The shape of D-glucosamine

The bioactive amino monosaccharideD-glucosamine has been generated in the gas phasevialaserablation ofD-glucosamine hydrochloride. Three cyclica-4C1pyranose forms have been identified usingFourier transform microwave techniques. Stereoelectronic hyperconjugative forces – essentially linkedwith the anomeric orgaucheeffect – and cooperative OH O, OH N and NH O chains, extendedalong the entire molecule, are found to be the main factors driving the conformational behavior. Theorientation of the NH2group within each conformer has been determined by the values of the nuclearquadrupole coupling constants. The results have been compared with those recently obtained for thearchetypicalD-glucose.Fil: Peña, Isabel. Universidad de Valladolid; EspañaFil: Kolesnikova, Lucie. Universidad de Valladolid; EspañaFil: Cabezas, Carlos. Universidad de Valladolid; EspañaFil: Bermudez, Celina. Universidad de Valladolid; EspañaFil: Berdakin, Matias. Universidad de Valladolid; España. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Simao, Alcides. Universidad de Valladolid; EspañaFil: Alonso, Jose A.. Universidad de Valladolid; Españ

On the use of metallic nanoparticulated catalysts for in-situ oil upgrading

An exhaustive review on the application of different metal-based nanoparticles for the upgrading of heavy oils has been performed. Particular emphasis has been put on those catalysts used for in-situ upgrading using various thermal treatment methods aiming at extracting heavy oils in a more effective manner. Different types of catalysts have been identified, such as monometallic (Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ce, and W), non-supported bimetallic (Ti/Zr), non-supported polymetallic (various mixtures of Co, Mo, Ni, W, Al, Zn, Cu), and supported (various metals on silica, alumina, carbon, zeolite, biogenic particles, complex inorganic and organic). Due to the great diversity of nanoparticulated catalysts (type, metal content, synthesis procedure, particle size) and evaluation conditions (experimental setup, reaction conditions, type of feed), it is not possible to make a direct comparison on their performance. Some results are highlighted on the effectiveness of the catalysts for heavy oil upgrading in terms of asphaltene adsorption, viscosity reduction, increase of API gravity, and coke formation. The reviewed literature indicates the need for more research on this topic as to develop more effective catalysts not only for increasing the recovery factor but also for permanent upgrading of the quality of heavy and extra-heavy oil

On the use of metallic nanoparticulated catalysts for in-situ oil upgrading

An exhaustive review on the application of different metal-based nanoparticles for the upgrading of heavy oils has been performed. Particular emphasis has been put on those catalysts used for in-situ upgrading using various thermal treatment methods aiming at extracting heavy oils in a more effective manner. Different types of catalysts have been identified, such as monometallic (Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ce, and W), non-supported bimetallic (Ti/Zr), non-supported polymetallic (various mixtures of Co, Mo, Ni, W, Al, Zn, Cu), and supported (various metals on silica, alumina, carbon, zeolite, biogenic particles, complex inorganic and organic). Due to the great diversity of nanoparticulated catalysts (type, metal content, synthesis procedure, particle size) and evaluation conditions (experimental setup, reaction conditions, type of feed), it is not possible to make a direct comparison on their performance. Some results are highlighted on the effectiveness of the catalysts for heavy oil upgrading in terms of asphaltene adsorption, viscosity reduction, increase of API gravity, and coke formation. The reviewed literature indicates the need for more research on this topic as to develop more effective catalysts not only for increasing the recovery factor but also for permanent upgrading of the quality of heavy and extra-heavy oil.The work is carried out under the support of the Russian Science Foundation related to the Project N◦ 21-73-30023 dated 17.03.20

X-ray induced coulomb explosion imaging of transient excited-state structural rearrangements in CS₂

Structural imaging of transient excited-state species is a key goal of molecular physics, promising to unveil rich information about the dynamics underpinning photochemical transformations. However, separating the electronic and nuclear contributions to the spectroscopic observables is challenging, and typically requires the application of high-level theory. Here, we employ site-selective ionisation via ultrashort soft X-ray pulses and time-resolved Coulomb explosion imaging to interrogate structural dynamics of the ultraviolet photochemistry of carbon disulfide. This prototypical system exhibits the complex motifs of polyatomic photochemistry, including strong non-adiabatic couplings, vibrational mode couplings, and intersystem crossing. Immediately following photoexcitation, we observe Coulomb explosion signatures of highly bent and stretched excited-state geometries involved in the photodissociation. Aided by a model to interpret such changes, we build a comprehensive picture of the photoinduced nuclear dynamics that follows initial bending and stretching motions, as the reaction proceeds towards photodissociation

X-ray induced Coulomb explosion imaging of transient excited-state structural rearrangements in CS2_2

Structural imaging of transient excited-state species is a key goal of molecular physics, promising to unveil rich information about the dynamics underpinning photochemical transformations. However, separating the electronic and nuclear contributions to the spectroscopic observables is challenging, and typically requires the application of high-level theory. Here, we employ site-selective ionisation via ultrashort soft X-ray pulses and time-resolved Coulomb explosion imaging to interrogate structural dynamics of the ultraviolet photochemistry of carbon disulfide. This prototypical system exhibits the complex motifs of polyatomic photochemistry, including strong non-adiabatic couplings, vibrational mode couplings, and intersystem crossing. Immediately following photoexcitation, we observe Coulomb explosion signatures of highly bent and stretched excited-state geometries involved in the photodissociation. Aided by a model to interpret such changes, we build a comprehensive picture of the photoinduced nuclear dynamics that follows initial bending and stretching motions, as the reaction proceeds towards photodissociation

Time-Resolved X-ray Photoelectron Spectroscopy: Ultrafast Dynamics in CS2_2 Probed at the S 2p Edge

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS2, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on ab initio multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels

Ultrafast dynamics of fluorene initiated by highly intense laser fields

We present an investigation of the ultrafast dynamics of the polycyclic aromatic hydrocarbon fluorene initiated by an intense femtosecond near-infrared laser pulse (810 nm) and probed by a weak visible pulse (405 nm). Using a multichannel detection scheme (mass spectra, electron and ion velocity-map imaging), we provide a full disentanglement of the complex dynamics of the vibronically excited parent molecule, its excited ionic states, and fragments. We observed various channels resulting from the strong-field ionization regime. In particular, we observed the formation of the unstable tetracation of fluorene, above-threshold ionization features in the photoelectron spectra, and evidence of ubiquitous secondary fragmentation. We produced a global fit of all observed time-dependent photoelectron and photoion channels. This global fit includes four parent ions extracted from the mass spectra, 15 kinetic-energy-resolved ionic fragments extracted from ion velocity map imaging, and five photoelectron channels obtained from electron velocity map imaging. The fit allowed for the extraction of 60 lifetimes of various metastable photoinduced intermediates