Can Coordination-Driven Supramolecular Self-Assembly Reactions Be Conducted from Fully Aliphatic Linkers?

The reaction between a preassembled CuI bimetallic molecular clip with a short intermetallic distance and a series of fully aliphatic cyano-capped ditopic linkers with increasing lengths was investigated. It is shown that, depending on the length of the ditopic linkers, the rational design of unprecedented supramolecular compact metallacycles containing fully aliphatic walls is possible. The specific preorganized molecular arrangement of the molecular clip used favors stabilizing interlinker London dispersion interactions, which allow, as the length of the linkers increases, the selective formation of discrete compact metallacycles at the expense of 1D coordination polymers. The generalizability of this approach was demonstrated by the reaction of fully aliphatic cyano-capped linkers with two other types of preassembled CuI bimetallic molecular clips that also had short intermetallic distances.

An Icosidodecahedral Supramolecule Based on Pentaphosphaferrocene: From a Disordered Average Structure to Individual Isomers.

Pentaphosphaferrocenes [CpR Fe(η5 -P5 )] (1) and CuI halides are excellent building blocks for the formation of discrete supramolecules. Herein, we demonstrate the potential of Cu(CF3 SO3 ) for the construction of the novel 2D polymer [{Cp*Fe(µ4 ,η5:1:1:1 -P5 )}{Cu(CF3 SO3 )}]n (2) and the unprecedented nanosphere (CH2 Cl2 )1.4 @[{CpBn Fe(η5 -P5 )}12 {Cu(CF3 SO3 )}19.6 ] (3). The supramolecule 3 has a unique scaffold beyond the fullerene topology, with 20 copper atoms statistically distributed over the 30 vertices of an icosidodecahedron. Combinatorics was used to interpret the average disordered structure of the supramolecules. In this case, only two pairs of enantiomers with D5 and D2 symmetry are possible for bidentate bridging coordination of the triflate ligands. DFT calculations showed that differences in the energies of the isomers are negligible. The benzyl ligands enhance the solubility of 3, enabling NMR-spectroscopic and mass-spectrometric investigations.

cyclo-P4 Building Blocks: Achieving Non-Classical Fullerene Topology and Beyond.

The cyclo-P4 complexes [CpR Ta(CO)2 (η4 -P4 )] (CpR : Cp''=1,3-C5 H3 tBu2 , Cp'''=1,2,4-C5 H2 tBu3 ) turned out to be predestined for the formation of hollow spherical supramolecules with non-classical fullerene-like topology. The resulting assemblies constructed with CuX (X=Cl, Br) showed a highly symmetric 32-vertex core of solely four- and six-membered rings. In some supramolecules, the inner cavity was occupied by an additional CuX unit. On the other hand, using CuI, two different supramolecules with either peanut- or pear-like shapes and outer diameters in the range of 2-2.5 nm were isolated. Furthermore, the spherical supramolecules containing Cp''' ligands at tantalum are soluble in CH2 Cl2 . NMR spectroscopic investigations in solution revealed the formation of isomeric supramolecules owing to the steric hindrance caused by the third tBu group on the Cp''' ligand. In addition, a 2D coordination polymer was obtained and structurally characterized.

Does primary stroke center certification change ED diagnosis, utilization, and disposition of patients with acute stroke?

BACKGROUND AND PURPOSE: We examined the impact of primary stroke center (PSC) certification on emergency department (ED) use and outcomes within an integrated delivery system in which EDs underwent staggered certification. METHODS: A retrospective cohort study of 30,461 patients seen in 17 integrated delivery system EDs with a primary diagnosis of transient ischemic attack (TIA), intracranial hemorrhage, or ischemic stroke between 2005 and 2008 was conducted. We compared ED stroke patient visits across hospitals for (1) temporal trends and (2) pre- and post-PSC certification-using logistic and linear regression models to adjust for comorbidities, patient characteristics, and calendar time, to examine major outcomes (ED throughput time, hospital admission, radiographic imaging utilization and throughput, and mortality) across certification stages. RESULTS: There were 15,687 precertification ED visits and 11,040 postcertification visits. Primary stroke center certification was associated with significant changes in care processes associated with PSC certification process, including (1) ED throughput for patients with intracranial hemorrhage (55 minutes faster), (2) increased utilization of cranial magnetic resonance imaging for patients with ischemic stroke (odds ratio, 1.88; 95% confidence interval, 1.36-2.60), and (3) decrease in time to radiographic imaging for most modalities, including cranial computed tomography done within 6 hours of ED arrival (TIA: 12 minutes faster, ischemic stroke: 11 minutes faster), magnetic resonance imaging for patients with ischemic stroke (197 minutes faster), and carotid Doppler sonography for TIA patients (138 minutes faster). There were no significant changes in survival. CONCLUSIONS: Stroke center certification was associated with significant changes in ED admission and radiographic utilization patterns, without measurable improvements in survival.

[Prolonged icterus as a difficult diagnostic problem in small children--own observations]. / Przedluzajaca sie zóltaczka jako trudny problem diagnostyczny w klinice malego dziecka--obserwacje wlasne.

UNLABELLED: THE AIM of the study was the retrospective evaluation of causes of prolonged icterus in children treated in the Second Department of Peadiatrics and Allergology in Lódz during the last 16 years. MATERIAL AND METHODS: 361 children aged 3 weeks to 15 months of 12650 patients hospitalised in our Clinic were analysed. All the examined children were divided into two groups group I consisted of 314 children with unconjugated hyperbilirubinemia and group II of 47 patients with cholestasis Additionally the cholestatic group was divided into two subgroups: IIa consisted of 41 children with intrahepatic cholestasis and IIb--six children with extrahepatic cholestasis. RESULTS: The most common reasons of icterus in groups I and IIa were respiratory tract infections and cytomegalovirus infections All of these children recovered. Metabolic diseases were diagnosed in 4 children (galactosemia, fructosemia and in two children mucoviscidosis) in 5 children other genetic syndromes (Crigler-Najjar, Allagille and in three Byler disease). Six children from group IIb with extrahepatic biliary atresia were transferred to the Department of Paediatric Surgery. All of them underwent Kasai operation. CONCLUSIONS: Small children's prolonged icterus needs immediate and intense investigations to set as fast as possible the correct diagnosis of its cause. Early diagnosis of its cause increases the prospect of effective treatment and prevents the child from potential development of hepatic failure.