Tailored Drug Delivery Platforms: Stimulus-Responsive Core-Shell Structured Nanocarriers.

Core-shell structured nanocarriers have come into the scientific spotlight in recent years due to their intriguing properties and wide applications in materials chemistry, biology, and biomedicine. Tailored core-shell structures to achieve desired performance have emerged as a research frontier in the development of smart drug delivery system. However, systematic reviews on the design and loading/release mechanisms of stimulus-responsive core-shell structured nanocarriers are uncommon. This review starts with the categories of core-shell structured nanocarriers with different means of drug payload, and then highlights the controlled release mechanism realized through stimulus-response processes triggered under different environments. Finally, some multifaceted perspectives on the design of core-shell structured materials as drug carriers are addressed. This work aims to provide new enlightenments and prospects in the drug delivery field for further developing advanced and smart nanocarriers.

High-Performance Recognition, Cell-Imaging, and Efficient Removal of Carbon Monoxide toward a Palladium-Mediated Fluorescent Sensing Platform.

Novel high-performance fluorescent approaches have always significant demand for room-temperature detection of carbon monoxide (CO), which is highly toxic even at low concentration levels and is not easy to recognize due to its colorless and odorless nature. In this paper, we constructed a palladium-mediated fluorescence turn-on sensing platform (TPANN-Pd) for the recognition of CO at room temperature, revealing simultaneously quick response speed (<30 s), excellent selectivity, superior sensitivity, and low detection limit (∼160 nM for CORM-3, ∼1.7 ppb for CO vapor). Moreover, rapid detection and efficient removal (24%) from the air by naked-eye vision has been successfully realized based on TPANN-Pd supramolecular gels. Furthermore, the developed sensing platform was elucidated with low cytotoxicity and high cellular uptake, and it was successfully applied to CO imaging in living cells, providing real-time monitoring of potential CO-involved reactions in biological systems.

Light-triggered Modulation of Supramolecular Chirality.

Dynamically controlling the supramolecular chirality is of great significance in development of functional chiral materials, which is thus essential for the specific function implementation. As an external energy input, light is remote and accurate for modulating chiral assemblies. In non-polarized light control, some photochemically reactive units (e. g., azobenzene, ɑ-cyanostilbene, spiropyran, anthracene) or photo-induced directionally rotating molecular motors were designed to drive chiral transfer or amplification. Besides, photoexcitation induced assembly based physical approach was also explored recently to regulate supramolecular chirality beyond photochemical reactions. In addition, circularly polarized light was applied to induce asymmetric arrangement of organic molecules and asymmetric photochemical synthesis of inorganic metallic nanostructures, in which both wavelength and handedness of circularly polarized light have effects on the induced supramolecular chirality. Although light-triggered chiral assemblies have been widely applied in photoelectric materials, biomedical fields, soft actuator, chiral catalysis and chiral sensing, there is a lack of systematic review on this topic. In this review, we summarized the recent studies and perspectives in the constructions and applications of light-responsive chiral assembled systems, aiming to provide better knowledge for the development of multifunctional chiral nanomaterials.

A New Microporous Lanthanide Metal-Organic Framework with a Wide Range of pH Linear Response.

Lanthanide metal-organic frameworks (Ln-MOFs) have attracted extensive attention because of their structural adjustability and wide optical function applications. However, MOFs with a wide linear pH response and stable framework structures in acidic or alkaline solutions are rare to date. Here, we used 4,4',4″-s-triazine-2,4,6-triyltribenzoate (H3TATB) as an organic ligand, coordinated with lanthanide ions (Eu3+/Tb3+), and synthesized a new metal-organic framework material. The material has a porous three-dimensional square framework structure and emits bright red or green fluorescence under 365 nm UV light. The carboxyl group of the ligand is prone to protonation in an acidic environment, and negatively charged OH- and ligand (TATB3-) have a competitive effect in an alkaline environment, which could affect the coordination ability of ligand. The luminescence degree of the framework decreases with the increase in the degree of acid and base. In particular, such fluorescence changes have a wide linear response (pH = 0-14), which can be used as a potential fluorescence sensing material for pH detection.

In Situ Regulation of Microphase Separation-Recognized Circularly Polarized Luminescence via Photoexcitation-Induced Molecular Aggregation.

Circularly polarized luminescence (CPL) has attracted great interest owing to its extensive optical information and chiral structural dependence. However, rationally regulating solid-phase CPL signals remains difficult because of the close packing of molecules in solid-state materials and the lack of structural visualization. In this work, we proposed a microphase-separation-recognized CPL regulation strategy via coassembly of a hexathiobenzene-based luminophore and chiral block copolymer (cBCP) with in situ photocontrollability. As a consequence to the continuous increase in the luminophore-to-cBCP ratio, the CPL signal of the supramolecular system exhibited an increasing trend until a critical point. Then, further increasing the ratio stretched the helical pitch of cBCP, which led to CPL reduction. With the photoexcitation-induced molecular aggregation of the luminophore, which was implemented using in situ photoirradiation, the helical pitch was retracted along with the restoration of the CPL signal. These processes were fully recognized and monitored by the microphase-separated nanomorphological change of the coassembled system, which indicated that such a structural contrast could be an effective method for rationally regulating the supramolecular chiropticity of solid-state materials.

Photoexcitation-Based Supramolecular Access to Full-Scale Phase-Diagram Structures through in situ Phase-Volume Ratio Phototuning.

Controlling phase separation and transition plays a core role in establishing and maintaining the function of diverse self-assembled systems. However, it remains challenging to achieve wide-range continuous phase transition for dynamically producing a variety of assembled structures. Here, we developed a far-from-equilibrium system, upon the integration of photoexcitation-induced aggregation molecules and block copolymers, to establish an in situ phase-volume ratio photocontrol strategy. Thus, full-scale phase-diagram structures, from lamellar structure to gyroidal, cylindrical, and finally to a spherical one, can be accessed under different irradiation periods. Moreover, the phase transition was accompanied by considerable aggregation-induced phosphorescence and hydrophilicity/hydrophobicity change for building a functional surface. This strategy allows for a conceptual advance of accessing a wide range of distinct self-assembled structures and functions in real time.

Mechanical stimuli-induced multiple photophysical responsive AIEgens with high contrast properties.

A new cyano-distyrylbenzene derivative with a mechano-force induced high contrast transition in color and emission was demonstrated here. Under mechanical stimuli, the emission peak can undergo a large wavelength shift from 440 nm to 650 nm, while the appearance color can switch from white to pink.

Rigid Polymer Network-Based Autonomous Photoswitches Working in the Solid State Encoded by Room-Temperature Phosphorescence.

Autonomous molecular switches with self-recoverability are of great theoretical and experimental interest since they can avoid additional chemical or energy imposition during the working process. Due to the high energy barrier, however, the solid state is generally unfavorable for materials to exhibit the autonomous switch behavior. To promote the practical usage of the autonomous molecular switch, herein, we propose a prototype of an autonomous photoswitch that can work in the solid state based on a rigid polymer network. A hexacarboxylic sodium-modified hexathiobenzene compound was employed as a photoexcitation-driven unit, which can undergo molecular aggregation upon irradiation because of the distinct conformational difference between the ground state and the photoexcited state. Then, we selected a relatively rigid polymer named poly(dimethyldiallylammonium)chloride (PDDA) to complex with the hexacarboxylic sodium-modified hexathiobenzene through electrostatic coupling. Through optimization, the photoexcitation-controlled molecular aggregation and its self-recovery can work well in the solid matrix of PDDA under rhythmical photoirradiation. This process can be easily encoded by a self-recoverable room-temperature phosphorescence, featuring an excellent performance of the autonomous switch.

Visualizing Material Processing via Photoexcitation-Controlled Organic-Phase Aggregation-Induced Emission.

Aggregation-induced emission (AIE) has been much employed for visualizing material aggregation and self-assembly. However, water is generally required for the preparation of the AIE aggregates, the operation of which limits numerous material processing behaviors. Employing hexathiobenzene-based small molecules, monopolymers, and block copolymers as different material prototypes, we herein achieve AIE in pure organic phases by applying a nonequilibrium strategy, photoexcitation-controlled aggregation. This strategy enabled a dynamic change of molecular conformation rather than chemical structure upon irradiation, leading to a continuous aggregation-dependent luminescent enhancement (up to ~200-fold increase of the luminescent quantum yield) in organic solvents. Accompanied by the materialization of the nonequilibrium strategy, photoconvertible self-assemblies with a steady-state characteristic can be achieved upon organic solvent processing. The visual monitoring with the luminescence change covered the whole solution-to-film transition, as well as the in situ photoprocessing of the solid-state materials.

Hierarchical Core-Shell Fe3O4@mSiO2@Chitosan Nanoparticles for pH-Responsive Drug Delivery.

Hierarchical nanoparticles are of great interest because they possess unique physicochemical properties and multiple functionalities, providing a wealth of possibilities for various applications. In this work, we have developed a well-designed method to prepare hierarchical magnetic nanoparticles Fe3O4@mSiO2@CS by integrating a solvothermal method for synthesizing the Fe3O4 core, a dualtemplating micelle system for preparing a layer of mesoporous silica (mSiO2) shell, and a silane coupling method via γ-glycidoxypropyltrimethoxysilane for binding a chitosan (CS) layer on the silica surface. The porous hierarchical nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), dynamic light scattering nanoparticle size analyzer, and specific surface area and pore size analyzer. The loading capacity and the release behavior of the as-prepared nanoparticles for doxorubicin hydrochloride were studied, and it was found that the drug release rate was faster at pH 6.0 than at pH 7.4, revealing the pH-responsive property of the nanoparticles.

Fluorescence to multi-colored phosphorescence interconversion of a novel, asterisk-shaped luminogen via multiple external stimuli.

We designed and characterized an asterisk-shaped luminogen, hexakis(pyridin-4-ylthio)benzene (HPTB). Via external stimuli such as CH3OH, H+, and Ag+, HPTB's luminogenic character transitioned from blue fluorescence to green, yellow, and orange phosphorescence. Results showed that this interconversion was a reversible process that was also reproducible in liquid and in the solid state.

Chirality Transfer in Coassembled Organogels Enabling Wide-Range Naked-Eye Enantiodifferentiation.

Enantiodifferentiation is crucial in organic chemistry, pharmacochemistry, material chemistry, and life science. However, it remains tremendously challenging to achieve a broad enantioselectivity to different types of chiral substrates via a single-material design. Here, we report a coassembled organogel strategy with chirality transfer to make an enantioselective generality possible. This coassembly contains two components: a chiral rigid molecular linker and an achiral block copolymer. Different from routine helically packed chiral self-assemblies, chirality transfer from the linker to the copolymer directed the coassembly to form a phase-segregated twisted nanofiber, in cooperation with H-bonding and microphase segregation. An organogel was accordingly formed by the further cross-linking in ethanol, where the rigid chiral linker served as the scaffold. On this basis, the system becomes highly sensitive, enabling a naked-eye sensing toward the single enantiomer of a diverse series of chiral species (including axial, point, planar, and polymeric chirality) via gel-to-micelle transformation, due to the asymmetric interaction hampering the chirality transfer in the coassembly and destroying the hierarchical structure. Such a strategy, based on a significant amplification of the stereoselective interactions, facilitates a simple and straightforward way to distinguish a broad optical activity independent of devices.

Structural Engineering of Luminogens with High Emission Efficiency Both in Solution and in the Solid State.

Developing molecules with high emission efficiency both in solution and the solid state is still a great challenge, since most organic luminogens are either aggregation-caused quenching or aggregation-induced emission molecules. This dilemma was overcome by integrating planar and distorted structures with long alkyl side chains to achieve DAπAD type emitters. A linear diphenyl-diacetylene core and the charge transfer effect ensure considerable planarity of these molecules in the excited state, allowing strong emission in dilute solution (quantum yield up to 98.2 %). On the other hand, intermolecular interactions of two distorted cyanostilbene units restrict molecular vibration and rotation, and long alkyl chains reduce the quenching effect of the π-π stacking to the excimer, eventually leading to strong emission in the solid state (quantum yield up to 60.7 %).

Dynamic Modulation of Supramolecular Chirality Driven by Factors from Internal to External Levels.

Supramolecular chirality, generated by the asymmetric assembly of chiral or achiral molecules, has attracted intense study owing to its potential to offer insights into natural biological structures and its crucial roles in advanced materials. The optical activity and stacking pathway of building molecules both greatly determine the chirality of the whole supramolecular structure. The flexibility of supramolecular structures makes their chirality easy to modulate through abundant means. Adjustment of the molecular structure or packing mode, or external stimuli that act like a finger gently pushing toy bricks, can greatly change the chirality of supramolecular assemblies. The dynamic regulation of chiral nanostructures on the intramolecular, intermolecular, and external levels could be regarded as the modulatory essence in numerous strategies, however, this perspective is ignored in most reviews in the literature. Herein, therefore, we focus on the ingenious dynamic modulation of chiral nanostructures by these factors. Through dynamic modulation with changes in chiroptical spectroscopy and electron microscopy, the mechanism of formation of supramolecular chirality is also elaborated.

Photoexcitation-controlled self-recoverable molecular aggregation for flicker phosphorescence.

Chemical systems with external control capability and self-recoverability are promising since they can avoid additional chemical or energy imposition during the working process. However, it remains challenging to employ such a nonequilibrium method for the engineering of optoelectronic function and for visualization. Here, we report a functional molecule that can undergo intense conformational regulation upon photoexcitation. It enables a dynamical change in hydrophobicity and a follow-up molecular aggregation in aqueous media, accordingly leading to an aggregation-induced phosphorescence (AIP) behavior. This successive performance is self-recoverable, allowing a rapid (second-scale cycle) and long-standing (>103 cycles) flicker ability under rhythmical control of the AIP. Compared with traditional bidirectional manipulations, such monodirectional photocontrol with spontaneous reset profoundly enhances the operability while mostly avoiding possible side reactions and fatigue accumulation. Furthermore, this material can serve as a type of luminescent probe for dynamically strengthening visualization in bioimaging.

Directed Self-Assembly of Templatable Block Copolymers by Easily Accessible Magnetic Control.

Magnetic control has been a prosperous and powerful contactless approach in arraying materials into high-order nanostructures. However, it is tremendously difficult to control organic polymers in this way on account of the weak magnetic response. The preparation of block copolymers (BCPs) with high magnetostatic energy is reported here, relying on an effective electrostatic coupling between paramagnetic ions and polymer side chains. As a result, the BCPs undergo a magnetically directed self-assembly to form microphase-segregated nanostructures with long-range order. It is emphasized that such a precisely controlled alignment of the BCPs is performed upon a single commercial magnet with low-intensity field (0.35 Tesla). This strategy is profoundly easy-to-handle in contrast to routine electromagnetic methods with high-intensity field (5-10 Tesla). More significantly, the paramagnetic metal component in the BCP samples can be smartly removed, providing a template effect with a preservation of the directed self-assembled nanofeatures for patterning follow-up functionalized species through the original binding site.

[Effects of mulberry/soybean intercropping on the plant growth and rhizosphere soil microbial number and enzyme activities].

A root separation experiment was conducted to investigate the plant growth and rhizosphere soil microbes and enzyme activities in a mulberry/soybean intercropping system. As compared with those in plastic barrier and nylon mesh barrier treatments, the plant height, leaf number, root length, root nodule number, and root/shoot ratio of mulberry and soybean in non-barrier treatment were significantly higher, and the soybean's effective nodule number was larger. The available phosphorous content in the rhizosphere soils of mulberry and soybean in no barrier and nylon mesh barrier treatments was increased by 10.3% and 11.1%, and 5.1% and 4.6%, respectively, as compared with that in plastic barrier treatment. The microbial number, microbial diversity, and enzyme activities in the rhizosphere soils of mulberry and soybean were higher in the treatments of no barrier and nylon mesh barrier than in the treatment of plastic barrier. All the results indicated that there was an obvious interspecific synergistic effect between mulberry and soybean in the mulberry/soybean intercropping system.

[Effects of mulberry-soybean intercropping on carbon-metabolic microbial diversity in saline-alkaline soil].

Aiming at the characteristics that mulberry-soybean intercropping could alleviate the damage of saline-alkaline soil, Biolog technique was adopted to study the effects of this intercropping on the diversity of carbon-metabolic microbial community in the rhizosphere of saline-alkaline soil. Under mulberry-soybean intercropping, the average well color development (AWCD) symbolizing the metabolic activity of soil microbes was obviously higher, as compared with that under mulberry or soybean monocropping, being the lowest under mulberry monocropping. The McIntosh index was also higher under intercropping than under monocropping, but the Shannon index and Simpson index had less difference between intercropping and monocropping, indicating that intercropping changed the composition and enhanced the diversity of the microbial community in the rhizosphere of saline-alkaline soil. Principal component analysis (PCA) showed that the carbon source utilization mode of the soil microbial community differed between intercropping and monocropping, and the main carbon sources were carbohydrate, carboxylic acid, and polymers. Soil pH and salinity were the main factors limiting the diversity of the microbial community in saline-alkaline soil, and intercropping could effectively decrease the soil pH and salinity and promote the improvement of soil microbial community diversity.

[Effects of Festuca arundinacea on the microbial community in crude oil-contaminated saline-alkaline soil].

By using the routine soil physical and chemical analysis methods and the Biolog technique, this paper studied the effects of Festuca arundinacea growth on the pH value, total salt content, and microbial community in the rhizosphere of crude dil-contaminated saline-alkaline soil in Songnen Plain of Northeast China. Crude oil contamination resulted in the increases of average well color development (AWCD), Shannon index (H), and carbon source utilization richness index (S), and altered the utilization patterns of carbon sources by the microbes. F. arundinacea had greater potential to remediate crude oil-contaminated soil. This plant could decrease the soil pH and soil total petroleum hydrocarbon (TPH) content, and increase the soil water content. The AWCD and S in F. arundinacea rhizosphere soil were obviously higher than those in the soil of naked land, providing a suitable environment for the growth and development of rhizosphere soil microbes.

[Effects of exogenous CaCl2 on the functions of flue-cured tobacco seedlings leaf photosystem II under drought stress].

Taking chlorophyll a fluorescence transient OJIP as the probe, this paper studied the effects of foliar spraying 10 mmol x L(-1) of CaCl2 on the functions of photosystem II (PS II) in tobacco seedling leaves under drought stress. Drought stress decreased the conversion efficiency of PS II primary light energy (F(v)/F(m)) and electron transport rate (ETR), and inhibited the primal process of photosynthesis, resulting in an obvious photoinhibition. After the spraying of CaCl2, the decrement of quantum yield for electron transport (phiE(o)) under drought stress was obviously lower, and the increment of electron transport efficiency of per reaction center (ET(o)/RC) was obviously higher, compared with those after the spraying of water. Foliar spraying CaCl2 increased the amount of PS II -captured light energy used for photosynthesis electron transport, the efficiency of surplus active reaction center, as well as the energy transport in electron transport chain, making the PS II remain relatively high activity under drought stress, and accordingly, the drought resistance of the tobacco seedlings was improved.