Iridium Corroles Exhibit Weak Near-Infrared Phosphorescence but Efficiently Sensitize Singlet Oxygen Formation.

Six-coordinate iridium(III) triarylcorrole derivatives, Ir[TpXPC)]L2, where TpXPC = tris(para-X-phenyl)corrole (X = CF3, H, Me, and OCH3) and L = pyridine (py), trimethylamine (tma), isoquinoline (isoq), 4-dimethylaminopyridine (dmap), and 4-picolinic acid (4pa), have been examined, with a view to identifying axial ligands most conducive to near-infrared phosphorescence. Disappointingly, the phosphorescence quantum yield invariably turned out to be very low, about 0.02 - 0.04% at ambient temperature, with about a two-fold increase at 77 K. Phosphorescence decay times were found to be around ~5 µs at 295 K and ~10 µs at 77 K. Fortunately, two of the Ir[TpCF3PC)]L2 derivatives, which were tested for their ability to sensitize singlet oxygen formation, were found to do so efficiently with quantum yields Φ(1O2) = 0.71 and 0.38 for L = py and 4pa, respectively. Iridium corroles thus may hold promise as photosensitizers in photodynamic therapy (PDT). The possibility of varying the axial ligand and of attaching biotargeting groups at the axial positions makes iridium corroles particularly exciting as PDT drug candidates

A thermally stable {FeNO}(8) complex: properties and biological reactivity of reduced MNO systems

Reduced nitrogen oxide ligands such as NO−/HNO or nitroxyl participate in chemistry distinct from nitric oxide (NO). Nitroxyl has been proposed to form at heme centers to generate the Enemark–Feltham designated {FeNO}8 system. The synthesis of a thermally stable {FeNO}8 species namely, [Co(Cp*)2][Fe(LN4)(NO)] (3), housed in a heme-like ligand platform has been achieved by reduction of the corresponding {FeNO}7 complex, [Fe(LN4)(NO)] (1), with decamethylcobaltocene [Co(Cp*)2] in toluene. This complex readily reacts with metMb, resulting in formation of MbNO via reductive nitrosylation by the coordinated HNO/NO−, which can be inhibited with GSH. These results suggest that 3 could serve as a potential HNO therapeutic. Spectroscopic, theoretical, and structural comparisons are made to 1 and the {CoNO}8 complex, [Co(LN4)(NO)] (2), an isoelectronic analogue of 3

Absorbing Phase Transition in a Four State Predator Prey Model in One Dimension

The model of competition between densities of two different species, called predator and prey, is studied on a one dimensional periodic lattice, where each site can be in one of the four states say, empty, or occupied by a single predator, or occupied by a single prey, or by both. Along with the pairwise death of predators and growth of preys, we introduce an interaction where the predators can eat one of the neighboring prey and reproduce a new predator there instantly. The model shows a non-equilibrium phase transition into a unusual absorbing state where predators are absent and the lattice is fully occupied by preys. The critical exponents of the system are found to be different from that of the Directed Percolation universality class and they are robust against addition of explicit diffusion.Comment: 10 pages, 6 figures, to appear in JSTA

Constraining the epoch of reionization with the variance statistic: simulations of the LOFAR case

Several experiments are underway to detect the cosmic redshifted 21-cm signal from neutral hydrogen from the Epoch of Reionization (EoR). Due to their very low signal-to-noise ratio, these observations aim for a statistical detection of the signal by measuring its power spectrum. We investigate the extraction of the variance of the signal as a first step towards detecting and constraining the global history of the EoR. Signal variance is the integral of the signal's power spectrum, and it is expected to be measured with a high significance. We demonstrate this through results from a simulation and parameter estimation pipeline developed for the Low Frequency Array (LOFAR)-EoR experiment. We show that LOFAR should be able to detect the EoR in 600 hours of integration using the variance statistic. Additionally, the redshift ($z_r$) and duration ($\Delta z$) of reionization can be constrained assuming a parametrization. We use an EoR simulation of $z_r = 7.68$ and $\Delta z = 0.43$ to test the pipeline. We are able to detect the simulated signal with a significance of 4 standard deviations and extract the EoR parameters as $z_r = 7.72^{+0.37}_{-0.18}$ and $\Delta z = 0.53^{+0.12}_{-0.23}$ in 600 hours, assuming that systematic errors can be adequately controlled. We further show that the significance of detection and constraints on EoR parameters can be improved by measuring the cross-variance of the signal by cross-correlating consecutive redshift bins.Comment: 13 pages, 14 figures, Accepted for publication in MNRA

Physics Potential of the ICAL detector at the India-based Neutrino Observatory (INO)

The upcoming 50 kt magnetized iron calorimeter (ICAL) detector at the India-based Neutrino Observatory (INO) is designed to study the atmospheric neutrinos and antineutrinos separately over a wide range of energies and path lengths. The primary focus of this experiment is to explore the Earth matter effects by observing the energy and zenith angle dependence of the atmospheric neutrinos in the multi-GeV range. This study will be crucial to address some of the outstanding issues in neutrino oscillation physics, including the fundamental issue of neutrino mass hierarchy. In this document, we present the physics potential of the detector as obtained from realistic detector simulations. We describe the simulation framework, the neutrino interactions in the detector, and the expected response of the detector to particles traversing it. The ICAL detector can determine the energy and direction of the muons to a high precision, and in addition, its sensitivity to multi-GeV hadrons increases its physics reach substantially. Its charge identification capability, and hence its ability to distinguish neutrinos from antineutrinos, makes it an efficient detector for determining the neutrino mass hierarchy. In this report, we outline the analyses carried out for the determination of neutrino mass hierarchy and precision measurements of atmospheric neutrino mixing parameters at ICAL, and give the expected physics reach of the detector with 10 years of runtime. We also explore the potential of ICAL for probing new physics scenarios like CPT violation and the presence of magnetic monopoles.Comment: 139 pages, Physics White Paper of the ICAL (INO) Collaboration, Contents identical with the version published in Pramana - J. Physic

HI 21cm Cosmology and the Bi-spectrum: Closure Diagnostics in Massively Redundant Interferometric Arrays

New massively redundant low frequency arrays allow for a novel investigation of closure relations in interferometry. We employ commissioning data from the Hydrogen Epoch of Reionization Array to investigate closure quantities in this densely packed grid array of 14m antennas operating at 100 MHz to 200 MHz. We investigate techniques that utilize closure phase spectra for redundant triads to estimate departures from redundancy for redundant baseline visibilities. We find a median absolute deviation from redundancy in closure phase across the observed frequency range of about 4.5deg. This value translates into a non-redundancy per visibility phase of about 2.6deg, using prototype electronics. The median absolute deviations from redundancy decrease with longer baselines. We show that closure phase spectra can be used to identify ill-behaved antennas in the array, independent of calibration. We investigate the temporal behavior of closure spectra. The Allan variance increases after a one minute stride time, due to passage of the sky through the primary beam of the transit telescope. However, the closure spectra repeat to well within the noise per measurement at corresponding local sidereal times (LST) from day to day. In future papers in this series we will develop the technique of using closure phase spectra in the search for the HI 21cm signal from cosmic reionization.Comment: 32 pages. 11 figures. Accepted to Radio Scienc

Molecular structure of a free-base β-Octaiodo -meso-tetraarylporphyrin. A rational route to cis porphyrin tautomers?

Although a cis tautomer has long been invoked as an intermediate in porphyrin tautomerism, the first such species was only recently isolated and structurally characterized in the form of a β-heptakis(trifluoromethyl)-meso-tetraarylporphyrin. Reported herein is the molecular structure of a β-octaiodo-meso-tetraarylporphyrin solvate, which also exhibits a cis tautomeric structure. Both structures implicate two factors as critical to the stabilization of the cis tautomeric form - a free-base porphyrin that is naturally strongly saddled on steric grounds and a hydroxylic or amphiprotic solvent that can provide hydrogen-bonded N-H···X-H···N (X = O in both the above examples) straps connecting the central NH groups with the antipodal unprotonated nitrogens. The results raise the prospect that a rational strategy affording cis porphyrin tautomers in a predictable manner may be within reach.</p

Synthesis and Molecular Structure of a Copper Octaiodocorrole.

Although rather delicate on account of their propensity to undergo deiodination, β-octaiodoporphyrinoids are of considerable interest as potential precursors to novel β-octasubstituted macrocycles. Presented herein are early results of our efforts to synthesize β-octaiodocorrole derivatives. Oxidative condensation of 3,4-diiodopyrrole and aromatic aldehydes failed to yield free-base octaiodocorroles. Treatment of copper meso-tris(p-cyanophenyl)corrole with N-iodosuccinimide and trifluoroacetic acid over several hours, however, yielded the desired β-octaiodinated product in ∼22% yield. Single-crystal X-ray structure determination of the product revealed a strongly saddled corrole macrocycle with metrical parameters very close to those of analogous Cu octabromocorrole complexes. The compound was also found to exhibit an exceptionally red-shifted Soret maximum (464 nm in dichloromethane), underscoring the remarkable electronic effect of β-octaiodo substitution

Simple, Axial Ligand-Mediated Route to Water-Soluble Iridium Corroles

The synthesis and purification of water-soluble porphyrin-type compounds for photodynamic therapy and other medical applications is often a tedious exercise. Here, we have investigated the simple stratagem of adding a water-soluble axial ligand to the standard protocol for iridium insertion into simple meso-triarylcorroles. Early results showed that six-coordinate Ir[TpXPC](dna)2 derivatives, in which TpXPC = tris(para-X-phenyl)corrole (X = CF3, CN, H, and OMe) and dna = dinicotinic acid, are highly water-soluble. In the end, however, all axially nitrogen-ligated complexes proved unstable with respect to chromatographic purification and storage. Five-coordinate water-soluble phosphine adducts, fortunately, proved a great improvement. From the point of view of ease of purification and storage, the best products proved to be Ir[TpXPC](L), where X = CF3 and OMe and L = tris(2-carboxyethyl)phosphine (tcep) and trisodium tris(3-sulfonatophenyl)phosphine (tppts); carefully optimized synthetic protocols are presented for these four compounds