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Design and synthesis a series of azo multi-arm liquid crystal monomers (M1-M3) with cholic acid as the chiral core, followed by side chain graft copolymerisation with polymethylhydrosiloxane (PMHS)...

Acute stress relates to high prevalence of anxiety, depression or even sudden death. Although dopaminergic system in amygdala-medial prefrontal cortex (mPFC) circuit is hyper-responsive to stress-induced anxiety, the mechanisms that control anxiety still remains unanswered. Here, the acute restraint stress model(ARS) was established to develop anxiety-like behavior. The D2-dopamine receptor (D2R) availability in amygdala and mPFC was assessed using [18F]-fallypride positron emission tomography(PET) and immunohistochemical assay. We revealed that ARS paradigm was successfully established, as evidenced by elevated plus-maze test(EPM) and increased corticosterone release. Moreover, PET imaging displayed elevated D2R availability in the amygdala and mPFC in ARS as compared to that in the naives. PET imaging combined with immunohistochemical assay confirmed that amygdaloid D2R was significantly implicated in stress-induced anxiety. Our findings delivered valuable insights into neuromechanism of amygdaloid D2R underlying stress-induced anxiety and might have important implications for developing therapeutics for anxiety by targeting amygdaloid D2R.

Using tartaric acid as the core, six azo H-shaped liquid crystal compounds M1-M6 with different terminal substituents were synthesised. All products were structurally well characterised by elementa...

Aconitum carmichaelii is a high-value medicinal herb widely used across China, Japan, and other Asian countries. Aconitine-type diterpene alkaloids (DAs) are the characteristic compounds in Aconitum. Although six transcriptomes, based on short-read next generation sequencing technology, have been reported from the Aconitum species, the terpene synthase (TPS) corresponding to DAs biosynthesis remains unidentified. We apply a combination of Pacbio isoform sequencing and RNA sequencing to provide a comprehensive view of the A. carmichaelii transcriptome. Nineteen TPSs and five alternative splicing isoforms belonging to TPS-b, TPS-c, and TPS-e/f subfamilies were identified. In vitro enzyme reaction analysis functional identified two sesqui-TPSs and twelve diTPSs. Seven of the TPS-c subfamily genes reacted with GGPP to produce the intermediate ent-copalyl diphosphate. Five AcKSLs separately reacted with ent-CPP to produce ent-kaurene, ent-atiserene, and ent-13-epi-sandaracopimaradie: a new diterpene found in Aconitum. AcTPSs gene expression in conjunction DAs content analysis in different tissues validated that ent-CPP is the sole precursor to all DAs biosynthesis, with AcKSL1, AcKSL2s and AcKSL3-1 responsible for C20 atisine and napelline type DAs biosynthesis, respectively. These data clarified the molecular basis for the C20-DAs biosynthetic pathway in A. carmichaelii and pave the way for further exploration of C19-DAs biosynthesis in the Aconitum species., Graphical abstract A Pacbio full-length transcriptome of Aconitum carmichaelii were publicly available. Twelve diterpene synthases were functional identified to responsible for atisine, napelline type diterpene alkaloids (DAs) and ent-13-epi-sandaracopimaradie biosynthesis, respectively.Image 1

Aggregation-induced emission (AIE) fluorophores exhibit strong fluorescence in an aggregated state but emit no or weak fluorescence in dilute solutions. This emerging class of AIE optical materials comprise a variety of functionalities. Here an AIE luminescence core, 1-hydroquinol-1,2,2-triphenylethene (HQTPE), has been designed and synthesized. This AIE core is simple but is fundamentally important to chemistry because of its intrinsic redox and pH activities. The incorporation of hydroquinone (HQ) moiety into a common AIE core tetraphenylethene (TPE) yields HQTPE with unique fluorescent properties like nonlinear self-quenching over most other AIE-active fluorophores (AIEgens) so far reported. There are differences of photochemical properties between HQTPE, 1-benzoquinol-1,2,2-triphenylethene (QTPE, the oxidized counterpart) and its anions. Interestingly, as the solution concentration is increased, AIEgen HQTPE shows stronger fluorescence but QTPE exhibits rapid quenching of fluorescence in a nonlinear fashion, which are in agreement with theoretical studies. The fluorescence of HQTPE is also highly dependent on the pH value of media. We have further explored HQTPE as an ultrasensitive redox probe and efficient deoxidizer, which could lead to potential applications in health care, food security, environmental monitoring, optic and electronic devices. Aggregation-induced emission (AIE) is exploited for several optoelectronic applications, but synthesizing molecules that respond to multiple stimuli is challenging. Here, the authors report a hydroquinone bearing an AIE-active core that responds to both redox and pH changes.

A series of mononuclear lanthanide complexes with the formula [Hex4N][Ln(DBM)4] (1Ln) (Ln = Nd and Tb), [But4N][Dy(DBM)4] (2), [Et4N][Dy(DBM)4] (3), [PhCH2N(CH3)3][Dy(DBM)4] (4) and [Hex4N][Dy(TTA)4] (5) formed by four β-diketonate ligands (i.e. DBM = dibenzoylmethane, TTA = 2-thenoyltrifluoroacetone) and four organic counter ammonium cations (i.e. Hex4N = tetrahexylammonium, But4N = tetrabutylammonium, Et4N = tetraethylammonium and PhCH2N+(CH3)3) were structurally and magnetically characterized. The organic ammonium as contactless cation pairs with [Ln(β-diketonate)4]−1 moieties, the impact of different remote organic cations and the first coordination sphere comprising distinct β-diketonates on their SMM performance were elaborately studied. This is an efficient method by virtue of the interaction of the remote organic ion pair to modulate their single-molecule magnetic (SMM) properties. More importantly, the tetrakis β-diketonate Dy(III) anion can be almost intactly grafted on functional GaN substrate through an anion exchange reaction, resulting in diminishing slow magnetic relaxation behavior, which presents potential application in future SMM devices.

Hydrogels are cross-linked hydrophilic macromolecules that contain a certain amount of water. Due to their biocompatible, highly tunable and hydrophilic nature, hydrogels have attracted much attention in the applications of chemical, biomedical and pharmaceutical fields over the past twenty years. In particular, thermo-sensitive hydrogels, which can undergo phase transition or swell/deswell as ambient temperature changes, endow the drug delivery system with enhanced local drug penetration, desirable spatial and temporal control, and improved drug bioavailability. These merits facilitate their extensive applications in drug delivery. In this review, we focus on advances in the development of different thermo-sensitive polymers as a scaffold for drug delivery, including poly(N-isopropylacrylamide) (pNIPAAM), poloxamer, polyethylene glycol/poly(lactic acid)co-(glycolic acid) (PEG/PLGA), and chitosan. The state-of-the-art thermo-sensitive hydrogels for various pharmaceutical applications, such as anti-tumor drug delivery, transdermal drug delivery, ocular drug delivery, nasal drug delivery, and buccal drug delivery, are elaborated. Finally, the future research perspectives and challenges are also discussed, which could facilitate the translation of thermo-sensitive hydrogels for drug delivery from bench to bedside.

A three-dimensional metal–organic framework, namely {[Zn3(BIBT)(BTC)5/3(μ3-OH)]·solvents}n (JXUST-4), has been synthesized by using ZnII ions, and BIBT and H3BTC ligands (BIBT = 4,7-bi(1H-imidazol-1-yl)benzo-[2,1,3]thiadiazole and H3BTC = 1,3,5-benzenetricarboxylic acid). JXUST-4 shows a new (3,3,7)-connected topology net containing a trinuclear ZnII cluster, uncoordinated N atoms of BIBT and uncoordinated carboxylate O atoms of H3BTC, which facilitates the interaction between the framework and analytes. Fluorescence studies indicate that JXUST-4 generates light yellow luminescence, which could be ascribed to ligand-centered emission. More importantly, JXUST-4 could be viewed as an effective fluorescent sensor toward acetylacetone through an obvious fluorescence red-shift with high sensitivity, efficient selectivity, and outstanding recycling capacity. Furthermore, the possible sensing mechanism of JXUST-4 toward acetylacetone is due to electron transfer and weak interactions between the analyte and framework.

A series of star-shaped liquid crystal (LC), respectively, based on phloroglucinol, pentaerythritol and glucose as cores, rod-shaped molecules (MeOSBAA, MeSBAA and ClSBAA) containing a schiff base ...

Hypoxia conditioning could increase the survival of transplanted neuronal progenitor cells (NPCs) in rats with cerebral ischemia but could also hinder neuronal differentiation partly by suppressing mitochondrial metabolism. In this work, the mitochondrial metabolism of hypoxia-conditioned NPCs (hcNPCs) was upregulated via the additional administration of resveratrol, an herbal compound, to resolve the limitation of hypoxia conditioning on neuronal differentiation. Resveratrol was first applied during the in vitro neuronal differentiation of hcNPCs and concurrently promoted the differentiation, synaptogenesis, and functional development of neurons derived from hcNPCs and restored the mitochondrial metabolism. Furthermore, this herbal compound was used as an adjuvant during hcNPC transplantation in a photothrombotic stroke rat model. Resveratrol promoted neuronal differentiation and increased the long-term survival of transplanted hcNPCs. 18-fluorine fluorodeoxyglucose positron emission tomography and rotarod test showed that resveratrol and hcNPC transplantation synergistically improved the neurological and metabolic recovery of stroke rats. In conclusion, resveratrol promoted the neuronal differentiation and therapeutic efficiency of hcNPCs in stroke rats via restoring mitochondrial metabolism. This work suggested a novel approach to promote the clinical translation of NPC transplantation therapy.

Background. Lipid abnormalities are prevalent among people living with human immunodeficiency virus (HIV) (PLWH) and contribute to increasing risk of cardiovascular events. This study aims to investigate the incidence of dyslipidemia and its risk factors in PLWH after receiving different first-line free antiretroviral regimens. Methods. PLWH who sought care at the Third People's Hospital of Shenzhen from January 2014 to December 2018 were included, and the baseline characteristics and clinical data during the follow-up were collected, including total cholesterol (TC), triglyceride (TG), low-density lipoprotein cholesterol (LDL-C) and high-density lipoprotein cholesterol (HDL-C). The risk factors of dyslipidemia after antiretroviral therapy were analyzed with the generalized estimating equation model. Results. Among the 7623 PLWH included, the mean levels of TC, HDL-C and LDL-C were 4.23 ± 0.85 mmol/L, 1.27 ± 0.29 mmol/L and 2.54 ± 0.65 mmol/L, respectively, and the median TG was 1.17 (IQR: 0.85−1.68) mmol/L. Compared with that in PLWH receiving tenofovir disoproxil fumarate (TDF) + lamivudine (3TC) + ritonavir-boosted lopinavir (LPV/r), zidovudine (AZT) + 3TC + efavirenz (EFV), and AZT + 3TC + LPV/r, the incidence of dyslipidemia was lower in PLWH receiving TDF + 3TC + EFV. In multivariate analysis, we found that the risks of elevations of TG, TC, and LDL-C were higher with TDF + 3TC + LPV/r (TG: odds ratio [OR] = 2.82, 95% confidence interval [CI]: 2.55−3.11, P

Traditional Chinese medicine (TCM) has been paid much attentions due to the prevention and treatment of steroid hormone disorders. Ginseng, the root of Panax ginseng C. A. Meyer (Araliaceae), is one of the most valuable herbs in complementary and alternative medicines around the world. A series of dammarane triterpenoid saponins, also known as phytosteroids, were reported as the primary ingredients of Ginseng, and indicated broad spectral pharmacological actions, including anti-cancer, anti-inflammation and anti-fatigue. The skeletons of the dammarane triterpenoid aglycone are structurally similar to the steroid hormones. Both in vitro and in vivo studies showed that Ginseng and its active ingredients have beneficial hormone-like role in hormonal disorders. This review thus summarizes the structural similarities between hormones and dammarane ginsenosides and integrates the analogous effect of Ginseng and ginsenosides on prevention and treatment of hormonal disorders published in recent twenty years (1998-2018). The review may provide convenience for anticipate structure-function relationship between saponins structure and hormone-like effect.

Five non-symmetric three-arm liquid crystals (LCs) based on chenodeoxycholic acid (CDCA), termed as EFSD, EFSL, EFXD, EFXL and EFDZ, were synthesised. EF, which is a chiral smectic A (SmA*) LC, was...

Neural stem/progenitor cells (NSPCs) persist in the mammalian subventricular zone throughout life, where they can be activated in response to physiological and pathophysiological stimuli. A recent study indicates metabotropic glutamate receptor 4 (mGluR4) is involved in regulating NSPCs behaviors. Therefore, defining mGluR4 function in NSPCs is necessary for determining novel strategies to enhance the intrinsic potential for brain regeneration after injuries. In this study, mGluR4 was functionally expressed in SVZ-derived NSPCs from male Sprague-Dawley rats, in which the cyclic adenosine monophosphate concentration was reduced after treatment with the mGluR4-specific agonist VU0155041. Additionally, lateral ventricle injection of VU0155041 significantly decreased 5-bromo-2'-deoxyuridine (BrdU)+ and Ki67+ cells, while increased Doublecortin (DCX)/BrdU double-positive cells in SVZ. In cultured NSPCs, mGluR4 activation decreased the ratio of BrdU+ cells, G2/M-phase cells, and inhibited Cyclin D1 expression, whereas it increased neuron-specific class III β-tubulin (Tuj1) expression and the number of Tuj1, DCX, and PSA-NCAM-positive cells. However, pharmacological blocking mGluR4 with the antagonist MSOP or knockdown of mGluR4 abolished the effects of VU0155041 on NSPCs proliferation and neuronal differentiation. Further investigation demonstrated that VU0155041 treatment down-regulated AKT phosphorylation and up-regulated expression of the phosphatase and tensin homolog protein (PTEN) in NSPCs culture. Moreover VU0155041-induced proliferating inhibition and neuronal differentiating amplification in NSPCs were significantly hampered by VO-OHpic, a PTEN inhibitor. We conclude that activation of mGluR4 in SVZ-derived NSPCs suppresses proliferation and enhances their neuronal differentiation, and regulation of PTEN may be involved as a potential intracellular target of mGluR4 signal. Cover Image for this issue: https://doi.org/10.1111/jnc.15052.

Chrysanthemum morifolium cv. Hang-ju (HJ) is considered as a healthy food supplement for a long time in Asia. But until now, there are few reports on the biological activity of HJ leaves, which is the main by-products of HJ. In this study, HJ leaves was extracted by water, ethanol and water: ethanol (30: 70), respectively. The results showed that the total polyphenol content of water extract, hydroalcoholic extract and ethanol extract was 75.1 ± 6.9 mg GAE/g, 162.2 ± 5.6 mg GAE/g and 128.5 ± 1.9 mg GAE/g, respectively. However, the ethanol extract has the highest antibacterial activity against the tested strains with a MIC of 0.25 mg/mL compared to water extract (MIC > 8.0 mg/mL) and ethanol extract (MIC = 0.50 mg/mL). The essential oil was extracted from HJ leaves by water distillation (0.5%), which showed higher antibacterial effect on gram-positive bacteria (MIC = 0.125 mg/mL) than ethanol extract. GC–MS was used for the preliminary identification of essential oil composition. The compound (1S,4aS,7R,8aS)-1,4a-dimethyl-7-(prop-1-en-2-yl)decahydronaphthalen-1-ol was first identified from HJ and found to be the most dominant compound. Furthermore, essential oil can significantly deform cell morphology and damage cell wall structure, which was confirmed by LIVE/DEAD® BacLight Viability Kit and scanning electron microscopy observations. The mentioned findings indicated that HJ leaves could be utilized as a natural additive in food industry with significant antimicrobial potential.

The 5α-reductase converts testosterone to dihydrotestosterone (DHT), and excess DHT could cause androgen-related diseases such as androgenetic alopecia and benign prostatic hyperplasia (BPH). To discover new 5α-reductase inhibitors, effective drug screening method with high throughput is thus essential. In this study, fully automated chip-based nanoelectrospray ionization-mass spectrometry (nano-ESI-MS) was innovatively utilized as a screening tool for 5α-reductase inhibitory assay in direct infusion mode, which simplified sample pretreatment and greatly improved experimental efficiency. The preliminary data indicated that curcumin, a natural anti-inflammatory compound, exhibited notably 5α-reductase inhibition activity. Moreover, the obtained results of the chip-based nano-ESI-MS were well consistent with those of HPLC-MS, which suggested that the chip-based nano-ESI-MS could be treated as a rapid and high-throughput drugs screening strategy in pharmaceutical development. Graphical abstract.

A series of non-symmetric dimers with the same chiral core, mandelic acid (MA), have been synthesised by varying the terminal group and the rigidity of the molecules, termed QBBMA-3F3BT, QBMA-3F3BT...

One new robustaflavone, (2S,2′′S)-2,3,2′′ ,3′′-tetrahydrorobustaflavone 7,4′,4′′′ -trimethyl ether (1), was isolated from the 75% aqueous EtOH extract of Selaginella uncinata. The structure and absolute configuration of 1 was established by extensive spectroscopic and circular dichroism analyses.

This paper designed and synthesised a series of V-shaped liquid crystal molecules (X-SBAnE) with resorcinol as the core and Schiff base as the mesogenic arms (X-SBAAn). The effects of polar...

Two series of novel four-arm azobenzene liquid crystal molecules were designed and synthesized, and their mesophase properties, photo-induced transition were studied. Two series of mesogeni...

We synthesized two series of cholesteric liquid-crystal elastomers by hydrosilylation among monomers MA containing a cholesteryl group, MB (MC) containing a phenolic hydroxyl group and MD a...

A new metal-organic framework (MOF) {[Cd2 (bbib)2 (ndc)2 ]⋅2DMF}n (JXUST-1) (bbib=1,3-bis(benzimidazolyl)benzene, H2 ndc=1,4-naphthalenedicarboxylic acid, DMF=N,N-dimethylformamide) has been solvothermally synthesized and characterized by single-crystal X-ray diffraction, PXRD, TGA, IR and elemental analysis. JXUST-1 exhibits a three-dimensional 6-connected pcu topology with a Schlafli symbol {412 .63 } constructed by [Cd2 (CO2 )3 ] secondary building units. Fluorescence studies show that this MOF can sensitively and selectively recognize Al3+ via a fluorescence enhancement effect, and the detection limit is 0.048 ppm. Furthermore, JXUST-1 displays relatively good thermal and chemical stabilities as well as reusability. All these results suggest JXUST-1 to be a highly selective and recyclable luminescent sensing material for the detection of Al3+ .

With cholic acid as the core, five multi-arm ester liquid crystals were synthesised with different terminal substituents. B1–B5 were mesogenic arms which were linked to multifunctional chir...

Seven symmetric liquid crystal (LC) dimers containing different chiral cores and LC arms have been synthesised, termed EPDA-(R,S)PD, TFBDA-(R,S)PD, TFBA-(R,S)PD, TFBDA-(R)PD, TFBA-(R)PD, TF...

A ZnII-based metal-organic framework (MOF) with a rare tcj topology has been solvothermally synthesized and displays relatively good thermal and chemical stabilities. Interestingly, the MOF can sensitively and selectively sense acetylacetone (acac) via a fluorescence enhancement effect with a detection limit of 0.10 ppm and good reusability, which demonstrates the first example of a MOF-based turn-on fluorescent sensor for acac.

A series of dinuclear dysprosium complexes bridged by pyridine-NO ligands with formula [Ln2(BTA)6(pyNO)2] (1Dy, Ln = Dy, 1Y, Ln = Y and 1Gd, Ln = Gd) (BTA = benzoyltrifluoroacetone, pyNO = pyridine-N-oxide) were structurally and magnetically characterized. The X-ray crystallographic analyses of the structures revealed that the NO group serves as the effective bridge to link two Dy(iii) centers and the periphery β-diketonate (BTA) ligands complete the rest of the coordination sphere. The dynamic magnetic measurements revealed that complex 1Dy displayed significant zero-field single-molecule magnetic (SMM) behaviour with 72 K energy barrier and 2.5 K hysteresis temperature. In order to extend this dinuclear system, double N-oxide bridged ligand 4,4'-bpdo(4,4'-bipyridine-N,N'-dioxide) was used, and consequently, a series of one-dimensional chain complexes possessing repeated [Ln2(BTA)6(pyNO)2] units were synthesized with formula [Ln2(BTA)6(4,4'-bpdo)]n·2EtOH (2Dy, Ln = Dy, 2Y, Ln = Y and 2Gd, Ln = Gd). The AC magnetic susceptibility measurements revealed that complex 2Dy exhibited significant zero-field slow magnetic relaxation behavior with a higher effective energy barrier of 87 K and a hysteresis temperature of 3 K than 1Dy albeit the separation between the repeated units is large.

An efficient photocatalyst of boron-doped titanium dioxide/titanium nanotube array-supported platinum particles (Pt–B/TiO2/Ti NTs) was fabricated for photocatalytic water splitting for hydrogen production through a two-step route. First, B/TiO2/Ti NTs were prepared by anodic oxidation using hydrofluoric acid as electrolyte and boric acid as a B source. Then, Pt particles were deposited on the surface of B/TiO2/Ti NTs by photo-assisted impregnation reduction. The structure and properties of Pt–B/TiO2/Ti NTs were characterized by various physical measurements which showed the successful fabrication of Pt–B/TiO2/Ti NTs. The Pt–B/TiO2/Ti NTs, with a B-doping content of 15 mmol L−1, showed the highest photocatalytic activity and exhibited a photocatalytic hydrogen-production rate of 384.9 μmol g−1 h−1, which was 9.2-fold higher than that of unmodified TiO2/Ti NTs (41.7 μmol g−1 h−1). This excellent photocatalytic performance was ascribed mainly to the synergistic effect of Pt and B, which could enhance the photocatalytic activity of TiO2/Ti NTs.

A series of dinuclear lanthanide complexes bridged by three pyridine-N-oxide (PyNO) ligands with formula [Dy2(hfac)6(4-cpyNO)3]·4H2O (Dy1), [Gd2(hfac)6(4-cpyNO)3]·4H2O (Gd1), [Dy2(hfac)6(4-mepyNO)3] (Dy2), [Gd2(hfac)6(4-mepyNO)3] (Gd2) (hfac− = hexafluoroacetylacetonate, 4-cpyNO = 4-cyanopyridine N-oxide, 4-mepyNO = 4-Methylpyridine N-oxide), and series of dinuclear lanthanide complexes bridged by two PyNO ligands with formula [Dy2(hfac)6(4-cpyNO)2] (Dy3), [Y2(hfac)6(4-cpyNO)2] (Y1), [Gd2(hfac)6(4-cpyNO)2] (Gd3), [Dy2(hfac)6(4-mepyNO)2] (Dy4), [Y2(hfac)6(4-mepyNO)2] (Y2), [Gd2(hfac)6(4-mepyNO)2] (Gd4), were structurally and magnetically characterized. The crystal structures revealed that pyridine-N-oxide serves as an effective bridge to link two Ln(III) centers, and periphery β-diketonate ligands complete the coordination sphere. The number of PyNO bridge can be rationally controlled by the stoichiometric ratio of reagents, which leads to different local coordination models and intramolecular Ln-Ln distances. Furthermore, elaborate modulation on the strength of magnetic coupling transmitted by PyNO bridge was successfully carried out by introducing electron-donating or -withdrawing substituents on the bridge ligand backbone. Magnetic measurements revealed that complex Dy3 displayed significant double zero-field slow magnetic relaxation process, while Dy1 and Dy2 showed field-induced SMM behavior. Significantly enhanced SMMs performance was observed in Dy4 with a hysteresis temperature of 2.5 K. The distinct slow magnetic relaxation behaviors were strongly related to their different individual Dy(III) ion magnetic anisotropy and Dy(III)-Dy(III) coupling, which were further confirmed by ab initio calculation.

Two new GdIII complexes with the formulas of [Gd(ma)2(H2O)2]·2H2O (1) and {[Gd(ma)(ox)0.5(H2O)]·2H2O}n (2) (H2ma = DL-malic acid and H2ox = oxalic acid) have been successfully prepared by using Gd2O3 or Gd(NO3)3 as metal ion sources. Complex 1 exhibits a discrete mononuclear structure, while complex 2 displays a three-dimensional ‘layer-pillar’ structure with ox2− anions as pillars that are generated in situ. Magnetic studies suggest the presence of ferromagnetic couplings between the intramolecular or interlayer GdIII ions and large magnetocaloric effects with −ΔSmaxm = 32.1 J kg−1 K−1 (1) and 44.6 J kg−1 K−1 (2) for ΔH = 7 T. Therefore, they are good candidates as magnetic refrigerants.

Three zinc(II) metal-organic frameworks have been solvothermally synthesized with V-shaped 1,3-bis(1-imidazolyl)benzene (bib) and 4,4'-oxydibenzoic acid (4,4'-H2oba), namely {[Zn(bib)(oba)]⋅solvents}n (1), {[Zn(bib)(oba)]·2H2O}n (2) and {[Zn2(bib)2(oba)2]⋅2EtOH⋅H2O}n (3). All of them are characterized by single-crystal X-ray diffraction, infrared spectra and powder X-ray diffraction. Complex 1 presents a two-fold interpenetrating three-dimensional structure with 4-connected (65.8) topology. While, complexes 2 and 3 exhibit double layer cavity and double chains based two-dimensional structure, respectively. Luminescent studies indicate that 2 and 3 display selectively sensitive to electron-deficient nitroaromatic explosives with excellent anti-interference abilities.

The development of multifunctional photosensitizers (PSs) with aggregation-induced emission (AIE) properties plays a critical role in promoting the progress of the photodynamic therapy (PDT). In this work, a multifunctional PS (named DSABBT NPs) with AIE activity has been designed and prepared to carry out ultrafast staining, excellent two-photon bioimaging, and high-efficiency image-guided PDT. Simply, DSABBT with AIE characteristic was synthesized by one-step Schiff reaction of 4-(diethylamino)-salicylaldehyde (DSA) and 4,7-bis(4-aminophenyl)-2,1,3-benzothiadiazole (BBT). Then, DSABBT and DSPE-PEG2000-cRGD generate nanoparticles (NPs) easily in an ultrapure water/tetrahydrofuran mixture through a facile nanoprecipitation at room temperature. We found that DSABBT NPs exhibit bright solid-state fluorescence with large stokes shifts (180 nm) and two-photon absorption cross-section (1700 GM). Importantly, DSABBT NPs exhibited excellent ability of ultrafast staining and two-photon imaging, which can readily label suborganelles by subtly shaking the living cells for 5 s under mild conditions. Moreover, DSABBT NPs displayed high singlet oxygen (1O2) generation capacity and remarkable image-guided PDT efficiency. Therefore, DSABBT NPs can act as the promising candidate for multifunctional PSs, which can destroy cancer cells and block malignant tumor growth via the production of reactive oxygen species upon irradiation conditions. These outcomes provide us with a selectable strategy for developing multifunctional theranostic systems.

The crosstalk between cancer cells and adipocytes is critical for breast cancer progression. However, the molecular mechanisms underlying these interactions have not been fully characterized. In the present study, plasminogen activator inhibitor-1 (PAI-1) was found to be a critical effector of the metastatic behavior of breast cancer cells upon adipocyte coculture. Loss-of-function studies indicated that silencing PAI-1 suppressed cancer cell migration. Furthermore, we found that PAI-1 was closely related to the epithelial-mesenchymal transition (EMT) process in breast cancer patients. A loss-of-function study and a mammary orthotopic implantation metastasis model showed that PAI-1 promoted breast cancer metastasis by affecting the EMT process. In addition, we revealed that leptin/OBR mediated the regulation of PAI-1 through the interactions between adipocytes and breast cancer cells. Mechanistically, we elucidated that leptin/OBR further activated STAT3 to promote PAI-1 expression via miR-34a&ndash, dependent and miR-34a&ndash, independent mechanisms in breast cancer cells. In conclusion, our study suggests that targeting PAI-1 and interfering with its upstream regulators may benefit breast cancer patients.

A new aggregation-induced emission (AIE) luminescence core, 1-hydroquinol-1,2,2-triphenylethene (HQTPE), has been designed and synthesized for the first time. This AIE core is amazingly simple but is fundamentally important to chemistry because of its intrinsic redox and pH activities. The incorporation of hydroquinone (HQ) moiety into a common AIE core tetraphenylethene (TPE) yields HQTPE with unique fluorescent properties over most other AIEgens so far reported. There are tremendous differences of photochemcical properties between HQTPE, 1-benzoquinol-1,2,2-triphenylethene (QTPE, the oxidized counterpart) and its anions. Interestingly, as the solution concentration is increased, AIEgen HQTPE shows stronger fluorescence but QTPE exhibits rapid quenching of fluorescence in a nonlinear fashion, which are in agreement with theoretical studies. The fluorescence of HQTPE is also highly dependent of pH value of media. We have further explored HQTPE as an ultrasensitive redox probe and efficient deoxidizer, which could lead to many potential applications in health care, food security, environmental monitoring, optic and electronic devices.

A simple Al3+ receptor, 2-hydroxyquinoline-3-aldehyde-(benzoyl)hydrazone (L), has been synthesized by condensing 2-hydroxyquinoline-3-aldehyde with benzoic hydrazide. L displayed a high selectivity and pronounced fluorescence enhancement for Al3+ over other common cations in water. Moreover, based on the Job’s plot, ESI-MS spectrometry, it could be considered that L and Al3+ were coordinated with a 1:1 ratio. In addition, the detection limit of L for sensing Al3+ was calculated to be 7.21 × 10−8 M, which was lower than the acceptable limit of Al3+ level in drinking water defined by World Health Organization (WHO) (1.85 × 10−6 M). These results indicated that this chemical sensor L could be used as a serviceable molecular probe for practical applications.

Six three-arm star-shaped liquid crystals (LCs) based on chenodeoxycholic acid (CDCA), termed as G-BH, G-YD, G-FD, G-DJ, G-DZ and G-BX, respectively, have been synthesised. CDCA was used as the chi...

Two LnIII complexes derived from one aromatic monocarboxylate ligand, namely [Tb2(mnba)6(H2O)4]n (1) and [Dy2(mnba)4(μ3-OH)2(H2O)]n (2) (Hmnba = m-nitrobenzoic acid), have been prepared by similar synthetic procedures and structurally characterized. Complex 1 contains two identical one-dimensional (1D) chains with the syn,syn-carboxylate as linkers, while complex 2 takes the 1D chain structure with μ3--OH and carboxylate as bridge. Magnetic studies indicate that ferromagnetic interactions between intra-chain metal centers exist in 1 and 2 and only complex 2 exhibits field-induced slow magnetic relaxation behavior.

A new series of multi-arm liquid crystals (D1–D5) based on cholic acid as the chiral core and ω-[4-(p-substituted azobenzeneoxy carbonyl]valeric acid (B1–B5) as the mesogenic arms were designed and...

A series of Salen-type Zn(II)–Dy(III) complexes [L1Zn(II)ClDy(III)(acac)2]·H2O (1), [L1Zn(II)BrDy(III)(acac)2]·H2O (2), [L1Zn(II)(H2O)Dy(III)(acac)2]·CH2Cl2·PF6 (3), [L2Zn(II)(H2O)Dy(III)(acac)2]·PF6 (4), and Co(III)–Dy(III) complexes [L1Co(III)Br2Dy(III)(acac)2]·CH2Cl2 (5), [L2Co(III)Cl2Dy(III)(acac)Cl(MeO)] (6), [L2Co(III)Cl2Dy(III)(acac)Cl(H2O)] (7), and [L2Co(III)Cl2Dy(III)(NO3)2(MeO)] (8) heterobinuclear single-molecule magnets (SMMs) were synthesized and magnetically characterized. These complexes were constructed by incorporating diamagnetic Zn(II) and Co(III) ions with acetylacetone (acac) and compartmental Schiff-base ligands (H2L1 = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-phenylenediamine; H2L2 = N,N′-bis(2-oxy-3-methoxybenzylidene)-1,2-diaminocyclohexane). In the Zn(II)–Dy(III) (1–4) system, the coordination environments of the Dy(III) ions are nearly identical, but the apical coordination atom to the Zn(II) ion is different. Complexes 1, 2, and 4 displayed no magnetic relaxation in the absenc...

A series of non-symmetric liquid crystal (LC) dimers with the same chiral core 1,2-propanediol (PD) have been synthesised, termed as ABBA-PD-TFBA, PBBA-PD-TFBA, ABA-PD-TFBA, PBA-PD-TFBA and AA-PD-T...

Six new coordination polymers (CPs) based on the V-shaped 1,3-bis(benzimidazolyl)benzene (bbib) have been synthesized under solvothermal conditions: [Zn(bbib)(ip)]n (1), {[Zn(bbib)(oba)]·solvents}n (2), {[Zn(bbib)(tp)]·DMF}n (3), [Cd(bbib)(ip)]n (4), {[Cd(bbib)(oba)]·H2O·solvents}n (5) and {[Cd(bbib)(tp)]·DMF}n (6) (ip = isophthalate, oba = 4,4′-oxybisbenzoate and tp = terephthalate). Complexes 1–3 display a plane minimal net, (4,4) sheet and a hexagonal plane net, respectively. The structures of 4–6 range from a 1D zigzag chain (4), 2D (4,4) sheet (5) to a 3D “pillar-layer” coordination framework with pcu α-Po topology (6). The structural transition from 1D to 3D among these complexes is realized with the aid of different auxiliary ligands. The results demonstrate that the conformations and coordination modes of dicarboxylate ligands make an impact on the structural diversity of ZnII/CdII coordination polymers. To the best of our knowledge, the CPs based on the bbib ligand have been successfully prepared for the first time. Moreover, complex 2 is a good bifunctional chemosensor for the detection of both Fe3+ and MnO4− with the detection limits of 3.31 ppm and 8.81 ppm, respectively, indicating that 2 could be used as an efficient fluorescent sensor with high sensitivity and selectivity for Fe3+ and MnO4−.

A series of asymmetric dinuclear dysprosium complexes, namely, [Dy2(L)2(DBM)2(H2O)]·2CH2Cl2 (2), Dy2(L)(DBM)4(H2O) (3), [Dy2(L)(BTFA)4(H2O)]·(Et2O) (4) and Dy2(L)(hmac)4(H2O) (5) (H2L = N,N′-bis(salicylidene)-o-phenylenediamine, DBM = dibenzoylmethane, BTFA = benzoyltrifluoroacetone and hmac = hexamethylacetylacetonate), are structurally and magnetically characterized. Complex 2 is elaborately designed by fine-tuning the local environment of one anisotropic center in a previously studied crystallographically independent {Dy2} SMM (1) displaying a separated two-step relaxation process, and consequently the one-to-one relationship between the spin sites and the relaxation processes is successfully confirmed. In addition, enhanced energy barriers were obtained among complexes 3–5 after introducing highly electron withdrawing groups on β-diketonate ligands. This work sheds light on the source of the complex multiple relaxations and provides a rational design of lanthanide SMMs with improved magnetic properties.

Four Zn/Dy heteronuclear SMMs constructed from hexadentate compartment Schiff base Zn-precursor and lanthanide ions were structurally and magnetically characterized, in which two [Zn-Dy] moieties are bridged by series of hydroxamic acid and resulting in double deck tetranuclear complexes with the molecular formulae [ZnL1Dy(HO)(pyz)]2⋅2CF3O3S⋅2H2O (1), [ZnL1Dy(CH3O)(aca)]2⋅2CF3O3S⋅2CH3OH (2), [ZnL2Dy(CH3O)(pyz)]2⋅2CF3O3S⋅2CH3OH (3) and [ZnL2Dy(CH3O)(pyi)]2⋅2CF3O3S⋅4CH3OH (4) (L1 = N,N′-bis(salicylidene)ethylenediimine, L2 = N,N′-bis(3-methoxysalicylidene)phenylene-1,2-diamine pyz = pyrazinehydroxamic acid, aca = acetohydroxamic acid and pyi = pyridiniumhydroxamic acid). The SMM properties were successfully modulated by introducing electron-donation or -withdrawing terminal on the hydroxamic acid. Complexes 1-4 showed significant zero-field SMM behavior with energy barriers 81 K to 92 K.

Four non-symmetric dimers containing mandelic acid as the chiral core have been synthesised, termed as QBMA-B, QBMA-BCN, QBMA-BBCN and QBBMA-BBCN, respectively. Chemical structures and liquid cryst...

A new series of multi-arm chiral liquid crystals (LCs) D1–D3 were synthesised and characterised. Cholic acid was used as the core and ω-[4-(p-alkoxybenzoloxy)phenoxycarbonyl]valeric acid (B1–B3) wa...

Four multi-arm liquid crystals (LCs) based on chenodeoxycholic acid, termed as 2G-PD, 2G-IB, 2G-BD and 5G-GC, respectively, have been synthesised by convergent method, which nematic LC, 6-(4-((4-ethoxybenzoyl)oxy)phenoxy)-6-oxohexanoic acid, was used as side arm, and chenodeoxycholic acid (CDCA) was used as the first core, 1,2-propanediol (PD), isosorbide (IB), 4,4′-biphenyldiol (BD) and glucose (GC) were used as the second core, respectively. The first generation product, CDCA2EA, displayed cholesteric phase. The second generation products 2G-BD and 5G-GC displayed cholesteric phase, while 2G-PD and 2G-IB exhibited nematic phase. The multi-arm LC, 2G-IB, did not display cholesteric phase although the two cores were all chiral ones. The result indicated that chirality of the second core sometimes made the multi-arm LCs display nematic phase when cholesteric CDCA-derivative were introduced into the second core. Some attention should be paid on molecular conformation besides the introduction of chiral cores for multi-chiral-core LCs to obtain cholesteric phase.

The cholesteric polysiloxanes (PLQ series) were obtained by reacting cholesteric monomer and phenolic hydroxyl monomer in different ratios with polysiloxanes. The chiral azo-containing polysiloxanes liquid-crystalline elastomers (LCEs) were synthesised by esterifying PLQ series with acyl acid of azo diacid catalysed by 4-dimethylaminopyridine (DMAP). The chemical structures and mesomorphic properties of monomers and polymers were confirmed by conventional spectroscopic methods. The elastomers displayed elastic properties, reversible phase transition and high thermal stability. The Tg values changed irregularly and Ti values decreased at the beginning and then increased afterwards. The chiral azo-LCEs showed colourful textures and a Grandjean texture could be observed, which exhibited a red shift with increasing content of azo moiety. PLQ2–PLQ6 exhibited selective reflection in the visible light region, but PLZ1–PLZ4 can only observe selective reflection when appropriate mechanical pressure was imp...

In this work, the changes in isoflavone levels and the expression of genes involved in their biosynthesis were studied in two Astragalus by UPLC-MS and real-time PCR after 10 days of UV-B treatment (λmax = 313 nm, 804 J m-2 ). Isoflavones were significantly induced by UV-B irradiation. The influence might be activated by the regulation of these target genes. Our results indicate that (1) the resistance of Astragalus membranaceus might not be as good as Astragalus mongholicus in the enhanced UV-B radiation environment; (2) the enhanced accumulation of calycosin and calycosin-7-glucoside with UV-B treatment in roots of A. mongholicus might be derived from formononetin which is synthesized in the leaves; (3) the glycosylation process could be stimulated and activated by the enhanced UV-B radiation in both A. mongholicus and A. membranaceus. In other words, glycosylation of isoflavones might play a crucial role for two Astragalus plants in response to UV-B stress. Overall, this study offered a feasible elicitation strategy to understand the accumulation pattern of isoflavone in A. mongholicus and A. membranaceus, and also provided a reference for the changes in isoflavone levels of Astragalus in UV-B enhanced environment in the future.

The aim of the study was to non-invasively evaluate the anticancer activity of a traditional Chinese medicine—Huaier, combined with paclitaxel (PTX) in breast cancer bearing mice by detecting dynamic metabolic changes with positron emission tomography (PET). Balb/c nude mice were randomly divided into one of the four groups: Huaier, PTX, PTX + Huaier, or the control. PET imaging with 2-deoxy-2-[18F]fluoro-d-glucose ([18F]FDG) was performed to monitor the metabolic changes in BT474 (luminal B) and MDA-MB-231 (triple-negative) breast cancer xenografts. Immunohistochemistry (IHC) study was performed immediately after the final PET scan to assess the expressions of phosphatidylinositol 3-kinase (PI3K), phospho-AKT (p-AKT), caspase-3, and vascular endothelial growth factor (VEGF). Compared to the control group, [18F]FDG accumulation demonstrated a significant decrease in PTX + Huaier (p