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Reactions of a chiral and quasi-spherical molecule [1S,4S-2,5–2.2.1-H2dabch]I2(1) with alkali metal halide MX (M = Na, K, Cs; X = Cl, Br) at room temperature produced a series of organic–inorganic hybrid (OIH) materials [1S,4S-2,5–2.2.1-H2dabch]NaBr3(2), [1S,4S-2,5–2.2.1-H2dabch]CsCl3·H2O (3) and [1S,4S-2,5–2.2.1-H2dabch]KBr3·H2O (4). The single-crystal X-ray diffraction analysis revealed that the organic–inorganic framework structures comprised of the templating ligand and alkali metal halides (NaBr, CsCl, KBr) displayed dimensions spanning from one-dimensional (1D) to three-dimensional (3D). Moreover, the results of both differential scanning calorimetry (DSC) and dielectric measurements demonstrated that compounds 1–4displayed reversible, high-temperature phase transitions and noticeable dielectric anomalies. In addition, the temperature-dependent second harmonic generation (SHG) results revealed crystals 1and 3can switch from the SHG-ON to the SHG-OFF state, which was proved by the variable-temperature X-ray diffraction. This research aims to streamline the exploration of multifunctional second harmonic generation (SHG) and dielectric materials that have been synthesized using chiral ligands and alkali metals. This will provide researchers with enhanced opportunities to delve further into this specific research domain.

Reported herein is direct C(sp3)–H arylation of unprotected benzyl anilines and alkylarenes via consecutive photoinduced electron transfer by visible light irradiation. Reductive quenching cycles and radical–radical cross-coupling were involved, and electron paramagnetic resonance experiments provide evidence for the formation of radical intermediates formed in situ. The protocol highlights transition metal free, external oxidant free, broad substrate scope, and high efficiency (>60 examples, up to 96%).

Solute Carrier Family 25 (SLC25) is the largest family of mitochondrial membrane proteins in the human body, consisting of 53 members. Mitochondrial phosphate carriers (MPiC), cellular iron metabolism, voltage-dependent anion channels (VDAC), and oxidative phosphorylation in the SLC25family play dominant roles in material transport, energy metabolism, etc. SLC25family-related proteins are involved in the regulation of the progression of a variety of cancers, including colon, gastric, and lung cancers. In addition, the SLC25family has been implicated in endoplasmic reticulum stress (ERS) and immunity. Since SLC25family proteins are involved in cancer progression and are associated with endoplasmic reticulum stress and immunity, exploring inhibitors of SLC25family-related proteins is essential. However, the exact mechanism of SLC25family-related proteins involved in cancer, as well as potential targets and SLC25inhibitors have not been reported in the literature. This article focuses on summarizing the relevance of the SLC25family to cancer, ERS, and immunity. This review also provides a comprehensive overview of SLC25family-related inhibitors.

Molecular ferroelectrics have attracted much attention because of their excellent piezoelectricity, mechanical workability, and second harmonic effect. Here, we successfully prepared two molecular ferroelectrics [1,5–3.2.2-Hdabcn]X (X = ClO4−, 1; ReO4−, 2) by reactions of a quasi-spherical amine 1,5-diazabicycle[3.2.2]nonane (1.5–3.2.2-dabcn) with HX aqueous solution. Compounds 1and 2undergo high-temperature phase transitions at 381 K (1) and 396 K (2). Before and after the phase transition, they crystallize in the polar point group mm2, and the centrosymmetric point groups mmmand 4/mmm, respectively. According to Aizu rules, these two compounds experience mmmFmm2 and 4/mmmFmm2 type ferroelectric phase transitions, respectively. The ferroelectricity of both compounds is well expressed in their polycrystalline film at room temperature with low coercive voltages of 13 V for 1and 25 V for 2. Using piezoelectric force microscopy (PFM), the 180° anti-parallel ferroelectric domains and the reversible polarization switching can be clearly observed in 1and 2. This high-temperature molecular ferroelectric material has great application potential in flexible materials, biomechanics, intelligent wearables and other fields.

Although research on organic–inorganic hybrid perovskites (OIHPs) has grown exponentially in the past two decades, the high phase transition temperature of OIHP materials is still one of the insurmountable difficulties. Herein, a series of A2BX4type OIHP materials [(2,n-DFBA)2PbCl4] (n= 3, for 1; n= 4, for 2; n= 5, for 3; n= 6, for 4) have been prepared by reactions of double-substituted difluorobenzylamine (difluorobenzylamine = DFBA) with lead chloride in concentrated HCl aqueous solution. It was found the OIHP compounds 1–3proceed a switchable phase transition with phase transition temperatures (Tc) at 449 K (1), 462 K (2) and 500 K (3), higher than that of the parent compound [(BA)2PbCl4] (BA = benzylammonium) at 438 K, but compound 4exhibits no phase transition. A crystal structure analysis elucidated that the organic template ligands DFBA lead in the inorganic part in compounds 1–3to a two-dimensional (2D) perovskite structure, while that in compound 4leads to a one-dimensional (1D) chain structure. The different double-substituted positions of fluorine atoms on benzylamine have important influences on the phase transition in compounds 1–4.

Diabetes mellitus (DM) is characterized by the irreversible destruction of insulin-secreting pancreatic β-islet cells and requires life-long exogenous insulin therapy. Umbilical cord Wharton's jelly-derived mesenchymal stem cells (WJ-MSCs) have been shown to improve islet function in animal models of diabetes. However, inadequate MSC homing to injured sites has limited their efficacy. Since efficient cell therapy heavily relies on appropriate homing to target tissues, increasing the specificity to the target organ and the extent of homing of the injected WJ-MSCs is paramount to successful clinical outcomes. Therefore, in this study, we synthesized Fe3O4@polydopamine nanoparticle (NP)-labeled MSCs and evaluated their therapeutic efficacy in a clinically relevant rat model of streptozotocin-induced diabetes using an external magnetic field. We found that NPs were successfully incorporated into WJ-MSCs and did not negatively affect stem cell properties. Magnetic targeting of WJ-MSCs contributed to long-term cell retention in pancreatic tissue and improved the islet function of diabetic rats, compared to injection of WJ-MSC alone. In addition, anti-inflammatory effects and the anti-apoptotic capacity of WJ-MSCs appeared to play a major role in the functional and structural recovery of the pancreas. Thus, therapy relying on the magnetic targeting of WJ-MSCs may serve as an effective approach for DM treatment.

Mesenchymal stem cell (MSC)-based therapy has emerged as a promising therapeutic strategy for tissue regeneration and repair. However, efficient targeted delivery to specific tissues remains an open challenge. Here, we non-invasively monitored the migration of MSCs labeled with Fe3O4@polydopamine nanoparticles (Fe3O4@PDA NPs) toward laser burn injury sites in a living rat model and evaluated the effects of the labeled MSCs at the injury site. The Fe3O4@PDA NPs could be effectively incorporated into the MSCs without any negative effects on stem cell properties. Furthermore, they enhanced the migration ability of the MSCs by up-regulating the expression level of C–X–C chemokine receptor type 4 (CXCR4). They also increased the secretion of some cytokines and the expression of healing-related genes in comparison with unlabeled MSCs. Labeled MSCs were intravenously administered into injured rats, and live imaging was performed to monitor MSC migration. Fluorescent signals of the labeled MSCs appeared at burn injury lesions 1 day after injection and then gradually increased up to 7 days. After 7 days, the group injected with the labeled MSCs showed less inflammation compared with those injected with the unlabeled MSCs. Additionally, the labeled MSC group showed increased cytokines and reduced pro-inflammatory factors compared with the unlabeled MSC group. The Fe3O4@PDA NPs enhanced stromal cell-derived factor-1/CXCR4-mediated MSC migration in vivo. Thus, we demonstrated the safety, feasibility, and potential efficacy of using the Fe3O4@PDA NPs for optimizing MSC-based therapeutic strategies for burn wound healing.

It is known that perovskites with the general chemical formula of ABX3(A, B = cations, X = anion) have been intensively studied over the last half century because of their diverse functional properties, such as ferroelectricity in BaTiO3, piezoelectricity in PZT (lead zirconate titanate), and recently developed photovoltaic properties in CH3NH3PbI3. However, rather less attention has been paid to their “inverse” analogs, antiperovskites, which have a chemical formula X3BA, where A and B are anions and X is a cation. Although most of important ferroelectrics are perovskites, no antiperovskite ferroelectrics have been found since the discovery of antiperovskites in 1930. Here, for the first time, we report a X3BA antiperovskite ferroelectric [(CH3)3NH]3(MnBr3)(MnBr4) (where (CH3)3NH is X, MnBr3is B, and MnBr4is A), which shows outstanding ferroelectricity with a significantly high phase transition temperature of 458 K as well as fascinating photoluminescence properties with two intense emissions. This finding opens a new avenue to explore the golden area of antiperovskites for high-performance functional materials.

Natural killer (NK)-cell-based immunotherapy has been reported to have promising prospects in the treatment of non-small cell lung cancer, one of the most common malignancies in the world. It has been proven that higher the NK cell infiltration into the tumor, the better is the curative effect. Therefore, it would be beneficial to develop a method that increases NK cell recruitment and infiltration into the tumor site. The purpose of this study was to establish an immune-cell delivery system for clear lung cancer cells based on magnetic nanoparticle (NP)-labeled NK cells that can be accumulated at the tumor site by placing a tiny external magnetic device inside animals. We developed superparamagnetic iron oxide NPs consisting of a magnetic Fe3O4core and a shell of polydopamine (PDA) for magnetic targeting therapy. Fe3O4@PDA NPs possess favorable physiological stability and biocompatibility that facilitate their active uptake by NK cells. The biology of NK cells was not affected by the presence of NPs. In vitroand in vivostudies showed that Fe3O4@PDA NP-labeled NK cells significantly inhibited tumor growth and reduced the expression of Ki-67 and increased the apoptosis of A549 cancer cells. H&E staining showed Fe3O4@PDA NP-labeled NK cells, under a magnetic field, had higher intra-tumoral iron density and increased accumulation of CD56+NK cells. Our results suggest that Fe3O4@PDA NPs are a promising magnetic nanomaterial that can manipulate immune cells, thereby inhibiting tumor growth.

Organic–inorganic hybrid metal halides have attracted significant attention in recent years due to their excellent optoelectronic properties and potential applications in solar cells. Herein, the organic–inorganic hybrid molecule [N,N-dimethyl-1,3-propanediamine]SbBr5(1) was synthesized by reacting a long-chain organic diamine N,N-dimethyl-1,3-propanediamine with SbBr3as a metal halide precursor in HBr aqueous solution. Compound 1possesses a one-dimensional chainlike structure with the second-harmonic generation switch and two continuous phase transitions above room temperature. The band gap of compound 1is about 2.62 eV, exhibiting a semiconductive property, which may have important implications for the development of new optoelectronic devices.

Direct N-allylation of azoles with hydrogen evolution has been achieved through the synergistic combination of organic photocatalysis and cobalt catalysis. The protocol bypasses stoichiometric oxidants and prefunctionalization of alkenes and produces hydrogen (H2) as the byproduct. This transformation highlights high step- and atom-economy, high efficiency, and broad functional group tolerance for further derivatization, which opens a door for C–N bond formation that is valuable in heterocyclic chemistry.

Switchable second harmonic generation (SHG) materials have potential applications in information storage, signal processing, and so on because they can switch between SHG-on and SHG-off states. In this work, we designed and synthesized three organic–inorganic hybrid Rb halide three-dimensional (3D) perovskite materials [1S,4S2,5-2.2.1-H2dabch]RbX3·0.5H2O (X = Cl, 1; Br, 2; I, 3) based on the chiral 1S,4S-2,5-diazabicyclo[2.2.1]heptane (1S,4S-2,5-2.2.1-dabch). The selection of homochiral organic cations ensures that the compounds 1∼3crystallize in the noncentrosymmetric and chiral space group P212121, which further leads to reversible SHG responses of the three compounds. Through differential scanning calorimetry (DSC) and dielectric measurements, it revealed that the phase transition point of the compounds 1∼3increased with RbCl, RbBr, and RbI. This is because the hydrogen interaction H···X between the inorganic framework [RbX3]nand the organic cation [1S,4S-2,5-2.2.1-H2dabch]2+is increased with the order of I > Br > Cl. This study can provide an effective molecular design strategy for the exploration and construction of temperature-tunable SHG switching materials.

Background: Inorganic nanocomposites especially Au nanostructures have exhibited outstanding physicochemical properties in biomedical fields. For further clinical applications on theranostics, especially drug delivery, numerous explorations of green and facile synthesis methods combining with pharmacoactive natural components have been investigated to construct safe and multifunctional bioactive Au nanoparticles (NPs). Ginsenoside Rh2is protopanaxadiol type compound isolated from plants of genus Panax, with excellent anticancer effect and antioxidant activity. In this research, we prepared the novel Au nanoparticles using ginsenoside Rh2as both reducing and stabilizing agents. Results: The synthesized Au@ginsenoside Rh2NPs were proved to exhibit desirable inhibitory effect on different cancer cell lines, which benefited from the inherent anticancer effect of the ginsenoside Rh2. Investigations in vitro indicated that Au@ginsenoside Rh2NPs inhibited cell proliferation, cell migration and invasion, induced cell cycle arrest, enhanced the reactive oxygen species (ROS) generation, and regulated the protein expressions of caspase-3, 8, 9 to trigger cell apoptosis as well. Conclusions: Because of the absence of toxic chemical surfactants, the eco-friendly synthesis method of Au NPs modified by natural phytochemicals avoided tedious separation and modification processes. On the other hand, Au@ginsenoside Rh2NPs also improved water solubility and bioavailability of the hydrophobic drug ginsenoside Rh2. It broadened minds for preparation and application of traditional Chinese medicines (TCMs) modified metal nanoparticles and deserved further study.

Correction for ‘In vivomigration of Fe3O4@polydopamine nanoparticle-labeled mesenchymal stem cells to burn injury sites and their therapeutic effects in a rat model’ by Xiuying Li et al., Biomater. Sci., 2019, 7, 2861–2872, DOI: 10.1039/C9BM00242A.

Even though hybrid organic–inorganic perovskites (HOIPs) have been studied by many scholars in recent years, there are not many reports on three-dimensional (3D) alkali metal cesium halide perovskites. Here, we report an unprecedented 3D HOIP molecule (1,5-3.2.2-H2dabcn)CsBr3(1), in which the 3D anionic framework is constructed by corner-sharing CsBr6octahedra and organic cations [1,5-3.2.2-H2dabcn]2+are located in the cavities formed by the octahedra. Organic cations interact with an inorganic metal frame via two N–H···Br hydrogen bonds. Compound 1undergoes a reversible order–disorder phase transition and exhibits switchable dielectric and second-harmonic generation (SHG) properties. Interestingly, product 1crystallizes in a non-centrosymmetric space group Pmn21at the low-temperature phase (LTP) and transforms into a centrosymmetric space group P2/mat the high-temperature phase (HTP). The space group Pmn21in the LTP has a higher symmetry than P2/min the HTP. This inverted symmetry breaking is very unusual.

An organic–inorganic hybrid molecule [3.3.0-H2dabco]ZnBr4(1) with switchable phase transition, dielectric anomaly, and second harmonic generation (SHG) effect was synthesized by reaction of 1,5-diazabicyclo[3.3.0]octane (3.3.0-dabco) with ZnBr2in concentrated hydrobromic acid aqueous solution. Differential scanning calorimetry (DSC) and dielectric measurements revealed that 1exhibits a reversible high-temperature phase transition, accompanied by a distinct step-like dielectric anomaly at 373 K. Exceptionally, the single crystal structure analysis at different temperatures revealed that 1undergoes reverse symmetry breaking during the phase transition, in which the high-symmetry space group Ccin the low temperature phase (LTP) is transformed to the low-symmetry space group P1̅ in the high temperature phase (HTP). In addition, with the conversion from the non-centrosymmetric (NCS) to the centrosymmetric (CS) space group, the SHG of 1can switch from SHG-ON to SHG-OFF for at least four cycles without obvious decay.

Four diiron hexacarbonyl complexes, [Fe2(μ‐SCH2‐o‐C6H4OMe)2(CO)6] (4a), [Fe2{μ‐SCH2‐o,m‐C6H3(OMe)2}2(CO)6] (4b), [Fe2{μ‐SCH2‐o,o′‐C6H3(CO2Me)(OMe)}2(CO)6] (4c) and the demethylated form of complex 4a, [Fe2(μ‐SCH2‐o‐C6H4OH)2(CO)6] (5a), were synthesised and fully characterised. Complexes 4band 4cwere also structurally analysed. Electrochemical investigations revealed that the integrity of the bridging linkages of the examined diiron complexes significantly affect their reduction reversibility and catalysis through a coupled chemical reaction in a unique ECE mechanism, widely adopted by complexes with the core {Fe2(CO)4–6}. Demethylation of complexes 4aand 1Me, [Fe2(μ‐SCH2)2CMe(CH2‐o‐C6H4OMe)(CO)6], by BBr3led to complexes (5aand 1H, [Fe2(μ‐SCH2)2CMe(CH2‐o‐C6H4OH)(CO)6]) with pendant phenol group(s), a weak acid. Deprotonation of the two complexes produced the pendant phenolate, which instantly intramolecularly substitutes the bound CO to yield species of the coordination form FeI–OR (R = phenolic moiety). Electrochemical investigation revealed that the pendant phenol groups in complexes 1H and 5ado not seem to improve their catalytic efficiency in proton reduction in the medium acetic acid/dichloromethane.

Reactions of the preformed cluster [Et4N][TpWμ3SμS2CuSCN2] 1 with pyridine py, 4,4′bipyridine 4,4′bipy, or 1,3bis4pyridylpropane bpp led to the formation of three neutral [TpWμ3SμS2Cu2]based compounds [TpWμ3SμS2Cu2SCNpy2] 2, [{TpWμ3SμS2Cu2SCN}24,4′bipy]·3.5H2O 3·3.5H2O, and [TpWμ3SμS2Cu2SCNbpp]24, respectively. Compounds 2–4were characterized by elemental analysis, IR spectra, UVVis spectra, 1H NMR, and Xray analysis. There are two linkage isomers [TpWμ3SμS2Cu2SCNpy2] and [TpWμ3SμS2Cu2NCSpy2], each of which has its own enantiomeric pair in the crystal of 2. Compound 3has a double butterflyshaped structure in which two [TpWμ3SμS2Cu2SCN] fragments are linked with a single 4,4′bipy bridge. For 4, the two butterflyshaped [TpWμ3SμS2Cu2SCN] fragments are interconnected by a pair of bpp bridges. The thirdorder nonlinear optical NLO performances of 2–4in DMF were also investigated by Zscan techniques.© WileyVCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009

The copolymerization of 3‐methylthiophene (MeT) and fluorene (FE) was successfully achieved in boron trifluoride diethyl etherate by the direct anodic oxidation of the monomer mixtures on a platinum electrode. The optimal feed ratio together with the best suitable potential for their copolymerization was determined. The as‐formed copolymer films, which were copolymerized with a feed ratio of FE/MeT = 2:1 at a constant potential of 1.3 V (vs a saturated calomel electrode), had the advantages of both poly(3‐methylthiophene) and polyfluorene, such as good electrochemical behavior, high conductivity, excellent thermal stability, and high film quality. The structure of the copolymer was investigated with ultraviolet–visible, infrared spectroscopy, and thermal analysis. Fluorescence spectroscopy studies revealed that the dedoped copolymer film in the solid state was a good blue‐light emitter with a strong emission at 435 nm and a shoulder at 459 nm. The emitting properties of the copolymer could be tuned by parameters during the electrochemical polymerization, such as the applied potential and monomer feed ratio. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4904–4915, 2006