Polymer-Protein Assemblies with Tunable Vesicular and Hierarchical Nanostructures.

The construction of variable structured multi-protein nano-assemblies is of great interest for the development of protein-based therapeutic systems. This study showcases the synthesis of polymer-protein assemblies with tunable structure like single- and multi-layer polymer-crosslinked protein vesicles, Janus protein vesicles and other hierarchical-structured assemblies by utilizing a dynamic template-assistant intermittent-assembly approach. The generalization of the methodology helps the protein assemblies to gain notable functional complexity. And we demonstrate compelling evidence highlighting the substantial impact of the topological morphology of protein nanoaggregates on their cellular uptake capacity.

Object Relocation Visual Tracking Based on Histogram Filter and Siamese Network in Intelligent Transportation.

Target detection and tracking algorithms are one of the key technologies in the field of autonomous driving in intelligent transportation, providing important sensing capabilities for vehicle localization and path planning. Siamese network-based trackers formulate the visual tracking mission as an image-matching process by regression and classification branches, which simplifies the network structure and improves the tracking accuracy. However, there remain many problems, as described below. (1) The lightweight neural networks decrease the feature representation ability. It is easy for the tracker to fail under the disturbing distractors (e.g., deformation and similar objects) or large changes in the viewing angle. (2) The tracker cannot adapt to variations of the object. (3) The tracker cannot reposition the object that has failed to track. To address these issues, we first propose a novel match filter arbiter based on the Euclidean distance histogram between the centers of multiple candidate objects to automatically determine whether the tracker fails. Secondly, the Hopcroft-Karp algorithm is introduced to select the winners from the dynamic template set through the backtracking process, and object relocation is achieved by comparing the Gradient Magnitude Similarity Deviation between the template and the winners. The experiments show that our method obtains better performance on several tracking benchmarks, i.e., OTB100, VOT2018, GOT-10k, and LaSOT, compared with state-of-the-art methods.

The characterisation of dental enamel using transmission Kikuchi diffraction in the scanning electron microscope combined with dynamic template matching.

The remarkable physical properties of dental enamel can be largely attributed to the structure of the hydroxyapatite (HAp) crystallites on the sub-micrometre scale. Characterising the HAp microstructure is challenging, due to the nanoscale of individual crystallites and practical challenges associated with HAp examination using electron microscopy techniques. Conventional methods for enamel characterisation include imaging using transmission electron microscopy (TEM) or specialised beamline techniques, such as polarisation-dependent imaging contrast (PIC). These provide useful information at the necessary spatial resolution but are not able to measure the full crystallographic orientation of the HAp crystallites. Here we demonstrate the effectiveness of enamel analyses using transmission Kikuchi diffraction (TKD) in the scanning electron microscope, coupled with newly-developed pattern matching methods. The pattern matching approach, using dynamic template matching coupled with subsequent orientation refinement, enables robust indexing of even poor-quality TKD patterns, resulting in significantly improved data quality compared to conventional diffraction pattern indexing methods. The potential of this method for the analysis of nanocrystalline enamel structures is demonstrated by the characterisation of a human enamel TEM sample and the subsequent comparison of the results to high resolution TEM imaging. The TKD - pattern matching approach measures the full HAp crystallographic orientation enabling a quantitative measurement of not just the c-axis orientations, but also the extent of any rotation of the crystal lattice about the c-axis, between and within grains. Results presented here show how this additional information highlights potentially significant aspects of the HAp crystallite structure, including intra-crystallite distortion and the presence of multiple high angle boundaries between adjacent crystallites with rotations about the c-axis. These and other observations enable a more rigorous understanding of the relationship between HAp structures and the physical properties of dental enamel.

Designing sequence-defined peptoids for fibrillar self-assembly and silicification.

In the biological environment, mineral crystals exquisitely controlled by biomacromolecules often show intricate hierarchical structures and superior mechanical properties. Among these biominerals, spicules, hybrid silica/protein superstructures serving as skeletal elements in demosponges, represent an excellent example for motivating the synthesis of silica materials. Herein, by designing sequence-defined peptoids containing side chains with a strong binding to silica, we demonstrated that self-assembly of these peptoids into fiber structures enables the mimicking of both biocatalytic and templating functions of silicatein filaments for the formation of silica fibers at near-neutral pH and ambient temperature. We further showed that the presence of amino groups is significant for the nucleation of silica on self-assembled peptoid nanofibers. Molecular dynamics simulation further confirmed that having silica-binding of amino side chains is critical for self-assembled peptoid fibers in triggering silica formation. We demonstrated that tuning inter-peptoid interactions by varying carboxyl and amino side chains significantly influences the assembly kinetics and final morphologies of peptoid assemblies as scaffolds for directing silica mineralization to form silica spheres, fibers, and sheets. The formation of silica shell on peptoid fibers increased the mechanical property of peptoid hydrogel materials by nearly 1000-fold, highlighting the great potential of using silicification to enhance the mechanical property of hydrogel materials for applications including tissue engineering. Since peptoids are highly robust and programmable, we expect that self-assembly of peptoids containing solid-binding side chains into hierarchical materials opens new opportunities in the design and synthesis of highly tunable scaffolds that direct the formation of composite nanomaterials.

Hydrogen bubble dynamic template fabrication of nanoporous Cu film supported by graphene nanaosheets: A highly sensitive sensor for detection of nitrite.

High surface area nanoporous Cu film (NPCF) has been successfully synthesized using a hydrogen bubble dynamic template on the graphene nanosheets (GNs) modified glassy carbon electrode (GCE). The effect of different synthesis conditions such as applied potential and deposition time on the NPCF morphology was investigated. The structure and constituent of the NPCF-GNs/GCE were characterized by scanning electron microscopy (SEM), energy-dispersive x-ray (EDX), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS) and electrochemical methods. The study on electrocatalytic performance of the NPCF-GNs/GCE demonstrated that this electrode has excellent catalytic activity toward nitrite oxidation. The quantitative measurement of nitrite by amperometric method showed a wide concentration range (0.1-100µmolL-1) with a detection limit and a sensitivity of 8.87 × 10-8molL-1 and 3.1 AL/molcm2, respectively. The excellent electrochemical response and high sensitivity of the proposed electrode were attributed to the 3D structure of NPCF and the synergic effect of NPCF and GNs. Furthermore, this electrode showed some other advantages including good repeatability, high reproducibility, long-term stability and anti-interference performance toward nitrite sensing. The applicability of the proposed electrode was proved by successful determination of nitrite in real samples (tap water, river water and sausage samples).

Rapid fabrication of support-free trimetallic Pt53Ru39Ni8 nanosponges with enhanced electrocatalytic activity for hydrogen evolution and hydrazine oxidation reactions.

Herein, a rapid and straightforward coreduction aqueous approach was developed for preparation of support-free trimetallic Pt53Ru39Ni8 nanosponges with clean surface. Plenty of hydrogen bubbles were in situ formed via the oxidation and hydrolysis of the reductant (sodium borohydride), which served as the dynamic template in the fabrication of the porous sponge-like structures. The shape, size, crystal structure, and composition of the products were characterized by a set of characterization techniques. The obtained Pt53Ru39Ni8 nanosponges displayed dramatically highly electrocatalytic performances for hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HOR) outperformed home-made PtNi nanoparticles (PtNi NPs), RuNi NPs and commercial PtRu black (50wt.%). The present route provides new insights for facile synthesis of other bi-, tri- and even multi-metallic nanocatalysts for potential applications in catalysis, energy conversion and storage.

The role of ether-functionalized ionic liquids in the sol-gel process: effects on the initial alkoxide hydrolysis steps.

The ether-functionalized imidazolium ionic liquids (IL) applied in the silica sol-gel process demonstrated a defined coordination potential. These IL display the capacity to control the system organization from the reactions' first moments through a dynamic system-assembling ability, being the sum of ionic and physical interactions, i.e. Coulomb forces, H-bonding and London forces. The initial hydrolysis steps of tetraethyl orthosilicate (TEOS) in the presence of these IL were followed by Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering (DLS), both in time-resolved experiments, in an attempt to correlate the structuring and the bonding dynamics of these systems.