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1.
Materials (Basel) ; 15(7)2022 Mar 26.
Article in English | MEDLINE | ID: mdl-35407780

ABSTRACT

Risk management and uncertainty models are practised in all branches of transport. Although unmanned aerial vehicles (UAVs) constitute a branch of the industry rather than transport as a whole, their development is oriented toward increasingly more serious applications involving the transport of goods and people. The constantly growing number of operations employing UAVs requires not only identification of hazard sources or risk assessment recommended by the applicable regulations, but also comprehensive risk management. In order to develop a systematic approach to risk management for air operations of UAVs, the classic risk management method can be used. This work proposes a novel multi-criteria risk model that may serve as the basis for further activities aimed at developing a risk management method for this domain. The model was based on six criteria and validated using a virtual route to risk assessment and valuation.

2.
Biochim Biophys Acta ; 1827(1): 30-7, 2013 Jan.
Article in English | MEDLINE | ID: mdl-22995216

ABSTRACT

In the Ni-substituted chlorophylls, an ultrafast (<60 fs) deactivation channel is created, which is not present in Ni-porphyrins. This observation prompted us to investigate in detail the mechanism of excitation-to-heat conversion in Ni-substituted chlorophylls, experimentally, using time-resolved laser-induced optoacoustic spectroscopy, and theoretically, using group theory approach. The Ni-substituted chlorophylls show exceptional photostability and the optoacoustic measurements confirm the prompt and very efficient (100%) excitation-into-heat conversion in these complexes. Considering their excellent spectral properties and the loss-free excitation-into-heat conversion they are likely to become a new class of versatile photocalorimetric references. The curious features of the Ni-substituted chlorophylls originate from the symmetry of a ligand field created in the central cavity. The central N-Ni(2+) bonds, formed via the donation of two electrons from each of the sp(2) orbitals of two central nitrogens to an empty [Formula: see text] hybrid centered on Ni(2+), have a considerable covalent character. The extreme rate of excited state relaxation is then not due to a ladder of the metal centered d-states, often invoked in metalloporphyrins, but seems to result from a peculiar topology of the potential energy surface (a saddle-shaped crossing) due to the covalent character of the N-Ni(2+) bonds. This is confirmed by a strong 0→0 character of electronic transitions in these complexes indicating a similarity of their equilibrium geometries in the ground (S(0)) and the excited states (both Q(X) and Q(Y)). The excitation energy is very efficiently converted into molecular vibrations and dissipated as heat, involving the central Ni(2+). These Ni-substituted pigments pose a fine exemplification of symmetry control over properties of excited states of transition metal complexes.


Subject(s)
Chlorophyll/radiation effects , Light , Nickel/radiation effects , Chlorophyll/chemistry , Chlorophyll/isolation & purification , Chlorophyll A , Energy Transfer/radiation effects , Hot Temperature , Models, Chemical , Nickel/chemistry , Photoacoustic Techniques , Photolysis , Plant Leaves/chemistry , Solvents/chemistry , Spectrum Analysis , Spinacia oleracea/chemistry , Time Factors , Vibration
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