Corrosion-Responsive Self-Healing Coatings.

Organic coatings are one of the most popular and powerful strategies for protecting metals against corrosion. They can be applied in different ways, such as by dipping, spraying, electrophoresis, casting, painting, or flow coating. They offer great flexibility of material designs and cost effectiveness.

Methods for Silk Property Analyses across Structural Hierarchies and Scales.

Silk from silkworms and spiders is an exceptionally important natural material, inspiring a range of new products and applications due to its high strength, elasticity, and toughness at low density, as well as its unique conductive and optical properties. Transgenic and recombinant technologies offer great promise for the scaled-up production of new silkworm- and spider-silk-inspired fibres. However, despite considerable effort, producing an artificial silk that recaptures the physico-chemical properties of naturally spun silk has thus far proven elusive.

Probing sub-5 Ångstrom micropores in carbon for precise light olefin/paraffin separation.

Olefin/paraffin separation is an important but challenging and energy-intensive process in petrochemical industry. The realization of carbons with size-exclusion capability is highly desirable but rarely reported. Herein, we report polydopamine-derived carbons (PDA-Cx, where x refers to the pyrolysis temperature) with tailorable sub-5 Å micropore orifices together with larger microvoids by one-step pyrolysis.

Competitiveness and Phylogenetic Relationship of Rhizobial Strains with Different Symbiotic Efficiency in : Conversion of Parasitic into Non-Parasitic Rhizobia by Natural Symbiotic Gene Transfer.

In Uruguayan soils, populations of native and naturalized rhizobia nodulate white clover. These populations include efficient rhizobia but also parasitic strains, which compete for nodule occupancy and hinder optimal nitrogen fixation by the grassland. Nodulation competitiveness assays using -tagged strains proved a high nodule occupancy by the inoculant strain U204, but this was lower than the strains with intermediate efficiencies, U268 and U1116.

Dual stimuli-responsive phosphorescence of a Pb(II) coordination polymer to acidic vapors and thermal treatment.

We present a new intensely phosphorescent Pb(II) coordination polymer (1) containing a heteroatomic ligand. It has a quantum yield of 21.62% and a lifetime of 25.

A long chain-induced depletion effect for abnormal grafting in the preparation of bimodal bidisperse polymer-grafted nanoparticles.

One of the challenging problems in the research field of polymer nanocomposites is how to prepare nanocomposites with high grafting density and strong ability of dispersion at the same time. For nanocomposites composed of bimodal bidisperse polymer chains and nanoparticles, the above requirements can be met by rationally adjusting the ratio of long and short polymer chains. In this study, the process of grafting bimodal bidisperse polymer chains onto the surface of nanoparticles in a grafting-to manner was investigated computer simulation and theoretical methods.

Organocatalytic Polymers from Affordable and Readily Available Building Blocks for the Cycloaddition of CO to Epoxides.

The catalytic cycloaddition of CO to epoxides to afford cyclic carbonates as useful monomers, intermediates, solvents, and additives is a continuously growing field of investigation as a way to carry out the atom-economic conversion of CO to value-added products. Metal-free organocatalytic compounds are attractive systems among various catalysts for such transformations because they are inexpensive, nontoxic, and readily available. Herein, we highlight and discuss key advances in the development of polymer-based organocatalytic materials that match these requirements of affordability and availability by considering their synthetic routes, the monomers, and the supports employed.

Histidine-based coordinative polymers for efficient intracellular protein delivery enhanced protein binding, cellular uptake, and endosomal escape.

Polymers are one of the most promising protein delivery carriers; however, their applications are hindered by low delivery efficacy owing to their undesirable performance in protein binding, cellular uptake and endosomal escape. Here, we designed a series of histidine-based coordinative polymers for efficient intracellular protein delivery. Coordination of metal ions such as Ni, Zn, and Cu with histidine residues on a polymer greatly improved its performance in protein binding, complex stability, cellular uptake and endosomal escape, therefore achieving highly improved protein delivery efficacy.

Assembly of biomimetic microreactors using caged-coacervate droplets.

Complex coacervates are liquid-like droplets that can be used to create adaptive cell-like compartments. These compartments offer a versatile platform for the construction of bioreactors inspired by living cells. However, the lack of a membrane significantly reduces the colloidal stability of coacervates in terms of fusion and surface wetting, which limits their suitability as compartments.

Local Chain Feature Mandated Self-Assembly of Block Copolymers.

This work demonstrates an effective and robust approach to regulate phase behaviors of a block copolymer by programming local features into otherwise homogeneous linear chains. A library of sequence-defined, isomeric block copolymers with globally the same composition but locally different side chain patterns were elaborately designed and prepared through an iterative convergent growth method. The precise chemical structure and uniform chain length rule out all inherent molecular defects associated with statistical distribution.

Deep-Blue Triplet-Triplet Annihilation Organic Light-Emitting Diode (CIE ≈ 0.05) Using Tetraphenylimidazole and Benzonitrile Functionalized Anthracene/Chrysene Emitters.

Herein, new deep-blue triplet-triplet annihilation (TTA) molecules, namely 4-(10-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)anthracen-9-yl)benzonitrile (TPIAnCN) and 4-(12-(4-(1,4,5-triphenyl-1H-imidazol-2-yl)phenyl)chrysen-6-yl)benzonitrile (TPIChCN), are designed, synthesized, and investigated as emitters for organic light-emitting diodes (OLED). TPIAnCN and TPIChCN are composed of polyaromatic hydrocarbons of anthracene (An) and chrysene (Ch) as the cores functionalized with tetraphenylimidazole (TPI) and benzonitrile (CN) moieties, respectively. The experimental and theoretical results verify their excellent thermal properties, photophysical properties, as well as electrochemical properties.

High-Performance Organohydrogel Artificial Muscle with Compartmentalized Anisotropic Actuation Under Microdomain Confinement.

Current hydrogel actuators mostly suffer from weak actuation strength and low responsive speed owing to their solvent diffusion-induced volume change mechanism. Here a skeletal muscle-inspired organohydrogel actuator is reported in which solvents are confined in hydrophobic microdomains. Organohydrogel actuator is driven by compartmentalized directional network deformation instead of volume change, avoiding the limitations that originate from solvent diffusion.

Confining the Sol-Gel Reaction at the Water/Oil Interface: Creating Compartmentalized Enzymatic Nano-Organelles for Artificial Cells.

Living organisms compartmentalize their catalytic reactions in membranes for increased efficiency and selectivity. To mimic the organelles of eukaryotic cells, we develop a mild approach for in situ encapsulating enzymes in aqueous-core silica nanocapsules. In order to confine the sol-gel reaction at the water/oil interface of miniemulsion, we introduce an aminosilane to the silica precursors, which serves as both catalyst and an amphiphilic anchor that electrostatically assembles with negatively charged hydrolyzed alkoxysilanes at the interface.

Shelterin reduces the accessibility of telomeric overhangs.

Telomeres terminate with a 50-300 bases long single-stranded G-rich overhang, which can be misrecognized as a DNA damage repair site. Shelterin plays critical roles in maintaining and protecting telomere ends by regulating access of various physiological agents to telomeric DNA, but the underlying mechanism is not well understood. Here, we measure how shelterin affects the accessibility of long telomeric overhangs by monitoring transient binding events of a short complementary peptide nucleic acid (PNA) probe using FRET-PAINT in vitro.

Osmotic Pressure as Driving Force for Reducing the Size of Nanoparticles in Emulsions.

We describe here a method to decrease particle size of nanoparticles synthesized by miniemulsion polymerization. Small nanoparticles or nanocapsules were obtained by generating an osmotic pressure to induce the diffusion of monomer molecules from the dispersed phase of a miniemulsion before polymerization to an upper oil layer. The size reduction is dependent on the difference in concentration of monomer in the dispersed phase and in the upper oil layer and on the solubility of the monomer in water.

Ring-Opening Co- and Terpolymerization of Epoxides, Cyclic Anhydrides, and l-Lactide Using Constrained Aluminum Inden Complexes.

Seven constrained aluminum inden complexes having different substituents and diamine backbones were developed for the ring-opening copolymerization (ROCOP) of epoxides and bulky cyclic anhydrides giving alternating polyesters with ranging from 49 to 226 °C. Among several catalyst/cocatalyst screenings, the aluminum inden complex having a rigid phenylene backbone coupled with 4-dimethylaminopyridine showed the best performance giving linear polyesters. In the case of cyclohexene oxide (CHO) and succinic anhydride (SA), the linear poly(CHO--SA) could be transformed to cyclic polymer when the polymerization was left under prolonged reaction time to induce intramolecular transesterification.

Crystallization Kinetics of a Liquid-Forming 2D Coordination Polymer.

We investigated a mechanism of crystal melting and crystallization behavior of a two-dimensional coordination polymer [Ag(L1)(CFSO)] (, L1 = 4,4'-biphenyldicarbonitrile) upon heating-cooling processes. The crystal showed melting at 282 °C, and the following gentle cooling induced the abrupt crystallization at 242 °C confirmed by DSC. A temperature-dependent structural change has been discussed through calorimetric, spectroscopic, and mechanical measurements.

Human Milk Sodium and Potassium as Markers of Mastitis in Mothers of Preterm Infants.

This prospective longitudinal study examined changes in milk sodium concentration (Na) and sodium:potassium ratio (Na:K), microbiological culture, milk production, and breast health in relation to mastitis after preterm birth. We studied women who gave birth at 29-34 weeks of gestation in a tertiary obstetric hospital in Perth, Western Australia. Milk samples, 24-hour milk production, and breast health data were collected every second day to day 10 postpartum, then every third day until infant discharge from the neonatal unit.

Coordination polymer-forming liquid Cu(2-isopropylimidazolate).

The structure of the melt state of one-dimensional (1D) coordination polymer crystal Cu(isopropylimidazolate) (melting temperature = 143 °C) was characterized by DSC, variable temperature PXRD, solid-state NMR (SSNMR), viscoelastic measurements, XAS, and DFT-AIMD calculations. These analyses suggested "coordination polymer-forming liquid" formation with preserved coordination bonds above . Variable chain configurations and moderate cohesive interaction in adjacent chains are the keys to the rarely observed polymer-forming liquid.

The location of protein oxidation in dystrophic skeletal muscle from the mdx mouse model of Duchenne muscular dystrophy.

Duchenne muscular dystrophy (DMD) is a severe childhood disease characterised by progressive muscle wasting caused by widespread myofibre necrosis. Implicated in the pathology of DMD is oxidative stress, caused by excessive generation of reactive oxygen and nitrogen species (RONS). One consequence of RONS exposure is post-translational oxidative modifications to proteins, which can cause loss of protein function.

Enhancement of Ethylene and Ethylene/1-Hexene (Co)polymerization Activities by Titanium(IV) and Zirconium(IV) Complexes Bearing Constrained Hydroxyindanone-Imine Ligands.

A new series of catalysts for ethylene and ethylene/1-hexene (co)polymerizations bearing constrained hydroxyindanone-imine ligands was developed for titanium(IV) and zirconium(IV) metals with variations of steric and electronic contributions on the ligands. X-ray crystal structures revealed significantly higher open space for the constrained titanium and zirconium complexes, compared to the conventional FI counterparts. Upon activation with MAO, significantly higher ethylene polymerization activities (up to 379.

Swap motion-directed twinning of nanocrystals.

Twinning frequently occurs in nanocrystals during various thermal, chemical, or mechanical processes. However, the nucleation and propagation mechanisms of twinning in nanocrystals remain poorly understood. Through in situ atomic resolution transmission electron microscopy observation at millisecond temporal resolution, we show the twinning in Pb individual nanocrystals via a double-layer swap motion where two adjacent atomic layers shift relative to one another.

Eutectic CsHSO-Coordination Polymer Glasses with Superprotonic Conductivity.

Superprotonic phase transition in CsHSO allows fast protonic conduction, but only at temperatures above the transition temperature of 141 °C (). Here, we preserve the superprotonic conductivity of CsHSO by forming a binary CsHSO-coordination polymer glass system, showing eutectic melting. Their anhydrous proton conductivities below are at least 3 orders of magnitude higher than CsHSO without compromising conductivity at higher temperatures or the need for humidification, reaching 6.

Advanced density-based methods for the characterization of materials, binding events, and kinetics.

Investigations of the densities of chemicals and materials bring valuable insights into the fundamental understanding of matter and processes. Recently, advanced density-based methods have been developed with wide measurement ranges ( 0-23 g cm), high resolutions ( 10 g cm), compatibility with different types of samples and the requirement of extremely low volumes of sample (as low as a single cell). Certain methods, such as magnetic levitation, are inexpensive, portable and user-friendly.