A Triptycene-Based Layered/Flower-Like 2D Conductive Metal-Organic Framework with 3D Extension as an Electrode for Efficient Li Storage.

2D metal-organic frameworks (2D MOFs) with π conjugation have attracted widespread attention in the field of lithium storage due to their unique electron transfer units and structural characteristics. However, the periodic 2D planar extension structure hides some active sites, which is not conducive to the utilization of its structural advantages. In this work, a series of triptycene-based 2D conductive MOFs (M-DBH, M = Ni, Mn, and Co) with 3D extension structures are constructed by coordinating 9,10-dihydro-9,10-[1,2]benzenoanthracene-2,3,6,7,14,15-hexaol with metal ions to explore their potential applications in lithium-ion and lithium-sulfur batteries. This is the first study in which 2D conductive MOFs with the 3D extended molecule are used as electrode materials for lithium storage. The designed material generates rich active sites through staggered stacking layers and shows excellent performance in lithium-ion and lithium-sulfur batteries. The capacity retention rate of Ni-DBH can reach over 70% after 500 cycles at 0.2 C in lithium-ion batteries, while the capacity of S@Mn-DBH exceeds 305 mAh g-1 after 480 cycles at 0.5 C in lithium-sulfur batteries. Compared with the materials with 2D planar extended structures, the M-DBH electrodes with 3D extended structures in this work exhibit better performance in terms of cycle time and lithium storage capacity.

Constructing Porous Energetic Spherulites via Solvation-Growth Coupling for Enhanced Combustion.

The fabrication of materials with hierarchical structures has garnered great interest, owing to the potential for significantly enhancing their functions. Herein, a strategy of coupling molecular solvation and crystal growth is presented to fabricate porous spherulites of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), an important energetic material. With the addition of polyvinylpyrrolidone in the antisolvent crystallization, the metastable solvate of CL-20 is formed and grows spherulitically, and spontaneously desolvates to obtain the porous spherulite when filtration, in which the characteristic peak of the nitro group of CL-20 shifts detected by the in situ micro-confocal Raman spectroscopy. The effect of polyvinylpyrrolidone is thought to induce the solvation of CL-20, confirmed by density functional theory calculations, meanwhile acting on the (020) face of CL-20 to trigger spherulitic growth, demonstrated through infrared spectroscopy and Rietveld refinement of powder X-ray diffraction. Moreover, compared to common CL-20 crystals, porous spherulites exhibit enhanced combustion with increases of 6.24% in peak pressure, 40.21% in pressurization rate, and 9.63% in pressure duration effect, indicating the capability of hierarchical structures to boost the energy release of energetic crystals. This work demonstrates a new route via solvation-growth coupling to construct hierarchical structures for organic crystals and provides insight into the structure-property relations for material design.

Chirality Supramolecular Systems: Helical Assemblies, Structure Designs, and Functions.

Chirality, as one of the most striking characteristics, exists at various scales in nature. Originating from the interactions of host and guest molecules, supramolecular chirality possesses huge potential in the design of functional materials. Here, an overview of the recent progress in structure designs and functions of chiral supramolecular materials is present. First, three design routes of the chiral supramolecular structure are summarized. Compared with the template-induced and chemical synthesis strategies that depend on accurate molecular identification, the twisted-assembly technique creates chiral materials through the ordered stacking of the nanowire or films. Next, chirality inversion and amplification are reviewed to explain the chirality transfer from the molecular level to the macroscopic scale, where the available external stimuli on the chirality inversion are also given. Lastly, owing to the optical activity and the characteristics of the layer-by-layer stacking structure, the supramolecular chirality materials display various excellent performances, including smart response, shape-memorization, superior mechanical performance, and applications in biomedical fields. To sum up, this work provides a systematic review of the helical assemblies, structure design, and applications of supramolecular chirality systems.

Uncovering the Recent Progress of CNC-Derived Chirality Nanomaterials: Structure and Functions.

Cellulose nanocrystal (CNC), as a renewable resource, with excellent mechanical performance, low thermal expansion coefficient, and unique optical performance, is becoming a novel candidate for the development of smart material. Herein, the recent progress of CNC-based chirality nanomaterials is uncovered, mainly covering structure regulations and function design. Undergoing a simple evaporation process, the cellulose nanorods can spontaneously assemble into chiral nematic films, accompanied by a vivid structural color. Various film structure-controlling strategies, including assembly means, physical modulation, additive engineering, surface modification, geometric structure regulation, and external field optimization, are summarized in this work. The intrinsic correlation between structure and performance is emphasized. Next, the applications of CNC-based nanomaterials is systematically reviewed. Layer-by-layer stacking structure and unique optical activity endow the nanomaterials with wide applications in the mineralization, bone regeneration, and synthesis of mesoporous materials. Besides, the vivid structural color broadens the functions in anti-counterfeiting engineering, synthesis of the shape-memory and self-healing materials. Finally, the challenges for the CNC-based nanomaterials are proposed.

Bifunctional Chiral Agent Enables One-pot Spontaneous Deracemization of Racemic Compounds.

A novel one-pot deracemization method using a bifunctional chiral agent (BCA) is proposed for the first time to convert a racemate to the desired enantiomer. Specifically, chiral α, (α-diphenyl-2-pyrrolidinemethanol) formed enantiospecific cocrystals with racemic dihydromyricetin, and used its own alkaline catalysis to catalyze the racemization between the (2R,3R)-enantiomer and (2S,3S)-enantiomer in solution, achieving a one-pot spontaneous deracemization. This strategy was also successfully extended to the deracemization of three other racemic compound drugs: (R,S)-carprofen, (R,S)-indoprofen, and (R,S)-indobufen. The one-pot deracemization method based on the BCA strategy provides a feasible approach to address the incompatibility between cocrystallization and racemization reactions that are commonly encountered in the cocrystallization-induced deracemization process and opens a new window to develop essential enantiomerically pure pharmaceutical products with atom economy.

Constructing Janus Microsphere Membranes for Particulate Matter Filtration, Directional Water Vapor Transfer, and High-Efficiency Broad-Spectrum Sterilization.

Commercial masks have significant drawbacks, including low water vapor transmission efficiency and limited ability to inhibit harmful microorganisms, whereas in this contribution, a series of Janus microsphere membranes are developed with hierarchical structures by quenching and crystallizing 12-hydroxystearic acid and halicin layer-by-layer on a polypropylene non-woven fabric, laminating them with hydrophilic cotton fibers in a one-pot process, and further demonstrate the potential of this composite system as masks. Through further optimization, excellent superhydrophobic/superhydrophilic properties (contact angle 157.1°/0°), superior filtering effects (93.54% for PM2.5 and 98.35% for PM10 ), with a low-filtration resistance (57 Pa) and a quality factor of up to 0.072 Pa-1 are achieved, all better than that of commercial N95 masks. In addition, the membrane allows for the directional transport of water vapor from the inside out, increasing the water vapor transmission rate by more than 20% compared with the monolayer hydrophobic microsphere membrane. It also has a bactericidal capacity of over 99.9999% against Escherichia coli and is tested for robustness and stability in various extreme environments. This work may shed light on designing novel filter media with versatile functions, meanwhile, the materials can also be used in protective equipment against the new coronavirus.

Kinetic Retraction at the Onset of Concomitant Crystallization and Implication on Polymorphic Formation.

The four-quadrant regimes of attainable polymorph crystallization (FQR-APC) plot was recently developed through numerical simulations of crystallization kinetics of a dipolymorphic system. Retraction in the polymorphic composition of the most stable form in crystallized samples was unveiled a characteristic indication of concomitant polymorphism. Comparisons were made with a recently developed concept, the Ostwald ratio (OR), in light of characterization of polymorphic formation. It was shown that both schemes display a good agreement in describing polymorphic outcomes, despite their distinct theoretical origins.

Insoluble Salt of Memantine with a Unique Fluorescence Phenomenon.

Alzheimer's disease is a chronic disease, and the long-term treatment of chronic diseases has always been a concern. Memantine (Mem) is approved by the US Food and Drug Administration for the treatment of moderate to severe Alzheimer's disease. In this study, reactions of memantine (Mem) with pamoic acid (Pam) were carried out to form insoluble salts (Mem-Pam). Four polymorphic forms (Forms I-IV) of Mem-Pam were successfully obtained through polymorphic screening, which were systematically characterized by X-ray powder diffraction (PXRD), thermal analysis (TGA and DSC), single-crystal X-ray diffraction (SXRD), and solid-state fluorescence. Compared with the hydrochloride form, the dissolution and release rates of these four forms are lower. The presence of pamoic acid reduces the release rate of memantine and makes it possible to achieve a sustained release of the drug. Interestingly, because of the presence of memantine, each polymorphic solid crystal of Mem-Pam has unique fluorescence emission. Therefore, memantine and pamoic acid have a synergistic effect on the fluorescence performance and can be expected to be used for real-time monitoring in continuous and controlled release drug delivery systems. In addition, the polymorphic solid crystals also exhibit reversible mechanochromic luminescence under the fumigation of acetonitrile vapor, which has a guiding role in the fluorescence design and synthesis of Pam substances and is expected to be used for information security, visual inspection of organic substances, etc.

Facile synthesis of multiphase cobalt-iron spinel with enriched oxygen vacancies as a bifunctional oxygen electrocatalyst.

The multiphase cobalt-iron spinel was firstly synthesized via a facile cold plasma method and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Compared with the single-phase obtained by the traditional calcination method, the CoFe2O4 and Co3O4 phase were obtained by the plasma method. The multivalence states of cobalt and iron facilitated electron transport in electrochemical reactions. The plasma sample had a small particle size (5 nm) due to the low operation temperature. Notably, electron impact produced more oxygen vacancies and a larger surface area on CoxFeyO4, which increased the active sites and electronic conductivity. Electrochemical investigations indicated that the multiphase spinel obtained with a quasi-four-electron transfer process showed an onset potential of 0.76 V versus the RHE for the oxygen reduction reaction. In the oxygen evolution reaction, the potential of current density at 10 mA cm-2 was 1.53 V versus RHE. As for the overall electrocatalytic activity, the multiphase spinel had a ΔE (the difference between E10(OER) and E1/2(ORR)) of 0.89 V, exhibiting greater bifunctional activity than the other prepared catalysts.

Insight into the Nucleation Mechanism of p-Methoxybenzoic Acid in Ethanol-Water System from Metastable Zone Width.

The metastable zone width (MSZW) of p-methoxybenzoic acid (PMBA) in an ethanol-water system was measured using the polythermal method. The nucleation order m obtained by the Nývlt's model indicates the nucleation of PMBA following a progressive nucleation mechanism at low saturation temperature (m = 3.18-7.50) and an instantaneous nucleation mechanism at high saturation temperature (m = 1.46-2.55). Then, combined with the metastable zone experiment and the Sangwal model, we found that the MSZW and the interfacial energy reached the maximum when the mass fraction of ethanol was 0.8, which resulted in the smallest crystal product size. Meanwhile, the maximum rcrit and ΔGcrit obtained based on the modified Sangwal model indicating the PMBA needs to overcome a higher nucleation barrier in the ethanol mass fraction of 0.8. Finally, we proposed a preferential strategy for adjusting MSZW by correlating the interfacial energy with the change in ethanol mass fraction, saturation temperature, and cooling rate, respectively.

Modular Assembly of Drug and Monodisperse SPIONs for Superior Magnetic and T2-Imaging Performance.

Development of superparamagnetic iron oxide nanoparticles (SPIONs) based theranostics has suffered due to its self-contradictory requirements on water dispersity and drug loadings. Generally well-dispersed SPIONs have excellent MRI performance but are insensitive to magnetism mediated delivery. Besides, loading hydrophobic drugs also hampers the stability of SPIONs which is critical for their biomedical applications. Considering these aspects, we employed curcumin as a cross-linking agent to facilitate the modular assembly of drug and monodisperse SPIONs (Cur/ALN-ß-CD-SPIONs). Interestingly, the saturation magnetization of Cur/ALN-ß-CD-SPIONs is higher than that of ALN-ß-CD-SPIONs, and the value of r2 indicating the negative contrast ability increases to 389.96 mM-1 s-1. Furthermore, the Cur/ALN-ß-CD-SPIONs are very stable in PBS buffer over 3 weeks. The mice treated with Cur/ALN-ß-CD-SPIONs by tail vein injection displayed a better tumor inhibition effect than that of free curcumin. This study provides a simple method for modular assembly of drug and monodisperse SPIONs, which is crucial to the design of SPIONs with superior T2-imaging performance and drug delivery.

Influence of Adsorption State and Molecular Interaction on Physical Stability of Confined Amorphous Vortioxetine.

The composites of amorphous vortioxetine (VXT) and ordered mesoporous silica were prepared. Three silica matrixes with different pore sizes were used here: Mobil Composition of Matter No.41 (MCM), Santa Barbara Amorphous No.15 (SBA), and mesostructured cellular foam (MCF). The amorphous composites behaved enhanced physical stability (303.15 K, 56.0 ± 0.4% RH) compared to bulk VXT amorphism. Interestingly, the physical stability of these amorphous composites showed a great difference. Amorphous VXT loaded in MCF crystallized within 1 week, while VXT-SBA composites could be stable over 3 months. The stability of VXT-MCM composites were somewhere in between. In addition, with VXT loading decreasing, the physical stability of confined amorphous VXT became better. Nitrogen adsorption measurements indicated that VXT molecules were adsorbed in SBA in a dispersive state while aggregated in MCM and MCF. VXT-VXT interactions in MCM could be stronger than that in SBA. 1H-13C solid-state nuclear magnetic resonance experiments demonstrated the weaker VXT-VXT interactions in SBA. The dispersive adsorption state and weak VXT-VXT interactions were benefit to the physical stability of amorphous VXT in SBA channels. In addition, dissolution profiles of confined amorphous VXT and bulk crystalline VXT were determined and the dissolution rate of VXT loaded in nanopores was faster than the latter.

Strategies for Liposome Drug Delivery Systems to Improve Tumor Treatment Efficacy.

In the advancement of tumor therapy, in addition to the search for new antitumor compounds, the development of nano-drug delivery systems has opened up new pathways for tumor treatment by addressing some of the limitations of traditional drugs. Liposomes have received much attention for their high biocompatibility, low toxicity, high inclusivity, and improved drug bioavailability. They are one of the most studied nanocarriers, changing the size and surface characteristics of liposomes to better fit the tumor environment by taking advantage of the unique pathophysiology of tumors. They can also be designed as tumor targeting drug delivery vehicles for the precise delivery of active drugs into tumor cells. This paper reviews the current development of liposome formulations, summarizes the characterization methods of liposomes, and proposes strategies to improve the effectiveness of tumor treatment. Finally, it provides an outlook on the challenges and future directions of the field. Graphical abstract.

Progress and Principle of Drug Nanocrystals for Tumor Targeted Delivery.

Drugs are referred to as drug nanocrystals when they exist as nanoscale crystal structures. This kind of nanocarrier has been widely utilized to increase the solubility and absorption for poorly aqueous soluble drugs after oral administration, or prolong the drug circulation when intravenous administration. The systemic cytotoxicity caused by antitumor drugs usually come from the nonspecific drug distribution. To solve the disadvantage of poor targetability, drug nanocrystals for tumor targeted delivery have been developed in recent years. In this review, the targeting mechanisms of various surface modified drug nanocrystals are introduced with the focus on passive targeting, active targeting and stimuli-responsive targeting in details. Function and application of common surface modified materials are also discussed.

Bending for Better: Flexible Organic Single Crystals with Controllable Curvature and Curvature-Related Conductivity for Customized Electronic Devices.

Electronic microdevices of self-bending coronene crystals are developed to reveal an unexplored link between mechanical deformation and crystal function. First, a facile approach towards length/width/curvature-controllable micro-crystals through bottom-up solution crystallization was proposed for high processability and stability. The bending crystal devices show a significant increase beyond seven orders of magnitude in conductivity than the straight ones, providing the first example of deformation-induced function enhancement in crystal materials. Besides, double effects caused by bending, including the change of π electron level as well as the enhancement of carrier mobility, were determined, respectively by the X-ray photoelectric spectroscopy and X-ray crystallography to coexist, contributing to the conductivity improvement. Our findings will promote future creation of flexible organic crystal systems with deformation-enhanced functional features towards customized smart devices.

Aggregation-induced emission and polymorphism/shape/size-dependent emission behaviours of fenamates for potential drug evaluation.

Rare multiple fluorescence properties including aggregation-induced emission and polymorphism/shape/size-dependent emission were found coexisting in a class of typical non-steroidal anti-inflammatory analgesic drugs, fenamates, which could provide a new approach toward future drug evaluation. Different from the complexity and biological incompatibility of the traditional AIE molecular design, this work opens new avenues to the development of new AIE systems.

Two new polymorphs and one dihydrate of lenalidomide: solid-state characterization study.

Purpose: Lenalidomide (LDM) is a blockbuster drug for multiple myeloma and non-Hodgkin's lymphoma, and contributed $ 6.974 billion in sales for Celgene in 2016. The aim of this research is to expand the crystal form landscape, characterize the physicochemical properties and thoroughly investigate the potential solid forms transformation for this famous drug. Materials and methods: In this study, a comprehensive solid-state screening was carried out. The physicochemical properties, stability and phase transformation were fully investigated using powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), solid state nuclear magnetic resonance (solid state NMR) and Infrared Spectroscopic Analysis (IR). Finally the differences of dissolution behavior were compared through powder dissolution test. Results: Two new anhydrous forms (α and ß) and one new dihydrate form (DH) of LDM were discovered through a comprehensive solid-state screening experiment. The new discovered DH showed better stability under accelerated storage condition (40 °C/75% RH) and in most organic solvents than other forms. The new discovered form α exhibited faster dissolution rate in the early phase and larger apparent solubility than the currently marketed form. Conclusions: These new forms exhibit a new chance for drug development in view of their pharmaceutical properties and intellectual property.

Legumain, an asparaginyl endopeptidase, mediates the effect of M2 macrophages on attenuating renal interstitial fibrosis in obstructive nephropathy.

Two distinct macrophage phenotypes contribute to kidney injury and repair during the progression of renal interstitial fibrosis; proinflammatory (M1) and antiinflammatory (M2) macrophages. Legumain, an asparaginyl endopeptidase of the cysteine protease family, is overexpressed in macrophages in some pathological conditions. However, the macrophage subtype and function of macrophage-derived legumain remains unclear. To resolve this we tested whether M2 macrophages contribute to the accumulation of legumain in the unilateral ureteral obstruction model. Legumain-null mice exhibited more severe fibrotic lesions after obstruction compared with wild-type control. In vitro, IL4-stimulated M2 polarization led to the overexpression and secretion of legumain. The levels of fibronectin and collagen I/III, major components of the extracellular matrix, were reduced in the conditioned medium of TGF-ß1-stimulated tubular epithelial cells or fibroblasts after treatment with legumain or conditioned medium from IL4-stimulated macrophages. Administration of the legumain inhibitor RR-11a exacerbated fibrotic lesions following obstruction. Therapeutically, adoptive transfer of legumain-overexpressing macrophages or IL4-stimulated macrophages ameliorated the deposition of collagen and fibronectin induced by ureteral obstruction, either in the wild-type mice or in lgmn-/- mice. Thus, M2 macrophages overexpress and secret legumain and legumain mediates the anti-fibrotic effect of M2 macrophages in obstructive nephropathy.

CPP-Assisted Intracellular Drug Delivery, What Is Next?

For the past 20 years, we have witnessed an unprecedented and, indeed, rather miraculous event of how cell-penetrating peptides (CPPs), the naturally originated penetrating enhancers, help overcome the membrane barrier that has hindered the access of bio-macromolecular compounds such as genes and proteins into cells, thereby denying their clinical potential to become potent anti-cancer drugs. By taking the advantage of the unique cell-translocation property of these short peptides, various payloads of proteins, nucleic acids, or even nanoparticle-based carriers were delivered into all cell types with unparalleled efficiency. However, non-specific CPP-mediated cell penetration into normal tissues can lead to widespread organ distribution of the payloads, thereby reducing the therapeutic efficacy of the drug and at the same time increasing the drug-induced toxic effects. In view of these challenges, we present herein a review of the new designs of CPP-linked vehicles and strategies to achieve highly effective yet less toxic chemotherapy in combating tumor oncology.

Formation and Transformation Behavior of Sodium Dehydroacetate Hydrates.

The effect of various controlling factors on the polymorphic outcome of sodium dehydroacetate crystallization was investigated in this study. Cooling crystallization experiments of sodium dehydroacetate in water were conducted at different concentrations. The results revealed that the rate of supersaturation generation played a key role in the formation of the hydrates. At a high supersaturation generation rate, a new sodium dehydroacetate dihydrate needle form was obtained; on the contrary, a sodium dehydroacetate plate monohydrate was formed at a low supersaturation generation rate. Furthermore, the characterization and transformation behavior of these two hydrated forms were investigated with the combined use of microscopy, powder X-ray diffraction (PXRD), Raman spectroscopy, Fourier transform infrared (FTIR), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and dynamic vapor sorption (DVS). It was found that the new needle crystals were dihydrated and hollow, and they eventually transformed into sodium dehydroacetate monohydrate. In addition, the mechanism of formation of sodium dehydroacetate hydrates was discussed, and a process growth model of hollow crystals in cooling crystallization was proposed.