We report the mechanism of the concentration-dependent self-assembly of a tetrapeptide. Peptide Boc-Trp-Leu-Trp-Leu-OMe self-assembles to form discrete nanospheres at a low concentration. Tryptophan side chains point outwards of the nanospheres while leucine side chains point towards the core of the nanospheres. The nanospheres fuse together to become microspheres with the increase in the peptide concentration. At higher concentrations of the peptide, the microspheres start clustering. This is stabilized by the aromatic interactions between the side chains of the tryptophan residues that cover the outer surface of the peptide microspheres. In addition to behaving like the conventional hollow sphere-based drug delivery vehicles which entraps the drug and performs stimuli-responsive release, this prototype can interact, stabilize, and intercalate hydrophobic dye carboxyfluorescein and anti-cancer drug curcumin even on the surface through aromatic interactions. The dye/drug can be released in acidic pH and in the presence of physiologically relevant ions such as potassium.
Although glassy relaxation is typically associated with disorder, here we report on a new type of glassy dynamics relating to dislocations within 2-D crystals of colloidal dimers. Previous studies have demonstrated that dislocation motion in dimer crystals is restricted by certain particle orientations. Here, we drag an optically trapped particle through such dimer crystals, creating dislocations. We find a two-stage relaxation response where initially dislocations glide until encountering particles that cage their motion. Subsequent relaxation occurs logarithmically slowly through a second process where dislocations hop between caged configurations. Finally, in simulations of sheared dimer crystals, the dislocation mean squared displacement displays a caging plateau typical of glassy dynamics. Together, these results reveal a novel glassy system within a colloidal crystal.
Shape anisotropy of colloidal nanoparticles has emerged as an important design variable for engineering assemblies with targeted structure and properties. In particular, a number of polyhedral nanoparticles have been shown to exhibit a rich phase behavior [Agarwal et al., Nature Materials, 2011, 10, 230]. Since real synthesized particles have polydispersity not only in size but also in shape, we explore here the phase behavior of binary mixtures of hard convex polyhedra having similar sizes but different shapes. Choosing representative particle shapes from those readily synthesizable, we study in particular four mixtures: (i) cubes and spheres (with spheres providing a non-polyhedral reference case), (ii) cubes and truncated octahedra, (iii) cubes and cuboctahedra, and (iv) cuboctahedra and truncated octahedra. The phase behavior of such mixtures is dependent on the interplay of mixing and packing entropy, which can give rise to miscible or phase-separated states. The extent of mixing of two such particle types is expected to depend on the degree of shape similarity, relative sizes, composition, and compatibility of the crystal structures formed by the pure components. While expectedly the binary systems studied exhibit phase separation at high pressures due to the incompatible pure-component crystal structures, our study shows that the essential qualitative trends in miscibility and phase separation can be correlated to properties of the pure components, such as the relative values of the order-disorder transition pressure (ODP) of each component. Specifically, if for a mixture A+B we have that ODP B
Monodisperse polyhedral nanocrystals with O(h) (octahedral) symmetry self-assemble into various mesophases and crystal structures at intermediate and high concentrations. In this work, the effect of quenched size polydispersity on phase and jamming behavior has been studied via molecular simulations for three representative O(h) polyhedral shapes; namely, cubes, cuboctahedrons, and truncated octahedrons. Polydispersity is set by the standard deviation "δ" of an underlying Gaussian distribution of particle sizes, and is "quenched" in that it is fixed in a given uniphase sample. Quenched polydisperse states are relevant to: (i) equilibrium behavior for small enough δ when phase segregation does not occur, and (ii) actual experimental behavior for arbitrary δ when dense states are reached at a rate faster than the relaxation of slow diffusion-driven fractionation modes. Space-filling polyhedrons (cubes and truncated octahedrons) are found to be more robust with respect to the nucleation of orientational and translational order at high polydispersities compared to the non-space-filling cuboctahedron, with the former shapes exhibiting an onset of jamming behavior at a critical polydispersity δ(t) that is about twice larger than that for the latter (δ(t) ≈ 0.08). Further, the orientational ordering in cubes is found to be highly resilient to polydispersity, leading to the formation of a dense, orientationally aligned, and translationally jammed state. Overall, increasing size polydispersity enhances the range of pressures where the mesophases occur.
In the energy sector, IoT manifests in the form of next-generation power grids that provide enhanced electrical stability, efficient power distribution, and utilization. The primary feature of a Smart Grid is the presence of an advanced bi-directional communication network between the Smart meters at the consumer end and the servers at the Utility Operators. Smart meters are broadly vulnerable to attacks on communication and physical systems. We propose a secure and operationally asymmetric mutual authentication and key-exchange protocol for secure communication. Our protocol balances security and efficiency, delegates complex cryptographic operations to the resource-equipped servers, and carefully manages the workload on the resource-constrained Smart meter nodes using unconventional lightweight primitives such as Physically Unclonable Functions. We prove the security of the protocol using well-established cryptographic assumptions. We implement the proposed scheme end-to-end in a Smart meter prototype using commercial-off-the-shelf products, a Utility server, and a credential generator as the trusted third party. Additionally, we demonstrate a physics-based attack named load modification attack on the Smart meter to demonstrate that merely securing the communication channel using authentication does not secure the meter, but requires further protections to ensure the correctness of the reported consumption. Hence, we propose a countermeasure to such an attack that goes side-by-side with our protocol implementation.
Hanasoge, S.; Agarwal, U.; Tandon, K.; Koelman, J.M.V.A. Published in:Physical Review E DOI:10.1103/PhysRevE.96.033313Published: 25/09/2017 Document VersionPublisher's PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication:• A submitted manuscript is the author's version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website.• The final author version and the galley proof are versions of the publication after peer review.• The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rightsCopyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal ? Take down policyIf you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Determining the pressure differential required to achieve a desired flow rate in a porous medium requires solving Darcy's law, a Laplace-like equation, with a spatially varying tensor permeability. In various scenarios, the permeability coefficient is sampled at high spatial resolution, which makes solving Darcy's equation numerically prohibitively expensive. As a consequence, much effort has gone into creating upscaled or low-resolution effective models of the coefficient while ensuring that the estimated flow rate is well reproduced, bringing to the fore the classic tradeoff between computational cost and numerical accuracy. Here we perform a statistical study to characterize the relative success of upscaling methods on a large sample of permeability coefficients that are above the percolation threshold. We introduce a technique based on mode-elimination renormalization group theory (MG) to build coarse-scale permeability coefficients. Comparing the results with coefficients upscaled using other methods, we find that MG is consistently more accurate, particularly due to its ability to address the tensorial nature of the coefficients. MG places a low computational demand, in the manner in which we have implemented it, and accurate flow-rate estimates are obtained when using MG-upscaled permeabilities that approach or are beyond the percola...
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