Insights into molecular chemistry of Chiapas amber using infrared-light microscopy,PIXE/RBS,and sulfur K-edge XANES spectroscopy

Chiapas amber is a natural occurring fossil resin structurally composed of long macromolecule chains with semicrystalline phases associated with both fossil and polymerization process. The most conspicuous characteristic of this fossil polymer is that it preserves ancient organic inclusions. In the present work, PIXE/RBS spectrometry (particle-induced X-ray emission/Rutherford backscattering) were combined with complementary K-edge XANES spectroscopy (X-ray absorption near-edge structure) to identify the amount of sulfur in Chiapas amber. Initially, the amber samples were examined using infrared reflected photomicrography. Amber is transparent to infrared light and so embedded plants and animals are easily visible, showing them in extraordinary detail, as if they were immersed in a water-like solution. The PIXE/RBS data show that the proportion of sulfur in amber is significantly higher than that found in recently formed resins, consistent with the biogeochemical process that transforms the resin into amber during long-term burial in geological deposits. The sulfur K-edge XANES spectra from amber confirm the sulfur abundance and reveal sulfur species in the reduced and intermediate oxidation states in amber. Almost no oxidized sulfur was found, whereas the recent resins show mostly oxidized sulfur fractions. This indicates that labile oxidized sulfur decays during fossilization and resin maturation must occur under conditions of oxygen depletion. The implications of the presence of sulfur in amber for organic preservation is also discussed here. Sulfur compounds work as a polymer additive that promotes intense resin solidification. This restricts the early oxidant-specific biodegradation of the embedded biomatter and, over geological time, provides greater stability against chemical changes.     

Surface effects on the diagnostic of carbon/nitrogen low‐pressure plasmas studied by differentially pumped mass spectrometry

In this work, the characterization of the species produced in reactive plasmas by differentially pumped mass spectrometry is addressed. A H₂/CH₄/N₂ mixture (90 : 5 : 5) was fed into a direct current glow discharge and analysed by conventional and cryo‐trap assisted mass spectrometry. The gaseous mixture was chosen because of its particular relevance in the inhibition of tritium‐rich carbon film deposition in fusion plasmas (scavenger technique) and in the deposition of amorphous hydrogenated carbon films by plasma‐assisted chemical vapour deposition. Important changes in the composition of the detected species upon surface modification of the reactor walls (stainless steel or covered by an amorphous hydrogenated carbon layer) or in the way they are sampled (length and spatial configuration of the stainless steel duct) were detected. They are analysed in terms of radical formation and recombination on the reactor walls or into the sampling duct, thus providing some insight into the underlying chemistry. In general, when the reactor walls are covered by an amorphous hydrogenated carbon layer, more hydrocarbons are produced, but the radical production is lower and seem to be less reactive than in stainless steel. Also, two sources of oxygen contamination in the plasma have been identified, from the native oxide layer in stainless steel and from unintended water contamination in the chamber, which modify considerably the detected species. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermo-oxidative evaluation of new cardol derivatives as antioxidants for mineral oils

In this study, the thermo-oxidative stability of two new phosphorylated derivatives of cardol, a compound from the cashew (Anacardium occidentale L.) industry waste CNSL (cashew nutshell liquid), were evaluated. The antioxidant capacity of these new molecules upon two mineral oils, NH10 and NH20 were also studied by thermogravimetric analysis (TG/DTG), observing the onset and offset temperatures variation. The results showed that both MP and DP Cardol increased considerably the onset and offset temperatures of NH10 and NH20 oils.     

[All]-S,S-dioxide Oligo-Thienylenevinylenes: Synthesis and Structural/Electronic Shapes from Their Molecular Force Fields

Oligo-S,S-dioxothienylenevinylenes have been prepared by transferring oxygen atoms to the sulfur atoms using the HOF ⋅ CH₃CN complex. Their photophysical properties are presented in comparison with their thiophenevinylene congeners. Together with their vibrational properties and molecular force fields, this study allows for the interpretation of the alteration of aromaticity and inter-ring exocyclic π-conjugation in this series.     

Nonadiabatic effects in the nuclear probability and flux densities through the fractional Schrödinger equation

Nonadiabatic effects in the nuclear dynamics of the H₂⁺ molecular ion, initiated by ionization of the H₂ molecule, is studied by means of the probability and flux distribution functions arising from the space fractional Schrödinger equation. In order to solve the fractional Schrödinger eigenvalue equation, it is shown that the quantum Riesz fractional derivative operator fulfills the usual properties of the quantum momentum operator acting on the bra and ket vectors of the abstract Hilbert space. Then, the fractional Fourier grid Hamiltonian method is implemented and applied to molecular vibrations. The eigenenergies and eigenfunctions of the fractional Schrödinger equation describing the vibrational motion of the H₂⁺ and D₂⁺ molecules are analyzed. In particular, it is shown that the position-momentum Heisenberg's uncertainty relationship holds independently of the fractional Schrödinger equation. Finally, the probability and flux distributions are presented, demonstrating the applicability of the fractional Schrödinger equation for taking into account nonadiabatic effects.     

Modelling the reflective thermal contribution to the acceleration of the Pioneer spacecraft

We present an improved method to compute the radiative momentum transfer in the Pioneer 10 and 11 spacecraft that takes into account both diffusive and specular reflection. The method allows for more reliable results regarding the thermal acceleration of the deep-space probes, confirming previous findings. A parametric analysis is performed in order to set upper and lower bounds for the thermal acceleration and its evolution with time.     

Theoretical Investigation of the Photoexcited NO2+H2O reaction at the Air–Water Interface and Its Atmospheric Implications

The atmospheric role of photochemical processes involving NO₂ beyond its dissociation limit (398 nm) is controversial. Recent experiments have confirmed that excited NO₂^* beyond 420 nm reacts with water according to NO₂^*+H₂O→HONO+OH. However, the estimated kinetic constant for this process in the gas phase is quite small (k≈10⁻¹⁵–3.4×10⁻¹⁴ cm³ molecule⁻¹ s⁻¹) suggesting minor atmospheric implications of the formed radicals. In this work, ab initio molecular dynamics simulations of NO₂ adsorbed at the air–water interface reveal that the OH production rate increases by about 2 orders of magnitude with respect to gas phase, attaining ozone reference values for NO₂ concentrations corresponding to slightly polluted rural areas. This finding substantiates the argument that chemistry on clouds can be an additional source of OH radicals in the troposphere and suggests directions for future laboratory experimental studies.