Regulating Charge Carrier Dynamics in Stable Perovskite Nanorods for Photo-Induced Atom Transfer Radical Polymerization.

Semiconducting nanocrystals have attracted world-wide research interest in artificial photosynthesis due to their appealing properties and enticing potentials in converting solar energy into valuable chemicals. Compared to 0D nanoparticles, 1D nanorods afford long-distance charge carriers separation and extended charge carriers lifetime due to the release of quantum confinement in axial direction. Herein, stable CsPbBr3 nanorods of distinctive dimensions are crafted without altering their properties and morphology via grafting hydrophobic polystyrene (PS) chains through a post-synthesis ligand exchange process. The resulting PS-capped CsPbBr3 nanorods exhibit a series of enhanced stabilities against UV irradiation, elevated temperature, and polar solvent, making them promising candidates for photo-induced atom transfer radical polymerization (ATRP). Tailoring the surface chemistry and dimension of the PS-capped CsPbBr3 nanorods endows stable, but variable reaction kinetics in the photo-induced ATRP of methyl methacrylate. The trapping-detrapping process of photogenerated charge carriers lead to extended lifetime of charge carriers in lengthened CsPbBr3 nanorods, contributing to a facilitated reaction kinetics of photo-induced ATRP. Therefore, by leveraging such stable PS-capped CsPbBr3 nanorods, the effects of surface chemistry and charge carriers dynamics on its photocatalytic performance are scrutinized, providing fundamental understandings for designing next-generation efficient nanostructured photocatalyst in artificial photosynthesis and solar energy conversion.

18F-Radiolabeling and Evaluation of an AMD3465 Derivative for PET Imaging of CXCR4 in a Mouse Breast Tumor Model.

The exploration of pharmaceutically active agents and positron emission tomography (PET) tracers targeting CXCR4 has been a focal point in cancer research given its pivotal role in the development and progression of various cancers. While significant strides have been made in PET imaging with radiometal-labeled tracers, the landscape of 18F-labeled small molecule tracers remains relatively limited. Herein, we introduce a novel and promising derivative, [18F]SFB-AMD3465, as a targeted PET tracer for CXCR4. The compound was synthesized by modifying the pyridine ring of AMD3465, which was subsequently labeled with 18F using [18F]SFB. The study provides comprehensive insights into the design, synthesis, and biological evaluation of [18F]SFB-AMD3465. In vitro and in vivo assessments demonstrated the CXCR4-dependent, specific, and sensitive uptake of [18F]SFB-AMD3465 in the CXCR4-overexpressing 4T1 cell line and the corresponding xenograft-bearing mouse model. These findings contribute to bridging the gap in 18F-labeled PET tracers for CXCR4 and underscore the potential of [18F]SFB-AMD3465 as a PET radiotracer for in vivo CXCR4 imaging.

BaTiO3 Catalyzed Ultrasonic-Driven Piezoelectric-Induced Reversible Addition-Fragmentation Chain-Transfer Polymerization in Aqueous Media.

Compared with normal stimulus such as light and heat, ultrasonic possesses much deeper penetration into tissues and organs and has lower scattering in heterogeneous systems as a noninvasive stimulus. Reversible addition-fragmentation chain-transfer polymerization (RAFT) in aqueous media is performed in a commercial ultrasonic wash bath with 40 kHz frequency ultrasonic, in the presence of piezoelectric tetragonal BaTiO3 (BTO) nanoparticles. Owing to the electron transfer from BTO under the ultrasonic action, the water can be decomposed to produce hydroxyl radical (HO•) and initiate the RAFT polymerization (piezo-RAFT). The piezo-RAFT polymerization exhibits features of controllable and livingness, such as linear increase of molar mass and narrow molar mass distributions (Mw/Mn < 1.20). Excellent temporal control of the polymerization and the chain fidelity of polymers are illustrated by "ON and OFF" experiment and chain extension, separately. Moreover, this ultrasonic-driven piezoelectric-induced RAFT polymerization in aqueous media can be directly used for the preparation of piezoelectric hydrogel which have potential application for stress sensor.

Dual-Regulation of Supramolecular Chirality in Achiral Side-Chain Azobenzene Liquid-Crystalline Polymers.

Azobenzene (Azo) liquid-crystalline polymers are intriguing due to their unique photo-induced isomerization and supramolecular chirality. However, clarification on multicomponent chiral induction towards Azo polymers remains ambiguous and challenging. Herein, chiral solvents and amines were employed to control the chiroptical activity of achiral Azo polymers. Methyl L-/D-lactate was added as the poor solvent and chiral inducer to achieve the first chiral induction in Azo aggregates. Chiral amines were utilized for the second chiral induction based on the acid-base interactions between the carboxyl groups of polymers and amines. The chiral enhancement and inversion of Azo units could be observed through the synergistic or antagonistic effect between solvents and amines. The impacts of solvent, chemical structures, feed ratio, enantiomeric excess, and temperature on supramolecular chirality were systematically studied. Furthermore, this system displayed the chiroptical switching property and chiral recovery under reversible irradiation.

Multiple/Two-Way Shape Memory Poly(urethane-urea-amide) Elastomers.

Multiple and two-way reversible shape memory polymers (M/2W-SMPs) are highly promising for many fields due to large deformation, lightweight, strong recovery stress, and fast response rates. Herein, a semi-crystalline block poly(urethane-urea-amide) elastomers (PUUAs) are prepared by the copolymerization of isocyanate-terminated polyurethane (OPU) and amino-terminated oligomeric polyamide-1212 (OPA). PUUAs, composed of OPA as stationary phase and PTMEG as reversible phase, exhibit excellent rigidity, flexibility, and resilience, and cPUUA-C7 -S25 exhibits the best tensile property with strength of 10.3 MPa and elongation at break of 360.2%. Besides, all the PUUAs possess two crystallization/melting temperatures and a glass transition temperature, which endow PUUAs with multiple and reversible two-way shape memory effect (M/2W-SME). Physically crosslinked PUUA-C0 -S25 exhibits excellent dual and triple shape memory, and micro chemically crosslinked cPUUA-C7 -S25 further shows quadruple shape memory behavior. Additionally, both PUUA-C0 -S25 and cPUUA-C7 -S25 have 2W-SME. Intriguingly, cPUUA-C7 -S25 can achieve a higher temperature (up to 165 °C) SME, which makes it suitable for more complex and changeable applications. Based on the advantages of M/2W-SME, a temperature-responsive application scenario where PUUAs can transform spontaneously among different shapes is designed. These unique M/2W-SME and high-temperature SME will enable the applications of high-temperature sensors, actuators, and aerospace equipment.

Ultrafast Visible-Light-Induced ATRP in Aqueous Media with Carbon Quantum Dots as the Catalyst and Its Application for 3D Printing.

Photoinduced atom transfer radical polymerization (ATRP) has been proved to be a versatile technique for polymer network formation. However, the slow polymerization rates of typical ATRP limited its application in the field of additive manufacturing (3D printing). In this work, we introduced carbon quantum dots (CQDs) for the first time to the ATRP in aqueous media and developed an ultrafast visible-light-induced polymerization system. After optimization, the polymerization could achieve a high monomer conversion (>90%) within 1 min, and the polydispersity index (PDI) of the polymer was lower than 1.25. This system was then applied as the first example of ATRP for the 3D printing of hydrogel through digital light processing (DLP), and the printed object exhibited good dimensional accuracy. Additionally, the excellent and stable optical properties of CQDs also provided interesting photoluminescence capabilities to the printed objects. We deduce this ATRP mediated 3D printing process would provide a new platform for the preparation of functional and stimuli-responsive hydrogel materials.

Recent Developments of Microscopic Study for Lanthanide and Manganese Doped Luminescent Materials.

Luminescent materials are indispensable for applications in lighting, displays and photovoltaics, which can transfer, absorb, store and utilize light energy. Their performance is closely related with their size and morphologies, exact atomic arrangement, and local configuration about photofunctional centers. Advanced electron microscopy-based techniques have enabled the possibility to study nanostructures with atomic resolution. Especially, with the advanced micro-electro-mechanical systems, it is able to characterize the luminescent materials at the atomic scale under various environments, providing a deep understanding of the luminescent mechanism. Accordingly, this review summarizes the recent achievements of microscopic study to directly image the microstructure and local environment of activators in lanthanide and manganese (Ln/Mn2+ )-doped luminescent materials, including: 1) bulk materials, the typical systems are nitride/oxynitride phosphors; and 2) nanomaterials, such as nanocrystals (hexagonal-phase NaLnF4 and perovskite) and 2D nanosheets (Ca2 Ta3 O10 and MoS2 ). Finally, the challenges and limitations are highlighted, and some possible solutions to facilitate the developments of advanced luminescent materials are provided.

General Route to Colloidal Nanocrystal Clusters with Precise Hierarchical Control via Star-like Nanoreactors.

A colloidal nanocrystal cluster (CNC) is a hierarchical nanostructure formed by clustering several nanocrystals into one nano-ensemble, which may exhibit unique optical or catalytic properties different from individual nanocrystals owing to the mutual interactions among neighboring component nanocrystals. However, there is still no universal synthetic route that could be applicable to diverse material compositions with precisely controlled hierarchical structures (i.e., nanocrystal number density, component nanocrystal size, and overall diameter of the CNC) up to now. Herein, a general and novel synthetic strategy was reported for crafting a wide range of inorganic CNCs (i.e., noble metal, semiconductor, and metal oxide) via utilizing amphiphilic star-like poly(4-vinylpyridine)-block-polystyrene diblock copolymers as nanoreactors prepared by sequential atom transfer radical polymerization. The hierarchical structure of rationally designed CNCs could be readily tailored by varying the P4VP molecular weight of star-like nanoreactors and the parameter optimization during the CNC preparation process, which was inaccessible by conventional synthetic methods.

Dual-Protected Metal Halide Perovskite Nanosheets with an Enhanced Set of Stabilities.

Approaches to achieve stable perovskite nanocrystals (PNCs) of interest, in particular those with large structural anisotropy, through protective coating of the inorganic shell at a single-nanocrystal (NC) level are comparatively few and limited in scope. Reported here is a robust amphiphilic-diblock-copolymer-enabled strategy for crafting highly-stable anisotropic CsPbBr3 nanosheets (NSs) by in situ formation of a uniform inorganic shell (1st shielding) that is intimately ligated with hydrophobic polymers (2nd shielding). The dual-protected NSs display an array of remarkable stabilities (i.e., thermal, photostability, moisture, polar solvent, aliphatic amine, etc.) and find application in white-light-emitting diodes. In principle, by anchoring other multidentate amphiphilic polymer ligands on the surface of PNCs, followed by templated-growth of shell materials of interest, a rich variety of dual-shelled, multifunctional PNCs with markedly improved stabilities can be created for use in optics, optoelectronics, and sensory devices.

Cell Type-Dependent Specificity and Anti-Inflammatory Effects of Charge-Reversible MSNs-COS-CMC for Targeted Drug Delivery in Cervical Carcinoma.

The surface charge of nanocarriers inevitably affects drug delivery efficiency; however, the cancer cell specificity, anti-inflammatory effects, and charge-reversal points remain to be further addressed in biomedical applications. The aim of this study was to comprehensively assess the cancer cell specificity of DOX-loaded mesoporous silica-chitosan oligosaccharide-carboxymethyl chitosan nanoparticles (DOX@MSNs-COS-CMC) in MCF-7 and HeLa cells, inhibit the production of inflammatory cytokines, and improve the drug accumulation in the tumor site. Intracellular results reveal that the retention time prolonged to 48 h in both HeLa and MCF-7 cells at pH 7.4. However, DOX@MSNs-COS-CMC exhibited a cell type-dependent cytotoxicity and enhanced intracellular uptake in HeLa cells at pH 6.5, due to the clathrin-mediated endocytosis and macropinocytosis in HeLa cells in comparison with the vesicular transport in MCF-7 cells. Moreover, Pearson's correlation coefficient value significantly decreased to 0.25 after 8 h, prompting endosomal escape and drug delivery into the HeLa nucleus. After the treatment of MSNs-COS-CMC at 200 µg/mL, the inflammatory cytokines IL-6 and TNF-α level decreased by 70% and 80%, respectively. Tumor inhibition of DOX@MSNs-COS-CMC was 0.4 times higher than free DOX, alleviating cardiotoxicity and inflammation in the HeLa xenograft tumor model. Charge-reversible DOX@MSNs-COS-CMC could be a possible candidate for clinical therapy of cervical carcinoma.

A Versatile Strategy for Unimolecular Micelle-Derived Hollow Polymer Nanoparticles as General Nanoreactors.

We reported the synthesis of a well-defined hollow polymer nanoparticle derived from star-shaped unimolecular micelles. ß-Cyclodextrin was first applied as an efficient macroinitiator to prepare a star-shaped PCL via ring-opening polymerization (ROP). Then, the star-shaped PCL was modified to be a macro-RAFT agent for photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of S-Cl monomers. The prepared unimolecular micelles can be photocross-linked under UV irradiation after a simple nucleophilic substitution reaction, which made -Cl groups to be -N3 groups. After the selective removal of the PCL core, hollow polymer nanoparticles were achieved and exhibited to be a general nanoreactor strategy for the fabrication of nanocrystals with well-controlled architectures. Compared with unimolecular micelle templates, the nanocrystals prepared by hollow templates are absolutely pure as no polymer chains are embedded in the inorganic nanocrystals. In addition, by changing the concentration of the precursor, the structure of the nanocrystal can be changed from a normal spherical structure to a hollow structure.

Hairy Uniform Permanently Ligated Hollow Nanoparticles with Precise Dimension Control and Tunable Optical Properties.

The ability to tailor the size and shape of nanoparticles (NPs) enables the investigation into the correlation between these parameters and optical, optoelectronic, electrical, magnetic, and catalytic properties. Despite several effective approaches available to synthesize NPs with a hollow interior, it remains challenging to have a general strategy for creating a wide diversity of high-quality hollow NPs with different dimensions and compositions on demand. Herein, we report on a general and robust strategy to in situ crafting of monodisperse hairy hollow noble metal NPs by capitalizing on rationally designed amphiphilic star-like triblock copolymers as nanoreactors. The intermediate blocks of star-like triblock copolymers can associate with metal precursors via strong interaction (i.e., direct coordination or electrostatic interaction), followed by reduction to yield hollow noble metal NPs. Notably, the outer blocks of star-like triblock copolymers function as ligands that intimately and permanently passivate the surface of hollow noble metal NPs (i.e., forming hairy permanently ligated hollow NPs with superior solubility in nonpolar solvents). More importantly, the diameter of the hollow interior and the thickness of the shell of NPs can be readily controlled. As such, the dimension-dependent optical properties of hollow NPs are scrutinized by combining experimental studies and theoretical modeling. The dye encapsulation/release studies indicated that hollow NPs may be utilized as attractive guest molecule nanocarriers. As the diversity of precursors are amenable to this star-like triblock copolymer nanoreactor strategy, it can conceptually be extended to produce a rich variety of hairy hollow NPs with different dimensions and functionalities for applications in catalysis, water purification, optical devices, lightweight fillers, and energy conversion and storage.

Unconventional Route to Uniform Hollow Semiconducting Nanoparticles with Tailorable Dimensions, Compositions, Surface Chemistry, and Near-Infrared Absorption.

Despite impressive recent advances in the synthesis of lead chalcogenide solid nanoparticles, there are no examples of lead chalcogenide hollow nanoparticles (HNPs) with controlled diameter and shell thickness as current synthetic approaches for HNPs have inherent limitations associated with their complexity, inability to precisely control the dimensions, and limited possibilities with regard to applicable materials. Herein, we report on an unconventional strategy for crafting uniform lead chalcogenide (PbS and PbTe) HNPs with tailorable size, surface chemistry, and near-IR absorption. Amphiphilic star-like triblock copolymers [polystyrene-block-poly(acrylic acid)-block-polystyrene and polystyrene-block-poly(acrylic acid)-block-poly(3,4-ethylenedioxythiophene)] were rationally synthesized and exploited as nanoreactors for the formation of uniform PbS and PbTe HNPs. Compared to their solid counterparts, the near-IR absorption of the HNPs is blue-shifted owing to the hollow interior. This strategy can be readily extended to other types of intriguing low-band-gap HNPs for diverse applications.

Precisely Size-Tunable Monodisperse Hairy Plasmonic Nanoparticles via Amphiphilic Star-Like Block Copolymers.

In situ precision synthesis of monodisperse hairy plasmonic nanoparticles with tailored dimensions and compositions by capitalizing on amphiphilic star-like diblock copolymers as nanoreactors are reported. Such hairy plasmonic nanoparticles comprise uniform noble metal nanoparticles intimately and perpetually capped by hydrophobic polymer chains (i.e., "hairs") with even length. Interestingly, amphiphilic star-like diblock copolymer nanoreactors retain the spherical shape under reaction conditions, and the diameter of the resulting plasmonic nanoparticles and the thickness of polymer chains situated on the surface of the nanoparticle can be readily and precisely tailored. These hairy nanoparticles can be regarded as hard/soft core/shell nanoparticles. Notably, the polymer "hairs" are directly and permanently tethered to the noble metal nanoparticle surface, thereby preventing the aggregation of nanoparticles and rendering their dissolution in nonpolar solvents and the homogeneous distribution in polymer matrices with long-term stability. This amphiphilic star-like block copolymer nanoreactor-based strategy is viable and robust and conceptually enables the design and synthesis of a rich variety of hairy functional nanoparticles with new horizons for fundamental research on self-assembly and technological applications in plasmonics, catalysis, energy conversion and storage, bioimaging, and biosensors.

Monodisperse Dual-Functional Upconversion Nanoparticles Enabled Near-Infrared Organolead Halide Perovskite Solar Cells.

Extending the spectral absorption of organolead halide perovskite solar cells from visible into near-infrared (NIR) range renders the minimization of non-absorption loss of solar photons with improved energy alignment. Herein, we report on, for the first time, a viable strategy of capitalizing on judiciously synthesized monodisperse NaYF4 :Yb/Er upconversion nanoparticles (UCNPs) as the mesoporous electrode for CH3 NH3 PbI3 perovskite solar cells and more importantly confer perovskite solar cells to be operative under NIR light. Uniform NaYF4 :Yb/Er UCNPs are first crafted by employing rationally designed double hydrophilic star-like poly(acrylic acid)-block-poly(ethylene oxide) (PAA-b-PEO) diblock copolymer as nanoreactor, imparting the solubility of UCNPs and the tunability of film porosity during the manufacturing process. The subsequent incorporation of NaYF4 :Yb/Er UCNPs as the mesoporous electrode led to a high efficiency of 17.8 %, which was further increased to 18.1 % upon NIR irradiation. The in situ integration of upconversion materials as functional components of perovskite solar cells offers the expanded flexibility for engineering the device architecture and broadening the solar spectral use.

Organic-Inorganic Nanocomposites via Placing Monodisperse Ferroelectric Nanocrystals in Direct and Permanent Contact with Ferroelectric Polymers.

Organic-inorganic nanocomposites composed of polymers and nanoparticles offer a vast design space of potential material properties, depending heavily on the properties of these two constituents and their spatial arrangement. The ability to place polymers in direct contact with functional nanoparticles via strong bonding, that is, stable chemical interaction without the dissociation of surface capping polymers, provides a means of preventing nanoparticles from aggregation and increasing their dispersibility in nanocomposites, and promises opportunities to explore new properties and construction of miniaturized devices. However, this is still a challenging issue and has not yet been largely explored. Here, we report an unconventional strategy to create in situ organic-inorganic nanocomposites comprising monodisperse ferroelectric nanoparticles directly and permanently tethered with ferroelectric polymers by capitalizing on rationally designed amphiphilic star-like diblock copolymer as nanoreactors. The diameter of ferroelectric nanoparticles and the chain length of ferroelectric polymers can be precisely tuned. The dielectric and ferroelectric properties of nanocomposites containing different sizes of ferroelectric nanoparticles were scrutinized. Such bottom-up crafting of intimate organic-inorganic nanocomposites offers new levels of tailorability to nanostructured materials and promises new opportunities for achieving exquisite control over the surface chemistry and properties of nanocomposites with engineered functionality for diverse applications in energy conversion and storage, catalysis, electronics, nanotechnology, and biotechnology.

Precisely size-tunable magnetic/plasmonic core/shell nanoparticles with controlled optical properties.

Star-like amphiphilic triblock copolymers were rationally designed and synthesized by combining two sequential atom-transfer radical polymerization reactions with a click reaction. Subsequently, a family of uniform magnetic/plasmonic core/shell nanoparticles was crafted by capitalizing on these triblock copolymers as nanoreactors. The diameter of the magnetic core and the thickness of the plasmonic shell could be independently and accurately controlled by varying the molecular weights (i.e., the chain lengths) of the inner and intermediate blocks of the star-like triblock copolymers, respectively. The surface plasmonic absorption of core/shell nanoparticles with different core diameters and shell thicknesses was systematically studied and theoretically modeled. This robust strategy provides easy access to a large variety of multifunctional nanoparticles with large lattice mismatches for use in optics, optoelectronics, catalysis, or bioimaging.

An unconventional route to monodisperse and intimately contacted semiconducting organic-inorganic nanocomposites.

We developed an unconventional route to produce uniform and intimately contacted semiconducting organic-inorganic nanocomposites for potential applications in thermoelectrics. By utilizing amphiphilic star-like PAA-b-PEDOT diblock copolymer as template, monodisperse PEDOT-functionalized lead telluride (PbTe) nanoparticles were crafted via the strong coordination interaction between PAA blocks of star-like PAA-b-PEDOT and the metal moieties of precursors (i.e., forming PEDOT-PbTe nanocomposites). As the inner PAA blocks are covalently connected to the outer PEDOT blocks, the PEDOT chains are intimately and permanently tethered on the PbTe nanoparticle surface, thereby affording a well-defined PEDOT/PbTe interface, which prevents the PbTe nanoparticles from aggregation, and more importantly promotes the long-term stability of PEDOT-PbTe nanocomposites. We envision that the template strategy is general and robust, and offers easy access to other conjugated polymer-inorganic semiconductor nanocomposites for use in a variety of applications.

Strictly biphasic soft and hard Janus structures: synthesis, properties, and applications.

Janus structures, named after the ancient two-faced Roman god Janus, comprise two hemistructures (e.g. hemispheres) with different compositions and functionalities. Much research has been carried out over the past few years on Janus structures because of the intriguing properties and promising potential applications of these unusually shaped materials. This Review discusses recent progress made in the synthesis, properties, and applications of strictly biphasic Janus structures possessing symmetrical structures but made of disparate materials. Depending on the chemical compositions, such biphasic structures can be categorized into soft, hard, and hybrid soft/hard Janus structures of different architectures, including spheres, rodlike, disclike, or any other shape. The main synthetic routes to soft, hard, and hybrid soft/hard Janus structures are summarized and their unique properties and applications are introduced. The perspectives for future research and development are also described.

Simple preparation of lignosulfonate stabilized eutectic gallium/indium liquid metal nanodroplets through ball milling process.

The combination of biomass and liquid metal (LM) makes the preparation process "greener" and application of LM composite materials more sustainable. Here we reported the solvent free preparation of lignosulfonate (LS) stabilized eutectic gallium/indium (EGaIn) LM nanodroplets through ball milling (BM), which was recognized to be efficient and environmentally-friendly alternatives to solution-based methods. By regulating the BM frequency and milling time, uniform LM nanodroplets with a size <200 nm can be achieved. Moreover, the surface of the EGaIn nanodroplets was covered by LS molecules, owing to the hydrogen bond formed between Ga2O3 and LS. Hydrophilic LS shell endowed the LS@EGaIn nanodroplets excellent colloidal stability in the aqueous media. The elongation at break and fracture strength of hydrogel with the addition of LS@EGaIn significantly improved with the addition of LS@EGaIn. Besides, the conductivity and excellent stress responsibility of the LS@EGaIn composite hydrogel illustrated its potential application as s a stress sensor, flexible wearable devices and other related applications. Moreover, it was predicted that LS can be replaced by other synthesized or biological macromolecules, and induced the formation of types of LM based composite materials through such a simple method.