41 research outputs found

    Silica Nanotubes Decorated by pH-Responsive Diblock Copolymers for Controlled Drug Release

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    A novel nanocontainer, which has silica nanotube (SNT) core and pH-sensitive polymer shell attaching on the exterior surface of silica nanotube, is presented in this paper. Polymer nanorods, which are conveniently fabricated though polymerization-induced self-assembly and reorganization method, are used as templates for the deposition of silica to fabricate hybrid nanorods. Calcination of as-synthesized silica hybrid nanorods leads to hollow SNTs. SNTs are functionalized with reversible addition–fragmentation chain transfer (RAFT) agent, then surface RAFT polymerization is conducted to get poly­(2-(diethylamino)­ethyl methacrylate)-<i>b</i>-poly­(oligo­(ethylene glycol) methacrylate)-coated SNTs (SNT-PDEAEMA-<i>b</i>-POEGMA). Doxorubicin (DOX) can be encapsulated in SNT-PDEAEMA-<i>b</i>-POEGMA, and controlled release of loaded DOX is achieved by adjusting pH of the medium. In vitro cell viability and cellular internalization study confirm the potential application of this nanocontainer in drug and gene delivery

    Peripheral Methyl Activation in η<sup>4</sup>‑1,2,3,4-Tetramethylcyclobutadienylcobalt Complexes: Template Synthesis and Subsequent Reactivity of Triphosphamacrocycles

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    The cationic complex (η<sup>4</sup>-1,2,3,4-tetramethylcyclobutadienyl)­cobalt­(trisacetonitrile), [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co­(NCCH<sub>3</sub>)<sub>3</sub>]<sup>+</sup> (<b>1</b>), allows the stepwise introduction of suitable phosphine precursors to the [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co]<sup>+</sup> fragment by replacement of the labile acetonitrile ligands. These reactions give rise to the piano-stool complexes [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co­(dppe)­(NCCH<sub>3</sub>)]<sup>+</sup> (<b>2</b>), [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co­(dppe)­(PH<sub>2</sub>Ph)]<sup>+</sup> (<b>3</b>), [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co­(dfppb)­(NCCH<sub>3</sub>)]<sup>+</sup> (<b>4</b>), and [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co­(dfppb)­(PH<sub>2</sub>Ph)]<sup>+</sup> (<b>5</b>), where dfppb = 1,2-bis­{di­(2-fluorophenyl)­phosphino}­benzene and dppe = 1,2-bis­(diphenylphosphino)­ethane. Complex <b>5</b> is a template for the synthesis of the P<sub>3</sub> macrocycle complex [(η<sup>4</sup>-C<sub>4</sub>Me<sub>4</sub>)­Co­{1,4-bis­(2-fluorophenyl)-7-phenyl­[<i>b</i>,<i>e</i>,<i>h</i>]­tribenzo-1,4,7-triphosphacyclononane}]<sup>+</sup> (<b>6</b>), through base-promoted intramolecular macrocyclization. The hydrogens of two of the ring methyls of the tetramethylcyclobutadienyl ligand in the macrocycle complex <b>6</b> are sufficiently acidic to undergo deprotonation by KO<sup>t</sup>Bu, promoting nucleophilic attack at the fluorine-bearing <i>ortho</i>-carbons of the 2-fluoroaryl groups on two of the phosphorus donors in <b>6</b>. The resultant hemi-incarcerand complex [{η<sup>4</sup>,κ<i>P</i>,κ<i>P</i>,κ<i>P</i>-Me<sub>2</sub>C<sub>4</sub>-[1,4-bis­(2-CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)-7-C<sub>6</sub>H<sub>5</sub>-[<i>b</i>,<i>e</i>,<i>h</i>]­tribenzo-1,4,7-triphosphacyclononane]-1,2}­Co]<sup>+</sup> (<i>cis</i>-<b>7</b>) contains a hybrid phosphorus/carbon donor ligand where the P<sub>3</sub> macrocycle is connected to the cyclobutadienyl function through two <i>cis</i>-2-methylphenyl links. The new complexes have been characterized fully by spectroscopic and analytical techniques including single-crystal X-ray structure determinations of <b>2</b>, <b>3</b>, <b>4</b>, <b>5</b>, <b>6</b>, and <i>cis</i>-<b>7</b>

    Rare Neutral Diphosphine Complexes of Scandium(III) and Yttrium(III) Halides

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    Reaction of Me<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PMe<sub>2</sub> or <i>o</i>-C<sub>6</sub>H<sub>4</sub>(PMe<sub>2</sub>)<sub>2</sub> (L–L) with a suspension of ScI<sub>3</sub> or YI<sub>3</sub> in MeCN solution under rigorously anhydrous and oxygen-free conditions produced the highly unusual complexes [ScI<sub>3</sub>(L–L)<sub>2</sub>], [YI<sub>3</sub>(Me<sub>2</sub>PCH<sub>2</sub>CH<sub>2</sub>PMe<sub>2</sub>)<sub>2</sub>], and [YI<sub>3</sub>{<i>o</i>-C<sub>6</sub>H<sub>4</sub>(PMe<sub>2</sub>)<sub>2</sub>}<sub>2</sub>MeCN]. X-ray crystal structures reveal that the scandium complexes adopt seven-coordinate, pentagonal-bipyramidal geometries with chelating diphosphines, while the eight-coordinate [YI<sub>3</sub>{<i>o</i>-C<sub>6</sub>H<sub>4</sub>(PMe<sub>2</sub>)<sub>2</sub>}<sub>2</sub>MeCN] is dodecahedral. The complexes were characterized by microanalysis and IR and multinuclear NMR spectroscopy. Solid-state NMR data (<sup>45</sup>Sc, <sup>89</sup>Y, <sup>31</sup>P) and variable-temperature solution NMR data (<sup>1</sup>H, <sup>31</sup>P­{<sup>1</sup>H}, <sup>45</sup>Sc) are presented and compared, leading to the conclusion that the same species are present in both the solid state and CH<sub>2</sub>Cl<sub>2</sub> solution. Attempts to prepare complexes with other scandium halides and with aryl diphosphines and <i>o</i>-C<sub>6</sub>H<sub>4</sub>(AsMe<sub>2</sub>)<sub>2</sub> are briefly described

    Systematic Review of Randomized Controlled Trials of Different Types of Patch Materials during Carotid Endarterectomy

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    <div><h3>Background and Purpose</h3><p>Carotid endarterectomy (CEA) with patch angioplasty produces greater results than with primary closure; however, there remains uncertainty on the optimal patch material in CEA. A systematic review of randomized controlled trials (RCTs) was performed to evaluate the effect of angioplasty using venous patch versus synthetic patch material, and Dacron patch versus polytetrafluoroethelene (PTFE) patch material during CEA.</p> <h3>Methods</h3><p>A multiple electronic health database screening was performed including the Cochrane library, Pubmed, Ovid, EMBASE and Google Scholar on all randomized controlled trials (RCTs) published before November 2012 that compared the outcomes of patients undergoing CEA with venous patch versus synthetic patch. RCTs were included if they compared carotid patch angioplasty with autologus venous patch versus synthetic patch material, or compared one type of synthetic patch with another.</p> <h3>Results</h3><p>Thirteen RCTs were identified. Ten trials, involving 1946 CEAs, compared venous patch with synthetic patch materials. Two trials, involving 400 CEAs in 380 patients, compared Dacron patch with PTFE patch. The hemostasis time in CEA with PTFE patch was significantly longer than with venous patch (<em>P</em><0.0001), and longer than with Dacron patch (<em>P</em><0.0001). There was no significant difference of mortality rate, stroke rate, restenosis, and operative time in CEA with venous patch versus synthetic patch material, or in CEA with Dacron patch versus PTFE patch (all <em>P</em>>0.05). One RCT of 95 CEAs in 92 patients compared bovine pericardium with Dacron patch, and demonstrated a statistically significant decrease in intraoperative suture line bleeding with bovine pericardium compared with Dacron patch (<em>P</em><0.001).</p> <h3>Conclusions</h3><p>The hemostasis time in CEA with PTFE patch was longer than with venous patch or Dacron patch. The overall perioperative and long-term mortality rate, stroke rate, restenosis, and operative time were similar when using venous patch versus synthetic patch material or Dacron patch versus PTFE patch material during CEA. More data are required to clarify differences between different patch materials.</p> </div

    Any stroke event is compared in both groups.

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    <p>Graphical representation of the results. <i>M-H:</i> Mantel-Haenszel.</p

    Mortality in both groups.

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    <p>Graphical representation of the results. <i>M-H</i> : Mantel-Haenszel.</p
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