Targeted Analysis of Mitochondrial Protein Conformations and Interactions by Endogenous ROS-Triggered Cross-Linker Release.

The study of in situ conformations and interactions of mitochondrial proteins plays a crucial role in understanding their biological functions. Current chemical cross-linking mass spectrometry (CX-MS) has difficulty in achieving in-depth analysis of mitochondrial proteins for cells without genetic modification. Herein, this work develops the reactive oxygen species (ROS)-responsive cross-linker delivery nanoparticles (R-CDNP) targeting mitochondria.

A "Bottom-Up" Strategy for High-Performance Benzocyclobutene (BCB)-Subnanometer Inorganic Nanocomposites.

Developing benzocyclobutene (BCB) nanocomposites with ultra-small inorganic sizes represents a formidable challenge, although it offers great potential to produce materials with customizable structural and rich functional properties. In this study, we present a "bottom-up" design strategy for creating cross-linked benzocyclobutene (BCB) nanocomposites with highly dispersed nanodomains, such as organoalkoxysilane. This approach leverages ring-opening metathesis polymerization (ROMP) and thermally induced cycloaddition reactions to embed oligomeric silsesquioxanes, achieving a unique molecular structure with promising low-dielectric applications.

Tracking the effects of PLGA-based nanoparticles on protein expression in living cells through quantitative proteomics.

Mass spectrometry (MS)-based proteomics can identify and quantify the differential abundance of expressed proteins in parallel, and bottom-up proteomic approaches are even approaching comprehensive coverage of the complex eukaryotic proteome. Protein-nanoparticle (NP) interactions have been extensively studied owing to their importance in biological applications and nanotoxicology. However, the proteome-level effects of NPs on cells have received little attention, although changes in protein abundance can reflect the direct effects of nanocarriers on protein expression.

Risk stratification of papillary thyroid cancers using multidimensional machine learning.

Background: Papillary thyroid cancer (PTC) is one of the most common endocrine malignancies with different risk levels. However, preoperative risk assessment of PTC is still a challenge in the worldwide. Here, the authors first report a Preoperative Risk Assessment Classifier for PTC (PRAC-PTC) by multidimensional features including clinical indicators, immune indices, genetic feature, and proteomics.

Bioinspired Microadhesives with Greatly Enhanced Reversible Adhesion Fabricated by Synthesized Silicone Elastomer with Increasing Phenyl Contents.

We present a facile chemical method for fabricating bioinspired microadhesives with significant improved reversible adhesion strength. Four kinds of polysiloxane with gradient varying phenyl contents were synthesized and used to fabricate microadhesives. The chemical structures and mechanical properties, as well as surface properties of the four microadhesives, were confirmed and characterized by ATR-FTIR, DSC, XPS, low-field NMR, tensile tests, and SEM, respectively.

A humidity-resistant bio-inspired microfibrillar adhesive fabricated using a phenyl-rich polysiloxane elastomer for reliable skin patches.

Steady adhesion under varying humidity conditions is fundamentally challenging due to the barrier of interfacial water molecules. Here, we demonstrate a humidity-resistant gecko-inspired microfibrillar adhesive fabricated by using a specific phenyl-rich polysiloxane. In contrast with the great decline of macroadhesion with increasing humidity for the typical polydimethylsiloxane (PDMS) microfibrillar adhesives, strong macroadhesion of a microfibrillar adhesive fabricated using synthetic phenyl-rich polysiloxane maintains adhesion well across a wide relative humidity range (1% to 95%).

Multi-tasking geometric phase element array based self-referenced vortex interferometer for three-dimensional topography.

Interferometry is a basic physical method to record and reconstruct the three-dimensional (3D) topography of a complex object. However, mainstream interferometers using two beams can be unstable in a volatile environment. Here, we present a self-referenced optical vortex interferometer employing multi-tasking geometric phase elements.

Directional, Low-Energy Driven Thermal Actuating Bilayer Enabled by Coordinated Submolecular Switching.

The authors reveal a thermal actuating bilayer that undergoes reversible deformation in response to low-energy thermal stimuli, for example, a few degrees of temperature increase. It is made of an aligned carbon nanotube (CNT) sheet covalently connected to a polymer layer in which dibenzocycloocta-1,5-diene (DBCOD) actuating units are oriented parallel to CNTs. Upon exposure to low-energy thermal stimulation, coordinated submolecular-level conformational changes of DBCODs result in macroscopic thermal contraction.

2D/2D Heterojunction systems for the removal of organic pollutants: A review.

Photocatalysis is considered to be an effective way to remove organic pollutants, but the key to photocatalysis is finding a high-efficiency and stable photocatalyst. 2D materials-based heterojunction has aroused widespread concerns in photocatalysis because of its merits in more active sites, adjustable band gaps and shorter charge transfer distance. Among various 2D heterojunction systems, 2D/2D heterojunction with a face-to-face contact interface is regarded as a highly promising photocatalyst.

The Evolution of Organosilicon Precursors for Low-k Interlayer Dielectric Fabrication Driven by Integration Challenges.

Since the application of silicon materials in electronic devices in the 1950s, microprocessors are continuously getting smaller, faster, smarter, and larger in data storage capacity. One important factor that makes progress possible is decreasing the dielectric constant of the insulating layer within the integrated circuit (IC). Nevertheless, the evolution of interlayer dielectrics (ILDs) is not driven by a single factor.

Arene Substitution Design for Controlled Conformational Changes of Dibenzocycloocta-1,5-dienes.

We report that an agile eight-membered cycloalkane can be stabilized by fusing a benzene ring on each side, substituted with proper functional groups. The conformational change of dibenzocycloocta-1,5-diene (DBCOD), a rigid-flexible-rigid organic moiety, from its Boat to Chair conformation requires an activation energy of 42 kJ/mol, which is substantially lower than those of existing submolecular shape-changing units. Experimental data corroborated by theoretical calculations demonstrate that intramolecular hydrogen bonding can stabilize Boat, whereas electron repulsive interaction from opposing ester substituents favors Chair.

Temperature and pH Responsive Janus Silica Nanoplates Prepared by the Sol-Gel Process and Postmodification.

During the process of emulsifying and hydrolyzing, reactive poly(3-(triethoxysilyl)propyl methacrylate)--polystyrene (PTEPM--PS) diblock copolymers can self-assemble and become cross-linked to form hollow spheres in situ with polystyrene on their inner surfaces. The addition of tetraethoxysilane (TEOS), which was hydrolyzed and condensed together with PTEPM block, can make those spheres as soft foldable capsules or hard hollow spheres depending on the amount of added TESO. Then postmodification, the surface-initiated Atom Transfer Radical Polymerization (ATRP) was applied to afford stimuli-responsive spheres, and the corresponding responsive Janus nanoplates (RJPs) were finally obtained by crushing those responsive hollow spheres (HSs) showing smart tunable emulsifiability and great potential in oily water purification.

Biomedically Relevant Self-Assembled Metallacycles and Metallacages.

Diverse metal-organic complexes (MOCs), shaped as rectangles, triangles, hexagons, prisms, and cages, can be formed by coordination between metal ions (Pt, Pd, Ru, Rh, Ir, Zn, Co, and Cd) and organic ligands, with potential applications as alternatives to conventional biomedical materials for therapeutic, sensing, and imaging purposes. MOCs have been investigated as anticancer drugs in the treatment of malignant tumors in lung, cervical, breast, colon, liver, prostate, ovarian, brain, stomach, bone, skin, mouth, thyroid, and other cancers. MOCs with one, two, and three cavities have also been investigated as drug carriers and prepared for the loading and release of different drugs.

Substrate specificity-enabled terminal protection for direct quantification of circulating MicroRNA in patient serums.

Currently, reported affinity pairings still lack in diversity, and thus terminal protection relying on steric hindrance is restricted in designing nucleic acid-based analytical systems. In this work, resistance to exonuclease is testified by group modification or backbone replacement, and the 3'-phosphate group (P) reveals the strongest exonuclease I-resistant capability. Due to the substrate specificity of enzymatic catalysis, this 3'-P protection works in a "direct mode".

Shape Memory Behavior of Carbon Black-reinforced Trans-1,4-polyisoprene and Low-density Polyethylene Composites.

Shape memory composites of trans-1,4-polyisoprene (TPI) and low-density polyethylene (LDPE) with easily achievable transition temperatures were prepared by a simple physical blending method. Carbon black (CB) was introduced to improve the mechanical properties of the TPI/LDPE composites. The mechanical, cure, thermal and shape memory properties of the TPI/LDPE/CB composites were investigated in this study.

Shape Memory Behavior of Natural Gum and Low-Density Polyethylene Blends with Two Response Temperatures.

A series of shape memory blends of natural gum (EUG) and low-density polyethylene (LDPE) with a bicontinuous cross-linked structure were prepared by a physical blending method, which could be used in the field of thermal response with two different temperatures. We report the shape memory properties of these blended materials with two response temperatures for the first time. The mechanical, curing, thermal and shape memory properties of the blends were studied in this manuscript.

Self-Assembly of Metallacages into Multidimensional Suprastructures with Tunable Emissions.

Cubic metallacages were arranged into multidimensional (one-, two-, and three-dimensional) suprastructures via multistep assembly. Four new shape-controllable, hybrid metallacages with modified substituents and tunable electronic properties were prepared using dicarboxylate ligands with various substituents (sodium sulfonate, nitro, methoxyl, and amine), tetra-(4-pyridylphenyl) ethylene, and cis-(PEt)Pt(OTf). The as-prepared metallacages were used as building blocks for further assembly.

Improved Lubricating Performance by Combining Oil-Soluble Hairy Silica Nanoparticles and an Ionic Liquid as an Additive for a Synthetic Base Oil.

This article reports on improved lubricating performance by combining oil-soluble poly(lauryl methacrylate) brush-grafted silica nanoparticles (hairy NPs or HNP) and an oil-miscible phosphonium-phosphate ionic liquid (IL) as a friction-reducing additive for a polyalphaolefin (PAO) oil. The HNP was synthesized by surface-initiated reversible addition-fragmentation chain transfer polymerization. At a total concentration of 2% and sufficiently high individual concentrations for HNP and IL in PAO, high-contact stress, ball-on-flat reciprocating tribological tests showed that the friction decreased by up to 23% compared with 2% HNP alone in PAO and by up to 35% compared to the PAO mixed with 2% IL.

Fluorescence Regulation of Copper Nanoclusters via DNA Template Manipulation toward Design of a High Signal-to-Noise Ratio Biosensor.

Because of bioaccumulation of food chain and disability of biodegradation, concentration of toxic mercury ions (Hg) in the environment dramatically varies from picomolar to micromolar, indicating the importance of well-performed Hg analytical methods. Herein, reticular DNA is constructed by introducing thymine (T)-Hg-T nodes in poly(T) DNA, and copper nanoclusters (CuNCs) with aggregate morphology are prepared using this reticular DNA as a template. Intriguingly, the prepared CuNCs exhibit enhanced fluorescence.

Water-soluble pillar[5]arene induced the morphology transformation of self-assembled nanostructures and had further application in paraquat detection.

Well-defined nanostructures were constructed by self-assembling hexamethylenediamine-functionalized tetrachloroperylene bisimides (compound A) in water/acetone. These structures could further reversibly transform into fluorescent vesicles by adding and removing water-soluble pillar[5]arene.

UCST-Type Thermosensitive Hairy Nanogels Synthesized by RAFT Polymerization-Induced Self-Assembly.

While lower critical solution temperature (LCST)-type thermosensitive nanogels have been intensively studied, the upper critical solution temperature (UCST)-type versions are much less explored. This communication reports a method for the synthesis of zwitterionic UCST nanogels by reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly in water-organic solvent mixtures. The nanogels were prepared by RAFT polymerization of 3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate, whose polymer is known to exhibit UCST behavior in water, conducted in ethanol-water mixtures at 70 °C using poly(poly(ethylene glycol) methyl ether methacrylate) as a macro-chain transfer agent (CTA) and a difunctional monomer as cross-linker.

Janus Silica Hollow Spheres Prepared via Interfacial Biosilicification.

A poly(ethylene glycol)-b-poly(L-lysine)-b-poly(styrene) (PEG-PLL-PS) triblock copolymer, which contains a cationic PLL block as the middle block, is synthesized via a combination of ring-opening polymerization (ROP) and atom-transfer radical polymerization (ATRP). The PEG-PLL-PS (ELS) triblock is employed as a macromolecular surfactant to form a stable oil-in-water (O/W) emulsion, which is subsequently used as the template to prepare Janus silica hollow spheres (JHS) via a one-pot biosilicification reaction. For the emulsion template, the middle PLL block assembles at the O/W interface and directs the biomimetic silica synthesis in the presence of phosphate buffer and silicic acid precursors.

Hydrogels assembled from star-shaped polypeptides with a dendrimer as the core.

A second or fourth generation dendrimer with primary amine as the peripheral terminal group was first synthesized via Michael addition and thiol-yne addition. A series of star-shaped polypeptides was synthesized by ring opening polymerization (ROP) of γ-(2-(2-methoxyethoxy)ethyl) l-glutamate (l-EG2Glu) N-carboxyanhydride (NCA) using the amine group terminated dendrimer as the initiator. Taking advantage of the well-defined dendrimer and ROP, the arm number and arm length can be easily controlled.

Nanoasperity: structure origin of nacre-inspired nanocomposites.

Natural nacre with superior mechanical property is generally attributed to the layered "brick-and-mortar" nanostructure. However, the role of nanograins on the hard aragonite platelets, which is so-called nanoasperity, is rarely addressed. Herein, we prepared silica platelets with aragonite-like nanoasperities via biomineralization strategy and investigated the effects of nanoasperity on the mechanical properties of resulting layered nanocomposites composed of roughened silica platelets and poly(vinyl alcohol).