Experimental and theoretical study of resonant core-hole spectroscopies of gas-phase free-base phthalocyanine

We studied N 1s−1 inner-shell processes of the free base Phthalocyanine molecule, H2Pc, in the gas-phase. This complex organic molecule contains three different nitrogen sites defined by their covalent bonds. We identify the contribution of each site in ionized, core–shell excited or relaxed electronic states by the use of different theoretical methods. In particular, we present resonant Auger spectra along with a tentative new theoretical approach based on multiconfiguration self-consistent field calculations to simulate them. These calculations may pave the road towards resonant Auger spectroscopy in complex molecules

Unveiled optical properties of tetrapyrollic pigments in cryogenic environments

An unexpected phenomenon was revealed in the laser induced fluorescence spectra of free-base (H₂Pc) and zinc (ZnPc) phthalocyanines trapped in rare gas and nitrogen matrices under a moderate increase in the laser intensity. In all matrices the intensity of an emission band near 755 nm increased drastically when pumping the S₁←S₀ transition. This observation was assigned to stimulated emission in a four-level scheme involving a vibronic transition from the lowest electronic state to a vibrational level of the ground state. In the present work, we expose new similar results obtained with porphyrin molecules, i.e. tetra-benzoporphin (TBP). With free-base H₂TBP, stimulated emission was observed in Ar or N₂ matrices, but not in Xe matrices. A possible reason could be a fast inter-system crossing rate due to the heavy atom effect induced by Xe. We also report the observation of persistent burnt spectral holes, although the low efficiency of this process is not competitive with stimulated emission and no decrease of the stimulated emission with time was observed. With ZnTBP, no stimulated emission could be recorded; however the appearance of rather strong phosphorescence was noticed. Similar studies focusing on the stimulated emission phenomenon is that they should allow new insights into site effects and site selectivity

Стимулированное излучение молекулами тетрабензопарфина в низкотемпературных матрицах благородных газов

В работе представлены результаты спектральных исследований молекул тетрабензопорфина (Н2ТБП), внедренных в твердотельные матрицы благородных газов (Ar, Xe)

Unilateral aplasia of both cruciate ligaments

Aplasia of both cruciate ligaments is a rare congenital disorder. A 28-year-old male presented with pain and the feeling of instability of his right knee after trauma. The provided MRI and previous arthroscopy reports did not indicate any abnormalities except cruciate ligament tears. He was referred to us for reconstruction of both cruciate ligaments. The patient again underwent arthroscopy which revealed a hypoplasia of the medial trochlea and an extremely narrow intercondylar notch. The tibia revealed a missing anterior cruciate ligament (ACL) footprint and a single bump with a complete coverage with articular cartilage. There was no room for an ACL graft. A posterior cruciate ligament could not be identified. The procedure was ended since a ligament reconstruction did not appear reasonable. A significant notch plasty if not a partial resection of the condyles would have been necessary to implant a ligament graft. It is most likely that this would not lead to good knee stability. If the surgeon would have retrieved the contralateral hamstrings at the beginning of the planned ligament reconstruction a significant damage would have occurred to the patient. Even in seemingly clear diagnostic findings the arthroscopic surgeon should take this rare abdnormality into consideration and be familiar with the respective radiological findings. We refer the abnormal finding of only one tibial spine to as the "dromedar-sign" as opposed to the two (medial and a lateral) tibial spines in a normal knee. This may be used as a hint for aplasia of the cruciate ligaments

Cellulosic films obtained from the treatment of sugarcane bagasse fibers with N -methylmorpholine- N -oxide (NMMO)

Ethanol/water organosolv pulping was used to obtain sugarcane bagasse pulp that was bleached with sodium chlorite. This bleached pulp was used to obtain cellulosic films that were further evaluated by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). A good film formation was observed when temperature of 74 °C and baths of distilled water were used, which after FTIR, TGA, and SEM analysis indicated no significant difference between the reaction times. The results showed this to be an interesting and promising process, combining the prerequisites for a more efficient utilization of agro-industrial residues.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP), (CNPq), and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Brazil; Fundação para a Ciência e a Tecnologia (FCT) and CEMU

Thermogravimetric and reaction kinetic analysis of biomass samples from an energy plantation

The products of a Hungarian experimental plantation for energy crops were investigated. Young shoots of poplar clones (Populus x euramericana and Populus x interamericana), black locust (Robinia pseudoacacia), willow (Salix alba), and an herbaceous plant (Miscanthus sinensis) revealed unexpectedly similar thermal behavior in inert and oxidative atmospheres, as well. An 8-fold difference in the level of grinding did not result in substantial differences in the thermal decomposition. The effect of oxygen in the ambient gas was studied at low sample masses (0.2-0.4 mg) that excluded the overheating due to the high reaction heat of the combustion process. The presence of oxygen affects the decomposition from ca. 220 degreesC. Nevertheless, the extrapolated onset temperature of the hemicellulose decomposition is practically the same at 0, 5, and 21 V/V% oxygen. A group of 12 experiments, representing two grinding levels, three plant genera and four different heating programs were evaluated simultaneously by the method of least squares employing the model of independent pseudocomponents. All evaluated experiments were well described by the same set of kinetic parameters; only the parameters describing the peak area of the partial processes differed. A technique was recommended for the appropriate handling of the nonrandom errors in the simultaneous evaluation of experiment series