Photoinduced Long-Distance Hydrogen-Atom Transfer in Molecules with a 7-Hydroxyquinoline Frame and a Carbaldehyde or Aldoxime Group as the Intramolecular Hydrogen Transporting Crane.

The photochemical properties of monomeric 7-hydroxyquinoline substituted at position 8 with carbaldehyde or aldoxime groups were studied for the molecules isolated in solid Ar low-temperature matrices (at 10 K). It was experimentally demonstrated that upon UV excitation, both carbaldehyde and aldoxime groups act as intramolecular cranes transmitting hydrogen atoms from the hydroxyl group to the remote nitrogen atom of the quinoline ring. Furthermore, in the case of 7-hydroxyquinoline-8-aldoxime (and its derivatives), the second photochemical channel was activated upon UV (λ > 360 nm) excitation. This process involves syn-anti isomerization around the double C═N bond in the aldoxime group. The structures of the reactant hydroxy tautomeric form and the photoproduced isomers of the studied molecules were unequivocally determined by means of IR spectroscopy combined with theoretical predictions of the IR spectra of the candidate structures.

7-Hydroxyquinoline-8-carbaldehydes. 1. Ground- and excited-state long-range prototropic tautomerization.

Ground- and excited-state long-range prototropic tautomerization were studied for a series of 7-hydroxyquinoline-8-carbaldehydes (7-HQCs) by (1)H and (13)C NMR spectroscopy, photostationary and time-resolved UV-vis spectroscopic methods, and quantum chemical computations. These molecules represent trifunctional proton-donating/accepting systems that have been proposed to serve as models of a reversible optically driven molecular switch composed of two moieties: a molecular "frame" (7-hydroquinolines, 7-HQs) and a proton "crane" (carbaldehyde group). The NMR and electronic absorption spectra indicate a solvent-dependent equilibrium between two tautomeric forms, OH (7-quinolinol)) and NH (7(1H)-quinolinone), already in the ground state of all the compounds under study (7-hydroxy-2-methoxy-4-methylquinoline-8-carbaldehyde, HMMQC, shows only a trace of the NH form in highly polar and/or protic media). Electronic absorption and fluorescence of 7-HQCs are rationalized in terms of the ground- and excited-state hydrogen atom transfer (HAT). This process was identified by comparing the UV-vis spectroscopic properties of 7-HQCs with those of 7-HQs, synthetic precursors of the former, as well as with the characteristics of corresponding protonated cations and deprotonated anions (part 2). The experimental results are corroborated by the density functional theory (DFT) and ab initio computations, which shed some light on the differences in photophysics between variously substituted 7-HQCs.

7-Hydroxyquinoline-8-carbaldehydes. 2. Prototropic equilibria.

Prototropic equilibria were studied for a series of 7-hydroxyquinoline-8-carbaldehydes (7-HQCs) by (1)H NMR spectroscopy, photostationary and time-resolved UV-vis spectroscopic methods, and quantum chemical computations. These molecules represent trifunctional proton-donating/accepting systems that in aqueous solutions may assume four main neutral and ionic structures: 7-quinolinol (OH), 7(1H)-quinolinone (NH), deprotonated anion (A), and protonated cation (C). Electronic absorption and fluorescence of 7-HQCs are rationalized in terms of the ground and excited-state long-range tautomerization (part 1) as well as protonation and deprotonation processes. The photophysical properties of neutral and ionic forms of 7-HQCs are compared with those of 7-hydroxyquinolines (7-HQs), synthetic precursors of the former. The experimental results are corroborated by ab initio computations.

Application of physicochemical data for water-quality assessment of watercourses in the Gdansk Municipality (South Baltic coast).

The paper presents water-quality evaluation based on an 8-year monitoring programme in the Gdansk Municipality region, on the Southern coast of the Baltic Sea. The studies were carried out from 2000 to 2007 by surface water analysis at 15 various sites within eight watercourses. Sampling sites included rather urbanized or developed lands, farming fields and non-polluted city recreational areas such as parks and forests. Most of the watercourses were sampled monthly at two locations, one within the upper course of the watercourse and the other near its mouth. In all samples, eight parameters of water quality were determined: total suspended solids, dissolved oxygen, water temperature, oxygen saturation, 5-day biochemical oxygen demand, chemical oxygen demand, total phosphorus and total nitrogen concentration. Interpretation of the obtained results revealed that examination of those basic physicochemical parameters permits to discriminate initially watercourses with respect to level of water contamination. During the research, a large dataset was obtained and it was described by both basic statistical parameters and chemometric method of cluster analysis. The paper presents relations between analysed parameters and influence of land exploitation mode on water quality and describes variation of the results both in space and time.

Tuneable white fluorescence from intramolecular exciplexes.

Crystal violet lactone (CVL) in solution displays unusually broad (FWHM > 9100 cm(-1)) dual fluorescence with the characteristics of white light. The emission combines a blue CT band from a local chromophore with an orange CT band from an intramolecular exciplex formed adiabatically at appropriate medium polarity. The fluorescence spectrum can be controlled by solvent polarity to yield tuneable emission colours in a broad range of coordinates in the CIE chromaticity diagram including the white region. We show that such dual emission is a general property of CVL-like D-A structures built on sp(3) carbon atoms. The dependence of excited state energetics on molecular structure allows the prediction of width, shape and other parameters of the dual fluorescence spectrum, and so enables the engineering and customised design of white fluorophores. The photophysics-structure relationship found for CVL and its analogues can be generalized into a novel concept of white light generation by small molecules. These D-A systems are studied as a template basis for design and development of white fluorophores.

Bioaerosols on Tri-city (Gdansk-Sopot-Gdynia) beaches.

Bioaerosol formation is an important process of mass and energy exchange between the sea and the atmosphere by means of droplets of marine dust. Studies of marine aerosol activity developed in the last decades of the 20th century. Those studies revealed that concentrations of bacteria in aerosol droplets were hundreds of times higher than were those measured in superficial marine waters. Moreover, it was determined that aerosol activity at sea can influence the sanitary condition of the air, especially in seaside areas. Examinations of air composition in coastal regions were performed on the beaches of the Tri-city, Sobieszewo, and Komary. Airborne microorganisms were also investigated in the marine zone at the Vistula river mouth. The air samples were collected by a filtration method using Sartorius apparatus. The exposed filters were then placed onto agar media in Petri dishes and incubated. All measurements are expressed in CFU/m3, i.e. colony forming units per cubic metre of examined air. Meteorological parameters such as temperature, humidity, and wind speed and direction were also measured. The obtained results revealed statistically significant trends between the total number of bacteria and fungal spores, and the sampling season. The greatest number of microorganisms was noted in spring and autumn. Correlation analysis showed that a statistically significant relationship exists between the microbial abundance and the wind direction, wind speed, and the sampling site location. The maximum number of fungal spores was detected in the areas of Gdynia and Gdansk Brzezno when south-west winds were blowing from the land. The highest number of bacteria was observed at the sampling stations located closest to the Vistula river mouth (Sobieszewo and Komary).

A bistable molecular switch driven by photoinduced hydrogen-atom transfer.

The occurrence of photoinduced hydrogen atom transfer between two remote spots of a molecule is experimentally demonstrated. This photoprocess involves the intermediacy of an intramolecular "crane". In an experimental case study, 7-hydroxy-4-methylquinoline-8-carbaldehyde monomers isolated in low-temperature Ar matrices are investigated. On UV (lambda>295 nm) irradiation, a hydrogen atom is transferred from the O(7)H group to the N(1) atom of the quinoline ring. Subsequent irradiation with UV (lambda>360 nm) light reveals that the phototransformation is partially photoreversible. In the studied hydrogen-atom-transfer process, the exocyclic carbaldehyde group plays the role of an intramolecular crane. The possible application of systems analogous to 7-hydroxy-4-methylquinoline-8-carbaldehyde as optically driven molecular switches is discussed.

Intramolecular Electron Transfer in Frozen Solvents: Charge Transfer and Local Triplet States Population Dynamics Revealed by Dual Phosphorescence.

In frozen solvents at 77 K, ultrafast (≤250 fs) photoinduced intramolecular electron transfer (ET) in bichromophoric donor-acceptor ([D-A]) diarylmethane lactones produces a covalently linked radical ion pair, 1[D•+-A•-]. Steady state and time-resolved luminescence measurements reveal that 1[D•+-A•-] decays to charge-separated (3[D•+-A•-]) and donor-centered ([3D*-A]) triplets, which display dual phosphorescence. 3[D•+-A•-] and [3D*-A] are formed in parallel via two intersystem crossing mechanisms: spin orbit charge transfer (SOCT) and hyperfine coupling (HFC), with solvent dependent branching ratio. The solvent drives the D-A alignment during the freezing process to adapt to increasing solvent polarity, producing inhomogeneous ground-state population distribution with solvent-dependent D-A exchange interaction, which plays a key role in partitioning into SOCT and HFC mechanisms. In polar glasses, a third phosphorescence band appears due to dissociative back ET in 3[D•+-A•-] resulting in excited open ring biradical.

Photoinduced intramolecular charge transfer to meta position of benzene ring in 6-aminophthalides.

Substitution of non-fluorescent phthalide (Pd) with amino group at meta (6) position in relation to the electron-accepting part of the lactone ring completely changes Pd photophysics: a new long-wavelength absorption band arises and the molecule becomes highly fluorescent. The experimental data and the analysis of vertical electronic transitions with TDDFT method indicate that the first absorption band in 6-aminophthalides (6-APds) comprises a single CT transition to the S1 state. Almost equal absorption and emission transition dipole moments indicate that S0 <--> S1 transition in all 6-APds is not affected by any mixing with other electronic states, the excited-state vibrational relaxation is not accompanied by significant conformational changes and the Stokes shifts reflect mainly solvation energetics of these molecules. Excited state dipole moments obtained from solvatochromic plots and from CASSCF calculations confirm large charge displacement from amino group towards the meta position of the benzene ring upon excitation of 6-APds to S1 state. Long fluorescence lifetimes and high fluorescence quantum yields demonstrate efficient and stable excited state charge separation in 6-APds. Taken together with sensitivity of 6-APds to polarity and proticity of the environment these properties make them good candidates for fluorescent probes of long-time scale molecular dynamics.