Fluorescence-Lifetime Imaging and Super-Resolution Microscopies Shed Light on the Directed- and Self-Assembly of Functional Porphyrins onto Carbon Nanotubes and Flat Surfaces.

Functional porphyrins have attracted intense attention due to their remarkably high extinction coefficients in the visible region and potential for optical and energy-related applications. Two new routes to functionalised SWNTs have been established using a bulky ZnII -porphyrin featuring thiolate groups at the periphery. We probed the optical properties of this zinc(II)-substituted, bulky aryl porphyrin and those of the corresponding new nano-composites with single walled carbon nanotube (SWNTs) and coronene, as a model for graphene. We report hereby on: i) the supramolecular interactions between the pristine SWNTs and ZnII -porphyrin by virtue of π-π stacking, and ii) a novel covalent binding strategy based on the Bingel reaction. The functional porphyrins used acted as dispersing agent for the SWNTs and the resulting nanohybrids showed improved dispersibility in common organic solvents. The synthesized hybrid materials were probed by various characterisation techniques, leading to the prediction that supramolecular polymerisation and host-guest functionalities control the fluorescence emission intensity and fluorescence lifetime properties. For the first time, XPS studies highlighted the differences in covalent versus non-covalent attachments of functional metalloporphyrins to SWNTs. Gas-phase DFT calculations indicated that the ZnII -porphyrin interacts non-covalently with SWNTs to form a donor-acceptor complex. The covalent attachment of the porphyrin chromophore to the surface of SWNTs affects the absorption and emission properties of the hybrid system to a greater extent than in the case of the supramolecular functionalisation of the SWNTs. This represents a synthetic challenge as well as an opportunity in the design of functional nanohybrids for future sensing and optoelectronic applications.

Diamagnetic Ru(2+) in Na2La2Ti2RuO10-x (0 < x < 2): A Series of Complex Oxides Prepared by Topochemical Reduction.

Reaction of the n = 3 Ruddlesden-Popper phase Na2La2Ti2RuO10 with a 5% H2/95% N2 atmosphere between 300 and 900 °C leads to the formation of phases of composition Na2La2Ti2RuO10-x (0 < x < 2) via topochemical reduction. Magnetization data collected from Na2La2Ti2RuO10-x samples in the range 0 < x < 1 show a rapid decline in susceptibility with increasing x, consistent with the conversion of S = 1, Ru(4+) centers at x = 0 to S = 0, Ru(2+) centers at x = 1. We believe this is the first report of diamagnetic Ru(2+) centers in an extended oxide phase. Further reduction of Na2La2Ti2RuO9 leads to the reduction of Ti(4+) to Ti(3+); however, Na2La2Ti2RuO10-x samples in the range 1 < x < 2 exhibit only a very weak paramagnetic response. Given the highly insulating nature of the phases, this suggests the electrons added on reduction of titanium are paired within a local Ti-Ti bonding network in a manner analogous to that observed for TinO2n-1 phases.

Understanding carbon dioxide adsorption on univalent cation forms of the flexible zeolite Rho at conditions relevant to carbon capture from flue gases.

A series of univalent cation forms of zeolite Rho (M(9.8)Al(9.8)Si(38.2)O(96), M = H, Li, Na, K, NH(4), Cs) and ultrastabilized zeolite Rho (US-Rho) have been prepared. Their CO(2) adsorption behavior has been measured at 298 K and up to 1 bar and related to the structures of the dehydrated forms determined by Rietveld refinement and, for H-Rho and US-Rho, by solid state NMR. Additionally, CO(2) adsorption properties of the H-form of the silicoalumino-phosphate with the RHO topology and univalent cation forms of the zeolite ZK-5 were measured for comparison. The highest uptakes at 0.1 bar, 298 K for both Rho and ZK-5 were obtained on the Li-forms (Li-Rho, 3.4 mmol g(-1); Li-ZK-5, 4.7 mmol g(-1)). H- and US-Rho had relatively low uptakes under these conditions: extra-framework Al species do not interact strongly with CO(2). Forms of zeolite Rho in which cations occupy window sites between α-cages show hysteresis in their CO(2) isotherms, the magnitude of which (Na(+),NH(4)(+) < K(+) < Cs(+)) correlates with the tendency for cations to occupy double eight-membered ring sites rather than single eight-membered ring sites. Hysteresis is not observed for zeolites where cations do not occupy the intercage windows. In situ synchrotron X-ray diffraction of the CO(2) adsorption on Na-Rho at 298 K identifies the adsorption sites. The framework structure of Na-Rho "breathes" as CO(2) is adsorbed and desorbed and its desorption kinetics from Na-Rho at 308 K have been quantified by the Zero Length Column chromatographic technique. Na-Rho shows much higher CO(2)/C(2)H(6) selectivity than Na-ZK-5, as determined by single component adsorption, indicating that whereas CO(2) can diffuse readily through windows containing Na(+) cations, ethane cannot.

A versatile route to edge-specific modifications to pristine graphene by electrophilic aromatic substitution.

Electrophilic aromatic substitution produces edge-specific modifications to CVD graphene and graphene nanoplatelets that are suitable for specific attachment of biomolecules.

Contrast Extravasation using Power Injectors for Contrast-Enhanced Computed Tomography in Children: Frequency and Injury Severity.

PURPOSE: To evaluate the safety of power injectors for contrast-enhanced computed tomography (CT) in children, namely: the prevalence and injury severity of contrast extravasations related to power injectors and the factors associated with these events. METHODS: The need to obtain informed consent was waived for this HIPAA-compliant and IRB approved retrospective study. Around 2429 contrast-enhanced CT performed with a power injector were identified during a 3-year period. Data collected included patient demographic, power injector, and contrast agent information. The patients' symptoms, severity of injury and treatment with contrast extravasation were recorded. Around 1496 cases (823 boys, 673 girls) were included in the analysis. Independent-sample t test and Chi-square were used. For a sub-analysis using the extravasation cases, nonparametric tests were used. RESULTS: The mean age was 9.5 ± 6.1 years. The most common access site, catheter site, and contrast agent used were the antecubital fossa, 22 gauge and Iohexol. The mean peak pressure was 68.9 ± 62.3 psi and the flow rate was 1.7 ± 0.9 mL/s. Eighteen cases of contrast extravasation were identified with a mean age of 11.2 ± 6.2 years. There were seven mild, six moderate, and five severe. Cases with extravasation had significantly higher peak pressure (p < 0.001) and flow rate (p < 0.001) compared to those without extravasation. Patients who received Iohexol-350 had significantly more contrast extravasation compared to those who used Iohexol-300 (p = 0.03). However, after post-hoc correction, only peak pressure (p < 0.01) and flow rate (p = 0.01) remained significant. CONCLUSION: The use of power injectors in children undergoing contrast-enhanced CT is associated with a low rate of extravasation and of long-term injury.