Synthesis, Crystal Structure and Photophysical Properties of Lanthanide Coordination Polymers of 4- 4-(9H-Carbazol-9-Yl)Butoxy Benzoate: The Effect of Bidentate Nitrogen Donors on Luminescence

A new aromatic carboxylate ligand, 4-[4-(9H-carbazol-9-yl)butoxy]benzoic acid (HL), has been synthesized by the replacement of the hydroxyl hydrogen of 4-hydroxy benzoic acid with a 9-butyl-9H-carbazole moiety. The anion derived from HL has been used for the support of a series of lanthanide coordination compounds [Ln = Eu (1), Gd (2) and Tb (3)]. The new lanthanide complexes have been characterized by a variety of spectroscopic techniques. Complex 3 was structurally authenticated by single-crystal X-ray diffraction and found to exist as a solvent-free 1D coordination polymer with the formula [Tb(L)(3)](n). The structural data reveal that the terbium atoms in compound 3 reside in an octahedral ligand environment that is somewhat unusual for a lanthanide. It is interesting to note that each carboxylate group exhibits only a bridging-bidentate mode, with a complete lack of more complex connectivities that are commonly observed for extended lanthanide-containing solid-state structures. Examination of the packing diagram for 3 revealed the existence of two-dimensional molecular arrays held together by means of CH-pi interactions. Aromatic carboxylates of the lanthanides are known to exhibit highly efficient luminescence, thus offering the promise of applicability as optical devices. However, due to difficulties that arise on account of their polymeric nature, their practical application is somewhat limited. Accordingly, synthetic routes to discrete molecular species are highly desirable. For this purpose, a series of ternary lanthanide complexes was designed, synthesized and characterized, namely [Eu(L)(3)(phen)] (4), [Eu(L)(3)(tmphen)] (5), [Tb(L)(3)(phen)] (6) and [Tb(L)(3)(tmphen)] (7) (phen = 1,10-phenanthroline and tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline). The photophysical properties of the foregoing complexes in the solid state at room temperature have been investigated. The quantum yields of the ternary complexes 4 (9.65%), 5 (21.00%), 6 (14.07%) and 7 (32.42%), were found to be significantly enhanced in the presence of bidentate nitrogen donors when compared with those of the corresponding binary compounds 1 (0.11%) and 3 (1.45%). Presumably this is due to effective energy transfer from the ancillary ligands.Council of Scientific and Industrial Research (CSIR-TAPSUN Project) SSL, NWP-55CSIR, New DelhiRobert A. Welch Foundation F-0003Chemistr

Group 13 Decamethylmetallocenium Cations

Salts containing the decamethylmetallocenium cations, [( C5Me5) M-2](+) ( or Cp*M-2(+)) of the group 13 "metals" B, Al and Ga have been prepared using a variety of synthetic routes. Precursor molecules of the type Cp*2MX ( X = Cl, Br, Me) exhibit structural features that vary significantly depending on the size and electronegativity of the central atom. While salt metathesis, halide abstraction and methanide abstraction methods represent viable routes for the preparation of salts of Cp*B-2(+) and Cp*Al-2(+), acidolysis of a Cp* group from Cp*Ga-3 is the most reliable method for the synthesis of the analogous gallium cation. Gallocenium cations are less stable than either of the lighter congeneric cations since they prove to be susceptible to decomposition reactions involving the "back-transfer" of ligands from the counter anion. Density functional theory (DFT) calculations revealed that, whereas Cp*Ga-2(+) is predicted to adopt a molecular structure more similar to that of Cp*B-2(+), the electronic structure of the gallium cation bears a greater resemblance to that of Cp*Al-2(+).Chemistr

PT-Symmetric Talbot Effects

We show that complex PT-symmetric photonic lattices can lead to a new class of self-imaging Talbot effects. For this to occur, we find that the input field pattern, has to respect specific periodicities which are dictated by the symmetries of the system. While at the spontaneous PT-symmetry breaking point, the image revivals occur at Talbot lengths governed by the characteristics of the passive lattice, at the exact phase it depends on the gain and loss parameter thus allowing one to control the imaging process.Comment: 5 pages, 3 figure

Cerebral venous thrombosis: a practical guide

All neurologists need to be able to recognise and treat cerebral venous thrombosis (CVT). It is difficult to diagnose, partly due to its relative rarity, its multiple and various clinical manifestations (different from ‘conventional’ stroke, and often mimicking other acute neurological conditions), and because it is often challenging to obtain and interpret optimal and timely brain imaging. Although CVT can result in death or permanent disability, it generally has a favourable prognosis if diagnosed and treated early. Neurologists involved in stroke care therefore also need to be aware of the treatments for CVT (with varying degrees of supporting evidence): the mainstay is prompt anticoagulation but patients who deteriorate despite treatment can be considered for endovascular procedures (endovascular thrombolysis or thrombectomy) or neurosurgery (decompressive craniotomy). This review summarises current knowledge on the risk factors, diagnosis, treatment and prognosis of CVT in adults, and highlights some areas for future research

Origin of electron cyclotron maser-induced radio emissions at ultra-cool dwarfs: magnetosphere-ionosphere coupling currents

A number of ultra-cool dwarfs emit circularly polarised radio waves generated by the electron cyclotron maser instability. In the solar system such radio is emitted from regions of strong auroral magnetic field-aligned currents. We thus apply ideas developed for Jupiter's magnetosphere, being a well-studied rotationally-dominated analogue in our solar system, to the case of fast-rotating UCDs. We explain the properties of the radio emission from UCDs by showing that it would arise from the electric currents resulting from an angular velocity shear in the fast-rotating magnetic field and plasma, i.e. by an extremely powerful analogue of the process which causes Jupiter's auroras. Such a velocity gradient indicates that these bodies interact significantly with their space environment, resulting in intense auroral emissions. These results strongly suggest that auroras occur on bodies outside our solar system.Comment: Accepted for publication in the Astrophysical Journa

Hubble Space Telescope observations of the NUV transit of WASP-12b

We present new observations of four closely-spaced NUV transits of the hot Jupiter-like exoplanet WASP-12b using HST/COS, significantly increasing the phase resolution of the observed NUV light curve relative to previous observations, while minimising the temporal variation of the system. We observe significant excess NUV absorption during the transit, with mean normalised in-transit fluxes of $F_\mathrm{norm}\simeq0.97$, i.e. $\simeq$2-5 $\sigma$ deeper than the optical transit level of $\simeq0.986$ for a uniform stellar disk (the exact confidence level depending on the normalisation method used). We further observe an asymmetric transit shape, such that the post-conjunction fluxes are overall $\simeq$2-3 $\sigma$ higher than pre-conjunction values, and characterised by rapid variations in count rate between the pre-conjunction and out of transit levels. We do not find evidence for an early ingress to the NUV transit as suggested by earlier HST observations. However, we show that the NUV count rate observed prior to the optical transit is highly variable, but overall $\simeq$2.2-3.0 $\sigma$ below the post-transit values and comparable in depth to the optical transit, possibly forming a variable region of NUV absorption from at least phase $\phi\simeq$0.83, limited by the data coverage.Comment: Accepted into the Astrophysical Journa

Thermodynamic Properties of Generalized Exclusion Statistics

We analytically calculate some thermodynamic quantities of an ideal $g$-on gas obeying generalized exclusion statistics. We show that the specific heat of a $g$-on gas ($g \neq 0$) vanishes linearly in any dimension as $T \to 0$ when the particle number is conserved and exhibits an interesting dual symmetry that relates the particle-statistics at $g$ to the hole-statistics at $1/g$ at low temperatures. We derive the complete solution for the cluster coefficients $b_l(g)$ as a function of Haldane's statistical interaction $g$ in $D$ dimensions. We also find that the cluster coefficients $b_l(g)$ and the virial coefficients $a_l(g)$ are exactly mirror symmetric ($l$=odd) or antisymmetric ($l$=even) about $g=1/2$. In two dimensions, we completely determine the closed forms about the cluster and the virial coefficients of the generalized exclusion statistics, which exactly agree with the virial coefficients of an anyon gas of linear energies. We show that the $g$-on gas with zero chemical potential shows thermodynamic properties similar to the photon statistics. We discuss some physical implications of our results.Comment: 24 pages, Revtex, Corrected typo

Inhomogeneous ground state and the coexistence of two length scales near phase transitions in real solids

Real crystals almost unavoidably contain a finite density of dislocations. We show that this generic type of long--range correlated disorder leads to a breakdown of the conventional scenario of critical behavior and standard renormalization group techniques based on the existence of a simple, homogeneous ground state. This breakdown is due to the appearance of an inhomogeneous ground state that changes the character of the phase transition to that of a percolative phenomenon. This scenario leads to a natural explanation for the appearance of two length scales in recent high resolution small-angle scattering experiments near magnetic and structural phase transitions.Comment: 4 pages, RevTex, no figures; also available from http://www.tp3.ruhr-uni-bochum.de/archive/tpiii_archive.htm

Effects of formulation on microbicide potency and mitigation of the development of bacterial insusceptibility

Risk assessments of the potential for microbicides to select for reduced bacterial susceptibility have been based largely on data generated through the exposure of bacteria to microbicides in aqueous solution. Since microbicides are normally formulated with multiple excipients, we have investigated the effect of formulation on antimicrobial activity and the induction of bacterial insusceptibility. We tested 8 species of bacteria (7 genera) before and after repeated exposure (14 passages), using a previously validated gradient plating system, for their susceptibilities to the microbicides benzalkonium chloride, benzisothiozolinone, chlorhexidine, didecyldimethyl ammonium chloride, DMDM-hydantoin, polyhexamethylene biguanide, thymol, and triclosan in aqueous solution (nonformulated) and in formulation with excipients often deployed in consumer products. Susceptibilities were also assessed following an additional 14 passages without microbicide to determine the stability of any susceptibility changes. MICs and minimum bactericidal concentrations (MBC) were on average 11-fold lower for formulated microbicides than for nonformulated microbicides. After exposure to the antimicrobial compounds, of 72 combinations of microbicide and bacterium there were 19 ≥4-fold (mean, 8-fold) increases in MIC for nonformulated and 8 ≥4-fold (mean, 2-fold) increases in MIC for formulated microbicides. Furthermore, there were 20 ≥4-fold increases in MBC (mean, 8-fold) for nonformulated and 10 ≥4-fold (mean, 2-fold) increases in MBC for formulated microbicides. Susceptibility decreases fully or partially reverted back to preexposure values for 49% of MICs and 72% of MBCs after further passage. In summary, formulated microbicides exhibited greater antibacterial potency than unformulated actives and susceptibility decreases after repeated exposure were lower in frequency and extent

Variable effects of exposure to formulated microbicides on antibiotic susceptibility in firmicutes and proteobacteria

Microbicides are broad-spectrum antimicrobial agents that generally interact with multiple pharmacological targets. While they are widely deployed in disinfectant, antiseptic, and preservative formulations, data relating to their potential to select for microbicide or antibiotic resistance have been generated mainly by testing the compounds in much simpler aqueous solutions. In the current investigation, antibiotic susceptibility was determined for bacteria that had previously exhibited decreased microbicide susceptibility following repeated exposure to microbicides either in formulation with sequestrants and surfactants or in simple aqueous solution. Statistically significant increases in antibiotic susceptibility occurred for 12% of bacteria after exposure to microbicides in formulation and 20% of bacteria after exposure to microbicides in aqueous solutions, while 22% became significantly less susceptible to the antibiotics, regardless of formulation. Of the combinations of a bacterium and an antibiotic for which British Society for Antimicrobial Chemotherapy breakpoints are available, none became resistant. Linear modeling taking into account phylogeny, microbicide, antibiotic, and formulation identified small but significant effects of formulation that varied depending on the bacterium and microbicide. Adaptation to formulated benzalkonium chloride in particular was more likely to increase antibiotic susceptibility than adaptation to the simple aqueous solution. In conclusion, bacterial adaptation through repeated microbicide exposure was associated with both increases and decreases in antibiotic susceptibility. Formulation of the microbicide to which the bacteria had previously adapted had an identifiable effect on antibiotic susceptibility, but it effect was typically small relative to the differences observed among microbicides. Susceptibility changes resulting in resistance were not observed. IMPORTANCE The safety of certain microbicide applications has been questioned due to the possibility that microbicide exposure could select for microbicide and antibiotic resistance. Evidence that this may happen is based mainly on in vitro experiments where bacteria have been exposed to microbicides in aqueous solution. Microbicides are, however, normally deployed in products formulated with surfactants, sequestrants, and other compounds. While this may influence the frequency and extent of susceptibility changes, few studies reported in the literature have assessed this. In the current investigation, therefore, we have investigated changes in antibiotic susceptibility in bacteria which exhibited decreased microbicide susceptibility following repeated exposure to microbicides in simple aqueous solutions and in formulation. We report that the microbicide formulation had an identifiable effect on antibiotic susceptibility, but it was typically small relative to the differences observed among microbicides. We did not observe susceptibility changes resulting in resistance