Removal and toxicity evaluation of a diverse group of drugs from water by a cyclodextrin polymer/pulsed light system.

The presence of pharmaceutical compounds (PhCs) in the effluents of wastewater treatment plants (WWTPs) is an ecological concern. The issue could be alleviated by trapping those substances by cyclodextrin (CD) polymers or photolyzing them by pulsed light (PL). Consequently, a sequential CD polymer/PL system was tested for the removal of PhCs. Firstly, a survey detected the presence of recurrent PhCs in the effluents of local WWTPs. Then, pure water was spiked with 21 PhCs, 100 µg/L each one. The three-dimensional network provides amphiphilic features to the CD polymer that reduced the pollutant concentration by 77 %. Sorption involves a plead of physical and chemical mechanisms hindering the establishment of a general removal model for all compounds. The performed simulations hint that the retention capacity mainly correlates with the computed binding energies, so that theoretical models are revealed as valuable tools for further improvements. The complementary action of PL rose the elimination to 91 %. The polymer can be reused at least 10 times for ibuprofen (model compound) removal, and was able to eliminate the ecotoxicity of an ibuprofen solution. Therefore, this novel sequential CD polymer/PL process seems to be an efficient alternative to eliminate PhCs from wastewater.

Effects of hydration on the proton transfer mechanism in the adenine-thymine base pair.

We report the first density functional study of water catalytic effect in the double proton transfer (DPT) taking place in the adenine-thymine (AT) base pair. To gain more insight regarding the accuracy of several theoretical methods, the ability of various functionals and models for describing the geometry of this system has first been checked. According to our results, BP86/6-311++G(d,p) is the best option for describing the solvation effects in AT when applied to a two-water-molecule-featuring model. The two possible mechanisms for DPT in solution are explored: in the first one, water molecules only remain passive elements, whereas in the second one they are directly included in the reaction path. For the noncatalyzed mechanism, the stable structures constitute the canonical form of the base pair and the first proton transfer product. Nevertheless, by involving the two water molecules in the reaction, we found three stable species: canonical base pair, first proton transfer product, and double proton transfer product. Although the thermodynamic analysis confirms that AT does not contribute to spontaneous mutation through proton transfer catalyzed by surrounding water, our results suggest that microhydration may play a crucial role for DPT reaction in others DNA or RNA basis pair.

Density functional theory study of the stability and vibrational spectra of the beta-carotene isomers.

A density functional theory analysis of the stability and vibrational spectra of the beta-carotene isomers is carried out. The study includes the 7-, 9-, 11-, 13-, and 15-monocis isomers and the 7,13'-, 9,13-, 9,13'-, 9,15-, 11,11'-, and 13,15-dicis isomers. The optimized geometries needed to study the stability of the isomers are calculated at the B3LYP/6-31G(d) level of theory, and their energies are further recalculated at the higher B3LYP/6-311+G(2d,2p) level. In addition, the Wiberg bond orders and the natural bond orbital charges of the isomers are computed study the effect of the torsion of the beta-ionone rings on the conjugation degree of the polyene chain. The infrared and Raman spectra of the beta-carotene isomers are then calculated at the B3LYP/6-31G(d) level, scaling the calculated frequencies with an overall factor to account for the anharmonicity effects. The calculated frequencies are shown to compare quite well with the experiment, and the normal modes of the key bands are theoretically interpreted.

Intermolecular proton transfer in microhydrated guanine-cytosine base pairs: a new mechanism for spontaneous mutation in DNA.

Accurate calculations of the double proton transfer (DPT) in the adenine-thymine base pair (AT) were presented in a previous work [J. Phys. Chem. A 2009, 113, 7892.] where we demonstrated that the mechanism of the reaction in solution is strongly affected by surrounding water. Here we extend our methodology to the guanine-cytosine base pair (GC), for which it turns out that the proton transfer in the gas phase is a synchronous concerted mechanism. The O(G)-H-N(C) hydrogen bond strength emerges as the key parameter in this process, to the extent that complete transfer takes place by means of this hydrogen bond. Since the main effect of the molecular environment is precisely to weaken this bond, the direct proton transfer is not possible in solution, and thus the tautomeric equilibrium must be assisted by surrounding water molecules in an asynchronous concerted mechanism. This result demonstrates that water plays a crucial role in proton reactions. It does not act as a passive element but actually catalyzes the DPT.

A density functional theory study of the structure and vibrational spectra of beta-carotene, capsanthin, and capsorubin.

A theoretical study of the structure and the vibrational spectra of the beta-carotene molecule and its derivatives capsanthin and capsorubin is carried out. We first investigate systematically the theoretical method which provides the best results for beta-carotene by performing ab initio calculations at the HF/6-31G(d), SVWN/6-31G(d), PBE0/6-31G(d), BLYP/6-31G(d), B3LYP/6-31G(d), B3LYP/6-31G(d,p), B3LYP/6-311G(d), and B3LYP/6-311G(d,p) levels and by using previous theoretical results available in the literature obtained at the AM1 and BPW91/6-31G(d) levels. The influence of both the level of calculation and the size of the basis set used in the geometry optimization and in the determination of the IR and Raman spectra of this molecule is thus analyzed. It is confirmed that the hybrid functional B3LYP with the basis 6-31G(d) is the method that gives the best results as a whole. By use of this level of calculation, we next optimize the molecular geometries of related molecules of capsanthin and capsorubin, which to the best of our knowledge have only been studied at the semiempirical AM1 level. In addition we calculate the IR and Raman spectra of these molecules at the B3LYP/6-31G(d) level of theory. The results obtained for capsanthin show on the one hand that the double bond of the beta-ionone ring is outside the polyene chain plane, due to the repulsion between the hydrogen atoms of the ring methyl groups and the hydrogen atoms of the polyene chain, and on the other hand that the carbonyl double bond in the other headgroup is very close to planarity with the polyene chain, since in this case such a repulsion does not exist. For the molecule of capsorubin the two carbonyl groups also take the same coplanar orientation relative to the polyene chain. The IR and Raman spectra theoretically computed for these two molecules are finally compared with their experimental spectra and the vibrational normal modes of the main signals are interpreted.

A theoretical study of the reaction of beta-carotene with the nitrogen dioxide radical in solution.

A theoretical study of the reaction of beta-carotene (BC) with the nitrogen dioxide radical (NO2*) in solution is carried out using the density functional theory (DFT) at the B3LYP/6-31G(d) level, to optimize the molecular geometries, and the polarizable continuum model (PCM), to account for solvent effects. The three most important reaction mechanisms--electron transfer from beta-carotene to the radical, hydrogen abstraction by the radical, and radical addition to form an adduct--are studied in detail. Three solvents with different polarities--heptane, methanol, and water--are employed to investigate the effect of the environment on the reaction mechanisms. Our results show that electron transfer is thermodynamically favored only in the polar solvents, the abstraction reactions are spontaneous in the three solvents, although faster in the polar ones, and the addition reactions are all endergonic and, therefore, unlikely to occur in any of the solvents. In both the abstraction and addition mechanisms, the attack of the radical takes place preferentially at the beta-ionone rings, in particular at positions H4 and C5, respectively. The higher stability of the reaction products in these cases is explained in terms of their molecular geometries and electronic structures.

Theoretical study of the tautomerism in the one-electron oxidized guanine-cytosine base pair.

Ionizing radiation on DNA mainly generates one-electron oxidized guanine-cytosine base pair (G(+·):C), and in the present paper we study all possible tautomers of G(+·):C by using ab initio approaches. Our calculations reveal that the tautomeric equilibrium follows a peculiar path, characterized by a stepwise mechanism: first the proton in the central hydrogen bond N1(G)-H1-N3(C) migrates from guanine to cytosine, and then the cytosine cation releases one proton from its amino group. During this second step, water acts as a proton acceptor, localizing the positive charge on one of the water molecules interacting with the guanine radical. In agreement with experimental findings, the computed energy barriers show that the deprotonation of the cytosine cation is the speed-limiting step in the tautomeric equilibrium. The influence of the number of water molecules incorporated in the theoretical model is analyzed in detail. The evolution of electronic properties along the reaction path is also discussed on the basis of partial atomic charges and spin density distributions. This work demonstrates that water indeed plays a crucial role in the tautomeric equilibra of base pairs.