Photodynamics of Zr-based MOFs: effect of explosive nitroaromatics.

The present work describes the spectroscopic and photodynamics of two different Zr mixed-linkers MOFs (Zr-NDC/Tz and Zr-NDC/CN) and their interaction with nitroaromatics. Both MOFs exhibit comparable spectroscopic behaviours, with a broad emission band mainly due to the naphthalene excimers within their three-dimensional structure. Flash photolysis experiments show a slow radiative electron-hole (e--h+) recombination, reflected as a large negative absorption band. The interaction with the selected nitroaromatic compounds produces a static fluorescence quenching of Zr-NDC/Tz. Interestingly, the addition of trinitrophenol (TNP) induces the formation of a charge-transfer complex, helped by intermolecular H-bonds formation, as shown by the steady-state and ps-time-resolved emission experiments. Remarkably, the (e--h+) recombination is strongly affected due to the inhibition of the ligand-to-cluster charge transfer process within the MOF. The quenching constants for the nitroaromatics lacking -OH groups are in the order of 102 M-1, while it is two orders of magnitude higher for the TNP (1.8 × 104 M-1). Both MOFs are highly selective toward TNP. We also demonstrate the possibility to recycle these MOFs without significant loses in their ability to detect TNP. Our findings give the clues to understand the fluorescence quenching mechanism of new Zr-based MOFs in presence of explosive-like molecules, opening the way to improve these nanomaterials as highly selective sensor of nitroaromatics.

Efficient light harvesting within a C153@Zr-based MOF embedded in a polymeric film: spectral and dynamical characterization.

Light harvesting is a natural phenomenon that scientists try to mimic in artificial systems. Having this in mind, attention has been focused on using new smart-materials for photonics. Herein, we report on the photobehaviour of a Zr-NDC MOF (NDC = dimethyl 2,6-naphthalenedicarboxylate) and its composite material, Coumarin153@Zr-NDC, embedded within a polymeric membrane of poly[bisphenol A carbonate-co-4,4'-(3,3,5-trimethylcyclohexylidene)diphenol carbonate] (PC). For the mixed matrix membrane (MMM) Zr-NDC/PC, we observed interparticle excimer-like formation, taking place in times shorter than 15 ps and giving rise to a red-shifted broad emission band. The interparticle interactions are supported by the SEM images, as they reflect the contact between the MOF crystals. The C153@Zr-NDC/PC material presents an energy transfer (ET) process from the excited MOF to the trapped C153 molecules in 820 ps, with a 35 nm red-shifted emission band corresponding to C153 in PC. The fluorescence quantum yield, as a result of this ET from the MOF, is high enough (25%) to explore the possibility of using this new composite material in a LED device. To elucidate the observed photobehavior, we compared it with those of C153/PC and (2,6-NDC + C153)/PC films. These results shed light on the spectroscopic and dynamical properties of these new composite materials formed by a highly fluorescent molecule, and easily synthesized MOFs and polymeric matrices, opening the way for more research based on these mixed inorganic and organic compounds for possible applications in the fields of luminescence sensing and emitting devices.

[A new clinical entity: ascending solar iris degeneration. Report of 284 cases]. / Une nouvelle entité clinique : la dégénérescence irienne solaire ascendante. À propos de 284 cas.

The observation in a certain number of subjects of an atypical iris depigmentation led us to study this phenomenon. Therefore, the authors engaged in a prospective study of 398 subjects (100 cases in the city of Marrakesh, and 298 in the city of Dakhla). The geography, clinical signs and environmental factors were studied. Depigmentation was observed in 55% of the population of Marrakesh and 77% of the population of Dakhla. It is bilateral, symmetric, very progressive, always begins in the inferior one-third of the iris, and always spares the superior iris covered by the eyelid. By the time the depigmentation reaches the middle one-third, the inferior one-third also begins to demonstrate stromal atrophy: (26 cases). Of the 45 subjects with normal iris pigmentation, 31 cases spend more than 8 hours per day in the shade, and 26 cases constantly use some means of solar protection (sunglasses, caps, "Taraza", "Feroual"). Thus, this acquired iris depigmentation of an ascending nature, accompanied by an advanced stage involving primarily inferior iris atrophy, appears to be closely associated with exposure to the sun. Ascending solar iris degeneration, if we may refer to it as such, is a clinical entity never before reported in the literature. Now that we are faced with this new condition, numerous questions arise, to which future research must respond. Are there other factors in addition to sun exposure, which may lead to the depigmentation? Does this condition lead to further ocular pathology (due to the depigmentation and stromal atrophy)? Must solar protection be prescribed systematically for anyone at risk?

Femto to millisecond observations of indole-based squaraine molecules photodynamics in solution.

We present femto-to-millisecond studies of the photodynamics of seven types of indole-based squaraine molecules (SQs) in solvents of different H-bonding ability and viscosity. These SQs can be classified into two families: SQs with two carboxylic groups in the side indole groups (symmetrical SQs) and with only one carboxylic group (asymmetrical SQs). Steady-state absorption and fluorescence techniques show narrow absorption and emission bands, with a small Stokes shift (about 300 cm(-1)). The femtosecond transient absorption spectra give a very short (∼100 fs) dynamics (assigned to IVR) and the associated spectra show two excited species assigned to two stereoisomers. A trans-cis photoisomerization occurs in a very fast time through a conical intersection. Pico-to-nanosecond emission experiments also reveal the presence of two fluorescing trans stereoisomers whose lifetimes show similar sensitivities to the nature of solvent. For example, lifetimes of 1.72, 0.46 and 0.29 ns were determined for the trans photoisomer of the SQ 41 in triacetin, dichloromethane and acetonitrile, respectively, reflecting the short decay of the S(1) state in highly polar and low viscous solvents. Flash photolysis experiments gave the transient absorption signals of the cis photoisomer that is formed after the twisting process at S(1). The cis-to-trans photoisomerization at the ground state happens in the µs time scale (1-4 µs), and it depends on the H-bonding ability and viscosity of the solvent. Thus, combining fs-ns and ns-µs experiments suggests that in the conical intersection region, only a small fraction of the twisted trans isomers are converted to the cis ones in the excited states. These results bring detailed and global insight into the large time window photodynamics of this family of SQs in solution.

Isomerization dynamics of the 2-phenylazo-1,3-dimethylimidazolium cation photoexcited to the S2 (π, π*) state as studied by transient absorption spectroscopy in the time domain of 10(-13) to 10(3) seconds.

Photoinduced isomerization of a novel photochromic cation, [2PA-Mmim](+) (2-phenylazo-1,3-dimethylimidazolium cation), was studied by optical spectroscopic methods. The UV-Vis absorption spectra of the [2PA-Mmim](+) cation show two prominent bands starting around 410 and 520 nm, corresponding to the S(0)-S(2) (π, π*) and S(0)-S(1) (n, π*) transitions, respectively. The photoisomerization mechanism is studied by femtosecond time-resolved transient absorption experiments performed after S(0)-S(2) (π, π*) excitation in several solvents with different viscosity, including ionic liquids. The transient absorption signals at two representative wavelengths were fitted by bi-exponential functions, which yield four decay components. The photoisomerization mechanism is discussed in light of the relaxation schemes available for azobenzene. Only one of the components depends on the solvent viscosity and it changes from 1.2 ps (dichloromethane, 0.4 cP) to 5.6 ps ([Bmim][BF(4)], 93 cP). This component is assigned to a molecule at the S(1) state, which is responsible for the "rotational" isomerization. The weak dependence on the solvent viscosity of this component is explained in terms of local change in the viscosity as a result of local heating due to excess energy released at S(2)-S(1) internal conversion. The other three components of ∼0.4, 1.0 and 10 ps are attributed to relaxation processes of the molecule at S(2), S(1) and S(0) states, respectively. The quantum yields for the forward E-Z photoisomerization are ∼0.15 after S(2) excitation. The backward Z-E isomerization is slow with a lifetime of 1 hour and an activation energy of 91 kJ mol(-1) through an "inversion" mechanism.

[Macular tuberculoma and optic neuritis: rare association with tuberculosis meningoencephalitis]. / Tuberculome maculaire et névrite optique : association rare au cours d'une méningo-encéphalite tuberculeuse.

INTRODUCTION: Tuberculosis is an endemic disease responsible for death and morbidity in developing countries. OBSERVATION: A 50-year-old man with no medical history was admitted to the emergency department for meningism associated with fever and confusion. The ophthalmic exam showed a decline in left visual acuity, reduced to light perception, VIth nerve left oculomotor paralysis, ocular fundus demonstrating a yellow tumor located on the posterior segment, measuring 1.5-2mm, papillomatous and prominent in the vitreous cavity. Fluorescein angiography showed a peritumoral choroiditis area, miliary tubercles of the choroid, and sectorial papillomatous edema. Color retinography unmasked inflamed posterior vitreous areas. Echography demonstrated a 4- to 5-mm oval hyperechogeneous and calcified tumor along with hyperechogeneous vitreous areas. Lumbar puncture showed lymphocytic meningitis associated with hyponatremia. The CT scan and MRI demonstrated optic neuritis. The antibiotic therapy was initiated and the outcome was favorable. CONCLUSION: This case report shows the importance of systematic ocular fundus in the presence of systemic tuberculosis and outlines the assessment of color retinography to unmask vitreous lesions. It shows the importance of radiological imaging in the semiological study of orbital and cerebral lesions.

[Hyperphosphatemia: an extremely rare cause of angioid streaks]. / L'hyperphosphatémie : une cause rarissime de stries angioïdes.

Angioid streaks are rare lesions of the fundus. They correspond to cracks in the Bruch membrane, which risk choroid neovessel emergence over time. We present the case of a 52-year-old diabetic patient who consulted for a macular syndrome of the left eye. The clinical examination revealed diffuse, bilateral nerve fibers with myelin, but particularly bilateral angioid streaks, complicated on the left by a juxtamacular choroid neovessel. The etiologic assessment revealed idiopathic hyperphosphatemia. We use this observation to discuss the originality of the case, the pathogenic assumption of its etiology, emphasizing the therapeutic difficulties.

Probing the behavior of confined water by proton-transfer reactions.

The picosecond dynamics of a bifunctional and H-bonding molecule, 7-hydroxyquinoline (7HQ), has been studied in a reverse micelle with increasing water content. The fluorescence kinetics has a complex behavior as the water content is changed. All reactions are irreversible, and a two-step mechanism is invoked to explain the observations. H2O/D2O exchange and excitation energy effects show that the second step has a higher barrier and that the corresponding reaction occurs through tunneling. The results clearly indicate two regimes of water nanopool behavior switching at W0 approximately 5 (W0 = [water]/[surfactant]). Water collective dynamics explains these observations. The lower fluidity of confined water within the reverse micelle with respect to normal bulk water alters the related H-bond network dynamics and therefore is responsible for the slower proton-transfer processes.

Femtosecond studies of protein-ligand hydrophobic binding and dynamics: human serum albumin.

In this contribution, we report studies of the nature of the dynamics and hydrophobic binding in protein-ligand complexes of human serum albumin with 2-(2'-hydroxyphenyl)-4-methyloxazole. With femtosecond time resolution, we examined the orientational motion of the ligand, its intrinsic nuclear motions, and the lifetime changes in the hydrophobic phase. For comparisons, with similar but chemical nanocavities, we also studied the same ligand in micelles and cyclodextrins. The hydrophobic interactions in the binding crevice are much stronger than those observed in cyclodextrins and micelles. The confined geometry restrains the nonradiative decay and significantly lengthens the excited-state lifetime. The observed dynamics over the femtosecond-to-nanosecond time scale indicate that the binding structure is rigid and the local motions of the ligand are nearly "frozen" in the protein. Another major finding is the elucidation of the directed dynamics by the protein. Proton transfer and intramolecular twisting of 2-(2'-hydroxyphenyl)-4-methyloxazole were observed to evolve along two routes: one involves the direct stretching motion in the molecular plane (approximately 200 fs) and is not sensitive to the environment; the second, less dominant, is related to the twisting motion (approximately 3 ps) of the two heterocyclic rings and drastically slows down in the protein hydrophobic pocket.

A coupled proton-transfer and twisting-motion fluorescence probe for lipid bilayers.

A new and sensitive molecular probe, 2-(2'-hydroxyphenyl)imidazo[1, 2-a]pyridine (HPIP), for monitoring structural changes in lipid bilayers is presented. Migration of HPIP from water into vesicles involves rupture of hydrogen (H) bonds with water and formation of an internal H bond once the probe is inside the vesicle. These structural changes of the dye allow the occurrence of a photoinduced intramolecular proton-transfer reaction and a subsequent twisting/rotational process upon electronic excitation of the probe. The resulting large Stokes-shifted fluorescence band depends on the twisting motion of the zwitterionic phototautomer and is characterized in vesicles of dimyristoyl-phosphatidylcholine and in dipalmitoyl-phosphatidylcholine at the temperature range of interest and in the presence of cholesterol. Because the fluorescence of aqueous HPIP does not interfere in the emission of the probe within the vesicles, HPIP proton-transfer/twisting motion fluorescence directly allows us to monitor and quantify structural changes within bilayers. The static and dynamic fluorescence parameters are sensitive enough to such changes to suggest this photostable dye as a potential molecular probe of the physical properties of lipid bilayers.

Femtosecond molecular dynamics of tautomerization in model base pairs.

Hydrogen bonds commonly lend robustness and directionality to molecular recognition processes and supramolecular structures. In particular, the two or three hydrogen bonds in Watson-Crick base pairs bind the double-stranded DNA helix and determine the complementarity of the pairing. Watson and Crick pointed out, however, that the possible tautomers of base pairs, in which hydrogen atoms become attached to the donor atom of the hydrogen bond, might disturb the genetic code, as the tautomer is capable of pairing with different partners. But the dynamics of hydrogen bonds in general, and of this tautomerization process in particular, are not well understood. Here we report observations of the femtosecond dynamics of tautomerization in model base pairs (7-azaindole dimers) containing two hydrogen bonds. Because of the femtosecond resolution of proton motions, we are able to examine the cooperativity of formation of the tautomer (in which the protons on each base are shifted sequentially to the other base), and to determine the characteristic timescales of the motions in a solvent-free environment. We find that the first step occurs on a timescale of a few hundred femtoseconds, whereas the second step, to form the full tautomer, is much slower, taking place within several picoseconds; the timescales are changed significantly by replacing hydrogen with deuterium. These results establish the molecular basis of the dynamics and the role of quantum tunnelling.

Picosecond fluorescence decay of lens protein gamma-II crystallin.

The fluorescence decay of tryptophan residues in the bovine lens protein gamma-II crystallin has been measured in aqueous buffer solutions. Results were obtained as a function of emission wavelength, temperature, dissolved oxygen, and denaturing solvent. The protein displayed complex fluorescence decay which fit a biexponential model with a long component (ns) and a short component (few hundred ps). Measured fluorescence quantum yields data for gamma-II crystallin allowed calculation of radiative and non-radiative rate constants. The radiative rate constant was consistent with that observed in other indole derivatives, while the non-radiative rate constant was quite large and accounted for the short lifetime in gamma-II. The temperature dependence of the non-radiative decay in gamma-II crystallin yielded a small activation energy of only 1-2 kcal/mol, compared to 4 kcal/mol for the reference compound NATA whose barrier is known to derive from the rotamer model.

Picosecond fluorescence decay in photolyzed lens protein alpha-crystallin.

Photolysis of calf lens protein alpha-crystallin in aqueous solutions has been monitored by observing changes in fluorescence decay following UV irradiation at 308 nm. The fluorescence decay was biexponential in dark controls and in photolyzed solutions. The recovered lifetime components in pH 7.4 phosphate buffer at 23 degrees C were 3.5 and 0.5 ns before irradiation and 2.7 and 0.5 ns after irradiation. As the UV dose increased, the relative weighting coefficient of the 2.7-ns decay component decreased, and that of the 0.5-ns component increased, resulting in an overall lifetime shortening. Similar results were obtained in 5 M guanidine hydrochloride solutions where lifetime components of 2.7 and 0.5 ns were observed. These observations were in contrast to the behavior of tryptophan monomer solutions which did not show any change in fluorescence decay kinetics upon UV photolysis but only a reduced fluorescence intensity. Steady-state fluorescence spectra and fluorescence quantum yields were also measured at 23 degrees C for unirradiated bovine alpha-crystallin and gave phi F = 0.11 +/- 0.01 in pH 7.4 buffer and phi F = 0.10 +/- 0.01 in 5 M guanidine hydrochloride solutions. The combined steady-state and fluorescence decay data were consistent with assignment of the long-lived fluorescence decay component in alpha-crystallin to emission from Trp-9, which is known to photolyze relatively rapidly. The short decay component was assigned to Trp-60, which photolyzed much more slowly. We thus provide an example of using steady-state photochemical data to assign fluorescence decay components in a multi-tryptophan protein.