Aerobic Visible-Light-Driven Borylation of Heteroarenes in a Gel Nanoreactor.

Heteroarene boronate esters constitute valuable intermediates in modern organic synthesis. As building blocks, they can be further applied to the synthesis of new materials, since they can be easily transformed into any other functional group. Efforts toward novel and efficient strategies for their preparation are clearly desirable.

Transient absorption spectroscopic studies on 4-nitroquinoline N-oxide: From femtoseconds to microseconds timescale.

The singlet excited state of 4-nitroquinoline N-oxide (NQNO*) has been characterized by different spectroscopic techniques, combining transient absorption with steady state and time-resolved emission spectroscopy. The energy of NQNO* has been established as 255 kJ/mol from the fluorescence spectrum, whereas its lifetime has been found to be 10 ps in the femto-laser flash photolysis (LFP) experiments, where a characteristic SS absorption band with maximum centered at 425 nm is observed. In a first stage, the triplet excited state of NQNO (NQNO*) has also been characterized by emission spectroscopy in solid matrix, at low temperature.

Pesticide Residues in Commercial Lettuce, Onion, and Potato Samples From Bolivia-A Threat to Public Health?

Bolivia does not have a surveillance program for pesticide residues in food. The few published studies have suggested that pesticide contamination in food may present a public health problem. Data are lacking for all foods except tomatoes and breast milk.

Solar filters as feasible acceptors of atomic oxygen.

The triazine derivative Tinosorb S has been shown to accept atomic oxygen generated by N-oxide photodeoxygenation. This is a unique example of a solar filter and mechanism-directed antioxidant. The concept has been proved by a combination of steady-state and laser-flash photolysis.

Photolabile N-hydroxypyrid-2(1H)-one derivatives of guanine nucleosides: a new method for independent guanine radical generation.

One-electron oxidized guanine is an important reactive intermediate in the formation of oxidatively generated damage in DNA and a variety of methods have been utilized for the abstraction of a single electron from the guanine moiety. In this study, an alternative approach for the site specific, independent generation of the guanine radical, utilizing N-hydroxypyrid-2(1H)-one as a photolabile modifier of guanine, is proposed. Novel photolabile 6-[(1-oxido-2-pyridinyl)oxo]-6-deoxy- and 2',6-dideoxy-guanosine derivatives capable of generating the neutral guanine radical (G(-H)*) upon photolysis were synthesized and characterized.

Photogeneration of 2-deoxyribonolactone in benzophenone-purine dyads. Formation of ketyl-C1' biradicals.

Photolysis of the title dyads under aerobic conditions leads to a 2-deoxyribonolactone derivative. Laser flash photolysis reveals that the process occurs from the short-lived benzophenone-like triplet excited state. A mechanism involving intramolecular electron transfer with the purine bases (adenine, guanine, or 8-oxoadenine) as donors is proposed.

Solar one-way photoisomerisation of 5',8-cyclo-2'-deoxyadenosine.

Under sunlight irradiation (5'S)-5',8-cyclo-2'-deoxyadenosine 2 photoisomerises to the (5'R) isomer 1, which is the more easily repaired damage when these cyclopurine lesions are formed in DNA.

Intramolecular interactions in the triplet excited states of benzophenone-thymine dyads.

Time-resolved and product studies on the synthesized dyads 1 and 2 have provided evidence that the benzophenone-to-thymine orientation strongly influences intramolecular photophysical and photochemical processes. The prevailing reaction mechanism has been established as a Paterno-Büchi cycloaddition to give oxetanes 3-6; however, the ability of benzophenone to achieve a formal hydrogen abstraction from the methyl group of thymidine has also been evidenced by the formation of photoproducts 7 and 8. These processes have been observed only in the case of the cisoid dyad 1.

Excited state enantiodifferentiating interactions between a chiral benzophenone derivative and nucleosides.

Time-resolved measurements using nanosecond laser flash photolysis have revealed significant enantiodifferentiation in the interaction between ketoprofen (a chiral benzophenone derivative) and two relevant nucleosides, namely, thymidine and 2'-deoxyguanosine. In both cases, the highest quenching rate constants have been observed for (R)-ketoprofen, the enantiomer with lower pharmacological activity. Photoproduct studies performed in the case of thymidine suggest that the enantiodifferentiating process corresponds to a Paterno-Büchi reaction, leading to the formation of oxetanes.

Stereo-differentiation in the excited state behaviour of naphthalene-thymine dyads.

Using two diastereomeric dyads containing naphthalene and thymine units, significant chiral discrimination has been found in the photophysical processes involving the naphthalene excited states: singlet deactivation by hydrogen bonding molecules, singlet-singlet energy transfer from thymine and triplet decay.

Singlet excited-state interactions in naphthalene-thymine dyads.

Two thymidine-derived nucleosides 1 and 2 were prepared by attaching a chiral naphthalene to the positions 5' and 3' of the sugar. The resulting dyads, which contain key substructures present in drugs and nucleic acids, exhibit different spatial arrangements (transoid or cisoid) of the fluorophore relative to the thymine unit. Emission measurements on these compounds in the presence of ROH molecules revealed a remarkable intramolecular prescence quenching for dyad 1.

The photochemistry of 8-bromo-2'-deoxyadenosine. A direct entry to cyclopurine lesions.

The UV photolysis of 8-bromo-2'-deoxyadenosine has been investigated in different solvents and in the presence of additives like halide anions. Photolytic cleavage of the C-Br bond leads to formation of the C8 radical. In methanol, subsequent hydrogen abstraction from the solvent is the main radical reaction; however, in water or acetonitrile intramolecular hydrogen abstraction from the sugar moiety, to give the C5' radical, is the major path.

Photosensitization of thymine nucleobase by benzophenone derivatives as models for photoinduced DNA damage: Paterno-Büchi vs energy and electron transfer processes.

Time-resolved and product studies have shown that there is a strong interaction between drugs containing the benzophenone chromophore and the free thymidine nucleoside. In quantitative terms, such an interaction is stronger for the lowest lying npi* triplet states (S-ketoprofen) than for mixed npi*-pipi* triplets (fenofibrate and fenofibric acid), as indicated by the quenching rate constants. This is consistent with a Paterno-Büchi photoreaction, where the initial step is the formation of a new bond between the excited carbonyl oxygen and one of the thymine olefinic carbons.

Electronic energy transfer and collection in luminescent molecular rods containing ruthenium(II) and osmium(II) 2,2':6',2"-terpyridine complexes linked by thiophene-2,5-diyl spacers.

The electronic absorption spectra, luminescence spectra and lifetimes (in MeCN at room temperature and in frozen n-C3H7CN at 77 K), and electrochemical potentials (in MeCN) of the novel dinuclear [(tpy)Ru(3)Os(tpy)]4+ and trinuclear [(tpy)Ru(3)Os(3)Ru(tpy)]6- complexes (3 = 2,5-bis(2,2':6',2''-terpyridin-4-yl)thiophene) have been obtained and are compared with those of model mononuclear complexes and homometallic [(tpy)Ru(3)Ru(tpy)]4+, [(tpy)Os(3)Os(tpy)]4+ and [(tpy)Ru(3)Ru(3)Ru(tpy)]6+ Complexes. The bridging ligand 3 is nearly planar in the complexes, as seen from a preliminary X-ray determination of [(tpy)Ru(3)Ru(tpy)][PF6]4, and confers a high degree of rigidity upon the polynuclear species. The trinuclear species are rod-shaped with a distance of about 3 nm between the terminal metal centres.