Ab initio simulations of the degradation of biodegradable batteries

Transient implantable medical bionics (TIMBs), such as biodegradable batteries that disappear after their operation are gaining attention. They potentially facilitate the deployment of novel instructive biomaterials for regenerative medicine. Implantable, biodegradable and biocompatible batteries may be capable of satisfying the power requirements of some biomedical devices before harmlessly degrading. One material of particular interest for the construction of biodegradable batteries is Bombyx Mori silk. Lancaster University is developing a biodegradable battery that will utilise silk both in the electrolyte and to encase the battery. Using the silk offers the battery a degree of protection that enables the device to operate for several days before it harmlessly degrades. Key to tuning the lifetime of the battery is understanding how the structure of the silk changes under different operating conditions and how this changes the diffusivity of the cations (i.e. Mg2+) and other species such as choline nitrate used as the ionic liquid in the electrolyte. This project will aim to further this understanding through the use of quantum mechanical methods. This project quantifies the behaviour of various molecules in the presence of SF, including water, choline and Mg ions. This helps to see how the biocompatible and biodegradable batteries will behave when made from SF. This is completed via DFT simulation as to perform the experiment is unfeasible. For example, the diffusion pathway of water can not be experimentally generated. Furthermore this project has generated ramachandran plots via DFT for silk fibroin which have not been carried out on this material previously. This allows for a detailed comparison with classical mechanical data. This understanding will allow for further work to elucidate and exploit the properties of SF. Further understanding will allow for fine-tuning of how long the SF biodegradable battery will take to break down; this can be changed for the required use. This will help to understand the ions contribution to the effect on the decay rate of the electrode

Atomistic Simulation of Water Incorporation and Mobility in Bombyx mori Silk Fibroin

Bombyx mori silk fibroin (SF) is a biopolymer that can be processed into materials with attractive properties (e.g., biocompatibility and degradability) for use in a multitude of technical and medical applications (including textiles, sutures, drug delivery devices, tissue scaffolds, etc.). Utilizing the information from experimental and computational SF studies, a simplified SF model has been produced (alanine–glycine [Ala–Gly]n crystal structure), enabling the application of both molecular dynamic and density functional theory techniques to offer a unique insight into SF-based materials. The secondary structure of the computational model has been evaluated using Ramachandran plots under different environments (e.g., different temperatures and ensembles). In addition, the mean square displacement of water incorporated into the SF model was investigated: the diffusion coefficients, activation energies, most and least favorable positions of water, and trajectory of water diffusion through the SF model are obtained. With further computational study and in combination with experimental data, the behavior/degradation of SF (and similar biomaterials) can be elucidated. Consequently, greater control of the aforementioned technologies may be achieved and positively affect their potential applications

Aeolianite and barrier dune construction spanning the last two glacial-interglacial cycles from the southern Cape coast, South Africa

The southern Cape region of South Africa has extensive coastal aeolianites and barrier dunes. Whilst previously reported, limited knowledge of their age has precluded an understanding of their relationship with the climatic and sea-level fluctuations that have taken place during the Late Quaternary. Sedimentological and geomorphological studies combined with an optical dating programme reveal aeolianite development and barrier dune construction spanning at least the last two glacial–interglacial cycles. Aeolianite deposition has occurred on the southern Cape coast at ca 67–80, 88–90, 104–128, 160–189 and >200 ka before the present. Using this and other published data coupled with a better understanding of Late Quaternary sea-level fluctuations and palaeocoastline configurations, it is concluded that these depositional phases appear to be controlled by interglacial and subsequent interstadial sea-level high stands. These marine transgressions and regressions allowed onshore carbonate-rich sediment movement and subsequent aeolian reworking to occur at similar points in the landscape on a number of occasions. The lack of carbonates in more recent dunes (Oxygen Isotope Stages 1/2 and 4/5) is attributed not to leaching but to changes to carbonate production in the sediment source area caused by increased terrigenous material and/or changes in the balance between the warm Agulhas and nutrient-rich Benguela ocean current

Resolving sub-angstrom ambient motion through reconstruction from vibrational spectra.

Metal/organic-molecule interactions underpin many key chemistries but occur on sub-nm scales where nanoscale visualisation techniques tend to average over heterogeneous distributions. Single molecule imaging techniques at the atomic scale have found it challenging to track chemical behaviour under ambient conditions. Surface-enhanced Raman spectroscopy can optically monitor the vibrations of single molecules but understanding is limited by the complexity of spectra and mismatch between theory and experiment. We demonstrate that spectra from an optically generated metallic adatom near a molecule of interest can be inverted into dynamic sub-Å metal-molecule interactions using a comprehensive model, revealing anomalous diffusion of a single atom. Transient metal-organic coordination bonds chemically perturb molecular functional groups > 10 bonds away. With continuous improvements in computational methods for modelling large and complex molecular systems, this technique will become increasingly applicable to accurately tracking more complex chemistries.We acknowledge financial support from EPSRC grant EP/G060649/1, EP/L027151/1, EP/G037221/1, EP/R013012/1, EPSRC NanoDTC, and EU grant THOR 829067 and ERC starting grant BioNet 757850. B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. We acknowledge use of the Rosalind computing facility at King’s College London. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC 397 (EP/P020194/1)

Synthesis and structure of [CeF4(Me2SO)2]—A rare neutral ligand complex of a lanthanide tetrafluoride

Hydrated cerium(IV) fluoride dissolves in hot dimethylsulfoxide to form yellow [CeF4(Me2SO)2], the X-ray structure of which reveals a chain polymer with eight-coordinate cerium bound to two terminal and four bridging fluorines and two O-bonded Me2SO molecules. The complex was also characterised by IR, 1H and 19F{1H} NMR and UV/visible spectroscopies. Attempts to use [CeF4(Me2SO)2] as a synthon to prepare other complexes with phosphine oxides or 2,2?-bipyridyl were unsuccessful. Thorium(IV) fluoride hydrate does not react with boiling dmso.<br/

An object memory bias induced by communicative reference

In humans, a good proportion of knowledge, including knowledge about objects and object kinds, is acquired via social learning by direct communication from others. If communicative signals raise the expectation of social learning about objects, intrinsic (permanent) features that support object recognition are relevant to store into memory, while extrinsic (accidental) object properties can be ignored. We investigated this hypothesis by instructing participants to memorise shape-colour associations that constituted either an extrinsic object property (the colour of the box that contained the object, Experiment 1) or an intrinsic one (the colour of the object, Experiment 2). Compared to a non-communicative context, communicative presentation of the objects impaired participants’ performance when they recalled extrinsic object properties, while their incidental memory of the intrinsic shape-colour associations was not affected. Communicative signals had no effect on performance when the task required the memorisation of intrinsic object properties. The negative effect of communicative reference on the memory of extrinsic properties was also confirmed in Experiment 3, where this property was object location. Such a memory bias suggests that referent objects in communication tend to be seen as representatives of their kind rather than as individuals

Multi-modal representation of effector modality in frontal cortex during rule switching.

We report a functional magnetic resonance imaging (fMRI) study which investigated whether brain areas involved in updating task rules within the frontal lobe of the cerebral cortex show activity related to the modality of motor response used in the task. Participants performed a rule switching task using different effector modalities. In some blocks participants responded with left/right button presses, whilst in other blocks left/right saccades were required. The color of a Cue event instructed a left or right response based upon a rule, followed by a Feedback which indicated whether the rule was to stay the same or "Flip" on the next trial. The findings revealed variation in the locus of activity within the ventrolateral frontal cortex dependent upon effector modality. Other frontal areas showed no significant difference in activity between response epochs but changed their pattern of connectivity with posterior cortical areas dependent upon response. Multivariate analysis revealed that the pattern of activity evoked by Flip rule Feedbacks within an apparently supra modal frontal region (dorsolateral frontal cortex) discriminated between response epochs. The results are consistent with the existence of multi-modal representations of stimulus-response (SR) rules within the frontal cerebral cortex

Lithic technological responses to Late Pleistocene glacial cycling at Pinnacle Point Site 5-6, South Africa

There are multiple hypotheses for human responses to glacial cycling in the Late Pleistocene, including changes in population size, interconnectedness, and mobility. Lithic technological analysis informs us of human responses to environmental change because lithic assemblage characteristics are a reflection of raw material transport, reduction, and discard behaviors that depend on hunter-gatherer social and economic decisions. Pinnacle Point Site 5-6 (PP5-6), Western Cape, South Africa is an ideal locality for examining the influence of glacial cycling on early modern human behaviors because it preserves a long sequence spanning marine isotope stages (MIS) 5, 4, and 3 and is associated with robust records of paleoenvironmental change. The analysis presented here addresses the question, what, if any, lithic assemblage traits at PP5-6 represent changing behavioral responses to the MIS 5-4-3 interglacial-glacial cycle? It statistically evaluates changes in 93 traits with no a priori assumptions about which traits may significantly associate with MIS. In contrast to other studies that claim that there is little relationship between broad-scale patterns of climate change and lithic technology, we identified the following characteristics that are associated with MIS 4: increased use of quartz, increased evidence for outcrop sources of quartzite and silcrete, increased evidence for earlier stages of reduction in silcrete, evidence for increased flaking efficiency in all raw material types, and changes in tool types and function for silcrete. Based on these results, we suggest that foragers responded to MIS 4 glacial environmental conditions at PP5-6 with increased population or group sizes, 'place provisioning', longer and/or more intense site occupations, and decreased residential mobility. Several other traits, including silcrete frequency, do not exhibit an association with MIS. Backed pieces, once they appear in the PP5-6 record during MIS 4, persist through MIS 3. Changing paleoenvironments explain some, but not all temporal technological variability at PP5-6.Social Science and Humanities Research Council of Canada; NORAM; American-Scandinavian Foundation; Fundacao para a Ciencia e Tecnologia [SFRH/BPD/73598/2010]; IGERT [DGE 0801634]; Hyde Family Foundations; Institute of Human Origins; National Science Foundation [BCS-9912465, BCS-0130713, BCS-0524087, BCS-1138073]; John Templeton Foundation to the Institute of Human Origins at Arizona State Universit