All experts involved in the development of these guidelines have submitted declarations of interest. These have been compiled in a report and published in a supplementary document simultaneously to the guidelines. The report is also available on the ESC website www.escardio.org/Guidelines See the European Heart Journal online for supplementary data that includes background information and detailed discussion of the data that have provided the basis of the guidelines.Click here to access the corresponding ESC CardioMed chapters.
Polymerization processes are probably the most relevant example of a chemical reaction activated by catalysts or radical initiators. Among polymers, polyethylene is by far the most common and largely produced. Here we present a high-pressure synthesis of high-density crystalline polyethylene by using only physical tools such as pressure and light. Low-density polyethylene is obtained by compressing ethylene at room temperature above 3 GPa in the ordered crystal phase, and a highly crystalline polymer is produced in the fluid phase at pressures lower than 1 GPa by using continuous-wave laser lines (lambda < or = 460 nm) as an optical catalyst. The photo-activation is based on a two-photon absorption process to pi* antibonding states, where the change in molecular geometry favours the polymeric chain formation. The high yield and crystallinity of the polymer recovered by the photoinduced reaction and the simplicity of the synthesis make this process appealing for large-scale applications.
Among the group IV elements, only carbon forms stable double bonds with oxygen at ambient conditions. At variance with silica and germania, the non-molecular single-bonded crystalline form of carbon dioxide, phase V, only exists at high pressure. The amorphous forms of silica (a-SiO2) and germania (a-GeO2) are well known at ambient conditions; however, the amorphous, non-molecular form of CO2 has so far been described only as a result of first-principles simulations. Here we report the synthesis of an amorphous, silica-like form of carbon dioxide, a-CO2, which we call 'a-carbonia'. The compression of the molecular phase III of CO2 between 40 and 48 GPa at room temperature initiated the transformation to the non-molecular amorphous phase. Infrared spectra measured at temperatures up to 680 K show the progressive formation of C-O single bonds and the simultaneous disappearance of all molecular signatures. Furthermore, state-of-the-art Raman and synchrotron X-ray diffraction measurements on temperature-quenched samples confirm the amorphous character of the material. Comparison with vibrational and diffraction data for a-SiO2 and a-GeO2, as well as with the structure factor calculated for the a-CO2 sample obtained by first-principles molecular dynamics, shows that a-CO2 is structurally homologous to the other group IV dioxide glasses. We therefore conclude that the class of archetypal network-forming disordered systems, including a-SiO2, a-GeO2 and water, must be extended to include a-CO2.
The pressure-induced chemical reaction of liquid butadiene was studied by Fourier transform infrared spectroscopy in a diamond anvil cell. Dimerization was found to occur above 0.7 gigapascal, giving vinylcyclohexene according to a cyclo-addiction reaction and only a trace amount of polybutadiene forms. By irradiating the high-pressure sample with a few milliwatts of the 488-nanometer argon+ laser line, the dimerization was completely inhibited, and the rapid formation of pure trans-polybutadiene was observed. The use of different excitation wavelength allows us to emphasize the selectivity of the process and to identify the active role of the 2(1)Ag state in this pressure- and laser-induced chemical reaction.
The polymerization of solid acetylene under pressure has been studied by Fourier transform infrared (FTIR) spectroscopy. Controlled laser irradiation cycles and the employment of infrared sensors to measure the sample pressure, allowed to separate the photochemical and the pressure effect on the injection and on the evolution of the reaction. The careful assignment of all the spectral features and analysis of their relative intensities and frequencies gave evidence to the specific effect of pressure and laser irradiation on the reaction products. Pressure induces an ordered growth of trans-polyenic species, while irradiation produces the opening of the double bonds and a consequent branching of the chains. Constant pressure measurements allowed to obtain precise information on the kinetics of the reaction. A monodimensional growth geometry, involving the molecules on the bc plane, agrees with the parameters extracted by the kinetic curves. Comparison between experiments at different temperatures suggests an activation of the reaction essentially due to the translational lattice modes.
Liquid water has a primary role in ruling life on Earth in a wide temperature and pressure range as well as a plethora of chemical, physical, geological, and environmental processes. Nevertheless, a full understanding of its dynamical and structural properties is still lacking. Water molecules are associated through hydrogen bonds, with the resulting extended network characterized by a local tetrahedral arrangement. Two different local structures of the liquid, called low-density (LDW) and high-density (HDW) water, have been identified to potentially affect many different chemical, biological, and physical processes. By combining diamond anvil cell technology, ultrafast pump-probe infrared spectroscopy, and classical molecular dynamics simulations, we show that the liquid structure and orientational dynamics are intimately connected, identifying the P-T range of the LDW and HDW regimes. The latter are defined in terms of the speeding up of the orientational dynamics, caused by the increasing probability of breaking and reforming the hydrogen bonds.
One-dimensional diamondoid polyaniline-like nanothreads combine the outstanding mechanical properties of carbon nanotubes with the versatility of NH2 groups.
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