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The diverse roles of the dynein motor in shaping microtubule networks and cargo transport complicate in vivo analysis of its functions significantly. To address this issue, we have generated a series of missense mutations in Drosophila Dynein heavy chain. We show that mutations associated with human neurological disease cause a range of defects, including impaired cargo trafficking in neurons. We also describe a novel microtubule-binding domain mutation that specifically blocks the metaphase-anaphase transition during mitosis in the embryo. This effect is independent from dynein's canonical role in silencing the spindle assembly checkpoint. Optical trapping of purified dynein complexes reveals that this mutation only compromises motor performance under load, a finding rationalized by the results of all-atom molecular dynamics simulations. We propose that dynein has a novel function in anaphase progression that depends on it operating in a specific load regime. More broadly, our work illustrates how in vivo functions of motors can be dissected by manipulating their mechanical properties., (© 2024 MRC Laboratory of Molecular Biology.)

Optimum protein function and biochemical activity critically depends on water availability because solvent thermodynamics drive protein folding and macromolecular interactions 1 . Reciprocally, macromolecules restrict the movement of 'structured' water molecules within their hydration layers, reducing the available 'free' bulk solvent and therefore the total thermodynamic potential energy of water, or water potential. Here, within concentrated macromolecular solutions such as the cytosol, we found that modest changes in temperature greatly affect the water potential, and are counteracted by opposing changes in osmotic strength. This duality of temperature and osmotic strength enables simple manipulations of solvent thermodynamics to prevent cell death after extreme cold or heat shock. Physiologically, cells must sustain their activity against fluctuating temperature, pressure and osmotic strength, which impact water availability within seconds. Yet, established mechanisms of water homeostasis act over much slower timescales 2,3 ; we therefore postulated the existence of a rapid compensatory response. We find that this function is performed by water potential-driven changes in macromolecular assembly, particularly biomolecular condensation of intrinsically disordered proteins. The formation and dissolution of biomolecular condensates liberates and captures free water, respectively, quickly counteracting thermal or osmotic perturbations of water potential, which is consequently robustly buffered in the cytoplasm. Our results indicate that biomolecular condensation constitutes an intrinsic biophysical feedback response that rapidly compensates for intracellular osmotic and thermal fluctuations. We suggest that preserving water availability within the concentrated cytosol is an overlooked evolutionary driver of protein (dis)order and function., (© 2023. The Author(s).)

Myosin VI (Myo6) is the only minus-end directed nanomotor on actin, allowing it to uniquely contribute to numerous cellular functions. As for other nanomotors, the proper functioning of Myo6 relies on precise spatiotemporal control of motor activity via a poorly defined off-state and interactions with partners. Our structural, functional, and cellular studies reveal key features of myosin regulation and indicate that not all partners can activate Myo6. TOM1 and Dab2 cannot bind the off-state, while GIPC1 binds Myo6, releases its auto-inhibition and triggers proximal dimerization. Myo6 partners thus differentially recruit Myo6. We solved a crystal structure of the proximal dimerization domain, and show that its disruption compromises endocytosis in HeLa cells, emphasizing the importance of Myo6 dimerization. Finally, we show that the L926Q deafness mutation disrupts Myo6 auto-inhibition and indirectly impairs proximal dimerization. Our study thus demonstrates the importance of partners in the control of Myo6 auto-inhibition, localization, and activation., (© 2023. Springer Nature Limited.)

Polarized cells rely on a polarized cytoskeleton to function. Yet, how cortical polarity cues induce cytoskeleton polarization remains elusive. Here, we capitalized on recently established designed 2D protein arrays to ectopically engineer cortical polarity of virtually any protein of interest during mitosis in various cell types. This enables direct manipulation of polarity signaling and the identification of the cortical cues sufficient for cytoskeleton polarization. Using this assay, we dissected the logic of the Par complex pathway, a key regulator of cytoskeleton polarity during asymmetric cell division. We show that cortical clustering of any Par complex subunit is sufficient to trigger complex assembly and that the primary kinetic barrier to complex assembly is the relief of Par6 autoinhibition. Further, we found that inducing cortical Par complex polarity induces two hallmarks of asymmetric cell division in unpolarized mammalian cells: spindle orientation, occurring via Par3, and central spindle asymmetry, depending on aPKC activity., Competing Interests: Declaration of interests J.L.W., E.D., D.B., and A.J.B.-S. are co-inventors on a patent application related to the designed polymer used in this paper., (Copyright © 2023 MRC Laboratory of Molecular Biology. Published by Elsevier Inc. All rights reserved.)

The Commander complex is required for endosomal recycling of diverse transmembrane cargos and is mutated in Ritscher-Schinzel syndrome. It comprises two sub-assemblies: Retriever composed of VPS35L, VPS26C, and VPS29; and the CCC complex which contains twelve subunits: COMMD1-COMMD10 and the coiled-coil domain-containing (CCDC) proteins CCDC22 and CCDC93. Combining X-ray crystallography, electron cryomicroscopy, and in silico predictions, we have assembled a complete structural model of Commander. Retriever is distantly related to the endosomal Retromer complex but has unique features preventing the shared VPS29 subunit from interacting with Retromer-associated factors. The COMMD proteins form a distinctive hetero-decameric ring stabilized by extensive interactions with CCDC22 and CCDC93. These adopt a coiled-coil structure that connects the CCC and Retriever assemblies and recruits a 16th subunit, DENND10, to form the complete Commander complex. The structure allows mapping of disease-causing mutations and reveals the molecular features required for the function of this evolutionarily conserved trafficking machinery., Competing Interests: Declaration of interests The authors declare that they have no conflicts of interest., (Copyright © 2023 The Author(s). Published by Elsevier Inc. All rights reserved.)

During morphogenesis, large-scale changes of tissue primordia are coordinated across an embryo. In Drosophila, several tissue primordia and embryonic regions are bordered or encircled by supracellular actomyosin cables, junctional actomyosin enrichments networked between many neighbouring cells. We show that the single Drosophila Alp/Enigma-family protein Zasp52, which is most prominently found in Z-discs of muscles, is a component of many supracellular actomyosin structures during embryogenesis, including the ventral midline and the boundary of the salivary gland placode. We reveal that Zasp52 contains within its central coiled-coil region a type of actin-binding motif usually found in CapZbeta proteins, and this domain displays actin-binding activity. Using endogenously-tagged lines, we identify that Zasp52 interacts with junctional components, including APC2, Polychaetoid and Sidekick, and actomyosin regulators. Analysis of zasp52 mutant embryos reveals that the severity of the embryonic defects observed scales inversely with the amount of functional protein left. Large tissue deformations occur where actomyosin cables are found during embryogenesis, and in vivo and in silico analyses suggest a model whereby supracellular Zasp52-containing cables aid to insulate morphogenetic changes from one another., Competing Interests: Competing interests The authors declare no competing or financial interests., (© 2023. Published by The Company of Biologists Ltd.)

Protein filaments are used in myriads of ways to organize other molecules within cells. Some filament-forming proteins couple the hydrolysis of nucleotides to their polymerization cycle, thus powering the movement of other molecules. These filaments are termed cytomotive. Only members of the actin and tubulin protein superfamilies are known to form cytomotive filaments. We examined the basis of cytomotivity via structural studies of the polymerization cycles of actin and tubulin homologs from across the tree of life. We analyzed published data and performed structural experiments designed to disentangle functional components of these complex filament systems. Our analysis demonstrates the existence of shared subunit polymerization switches among both cytomotive actins and tubulins, i.e., the conformation of subunits switches upon assembly into filaments. These cytomotive switches can explain filament robustness, by enabling the coupling of kinetic and structural polarities required for cytomotive behaviors and by ensuring that single cytomotive filaments do not fall apart.

Asymmetric cell division gives rise to two daughter cells that inherit different determinants, thereby acquiring different fates. Polarized trafficking of endosomes containing fate determinants recently emerged as an evolutionarily conserved feature of asymmetric cell division to enhance the robustness of asymmetric cell fate determination in flies, fish and mammals. In particular, polarized sorting of signalling endosomes by an asymmetric central spindle contributes to asymmetric cell division in Drosophila melanogaster. However, how central spindle asymmetry arises remains elusive. Here we identify a moonlighting function of the Elongator complex-an established protein acetylase and tRNA methylase involved in the fidelity of protein translation-as a key factor for central spindle asymmetry. Elongator controls spindle asymmetry by stabilizing microtubules differentially on the anterior side of the central spindle. Accordingly, lowering the activity of Elongator on the anterior side using nanobodies mistargets endosomes to the wrong cell. Molecularly, Elongator regulates microtubule dynamics independently of its acetylation and methylation enzymatic activities. Instead, Elongator directly binds to microtubules and increases their polymerization speed while decreasing their catastrophe frequency. Our data establish a non-canonical role of Elongator at the core of cytoskeleton polarity and asymmetric signalling., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Urea is a molecule of great interest in chemistry and biology. In particular, it is considered a key building block in prebiotic chemistry on Earth. The hypothesis of its possible exogenous origin has been reinforced after the recent detection of this molecule in the interstellar medium, where it is believed to form in the ice mantles of dust grains. In this work the infrared spectra of urea ices and urea:H 2 O ice mixtures have been studied both experimentally and theoretically. Urea ices were generated by vapour deposition at temperatures between 10 K and 270 K. It was found that an amorphous phase is formed at temperatures below 200 K. A theoretical modelling of crystalline urea and of a tentative amorphous urea solid phase, as well as of amorphous urea:H 2 O ice mixtures, has been performed. The corresponding infrared spectra were simulated with density functional theory. The main spectral features observed in the various solid samples are interpreted with the help of the theoretical results. Infrared band strengths are also provided for amorphous and crystalline urea. The infrared spectroscopic information given in this work is expected to be useful for the detection and quantification of urea in astrophysical ices.

The TRAPP complexes are nucleotide exchange factors that play essential roles in membrane traffic and autophagy. TRAPPII activates Rab11, and TRAPPIII activates Rab1, with the two complexes sharing a core of small subunits that affect nucleotide exchange but being distinguished by specific large subunits that are essential for activity in vivo. Crystal structures of core subunits have revealed the mechanism of Rab activation, but how the core and the large subunits assemble to form the complexes is unknown. We report a cryo-EM structure of the entire Drosophila TRAPPIII complex. The TRAPPIII-specific subunits TRAPPC8 and TRAPPC11 hold the catalytic core like a pair of tongs, with TRAPPC12 and TRAPPC13 positioned at the joint between them. TRAPPC2 and TRAPPC2L link the core to the two large arms, with the interfaces containing residues affected by disease-causing mutations. The TRAPPC8 arm is positioned such that it would contact Rab1 that is bound to the core, indicating how the arm could determine the specificity of the complex. A lower resolution structure of TRAPPII shows a similar architecture and suggests that the TRAPP complexes evolved from a single ur-TRAPP., (© 2021 The Authors. Published under the terms of the CC BY 4.0 license.)

The excitation functions (reaction cross-section as a function of collision energy) of the F + HD(v = 0, 1; j = 0, 1) benchmark system have been calculated in the 0.01-6 meV collision energy interval using a time-independent hyperspherical quantum dynamics methodology. Special attention has been paid to orbiting resonances, which bring about detailed information on the three-atom interaction during the reactive encounter. The location of the resonances depends on the rovibrational state of the reactants HD(v,j), but is the same for the two product channels HF + D and DF + H, as expected for these resonances that are linked to the van der Waals well at the entrance. The resonance intensities depend both on the entrance and on the exit channels. The peak intensities for the HF + D channel are systematically larger than those for DF + H. Vibrational excitation leads to an increase of the peak intensity by more than an order of magnitude, but rotational excitation has a less drastic effect. It deceases the resonance intensity of the F + HD(v = 1) reaction, but increases somewhat that of F + HD(v = 0). Polarization of the rotational angular momentum with respect to the initial velocity reveals intrinsic directional preferences in the F + HD(v = 0, 1; j = 1) reactions that are manifested in the resonance patterns. The helicities (Ω = 0, Ω = ±1) possible for j = 1 contribute to the resonances, but that from Ω± 1 is, in general, dominant and in some cases exclusive. It corresponds to a preferential alignment of the HD internuclear axis perpendicular to the initial direction of approach and, thus, to side-on collisions. This work also shows that external preparation of the reactants, following the intrinsic preferences, would allow the enhancement or reduction of specific resonance features, and would be of great help for their eventual experimental detection.

When combined with NMR spectroscopy, high hydrostatic pressure is an alternative perturbation method used to destabilize globular proteins that has proven to be particularly well suited for exploring the unfolding energy landscape of small single-domain proteins. To date, investigations of the unfolding landscape of all-β or mixed-α/β protein scaffolds are well documented, whereas such data are lacking for all-α protein domains. Here we report the NMR study of the unfolding pathways of GIPC1-GH2, a small α-helical bundle domain made of four antiparallel α-helices. High-pressure perturbation was combined with NMR spectroscopy to unravel the unfolding landscape at three different temperatures. The results were compared to those obtained from classical chemical denaturation. Whatever the perturbation used, the loss of secondary and tertiary contacts within the protein scaffold is almost simultaneous. The unfolding transition appeared very cooperative when using high pressure at high temperature, as was the case for chemical denaturation, whereas it was found more progressive at low temperature, suggesting the existence of a complex folding pathway.

Silicon is present in interstellar dust grains, meteorites and asteroids, and to date thirteen silicon-bearing molecules have been detected in the gas-phase towards late-type stars or molecular clouds, including silane and silane derivatives. In this work, we have experimentally studied the interaction between atomic silicon and hydrogen under physical conditions mimicking those at the atmosphere of evolved stars. We have found that the chemistry of Si, H and H 2 efficiently produces silane (SiH 4 ), disilane (Si 2 H 6 ) and amorphous hydrogenated silicon (a-Si:H) grains. Silane has been definitely detected towards the carbon-rich star IRC+10216, while disilane has not been detected in space yet. Thus, based on our results, we propose that gas-phase reactions of atomic Si with H and H 2 are a plausible source of silane in C-rich AGBs, although its contribution to the total SiH 4 abundance may be low in comparison with the suggested formation route by catalytic reactions on the surface of dust grains. In addition, the produced a-Si:H dust analogs decompose into SiH 4 and Si 2 H 6 at temperatures above 500 K, suggesting an additional mechanism of formation of these species in envelopes around evolved stars. We have also found that the exposure of these dust analogs to water vapor leads to the incorporation of oxygen into Si-O-Si and Si-OH groups at the expense of SiH moieties, which implies that, if this type of grains are present in the interstellar medium, they will be probably processed into silicates through the interaction with water ices covering the surface of dust grains.

Interstellar carbonaceous dust is mainly formed in the innermost regions of circumstellar envelopes around carbon-rich asymptotic giant branch (AGB) stars. In these highly chemically stratified regions, atomic and diatomic carbon, along with acetylene are the most abundant species after H 2 and CO. In a previous study, we addressed the chemistry of carbon (C and C 2 ) with H 2 showing that acetylene and aliphatic species form efficiently in the dust formation region of carbon-rich AGBs whereas aromatics do not. Still, acetylene is known to be a key ingredient in the formation of linear polyacetylenic chains, benzene and polycyclic aromatic hydrocarbons (PAHs), as shown by previous experiments. However, these experiments have not considered the chemistry of carbon (C and C 2 ) with C 2 H 2 . In this work, by employing a sufficient amount of acetylene, we investigate its gas-phase interaction with atomic and diatomic carbon. We show that the chemistry involved produces linear polyacetylenic chains, benzene and other PAHs, which are observed with high abundances in the early evolutionary phase of planetary nebulae. More importantly, we have found a non-negligible amount of pure and hydrogenated carbon clusters as well as aromatics with aliphatic substitutions, both being a direct consequence of the addition of atomic carbon. The incorporation of alkyl substituents into aromatics can be rationalized by a mechanism involving hydrogen abstraction followed by methyl addition. All the species detected in gas phase are incorporated into the nanometric sized dust analogues, which consist of a complex mixture of sp, sp 2 and sp 3 hydrocarbons with amorphous morphology.

Evolved stars are a foundry of chemical complexity, gas and dust that provides the building blocks of planets and life, and dust nucleation first occurs in their photosphere. Despite their importance, the circumstellar regions enveloping these stars remain hidden to many observations, thus dust formation processes are still poorly understood. Laboratory astrophysics provides complementary routes to unveil these chemical processes, but most experiments rely on combustion or plasma decomposition of molecular precursors under physical conditions far removed from those in space. We have built an ultra-high vacuum machine combining atomic gas aggregation with advanced in-situ characterization techniques to reproduce and characterize the bottom-up dust formation process. We show that carbonaceous dust analogues formed from low-pressure gas-phase condensation of C atoms in a hydrogen atmosphere, in a C/H 2 ratio similar to that reported for evolved stars, leads to the formation of amorphous C nanograins and aliphatic C-clusters. Aromatic species or fullerenes do not form effectively under these conditions, raising implications for the revision of the chemical mechanisms taking place in circumstellar envelopes., Competing Interests: Competing interests. The authors declare no competing interests.

One of the most relevant features of the O( 3 P) + H 2 reaction is that it occurs on two different potential energy surfaces (PESs) of symmetries A' and A'' that correlate reactants and products. The respective saddle points, which correspond to a collinear arrangement, are the same for both PESs, whilst the barrier height rises more abruptly on the 3 A' PES than on the 3 A'' PES. Accordingly, the reactivity on the 3 A'' PES should be always higher than on the 3 A' PES. In this work, we present accurate quantum-scattering calculations showing that this is not always the case for rotationless reactants, where dynamical factors near the reaction threshold cause the 3 A' PES to dominate at energies around the barrier. Further calculation of cross sections and Λ-doublet populations has allowed us to establish how the reaction mechanism changes from the deep tunneling regime to hyperthermal energies.

The ionic polymerization of acetylene in cold plasmas of C 2 H 2 /He and C 2 H 2 /Ar has been experimentally studied and modeled in radio frequency (rf) discharges with conditions selected to avoid particle formation. Steady-state distributions of positive and negative ions were measured with mass spectrometry. All the measured distributions are dominated by ions with an even number of carbon atoms, reflecting the characteristic polyyne structures typical for the polymerization of acetylene. The distributions show a monotonic decrease in intensity from ions with two carbon atoms until the highest number of atoms detected. For cations, the distributions extend until 12 carbon atoms. The anion distributions extend further, and negative ions with 20 C atoms are observed in the C 2 H 2 /Ar plasma. From the measured mass spectra it is not possible to decide on the possible presence of aromatic species in ions with more than six carbon atoms. A simple model assuming a homogeneous discharge was used to describe the plasma kinetics and could account for the measured ion distributions with reasonable values of charge density and electron temperature. The results of this work stress the important role of the vinylidene anion and indicate that Ar and He do not have much influence on the carbon chemistry.

Context: Dinitriles with a saturated hydrocarbon skeleton and a -C≡N group at each end can have large electric dipole moments. Their formation can be related to highly reactive radicals such as CH 2 CN, C 2 N or CN. Thus, these saturated dinitriles are potential candidates to be observed in the ISM., Aims: Our goal is the investigation of the rotational spectrum of one of the simplest dinitriles N≡C-CH 2 -CH 2 -C≡N, succinonitrile, whose actual rotational parameters are not precise enough to allow its detection in the ISM. In addition, the rotational spectra for its vibrational exicted states will be analyzed., Methods: The rotational spectra of succinonitrile was measured in the frequency range 72-116.5 GHz using a new broadband millimeter-wave spectrometer based on radio astronomy receivers with Fast Fourier Transform backends. The identification of the vibrational excited states of succinonitrile was supported by high-level ab initio calculations on the harmonic and anharmonic force fields., Results: A total of 459 rotational transitions with maximum values of J and K a quantum numbers 70 and 14, respectively, were measured for the ground vibrational state of succinonitrile. The analysis allowed us to accurately determine the rotational, quartic and sextic centrifugal distortion constants. Up to eleven vibrational excited states, resulting from the four lowest frequency vibrational modes ν 13 , ν 12 , ν 24 and ν 23 were identified. In addition to the four fundamental modes, we observed overtones together with some combination states. The rotational parameters for the ground state were employed to unsuccessfully search for succinonitrile in the cold and warm molecular clouds Orion KL, Sgr B2(N), B1-b and TMC-1, using the spectral surveys captured by IRAM 30m at 3mm and the Yebes 40m at 1.3cm and 7mm.

Time-independent, fully converged, quantum dynamical calculations have been performed for the F + HD (v = 0, j = 0) and F + HD (v = 1, j = 0) reactions on an accurate potential energy surface down to collision energies of 0.01 meV. The two isotopic exit channels, HF + D and DF + H, have been investigated. The calculations reproduce satisfactorily the Feshbach resonance structures for collision energies between 10 and 40 meV, previously reported in the literature for the HF + D channel. Contrary to the results of a former literature work, vibrational excitation of HD is found to enhance reactivity in all cases down to the lowest collision energy investigated. Shape-type orbiting resonances are found for collision energies lower than 2 meV. The resonances appear as peaks in the reaction cross sections that are associated to specific values of the total angular momentum, J. In contrast with the Feshbach resonances at higher energies, the orbiting resonance structure, which is caused by the van der Waals well of the entrance channel, is identical for the HF + D and DF + H exit channels. The orbiting resonance peaks for F + HD (v = 0) are very small, but those for F + HD (v = 1) could be observed, in principle, with a combination of Raman pumping and merged beams methods.

We present a new experimental setup devoted to the study of gas phase molecules and processes using broad band high spectral resolution rotational spectroscopy. A reactor chamber has been equipped with radio receivers similar to those used by radio astronomers to search for molecular emission in space. The whole Q (31.5-50 GHz) and W bands (72-116.5 GHz) are available for rotational spectroscopy observations. The receivers are equipped with 16×2.5 GHz Fast Fourier Transform spectrometers with a spectral resolution of 38.14 kHz allowing the simultaneous observation of the complete Q band and one third of the W band. The whole W band can be observed in three settings in which the Q band is always observed. Species such as CH 3 CN, OCS, and SO 2 are detected, together with many of their isotopologues and vibrationally excited states, in very short observing times. The system permits automatic overnight observations and integration times as long as 2.4×10 5 seconds have been reached. The chamber is equipped with a radiofrequency source to produce cold plasmas and with four ultraviolet lamps to study photochemical processes. Plasmas of CH 4 , N 2 , CH 3 CN, NH 3 , O 2 , and H 2 , among other species, have been generated and the molecular products easily identified by their rotational spectrum, and mass spectrometry and optical spectroscopy. Finally, the rotational spectrum of the lowest energy conformer of CH 3 CH 2 NHCHO (N-Ethylformamide), a molecule previously characterized in microwave rotational spectroscopy, has been measured up to 116.5 GHz allowing the accurate determination of its rotational and distortion constants and its search in space.

Methyl isocyanate (CH 3 NCO) was recently found in hot cores and suggested on comet 67P/CG. The incorporation of this molecule into astrochemical networks requires data on its formation and destruction. In this work, ices of pure CH 3 NCO and of CH 3 NCO(4-5%)/H 2 O mixtures deposited at 20 K were irradiated with a UV D 2 lamp (120-400 nm) and bombarded by 5 keV electrons to mimic the secondary electrons produced by cosmic rays (CRs). The destruction of CH 3 NCO was studied using IR spectroscopy. After processing, the ν a -NCO band of CH 3 NCO disappeared and IR bands corresponding to CO, CO 2 , OCN - and HCN/CN - appeared instead. The products of photon and electron processing were very similar. Destruction cross sections and half-life doses were derived from the measurements. Water ice provides a good shield against UV irradiation (half-life dose of ~ 64 eV molecule -1 for CH 3 NCO in water-ice), but not so good against high-energy electrons (half-life dose ~ 18 eV molecule -1 ). It was also found that CH 3 NCO does not react with H 2 O over the 20-200 K temperature range. These results indicate that hypothetical CH 3 NCO in the ices of dense clouds should be stable against UV photons and relatively stable against CRs over the lifetime of a cloud (~ 10 7 yr), and could sublime in the hot core phase. On the surface of a Kuiper belt object (the original location of comet 67P/CG) the molecule would be swiftly destroyed, both by photons and CRs, but embedded below just 10 μm of water-ice, the molecule could survive for ~ 10 9 yr.

The increasing demand for nanostructured materials is mainly motivated by their key role in a wide variety of technologically relevant fields such as biomedicine, green sustainable energy or catalysis. We have succeeded to scale-up a type of gas aggregation source, called a multiple ion cluster source, for the generation of complex, ultra-pure nanoparticles made of different materials. The high production rates achieved (tens of g/day) for this kind of gas aggregation sources, and the inherent ability to control the structure of the nanoparticles in a controlled environment, make this equipment appealing for industrial purposes, a highly coveted aspect since the introduction of this type of sources. Furthermore, our innovative UHV experimental station also includes in-flight manipulation and processing capabilities by annealing, acceleration, or interaction with background gases along with in-situ characterization of the clusters and nanoparticles fabricated. As an example to demonstrate some of the capabilities of this new equipment, herein we present the fabrication of copper nanoparticles and their processing, including the controlled oxidation (from Cu 0 to CuO through Cu 2 O, and their mixtures) at different stages in the machine.

Interstellar (IS) dust analogs, based on amorphous hydrogenated carbon (a-C:H) were generated by plasma deposition in RF discharges of CH 4 + He mixtures. The a-C:H samples were characterized by means of secondary electron microscopy (SEM), infrared (IR) spectroscopy and UV-visible reflectivity. DFT calculations of structure and IR spectra were also carried out. From the experimental data, atomic compositions were estimated. Both IR and reflectivity measurements led to similar high proportions (≈ 50%) of H atoms, but there was a significant discrepancy in the sp 2 /sp 3 hybridization ratios of C atoms (sp 2 /sp 3 = 1.5 from IR and 0.25 from reflectivity). Energetic processing of the samples with 5 keV electrons led to a decay of IR aliphatic bands and to a growth of aromatic bands, which is consistent with a dehydrogenation and graphitization of the samples. The decay of the CH aliphatic stretching band at 3.4 µm upon electron irradiation is relatively slow. Estimates based on the absorbed energy and on models of cosmic ray (CR) flux indicate that CR bombardment is not enough to justify the observed disappearance of this band in dense IS clouds.

We present a proof of concept on the coupling of radio astronomical receivers and spectrometers with chemical reactors and the performances of the resulting setup for spectroscopy and chemical simulations in laboratory astrophysics. Several experiments including cold plasma generation and UV photochemistry were performed in a 40 cm long gas cell placed in the beam path of the Aries 40 m radio telescope receivers operating in the 41-49 GHz frequency range interfaced with fast Fourier transform spectrometers providing 2 GHz bandwidth and 38 kHz resolution. The impedance matching of the cell windows has been studied using different materials. The choice of the material and its thickness was critical to obtain a sensitivity identical to that of standard radio astronomical observations. Spectroscopic signals arising from very low partial pressures of CH 3 OH, CH 3 CH 2 OH, HCOOH, OCS, CS, SO 2 (<10 -3 mbar) were detected in a few seconds. Fast data acquisition was achieved allowing for kinetic measurements in fragmentation experiments using electron impact or UV irradiation. Time evolution of chemical reactions involving OCS, O 2 and CS 2 was also observed demonstrating that reactive species, such as CS, can be maintained with high abundance in the gas phase during these experiments.

Methyl isocyanate has been recently detected in comet 67P/ Churyumov-Gerasimenko (67P/CG) and in the interstellar medium. New physicochemical studies on this species are now necessary as tools for subsequent studies in astrophysics. In this work, infrared spectra of solid CH 3 NCO have been obtained at temperatures of relevance for astronomical environments. The spectra are dominated by a strong, characteristic multiplet feature at 2350-2250 cm -1 , which can be attributed to the antisymmetric stretching of the NCO group. A phase transition from amorphous to crystalline methyl isocyanate is observed at ~ 90 K. The band strengths for the absorptions of CH 3 NCO in ice at 20 K have been measured. Deuterated methyl isocyanate is used to help with the spectral assignment. No X-ray structure has been reported for crystalline CH 3 NCO. Here we advance a tentative theoretical structure, based on Density Functional Theory (DFT) calculations, derived taking as a starting point the crystal of isocyanic acid. A harmonic theoretical spectrum is calculated then for the proposed structure, and compared with the experimental data. A mixed ice of H 2 O and CH 3 NCO was formed by simultaneous deposition of water and methyl isocyanate at 20 K. The absence of new spectral features indicates that methyl isocyanate and water do not react appreciably at 20 K, but form a stable mixture. The high CH 3 NCO/H 2 O ratio reported for comet 67P/CG, and the characteristic structure of the 2350-2250 cm -1 band, make of it a very good candidate for future astronomical searches.

Omecamtiv mecarbil is a selective, small-molecule activator of cardiac myosin that is being developed as a potential treatment for heart failure with reduced ejection fraction. Here we determine the crystal structure of cardiac myosin in the pre-powerstroke state, the most relevant state suggested by kinetic studies, both with (2.45 Å) and without (3.10 Å) omecamtiv mecarbil bound. Omecamtiv mecarbil does not change the motor mechanism nor does it influence myosin structure. Instead, omecamtiv mecarbil binds to an allosteric site that stabilizes the lever arm in a primed position resulting in accumulation of cardiac myosin in the primed state prior to onset of cardiac contraction, thus increasing the number of heads that can bind to the actin filament and undergo a powerstroke once the cardiac cycle starts. The mechanism of action of omecamtiv mecarbil also provides insights into uncovering how force is generated by molecular motors.Omecamtiv mecarbil (OM) is a cardiac myosin activator that is currently in clinical trials for heart failure treatment. Here, the authors give insights into its mode of action and present the crystal structure of OM bound to bovine cardiac myosin, which shows that OM stabilizes the pre-powerstroke state of myosin.

Cadherin linkages between adjacent stereocilia and microvilli are essential for mechanotransduction and maintaining their organization. They are anchored to actin through interaction of their cytoplasmic domains with related tripartite complexes consisting of a class VII myosin and adaptor proteins: Myo7a/SANS/Harmonin in stereocilia and Myo7b/ANKS4B/Harmonin in microvilli. Here, we determine high-resolution structures of Myo7a and Myo7b C-terminal MyTH4-FERM domain (MF2) and unveil how they recognize harmonin using a novel binding mode. Systematic definition of interactions between domains of the tripartite complex elucidates how the complex assembles and prevents possible self-association of harmonin-a. Several Myo7a deafness mutants that map to the surface of MF2 disrupt harmonin binding, revealing the molecular basis for how they impact the formation of the tripartite complex and disrupt mechanotransduction. Our results also suggest how switching between different harmonin isoforms can regulate the formation of networks with Myo7a motors and coordinate force sensing in stereocilia.

A theoretical study of the structure and mid infrared (IR) spectra of interstellar hydrocarbon dust analogs is presented, based on DFT calculations of amorphous solids. The basic molecular structures for these solids are taken from two competing literature models. The first model considers small aromatic units linked by aliphatic chains. The second one assumes a polyaromatic core with hydrogen and methyl substituents at the edges. The calculated spectra are in reasonably good agreement with those of aliphatic-rich and graphitic-rich samples of hydrogenated amorphous carbon (HAC) generated in our laboratory. The theoretical analysis allows the assignment of the main vibrations in the HAC spectra and shows that there is a large degree of mode mixing. The calculated spectra show a marked dependence on the density of the model solids, which evinces the strong influence of the environment on the strengths of the vibrational modes. The present results indicate that the current procedure of estimating the hydrogen and graphitic content of HAC samples through the decomposition of IR features into vibrational modes of individual functional groups is problematic owing to the mentioned mode mixing and to the difficulty of assigning reliable and unique band strengths to the various molecular vibrations. Current band strengths from the literature might overestimate polyaromatic structures. Comparison with astronomical observations suggests that the average structure of carbonaceous dust in the diffuse interstellar medium lies probably in between those of the two models considered, though closer to the more aliphatic structure.

The chloroniumyl cation, HCl + , has been recently identified in space from Herschel 's spectra. A joint analysis of extensive vis-UV spectroscopy emission data together with a few high-resolution and high-accuracy millimiter-wave data provided the necessary rest frequencies to support the astronomical identification. Nevertheless, the analysis did not include any infrared (IR) vibration-rotation data. Furthermore, with the end of the Herschel mission, infrared observations from the ground may be one of the few available means to further study this ion in space. In this work, we provide a set of accurate rovibrational transition wavenumbers as well as a new and improved global fit of vis-UV, IR and millimiter-wave spectroscopy laboratory data, that will aid in future studies of this molecule.

Direct inhibition of smooth muscle myosin (SMM) is a potential means to treat hypercontractile smooth muscle diseases. The selective inhibitor CK-2018571 prevents strong binding to actin and promotes muscle relaxation in vitro and in vivo. The crystal structure of the SMM/drug complex reveals that CK-2018571 binds to a novel allosteric pocket that opens up during the "recovery stroke" transition necessary to reprime the motor. Trapped in an intermediate of this fast transition, SMM is inhibited with high selectivity compared with skeletal muscle myosin (IC 50 = 9 nM and 11,300 nM, respectively), although all of the binding site residues are identical in these motors. This structure provides a starting point from which to design highly specific myosin modulators to treat several human diseases. It further illustrates the potential of targeting transition intermediates of molecular machines to develop exquisitely selective pharmacological agents., Competing Interests: S.C. and X.Q. are former employees and potential shareholders of Cytokinetics, Inc. J.J.H., G.C., P.-P.L., B.P.M., and F.I.M. are current employees and shareholders of Cytokinetics, Inc. E.B., K.R., and C.R. received research support from Cytokinetics, Inc.

The effects of cosmic rays on the carriers of the interstellar 3.4 μm absorption band have been investigated in the laboratory. This band is attributed to stretching vibrations of CH 3 and CH 2 in carbonaceous dust. It is widely observed in the diffuse interstellar medium (ISM), but disappears in dense clouds. Destruction of CH 3 and CH 2 by cosmic rays could become relevant in dense clouds, shielded from the external ultraviolet field. For the simulations, samples of hydrogenated amorphous carbon (a-C:H) have been irradiated with 5 keV electrons. The decay of the band intensity vs electron fluence reflects a-C:H dehydrogenation, which is well described by a model assuming that H 2 molecules, formed by the recombination of H atoms liberated through CH bond breaking, diffuse out of the sample. The CH bond destruction rates derived from the present experiments are in good accordance with those from previous ion irradiation experiments of HAC. The experimental simplicity of electron bombardment has allowed the use of higher energy doses than in the ion experiments. The effects of cosmic rays on the aliphatic components of cosmic dust are found to be small. The estimated cosmic ray destruction times for the 3.4 μm band carriers lie in the 10 8 yr range and cannot account for the disappearance of this band in dense clouds, which have characteristic lifetimes of 3 × 10 7 yr. The results invite a more detailed investigation of the mechanisms of CH bond formation and breaking in the intermediate region between diffuse and dense clouds.

Myosins containing MyTH4-FERM (myosin tail homology 4-band 4.1, ezrin, radixin, moesin, or MF) domains in their tails are found in a wide range of phylogenetically divergent organisms, such as humans and the social amoeba Dictyostelium (Dd). Interestingly, evolutionarily distant MF myosins have similar roles in the extension of actin-filled membrane protrusions such as filopodia and bind to microtubules (MT), suggesting that the core functions of these MF myosins have been highly conserved over evolution. The structures of two DdMyo7 signature MF domains have been determined and comparison with mammalian MF structures reveals that characteristic features of MF domains are conserved. However, across millions of years of evolution conserved class-specific insertions are seen to alter the surfaces and the orientation of subdomains with respect to each other, likely resulting in new sites for binding partners. The MyTH4 domains of Myo10 and DdMyo7 bind to MT with micromolar affinity but, surprisingly, their MT binding sites are on opposite surfaces of the MyTH4 domain. The structural analysis in combination with comparison of diverse MF myosin sequences provides evidence that myosin tail domain features can be maintained without strict conservation of motifs. The results illustrate how tuning of existing features can give rise to new structures while preserving the general properties necessary for myosin tails. Thus, tinkering with the MF domain enables it to serve as a multifunctional platform for cooperative recruitment of various partners, allowing common properties such as autoinhibition of the motor and microtubule binding to arise through convergent evolution.

The dynamics of the D + MuH(v = 1) reaction has been investigated using time-independent quantum mechanical calculations. The total reaction cross sections and rate coefficients have been calculated for the two exit channels of the reaction leading, respectively, to DMu + H and DH + Mu. Over the 100-1000 K temperature range investigated the rate coefficients for the DMu + H channel are of the order of 10(-10) cm(3) s(-1) and those for the DH + Mu channel vary between 1 × 10(-12) and 8 × 10(-11) cm(3) s(-1). These results point to a virtually barrierless reaction for the DMu + H channel and to the presence of a comparatively small barrier for the DH + Mu channel and are consistent with the profiles of their respective collinear vibrationally adiabatic potentials (VAPs). The effective barrier in the VAP of the DH + Mu channel is located in the reactant valley and, consequently, translation is found to be more efficient than vibration for the promotion of the reaction over a large energy interval in the post threshold region. Below this barrier, the DH + Mu channel can be accessible through an indirect mechanism implying crossing from the DMu + H pathway. The most salient feature found in the present study is revealed in the total reaction cross section for the DMu + H channel, which shows a sharp resonance caused by the presence of a deep well in the vibrationally adiabatic potential. This well has a dynamical origin, reminiscent of that found recently in the vibrationally bonded BrMuBr complex [Fleming, et al., Angew. Chem., Int. Ed., 2014, 53, 1], and is due to the stabilizing effect of the light Mu atom oscillating between the heavier H and D isotopes and to the bond softening associated with vibrational excitation of MuH.

We have analyzed the influence of the rotational excitation on the H + D2(v = 0, j) reaction through quantum mechanical (QM) and quasiclassical trajectories (QCT) calculations at a wide range of total energies. The agreement between both types of calculations is excellent. We have found that the rotational excitation largely increases the reactivity at large values of the total energy. Such an increase cannot be attributed to a stereodynamical effect but to the existence of recrossing trajectories that become reactive as the target molecule gets rotationally excited. At low total energies, however, recrossing is not significant and the reactivity evolution is dominated by changes in the collision energy; the reactivity decreases with the collision energy as it shrinks the acceptance cone. When state-to-state results are considered, rotational excitation leads to cold product's rovibrational distributions, so that most of the energy is released as recoil energy.

A theoretical model of hydrogenated amorphous carbon (HAC) is developed and applied to study the interaction of glycine with HAC surfaces at astronomical temperatures. Two models with different H content are tried for the HAC surface. The theory is applied at the Density Functional Theory (DFT) level, including a semiempirical dispersion correlation potential, d-DFT or Grimme DFT-D2. The level of theory is tested on glycine adsorption on a Si(001) surface. Crystalline glycine is also studied in its two stable phases, α and β, and the metastable γ phase. For the adsorption on Si or HAC surfaces, molecular glycine is introduced in the neutral and zwitterionic forms, and the most stable configurations are searched. All theoretical predictions are checked against experimental observations. HAC films are prepared by plasma enhanced vapor deposition at room temperature. Glycine is deposited at 20 K into a high vacuum, cold temperature chamber, to simulate astronomical conditions. Adsorption takes place through the acidic group COO(-) and when several glycine molecules are present, they form H-bond chains among them. Comparison between experiments and predictions suggests that a possible way to improve the theoretical model would require the introduction of aliphatic chains or a polycyclic aromatic core. The lack of previous models to study the interaction of amino-acids with HAC surfaces provides a motivation for this work.

The chemistry of low pressure H 2 + O 2 discharges with different mixture ratios has been studied in a hollow cathode DC reactor. Neutral and positive ion distributions have been measured by mass spectrometry, and Langmuir probes have been used to provide charge densities and electron temperatures. A simple zero order kinetic model including neutral species and positive and negative ions, which takes into account gas-phase and heterogeneous chemistry, has been used to reproduce the global composition of the plasmas over the whole range of mixtures experimentally studied, and allows for the identification of the main physicochemical mechanisms that may explain the experimental results. To our knowledge, no combined experimental and modelling studies of the heavy species kinetics of low pressure H 2 + O 2 plasmas including ions has been reported before. As expected, apart from the precursors, H 2 O is detected in considerable amounts. The model also predicts appreciable concentrations of H and O atoms and the OH radical. The relevance of the metastable species O( 1 D) and O 2 (a 1 Δ g ) is analysed. Concerning the charged species, positive ion distributions are dominated by H 3 O + for a wide range of intermediate mixtures, while H 3 + and O 2 + are the major ions for the higher and lower H 2 /O 2 ratios, respectively. The mixed ions OH + , H 2 O + and HO 2 + are also observed in small amounts. Negative ions are shown to have a limited relevance in the global chemistry; their main contribution is the reduction of the electron density available for electron impact processes.

The recent discovery of ArH + in the interstellar medium has awakened the interest in the chemistry of this ion. In this work, the ion-molecule kinetics of cold plasmas of Ar/H 2 is investigated in glow discharges spanning the whole range of [H 2 ]/([H 2 ]+[Ar]) proportions for two pressures, 1.5 and 8 Pa. Ion concentrations are determined by mass spectrometry, and electron temperatures and densities, with Langmuir probes. A kinetic model is used for the interpretation of the results. The selection of experimental conditions evinces relevant changes with plasma pressure in the ion distributions dependence with the H 2 fraction, particularly for the major ions: Ar + , ArH + and H 3 + . At 1.5 Pa, ArH + prevails for a wide interval of H 2 fractions: 0.3<[H 2 ]/([H 2 ]+[Ar])<0.7. Nevertheless, a pronounced displacement of the ArH + maximum towards the lowest H 2 fractions is observed at 8 Pa, in detriment of Ar + , which becomes restricted to very small [H 2 ]/([H 2 ]+[Ar]) ratios, whereas H 3 + becomes dominant for all [H 2 ]/([H 2 ]+[Ar]) > 0.1. The analysis of the data with the kinetic model allows the identification of the sources and sinks of the major ions over the whole range of experimental conditions sampled. Two key factors turn out to be responsible for the different ion distributions observed: the electron temperature, which determines the rate of Ar + formation and thus of ArH + , and the equilibrium ArH + + H 2 ⇄ H 3 + + Ar, which can be strongly dependent of the degree of vibrational excitation of H 3 + . The results are discussed and compared with previously published data on other Ar/H 2 plasmas.

The symmetric stretching vibration (breathing mode) of methane is forbidden in the infrared spectra of gases. However, it has been observed in the spectra of low-pressure ice mixtures of methane and water, studied as models for astronomical ices. We investigate the possible origin of the activation of this mode by means of solid state calculations of amorphous water (ASW) samples into which methane molecules are introduced. Activation is predicted either by the interaction of the CH4 and H2O molecules in pore walls or via a strong mode coupling that takes place between the breathing mode of CH4 and the O-H stretching mode of H2O when both vibrations coincide in frequency. These two mechanisms would be favored for low-density or high density ASW, respectively. A possible experimental observation of this activation in compact ASW is discussed.

The dynamics of the asymmetric D + MuH (Mu = Muonium) reaction leading to Mu exchange, DMu + H, and H abstraction, DH + Mu, channels has been investigated using time-independent quantum mechanical (QM) calculations. Reaction probabilities, cross sections, cumulative reaction probabilities, and rate coefficients were determined for the two exit channels of the reaction. Quasiclassical trajectory (QCT) calculations were also performed in order to check the reliability of the method for this reaction and to discern the genuine quantum effects. Overall, the Mu exchange channel exhibits more structured reaction probabilities and cross sections with much larger rate coefficients than the H abstraction counterpart. Over the 100-1000 K temperature interval considered in this study, the QM rate coefficients for the Mu exchange vary between ≈5 × 10(-15) and 2 × 10(-11) cm(3) s(-1) and those for the generation of DH + Mu between 2 × 10(-18) and 3.5 × 10(-12) cm(3) s(-1). In common with the rest of the isotopologues of the H + H2 system, the height of the respective barriers in the collinear (symmetric stretch) vibrationally adiabatic potential energy curves matches the classical total energy threshold very accurately. Indeed, the lower and narrower vibrationally adiabatic collinear barrier as compared with that for the DH + Mu formation determines the preponderance of the DMu + H channel. Comparison of QM and QCT results and their analysis show that tunneling accounts for the reactivity at energies below the height of these barriers and that its effect on the rate coefficients becomes appreciable below 300 K. As expected, with growing temperature the contribution of tunneling to the global reactivity decreases markedly, but the rate coefficients are still much higher for the Mu exchange channel due to the effect of MuH rotational excitation that boosts the formation of DMu while diminishing the H abstraction channel that leads to DH formation. The analysis of the thermal cumulative reaction probabilities of the two channels indicates that at the lowest energies/temperatures the reaction into the DH + Mu channel takes place via'leakage' from collisions proceeding along the DMu + H reaction path.

Carbon dioxide and ammonia are two of the most abundant species in astrophysical media, where they can react in the solid phase under certain conditions. This contribution presents a study of this reaction both in the presence of water and for anhydrous samples. It is shown that after deposition at 15 K, the reaction can start by warming the deposit, and the process continues on up to a temperature of 220 K. Reaction products are studied using infrared spectroscopy and mass spectrometry. For anhydrous samples, a 2 : 1 stoichiometry mixture of NH3 : CO2 gives the highest yield of products. The reaction is favored when a small amount of water is present, which enables ammonia and carbon dioxide molecules to collide within the pores and channels of the amorphous water solid. Large concentration of water, on the other hand, hampers such collisions. The main reaction product is found to be ammonium carbamate, but also carbamic acid is formed, and, in the presence of water, ammonium bicarbonate is produced as well. Theoretical calculations are carried out to provide the basis for the assignment of the spectra. Some of the experiments presented in this contribution consist of the generation of a compact water ice matrix where the carbamate and ammonium ions are embedded. If such a system was found in astrophysical media, it is shown that the ammonium ion could not be detected, whereas two infrared features of the carbamate ion in the 1040 to 1115 cm(-1) (9 to 9.6 μm) region could enable the observation of this species.

The effect of UV photon (120-200 nm) and electron (2 keV) irradiation of analogues of interstellar carbonaceous dust and of glycine were investigated by means of IR spectroscopy. Films of hydrogenated amorphous carbon (HAC), taken as dust analogues, were found to be stable under UV photon and electron bombardment. High fluences of photons and electrons, of the order of 10(19) cm(-2), were needed for a film depletion of a few percent. UV photons were energetically more effective than electrons for depletion and led to a certain dehydrogenation of the HAC samples, whereas electrons led seemingly to a gradual erosion with no appreciable changes in the hydrocarbon structure. The rates of change observed may be relevant over the lifetime of a diffuse cloud, but cannot account for the rapid changes in hydrocarbon IR bands during the evolution of some proto-planetary nebulae. Glycine samples under the same photon and electron fluxes decay at a much faster rate, but tend usually to an equilibrium value different from zero, especially at low temperatures. Reversible reactions re-forming glycine, or the build-up of less transparent products, could explain this behavior. CO2 and methylamine were identified as UV photoproducts. Electron irradiation led to a gradual disappearance of the glycine layers, also with formation of CO2. No other reaction products were clearly identified. The thicker glycine layers (a few hundred nm) were not wholly depleted, but a film of the order of the electron penetration depth (80 nm), was totally destroyed with an electron fluence of -1 x 10(18) cm(-2). A 60 nm ice layer on top of glycine provided only partial shielding from the 2 keV electrons. From an energetic point of view, 2 keV electrons are less efficient than UV photons and, according to literature data, much less efficient than MeV protons for the destruction of glycine. The use of keV electrons to simulate effects of cosmic rays on analogues of interstellar grains should be taken with care, due to the low penetration depths of electrons in many samples of interest.

Cyanate and bicarbonate are two ions that play active roles in many fields of physics and chemistry, including biological sciences and astrochemistry. We present here a comprehensive study of these species covering a range of phases and methodologies. We have performed theoretical calculations on the isolated ions and their hydrates with one to four water molecules, and in clusters with 15 water molecules. The predicted infrared spectra are compared with observed spectra from experiments where liquid droplets of their solutions are frozen at 14 K on a substrate, to mimic some astrophysical conditions. Crystals of cyanate and bicarbonate sodium and potassium salts are also studied experimental and theoretically. As well, the spontaneous decomposition of cyanate into bicarbonate is documented from the spectra of an aged solution. Finally, the possible astrophysical observation of bicarbonate in water-containing particles is discussed.

The ion-molecule chemistry of the astronomically relevant H(3)(+), N(2)H(+), and NH(4)(+) ions has been investigated in the weakly ionized cold plasmas formed in glow discharges of H(2) with small amounts of nitrogen. The concentrations of neutrals and ions were determined by means of mass spectrometry, and electron temperatures and densities were measured using Langmuir probes. A kinetic model was used for the interpretation of the results. The selection of experimental conditions allowed the generation of ion distributions with different relative weights of the mentioned protonated species and the model calculations showed that the observed ion distributions can be explained by the occurrence of a very efficient H(3)(+) → N(2)H(+) → NH(4)(+) proton transfer chain. The NH(4)(+) ion, which is dominant in most of the cases studied, is ultimately derived from the small amount of NH(3) produced at the reactor walls. NH(4)(+) tends to be preponderant in the ion distributions even for NH(3) density ratios as low as 1%. Due to the high proton affinity of ammonia, this molecule is readily transformed into NH(4)(+) upon collision with H(3)(+) or N(2)H(+). It is conjectured that these results can be extrapolated to most of the small molecules predominant in the interstellar medium, which also have proton affinities lower than that of NH(3). The results support the predictions of astrochemical models indicating that NH(4)(+) could be a preponderant ion in some warm environments like hot cores, where NH(3) molecules have desorbed from the grains.

Quantum mechanical (QM) and quasiclassical trajectory (QCT) calculations have been carried out for the exchange reactions of D and Mu (Mu = muonium) with hydrogen molecules in their ground and first vibrational states. In all the cases considered, the QM rate coefficients, k(T), are in very good agreement with the available experimental results. In particular, QM calculations on the most accurate potential energy surfaces (PESs) predict a rate coefficient for the Mu + H(2) (ν = 1) reaction which is very close to the preliminary estimate of its experimental value at 300 K. In contrast to the D + H(2) (ν = 0,1) and the Mu + H(2) (ν = 0) reactions, the QCT calculations for Mu + H(2) (ν = 1) predict a much smaller k(T) than that obtained with the accurate QM method. This behaviour is indicative of tunneling. The QM reaction probabilities and total reactive cross sections show that the total energy thresholds for the reactions of Mu with H(2) in ν = 0 and ν = 1 are very similar, whereas for the corresponding reaction with D the ν = 0 total energy threshold is about 0.3 eV lower than that for ν = 1. The results just mentioned can be explained by considering the vibrational adiabatic potentials along the minimum energy path. The threshold for the reaction of Mu with H(2) in both ν = 0 and ν = 1 states is the same and is given by the height of the ground vibrational adiabatic collinear potential, whereas for the D + H(2) reaction the adiabaticity is preserved and the threshold for the reaction in ν = 1 is very close to the height of the ν = 1 adiabatic collinear barrier. For Mu + H(2) (ν = 1) the reaction takes place by crossing from the ν = 1 to the ν = 0 adiabat, since the exit channel leading to MuH (ν = 1) is not energetically accessible. At the lowest possible energies, the non-adiabatic vibrational crossing implies a strong tunneling effect through the ν = 1 adiabatic barrier. Absence of tunneling in the classical calculations results in a threshold that coincides with the height of the ν = 1 adiabatic barrier. Most interestingly, the expected tunneling effect in the reaction of Mu with hydrogen molecules occurs for H(2) (ν = 1) but not for H(2) (ν = 0) where zero-point-energy effects clearly dominate.

An investigation of porosity and isothermal crystallization kinetics of amorphous ice produced either by background water vapour deposition (ASW) or by hyperquenching of liquid droplets (HGW) is presented. These two types of ice are relevant for astronomical ice research (Gálvez et al., Astrophys. J., 2010, 724, 539) and are studied here for the first time under comparable experimental conditions. From CH(4) isothermal adsorption experiments at 40 K, surface areas of 280 ± 30 m(2) g(-1) for the ASW deposits and of 40 ± 12 m(2) g(-1) for comparable HGW samples were obtained. The crystallization kinetics was studied at 150 K by following the evolution of the band shape of the OD stretching vibration in HDO doped ASW and HGW samples generated at 14 K, 40 K and 90 K. Comparable rate constants of ∼7 × 10(-4) s(-1) were obtained in all cases. However a significant difference was found between the n Avrami parameter of the samples generated at 14 K (n∼ 1) and that of the rest (n > 2). This result hints at the possible existence of a structurally different form of amorphous ice for very low generation temperatures, already suggested in previous literature works.