Supramolecular crystals of Mn(15-crown-5)(MnCl4)(DMF) with dielectric phase transition, high quantum yield and phase transition-induced luminescence enhancement behavior.

The supramolecular crystals, Mn(15-crown-5)(MnCl4)(DMF), (1; 15-crown-5 = 1,4,7,10,13-pentaoxacyclopentadecane), were synthesized via a self-assembly strategy under ambient conditions. Comprehensive characterization of the crystals involved microanalysis for C, H, and N elements, thermogravimetric (TG) analysis, differential scanning calorimetry (DSC) and single-crystal X-ray diffraction techniques. The results reveal that 1 undergoes a two-step thermotropic and isostructural phase transition at around 217 K and 351 K upon heating. All three phases belong to the same space group (P212121) with analogous cell parameters. These two phase transitions primarily involve the thermally activated ring rotational dynamics of the 15-crown-5 molecule, with only the transition at ca. 351 K being associated with a dielectric anomaly. 1 exhibits intense luminescence with a peak at ∼600 nm and a high quantum yield of 68%. The mechanisms underlying this intense luminescence are likely linked to low-symmetry ligand fields. Additionally, 1 displays phase transition-induced luminescence enhancement behavior, and the possible mechanism is further discussed.

Thermotropic Structure Phase Transitions and Two Types of Thermochromic Behaviors in a Bromoargentate Cluster [Pr-dabco]2Ag4Br6.

Organic-inorganic silver halide hybrids show abundant phase transitions and thermochromism. However, it is very rare that silver halides exhibit thermochromism related to thermotropic structure phase transition. Herein, a bromoargentate hybrid, [Pr-dabco]2Ag4Br6 (1) (Pr-dabco+ = 1-propyl-1,4-diazabicyclo-[2.2.2]octan-1-ium), with tetranuclear [Ag4Br6]2- clusters was prepared and characterized by microanalysis, ultraviolet-visible (UV-vis) diffuse reflectance spectroscopy, and thermogravimetric (TG) and differential scanning calorimetry (DSC) techniques. Interestingly, 1 undergoes an irreversible structure phase transition at ∼436 K in the first heating process, which is accompanied by an abrupt color change from colorless to yellow; however, a reversible color change between pale yellow and yellow is observed in the next heating-cooling cycles. Notably, DSC measurement revealed that a reversible phase transition is associated with the change in color between pale yellow and yellow, while the powder X-ray diffraction (PXRD) patterns corresponding to pale yellow and yellow phases are quite similar to each other. These observations demonstrate that thermochromism in the next heating-cooling runs is associated with a reversible structure phase transition, which perhaps concerns the disorder-order transformation of alkyl chains in the cationic ligand [Pr-dabco]+, and relevant to the anharmonic fluctuations of the Ag-Br and Ag-N bonds, a strong electron-phonon coupling effect is seen within the bromoargentate cluster.

Phase transition and ionic conduction enhancement induced by co-doping of LiI and MnI2 in a one-dimensional lead iodide perovskite.

Herein, we demonstrated the unique advantage of a mechanochemical reaction to prepare a salt with hard and soft acid and base ions concurrently by solution synthesis owing to the soft acid preferring to combine with the soft base and vice versa. We prepared Bu4N1-xLixMnxPb1-xI3 (x = 0.011-0.14) by mechanochemical synthesis. The doping induced a structural phase transition at ∼342 K and much enhancement of ionic conduction above 342 K for all co-doped hybrids regarding Bu4NPbI3 because of the voids around the Mn2+/Li+ ions by doping.

Organic-inorganic haloargentate hybrids of [Me-dabco]Ag2X3 (X = I or Br) with halide ions manipulating the crystal structure, phase transition, and dielectric behavior.

Two haloargentate hybrids, [Me-dabco]Ag2X3 (Me-dabco = 1-methyl-1,4-diazabicyclo-[2.2.2]octan-1-ium, X = I (1) or Br (2)), with the same formula but different structures have been synthesized by a slow evaporation method and characterized by microanalysis, infrared spectroscopy, thermogravimetric, and powder X-ray diffraction techniques. Hybrid 1 consists of completely isolated [Ag4I6]2- clusters, while hybrid 2 exhibits a complicated one-dimensional (1D) chain structure formed by four different configurations of neutral chains and two dissimilar configurations of anionic chains. Hybrid 2 undergoes two reversible order-disorder phase transitions, while hybrid 1 displays one reversible and one irreversible structural phase transition. Both 1 and 2 displayed step-like dielectric anomalies in the vicinity of the phase transition temperature. The corresponding dielectric constants in the high dielectric states are approximately 13 and 6 times higher than those in the low dielectric states for 1 and 2, respectively. Interestingly, the subtle change of halides from I- to Br- significantly affects the aggregated structure of haloargentate, the phase transition, and dielectric behaviors, revealing the typical 'butterfly effect' with the ion radii of halides in these two haloargentate hybrids.

A {Cu2I3-}∞ chain hybrid with two-step phase transition, switchable dielectrics, thermochromism and piezochromism.

Stimuli-responsive smart materials have applications in a range of technologies. Herein, we present a hybrid (1), built from Me3EtN+ organic cations and {Cu2I3-}∞ inorganic chains with Cu⋯Cu metal⋯metal interactions. The two-step phase transition undergone in 1 on the first heating and the phase transition at a lower temperature show symmetry-broken features, leading to switchable dielectrics; the one at a higher temperature displays isomorphic characteristics. Besides the switchable dielectrics, 1 exhibited other multi-stimuli-responsive functionalities, including thermochromism and piezochromism. Combining temperature-dependent powder and single crystal X-ray diffraction, as well as variable-temperature UV-visible absorption spectrum and EPR spectrum analyses, it is demonstrated that the thermochromism is due to the synergy of anharmonic fluctuations with electron-phonon couplings, and the piezochromism arises from compression inducing a lattice distortion in 1. Our study provides insight into understanding the thermochromic and piezochromic mechanisms of cuprous halide-based hybrids, and paves a pathway for designing new multi-stimuli-responsive hybrid materials.

YiQiFuMai Lyophilized Injection ameliorates tPA-induced hemorrhagic transformation by inhibiting cytoskeletal rearrangement associated with ROCK1 and NF-κB signaling pathways.

ETHNOPHARMACOLOGICAL RELEVANCE: Thrombolytic therapy with tissue plasminogen activator (tPA) after ischemic stroke exacerbates blood-brain barrier (BBB) breakdown and leads to hemorrhagic transformation (HT). YiQiFuMai Lyophilized Injection (YQFM) is a modern preparation derived from Sheng-mai San (a traditional Chinese medicine). YQFM attenuates the BBB dysfunction induced by cerebral ischemia-reperfusion injury. However, whether YQFM can suppress tPA-induced HT remains unknown. AIM OF THE STUDY: We investigated the therapeutic effect of YQFM on tPA-induced HT and explored the underlying mechanisms in vivo and in vitro to improve the safety of tPA use against stroke. METHODS: Male C57BL/6J mice were subjected to 45 min of ischemia and 24 h of reperfusion. tPA (10 mg/kg) were infused 2 h after occlusion and YQFM (0.671 g/kg) was injected 2.5 h after occlusion. The in vitro effect of YQFM (100, 200, 400 µg/mL) on tPA (60 µg/mL)-induced dysfunction of the microvascular endothelial barrier in the brain following oxygen-glucose deprivation/reoxygenation (OGD/R) was observed in bEnd.3 cells. RESULTS: YQFM suppressed tPA-induced high hemoglobin level in the brain, mortality, neurologic severity score, BBB permeability, expression and activation of matrix metalloproteinase (MMP)-9 and MMP-2, and degradation of tight-junction proteins. Furthermore, YQFM significantly blocked tPA-induced brain microvascular endothelial permeability and phosphorylation of Rho-associated kinase (ROCK)1, myosin light chain (MLC), cofilin and p65 in vivo and in vitro. CONCLUSION: YQFM suppressed tPA-induced HT by inhibiting cytoskeletal rearrangement linked with ROCK-cofilin/MLC pathways and inhibiting the nuclear factor-kappa B pathway to ameliorate BBB damage caused by tPA.

A Survey of Application of Complementary and Alternative Medicine in Chinese Patients with Parkinson's Disease: A Pilot Study.

OBJECTIVE: To investigate the prevalence and spectrum of complementary and alternative medicine (CAM) application and its related-factors in Parkinson's disease (PD) patients in China. METHODS: A structured questionnaire regarding the use of CAMs was administered to PD patients by face-to-face interview. Demographic and social variables, clinical characteristics and treatments, and the related factors of PD were also surveyed. RESULTS: Ninety out of 113 patients (79.6%) reported that they had received CAMs treatment, of which 48.6% (55/113) patients had received CAMs treatment for PD. The top 3 kinds of CAMs for PD were Chinese materia medica, rehabilitation exercise, and acupuncture ordinally. The source of information regarding CAMs treatment mainly came from relatives and friends (51.8%, 73 cases), followed by physicians (31.9%, 45 cases), and medias such as television, newspapers or the internet (16.3%, 28 cases). Fifty percent of CAM users reported a good therapeutic efficacy, whereas 39% patients reported that they felt neither better nor worse after the treatment, while 11% patients claimed worsening of symptoms. Multiple correspondence analyses survey found the main factors affecting the selectivity of CAMs ranked in the following order: income, education, occupation, habitation, age at onset, Hoehn and Yahr staging, PD duration, and gender. CONCLUSION: CAMs, especially Chinese materia medica, rehabilitation exercise, and acupuncture, are widely used for PD patients in China.

Multi-step structural phase transitions with novel symmetry breaking and inverse symmetry breaking characteristics in a [Ag4I6]2- cluster hybrid crystal.

In this study, a multi-step phase transition hybrid composed of (Pr-dabco)2Ag4I6 clusters (Pr-dabco+ = 1-propyl-1,4-diazabicyclo[2.2.2]octan-1-ium) has been prepared and characterized by microanalysis, IR and UV-vis spectroscopy, TG and DSC techniques, etc. This hybrid is thermally stable up to ∼486 K with five phases in the temperature region below 486 K. The phase transition shows symmetry breaking (SB) character between phases II (space group P21/c) and III (space group Pa3[combining macron]), while inverse symmetry breaking (ISB) between phases II and I (space group Pbca), and it is rather exceptional for matter to exhibit simultaneously SB and ISB nature in two successive phase transitions. Most importantly, each phase transition is associated with a dielectric anomaly, and phase V appears to be a plastic crystal with extra high ac conductivity (>10-2 S cm-1). Our work opens up new avenues to find a multi-phase transition material in silver halide hybrids.