Reconsidering the Reality of Southeastern Mesoamerica: Continuity, Diversity, and Inter-Valley Interaction in Western Honduras

The late fifth century AD was a time of rapid transformation in non-­‐Maya southeastern Mesoamerica. From this time forward, the landscape of western Honduras would become filled with increasingly complex polities and rising populations. So too is there evidence for a distinctive change in material culture, such as the development of widely shared regional polychrome ceramic traditions and the stabilization of obsidian exchange networks. Arguably, more than any other period in prehistory, it is during the Late Classic that a unique cultural identity emerges from this part of southeastern Mesoamerica. In this paper we seek to answer the question, can we characterize the diverse peoples and communities of Late Classic western Honduras as belonging to a culture area of shared affiliation and concordant identities, or is “southeastern Mesoamerica” nothing more than a geographic designation, which encompasses a diversity of strategies just different enough to defy uniform classification? To address this question we place the findings of our own research in the broader context of the long-­‐term research projects conducted by our colleagues since the 1980s. In particular, we emphasize the inter-­‐valley interactions among these polities to illuminate the shared and divergent paths taken by these communities during this period

Failure of hydrogenation in protecting polycyclic aromatic hydrocarbons from fragmentation

A recent study of soft X-ray absorption in native and hydrogenated coronene cations, C$_{24}$H$_{12+m}^+$ $m=0-7$, led to the conclusion that additional hydrogen atoms protect (interstellar) Polycyclic Aromatic Hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014)]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C$_{16}$H$_{10+m}^+$, $m=0$, 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.Comment: 10 pages, 5 figure

Improved Laboratory Transition Probabilities for Er II and Applications to the Erbium Abundances of the Sun and Five r-Process Rich, Metal-Poor Stars

Recent radiative lifetime measurements accurate to +/- 5% (Stockett et al. 2007, J. Phys. B 40, 4529) using laser-induced fluorescence (LIF) on 8 even-parity and 62 odd-parity levels of Er II have been combined with new branching fractions measured using a Fourier transform spectrometer (FTS) to determine transition probabilities for 418 lines of Er II. This work moves Er II onto the growing list of rare earth spectra with extensive and accurate modern transition probability measurements using LIF plus FTS data. This improved laboratory data set has been used to determine a new solar photospheric Er abundance, log epsilon = 0.96 +/- 0.03 (sigma = 0.06 from 8 lines), a value in excellent agreement with the recommended meteoric abundance, log epsilon = 0.95 +/- 0.03. Revised Er abundances have also been derived for the r-process-rich metal-poor giant stars CS 22892-052, BD+17 3248, HD 221170, HD 115444, and CS 31082-001. For these five stars the average Er/Eu abundance ratio, = 0.42, is in very good agreement with the solar-system r-process ratio. This study has further strengthened the finding that r-process nucleosynthesis in the early Galaxy which enriched these metal-poor stars yielded a very similar pattern to the r-process which enriched later stars including the Sun.Comment: 20 pages, 4 tables, 10 figures; To be published in the Astrophysical Journal Supplemen

Protomers of the green and cyan fluorescent protein chromophores investigated using action spectroscopy

The photophysics of biochromophore ions often depends on the isomeric or protomeric distribution, yet this distribution, and the individual isomer contributions to an action spectrum, can be difficult to quantify. Here, we use two separate photodissociation action spectroscopy instruments to record electronic spectra for protonated forms of the green (pHBDI+) and cyan (Cyan+) fluorescent protein chromophores. One instrument allows for cryogenic (T = 40±10 K) cooling of the ions, while the other offers the ability to perform protomer-selective photodissociation spectroscopy. We show that both chromophores are generated as two protomers when using electrospray ionisation, and that the protomers have partially overlapping absorption profiles associated with the S1 ← S0 transition. The action spectra for both species span the 340–460 nm range, although the spectral onset for the pHBDI+ protomer with the proton residing on the carbonyl oxygen is red-shifted by ≈40 nm relative to the lower-energy imine protomer. Similarly, the imine and carbonyl protomers are the lowest energy forms of Cyan+, with the main band for the carbonyl protomer red-shifted by ≈60 nm relative to the lower-energy imine protomer. The present strategy for investigating protomers can be applied to a wide range of other biochromophore ions

Ultraslow radiative cooling of Cn-(n = 3–5)

Ultraslow radiative cooling lifetimes and adiabatic detachment energies for three astrochemically relevant anions, C−n (n = 3–5), are measured using the Double ElectroStatic Ion Ring ExpEriment (DESIREE) infrastructure at Stockholm University. DESIREE maintains a background pressure of ≈10−14 mbar and temperature of ≈13 K, allowing storage of mass-selected ions for hours and providing conditions coined a “molecular cloud in a box.” Here, we construct two-dimensional (2D) photodetachment spectra for the target anions by recording photodetachment signal as a function of irradiation wavelength and ion storage time (seconds to minute time scale). Ion cooling lifetimes, which are associated with infrared radiative emission, are extracted from the 2D photodetachment spectrum for each ion by tracking the disappearance of vibrational hot-band signal with ion storage time, giving 1e cooling lifetimes of 3.1 ± 0.1 s (C−3), 6.8 ± 0.5 s (C−4), and 24 ± 5 s (C−5). Fits of the photodetachment spectra for cold ions, i.e., those stored for at least 30 s, provide adiabatic detachment energies in good agreement with values from laser photoelectron spectroscopy on jet-cooled anions, confirming that radiative cooling has occurred in DESIREE. Ion cooling lifetimes are simulated using a simple harmonic cascade model, finding good agreement with experiment and providing a mode-by-mode understanding of the radiative cooling properties. The 2D photodetachment strategy and radiative cooling modeling developed in this study could be applied to investigate the ultraslow cooling dynamics of a wide range of molecular anions

Action spectroscopy of the isolated red Kaede fluorescent protein chromophore

Incorporation of fluorescent proteins into biochemical systems has revolutionized the field of bioimaging. In a bottom-up approach, understanding the photophysics of fluorescent proteins requires detailed investigations of the light-absorbing chromophore, which can be achieved by studying the chromophore in isolation. This paper reports a photodissociation action spectroscopy study on the deprotonated anion of the red Kaede fluorescent protein chromophore, demonstrating that at least three isomers–assigned to deprotomers–are generated in the gas phase. Deprotomer-selected action spectra are recorded over the S1 ← S0 band using an instrument with differential mobility spectrometry coupled with photodissociation spectroscopy. The spectrum for the principal phenoxide deprotomer spans the 480–660 nm range with a maximum response at ≈610 nm. The imidazolate deprotomer has a blue-shifted action spectrum with a maximum response at ≈545 nm. The action spectra are consistent with excited state coupled-cluster calculations of excitation wavelengths for the deprotomers. A third gas-phase species with a distinct action spectrum is tentatively assigned to an imidazole tautomer of the principal phenoxide deprotomer. This study highlights the need for isomer-selective methods when studying the photophysics of biochromophores possessing several deprotonation sites

Radiative cooling of carbon cluster anions C2n+1− (n = 3–5)

Radiative cooling of carbon cluster anions C2n+1− (n = 3–5) is investigated using the cryogenic electrostatic ion storage ring DESIREE. Two different strategies are applied to infer infrared emission on slow (milliseconds to seconds) and ultraslow (seconds to minutes) timescales. Initial cooling of the ions over the millisecond timescale is probed indirectly by monitoring the decay in the yield of spontaneous neutralization by thermionic emission. The observed cooling rates are consistent with a statistical model of thermionic electron emission in competition with infrared photon emission due to vibrational de-excitation. Slower cooling over the seconds to minutes timescale associated with infrared emission from low-frequency vibrational modes is probed using time-dependent action spectroscopy. For C9− and C11−, cooling is evidenced by the time-evolution of the yield of photo-induced neutralization following resonant excitation of electronic transitions near the detachment threshold. The cross-section for resonant photo-excitation is at least two orders of magnitude greater than for direct photodetachment. In contrast, C7− lacks electronic transitions near the detachment threshold

Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene

Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0–19.5 eV range, revealing that prompt autoionization from the plasmon resonance dominates the photophysics for hν = 11.5–16.0 eV. Minimal photo-induced dissociation, whether originating from an excited state impulsive bond rupture or through internal conversion followed by a statistical bond cleavage process, occurs over the microsecond timescale (as limited by the experimental setup). The direct photoionization cross section and photoelectron angular distributions are simulated using an ezDyson model combining Dyson orbitals with Coulomb wave photoejection. When considering these data in conjunction with recent radiative cooling measurements on 1-CNN+, which showed that cations formed with up to 5 eV of internal energy efficiently stabilize through recurrent fluorescence, we conclude that the organic backbone of 1-CNN is resilient to photodestruction by VUV and soft XUV radiation. These dynamics may prove to be a common feature for the survival of small polycyclic aromatic hydrocarbons in space, provided that the cations have a suitable electronic structure to support recurrent fluorescence