Athermal and Soft Multi-Nanopatterning of Azopolymers: Phototunable Mechanical Properties

Imprinting nanopatterns on flexible substrates has diverse applications in advanced fabrication. However, the traditional thermal nanoimprint lithography (T-NIL) often causes shrinkage upon cooling. Here, a simple yet versatile method is introduced to fabricate multiple nanopatterns on a flexible substrate coated with an azopolymer by combining athermal nanoimprint lithography (AT-NIL) and photolithography. The azopolymer has various mechanical properties upon photoirradiation: 1) phototunable glass-transition temperatures (T_g) and concomitantly photoinduced switch from glassy plastic to viscoplastic polymer; 2) prominent modulation of viscoplasticity under light illumination at different wavelengths. Regionally selective multiple nanopatterns are conveniently fabricated, presenting angle-dependent structural color images on poly(ethylene terephthalate) (PET) substrates. The flexible, athermal and multiple nanopatterning method has the potential for on-demand fabrication of complex nanopatterns.     

Space-Confined Atomic Clusters Catalyze Superassembly of Silicon Nanodots within Carbon Frameworks for Use in Lithium-Ion Batteries

Incorporating nanoscale Si into a carbon matrix with high dispersity is desirable for the preparation of lithium-ion batteries (LIBs) but remains challenging. A space-confined catalytic strategy is proposed for direct superassembly of Si nanodots within a carbon (Si NDs⊂C) framework by copyrolysis of triphenyltin hydride (TPT) and diphenylsilane (DPS), where Sn atomic clusters created from TPT pyrolysis serve as the catalyst for DPS pyrolysis and Si catalytic growth. The use of Sn atomic cluster catalysts alters the reaction pathway to avoid SiC generation and enable formation of Si NDs with reduced dimensions. A typical Si NDs⊂C framework demonstrates a remarkable comprehensive performance comparable to other Si-based high-performance half LIBs, and higher energy densities compared to commercial full LIBs, as a consequence of the high dispersity of Si NDs with low lithiation stress. Supported by mechanic simulations, this study paves the way for construction of Si/C composites suitable for applications in future energy technologies.     

Continuous and Segmented Semiconducting Fiber-like Nanostructures with Spatially Selective Functionalization by Living Crystallization-Driven Self-Assembly

Fiber-like π-conjugated nanostructures are important components of flexible organic electronic and optoelectronic devices. To broaden the range of potential applications, one needs to control not only the length of these nanostructures, but the introduction of diverse functionality with spatially selective control. Here we report the synthesis of a crystalline-coil block copolymer of oligo(p-phenylenevinylene)-b-poly(2-vinylpyridine) (OPV₅-b-P2VP₄₄), in which the basicity and coordinating/chelating ability of the P2VP segment provide a landscape for the incorporation of a variety of functional inorganic NPs. Through a self-seeding strategy, we were able to prepare monodisperse fiber-like micelles of OPV₅-b-P2VP₄₄ with lengths ranging from 50 to 800 nm. Significantly, the exposed two ends of OPV core of these fiber-like micelles remained active toward further epitaxial deposition of OPV₅-b-PNIPAM₄₉ and OPV₅-b-P2VP₄₄ to generate uniform A-B-A and B-A-B-A-B segmented block comicelles with tunable lengths for each block. The P2VP domains in these (co-)micelles can be selectively decorated with inorganic and polymeric nanoparticles as well as metal oxide coatings, to afford hybrid fiber-like nanostructures. This work provides a versatile strategy toward the fabrication of narrow length dispersity continuous and segmented π-conjugated OPV-containing fiber-like micelles with the capacity to be decorated in a spatially selective way with varying functionalities.     

Palladium-Catalyzed Electrophilic Functionalization of Pyridine Derivatives through Phosphonium Salts

Herein, we report a highly efficient and practical method for pyridine-derived heterobiaryl synthesis through palladium-catalyzed electrophilic functionalization of easily available pyridine-derived quaternary phosphonium salts. The nice generality of this reaction was goes beyond arylation, enabling facile incorporation of diverse carbon-based fragments, including alkenyl, alkynyl, and also allyl fragments, onto the pyridine core. Notably, the silver salt additive is revealed to be of vital importance for the success of this transformation and its pivotal role as transmetallation mediator, which guarantees a smooth transfer of pyridyl group to palladium intermediate, is also described.     

Manipulating the Click Reactivity of Dibenzoazacyclooctynes: From Azide Click Component to Caged Acylation Reagent by Silver Catalysis

Strain-promoted azide–alkyne cycloaddition using dibenzoazacyclooctyne (DBCO) is widely applied in copper-free bioorthogonal reactions. Reported here is the efficient acid-promoted rearrangement and silver-catalyzed amidation of DBCO, which alters its click reactivity robustly. In the switched click reaction, DBCO, as a caged acylation reagent, enables rapid peptide/protein modification after decaging facilitated by silver catalysts, rendering site-specific conjugation of an IgG antibody by a Fc-targeting peptide.     

A Robust Mixed-Lanthanide PolyMOF Membrane for Ratiometric Temperature Sensing

Temperature sensors play a significant role in biology, chemistry, and engineering, especially those that can work accurately in a noninvasive manner. We adopted a photoinduced post-synthetic copolymerization strategy to realize a membranous ratiometric luminescent thermometer based on the emissions of two lanthanide ions. This novel mixed-lanthanide polyMOF membrane exhibits not only the integrity and temperature sensing behaviour of the Ln-MOF powder but also excellent mechanical properties, such as flexibility, elasticity, and processability. Moreover, the polyMOF membrane shows remarkable stability under harsh conditions, including high humidity, strong acid and alkali (pH 0–14), which allowed the mapping of temperature distributions in extreme circumstances. This work highlights a simple strategy for polyMOF membrane formation and pushes forward the further practical application of Ln-MOF-based luminescent thermometers in various fields and conditions.     

Silica microbeads capture fetal nucleated red blood cells for noninvasive prenatal testing of fetal ABO genotype

ABO hemolytic disease of the newborn (ABO-HDN), which may cause neonatal jaundice and polycythemia, or even stillbirth or neonatal death, is widespread in China. Prenatal testing for the fetal ABO blood group can reduce unnecessary concerns or ensure prompt treatment. Herein, we presented a method to employ high-density silica microbeads (SiO₂ MBs) for capturing fetal nucleated red blood cells (fnRBCs) in maternal peripheral blood, and we detected the ABO genotype of the fetus using these captured cells. We evaluated 52 patients using the SiO₂ MBs. Among 26 pregnant women with type O blood, 8 (30.8%) of the fetuses had type A blood, 5 (19.2%) had type B blood, and 13 (50%) had type O blood. SRY genes were detected in all 27 male fetuses. This study represents a simple and effective method for noninvasive prenatal detection of the fetal ABO genotype. We believe that this method has great potential for noninvasive prenatal testing of the fetal Rh blood group and other fetal diseases as well.     

A self-penetrating and chemically stable zinc (ii)-organic framework as multi-responsive chemo-sensor to detect pesticide and antibiotics in water

Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)_0.5(bimb)]·H₂O}_n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {8⁶} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium.     

Promotion of a quality standard for Porana sinensis Hemsl. based on the efficacy-oriented Effect-Constituent Index

Multicompound determination for the quality control of traditional Chinese medicine (TCM) may often be inadequate, since these compounds may not be associated with, or fully represent, the clinical effects of TCM. Moreover, the individual contributions of each constituent to the pharmacological effect are often not considered. In China, Porana sinensis is widely used as a substitute for Erycibe sources to treat joint pain and rheumatoid arthritis. The existing quality control methods for P. sinensis neither consider the individual contributions of various compounds nor control the actual quality associated with different clinical efficacies. In the present study, a novel efficacy-oriented approach, named the effect-constituent index (ECI), was established for P. sinensis. Analyses of the spectrum–effect relationship and components in rat plasma were conducted to systematically and scientifically select quality markers. Quantitative analysis of multicomponents via a single marker method was introduced to enhance the practical application value of the established ECI. The established ECI shows a good ability to distinguish and predict the bioeffect-based quality of P. sinensis. The present study also provides a reference for the establishment and application of ECI as a quality control method for TCMs.