Search

We present optical and near-infrared (NIR, Y-, J-, H-band) observations of 42 Type Ia supernovae (SNe Ia) discovered by the untargeted intermediate Palomar Transient Factory survey. This new data set covers a broad range of redshifts and host galaxy stellar masses, compared to previous SN Ia efforts in the NIR. We construct a sample, using also literature data at optical and NIR wavelengths, to examine claimed correlations between the host stellar masses and the Hubble diagram residuals. The SN magnitudes are corrected for host galaxy extinction using either a global total-to-selective extinction ratio, R V = 2.0, for all SNe, or a best-fit R V for each SN individually. Unlike previous studies that were based on a narrower range in host stellar mass, we do not find evidence for a “mass step,” between the color- and stretch-corrected peak J and H magnitudes for galaxies below and above . However, the mass step remains significant (3σ) at optical wavelengths (g, r, i) when using a global R V , but vanishes when each SN is corrected using their individual best-fit R V . Our study confirms the benefits of the NIR SN Ia distance estimates, as these are largely exempted from the empirical corrections dominating the systematic uncertainties in the optical.

In this contribution, we achieve the primary goal of the active galactic nucleus (AGN) STORM campaign by recovering velocity-delay maps for the prominent broad emission lines (Lyα, C iv, He ii, and Hβ) in the spectrum of NGC 5548. These are the most detailed velocity-delay maps ever obtained for an AGN, providing unprecedented information on the geometry, ionization structure, and kinematics of the broad-line region. Virial envelopes enclosing the emission-line responses show that the reverberating gas is bound to the black hole. A stratified ionization structure is evident. The He ii response inside 5-10 lt-day has a broad single-peaked velocity profile. The Lyα, C iv, and Hβ responses extend from inside 2 to outside 20 lt-day, with double peaks at ±2500 km s-1 in the 10-20 lt-day delay range. An incomplete ellipse in the velocity-delay plane is evident in Hβ. We interpret the maps in terms of a Keplerian disk with a well-defined outer rim at R = 20 lt-day. The far-side response is weaker than that from the near side. The line-center delay days gives the inclination i ≈ 45°. The inferred black hole mass is M BH ≈ 7 × 107 M o˙. In addition to reverberations, the fit residuals confirm that emission-line fluxes are depressed during the "BLR Holiday"identified in previous work. Moreover, a helical "Barber-Pole"pattern, with stripes moving from red to blue across the C iv and Lyα line profiles, suggests azimuthal structure rotating with a 2 yr period that may represent precession or orbital motion of inner-disk structures casting shadows on the emission-line region farther out.

We present geometric and dynamical modeling of the broad line region (BLR) for the multi-wavelength reverberation mapping campaign focused on NGC 5548 in 2014. The data set includes photometric and spectroscopic monitoring in the optical and ultraviolet, covering the Hβ, C iv, and Ly broad emission lines. We find an extended disk-like Hβ BLR with a mixture of near-circular and outflowing gas trajectories, while the C iv and Ly BLRs are much less extended and resemble shell-like structures. There is clear radial structure in the BLR, with C iv and Ly emission arising at smaller radii than the Hβ emission. Using the three lines, we make three independent black hole mass measurements, all of which are consistent. Combining these results gives a joint inference of . We examine the effect of using the V band instead of the UV continuum light curve on the results and find a size difference that is consistent with the measured UV-optical time lag, but the other structural and kinematic parameters remain unchanged, suggesting that the V band is a suitable proxy for the ionizing continuum when exploring the BLR structure and kinematics. Finally, we compare the Hβ results to similar models of data obtained in 2008 when the active galactic nucleus was at a lower luminosity state. We find that the size of the emitting region increased during this time period, but the geometry and black hole mass remained unchanged, which confirms that the BLR kinematics suitably gauge the gravitational field of the central black hole.

The nature and role of the binary companion of carbon-oxygen white dwarf stars that explode as Type Ia supernovae (SNe Ia) are not yet fully understood. Past detections of circumstellar material (CSM) that contain hydrogen for a small number of SN Ia progenitor systems suggest that at least some have a nondegenerate companion. In order to constrain the prevalence, location, and quantity of CSM in SN Ia systems, we performed a near-ultraviolet (NUV) survey with the Hubble Space Telescope (HST) to look for the high-energy signature of SN Ia ejecta interacting with the CSM. Our survey revealed that SN 2015cp, an SN 1991T-like overluminous SN Ia, was experiencing late-onset interaction between its ejecta and the surrounding CSM 664 days after its light-curve peak. We present ground- and space-based follow-up observations of SN 2015cp that reveal optical emission lines of H and Ca, typical signatures of ejecta-CSM interaction. We show how SN 2015cp was likely similar to the well-studied SN Ia-CSM event PTF11kx, making it the second case in which an unambiguously classified SN Ia was observed to interact with a distant shell of CSM that contains hydrogen (R CSM 10 16 cm). The remainder of our HST NUV images of SNe Ia were nondetections that we use to constrain the occurrence rate of observable late-onset CSM interaction. We apply theoretical models for the emission from ejecta-CSM interaction to our NUV nondetections and place upper limits on the mass and radial extent of CSM in SN Ia progenitor systems.

We present an exquisite 30 minute cadence Kepler (K2) light curve of the Type Ia supernova (SN Ia) 2018oh (ASASSN-18bt), starting weeks before explosion, covering the moment of explosion and the subsequent rise, and continuing past peak brightness. These data are supplemented by multi-color Panoramic Survey Telescope (Pan-STARRS1) and Rapid Response System 1 and Cerro Tololo Inter-American Observatory 4 m Dark Energy Camera (CTIO 4-m DECam) observations obtained within hours of explosion. The K2 light curve has an unusual two-component shape, where the flux rises with a steep linear gradient for the first few days, followed by a quadratic rise as seen for typical supernovae (SNe) Ia. This "flux excess" relative to canonical SN Ia behavior is confirmed in our i-band light curve, and furthermore, SN 2018oh is especially blue during the early epochs. The flux excess peaks 2.14 ± 0.04 days after explosion, has a FWHM of 3.12 ± 0.04 days, a blackbody temperature of K, a peak luminosity of , and a total integrated energy of . We compare SN 2018oh to several models that may provide additional heating at early times, including collision with a companion and a shallow concentration of radioactive nickel. While all of these models generally reproduce the early K2 light curve shape, we slightly favor a companion interaction, at a distance of ∼ based on our early color measurements, although the exact distance depends on the uncertain viewing angle. Additional confirmation of a companion interaction in future modeling and observations of SN 2018oh would provide strong support for a single-degenerate progenitor system.

We performed a wide-area (2000 deg2) g and I band experiment as part of a two month extension to the Intermediate Palomar Transient Factory. We discovered 36 extragalactic transients including iPTF17lf, a highly reddened local SN Ia, iPTF17bkj, a new member of the rare class of transitional Ibn/IIn supernovae, and iPTF17be, a candidate luminous blue variable outburst. We do not detect any luminous red novae and place an upper limit on their rate. We show that adding a slow-cadence I band component to upcoming surveys such as the Zwicky Transient Facility will improve the photometric selection of cool and dusty transients.

Early observations of Type Ia supernovae (SNe Ia) provide a unique probe oftheir progenitor systems and explosion physics. Here we report the intermediatePalomar Transient Factory (iPTF) discovery of an extraordinarily young SN Ia,iPTF 16abc. By fitting a power law to our early light curve, we infer thatfirst light for the SN, that is when the SN could have first been detected byour survey, occurred only $0.15\pm_{0.07}^{0.15}$ days before our firstdetection. In the $\sim$24 hr after discovery, iPTF 16abc rose by $\sim$2 mag,featuring a near-linear rise in flux for $\gtrsim$3 days. Early spectra showstrong C II absorption, which disappears after $\sim$7 days. Unlike theextensivelyobserved SN Ia SN 2011fe, the $(B-V)_0$ colors of iPTF 16abc areblue and nearly constant in the days after explosion. We show that our earlyobservations of iPTF 16abc cannot be explained by either SN shock breakout andthe associated, subsequent cooling or the SN ejecta colliding with a stellarcompanion. Instead, we argue that the early characteristics of iPTF 16abc,including (i) the rapid, near-linear rise, (ii) the nonevolving blue colors,and (iii) the strong C II absorption, are the result of either ejectainteraction with nearby, unbound material or vigorous mixing of radioactive$^{56}$Ni in the SN ejecta, or a combination of the two. In the next few years,dozens of very young \textit{normal} SNe Ia will be discovered, andobservations similar to those presented here will constrain the white dwarfexplosion mechanism.

Merging neutron stars offer an excellent laboratory for simultaneously studying strong-field gravity and matter in extreme environments. We establish the physical association of an electromagnetic counterpart (EM170817) with gravitational waves (GW170817) detected from merging neutron stars. By synthesizing a panchromatic data set, we demonstrate that merging neutron stars are a long-sought production site forging heavy elements by r-process nucleosynthesis. The weak gamma rays seen in EM170817 are dissimilar to classical short gamma-ray bursts with ultrarelativistic jets. Instead, we suggest that breakout of a wide-angle, mildly relativistic cocoon engulfing the jet explains the low-luminosity gamma rays, the high-luminosity ultraviolet-optical-infrared, and the delayed radio and x-ray emission. We posit that all neutron star mergers may lead to a wide-angle cocoon breakout, sometimes accompanied by a successful jet and sometimes by a choked jet.

A long-standing paradigm in astrophysics is that collisions-or mergers-of two neutron stars form highly relativistic and collimated outflows (jets) that power γ-ray bursts of short (less than two seconds) duration. The observational support for this model, however, is only indirect. A hitherto outstanding prediction is that gravitational-wave events from such mergers should be associated with γ-ray bursts, and that a majority of these bursts should be seen off-axis, that is, they should point away from Earth. Here we report the discovery observations of the X-ray counterpart associated with the gravitational-wave event GW170817. Although the electromagnetic counterpart at optical and infrared frequencies is dominated by the radioactive glow (known as a kilonova') from freshly synthesized rapid neutron capture (r-process) material in the merger ejecta, observations at X-ray and, later, radio frequencies are consistent with a short γ-ray burst viewed off-axis. Our detection of X-ray emission at a location coincident with the kilonova transient provides the missing observational link between short γ-ray bursts and gravitational waves from neutron-star mergers, and gives independent confirmation of the collimated nature of the γ-ray-burst emission.

During the Space Telescope and Optical Reverberation Mapping Project observations of NGC 5548, the continuum and emission-line variability became decorrelated during the second half of the six-month-long observing campaign. Here we present Swift and Chandra X-ray spectra of NGC 5548 obtained as part of the campaign. The Swift spectra show that excess flux (relative to a power-law continuum) in the soft X-ray band appears before the start of the anomalous emission-line behavior, peaks during the period of the anomaly, and then declines. This is a model-independent result suggesting that the soft excess is related to the anomaly. We divide the Swift data into on- and off-anomaly spectra to characterize the soft excess via spectral fitting. The cause of the spectral differences is likely due to a change in the intrinsic spectrum rather than to variable obscuration or partial covering. The Chandra spectra have lower signal-to-noise ratios, but are consistent with the Swift data. Our preferred model of the soft excess is emission from an optically thick, warm Comptonizing corona, the effective optical depth of which increases during the anomaly. This model simultaneously explains all three observations: the UV emission-line flux decrease, the soft-excess increase, and the emission-line anomaly.

The optical transient PTF11kx exhibited both the characteristic spectral features of Type Ia supernovae (SNe Ia) and the signature of ejecta interacting with circumstellar material (CSM) containing hydrogen, indicating the presence of a nondegenerate companion. We present an optical spectrum at 1342 days after peak from Keck Observatory, in which the broad component of Hα emission persists with a similar profile as in early-time observations. We also present Spitzer IRAC detections obtained 1237 and 1818 days after peak, and an upper limit from Hubble Space Telescope ultraviolet imaging at 2133 days. We interpret our late-time observations in the context of published results - and reinterpret the early-time observations - in order to constrain the CSM's physical parameters and to compare to theoretical predictions for recurrent-nova systems. We find that the CSM's radial extent may be several times the distance between the star and the CSM's inner edge, and that the CSM column density may be two orders of magnitude lower than previous estimates. We show that the Hα luminosity decline is similar to other SNe with CSM interaction and demonstrate how our infrared photometry is evidence for newly formed, collisionally heated dust. We create a model for PTF11kx's late-time CSM interaction and find that X-ray reprocessing by photoionization and recombination cannot reproduce the observed Hα luminosity, suggesting that the X-rays are thermalized and that Hα radiates from collisional excitation. Finally, we discuss the implications of our results regarding the progenitor scenario and the geometric properties of the CSM for the PTF11kx system.

With the advent of new wide-field, high-cadence optical transient surveys, our understanding of the diversity of core-collapse supernovae has grown tremendously in the last decade. However, the pre-supernova evolution of massive stars, which sets the physical backdrop to these violent events, is theoretically not well understood and difficult to probe observationally. Here we report the discovery of the supernova iPTF 13dqy= SN 2013fsa mere 1/43 h after explosion. Our rapid follow-up observations, which include multiwavelength photometry and extremely early (beginning at 1/46 h post-explosion) spectra, map the distribution of material in the immediate environment ( ‰210 15 cm) of the exploding star and establish that it was surrounded by circumstellar material (CSM) that was ejected during the final 1/41 yr prior to explosion at a high rate, around 10 '3 solar masses per year. The complete disappearance of flash-ionized emission lines within the first several days requires that the dense CSM be confined to within ‰210 15 cm, consistent with radio non-detections at 70-100 days. The observations indicate that iPTF 13dqy was a regular type II supernova; thus, the finding that the probable red supergiant progenitor of this common explosion ejected material at a highly elevated rate just prior to its demise suggests that pre-supernova instabilities may be common among exploding massive stars.

We present the results of an optical spectroscopic monitoring program targeting NGC 5548 as part of a larger multiwavelength reverberation mapping campaign. The campaign spanned 6 months and achieved an almost daily cadence with observations from five ground-based telescopes. The Hβ and He ii λ4686 broad emission-line light curves lag that of the 5100 +-optical continuum by 4.17+0.36-0.36 and 0.79+0.35-0.34 days, respectively. The Hβ lag relative to the 1158 ultraviolet continuum light curve measured by the Hubble Space Telescope is ∼50% longer than that measured against the optical continuum, and the lag difference is consistent with the observed lag between the optical and ultraviolet continua. This suggests that the characteristic radius of the broad-line region is ∼50% larger than the value inferred from optical data alone. We also measured velocity-resolved emission-line lags for Hβ and found a complex velocity-lag structure with shorter lags in the line wings, indicative of a broad-line region dominated by Keplerian motion. The responses of both the Hβ and He ii emission lines to the driving continuum changed significantly halfway through the campaign, a phenomenon also observed for C iv, Lyα, He ii(+O iii]), and Si iv(+O iv]) during the same monitoring period. Finally, given the optical luminosity of NGC 5548 during our campaign, the measured Hβ lag is a factor of five shorter than the expected value implied by the R BLR-L AGN relation based on the past behavior of NGC 5548.

In this paper, we report observations of a peculiar SN Ia iPTF13asv (a.k.A., SN2013cv) from the onset of the explosion to months after its peak. The early-phase spectra of iPTF13asv show an absence of iron absorption, indicating that synthesized iron elements are confined to low-velocity regions of the ejecta, which, in turn, implies a stratified ejecta structure along the line of sight. Our analysis of iPTF13asv's light curves and spectra shows that it is an intermediate case between normal and super-Chandrasekhar events. On the one hand, its light curve shape (B-band ) and overall spectral features resemble those of normal SNe Ia. On the other hand, its large peak optical and UV luminosity (, ) and its low but almost constant Si ii velocities of about 10,000 km s-1 are similar to those in super-Chandrasekhar events, and its persistent carbon signatures in the spectra are weaker than those seen commonly in super-Chandrasekhar events. We estimate a 56Ni mass of and a total ejecta mass of . The large ejecta mass of iPTF13asv and its stratified ejecta structure together seemingly favor a double-degenerate origin.

KA1858+4850 is a narrow-line Seyfert 1 galaxy at redshift 0.078 and is among the brightest active galaxies monitored by the Kepler mission. We have carried out a reverberation mapping campaign designed to measure the broad-line region size and estimate the mass of the black hole in this galaxy. We obtained 74 epochs of spectroscopic data using the Kast Spectrograph at the Lick 3 m telescope from 2012 February to November, and obtained complementary V-band images from five other ground-based telescopes. We measured the Hβ light curve lag with respect to the V-band continuum light curve using both cross-correlation techniques (CCF) and continuum light curve variability modeling with the JAVELIN method and found rest-frame lags of days and τJAVELINdays. The Hβ rms line profile has a width of σline = 770 ± 49 km s-1. Combining these two results and assuming a virial scale factor of f = 5.13, we obtained a virial estimate of for the mass of the central black hole and an Eddington ratio of L/L Edd 0.2. We also obtained consistent but slightly shorter emission-line lags with respect to the Kepler light curve. Thanks to the Kepler mission, the light curve of KA1858+4850 has among the highest cadences and signal-to-noise ratios ever measured for an active galactic nucleus; thus, our black hole mass measurement will serve as a reference point for relations between black hole mass and continuum variability characteristics in active galactic nuclei.

The Type Ia supernova (SN Ia) SN 2000cx was one of the most peculiar transients ever discovered, with a rise to maximum brightness typical of a SN Ia, but a slower decline and a higher photospheric temperature. 13 yr later SN 2013bh (also known as iPTF13abc), a near identical twin, was discovered and we obtained optical and near-infrared photometry and low-resolution optical spectroscopy from discovery until about 1 month past r-band maximum brightness. The spectra of both objects show iron-group elements [Co II, Ni II, FeII, Fe III and high-velocity features (HVFs) of Ti II], intermediate-mass elements (Si II, Si III and S II) and separate normal velocity features (~12 000 km s-1) and HVFs (~24 000 km s-1) of Ca II. Persistent absorption from Fe III and Si III, along with the colour evolution, implies high blackbody temperatures for SNe 2013bh and 2000cx (~12 000 K). Both objects lack narrow Na I D absorption and exploded in the outskirts of their hosts, indicating that the SN environments were relatively free of interstellar or circumstellar material and may imply that the progenitors came from a relatively old and low-metallicity stellar population. Models of SN 2000cx, seemingly applicable to SN 2013bh, imply the production of up to 1 M of 56Ni and (4.3-5.5) × 10-3 M⊙ of fast-moving Ca ejecta. © 2013 The Authors Published by Oxford University Press on behalf of the Royal Astronomical Society.

The Type Ia supernova (SN Ia) 2013dy in NGC 7250 (d ≈ 13.7 Mpc) was discovered by the Lick Observatory Supernova Search. Combined with a prediscovery detection by the Italian Supernova Search Project, we are able to constrain the first-light time of SN 2013dy to be only 0.10 ± 0.05 days (2.4 ± 1.2 hr) before the first detection. This makes SN 2013dy the earliest known detection of an SN Ia. We infer an upper limit on the radius of the progenitor star of R 0 ≲ 0.25 R ⊙, consistent with that of a white dwarf. The light curve exhibits a broken power law with exponents of 0.88 and then 1.80. A spectrum taken 1.63 days after first light reveals a C II absorption line comparable in strength to Si II. This is the strongest C II feature ever detected in a normal SN Ia, suggesting that the progenitor star had significant unburned material. The C II line in SN 2013dy weakens rapidly and is undetected in a spectrum 7 days later, indicating that C II is detectable for only a very short time in some SNe Ia. SN 2013dy reached a B-band maximum of MB = -18.72 ± 0.03 mag ∼17.7 days after first light. © 2013. The American Astronomical Society. All rights reserved.

The nearby Supernova 1987A was accompanied by a burst of neutrino emission, which indicates that a compact object (a neutron star or black hole) was formed in the explosion. There has been no direct observation of this compact object. In this work, we observe the supernova remnant with JWST spectroscopy, finding narrow infrared emission lines of argon and sulfur. The line emission is spatially unresolved and blueshifted in velocity relative to the supernova rest frame. We interpret the lines as gas illuminated by a source of ionizing photons located close to the center of the expanding ejecta. Photoionization models show that the line ratios are consistent with ionization by a cooling neutron star or a pulsar wind nebula. The velocity shift could be evidence for a neutron star natal kick.

X-ray emission is one of the signposts of circumstellar interaction in supernovae (SNe), but until now, it has been observed only in core-collapse SNe. The level of thermal X-ray emission is a direct measure of the density of the circumstellar medium (CSM), and the absence of X-ray emission from Type Ia SNe has been interpreted as a sign of a very low density CSM. In this paper, we report late-time (500-800 d after discovery) X-ray detections of SN 2012ca in Chandra data. The presence of hydrogen in the initial spectrum led to a classification of Type Ia-CSM, ostensibly making it the first SN Ia detected with X-rays. Our analysis of the X-ray data favours an asymmetric medium, with a high-density component which supplies the X-ray emission. The data suggest a number density >10 8 cm -3 in the higher density medium, which is consistent with the large observed Balmer decrement if it arises from collisional excitation. This is high compared to most core-collapse SNe, but it may be consistent with densities suggested for some Type IIn or superluminous SNe. If SN 2012ca is a thermonuclear SN, the large CSM density could imply clumps in the wind, or a dense torus or disc, consistent with the single-degenerate channel. A remote possibility for a core-degenerate channel involves a white dwarf merging with the degenerate core of an asymptotic giant branch star shortly before the explosion, leading to a common envelope around the SN.

(NH4)14Na4[(Np3W4O15)(H2O)3(BiW9O33)3].62H2O (1) and (NH4)14.5Na3.5[(Np3W4O15)(H2O)3(SbW9O33)3].40.5H2O (2) each contain three neptunyl(v) moieties encapsulated within heteropolyoxotungstate frameworks in which axial {NpO2}+ oxygens form one face of a WO6 octahedron.

Polymetallic nanodimensional assemblies have been prepared via metal directed assembly of dithiocarbamate functionalized cavitand structural frameworks with late transition metals (Ni, Pd, Cu, Au, Zn, and Cd). The coordination geometry about the metal centers is shown to dictate the architecture adopted. X-ray crystallographic studies confirm that square planar coordination geometries result in "cagelike" octanuclear complexes, whereas square-based pyramidal metal geometries favor hexanuclear "molecular loop" structures. Both classes of complex are sterically and electronically complementary to the fullerenes (C(60) and C(70)). The strong binding of these guests occurred via favorable interactions with the sulfur atoms of multiple dithiocarbamate moieties of the hosts. In the case of the tetrameric copper(II) complexes, the lability of the copper(II)-dithiocarbamate bond enabled the fullerene guests to be encapsulated in the electron-rich cavity of the host, over time. The examination of the binding of fullerenes has been undertaken using spectroscopic and electrochemical methods, electrospray mass spectrometry, and molecular modeling.

The novel 8-coordinate zirconium compound (NH(4))(6)[Zr(PMo(12)O(40))(PMo(11)O(39))].26H(2)O (1) has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, and vibrational and (31)P NMR spectroscopy. It is the first example of a metal complex containing both parent, [PMo(12)O(40)](3)(-), and monovacant lacunary, [PMo(11)O(39)](7)(-), anions. Furthermore, this is the first crystallographic determination of the [PMo(11)O(39)](7)(-) anion.

Porous materials resembling zeolites that are composed of organic and inorganic building units were synthesized and characterized. Control of pore and channel size was achieved by using different-sized cations. The metal-assembled, anionic cage molecule, Co(4)1(2)(8-), with a hydrophobic cavity and four carboxylate rich arms, was used as a structural unit for the formation of materials with pores and channels. When assembled into a solid material with dications (Mg(2+), Ca(2+), Sr(2+), and Ba(2+)), Co(4)1(2)(8-) arranges into sheets of cages linked together by cations. The series of materials based on Co(4)1(2)(8-) and containing alkaline earth cations was characterized using X-ray crystallography. The magnesium material packs with cages close together, has small channels, and has cation-carboxylate linkages in three dimensions. The calcium material has cages packed with voids between them and has 5 x 10 A channels and 10 x 21 A pores. The strontium and barium materials also pack with voids between the cages and similarly to each other. They have 11 x 13 A and 11 x 11 A channels and 10 x 27 A and 9 x 27 A pores, respectively. Each of these materials has many (20-50) solvent water molecules associated with each cage. The associated water can be removed from and adsorbed by the materials. The heat of water binding has been measured to be -52 kJ/mol (Mg(4)Co(4)1(2)); -47 kJ/mol (Ca(4)Co(4)1(2)); -48 kJ/mol (Sr(4)Co(4)1(2)); -49 kJ/mol (Ba(4)Co(4)1(2)).

Chemical oxidation of two preformed dinuclear copper(II) dithiocarbamate macrocycles leads to the formation of a novel mixed-valence tetranuclear copper(II)/copper(III) dithiocarbamate [2]catenane in near quantitative yield. Structural (see X-ray crystal structure), magnetic susceptibility, electrospray mass spectrometry, and electrochemical studies all support the formation of a Cu II Cu III Cu II Cu III tetranuclear catenane dication., (Copyright © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)

Bis(tripyrrolyl) cryptands are prepared via a [2 + 3] Schiff base condensation of formyltripyrrolyls with diamines; an ethyl-spaced hexapyrrole cryptand is shown to bind strongly ethane-1,2-diamine and ethane-1,2-diol in chloroform solution.

The complex Co4 1(2)8- is a tetranuclear cobalt(II) cage compound that assembles in aqueous solutions above pH 4 and is capable of encapsulating a variety of organic guest molecules, for example, benzene, hexane, chlorobutane, butanol, and ethyl acetate. Ligand 1 is a resorc[4]arene-based molecule with iminodiacetate moieties appended to its upper rim. 1H NMR studies of Co4 1(2)8-.guest complexes demonstrate inclusion of nonpolar hydrocarbons, substituted phenyls, alcohols, halogen-containing hydrocarbons, and polar organic molecules. The complex Co4 1(2)8- acts as an NMR shift reagent and causes substantial upfield isotropic hydrogen shifts (-30 to -40 ppm) in the guest molecule and separation of the guest hydrogen chemical shifts by typically 12 ppm. The complex Co4 1(2)8- will encapsulate molecules with fewer than eight atoms in a linear chain, mono- and disubstituted benzenes, and polar molecules with greater than two carbon atoms. The solid-state structure of Ba4[Co4 1(2).C6H5C2H5] shows a disordered guest molecule encapsulated within the cavity of Co4 1(2)8-. The cavity dimensions, bond lengths, and bond angles of Ba4[Co4 1(2).C6H5C2H5] are very similar to those determined in Ba4[Co4 1(2).6H2O].

Large cavities and portals are present in the nanoscale molecular architectures formed from dithiocarbamate-functionalized resorcarene ligands and zinc(II) or copper(III) ions. With Zn(II) a molecular loop based on a triangle of resorcarene cups is prepared-the cavity is circular (shown on the left). A molecular cage based on a distorted tetrahedron of four resorcarene ligands assembled by eight Cu(III) ions contains triangular-shaped portals suitable for guest passage (shown on the right).

New Zealand white rabbits were divided into 4 groups for the study of the etiology of corticosteroid-induced osteonecrosis (avascular necrosis). Group A and B received intramuscular injections of methylprednisolone acetate and methylprednisolone succinate respectively. Group C, on semirestricted diets, and Group D, on ad libitum diets, were controls. Osteocyte death, necrotic debris and intravascular fat emboli were evident in sections of proximal and distal femur by the 2nd week in experimental animals. Blood analysis revealed elevated lipid and prostaglandin levels. Osteoporosis was first observed at 6 weeks. Evidence of advanced osteonecrosis was present histologically at 18 weeks. It is concluded that osteonecrosis probably develops as the result of the interaction of several corticosteroid-induced alterations, including circulating fat emboli and inflammatory unbound free fatty acids or prostaglandins. Osteoporosis may also be a factor in explaining the sporadic nature of the disorder.

The cases of eighteen patients who underwent thoracotomy for treatment of tracheoesophageal fistula or esophageal atresia were reviewed after a follow-up of ten years or more. In nine patients spinal curves of 10 degrees or more had developed, and eight of the nine curves were convex away from the side of incision. Curves were found to have appeared at any time from early childhood to skeletal maturity, but those that developed before the adolescent growth spurt were most likely to progress. Patients who have undergone thoracotomy early in childhood should be watched carefully for the development of scoliosis.