The survival and outcome of older patients with primary aneurysmal subarachnoid haemorrhage: a 2-year follow-up, multi-centre, observational study.

BACKGROUND AND PURPOSE: The management of older aneurysmal subarachnoid haemorrhage (aSAH) cases is a clinical challenge. This study aimed to analyse the survival and functional outcomes in older aSAH patients (age ≥ 70 years) to provide evidence for making treatment decisions for such patients. METHODS: We performed a 2-year follow-up analysis of the Chinese Multi-Centre Cerebral Aneurysm Database for older patients suffering from aSAH from 2017 to 2020. A survival analysis was used to investigate the mean survival and hazard ratios for death. Binary logarithmic regression was performed to investigate the odds ratio for independent survival and dependent survival. RESULTS: A total of 1,136 consecutive older patients with aSAH were assessed in this study, and 944 patients (83.1%) were followed up. The overall mean survival was 37.79 ± 1.04 months. A total of 380 (40.25%) patients died within 2 years after aSAH. In survival analysis, the predictors of mortality were older age, intracerebral haemorrhage (ICH) history, Hunt-Hess (H-H) grade, World Federation of Neurosurgical Societies (WFNS) grade and operative treatment decreased the risk of mortality compared to conservative treatment. In binary logarithmic regression, the predictors of dependent survival were hypertension, diabetes, WFNS grade. CONCLUSIONS: The risk for 2-year mortality after aSAH increases markedly with older age, ICH history, H-H grade and WFNS grade. Risk factors for 2-year dependent survival were associated with hypertension, diabetes and WFNS grade in older patients with aSAH. Operative treatment markedly decreased mortality but did not significantly decrease the morbidity of dependent survival compared to conservative treatment.

Bifunctional Lanthanide-Based Coordination Polymers: Conversion of CO2 and Highly Selective Luminescence Sensing for Acetylacetone.

A series of bifunctional Ln(III)-based coordination polymers (CPs) {Ln(L)(DMA)2(NO3)}n [Ln(III) = Eu (1), Gd (2), and Dy (3); organic ligand H2L = 2,2'-(1,3,5,7-tetrahydroxyoctahydro-4,8-ethanopyrrolo[3,4-f]isoindole-2,6(1H,3H)-diyl)diacetic acid)] have been successfully synthesized. CPs 1-3 are isostructural and constructed from the dimeric Ln2 unit in which two adjacent LnIII ions are bridged by two µ3-carboxyl oxygens, and the Ln2 dimeric unit is connected by two NO3- ions, four DMA molecules, and four completely protonated L2- ligands forming a 2D layer structure. The magnetic research reveals that CP 2 shows a significant cryogenic magnetocaloric effect (-ΔSm = 22.9 J kg-1 K-1; T = 2.0 K and ΔH = 7.0 T), whereas CP 3 exhibits slow magnetic relaxation property under Hdc = 0 Oe field. Additionally, the luminescence explorations revealed that CP 1 can act as a recyclable luminescent probe for pollutant acetylacetone among various small organic solvent molecules, and the corresponding detection limit is 10-7 mol/L. More importantly, CP 1 also exhibits good catalytic performance in the cycloaddition reaction of CO2 and epoxides or cyanamides under mild conditions. As far as we know, CP 1 represents the first bifunctional lanthanide homogeneous catalyst that can efficiently catalyze the reaction of cyanamides/epoxides with CO2 simultaneously.

Two novel Ln8 clusters bridged by CO32- effectively convert CO2 into oxazolidinones and cyclic carbonates.

It is difficult and challenging to design and construct high-nuclearity Ln(III)-based clusters due to the high coordination numbers and versatile coordination geometries of Ln(III) ions. Herein, two novel octanuclear Ln(III)-based clusters [Ln8(H2L-)4(HL2-)4(NO3)6 (CO3)2](NO3)2·2CH3CN (Ln = Nd (1) and Sm (2)) have been synthesized under solvothermal conditions. The X-ray single analysis reveals that both 1 and 2 are octanuclear structures and the eight central Ln(III) ions are bridged by two CO32- anions. Catalytic study revealed that 1 and 2 can effectively catalyze the cycloaddition reaction of CO2 and aziridines or epoxides simultaneously under mild conditions. What is more, cluster 1, as a heterogeneous catalyst, can be reused at least three times without obvious loss in catalytic activity for coupling of CO2 and epoxides. To our knowledge, cluster 1 is the first Ln(III)-based cluster catalyst used for the conversion of CO2 with aziridines or epoxides simultaneously. This work provides a successful strategy to integrate high-nuclear Ln(III)-based clusters for CO2 conversion, which may open a new space for the construction of multifunctional high-nuclear Ln(III)-based clusters as efficient catalysts for CO2 conversion.

Fabrication of Magnetic Al-Based Fe3O4@MIL-53 Metal Organic Framework for Capture of Multi-Pollutants Residue in Milk Followed by HPLC-UV.

The efficient capture of multi-pollutant residues in food is vital for food safety monitoring. In this study, in-situ-fabricated magnetic MIL-53(Al) metal organic frameworks (MOFs), with good magnetic responsiveness, were synthesized and applied for the magnetic solid-phase extraction (MSPE) of chloramphenicol, bisphenol A, estradiol, and diethylstilbestrol. Terephthalic acid (H2BDC) organic ligands were pre-coupled on the surface of amino-Fe3O4 composites (H2BDC@Fe3O4). Fe3O4@MIL-53(Al) MOF was fabricated by in-situ hydrothermal polymerization of H2BDC, Al (NO3)3, and H2BDC@Fe3O4. This approach highly increased the stability of the material. The magnetic Fe3O4@MIL-53(Al) MOF-based MSPE was combined with high-performance liquid chromatography-photo diode array detection, to establish a novel sensitive method for analyzing multi-pollutant residues in milk. This method showed good linear correlations, in the range of 0.05-5.00 µg/mL, with good reproducibility. The limit of detection was 0.004-0.108 µg/mL. The presented method was verified using a milk sample, spiked with four pollutants, which enabled high-throughput detection and the accuracies of 88.17-107.58% confirmed its applicability, in real sample analysis.

Molecular assemblies from linear-shaped Ln4 clusters to Ln8 clusters using different ß-diketonates: disparate magnetocaloric effects and single-molecule magnet behaviours.

A series of tetranuclear lanthanide-based clusters [Ln4(dbm)6(L)2(CH3OH)4]·2CH3OH (Ln(III) = Gd (1), Dy (2), and Ho (3); H3L = 2-[(2-(hydroxyimino)propanehydrazide)methyl]-2,3-dihydroxybenzaldehyde, Hdbm = dibenzoylmethane) and octanuclear lanthanide-based clusters [Ln8(HL)10(CH3O)4(CH3OH)2]·6CH3OH (Ln(III) = Gd (4), Dy (5)) were assembled using a polydentate Schiff-base ligand H3L and two different ß-diketone salts via a solvothermal method, and their structures and magnetic properties have been characterized. Interestingly, ß-diketones play an important role in assembling and affecting the structures of Ln4 to Ln8 clusters. This is the first use of ß-diketone to affect the structures of polynuclear Ln(III)-based clusters from linear-shaped Ln4 clusters to Ln8 clusters. Magnetic studies revealed that antiferromagnetic interactions exist in clusters 1-Gd4 and 4-Gd8. More importantly, clusters 1-Gd4 and 4-Gd8 display significant cryogenic magnetic refrigeration properties (-ΔSm = 24.88 J kg-1 K-1 for 1-Gd4 and -ΔSm = 32.52 J kg-1 K-1 for 4-Gd8); the results show that cluster 4-Gd8 exhibits a larger magnetocaloric effect than 1-Gd4. Cluster 2-Dy4 shows remarkable single-molecule magnet (SMM) behavior (ΔE/kB = 67.5 K and τ0 = 3.06 × 10-7 s) under a zero dc field, and 5-Dy8 exhibits a field-induced SMM-like behavior (ΔE/kB = 39.83 K and τ0 = 2.12 × 10-7 s) under a 5000 Oe dc field.

Piceatannol protects against cerebral ischemia/reperfusion­induced apoptosis and oxidative stress via the Sirt1/FoxO1 signaling pathway.

Reperfusion is a critical therapeutic intervention used following acute ischemic stroke; however, it may cause cerebral ischemia/reperfusion injury (CIRI) and aggravate brain damage. Piceatannol (Pic), a hydroxylated analog of resveratrol, has been reported to exhibit anti­inflammatory effects. However, the detailed molecular mechanisms and its effects on CIRI have not been sufficiently assessed, and, to the best of our knowledge, current methods of prevention of CIRI are limited. The aim of the present study was to investigate the effects of Pic on improving neurological function in a mouse model of CIRI. For the animal experiments, 8­week­old C57BL/6 mice were raised and randomly grouped, and an in vivo model of CIRI was established. Mice were administered a low (10 mg/kg/day) or high­dose (20 mg/kg/d) of Pic 1 h after CIRI orally and once daily for the next 6 days. Neurological dysfunction was assessed using a modified neurological severity score and a rotarod test 1 week after CIRI establishment, and the cognitive status of the mice was assessed using a Morris water maze. Hematoxylin and eosin staining was used to evaluate the histopathological changes. The expression levels of sirtuin 1 (Sirt1), FoxO1, cleaved caspase­3 (CC­3), Bax and Bcl­2 were measured using western blotting. Intracellular reactive oxygen species (ROS) generation, antioxidant enzymes [superoxide dismutase, glutathione (GSH) peroxidase and catalase] and non­enzymatic antioxidants (GSH) were also detected using spectrophotometry. After inhibition of the Sirt1/FoxO1 pathway, a TUNEL assay was used for the detection of apoptotic cells in vitro and in vivo. The co­localization of neuron­specific nuclear protein and CC­3 was assessing using immunofluorescent staining. Pic improved neurological functions and ameliorated hippocampal neuronal pathology following CIRI. In addition, the expression levels of CC­3 and Bax and intracellular ROS levels were increased, while levels of antioxidant and non­enzymatic enzymes were decreased in the mouse model of CIRI. Low and high doses of Pic significantly decreased ROS production and the expression levels of apoptosis­related proteins, but increased antioxidant enzyme levels. However, a high­dose of Pic did not result in increased levels of non­enzymatic enzymes. Furthermore, low and high doses of Pic treatment significantly activated the Sirt1/FoxO1 pathway. Following inhibition of the Sirt1/FoxO1 pathway, the percentage of TUNEL­positive cells and expression of CC­3 were increased, and CC­3 was enriched in neurons. The antioxidant effects of Pic were blocked by inhibition of Sirt1 in vitro and in vivo. In conclusion, these results suggested that Pic may exert a neuroprotective effect against in hippocampal neurons via the Sirt1/FoxO1 pathway.

Solvent-Dependent Assembly and Magnetic Relaxation Behaviors of [Cu4I3] Cluster-Based Lanthanide MOFs: Acting as Efficient Catalysts for Carbon Dioxide Conversion with Propargylic Alcohols.

Two structurally similar metal-organic frameworks (MOFs) [Dy2Cu4I3(IN)7(DMF)2]·DMF (1) and [Dy2Cu4I3(IN)7(DMA)2]·DMA (2) (HIN = isonicotinic acid) feathering different coordinated solvent molecules were successfully isolated by tuning the types of solvents in the reaction system. Structural tests indicate that 1 and 2 are both built from 1D Dy(III) chains and copper iodide clusters [Cu4I3], generating into three-dimensional frameworks with an open 1D channel along the a axis. 1 and 2 display extensive and excellent solvent stability. Magnetic studies of 1 and 2 indicate that they exhibit interesting solvent-dependent magnetization dynamics. Importantly, 1 and 2 can act as highly effective catalysts for the carboxylic cyclization of propargyl alcohols with carbon dioxide (CO2) under ambient operating conditions. Additionally, the substrate scope was further explored over compound 1 based on the optimal conditions, and it exhibits efficient cyclic carboxylation of various terminal propargylic alcohols with CO2. This research offers an effective approach for the solvent-guided synthesis of MOFs materials and also presents the great application value of MOFs in CO2 chemical conversion.

Long-term chemogenetic activation of M1 glutamatergic neurons attenuates the behavioral and cognitive deficits caused by intracerebral hemorrhage.

Acute spontaneous intracerebral hemorrhage (ICH) is a life-threatening disease. It is often accompanied by severe neurological sequelae largely caused by the loss of integrity of the neural circuits. However, these neurological sequelae have few strong medical interventions. Designer receptors exclusively activated by designer drugs (DREADDs) are important chemogenetic tools capable of precisely modulating the activity of neural circuits. They have been suggested to have therapeutic effects on multiple neurological diseases. Despite this, no empirical research has explored the effects of DREADDs on functional recovery after ICH. We aimed to explore whether the long-term excitation of glutamatergic neurons in primary motor cortex (M1) by DREADD could promote functional recovery after ICH. We used CaMKII-driven Gq/Gi-DREADDs to activate/inhibit M1 glutamatergic neurons for 21 consecutive days, and examined their effects on behavioral and cognitive deficits caused by ICH in a mouse model of ICH targeting striatum. Long-term chemogenetic activation of the M1 glutamatergic neurons increased the spatial memory and sensorimotor ability of mice suffering from ICH. It also attenuated the mitochondrial dysfunctions of striatal neurons by raising the ATP levels and mitochondrial membrane potential while decreasing the 8-OHdG levels. These results strongly suggest that selective stimulation of the M1 glutamatergic neurons contributes to functional recovery after ICH presumably through alleviation of mitochondrial dysfunctions.

Modulation of the properties of dinuclear lanthanide complexes through utilizing different ß-diketonate co-ligands: near-infrared luminescence and magnetization dynamics.

A family of new dinuclear lanthanide complexes as the simplest entities showing intramolecular magnetic interactions, [Ln2(dbm)2(L)2(CH3OH)2] (Ln = Tb (1), Dy (2), Ho (3), Er (4), Yb (5), Lu (6)), [Ln2(acac)2(L)2(EtOH)2] (Ln = Dy (7), Er (8)), [Dy2(TTA)2(L)2(CH3OH)2]·2CH2Cl2 (9) and [Dy2(tfa)2(L)2(CH3OH)2] (10) (H2L = N'-(2-hydroxy-5-methylphenyl)-pyrazine-2-carbohydrazide, Hdbm = 1,3-diphenyl-1,3-propanedione, Hacac = acetylacetone, HTTA = 2-thenoyltrifluoroacetone, Htfa = trifluoroacetylacetone), were constructed successfully by the reaction of a Schiff base ligand H2L and four different ß-diketonate salts. As for complexes 4, 5 and 8, all exhibit the characteristic emission peaks of the corresponding Er3+, Yb3+ and Er3+ ions, respectively. Meanwhile, the excitation wavelength (510 nm) of 5 is located in the visible region, confirming its significant potential application value. Magnetic studies indicate that complexes 9 and 10 exhibit characteristic slow relaxation of magnetization with the energy barriers (Ueff) of 102 K for 9 and 140 K for 10 under a zero dc field. Under the optimized dc fields, slow magnetic relaxations are present in 2 and 7, and the Ueff values of 9 and 10 have been improved. This proves that the ß-diketonate co-ligands deserve an important role in regulating Dy-SMMs influenced by the diverse perturbations of the axial crystal field originating from minor changes in the coordination environment.

Linear-shaped Ln and Ln clusters constructed by a polydentate Schiff base ligand and a ß-diketone co-ligand: structures, fluorescence properties, magnetic refrigeration and single-molecule magnet behavior.

Herein, ten new linear-shaped LnIII4 and LnIII6 clusters, with the formula [Ln4(acac)6L2(CH3O)2(CH3OH)4]·xCH3OH (Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), and Tm (8), Hacac = acetylacetone), [Ln6(acac)4L4(CH3O)6]·xCH3OH (Er (7) and Yb (9)), and [Lu4(acac)6L2(OH)2]·2CH2Cl2 (10), based on a polydentate Schiff base ligand, H2L, and a ß-diketone co-ligand were successfully synthesized and structurally characterized. Single crystal X-ray diffraction measurements reveal that the structures of the clusters 1-6, 8 and 10 are very similar and their central Ln(iii) ions are linearly arranged Ln4; however, the clusters 7 and 9 possess a rare linearly arranged Ln6. The investigations on the solid-state fluorescence properties show that the clusters 2, 3, 5 and 6 display the characteristic lanthanum luminescence at room temperature. Magnetic studies reveal that weak antiferromagnetic interactions exist between adjacent Gd(iii) ions in cluster 4. More importantly, the cluster 4 exhibits significant MCE with the maximum -ΔSm value of 27.96 J kg-1 K-1 at 2.0 K and 7.0 T, whereas the cluster 6 displays a slow magnetic relaxation behavior under a zero dc field with the effective energy barrier ΔE/kB = 8.64 K and τ0 = 6.98 × 10-6 s.

Dynamically NAND gate system on DNA origami template.

Molecular logic gates play an important role in many fields and DNA-based logic gates are the basis of DNA computers. A dynamically NAND gate system on the DNA origami template is established in this paper. Naturally, the system is stable in solution without any reaction. Different logical values are mapped into different DNA input strands. When logical values are entered into the system, the corresponding DNA input strands undergo a directed hybridization chain reaction (HCR) at corresponding positions on the DNA origami template. The operation results are identified by disassembly between the nanogold particles (AuNPs) and DNA origami template. The nanogold particles remain on the DNA origami template, indicating that the result is true; The nanogold particles are dynamically separated from the DNA origami template, indicating that the result is false. The simulation of the system through Visual DSD shows that the reaction strictly followed the designed direction, and no error products are generated during the reaction. These simulation results show that the system has the advantages of feasibility, stability and intelligence.

Water Stable [Tb4] Cluster-Based Metal-Organic Framework as Sensitive and Recyclable Luminescence Sensor of Quercetin.

A novel 3D metal-organic framework (MOF){[Tb3(CBA)2(HCOO)(µ3-OH)4(H2O)]·2H2O·0.5DMF} n (S-1) was synthesized by the solvothermal method. The crystal structure indicates that [Tb4O4] cubane clusters self-assemble into an infinite chain by sharing vertex, which is further linked to adjacent chains through 1,1-cyclobutanedicarboxylic acid ligand (H2CBA), resulting in a honeycomb arrayed framework. S-1 possesses excellent water stability and still retains intact structure after exposure to water for 10 weeks or boiling water for 10 weeks. Interestingly, S-1 acts as a luminescence sensor to selectively and sensitively detect quercetin with the limit of detection (LOD) as low as 0.23 ppm (7.6 × 10-7 M). The relationship between relative luminescence intensity and concentration obeys linear in the range of 0-300 ppm (0-993 µM), which allows quantitative detection of quercetin. Importantly, S-1 can be reused at least six times with almost no change in luminescent intensity. Compared with the high performance liquid chromatography-mass spectrometry (HPLC-MS) method, S-1 was used to determine the content of quercetin in onionskin and apple peel samples with satisfactory results. Furthermore, a portable S-1 test paper is also developed and expected to be applied in practice. To our knowledge, S-1 is the first example of MOFs as luminescent sensor for quercetin.

A new family of dinuclear lanthanide complexes constructed from an 8-hydroxyquinoline Schiff base and ß-diketone: magnetic properties and near-infrared luminescence.

Six phenoxo-O bridged dinuclear lanthanide(iii) complexes have been assembled utilizing the 2-[(4-nitrophenyl)imino]methyl-8-hydroxyquinoline (HL) and dibenzoylmethane (Hdbm) ligands: [Ln2(dbm)4L2] (Ln = Nd (1), Eu (2), Gd (3), Tb (4), Dy (5) and Er (6)). Complexes 1 and 6 exhibit the characteristic emission peaks of the corresponding Nd3+ and Er3+ ions, respectively. Meanwhile, the excitation wavelength (470 nm) for complex 1 is located in the visible-light region, confirming a practical application value. The studies on magnetic properties reveal that complex 3 features a magnetocaloric effect with a magnetic entropy change of -ΔSm = 14.36 J kg-1 K-1 at 4 K for ΔH = 7 T. What's more, the dynamic magnetic studies for complex 5 show that it exhibits slow magnetic relaxation behavior, typical of SMM behavior, resulting in an energy barrier of ΔE/kB = 75 K with the pre-exponential factor τ0 = 2.2 × 10-7 s. Meanwhile, this research demonstrates that the magnetic properties can be modulated by regulating the electron-donating/withdrawing effects of the substituents on the ligands.

Two luminescent lanthanide(iii) metal-organic frameworks as chemosensors for high-efficiency recognition of Cr(vi) anions in aqueous solution.

Two new lanthanide(iii) metal-organic frameworks (MOFs) {[(CH3)2NH2]2[Ln4(FDA)7(DMF)2]·0.5DMF}n [Ln = Eu (1), and Tb (2)] based on furan-2,5-dicarboxylic acid (H2FDA) have been successfully assembled and well characterized in detail. These MOFs are isostructural and demonstrate 12-connected sqc15 topologies, which are rarely observed in MOF chemistry, especially in lanthanide(iii) MOFs. Moreover, these two MOFs could show a tolerance towards moisture and organic solvents and satisfactory chemical stabilities. More importantly, they exhibit sensitive and selective luminescence quenching response towards Cr2O72- and CrO42- anions in aqueous solution with the average quenching Ksv values of 1.25 × 104 L mol-1 (Cr2O72-) and 3.56 × 103 L mol-1 (CrO42-) for 1 and 1.46 × 104 L mol-1 (Cr2O72-) and 4.35 × 103 L mol-1 (CrO42-) for 2 and the detection limits of 1.14 × 10-4 mol L-1 (Cr2O72-) and 1.12 × 10-4 mol L-1 (CrO42-) for 1 and 7.42 × 10-5 mol L-1 (Cr2O72-) and 1.27 × 10-4 mol L-1 (CrO42-) for 2. The high quenching Ksv values and low detection limits make them more feasible in sensing Cr(vi) anions in aqueous solution. The possible detection mechanism has been discussed in detail.

Neuroprotective effects of dexmedetomidine on traumatic brain injury: Involvement of neuronal apoptosis and HSP70 expression.

The aim of the present study was to investigate the protective effect of dexmedetomidine (Dex) on traumatic brain injury (TBI), and further evaluate whether the underlying neuroprotective mechanisms are associated with neurological apoptosis and the expression of 70 kDa heat shock protein (HSP70) in the hippocampus. A total of 90 adult male Sprague­Dawley rats were randomly assigned into 3 groups (n=30/group): Sham, TBI and Dex groups. The rat models of TBI were established using a modified weight­drop device and Dex (15 µg/kg) was intravenously administered immediately following TBI. The brain edema and neurological function outcomes of TBI were assessed using wet­dry weight analysis and the Neurological Severity Score method. The expression levels of B­cell lymphoma­2 (Bcl­2) and Bcl­2­associated X protein (Bax) in the rat hippocampus were evaluated using immunohistochemical staining and western blot analysis. The protein levels of HSP70 in the hippocampal region were analyzed using western blot analysis. The results of the present study revealed that administration of Dex post­TBI improved brain edema and neurological outcomes, due to the attenuation of the TBI­induced reduction of Bax expression and increase of Bcl­2 and HSP70 expression. In conclusion, the results of the present study suggested that administration of Dex may serve as a neuroprotective agent against brain injury, at least partially via the inhibition of neuronal apoptosis and upregulation of HSP70 expression in the hippocampus.

Wheel-like Ln18 Cluster Organic Frameworks for Magnetic Refrigeration and Conversion of CO2.

Two isostructural 2D MOFs ([Ln7(CDA)6(HCOO)3(µ3-OH)6(H2O)8] n, abbreviated as 1-Gd and 2-Dy) were successfully synthesized under solvothermal conditions. The self-assembly of lanthanide(III) nitrate and 1,1'-cyclopropane-dicarboxylic acid (H2CDA) resulted in wheel-like Ln18 cluster second building units (SBU), which are further linked to six neighboring wheels to generate a 2D ordered honeycomb array. Both 1-Gd and 2-Dy exhibit high thermal stability and decompose above 330 °C. Moreover, they have good solvent stability in ten common solvents and pH stability with pH values from 1 to 13. Magnetic studies reveal that 1-Gd exhibits weak antiferromagnetic coupling between adjacent Gd3+ ions and has a large magnetocaloric effect of 47.30 J kg-1 K-1 (Δ H = 7.0 T at 2 K), while 2-Dy shows ferromagnetic interaction between adjacent Dy3+ ions. Interestingly, 1-Gd and 2-Dy can catalyze the cycloaddition of CO2 to epoxides under mild conditions and can be reused at least five rounds with negligible loss of catalytic performance.

Magnetic properties and structure of tetranuclear lanthanide complexes based on 8-hydroxylquinoline Schiff base derivative and ß-diketone coligand.

Five tetranuclear lanthanide complexes [Gd4(dbm)4(L)6(µ3-OH)2]·5CH3CN (1), [Tb4(dbm)4(L)6(µ3-OH)2]·2CH3CH2OH·4CH3CN (2), [Dy4(dbm)4(L)6(µ3-OH)2]·4CH3CN·2H2O (3), [Ho4(dbm)4(L)6(µ3-OH)2]·CH3CH2OH·4CH3CN·2H2O (4) and [Er4(dbm)4(L)6(µ3-OH)2] (5) are obtained from the reaction of 5-(4-pyridinecarboxaldehyde)amino-8-hydroxylquinoline (HL) and Ln(dbm)3·2H2O (dbm = 1,3-diphenyl-1,3-propanedione). Complexes 1-5 are isomorphous and crystallize in the monoclinic space group P21/c. The metal ions in 1-5 adopt an approximately square-antiprismatic coordination environment. Magnetic studies indicate that complex 1 features a magnetocaloric effect (MCE) with the magnetic entropy change of -ΔSm(T) = 16.35 J kg-1 K-1 at 3 K for ΔH = 7 T. Additionally, complex 3 displays single molecule magnet (SMM) behavior, exhibiting an effective energy barrier of the relaxation of magnetization Ueff/kB = 89.38 K and pre-exponential factor τ0 = 3.32 × 10-8 s.

Therapeutic effects of conditioned medium from bone marrow-derived mesenchymal stem cells on epithelial-mesenchymal transition in A549 cells.

Pulmonary fibrosis (PF) is a chronic lung disease. The transforming growth factor-ß1 (TGF-ß1)/Smad3 signaling pathway plays an important role in the pathogenesis of pulmonary fibrosis. Bone marrow-derived mesenchymal stem cells (BMSCs) have been shown to be a modulator of the molecular aspects of the fibrosis pathway. However, it is still unknown as to whether the conditioned medium from BMSCs (BMSCs-CM) inhibits the epithelial-mesenchymal transition (EMT) process. This study confirmed the hypothesis that BMSCs-CM exerts an anti-fibrotic effect on human type II alveolar epithelial cells (A549) by suppressing the phosphorylation of Smad3. We used the A549 cells in vitro to detect morphological evidence of EMT by phase-contrast microscopy. These cells were randomly divided into 4 groups as follows: the control group, the TGF-ß1 group, the SIS3 (specific inhibitor of Smad3) group and the BMSCs-CM group. The immunofluorescence method was used to determined the location of E-cadherin (E-calcium mucins; E-cad), α-smooth muscle actin (α-SMA) and p-Smad3. The expression levels of E-cad, CK8, α-SMA, vimentin, p-Smad3, Snail1, collagen I (COLI) and collagen III (COLIII) were detected by western blot analysis. Following exposure to TGF-ß1, the A549 cells displayed a spindle-shaped fibroblast-like morphology. In accordance with these morphological changes, the expression levels of E-cad and CK8 were downregulated, while the expression levels of α-SMA and vimentin were upregulated. Along with this process, the expression levels of p-Smad3, Snail1, COLI and COLIII were increased. However, the cells in the BMSCs-CM group and SIS3 group exhibited a decrease in the levels of α-SMA and vimentin (which had been upregulated by TGF-ß1), and an increase in the levels of E-cad and CK8 expression (which had been downregulated by TGF-ß1). On the whole, these results indicated that BMSCs-CM suppressed the EMT which might be associated with TGF-ß1/Smad3. This study provides the theoretical basis for the research of the mechanisms responsible for pulmonary disease.

Tuning the luminescence of two 3d-4f metal-organic frameworks for the fast response and highly selective detection of aniline.

Two 3D solvent-stable zinc(ii)-lanthanide(iii) heterometallic metal-organic frameworks (MOFs) {[(CH3)2NH2]2[Zn2Ln2(FDA)6(DMF)2]·2DMF}n [Ln = Eu (Zn-Eu) and Tb (Zn-Tb); H2FDA = furan-2,5-dicarboxylic acid] based on Zn2Ln2(COO)10 tetrametallic clusters and furan-2,5-dicarboxylic acid have been successfully synthesized. These MOFs can serve as luminescent sensors for the fast response and highly selective detection of aniline via luminescence quenching. More importantly, a linear correlation is observed between their luminescence and the low concentration of aniline and the detection limits of aniline are 7.5 µmol L-1 for Zn-Eu and 5.2 µmol L-1 for Zn-Tb.

A unique zinc-organic framework constructed through in situ ligand synthesis for conversion of CO2 under mild conditions and as a luminescence sensor for Cr2O72-/CrO42.

A novel zinc-organic framework, {[Zn3(tza)2(µ2-OH)2(H2O)2]·H2O}n (1) (H2tza = 1H-tetrazolate-5-acetic acid), was synthesized through an in situ generated tetrazole ligand under hydrothermal conditions. In compound 1, tza2- ligands and Zn2+ are interlinked to form 2D layers, which are further pillared through µ2-OH groups to generate a 3D framework. Thermogravimetric analysis and powder X-ray diffraction confirm that 1 has high thermal stability, pH stability and solvent stability. Catalytic studies show that 1 exhibits excellent catalytic ability for the cycloaddition of CO2 with epoxides under 50 °C and 0.1 MPa. Importantly, 1 can be reused at least six times. Furthermore, luminescence investigations indicate that 1 can serve as a recyclable luminescence sensor to efficiently detect Cr2O72-/CrO42-, and the detection limit can reach 10-6 mol L-1 and 4 × 10-6 mol L-1, respectively.