Visible-light triggered selective reduction of nitroarenes to azo compounds catalysed by Ag@organic molecular cages.

Herein, a new Ag nanoparticle (Ag NP) loaded organic molecular cage is reported. The obtained Ag@1 can act as a highly efficient heterogeneous catalyst for the selective reduction of nitroarenes to azo compounds under visible-light irradiation.

Predicting microRNA-disease associations using bipartite local models and hubness-aware regression.

The development and progression of numerous complex human diseases have been confirmed to be associated with microRNAs (miRNAs) by various experimental and clinical studies. Predicting potential miRNA-disease associations can help us understand the underlying molecular and cellular mechanisms of diseases and promote the development of disease treatment and diagnosis. Due to the high cost of conventional experimental verification, proposing a new computational method for miRNA-disease association prediction is an efficient and economical way. Since previous computational models ignored the hubness phenomenon, we presented a novel computational model of Bipartite Local models and Hubness-Aware Regression for MiRNA-Disease Association prediction (BLHARMDA). In this method, we first used known miRNA-disease associations to calculate the Jaccard similarity between miRNAs and between diseases, then utilized a modified kNNs model in the bipartite local model method. As a result, we effectively alleviated the detriments from 'bad' hubs. BLHARMDA obtained AUCs of 0.9141 and 0.8390 in the global and local leave-one-out cross validation, respectively, which outperformed most of the previous models and proved high prediction performance of BLHARMDA. Besides, the standard deviation of 0.0006 in 5-fold cross validation confirmed our model's prediction stability and the averaged prediction accuracy of 0.9120 showed the high precision of our model. In addition, to further evaluate our model's accuracy, we implemented BLHARMDA on three typical human diseases in three different types of case studies. As a result, 49 (Esophageal Neoplasms), 50 (Lung Neoplasms) and 50 (Carcinoma Hepatocellular) out of the top 50 related miRNAs were validated by recent experimental discoveries.

Ratiometric Luminescent Detection of Organic Amines Due to the Induced Lactam-Lactim Tautomerization of Organic Linker in a Metal-Organic Framework.

Here we demonstrate that a fluorescent benzothiadiazole (BTD)-conjugated terphenyldicarboxylate (TPDC) linker (denoted as H2-ostpdc) has been hybridized by a quinoxaline-2,3-(1H,4H)-dione (QD) moiety possessing lactam-lactim tautomerism, which was further integrated into a robust and porous UiO-68 type zirconium metal-organic framework (MOF UiO-68-osdm) by utilizing the mixed two dicarboxylate struts with the same ligand lengths. The resultant MOF UiO-68-osdm can work as a ratiometric luminescent sensor for visual and selective detection of alkyl amines. Furthermore, it can discriminate secondary alkylamines from other type amine species.

Synthesis, Structure, and Ligand-Centered Catalytic Properties of MII Coordination Polymers (M=ZnII , CdII , HgII ) with Open Pyridyl N-Oxide Sites.

Four MII (M=ZnII , CdII , HgII ) coordination polymers were designed and synthesized based on two pyridine N-oxide bridging ligands: 3,5-bis(4-pyridyl)pyridine N-oxide and 2,6-bis(3-pyridyl)pyridine N-oxide. The resulting polymers all feature a one-dimensional chain motif and contain free pyridyl moieties. More importantly, they exhibit interesting ligand-centered (pyridyl N-oxide) catalytic behavior, and can be used as highly heterogeneous catalysts to promote the Knoevenagel condensation reaction under ambient conditions.

Co(II)-MOF: A Highly Efficient Organic Oxidation Catalyst with Open Metal Sites.

A porous Co(II)-MOF (1) was synthesized by the combination of a bent imidazole-bridged ligand and p-phthalic acid (PTA) with Co(OAc)2 under solvothermal conditions. This Co(II)-MOF (1) is able to undergo a reversible MeOH substitution reaction on the Co(II) center via a single-crystal-to-single-crystal process. The desolvated Co(II)-MOF (2) with the open Co(II) sites is very stable (up to 350 °C). Furthermore, 2 is a highly active heterogeneous catalyst for various organic substrates oxidation in the presence of tert-butyl hydroperoxide (TBHP) under milder conditions. The importance of open Co(II) sites in 2 for the organic substrates oxidation is directly evidenced by the single-crystal X-ray diffraction.

A nanoporous Ag(I)-MOF showing unique selective adsorption of benzene among its organic analogues.

A stable porous Ag(I)-MOF with new topology is constructed from AgSbF6 and 3,6-bis[2-(4-oxide-quinoxaline)-yl]-4,5-diaza-3,5-octadiene (L). This compound can be a highly selective porous MOF material to effectively separate benzene from its six-membered cyclic organic analogues such as cyclohexane, cyclohexene and o-, m-, p-xylene under ambient conditions in both vapor and liquid phases.

Oxygen and methanol mediated irreversible coordination polymer structural transformation from a 3D Cu(I)-framework to a 1D Cu(II)-chain.

An interesting irreversible structural transformation visible to the naked-eye occurs when a 3D Cu(I)-polymeric complex Cu2L(NO3)2(DMF)0.4 (1) is suspended in CH3OH in air to produce a 1D-Cu(II) polymeric complex Cu(µ-OCH3)(L)(NO3) (2) (L = 1,2-bis[4-(pyrimidin-4-yl)phenoxy]ethane). The transformation mechanism from 1 to 2 was also investigated.

Factors influencing outcomes after cardiopulmonary resuscitation in emergency department.

BACKGROUND: The outcome of cardiopulmonary resuscitation (CPR) may depend on a variety of factors related to patient status or resuscitation management. To evaluate the factors influencing the outcome of CPR after cardiac arrest (CA) will be conducive to improve the effectiveness of resuscitation. Therefore, a study was designed to assess these factors in the emergency department (ED) of a city hospital. METHODS: A CPR registry conforming to the Utstein-style template was conducted in the ED of the First Affiliated Hospital of Wenzhou Medical College from January 2005 to December 2011. The outcomes of CPR were compared in various factors groups. The primary outcomes were rated to return of spontaneous circulation (ROSC), 24-hour survival, survival to discharge and discharge with favorable neurological outcomes. Univariate analysis and multivariable logistic regression analysis were performed to evaluate factors associated with survival. RESULTS: A total of 725 patients were analyzed in the study. Of these patients, 187 (25.8%) had ROSC, 100 (13.8%) survived for 24 hours, 48 (6.6%) survived to discharge, and 23 (3.2%) survived to discharge with favorable neurologic outcomes. A logistic regression analysis demonstrated that the independent predictors of ROSC included traumatic etiology, first monitored rhythms, CPR duration, and total adrenaline dose. The independent predictors of 24-hour survival included traumatic etiology, cardiac etiology, first monitored rhythm and CPR duration. Previous status, cardiac etiology, first monitored rhythms and CPR duration were included in independent predictors of survival to discharge and neurologically favorable survival to discharge. CONCLUSIONS: Shockable rhythms, CPR duration ≤15 minutes and total adrenaline dose ≤5 mg were favorable predictors of ROSC, whereas traumatic etiology was unfavorable. Cardiac etiology, shockable rhythms and CPR duration ≤15 minutes were favorable predictors of 24-hour survival, whereas traumatic etiology was unfavorable. Cardiac etiology, shockable rhythms, CPR duration ≤15 minutes were favorable predictors of survival to discharge and neurologically favorable survival to discharge, but previous terminal illness or multiple organ failure (MOF) was unfavorable.

Effects of Hemin on neuroglobin expression after cardiopulmonary resuscitation in rats.

BACKGROUND: Despite a large amount of resuscitation research, the survival rate after cardiac arrest remains low, and brain injury is the key issue. Neuroglobin (NGB) is an oxygen-binding heme protein found in the brain with a protection role against ischemic-hypoxic brain injury. Hemin is an effective activator of neuroglobin. This study was undertaken to assess the effect of hemin on expression of neuroglobin (NGB) in the cerebral cortex, neuro-deficit score (NDS) and pathological changes after cardiopulmonary resuscitation (CPR) in rats. METHODS: A total of 120 male Sprague-Dawley (SD) rats were randomly divided into a control group (A), a CPR group (B) and a Hemin group (C). The animal model of cardiac arrest (CA) induced by asphyxia and CPR was established. NGB expression in the cerebral cortex with immunohistochemistry, NDS and pathological changes in the cerebral cortex were examined at 3, 6, 12, 24 hours after recovery of spontaneous circulation (ROSC) in each group. Experimental data were treated as one-factor analysis of variance and the Tukey test. RESULTS: In comparison with group A, NGB expression was increased significantly at 12 and 24 hours after ROSC (P<0.05 or P<0.01), NDS was decreased significantly at each time point after ROSC (P<0.01), and pathological changes were severe at each time point after ROSC in group B. In comparison with group A, NGB expression was increased significantly at 6, 12, 24 hours after ROSC (P<0.05 or P<0.01), NDS was decreased significantly at 3, 6, 12 hours after ROSC (P<0.01) in group C. In comparison with group B, NGB expression was increased significantly at 12 and 24 hours after ROSC, NDS was increased significantly at 12 and 24 hours after ROSC, and pathological changes were milder in group C. CONCLUSION: There were increased NGB expression in the cerebral cortex, decreased NDS, and severe pathological changes after CPR in rats. Hemin treatment up-regulated expression of NGB, improved NDS, mitigated pathological changes, and alleviated cerebral injury after CPR.

Effect of exogenous phosphocreatine on cardiomycytic apoptosis and expression of Bcl-2 and Bax after cardiopulmonary resuscitation in rats.

BACKGROUND: Ischemia-reperfusion injury in the myocardium after cardiac arrest (CA) and cardiopulmonary resuscitation (CPR) is an important pathologic basis of post-cardiac arrest of syndrome (PCAS), and apoptosis is one of the major mechanisms in myocardial ischemia-reperfusion injury. To lessen myocardial ischemia-reperfusion injury after cardiac arrest and CPR, it is important to reduce energy consumption and to increase energy supply in the myocardium. This study aimed to observe changes of cell apoptosis and expression of Bcl-2 and Bax protein on the myocardium after CPR in rats, and the protective effects of different doses of exogenous phosphocreatine (creatine phosphate, CP) on them. METHODS: A total of 32 male adult Sprague-Dawley rats were randomly divided into 4 groups: control group (group A), CPR group (group B), low-dose CP group (group C, CP 0.5 g/kg at beginning of CPR and 1.0 g/kg at 2 hours after CPR) and high-dose CP group (group D, CP 1.0 g/kg at beginning of CPR and 2.0 g/kg at 2 hours after CPR). Cardiac arrest was induced by asphyxiation and CPR started at 7 minutes after asphyxiation in groups B, C and D. Myocardium samples were taken at 24 hours after CPR. Cardiomycytic apoptosis was detected by the TdT-mediated dUTP-biotin nick end labeling (TUNEL) method. The expression of Bcl-2 and Bax protein was measured by immunohistochemistry. RESULTS: Cardiomyocytic apoptosis index (AI) and expression of Bcl-2 and Bax protein increased more significantly in groups B, C and D than in group A (P<0.01), but Bcl-2/Bax ratio significantly decreased (P<0.01). Cardiomyocytic AI and expression of Bcl-2 and Bax protein decreased more significantly in groups C and D than in group B (P<0.01), but Bcl-2/Bax ratio increased more significantly (P<0.01). Cardiomyocytic AI and expression of Bcl-2 and Bax protein decreased more significantly in group D than in group C (P<0.05), but Bcl-2/Bax ratio increased more significantly (P<0.05). CONCLUSION: Exogenous phosphocreatine, especially at a large dose, could inhibit cardiomyocytic apoptosis and alleviate myocardial injury after CPR in rats.

Synthesis and characterization of new coordination polymers with tunable luminescent properties generated from bent 1,2,4-triazole-bridged N,N'-dioxides and Ln(III) salts.

A new bent 1,2,4-triazole-bridged N,N'-dioxide ligand, namely, 3,5-bis(3-pyridyl-N-oxide)-4-amino-1,2,4-triazole (L2), was designed and synthesized by the oxidation of 3,5-bis(3-pyridyl)-4-amino-1,2,4-triazole with H(2)O(2) in the presence of HOAc at ambient temperatures. Eleven Ln(III)-based coordination polymers have been successfully prepared by the solution reactions of L2 with various Ln(III)-perchlorates. The structures of these new Ln(III) polymers clearly reflect the effect of the lanthanide contraction. Compounds 1-6 feature a two-dimensional net, in which the Ln(III) atoms adopt a nine-coordinate {LnO(9)} sphere due to their larger ionic radii, whereas the Ln(III) centers in the one-dimensional double-stranded chains of 7-11 with smaller ionic radii lie in a {LnO(8)} coordination environment. In addition, the tunable emission intensity was realized on 7 by controlling the type of the involved counterion on the basis of a reversible solid-state anion exchange. Such reversible solid-state anion exchange might provide an alternative approach to tuning the luminescence.

Value of left ventricular regional ejection fraction determined by real-time three-dimensional echocardiography in diagnosis of aneurysm: compared with left ventriculography / 中华医学杂志(英文版)

<p><b>BACKGROUND</b>Regional ejection fraction (EF(R)) measured by real-time three-dimensional echocardiography (RT-3DE) provides a novel method for quantifying left-ventricular (LV) regional systolic function. We aimed to explore the diagnostic value of regional ejection fraction (EFR) derived from RT-3DE in detecting LV aneurysms in patients with myocardial infarction.</p><p><b>METHODS</b>Thirty-eight patients with myocardial infarction were prospectively enrolled and underwent electrocardiography (ECG), two-dimensional echocardiography (2-DE), RT-3DE and left ventriculography (LVG). Subjects with a negative EFR in at least one segment on RT-3DE were considered as having a ventricular aneurysm. We compared the sensitivity, specificity, Youden's index, and positive and negative predictive values of ECG, 2-DE and RT-3DE in determining LV aneurysm with detection by LVG.</p><p><b>RESULTS</b>On LVG an LV aneurysm was diagnosed in 16 (42.1%) patients. The sensitivity and specificity were 62.5% and 86.4% for ECG, 81.2% and 95.4% for 2-DE, and 100.0% and 90.9% for RT-3DE in diagnosing LV aneurysm. Youden's indexes for ECG, 2-DE and RT-3DE were 0.49, 0.77 and 0.91, respectively. Positive and negative predictive values were 76.9% and 76.0% for ECG, 92.9% and 87.5% for 2-DE, and 88.9% and 100.0% for RT-3DE.</p><p><b>CONCLUSIONS</b>RT-3DE-derived EFR provides a novel, reliable index in the diagnosis of LV aneurysm and has excellent sensitivity and specificity.</p>

[Protective effect of ulinastatin on myocardium after cardiopulmonary resuscitation in rats].

OBJECTIVE: To investigate the changes in serum creatine kinase isoenzyme (CK-MB) and cardiac troponin I (cTnI) levels and the ultrastructure of myocardium, and the effect of ulinastatin after cardiopulmonary resuscitation (CPR) in rats. METHODS: One hundred and twenty Sprague-Dawley (SD) rats were randomly divided into sham operation group, CPR group and ulinastatin group. And each group was divided into five subgroups (n=8) according to time points of 0.5, 3, 6, 12, 24 hours after tracheostomy in sham operation group or after restoration of spontaneous circulation (ROSC) in CPR group and ulinastatin group. Cardiac arrest (CA) and CPR models were reproduced by asphyxia in CPR group and ulinastatin group, with injection of ulinastatin 100 kU/kg via carotid 2 minutes after ROSC in ulinastatin group. Normal saline was given in the same dosage as ulinastatin in CPR group. Serum samples was taken at each time point of subgroups for measuring serum levels of CK-MB and cTnI. The ultrastructure changes in myocardium were observed under the electron microscope. RESULTS: The serum levels of CK-MB and cTnI were increased from 0.5 hours after ROSC in CPR group and ulinastatin group compared with sham operation group ( all P<0.01), and CK-MB peaked at 12 hours, then decreased. The serum CK-MB or cTnI levels started to decreased from 3 hours or 0.5 hours after ROSC in ulinastatin group compared with CPR group (P<0.05 or P<0.01). There were milder pathological changes of ultrastructure of myocardium in ulinastatin group than in CPR group. CONCLUSION: Ulinastatin could decrease serum levels of CK-MB and cTnI, and alleviate myocardial injury after CPR in rats.

[A protocol for diagnosis and treatment of Vibrio vulnificus sepsis].

OBJECTIVE: Vibrio vulnificus sepsis is one of the most fatal disease with a high mortality which exceeds 50%. But at present there is no evidence-based guidelines for diagnosis and therapy of Vibrio vulnificus sepsis because of its dispersion in occurrence and low incidence. METHODS: Based on our ten-year research and review of literature, we try to draft a protocol to improve the diagnostic criteria and treatment of Vibrio vulnificus sepsis. Animal experiments and clinical research were undertaken and the related literature from CINK and PUBMED were reviewed. RESULTS: (1)A criterion for early clinical diagnosis of Vibrio vulnificus sepsis was proposed, including an abrupt onset with fever during the months from April to November, characteristic cutaneous lesions (most commonly haemorrhagic bullae on the extremities) or even extensive necrosis of skin and muscular tissue, progressive hypotension or shock accompanied by multiple organ dysfunction syndrome (MODS), preexisting liver disease or chronic abuse use of alcohol, and consumption of raw seafood or contact with seawater within 1-2 weeks. (2)The best antibiotic therapy is early administration of a combination of the third-generation cephalosporins and the quinolones in full dosage. (3)Aggressive wound debridement, appropriate dermoplasty and supportive care contribute to a better outcome. CONCLUSION: This protocol will help improve the outcome of patients with Vibrio vulnificus sepsis. But it is a crude guideline and needs to be updated when some important new knowledge becomes available.

[Expression of mRNA of matrix metalloproteinase and tissue inhibitor of matrix metalloproteinase after cardiopulmonary resuscitation for asphyxial cardiac arrest in rat].

OBJECTIVE: To study the change in mRNA expression of matrix metalloproteinase (MMPs) and tissue inhibitor-1 of matrix metalloproteinase (TIMP-1) in brain after cardiopulmonary resuscitation (CPR) for asphyxial cardiac arrest in rat. METHODS: The animal model of cardiac arrest was reproduced by clamping endotracheal tube at the expiration. Eighty male SD rats were randomly divided into two groups: control group and resuscitation group, and they were again divided into 0, 0.5, 3, 6, 9 hours subgroups (n=8). Evans blue content and mRNA expressions of MMPs and TIMP-1 in the brain after CPR were determined respectively. RESULTS: The mRNA expression of MMP-9 and TIMP-1 was up-regulated 3 hours after restoration of spontaneous circulation (ROSC). At 6 hours after ROSC, they were markedly high, and the ratio of MMP-9/TIMP-1 was higher too. The mRNA expression of MMP-2 showed no significant change at 9 hours after ROSC. CONCLUSION: The mRNA expression of MMP-9 and TIMP-1 and MMP-9/TIMP-1 are increased at early stage after CPR, but the mRNA expression of MMP-2 shows no significant change.

Self-assembly of coordination polymers from AgX (X = SbF(6)(-), PF(6)(-), and CF(3)SO(3)(-)) and oxadiazole-containing ligands.

The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L1), 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L2), and 2,5-bis(3-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers (1, 2, 3, and 5) and one new bimetallic macrocyclic supramolecular complex (4) were synthesized from solution reactions of L1-L3 with inorganic Ag(I) salts, respectively. Compounds [[Ag(L1)]SbF(6)](n) (1) (1, monoclinic, P2(1)/c, a = 6.6846(4) A, b = 27.1113(15) A, c = 8.6802(5) A, beta = 94.1080(10) degrees, Z = 4) and [[Ag(L1)]PF(6)](n) (2) (2, monoclinic, P2(1)/c, a = 6.6753(3) A, b = 27.2824(14) A, c = 8.2932(4) A, beta = 94.6030(10) degrees, Z = 4) were obtained from the reactions of L1 with AgSbF(6) and AgPF(6) in a CH(2)Cl(2)/CH(3)OH mixed solvent system, respectively. Compounds 1 and 2 are isostructural and feature a novel two-dimensional zeolite-like net with two different individual rings. [[Ag(L2)]SbF(6)](n) (3) (3, monoclinic, P2(1)/c, a = 5.5677(3) A, b = 17.3378(9) A, c = 15.6640(8) A, beta = 94.4100(10) degrees, Z = 2) and [Ag(2)(L2)(2)](SbF(6))(2) (4) (4, triclinic, P1, a = 8.7221(5) A, b = 9.2008(6) A, c = 10.7686(7) A, alpha = 70.6270(10) degrees, beta = 75.7670(10) degrees, gamma = 73.7560(10) degrees, Z = 1) were obtained from one-pot reaction of L2 with AgSbF(6) in a CH(2)Cl(2)/CH(3)OH mixed solvent system. Compound 3 features a one-dimensional chain pattern, while compound 4 adopts a novel bimetallic macrocyclic structural motif which consists of Ag(2)(L2)(2) ringlike units (crystallographic dimensions, 8.06 x 7.42 A(2)). [[Ag(L3)]SO(3)CF(3)](n) (5) is generated from L3 and AgSO(3)CF(3) in a CH(2)Cl(2)/CH(3)OH mixed solvent system and crystallizes in the unusual space group Pbcn, with a = 9.8861(5) A, b = 20.2580(10) A, c = 17.5517(8) A, Z = 8. It adopts novel two-dimensional sheets that are cross-linked to each other by strong interlayer N-H...O hydrogen bonding interactions into a novel H-bonded three-dimensional network.