately, system performance will be greatly degraded, if burst scheduling requests cannot be processed in time. This article quantitatively studied the negative impact of control path overloading on the performance of OBS networks. Results have shown that control path overloading greatly affects the performance of the OBS routers, especially for systems with large WDM channel counts. In order to remove this performance bottleneck, we have designed and implemented an ultra fast pipelined burst scheduler that is able to process a burst request every two clock cycles, regardless of the number of WDM channels per link. The design has been implemented in Verilog HDL and synthesized to FPGAs. Circuit level simulation results confirm the correctness of the design. The circuit has achieved 100 MHz in Altera Cyclone II devices, allowing the scheduler to process a burst request every 20 ns. To the authors’ best knowledge, this is the fastest implementation of burst scheduling algorithms.     

A probabilistic model-based approach to consistent white matter tract segmentation

Since the invention of diffusion magnetic resonance imaging (dMRI), currently the only established method for studying white matter connectivity in a clinical environment, there has been a great deal of interest in the effects of various pathologies on the connectivity of the brain. As methods for in vivo tractography have been developed, it has become possible to track and segment specific white matter structures of interest for particular study. However, the consistency and reproducibility of tractography-based segmentation remain limited, and attempts to improve them have thus far typically involved the imposition of strong constraints on the tract reconstruction process itself. In this work we take a different approach, developing a formal probabilistic model for the relationships between comparable tracts in different scans, and then using it to choose a tract, a posteriori, which best matches a predefined reference tract for the structure of interest. We demonstrate that this method is able to significantly improve segmentation consistency without directly constraining the tractography algorithm.     

Fast quasi-flat zones filtering using area threshold and region merging

Quasi-flat zones are morphological operators which segment the image into homogeneous regions according to certain criteria. They are used as an image simplification tool or an image segmentation pre-processing, but they induced a very important oversegmentation. Several filtering methods have been proposed to deal with this issue but they suffer from different drawbacks, e.g., loss of quality or edge deformation. In this article, we propose a new method based on existing approaches which achieves better or similar results than existing approaches, does not suffer from their drawbacks and requires less computation time. It consists of two successive steps. First, small quasi-flat zones are removed according to a minimal area threshold. They are then filled through the growth of remaining zones.     

Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

The Ferroelectric Field Effect within an Integrated Core/Shell Nanowire

The synthesis of cylindrical silicon‐core and ferroelectric oxide perovskite‐shell nanowires and their response characteristics as individual three‐terminal nanoscale electronic devices is reported. The co‐axial nanowire geometry facilitates large ferroelectric field‐effect modulation (>10⁴) of nanowire conductivity following sequential application and removal of an applied dc field. Source‐drain current–voltage traces collected during sweeps of ferroelectric gate potential and switching of the component of shell outward and inward polarization provide direct evidence of ferroelectric coupling on nanowire channel conductance. Despite a very small (1:20) ferroelectric‐to‐semiconductor channel thickness ratio, an unexpectedly strong electrostatic coupling of ferroelectric polarization to channel conductance is observed because of the co‐axial gate geometry and curvature‐induced strain enhancement of ferroelectric polarization.     

Biodegradable Polyanhydrides as Encapsulation Layers for Transient Electronics

Bioresorbable electronic systems represent an emerging class of technology of interest due to their ability to dissolve, chemically degrade, disintegrate, and/or otherwise physically disappear harmlessly in biological environments, as the basis for temporary implants that avoid the need for secondary surgical extraction procedures. Polyanhydride‐based polymers can serve as hydrophobic encapsulation layers for such systems, as a subset of the broader field of transient electronics, where biodegradation eventually occurs by chain scission. Systematic experimental studies that involve immersion in phosphate‐buffered saline solution at various pH values and/or temperatures demonstrate that dissolution occurs through a surface erosion mechanism, with little swelling. The mechanical properties of this polymer are well suited for use in soft, flexible devices, where integration can occur through a mold‐based photopolymerization technique. Studies of the dependence of the polymer properties on monomer compositions and the rates of permeation on coating thicknesses reveal some of the underlying effects. Simple demonstrations illustrate the ability to sustain operation of underlying biodegradable electronic systems for durations between a few hours to a week during complete immersion in aqueous solutions that approximate physiological conditions. Systematic chemical, physical, and in vivo biological studies in animal models reveal no signs of toxicity or other adverse biological responses.     

Porous Silicon Nanoparticles Embedded in Poly(lactic‐co‐glycolic acid) Nanofiber Scaffolds Deliver Neurotrophic Payloads to Enhance Neuronal Growth

Scaffolds made from biocompatible polymers provide physical cues to direct the extension of neurites and to encourage repair of damaged nerves. The inclusion of neurotrophic payloads in these scaffolds can substantially enhance regrowth and repair processes. However, many promising neurotrophic candidates are excluded from this approach due to incompatibilities with the polymer or with the polymer processing conditions. This work provides one solution to this problem by incorporating porous silicon nanoparticles (pSiNPs) that are preloaded with the therapeutic into a polymer scaffold during fabrication. The nanoparticle‐drug‐polymer hybrids are prepared in the form of oriented poly(lactic‐co‐glycolic acid) nanofiber scaffolds. Three different therapeutic payloads are tested: bpV(HOpic), a small molecule inhibitor of phosphatase and tensin homolog (PTEN); an RNA aptamer specific to tropomyosin‐related kinase receptor type B (TrkB); and the protein nerve growth factor (NGF). Each therapeutic is loaded using a loading chemistry that is optimized to slow the rate of release of these water‐soluble payloads. The drug‐loaded pSiNP‐nanofiber hybrids release approximately half of their TrkB aptamer, bpV(HOpic), or NGF payload in 2, 10, and >40 days, respectively. The nanofiber hybrids increase neurite extension relative to drug‐free control nanofibers in a dorsal root ganglion explant assay.