Facile Synthesis of a Long Afterglow Calcium-Organic Framework in Water.

Presented here is a water-stable Ca-MOF that has been facilely synthesized from the metastable 3D framework in water and exhibits room-temperature phosphorescence with second scale long afterglow.

Macrocyclic Inorganic Tin-Containing Oxo Clusters: Heterometallic Strategy for Configuration and Catalytic Activity Modulation.

In this work, the first examples of inorganic macrocyclic tin-oxo clusters which are stabilized by sulfate ligands are reported. As determined by X-ray diffraction and photoelectron spectroscopy analyses, the prepared inorganic Sn10 -oxo cluster displays interesting mixed valence behaviors, with 8 Sn4+ located at the cyclic skeleton and two Sn2+ encapsulated in the center. When further introducing Ti4+ and In3+ ions to the synthetic systems, heterometallic Sn2 Ti6 and SnIn5 Ti6 complexes with Ti6 (SO4 )9 and SnIn5 (SO4 )12 macrocyclic skeletons were prepared whose configuration and packing models were affected by the ionic radius of incorporated metals. Moreover, comparative CO2 reduction experiments confirm that such heterometallic composition can significantly improve the catalytic activities of these inorganic macrocyclic oxo clusters. This work represents a milestone in constructing inorganic tin complexes and also macrocyclic metal oxo clusters with tunable configurations and properties.

Associations of lens thickness and axial length with outcomes of laser peripheral iridotomy.

AIM: To investigate the association of axial length (AL), lens thickness (LT), and lens vault (LV) with postoperative anterior chamber angle metrics after laser peripheral iridotomy (LPI). METHODS: Prospective observational study of 69 patients (97 eyes) were diagnosed as primary angle-closure suspect (PACS), primary angle closure (PAC) or primary angle-closure glaucoma (PACG). AL, LT, anterior central chamber depth (ACD), angle opening distance (AOD), trabecular iris angle (TIA), and angle recess area (ARA) were measured before and 1wk after LPI. The association between AL, LT, LV with ACD, AOD, TIA, ARA were analyzed by comparing the differences between preoperative and postoperative measurements for anterior segment biometric parameters. RESULTS: ACD, AOD, TIA, and ARA were significantly increased after LPI (all P<0.05). Greater LT was significantly associated with greater postoperative increases in ACD, AOD, TIA, and ARA (all P<0.05). AL was not significantly associated with changes of anterior segment biometric parameters. Greater LV was significantly associated with greater postoperative increases in ACD, AOD, and TIA (all P<0.05), but was not significantly associated with changes of ARA. CONCLUSION: Greater baseline LT and LV measurements are associated with greater increases in anterior segment biometric parameters after laser peripheral iridotomy. AL are not associated with the change of anterior segment biometric parameters.

Experimental and Theoretical Studies on Effects of Structural Modification of Tin Nanoclusters for Third-Order Nonlinear Optical Properties.

Tin oxide based materials have attracted much attention as new sources for nonlinear optical (NLO) devices, while the electronic mechanism behind the structure and nonlinearity is still unclear. In this work, by precisely controlling different functionalization ligands, here a series of binuclear [(nBuSn)2(TEOA)2L2] (L = monocarboxylic acid ligand) complexes have been synthesized and characterized; we also adopted a new method to make the metal clusters and PMMA blend together for NLO testing. Importantly, the electronic structure, static third-order NLO properties, sum over states (SOS) have been studied by both experimental and density function theory (DFT) analysis. The effects for general NLO polarizability under various conditions, including different substitutions ligands and replacement of the metal cores, have been further investigated. The results indicate the static second hyperpolarizabilities (γ) is inversely proportional to the band gap decreases. Notably, the theory predicts that the third-order nonlinear coefficient will double through the synergistic effects of pull-push groups. The hole-electron analysis of the main excited states indicates the simultaneous introduction of pull-push electron groups into the system cause the excitation of the valence layer from LE to LLCT, which also leads to significant increase in the γ value of complex 13. This work demonstrates that an efficient adjustment for the intensity of NLO polarizability can be achieved by regulating the substitutions and the material structures, providing a new potential for the application of tin-oxo clusters in the field of nonlinear optics.

Luminescent Sm(III) complex bearing dynamic imine bonds as a multi-responsive fluorescent sensor for F- and PO43- anions together with Zn2+ cation in water samples.

We have designed and synthesized a new luminescent mononuclear samarium (III) complex Sm-2h based on the [1 + 1] Schiff-base macrocycle H2L2h, derived from the cyclocondensation reaction between dialdehyde and diamine precursors, and its exact architecture is determined to be [Sm(HL2h) (NO3)2]. The sensing ability of complex Sm-2h is carefully evaluated for various common inorganic ions in solution. It is shown that complex Sm-2h is a multi-responsive fluorimetric sensor with high selectivity for F- and PO43- anions together with Zn2+ cation. The sensing process is rapid within 60 s for F- and PO43- ions and 300 s for Zn2+ ion. Further detailed responsive investigations suggest that its sensing behavior has excellent linear relationship between the fluorescence intensity (or absorption value) and ion concentration. The limit of detection (LOD) for sensing F-, PO43- and Zn2+ ions are as low as 2.61 µM (2.94 µM), 1.92 µM (1.64 µM) and 5.67 µM (3.53 µM), respectively, verified by fluorimetric (or colorimetric) titration experiments. ESI mass spectra prove that these efficient detections originate from the structure collapse of sensor Sm-2h because of the ion-induced imine bond breakage. Moreover, sensor Sm-2h shows excellent sensing performances for F-, PO43- and Zn2+ ions in real water samples, and we also have developed a convenient method to detect these three ions by use of the sensor impregnated test paper strips, providing rapid and distinguishable fluorimetric color changes. Therefore, the macrocyclic Sm(III) complex Sm-2h could be regarded as a valuable candidate for monitoring F-, PO43- and Zn2+ ions in practical applications.

[Effects of phytoremediation on soil enzyme activity and thermodynamic characteristics of enzymatic reaction in severe saline-alkali land.] / æ¤è¢«ä¿®å¤å¯¹é‡åº¦ç›ç¢±åœ°åœŸå£¤é ¶æ´»æ€§å’Œé ¶ååº”çƒ­åŠ›å­¦ç‰¹å¾çš„å½±å“.

With the environmental changes and the increases of anthropogenic disturbance, the area and degree of salinization in saline-alkaline lands of Songnen Plain have been increasing with an unprecedented rate. In this study, the effects of restoration of natural vegetation, Leymus chinensis, Avena sativa and Medicago sativa, on the enzymatic activities and thermomechanical characteristics of enzyme catalyzed reaction of two oxidoreductases (catalase, polyphenol oxidase) and three hydrolases (alkaline phosphatase, sucrase, urease) were investigated in heavily saline-alkaline soils from western Songnen Plain. The results showed that the activities of those five soil enzyme as well as the activation free energy (ΔG) increased with increasing temperature, reaching respective maximum at 40 and 45 ℃. The activation enthalpy (ΔH) and entropy (ΔS) of soil enzyme did not change with increasing temperature. The temperature coefficient (Q10) slightly changed and ranged from 1.05 to 1.36 by every 10 ℃ enhancement of temperature. Compared with the bare land, catalase activity increased in natural vegetation and L. chinensis rehabilitated land, but decreased in A. sativa and M. sativa remediation land. The change of ΔG of catalase showed a contrary trend with that of enzyme activities, while ΔH and ΔS increased in the restoration areas of L. chinensis and A. sativa, and decreased in the restoration of natural vegetation and M. Sativa. The activity of polyphenol oxidase decreased or remained unchanged in all restoration sites, and ΔH and ΔS decreased in natural vegetation and L. chinensis restoration sites, while remained unchanged in A. sativa and M. sativa restoration sites. ΔG of polyphenol oxidase reached the maximum at 40 ℃ in each restoration site and decreased or remained unchanged at other temperatures. The activities of three hydrolytic enzymes increased in each restoration site compared with the bare land, and the ΔG of the enzymes decreased or remained unchanged in each repaired area, while ΔH and ΔS varied greatly among the restoration sites. Taken together, significant responses of soil enzyme activity and their thermodynamic characteristics to temperature change and vegetation restoration were detected, which would provide better understanding for the restoration of heavily salinized soil.

Series of Highly Luminescent Macrocyclic Sm(III) Complexes: Functional Group Modifications Together with Luminescence Performances in Solid-State, Solution, and Doped Poly(methylmethacrylate) Film.

Here, we report our trials to regulate the luminescence performance of the macrocyclic samarium(III) complex and prepare four excellent luminescent Sm(III) complex-doped poly(methylmethacrylate) (PMMA) composites. Four 23-membered [1 + 1] Schiff-base macrocyclic mononuclear Sm(III) complexes, Sm-2 a -Sm-2 d , originating from dialdehydes with different pendant arms and 1,2-bis(2-aminoethoxy)ethane, have been constructed by the template method. Crystal structures reveal that every Sm(III) ion with the coordination geometry of a distorted bicapped square antiprism is capsulated by the macrocyclic cavity environment forming the "lasso-type" protection. Relative photophysical properties of macrocyclic Sm(III) complexes are carefully investigated in solid-state, methanol solution, and doped PMMA film, and all these show characteristic emissions of the Sm(III) ion associated with satisfactory lifetimes and quantum yields in all media, which could be comparable to reported outstanding examples. Especially, the luminescence performance for this type of Sm(III) complex could be regulated in the solid state by the use of different functional groups in the pendant arm while it is not achieved in solution and the doped PMMA composite. High emitting and air-stable plastic materials could be obtained when these Sm(III) complexes are doped in PMMA with 0.1 wt % mixing ratio, and the corresponding maximum lifetime and quantum yield are 61.2 µs and 0.63% in the case of complex Sm-2 a , respectively. We believe that these highly luminescent "lasso-type" Sm(III) complexes and doped PMMA composites are valuable references in the design of luminescent lanthanide(III) hybrid materials.

An excellent colorimetric and "turn off" fluorescent probe for tetrahydrofuran based on a luminescent macrocyclic samarium(iii) complex.

In this paper we report a novel probe based on a luminescent 23-membered [1 + 1] Schiff-base macrocyclic mononuclear Sm(iii) complex Sm-2e, originating from the dialdehyde H2Qe and 1,2-bis(2-aminoethoxy)ethane precursors, which is synthesized by the Sm(iii) ion template method. X-ray structural analyses confirm that each ten-coordinate Sm(iii) center with the coordination geometry of a distorted bicapped square antiprism is fully encapsulated by a flexible macrocyclic ligand H2L2e to form a "lasso-type" architecture, and this architecture could enable efficient energy transfer in various solvents confirmed by long lifetimes (33.5-65.2 µs) and high quantum yields (0.23-0.76%) of the Sm(iii) ion. Simultaneously, complex Sm-2e could serve as a probe for sensing organic solvents. Particularly, this complex probe Sm-2e exhibits a highly selective, rapid and sensitive response to tetrahydrofuran (THF), which is easily distinguished by a large absorption shift, even visible to the naked eye, and complete fluorescence quenching. Moreover, the limit of detection for THF is about 0.20% determined by titration experiments, and good selectivity for THF could still be realized in mixture solvents. Consequently, this colorimetric and "turn off" fluorescent probe Sm-2e could be a valuable candidate as a sensor material for sensing THF which has been rarely reported.

Toosendanin inhibits growth and induces apoptosis in colorectal cancer cells through suppression of AKT/GSK-3ß/ß-catenin pathway.

AKT/GSK-3ß/ß-catenin signaling pathway plays an important role in the progression of colorectal cancer (CRC). Toosendanin (TSN) is a triterpenoid extracted from the bark or fruits of Melia toosendan Sieb et Zucc and possesses antitumour effects on various human cancer cells. However, its effect on CRC remains poorly understood. The present study investigated the effect of TSN on CRC SW480 cells and the AKT/GSK-3ß/ß-catenin signaling. Proliferation assay, flow cytometry and Hoechst 33342 nuclear staining demonstrated TSN dose-dependently inhibited cell viability and induced cell apoptosis as well as cell cycle arrest in S phase. Confocal laser scanning microscope showed ß-catenin transferred to the outside of the nucleus in TSN-treated cells. Quantitative real-time PCR and western blot analysis found that TSN effectively modulated molecules related to apoptosis and AKT/GSK-3ß/ß-catenin signaling. Moreover, TSN administration significantly inhibited CRC growth in a mouse tumor xenograft model. In conclusion, our findings indicate that TSN inhibits growth and induces apoptosis in CRC cells through suppression of AKT/GSK-3ß/ß-catenin pathway, suggesting that TSN may have potential for use in CRC treatment.

Management of differentiated thyroid carcinoma with bone metastasis: a case report and review of the Chinese literature.

Differentiated thyroid carcinoma (DTC) is a common malignancy. The general treatments are thyroidectomy of the affected lobe along with lymphadenectomy. However, bone metastasis is rare in DTC compared with other malignancies and the management of metastasis foci is still controversial. Here we present a case of follicular thyroid carcinoma with the 6th cervical vertebra body metastasis successfully treated by total thyroidectomy, cervical corpectomy, and internal fixation, followed by hormone replacement therapy and radioiodine therapy. Eleven additional patients diagnosed as thyroid carcinoma with bone metastasis collected from Chinese literature between January 1996 and December 2013 were also reviewed. The mean age of the 12 patients at presentation was (53.9±9.2) years (rang, 42-72 years) and the male to female ratio was 1:2. Nine cases received total/near-total thyroidectomy or lobectomy while the other three patients refused for personal reasons. The interventions for bone metastasis were one-stage operation (9/12), I(131) adjuvant therapy (3/12), chemotherapy (1/12), and no intervention (1/12). During the follow-up, two patients died of metastatic carcinoma recurrence, one died of multiple organ metastasis, and one with an unknown reason. We conclude that the management of thyroid carcinoma with bone metastasis needs multidisciplinary cooperation. Surgical resection is still the first choice for cure, while the combined one-stage operation on the primary and metastatic sites followed by hormone replacement therapy and radioiodine therapy is an applicable treatment.

Colonic interposition between the liver and left diaphragm - management of Chilaiditi syndrome: A case report and literature review.

Chilaiditi syndrome refers to a medical condition that is indicated by the presence of Chilaiditi sign, the radiological observation of a colonic interposition between the liver and the diaphragm, and is associated with other clinical symptoms. Chilaiditi syndrome is a rare entity and therefore, is often misdiagnosed in clinical practice, however, it may be accompanied by a series of severe complications, such as bowel obstruction and perforation. The current study describes a 47-year-old male who presented with repeated abdominal pain and acute intestinal obstruction. The patient was diagnosed with Chilaiditi syndrome via radiological observation and was cured by conservative treatment. The clinical data of seven additional patients with Chilaiditi syndrome, which was reported in the Chinese literature between January 1990 and January 2013, were also collected. The pathogenesis, clinical manifestation, diagnosis and treatment of this syndrome have been reviewed and analyzed. The current study may be useful to familiarize clinical practitioners with Chilaiditi syndrome, in order to avoid a misdiagnosis during clinical treatment.

Molecular characterization of the glucose-regulated protein 78 (GRP78) gene in planarian Dugesia japonica.

GRP78 (78 kDa glucose-regulated protein) has ubiquitously existed in nearly all organisms from yeast to humans, reflecting the central roles it plays in cell survival. In this report, we isolated and sequenced the full-length cDNA of GRP78 (designated DjGRP78) from the planarian Dugesia japonica. The cDNA is 2121 bp, including an open reading frame (ORF) of 1983 bp encoding a polypeptide of 660 amino acids with three HSP70 family signatures. DjGRP78 contains signal peptides at the N-terminus and a KTEL peptide motif at the C-terminus, which suggests that it localizes in the endoplasmic reticulum (ER). Fluorescent real time RT-PCR was employed to detect the expression pattern of Djgrp78 in response to different stressors. Our results show that heat shock and heavy metals (Hg(2+) and Pb(2+)) induce Djgrp78 expression, but starvation does not. Interestingly, we found that Djgrp78 was up-regulated in planarians with septic tissues, and also verified that it was up-regulated in response to bacterial challenge. Our data indicate that Djgrp78 may be a multifunctional gene, and play important roles in physiological and pathological stress in planarians.