Nido-Hydroborate-Based Electrolytes for All-Solid-State Lithium Batteries

Hydroborate-based solid electrolytes have recently been successfully employed in high voltage, room temperature all-solid-state sodium batteries. The transfer to analogous lithium systems has failed up to now due to the lower conductivity of the corresponding lithium compounds and their high cost. Here LiB₁₁H₁₄ nido-hydroborate as a cost-effective building block and its high-purity synthesis is introduced. The crystal structures of anhydrous LiB₁₁H₁₄ as well as of LiB₁₁H₁₄-based mixed-anion solid electrolytes are solved and high ionic conductivities of 1.1 × 10⁻⁴ S cm⁻¹ for Li₂(B₁₁H₁₄)(CB₁₁H₁₂) and 1.1 × 10⁻³ S cm⁻¹ for Li₃(B₁₁H₁₄)(CB₉H₁₀)₂ are obtained, respectively. LiB₁₁H₁₄ exhibits an oxidative stability limit of 2.6 V versus Li⁺/Li and the proposed decomposition products are discussed based on density functional theory calculations. Strategies are discussed to improve the stability of these compounds by modifying the chemical structure of the nido-hydroborate cage. Galvanostatic cycling in symmetric cells with two lithium metal electrodes shows a small overpotential increase from 22.5 to 30 mV after 620 h (up to 0.5 mAh cm⁻²), demonstrating that the electrolyte is compatible with metallic anodes. Finally, the Li₂(B₁₁H₁₄)(CB₁₁H₁₂)  electrolyte is employed in a proof-of-concept half cell with a TiS₂ cathode with a capacity retention of 82% after 150 cycles at C/5.     

Knowledge‐Based Conceptual Synthesis of Industrial‐Scale Downstream Processes for Biochemical Products

A generic, knowledge‐based guideline assisting downstream process synthesis for biochemical products is presented. It offers process designers a structured process design methodology supporting them in capturing potentially relevant information, which might be beyond their expertise. The guideline is based on heuristic knowledge which was collected, structured in a generic way, and clearly represented. The generation of alternative downstream routes as starting points for experiments, simulation, and cost calculation is hereby accelerated. The application of the guideline is demonstrated on the example of penicillin V downstream processing from fermentation broth.     

Effects of gamma-sterilization on DOC, uranium and arsenic remobilization from organic and microbial rich stream sediments

Organic-rich sediments are known to be effective accumulators for uranium and arsenic. Much is known about the capacity for metal or metalloid fixation by microbes and organic compounds as well as inorganic sediment particles. Experiments investigating the effect of microbes on the process of metal fixation in sediments require sterilized sediments as control treatment which is often realized by gamma-sterilization. Only few studies show that gamma-sterilization has an effect on the remobilization of metal and metalloids and on their physico-chemical properties. These studies deal with sediments with negligible organic content whereas almost nothing is known about organic-rich sediments including a probably high microbial activity. In view of this, we investigated the effect of gamma-sterilization of organic-rich sediments on uranium and arsenic fixation and release. After ten days within an exposure experiment we found a significant higher remobilization of uranium and arsenic in sterile compared to unsterile treatments. In line with these findings the content of dissolved organic carbon (DOC), manganese, and iron increased to even significantly higher concentration in the sterile compared to unsterile treatment. Gamma-sterilization seems to change the physico-chemical properties of organic-rich sediments. Microbial activity is effectively eliminated. From increased DOC concentrations in overlaying water it is concluded that microbes are eventually killed with leaching of cellular compounds in the overlaying water. This decreases the adsorption capacity of the sediment and leads to enhanced uranium and arsenic remobilization.     

Partikelform und Porosität von biogenen Pyrolysekoksen

Char particles from pyrolyzed biomass vary in particle size and shape. On average, the particles are more elongated the larger their size. The average size‐specific elongation is almost alike for all investigated samples, i.e. independent from their source material and process. The particle collectives cannot be characterized accurately with classical particle size distributions, which assume spherical particle shape. Accounting for their shape, they can be described more accurately with particle size distributions that are based on an ellipsoid model. The high bulk porosity is mainly attributed to the spaces between particles.     

Living Materials Herald a New Era in Soft Robotics

Living beings have an unsurpassed range of ways to manipulate objects and interact with them. They can make autonomous decisions and can heal themselves. So far, a conventional robot cannot mimic this complexity even remotely. Classical robots are often used to help with lifting and gripping and thus to alleviate the effects of menial tasks. Sensors can render robots responsive, and artificial intelligence aims at enabling autonomous responses. Inanimate soft robots are a step in this direction, but it will only be in combination with living systems that full complexity will be achievable. The field of biohybrid soft robotics provides entirely new concepts to address current challenges, for example the ability to self‐heal, enable a soft touch, or to show situational versatility. Therefore, “living materials” are at the heart of this review. Similarly to biological taxonomy, there is a recent effort for taxonomy of biohybrid soft robotics. Here, an expansion is proposed to take into account not only function and origin of biohybrid soft robotic components, but also the materials. This materials taxonomy key demonstrates visually that materials science will drive the development of the field of soft biohybrid robotics.     

Evaluation of polycaprolactone − poly‐D,L‐lactide copolymer as biomaterial for breast tissue engineering

The potential of the copolymer polycaprolactone‐co‐ poly‐d ,l ‐lactic acid (PCLLA ) as a biomaterial for scaffold‐based therapy for breast tissue engineering applications was assessed. First, the synthesized PCLLA was evaluated for its processability by means of additive manufacturing (AM ). We found that the synthesized PCLLA could be fabricated into scaffolds with an overall gross morphology and porosity similar to that of polycaprolactone. The PCLLA scaffolds possessed a compressive Young's modulus (ca 46 kPa ) similar to that of native breast (0.5 ? 25 kPa ), but lacked thermal stability and underwent thermal degradation during the fabrication process. The PCLLA scaffolds underwent rapid degradation in vitro which was characterized by loss of the scaffolds' mechanical integrity and a drastic decrease in mass‐average molar mass (M _w) and number‐average molar mass (M _n) after 4 weeks of immersion in phosphate buffer solution maintained at 37 °C. The tin‐catalysed PCLLA scaffold was also found to have cytotoxic effects on cells. Although the initial mechanical properties of the PCLLA scaffolds generally showed potential for applications in breast tissue regeneration, the thermal stability of the copolymer for AM processes, biocompatibility towards cells and degradation rate is not satisfactory at this stage. Therefore, we conclude that research efforts should be geared towards fine‐tuning the copolymer synthesizing methods. © 2016 Society of Chemical Industry     

Characterization of spatial inhomogeneities and dynamic properties of random cross-linked polystyrene networks by dynamic light scattering

The network inhomogeneity and the cooperative motion of the network chains of random cross-linked poly(styrene-co-maleic anhydride) gels were investigated by dynamic light scattering. Measurements were performed for gels in the preparation state as well as in the swelling equilibrium. Network inhomogeneities and cooperative motion were analyzed at varying the cross-linker concentration and the polymer volume fraction. While the cross-linker concentration has only a minor influence on the inhomogeneity and the diffusion constant D_coop, the polymer volume fraction clearly influences both measured properties. The concentration dependence of D_coop can be well described by a power law, as known for semi-dilute polymer solutions. In the preparation state the networks appear homogeneous, exhibiting dynamic contributions to the scattering intensity of 70-90%. Swollen to equilibrium stage, significant heterogeneities emerge, reducing the dynamic contributions to 10-20%.     

Mortality salience and the spreading activation of worldview-relevant constructs: Exploring the cognitive architecture of terror management.

Seven experiments assessed the hypothesis derived from terror management theory that reminding people of their mortality would increase accessibility of constructs central to their worldview. Experiment 1 found that mortality primes, relative to control primes, increased accessibility of nationalistic constructs for men but not for women. Experiment 2 replicated this finding and also found that mortality salience increased romantic accessibility for women but not for men. Four subsequent experiments supported the role of unconscious death-related ideation in producing these effects. A final experiment demonstrated that situational primes can increase the accessibility of nationalistic constructs for women after mortality salience. The roles of situational cues and individual differences in the effects of exposure to death-related stimuli on worldview-relevant construct accessibility are discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)