The paper introduces general considerations on structural properties of aromatic, antiaromatic and non-aromatic conjugated systems in terms of potential energy along bond length alternation and distortion coordinates, taking as examples benzene, cyclobutadiene and cyclooctatetraene. Pentalene, formally derived from cyclooctatetraene by cross linking, is also considered as a typical antiaromatic system. The main interest is concerned with [n]annulenes and model [n]annulene molecular systems, n ranging from 10 to 18. The rich variety of conformational and configurational isomers and of dynamical processes among them is described. Specific attention is devoted to bridged [10]- and [14]annulenes in the ground and lowest excited states as well as to s-indacene and biphenylene. Experimental data obtained from vibrational and electronic spectroscopies are discussed and compared with ab initio calculation results. Finally, porphyrin, tetraoxaporphyrin dication and diprotonated porphyrin are presented as annulene structures adopting planar/non-planar geometries depending on the steric hindrance in the inner macrocycle ring. Radiative and non-radiative relaxation processes from excited state levels have been observed by means of time-resolved fluorescence and femtosecond transient absorption spectroscopy. A short account is also given of porphycene, the structural isomer of porphyrin, and of porphycene properties.
Dimethoate (DMT) is an organophosphate insecticide commonly used to protect fruit trees and in particular olive trees. Since it is highly water-soluble, its use on olive trees is considered quite safe, because it flows away in the residual water during the oil extraction process. However, its use is strictly regulated, specially on organic cultures. The organic production chain certification is not trivial, since DMT rapidly degrades to omethoate (OMT) and both disappear in about two months. Therefore, simple, sensitive, cost-effective and accurate methods for the determination of dimethoate, possibly suitable for in-field application, can be of great interest. In this work, a quick screening method, possibly useful for organic cultures certification will be presented. DMT and OMT in water and on olive leaves have been detected by surface enhanced Raman spectroscopy (SERS) using portable instrumentations. On leaves, the SERS signals were measured with a reasonably good S/N ratio, allowing us to detect DMT at a concentration up to two orders of magnitude lower than the one usually recommended for in-field treatments. Moreover, detailed information on the DMT distribution on the leaves has been obtained by Raman line- (or area-) scanning experiments.
Plasmonic systems are becoming a favourable alternative to dye molecules in the generation of photoacoustic signals for spectroscopy and imaging. In particular, inorganic nanoparticles are appealing because of their versatility. In fact, as the shape, size and chemical composition of nanoparticles are directly correlated with their plasmonic properties, the excitation wavelength can be tuned to their plasmon resonance by adjusting such traits. This feature enables an extensive spectral range to be covered. In addition, surface chemical modifications can be performed to provide the nanoparticles with designed functionalities, e.g., selective affinity for specific macromolecules. The efficiency of the conversion of absorbed photon energy into heat, which is the physical basis of the photoacoustic signal, can be accurately determined by photoacoustic methods. This review contrasts studies that evaluate photoconversion in various kinds of nanomaterials by different methods, with the objective of facilitating the researchers' choice of suitable plasmonic nanoparticles for photoacoustic applications.
1 October 2012 in Photochemical & Photobiological Sciences
The transient evolution of protoporphyrin IX (PPIX) and hemin following the Soret band excitation was measured in the 410–600 nm spectral region with sub-picosecond time resolution. In PPIX the relaxation pathway was characterized in the femto- and picosecond time scale by two processes with time constants of 350 fs and ∼6 ps, describing the evolution of the system through internal Qy → Qx conversion and vibrational relaxation and cooling in the Qx state. The lifetime of the Qx state was found to be 10.4 ns by time resolved fluorescence measurements. In hemin, the ground state is completely recovered in tens of picoseconds through pathways involving CT and (d,d) states. The experimentally observed vibrational dynamics is mainly due to “hot” ground state transitions.
The Stoddart’s blue box (BB) (cyclobis(paraquat-p-phenylene))/iodide binary system was recently demonstrated to give rise to porous three-dimensional networks which can hardly be classified as common XOF-type materials (X = M, C, S, i.e., metal, covalent, or supramolecular organic frameworks), leading to the definition of permutable organized frameworks (POFs). The ternary BB/iodide/iodine system was reported to generate pentaiodide-based structures constituted by the most complex interlocked polyiodides so far isolated (up to an infinite supramolecular pseudopolyrotaxane with a poly[3]catenane axle). The missing link, i.e., the XRD structure of the BB/triiodide complex, is herein reported: structural similarities and novel Raman evidence, opening perspectives in the genesis of solid-state BB-based complex polyiodide networks from solution.