Vibrational Excitons in CH-Stretching Fundamental and Overtone Vibrational Circular Dichroism Spectra

A set of vibrational circular dichroism (VCD) spectra in the CH-stretching fundamental region for about twenty compounds belonging to the class of essential oils was empirically analyzed by the use of a sort of vibrational exciton mechanism, involving three centers. Through a general formula applicable to many coupled dipole oscillators, the rotational strengths of the previously identified vibrational excitons are evaluated. The results are then critically reviewed by the use of recent ab initio methodology, as applied to selected molecules of the original set. Further insight is gained by model calculations adding up the contribution of the coupling between electric dipole moments associated with normal mode behavior and that of the polarizability from polarizable groups. The former part is responsible for the excitonic behavior of the VCD spectra. For the same selected molecules we have also investigated whether some excitonic behavior is taking place in the second overtone region, and have concluded that this is not the case

Li-decorated BC3 nanopores: Promising materials for hydrogen storage

In the quest of new absorbent for hydrogen storage, we investigate the capacities of slit pores formed by two BC3 sheets decorated with Li atoms. Their hydrogen storage capacities are determined using density-functional theory in conjunction with a quantum-thermodynamic model that allows to simulate real operating conditions, i.e., finite temperatures and different loading and depletion pressures applied to the adsorbent in the charge-delivery cycles. We show that the capacities of the adsorbed hydrogen phase of Li-decorated BC3 slit pores are larger than those reported recently for graphene and Li-decorated borophene slit pores. On the other hand, the usable volumetric and gravimetric capacities of Li-decorated BC3 slit pores can meet the targets stipulated by the U.S. Department of Energy (DOE) for onboard hydrogen storage at moderate temperatures and loading pressures well below those used in the tanks employed in current technology. In particular, the usable volumetric capacity for pore widths of about 10 {\AA} meets the DOE target at a loading pressure of 6.6 MPa when depleting at ambient pressure. Our results highlight the important role played by the rotational degree of freedom of the H2 molecule in determining the confining potential within the slip pores and their hydrogen storage capacities.Comment: Article itself: 26 pages, 12 figures, 13 equations, 1 table, 78 cited articles; Supporting information: 8 pages, 6 figures, 6 equation

Why did Swiss citizens vote to ban tobacco advertising?

In February 2022, Swiss citizens agreed to modify the Swiss Constitution to ban tobacco advertising reaching children and adolescents. This case study analyses the arguments used by both opponents and supporters of the constitutional amendment. Opponents argued that the proposed regulation went too far, threatened the economy, restricted personal freedom, was superfluous as the current law already protected youth and that it opened the door to marketing bans of other harmful products. Proponents focused on youth protection and invoked the burden of smoking on public health and the fact that advertising bans are an effective evidence-based measure. A comparison with previous campaigns to ban tobacco advertising that had failed suggests factors accounting for the positive vote in 2022. These include the strategic framing of youth protection, the separation of tobacco from other issues (such as alcohol advertising), the deteriorating image of the tobacco industry and the ability of the proponents to mobilise a broad coalition of health and youth organisations, with improved funding and communication. The lessons may be instructive for other campaigns seeking to regulate commercial determinants of health

Prenatal Diagnosis of Gómez-López-Hernández Syndrome.

Gómez-López-Hernández syndrome (GLHS), also known as cerebello-trigeminal-dermal dysplasia, is an extremely rare neurocutaneous disease, classically described by the triad of rhombencephalosynapsis (RES), bilateral focal alopecia, and trigeminal anesthesia. The clinical and radiographic spectrum of GLHS is now known to be broader, including craniofacial and supratentorial anomalies, as well as neurodevelopmental issues. Here, we present a case of antenatally diagnosed GLHS with RES, hydrocephaly, and craniofacial anomalies identified on ultrasound (low-set ears with posterior rotation, hypertelorism, midface hypoplasia, micrognathia, and anteverted nares) which were confirmed by autopsy after termination of pregnancy at 23 weeks of gestation. As no known genetic causes have been identified and the classical triad is not applicable to prenatal imaging, prenatal diagnosis of GLHS is based on neuroimaging and the identification of supporting features. In presence of an RES associated with craniofacial abnormalities in prenatal (brachycephaly, turricephaly, low-set ears, midface retrusion, micrognathia), GLHS should be considered as "possible" according to postnatal criteria

Maxwell homogenization scheme for piezoelectric composites with arbitrarily-oriented spheroidal inhomogeneities

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General Non-equilibrium Theory of Colloid Dynamics

A non-equilibrium extension of Onsager's canonical theory of thermal fluctuations is employed to derive a self-consistent theory for the description of the statistical properties of the instantaneous local concentration profile n(r,t) of a colloidal liquid in terms of the coupled time evolution equations of its mean value n(r,t) and of the covariance {\sigma}(r,r';t) \equiv of its fluctuations {\delta}n(r, t) = n(r, t) - n(r, t). These two coarse-grained equations involve a local mobility function b(r, t) which, in its turn, is written in terms of the memory function of the two-time correlation function C(r, r' ; t, t') \equiv <{\delta}n(r, t){\delta}n(r',t')>. For given effective interactions between colloidal particles and applied external fields, the resulting self-consistent theory is aimed at describing the evolution of a strongly correlated colloidal liquid from an initial state with arbitrary mean and covariance n^0(r) and {\sigma}^0(r,r') towards its equilibrium state characterized by the equilibrium local concentration profile n^(eq)(r) and equilibrium covariance {\sigma}^(eq)(r,r'). This theory also provides a general theoretical framework to describe irreversible processes associated with dynamic arrest transitions, such as aging, and the effects of spatial heterogeneities

Molecular dynamics simulation of aqueous solutions of 26-unit segments of p(NIPAAm) and of p(NIPAAm) "doped" with amino acid based comonomers

We have performed 75-ns molecular dynamics (MD) simulations of aqueous solutions of a 26-unit NIPAAm oligomer at two temperatures, 302 and 315 K, below and above the experimentally determined lower critical solution temperature (LCST) of p(NIPAAm). We have been able to show that at 315 K the oligomer assumes a compact form, while it keeps a more extended form at 302 K. A similar behavior has been demonstrated for a similar NIPAAm oligomer, where two units had been substituted by methacryloyl-l-valine (MAVA) comonomers, one of them being charged and one neutral. For another analogous oligomer, where the same units had been substituted by methacryloyl-l-leucine (MALEU) comonomers, no transition from the extended to the more compact conformation has been found within the same simulation time. Statistical analysis of the trajectories indicates that this transition is related to the dynamics of the oligomer backbone, and to the formation of intramolecular hydrogen bonds and water-bridges between distant units of the solute. In the MAVA case, we have also evidenced an important role of the neutral MAVA comonomer in stabilizing the compact coiled structure. In the MALEU case, the corresponding comonomer is not equally efficacious and, possibly, is even hindering the readjustment of the oligomer backbone. Finally the self-diffusion coefficient of water molecules surrounding the oligomers at the two temperatures for selected relevant times is observed to characteristically depend on the distance from the solute molecules

The Intestinal Microbiota Contributes to the Ability of Helminths to Modulate Allergic Inflammation

We thank Manuel Kulagin for technical help, Pierre Bonnaventure for portal vein blood sampling, Francisco Sepulveda for technical assistance in GS-MS acquisition, and Dorothee Hahne (Metabolomics Australia, University of Western Australia) for human samples SCFA isolation, acquisition, and analysis. We also thank Cristina Cartoni (Phenotyping Unit, EPFL) for Milliplex analysis, Jessica Dessimoz and her team from the Histology Core Facility (EPFL), Miguel Garcia and his team from the Flow Cytometry Core Facility (EPFL), and staff from the EPFL CPG animal house for excellent animal care. The computations were partially performed at the Vital-IT Center for high-performance computing of the SIB Swiss Institute of Bioinformatics (http://www.vital-it.ch). The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP/2007-2013) / ERC Grant Agreement n. 310948. Funding for A.W.W. and a subset of the 16S rRNA gene sequencing was provided by the Wellcome Trust (grant number WT 098051). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.Peer reviewedPublisher PD

Thermodynamic Field Theory with the Iso-Entropic Formalism

A new formulation of the thermodynamic field theory (TFT) is presented. In this new version, one of the basic restriction in the old theory, namely a closed-form solution for the thermodynamic field strength, has been removed. In addition, the general covariance principle is replaced by Prigogine's thermodynamic covariance principle (TCP). The introduction of TCP required the application of an appropriate mathematical formalism, which has been referred to as the iso-entropic formalism. The validity of the Glansdorff-Prigogine Universal Criterion of Evolution, via geometrical arguments, is proven. A new set of thermodynamic field equations, able to determine the nonlinear corrections to the linear ("Onsager") transport coefficients, is also derived. The geometry of the thermodynamic space is non-Riemannian tending to be Riemannian for hight values of the entropy production. In this limit, we obtain again the same thermodynamic field equations found by the old theory. Applications of the theory, such as transport in magnetically confined plasmas, materials submitted to temperature and electric potential gradients or to unimolecular triangular chemical reactions can be found at references cited herein.Comment: 35 page

Statistical properties of fracture precursors

We present the data of a mode-I fracture experiment. The samples are broken under imposed pressure. The acoustic emission of microfractures before the breakup of the sample is registered. From the acoustic signals, the position of microfractures and the energy released are calculated. A measure of the clustering of microfractures yields information about the critical load. The statistics from energy measurements strongly suggest that the fracture can be viewed as a critical phenomenon; energy events are distributed in magnitude as a power law, and a critical exponent is found for the energy near fracture