Development and Validation of a Parameter-Free Model Chemistry for the Computation of Reliable Reaction Rates

A recently developed model chemistry (jun-Cheap) has been slightly modified and proposed as an effective, reliable, and parameter-free scheme for the computation of accurate reaction rates with special reference to astrochemical and atmospheric processes. Benchmarks with different sets of state-of-the-art energy barriers spanning a wide range of values show that, in the absence of strong multireference contributions, the proposed model outperforms the most well-known model chemistries, reaching a subchemical accuracy without any empirical parameter and with affordable computer times. Some test cases show that geometries, energy barriers, zero point energies, and thermal contributions computed at this level can be used in the framework of the master equation approach based on the ab initio transition-state theory for obtaining accurate reaction rates.A recently developed model chemistry (jun-Cheap) has been slightly modified and proposed as an effective, reliable, and parameter-free scheme for the computation of accurate reaction rates with special reference to astrochemical and atmospheric processes. Benchmarks with different sets of state-of-the-art energy barriers spanning a wide range of values show that, in the absence of strong multireference contributions, the proposed model outperforms the most well-known model chemistries, reaching a subchemical accuracy without any empirical parameter and with affordable computer times. Some test cases show that geometries, energy barriers, zero point energies, and thermal contributions computed at this level can be used in the framework of the master equation approach based on the ab initio transition-state theory for obtaining accurate reaction rates

Gliding on Ice in search of accurate and cost-effective computational methods for Astrochemistry on Grains: the puzzling case of the HCN isomerization

The isomerization of hydrogen cyanide to hydrogen isocyanide on icy grain surfaces is investigated by an accurate composite method (jun-Cheap) rooted in the coupled cluster ansatz and by density functional approaches. After benchmarking density functional predictions of both geometries and reaction energies against jun-Cheap results for the relatively small model system HCN···(H2O)2, the best performing DFT methods are selected. A large cluster containing 20 water molecules is then employed within a QM/QM′ approach to include a realistic environment mimicking the surface of icy grains. Our results indicate that four water molecules are directly involved in a proton relay mechanism, which strongly reduces the activation energy with respect to the direct hydrogen transfer occurring in the isolated molecule. Further extension of the size of the cluster up to 192 water molecules in the framework of a three-layer QM/QM′/MM model has a negligible effect on the energy barrier ruling the isomerization. Computation of reaction rates by the transition state theory indicates that on icy surfaces, the isomerization of HNC to HCN could occur quite easily even at low temperatures thanks to the reduced activation energy that can be effectively overcome by tunneling

Virtual Reality bridge between Chemistry and Cultural Heritage: the "Sala degli Stemmi" Case Study

In this contribution, we present a multiscale and multidisciplinary VR architecture that aims at creating a common environment where cultural heritage and chemistry meet in order to strengthen the role already played by chemistry in the process of restoration of cultural goods. Our aim is to create a user friendly platform where experts of both fields can share data and ideas in a direct way, in order to achieve deeper insights into cultural goods combining the scientific and historical points of view. As a case study we present the 3D reconstruction of the "Sala degli Stemmi", which is one of the two historical rooms at Palazzo della Carovana in Pisa, presenting a number of artworks that underwent a process of chemical analysis and restoration in 2012. The whole architecture has been developed using the Unity game engine, and it is usable with HTC Vive headsets. The implementation of the VR environment and the potential applications, from both the scientific and educational points of view, are discussed in some detail

Tgfbi/Bigh3 silencing activates ERK in mouse retina.

BIGH3 is a secreted protein, part of the extracellular matrix where it interacts with collagen and integrins on the cell surface. BIGH3 can play opposing roles in cancer, acting as either tumor suppressor or promoter, and its mutations lead to different forms of corneal dystrophy. Although many studies have been carried out, little is known about the physiological role of BIGH3. Using the cre-loxP system, we generated a mouse model with disruption of the Bigh3 genomic locus. Bigh3 silencing did not result in any apparent phenotype modifications, the mice remained viable and fertile. We were able to determine the presence of BIGH3 in the retinal pigment epithelium (RPE). In the absence of BIGH3, a transient decrease in the apoptotic process involved in retina maturation was observed, leading to a transient increase in the INL thickness at P15. This phenomenon was accompanied by an increased activity of the pro-survival ERK pathway

Rotating Black Holes in Higher Dimensions with a Cosmological Constant

We present the metric for a rotating black hole with a cosmological constant and with arbitrary angular momenta in all higher dimensions. The metric is given in both Kerr-Schild and Boyer-Lindquist form. In the Euclidean-signature case, we also obtain smooth compact Einstein spaces on associated S^{D-2} bundles over S^2, infinitely many for each odd D\ge 5. Applications to string theory and M-theory are indicated.Comment: 8 pages, Latex. Short version, with more compact notation, of hep-th/0404008. To appear in Phys. Rev. Let

A twist on the reaction of the CN radical with methylamine in the interstellar medium: new hints from a state-of-the-art quantum-chemical study

Despite the fact that the majority of current models assume that interstellar complex organic molecules (iCOMs) are formed on dust-grain surfaces, there is some evidence that neutral gas-phase reactions play an important role. In this paper, we investigate the reaction occurring in the gas phase between methylamine (CH$_3$NH$_2$) and the cyano (CN) radical, for which only fragmentary and/or inaccurate results have been reported to date. This case study allows us to point out the pivotal importance of employing quantum-chemical calculations at the state of the art. Since the two major products of the CH$_3$NH$_2$ + CN reaction, namely the CH$_3$NH and CH$_2$NH$_2$ radicals, have not been spectroscopically characterized yet, some effort has been made for filling this gap.Comment: 14 pages, 6 figures, MNRAS in pres

Characterizing the cosmological gravitational wave background: Anisotropies and non-Gaussianity

A future detection of the stochastic gravitational wave background (SGWB) with gravitational wave (GW) experiments is expected to open a new window on early universe cosmology and on the astrophysics of compact objects. In this paper we study SGWB anisotropies, that can offer new tools to discriminate between different sources of GWs. In particular, the cosmological SGWB inherits its anisotropies both (i) at its production and (ii) during its propagation through our perturbed universe. Concerning (i), we show that it typically leads to anisotropies with order one dependence on frequency. We then compute the effect of (ii) through a Boltzmann approach, including contributions of both large-scale scalar and tensor linearized perturbations. We also compute for the first time the three-point function of the SGWB energy density, which can allow one to extract information on GW non-Gaussianity with interferometers. Finally, we include nonlinear effects associated with long wavelength scalar fluctuations, and compute the squeezed limit of the 3-point function for the SGWB density contrast. Such limit satisfies a consistency relation, conceptually similar to that found in the literature for the case of cosmic microwave background perturbations

Anisotropies and non-Gaussianity of the cosmological gravitational wave background

The stochastic gravitational wave background (SGWB) is expected to be a key observable for gravitational wave (GW) interferometry. Its detection will open a new window to early Universe cosmology and to the astrophysics of compact objects. Using a Boltzmann approach, we study the angular anisotropies of the GW energy density, which is an important tool to disentangle the different cosmological and astrophysical contributions to the SGWB. Anisotropies in the cosmological background are imprinted both at its production and by GW propagation through the large-scale scalar and tensor perturbations of the Universe. The first contribution is not present in the cosmic microwave background radiation (as the Universe is not transparent to photons before recombination), causing an order 1 dependence of the anisotropies on frequency. Moreover, we provide a new method to characterize the cosmological SGWB through its possible deviation from Gaussian statistics. In particular, the SGWB will become a new probe of the primordial non-Gaussianity of the large-scale cosmological perturbations

Gastric aspiration, epithelial injury and chronic lung allograft rejection

Introduction For patients with a variety of end stage lung diseases, lung transplantation has become an effective therapy. Chronic allograft rejection occurs in over 50% of patients 5 years post transplantation however. Although alloimmune-mediated injury directed against endothelial and epithelial structures were traditionally thought to be the major culprit, non-alloimmunologic inflammation after bile acid aspiration has been implicated in cystic fibrosis (CF) lung injury, after transplantation. Hypothesis Reflux with aspiration of bile acid is present in the lower airways of people with cystic fibrosis associated lung injury before and after transplantation. Bile acid challenge would cause cytoxicity and release of inflammatory mediators from patient derived primary epithelial cells (PBECs), before and after transplantation. Methods PBECs from lung transplantation patients, explanted CF patient cultures and a goblet cell line were used to perform proof of concept experiments. In these experiments the effect of individual primary and secondary bile acids, porcine pepsin, different patient derived gastric juices (whole or filtered and dialysed) samples and an artificial bile acid mixture were evaluated. Cell death, Interleukin 8 (IL-8), Interleukin 6 (IL-6) and Granulocyte Macrophage Colony Stumulating Factor (GMCSF) production were measured by Titer blue and multiplex ELISA. Results Epithelial cells can be cultured successfully from the bronchial brushings of lung transplant recipient, CF patient explanted lungs and a Goblet cell line. In work connected with this study my research group has demonstrated that the lungs of people with advanced CF lung disease removed at the time of transplantation contained significant levels of bile acids higher than expected based on normal serum levels. I therefore tested the effects of bile acids on PBECs from lung transplant and CF patients. Challengesof ≥10mol/l was associated with significant cell death. Potentially physiological challenges with 1, 5 and 10 mol/l bile acids led to a significant release of pro-neutrophilic cytokines from lung transplant PBECs and CF PBECs .The goblet cell line HT-29 MTX was resistant to bile acids. Conclusion Aspiration of bile acids in CF lungs before and after transplantation may cause cell damage and inflammation. This injury may benefit from medical and surgical treatments for reflux, which may benefit the lung allograft generally.EThOS - Electronic Theses Online ServiceGBUnited Kingdo