Rosslutz1685

Secondly, we characterize in detail the normal modes of vibration of the reactants. In the VSC experiments, reaction rates were modified only when specific vibrations of the reactants were coupled to a cavity mode. We find that these vibrations are highly mixed among the different fragments of the reactants leading to a completely new assignment of the IR peaks coupled to cavity modes in the original experimental works. Our results are fundamental for the interpretation of the VSC experiments given that in the absence of a theory explaining these results, the current phenomenological understanding relies on the assignment of the character of the vibrational IR peaks.The homoleptic homodinuclear nickel carbonyl anions Ni2(CO)n- (n = 4-6) are mass-selected in the gas phase and examined with anion photoelectron velocity-map imaging spectroscopy combined with density functional calculations. The doubly carbonyl-bridged structures are found to be favorable for Ni2(CO)n- (n = 4-6). The nature of Ni-Ni bonding in these complexes is analysed with the aid of a range of state-of-the-art quantum chemistry methods. Despite the absence of direct multiple Ni-Ni bonds, the two nickel atoms in Ni2(CO)n- (n = 4-6) complexes are joined by two bridging carbonyl ligands via the sharing three-center two-electron Ni-C-Ni bond in turn to achieve the (16,16), (16,18), and eventually the favored (18,18) configurations.The low surface area, poor electrical conductivity, and rapid electron-hole recombination in bulk C3N4 limit its photocatalytic activity, which makes it challenging to improve the performance of bulk C3N4. Herein, an effective strategy is proposed to fabricate Co3O4/C3N4 heterojunctions (Co3O4 nanoparticles grown on C3N4 nanosheets), where bulk C3N4 is exfoliated to thin nanosheets. The bulk C3N4 precursor was synthesized with the hydrothermal treatment of melamine solution, and Co2+ ions were then inserted into the interlayer of the precursor through a vacuum-assisted intercalation process. Subsequently, the precursor was exfoliated to C3N4 nanosheets, and 15 nm Co3O4 nanoparticles were simultaneously formed using in situ thermal polycondensation. Sardomozide mouse The Brunauer-Emmett-Teller (BET) specific surface area of the prepared heterojunction was 21 times higher than that of bulk C3N4, and thus more active sites were exposed on the surface of the heterostructure. Co3O4 nanoparticles contained oxygen vacancies, and the type-II transfer mechanism between these nanoparticles and C3N4 could be used to effectively separate photogenic carriers and improve the electron mobility. As expected, the heterostructure exhibited an excellent photocatalyzed degradation rate of 99.5% for methylene blue within 30 min (10 mg catalyst, wavelength >420 nm) under visible light irradiation, which was nearly three times higher than that of bulk C3N4. Electron paramagnetic resonance (EPR) analysis indicated that ˙O2- was the main reactive oxidizing species during the degradation process.Hydrazine is a well-known genotoxic impurity which may be present in some important drugs, such as isoniazid and hydralazine. It may be ingested along with the drug or generated as a metabolite in the human body. Hence, monitoring the level of hydrazine in the human body is of great importance. A hemicyanine-based NIR fluorescent probe, Hcy-DB, was designed and synthesized for hydrazine detection. This probe exhibited a dramatic off-on NIR fluorescence response toward hydrazine in PBS-DMSO buffer and the detection limit was calculated to be 4.38 ppb. The bioimaging of hydrazine in living H1975 cells was successfully demonstrated. Moreover, the real time imaging of hydrazine, either injected as a foreign agent or generated as a metabolite of isoniazid, was demonstrated in mice and the results clearly disclosed the hydrazine level variation in the liver and kidneys. The injected exogenous hydrazine was mainly distributed in the kidneys and then excreted slowly. After the intragastric administration of isoniazid, hydrazine was quickly generated as a metabolite in the liver and reached a maximum in about 20 min, and then it was excreted slowly through the kidneys. Generally, the investigation provided a promising tool to monitor the level of hydrazine in vivo and thus help to evaluate and control its toxicity more rationally.Compared with the highly active anatase TiO2, rutile TiO2 usually presents poor photocatalytic performance due to high electron-hole recombination. Herein, we propose a surface domain heterojunction (SDH) structure between adjacent micro-domains with and without chemisorbed chlorine on rutile TiO2, which utilizes the potential difference between these domains to form a built-in field that promotes charge separation. Single-crystal rutile TiO2 nanorods assembled into radial microspheres with SDHs were fabricated, and these exhibited excellent solar-driven photocatalytic hydrogen evolution, ∼8-fold higher than that of the pristine one. Experimental results and density functional theory calculations reveal that the exceptional photocatalytic performance can be attributed to the in situ formation of chemisorbed chlorine, which forms SDHs that separate electrons and holes efficiently and results in surface reconfiguration, exposing the tri-active sites, increasing the O-site active centers and enhancing the catalytic activity of the 4-coordinated (Ti4c) and 5-coordinated Ti sites (Ti5c). This SDH strategy can extend to other halogen elements and thus provides an universal approach for the rational design of high-efficiency TiO2 photocatalysts toward sustainable solar-fuel evolution.The far infrared spectra of three deuterated isotopologues of ethylene glycol, CH2OD-CH2OD, CH2OD-CH2OH and CH2OH-CH2OD, where the latter two species differ in their intramolecular hydrogen-bonding arrangement, are studied using highly correlated ab initio methods, vibrational second order perturbation theory and a variational procedure of reduced dimensionality. New subroutines suitable for the study of large systems with more than two interacting large amplitude motions were implemented and applied. The molecular symmetry of ethylene glycol decays by the formation of weak intramolecular bonds producing very asymmetrical stable structures. Three internal rotations contribute to the formation of a very anisotropic potential energy surface and to the puzzling distribution of the rovibrational energy levels. The ground vibrational state rotational constants and the centrifugal distortion constants (S-reduction, Ir representation) corresponding to the aGg' (G1) and gGg' (G2) forms are provided for the studied isotopologues.