Publications

Tissues are composed of diverse cell subpopulations each with distinct metabolic characteristics that influence overall behavior. Unfortunately, traditional histopathology imaging techniques are 'blind' to the spatially ordered metabolic dynamics within tissue. While mass spectrometry imaging enables spatial mapping of molecular composition, resulting images are only a static snapshot in time of molecules involved in highly dynamic processes; kinetic information of flux through metabolic pathways is lacking. To address this limitation, we developed kinetic mass spectrometry imaging (kMSI), a novel technique integrating soft desorption/ionization mass spectrometry with clinically accepted in vivo metabolic labeling of tissue with deuterium to generate images of kinetic information of biological processes. Applied to a tumor, kMSI revealed heterogeneous spatial distributions of newly synthesized versus pre-existing lipids, with altered lipid synthesis patterns distinguishing region-specific intratumor subpopulations. Images also enabled identification and correlation of metabolic activity of specific lipids found in tumor regions of varying grade.

We prepared the enantiomers of the natural product cycloprodigiosin using an expedient five-step synthetic sequence that takes advantage of a Schöllkopf–Barton–Zard (SBZ) pyrrole annulation with a chiral isocyanoacetate and a nitrocyclohexene derivative. Using chiral HPLC and X-ray crystallographic analyses of the synthetically prepared material and natural isolate (isolated from the marine bacterium Pseudoalteromonas rubra), naturally occurring cycloprodigiosin was determined to be a scalemic mixture occurring in an enantiomeric ratio of 83:17 (R)/(S) at C4'.

We present broadband (radio, optical, and X-ray) light curves and spectra of the afterglows of four long-duration gamma-ray bursts (GRBs; GRBs 090323, 090328, 090902B, and 090926A) detected by the Gamma-Ray Burst Monitor and Large Area Telescope (LAT) instruments on the Fermi satellite. With its wide spectral bandpass, extending to GeV energies, Fermi is sensitive to GRBs with very large isotropic energy releases (1054 erg). Although rare, these events are particularly important for testing GRB central-engine models. When combined with spectroscopic redshifts, our afterglow data for these four events are able to constrain jet collimation angles, the density structure of the circumburst medium, and both the true radiated energy release and the kinetic energy of the outflows. In agreement with our earlier work, we find that the relativistic energy budget of at least one of these events (GRB 090926A) exceeds the canonical value of 1051 erg by an order of magnitude. Such energies pose a severe challenge for models in which the GRB is powered by a magnetar or a neutrino-driven collapsar, but remain compatible with theoretical expectations for magnetohydrodynamical collapsar models (e.g., the Blandford-Znajek mechanism). Our jet opening angles (θ) are similar to those found for pre-Fermi GRBs, but the large initial Lorentz factors (Γ0) inferred from the detection of GeV photons imply θΓ0 ≈ 70-90, values which are above those predicted in magnetohydrodynamic models of jet acceleration. Finally, we find that these Fermi-LAT events preferentially occur in a low-density circumburst environment, and we speculate that this might result from the lower mass-loss rates of their lower-metallicity progenitor stars. Future studies of Fermi-LAT afterglows at radio wavelengths with the order-of-magnitude improvement in sensitivity offered by the Extended Very Large Array should definitively establish the relativistic energy budgets of these events.

A series of three-coordinate norbornylpalladium amido complexes ligated by bulky N-heterocyclic carbene (NHC) ligands were prepared that undergo reductive eliminations to form the alkyl-nitrogen bond of alkylamine products. The rates of reductive elimination reveal that complexes containing more-electron-donating amido groups react faster than those with less-electron-donating amido groups, and complexes containing more-sterically bulky amido groups undergo reductive elimination more slowly than complexes containing less-sterically bulky amido groups. Complexes ligated by more-electron-donating ancillary NHC ligands undergo reductive elimination faster than complexes ligated by less-electron-donating NHC ligands. In contrast to the reductive elimination of benzylamines from bisphosphine-ligated palladium amides, these reactions occur with retention of configuration at the alkyl group, indicating that these reductive eliminations proceed by a concerted pathway. The experimentally determined free energy barrier of 26 kcal/mol is close to the computed free energy barrier of 23.9 kcal/mol (363 K) for a concerted reductive elimination from the isolated, three-coordinate NHC-ligated palladium anilido complex.

Significance Are plants limited by resources or by consumers? Feeding interactions are difficult to observe in nature, so their impacts are commonly underestimated. A record of freshwater diatom frustules in a sediment core collected off the mouth of the Eel River in northern California correlated positively with algal biomass during years when upstream river reaches were surveyed. Our short-term experiments have suggested that year-to-year variation in river algal biomass during the summer growth season was driven by whether or not armored grazers had been scoured away by winter floods. The marine core record also suggests that over 83 years, controls of summer algal production were mediated more by hydrologic impacts on grazers than by their influence on growth conditions for algae.

This paper describes the Hubble Space Telescope imaging data products and data reduction procedures for the Cosmic Assembly Near-infrared Deep Extragalactic Legacy Survey (CANDELS). This survey is designed to document the evolution of galaxies and black holes at z 1.5-8, and to study Type Ia supernovae at z > 1.5. Five premier multi-wavelength sky regions are selected, each with extensive multi-wavelength observations. The primary CANDELS data consist of imaging obtained in the Wide Field Camera 3 infrared channel (WFC3/IR) and the WFC3 ultraviolet/optical channel, along with the Advanced Camera for Surveys (ACS). The CANDELS/Deep survey covers ~125 arcmin2 within GOODS-N and GOODS-S, while the remainder consists of the CANDELS/Wide survey, achieving a total of ~800 arcmin2 across GOODS and three additional fields (Extended Groth Strip, COSMOS, and Ultra-Deep Survey). We summarize the observational aspects of the survey as motivated by the scientific goals and present a detailed description of the data reduction procedures and products from the survey. Our data reduction methods utilize the most up-to-date calibration files and image combination procedures. We have paid special attention to correcting a range of instrumental effects, including charge transfer efficiency degradation for ACS, removal of electronic bias-striping present in ACS data after Servicing Mission 4, and persistence effects and other artifacts in WFC3/IR. For each field, we release mosaics for individual epochs and eventual mosaics containing data from all epochs combined, to facilitate photometric variability studies and the deepest possible photometry. A more detailed overview of the science goals and observational design of the survey are presented in a companion paper.

Arsen im Grundwasser gefährdet die Gesundheit der Bevölkerung in Entwicklungsländer wie Bangladesh. Daher wird dort dringend ein zuverlässiges und transportables Gerät zum Arsennachweis benötigt. Ein hoch empfindliches System, das mithilfe von oberflächenverstärkter Raman-Spektroskopie (SERS, siehe Bild) Arsenat in Wasser bis hinab zu 1 ppb quantitativ bestimmt, könnte in dieser Hinsicht interessant sein.

In the most precise distance ladder determination of $H_0$, the observed near-infrared (NIR) fluxes of Cepheids are corrected for dust, assuming that the extinction law in large, star-forming spiral hosts of Type Ia supernovae (SN Ia) is similar to the Milky Way's average value of $R_V \approx 3.1$. Intriguingly, studies of SNe Ia often point to lower values for their hosts ($R_V \sim 2$). Ambiguities related to $R_V$ may limit future efforts to measure $H_0$ beyond $\sim 1\%$ precision. To better resolve extragalactic extinction laws, we directly measure the wavelength-dependent absorption of background galaxies seen in HST and JWST images (0.5--2.7 $μ$m). We take the following steps: (i) subtract foreground stars to measure accurate photometry of background galaxies with a tool, $\texttt{SPHOT}$; (ii) measure their redshifts and spectroscopic features with Keck/DEIMOS; (iii) determine their intrinsic spectral energy distributions from the empirical templates which match the absorption lines and breaks in observed spectroscopic features, and (iv) measure $R_V$ by fitting the extinction model to the difference between the template and the observed SEDs. The above steps are tested with artificial datasets to insure they accurately recover the input $R_V$. We apply this set of steps to a first case, NGC 5584, a SN Ia host and a calibrator of the Hubble constant. The estimated value of $R_V$ for NGC 5584, $R_V=3.59^{+0.99}_{-0.62}(\text{stat})\pm0.19(\text{syst})$, is consistent with the MW-like extinction law, and it is $\gtrsim 3.5σ$ away from $R_V=2$ as favored by SN Ia. If additional hosts show similar results, it would suggest that SN Ia extinction may not be solely due to mean interstellar dust. We are now undertaking a statistical study of 5-10 SH0ES hosts to determine the distribution of host extinction laws.