Crystal-field engineering of ultrabroadband mid-infrared emission in Co2+-doped nano-chalcogenide glass composites

Tunable and ultrabroadband mid-infrared (MIR) emissions in the range of 2.5–4.5 μm are firstly reported from Co²⁺-doped nano-chalcogenide (ChG) glass composites. The composites embedded with a variety of binary (ZnS, CdS, ZnSe) and ternary (ZnCdS, ZnSSe) ChG nanocrystals (NCs) can be readily obtained by a simple one-step thermal annealing method. They are highly transparent in the near- and mid-infrared wavelength region. Low-cost and commercially available Er³⁺-doped fiber lasers can be used as the excitation source. By crystal-field engineering of the embedded NCs through cation- or anion-substitution, the emission properties of Co²⁺ including its emission peak wavelength and bandwidth can be tailored in a broad spectral range. The phenomena can be accounted for by crystal-field theory. Such nano-ChG composites, perfectly filling the 3–4 μm spectral gap between the oscillations of Cr²⁺ and Fe²⁺ doped IIVI ChG crystals, may find important MIR photonic applications (e.g., gas sensing), or can be used directly as an efficient pump source for Fe²⁺: IIVI crystals which are suffering from lack of pump sources.     

Chitosan Microspheres as Carriers for pH‐Indicating Species in Corrosion Sensing

Chitosan microspheres containing bromocresol green, cresol red, and phenolphthalein for corrosion detection, through pH change, are synthesized in order to be used in protective coatings for aluminium alloys. Microspheres containing corrosion detection species are characterized morphologically (SEM) and physico‐chemically (FTIR, TGA). Release studies (UV–vis) are performed in corrosion‐promoting conditions (pH, NaCl), and detection studies by immersion in media associated with corrosion activity while microspheres' sensing activity is evaluated visually. Electrochemical characterization of AA2024 substrates in the presence of chitosan spheres is performed to understand material performance, and a color change is observed as a result of local pH increase in cathodic areas when corrosion takes place. These findings can be correlated with the results from release studies and seem a promising approach for corrosion sensing purposes, not only because pH increase is possible to detect due to corrosion, but also because chitosan is considered an environmentally friendly material.     

Perception‐aware autonomous mast motion planning for planetary exploration rovers

Highly accurate real‐time localization is of fundamental importance for the safety and efficiency of planetary rovers exploring the surface of Mars. Mars rover operations rely on vision‐based systems to avoid hazards as well as plan safe routes. However, vision‐based systems operate on the assumption that sufficient visual texture is visible in the scene. This poses a challenge for vision‐based navigation on Mars where regions lacking visual texture are prevalent. To overcome this, we make use of the ability of the rover to actively steer the visual sensor to improve fault tolerance and maximize the perception performance. This paper answers the question of where and when to look by presenting a method for predicting the sensor trajectory that maximizes the localization performance of the rover. This is accomplished by an online assessment of possible trajectories using synthetic, future camera views created from previous observations of the scene. The proposed trajectories are quantified and chosen based on the expected localization performance. In this study, we validate the proposed method in field experiments at the Jet Propulsion Laboratory (JPL) Mars Yard. Furthermore, multiple performance metrics are identified and evaluated for reducing the overall runtime of the algorithm. We show how actively steering the perception system increases the localization accuracy compared with traditional fixed‐sensor configurations.     

Three‐dimensional color prediction modeling of single‐ and double‐layered woven fabrics

In this research, the three‐dimensional structural and colorimetric modeling of three‐dimensional woven fabrics was conducted for accurate color predictions. One‐hundred forty single‐ and double‐layered woven samples in a wide range of colors were produced. With the consideration of their three‐dimensional structural parameters, three‐dimensional color prediction models, K/S‐, R‐, and L*a*b*‐based models, were developed through the optimization of previous two‐dimensional models which have been reported to be the three most accurate models for single‐layered woven structures. The accuracy of the new three‐dimensional models was evaluated by calculating the color differences ΔL*, ΔC*, Δh°, and ΔE_CMC(2:1) between the measured and the predicted colors of the samples, and then the error values were compared to those of the two‐dimensional models. As a result, there has been an overall improvement in color predictions of all models with a decrease in ΔE_CMC(2:1) from 10.30 to 5.25 units on average after the three‐dimensional modeling.     

A novel bio‐based phthalonitrile resin derived from catechin: synthesis and comparison of curing behavior with petroleum‐based counterpart

The development of bio‐based thermosetting resins with good thermal stability can potentially afford sustainable polymers as replacements for petroleum‐based polymers. We report a practical route to a novel catechin‐based phthalonitrile resin precursor (CA‐Ph), which contains free phenolic hydroxyl groups that result in ‘self‐curing’ at elevated temperatures to afford a thermostable polymer. Comparison of the performance of this CA‐Ph resin with that of a conventional petroleum‐based bisphenol A phthalonitrile resin (BPA‐Ph; containing 5 wt% of the curing agent 4,4′‐diaminodiphenylsulfone) revealed that CA‐Ph exhibits a lower melting point and curing temperature. Cured CA‐Ph resin retains 95% of its weight at 520 °C under a nitrogen atmosphere, which compares favorably with results obtained for BPA‐Ph resin that retains 95% of its weight at a lower temperature of 484 °C. Kinetic results indicated that the curing reactions of both CA‐Ph and BPA‐Ph systems follow an autocatalytic mechanism. These results suggest that catechin is a useful bio‐based feedstock for the preparation of self‐curing and thermally stable phthalonitrile resins for advanced technological applications. © 2017 Society of Chemical Industry     

Interaction of graphene,MnOx, and Ca2+ for enhanced biomimetic, ‘bubble-free’ oxygen evolution reaction at mild pH

Water electrolysis powered by renewable electricity will likely be critical to a future hydrogen economy. However, the typical use of strongly acidic or alkaline electrolytes necessitates the use of expensive materials, while bubbles add to capital and operational costs, due to blocking of the electrode surface and the necessary use of pumps and gas-liquid separators. Here ‘bubble-free’ oxygen evolution at mild pH is carried out using an electrocatalyst that mimics photosystem II (PSII). The bubble-free electrode includes a gas-extracting Gore-Tex® membrane. Edge-functionalised graphene (EFG) is included to mimic the metal-binding local protein environment, and the tyrosine residue, in the oxygen evolving complex (OEC) of PSII, while MnO_x and Ca²⁺ are incorporated to mimic the Mn₄CaO₅ cluster. Interaction between EFG, MnO_x, and Ca²⁺ results in a significant, 130 mV fall in the overpotential required to drive electrocatalytic oxygen evolution at 10 mA cm⁻², compared to the electrode without these biomimetic components.     

Regulation of sensory nerve conduction velocity of human bodies responding to annual temperature variations in natural environments

The extensive research interests in environmental temperature can be linked to human productivity / performance as well as comfort and health; while the mechanisms of physiological indices responding to temperature variations remain incompletely understood. This study adopted a physiological sensory nerve conduction velocity (SCV) as a temperature‐sensitive biomarker to explore the thermoregulatory mechanisms of human responding to annual temperatures. The measurements of subjects’ SCV (over 600 samples) were conducted in a naturally ventilated environment over all four seasons. The results showed a positive correlation between SCV and annual temperatures and a Boltzmann model was adopted to depict the S‐shaped trend of SCV with operative temperatures from 5°C to 40°C. The SCV increased linearly with operative temperatures from 14.28°C to 20.5°C and responded sensitively for 10.19°C‐24.59°C, while tended to be stable beyond that. The subjects’ thermal sensations were linearly related to SCV, elaborating the relation between human physiological regulations and subjective thermal perception variations. The findings reveal the body SCV regulatory characteristics in different operative temperature intervals, thereby giving a deeper insight into human autonomic thermoregulation and benefiting for built environment designs, meantime minimizing the temperature‐invoked risks to human health and well‐being.     

Supramolecular Assembly of Aminoethylene‐Lipopeptide PMO Conjugates into RNA Splice‐Switching Nanomicelles

Phosphorodiamidate morpholino oligomers (PMOs) are oligonucleotide analogs that can be used for therapeutic modulation of pre‐mRNA splicing. Similar to other classes of nucleic acid‐based therapeutics, PMOs require delivery systems for efficient transport to the intracellular target sites. Here, artificial peptides based on the oligo(ethylenamino) acid succinyl‐tetraethylenpentamine (Stp), hydrophobic modifications, and an azide group are presented, which are used for strain‐promoted azide‐alkyne cycloaddition conjugation with splice‐switching PMOs. By systematically varying the lead structure and formulation, it is determined that the type of contained fatty acid and supramolecular assembly have a critical impact on the delivery efficacy. A compound containing linolenic acid with three cis double bonds exhibits the highest splice‐switching activity and significantly increases functional protein expression in pLuc/705 reporter cells in vitro and after local administration in vivo. Structural and mechanistic studies reveal that the lipopeptide PMO conjugates form nanoparticles, which accelerate cellular uptake and that the content of unsaturated fatty acids enhances endosomal escape. In an in vitro Duchenne muscular dystrophy exon skipping model using H2K‐mdx52 dystrophic skeletal myotubes, the highly potent PMO conjugates mediate significant splice‐switching at very low nanomolar concentrations. The presented aminoethylene‐lipopeptides are thus a promising platform for the generation of PMO‐therapeutics with a favorable activity/toxicity profile.