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PubMed2000

Artificial Molecular Machines.

The miniaturization of components used in the construction of working devices is being pursued currently by the large-downward (top-down) fabrication. This approach, however, which obliges solid-state physicists and electronic engineers to manipulate progressively smaller and smaller pieces of matter, has its intrinsic limitations. An alternative approach is a small-upward (bottom-up) one, starting from the smallest compositions of matter that have distinct shapes and unique properties-namely molecules. In the context of this particular challenge, chemists have been extending the concept of a macroscopic machine to the molecular level. A molecular-level machine can be defined as an assembly of a distinct number of molecular components that are designed to perform machinelike movements (output) as a result of an appropriate external stimulation (input). In common with their macroscopic counterparts, a molecular machine is characterized by 1) the kind of energy input supplied to make it work, 2) the nature of the movements of its component parts, 3) the way in which its operation can be monitored and controlled, 4) the ability to make it repeat its operation in a cyclic fashion, 5) the timescale needed to complete a full cycle of movements, and 6) the purpose of its operation. Undoubtedly, the best energy inputs to make molecular machines work are photons or electrons. Indeed, with appropriately chosen photochemically and electrochemically driven reactions, it is possible to design and synthesize molecular machines that do work. Moreover, the dramatic increase in our fundamental understanding of self-assembly and self-organizational processes in chemical synthesis has aided and abetted the construction of artificial molecular machines through the development of new methods of noncovalent synthesis and the emergence of supramolecular assistance to covalent synthesis as a uniquely powerful synthetic tool. The aim of this review is to present a unified view of the field of molecular machines by focusing on past achievements, present limitations, and future perspectives. After analyzing a few important examples of natural molecular machines, the most significant developments in the field of artificial molecular machines are highlighted. The systems reviewed include 1) chemical rotors, 2) photochemically and electrochemically induced molecular (conformational) rearrangements, and 3) chemically, photochemically, and electrochemically controllable (co-conformational) motions in interlocked molecules (catenanes and rotaxanes), as well as in coordination and supramolecular complexes, including pseudorotaxanes. Artificial molecular machines based on biomolecules and interfacing artificial molecular machines with surfaces and solid supports are amongst some of the cutting-edge topics featured in this review. The extension of the concept of a machine to the molecular level is of interest not only for the sake of basic research, but also for the growth of nanoscience and the subsequent development of nanotechnology.

Journal Article↗

PubMed2006

Tetranuclear polybipyridyl complexes of Ru(II) and Mn(II), their electro- and photo-induced transformation into di-mu-oxo Mn(III)Mn(IV) hexanuclear complexes.

Three heterotetranuclear complexes, [{Ru(II)(bpy)(2)(L(n))}(3)Mn(II)](8+) (bpy = 2,2'-bipyridine, n = 2, 4, 6), in which a Mn(II)-tris-bipyridine-like centre is covalently linked to three Ru(II)-tris-bipyridine-like moieties using bridging bis-bipyridine L(n) ligands, have been synthesised and characterised. The electrochemical, photophysical and photochemical properties of these complexes have been investigated in CH(3)CN. The cyclic voltammograms of the three complexes exhibit two successive very close one-electron metal-centred oxidation processes in the positive potential region. The first, which is irreversible, corresponds to the Mn(II)/Mn(III) redox system (E(pa) approximately 0.82 V vs Ag/Ag(+) 0.01 M in CH(3)CN-0.1 M Bu(4)NClO(4)), whereas the second which is, reversible, is associated with the Ru(II)/Ru(III) redox couple (E(1/2) approximately 0.91 V). In the negative potential region, three successive reversible four electron systems are observed, corresponding to ligand-based reduction processes. The three stable dimeric oxidized forms of the complexes, [Mn(2)(III,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](11+), [Mn(2)(IV,IV)O(2){Ru(II)(bpy)(2)(L(n))}(4)](12+) and [Mn(2)(IV,IV)O(2){Ru(III)(bpy)(2)(L(n))}(4)](16+) are obtained in fairly good yields by sequential electrolyses after consumption of respectively 1.5, 0.5 and 3 electrons per molecule of initial tetranuclear complexes. The formation of the di-micro-oxo binuclear complexes are the result of the instability of the {[Ru(II)(bpy)(2)(L(n))](3)Mn(III)}(9+) species, which react with residual water, via a disproportionation reaction and the release of one ligand, [Ru(II)(bpy)(2)(L(n))](2+). A quantitative yield can be obtained for these reactions if the electrochemical oxidations are performed in the presence of an added external base like 2,6-dimethylpyridine. Photophysical properties of these compounds have been investigated showing that the luminescence of the Ru(II)-tris-bipyridine-like moieties is little affected by the presence of manganese within the tetranuclear complexes. A slight quenching of the excited states of the ruthenium moieties, which occurs by an intramolecular process, has been observed. Measurements made at low concentration (<1 x 10(-5) M) indicate that some decoordination of Mn(2+) arises in 1a-c. These measurements allow the calculation of the association constants for these complexes. Finally, photoinduced oxidation of the tetranuclear complexes has been performed by continuous photolysis experiments in the presence of a large excess of a diazonium salt, acting as a sacrificial oxidant. The three successive oxidation processes, Mn(II)--> Mn(III)Mn(IV), Mn(III)Mn(IV)--> Mn(IV)Mn(IV) and Ru(II)--> Ru(III) are thus obtained, the addition of 2,6-dimethylpyridine in the medium giving an essentially quantitative yield for the two first photo-induced oxidation steps as found for electrochemical oxidation.

Electrochemistry↗

PubMed2006

Compensation for PSII photoinactivation by regulated non-photochemical dissipation influences the impact of photoinactivation on electron transport and CO2 assimilation.

The extent to which PSII photoinactivation affects electron transport (PhiPSII) and CO2 assimilation remains controversial, in part because it frequently occurs alongside inactivation of other components of photosynthesis, such as PSI. By manipulating conditions (darkness versus low light) after a high light/low temperature treatment, we examined the influence of different levels of PSII inactivation at the same level of PSI inactivation on PhiPSII and CO2 assimilation for Arabidopsis. Furthermore, we compared PhiPSII at high light and optimum temperature for wild-type Arabidopsis and a mutant (npq4-1) with impaired capacities for energy dissipation. Levels of PSII inactivation typical of natural conditions (< 50%) were not associated with decreases in PhiPSII and CO2 assimilation at photon flux densities (PFDs) above 150 micromol m(-2) s(-1). At higher PFDs, the light energy being absorbed was in excess of the energy that could be utilized by downstream processes. Arabidopsis plants downregulate PSII activity to dissipate such excess in accordance with the level of PSII photoinactivation that also serves to dissipate absorbed energy. Therefore, the overall levels of non-photochemical dissipation and the efficiency of photochemistry were not affected by PSII inactivation at high PFD. Under low PFD conditions, such compensation is not necessary, because the amount of light energy absorbed is not in excess of that needed for photochemistry, and inactive PSII complexes are dissipating energy. We conclude that moderate photoinactivation of PSII complexes will only affect plant performance when periods of high PFD are followed by periods of low PFD.

Arabidopsis↗

PubMed2005

TiO2 nanoparticles in mesoporous TUD-1: synthesis, characterization and photocatalytic performance in propane oxidation.

A series of TiO2-TUD-1 samples was synthesized with a variable Ti loading in the range Si/Ti = 100, 20, 2.5, and 1.6, by using a one-pot surfactant-free procedure. The materials obtained were characterized by elemental analysis; X-ray diffraction (XRD); N2 sorption measurements; high-resolution TEM (HR-TEM); 29Si NMR, UV-visible and Raman spectroscopy. As a function of increasing metal loading either isolated Ti atoms, or (above a Ti loading of approximately 2.5 wt- %) combinations of isolated Ti atoms and anatase (TiO2) nanoparticles were obtained; both were incorporated in the highly porous siliceous matrix. The photocatalytic performance of these materials was tested by studying the propane oxidation process following irradiation at lambda = 365 nm, selectively activating the anatase nanoparticles. In comparison to commercial anatase powder, TiO2 nanoparticles in TUD-1 showed high photochemical selectivity towards acetone, the sample with a Si/Ti ratio of 1.6 being the most selective. Size and confinement effects are consistent with the difference in performance of the TUD-1 materials and TiO2, limiting the number of electron transfers available for each propane molecule.

Journal Article↗

PubMed2002

Seasonal responses of photosynthetic electron transport in Scots pine (Pinus sylvestris L.) studied by thermoluminescence.

The potential of photosynthesis to recover from winter stress was studied by following the thermoluminescence (TL) and chlorophyll fluorescence changes of winter pine needles during the exposure to room temperature (20 degrees C) and an irradiance of 100 micromol m(-2) s(-1). TL measurements of photosystem II (PSII) revealed that the S(2)Q(B)(-) charge recombinations (the B-band) were shifted to lower temperatures in winter pine needles, while the S(2)Q(A)(-) recombinations (the Q-band) remained close to 0 degrees C. This was accompanied by a drastically reduced (65%) PSII photochemical efficiency measured as F(v)/ F(m,) and a 20-fold faster rate of the fluorescence transient from F(o) to F(m) as compared to summer pine. A strong positive correlation between the increase in the photochemical efficiency of PSII and the increase in the relative contribution of the B-band was found during the time course of the recovery process. The seasonal dynamics of TL in Scots pine needles studied under field conditions revealed that between November and April, the contribution of the Q- and B-bands to the overall TL emission was very low (less than 5%). During spring, the relative contribution of the Q- and B-bands, corresponding to charge recombination events between the acceptor and donor sides of PSII, rapidly increased, reaching maximal values in late July. A sharp decline of the B-band was observed in late summer, followed by a gradual decrease, reaching minimal values in November. Possible mechanisms of the seasonally induced changes in the redox properties of S(2)/S(3)Q(B)(-) recombinations are discussed. It is proposed that the lowered redox potential of Q(B) in winter needles increases the population of Q(A)(-), thus enhancing the probability for non-radiative P680(+)Q(A)(-) recombination. This is suggested to enhance the radiationless dissipation of excess light within the PSII reaction center during cold acclimation and during cold winter periods.

Acclimatization↗

PubMed2004

Characterising sources and sinks of rural VOC in eastern France.

Fifty non-methane hydrocarbons (NMHC) and seventeen carbonyl compounds were measured at a French rural site from 1997 to 2001, as part of the EMEP programme. Data handling was based on an original source-receptor approach. First, the examination of the levels and trends was completed by the comparison of the seasonal distribution of rural and urban VOC/acetylene ambient ratios. This analysis has shown that most of the compounds derived from mixing and photochemical transformation of mid-range transported urban pollutants from the downwind urban area. Then, identified sources and sinks were temporally apportioned. Urban air masses mixing explains, at least, 80% of the wintertime levels of anthropogenic NMHC and isoprene. In summer, photochemistry dominates the day-to-day distribution of anthropogenic NMHC whilst summertime isoprene is also controlled by in-situ biogenic emissions. Then, the results of C(1)-C(3) carbonyls were discussed with respect to their direct biogenic and anthropogenic emissions and photochemical production through the [carbonyl/auto-exhaust tracers] emission ratio. Diluted vehicle exhaust emissions mainly contribute to the total content of lower aldehydes in winter while other processes control lower ketones. Secondary production is predominant in summer with at least a 50% high intensity. Its dependence upon temperature and radiation is also demonstrated. Finally, the importance of the primary and secondary biogenic production of acetone and formaldehyde is assessed. In particular, biogenic contribution would explain 37 +/- 25% of acetone levels in summer.

Air Pollutants↗

PubMed1993

Photochemical conversion of the O-intermediate to 9-cis-retinal-containing products in bacteriorhodopsin films.

The photochemical activity of the O-state was investigated in bacteriorhodopsin (BR) films containing wildtype BR at pH 6.5 in the presence of glycerol. The formation of a photoproduct of O with an absorption maximum at 490 nm and 9-cis-retinal configuration was found. This 490-nm product was named P and shows a slow thermal reaction into a compound with a maximal absorption at 380 nm which was named Q and contains free 9-cis-retinal in the proteins binding site. The photoproducts of O, i.e., P and Q, are very similar, or even identical, to those previously observed in blue membranes. Common to the O-state and blue membrane forms of bacteriorhodopsin is a protonated aspartic acid 85, and we suggest that it is the reduced negative charge around the Schiff base which is responsible for the 9-cis photoisomerization. The release of a proton from aspartic acid 85 is linked to the conversion of the O-state back to the initial state of BR. Therefore the conditions of low proton mobility in BR films containing glycerol favor the accumulation of the O-state. For optical and holographic applications such BR films are very attractive. It is possible to create photoproducts with red light which are thermally stable at room temperature and that can be photochemically erased. Dependent on the light composition both properties can be realized in the same sample material. This feature may bridge the gap between information processing and short-term and long-term storage of information with BR.

Bacteriorhodopsins↗

PubMed2002

Dynamic oxidation of gaseous mercury in the Arctic troposphere at polar sunrise.

Gaseous elemental mercury (Hg0) is a globally distributed air toxin with a long atmospheric residence time. Any process that reduces its atmospheric lifetime increases its potential accumulation in the biosphere. Our data from Barrow, AK, at 71 degrees N show that rapid, photochemically driven oxidation of boundary-layer Hg0 after polar sunrise, probably by reactive halogens, creates a rapidly depositing species of oxidized gaseous mercury in the remote Arctic troposphere at concentrations in excess of 900 pg m(-3). This mercury accumulates in the snowpack during polar spring at an accelerated rate in a form that is bioavailable to bacteria and is released with snowmelt during the summer emergence of the Arctic ecosystem. Evidence suggests that this is a recent phenomenon that may be occurring throughout the earth's polar regions.

Air Pollutants↗

PubMed2005

Structural changes of purple membrane and bacteriorhodopsin during its denaturation induced by high pH.

Bacteriorhodopsin (bR) trimers naturally form two-dimensional hexagonal crystals in purple membrane (PM), which make it very stable. However, the dnaturation of bR was found to occur during a very narrow pH range when the pH was increased above 12.0, as indicated by inactivation of the photochemical cycle observed by flash photolysis kinetic spectra. Here, atomic force microscopy was used to study the surface structural changes of PM during the denaturation process induced by high pH. Together with the absorption and fluorescence spectra, it was found that the structural changes could be divided into three steps. First, some hydrophobic amino acids of bR become exposed to the aqueous environment and PM loses its 2D crystalline structure, transforming into the so-called "nonisland" structure. Second, bR molecules are extracted out of membrane and form protrusions on the surface like islands in the sea; therefore, the "nonisland" structure transforms into the "island" structure. Finally, most bRs break off from the membrane and form large depositions.

Bacteriorhodopsins↗

PubMed2005

The quantum yield of CO2 fixation is reduced for several minutes after prior exposure to darkness. Exploration of the underlying causes.

Previous work has shown that the apparent quantum yield of CO2 fixation can be reduced for up to several minutes after prior exposure to darkness. In the work reported here, we investigated this phenomenon more fully and have deduced information about the underlying processes. This was done mainly by concurrent measurements of O2 and CO2 exchange in an oxygen-free atmosphere. Measurements of O2 evolution indicated that photochemical efficiency was not lost through dark adaptation, and that O2 evolution could proceed immediately at high rates provided that there were reducible pools of photosynthetic intermediates. Part of the delay in reaching the full quantum yield of CO2 fixation could be attributed to the need to build up pools of photosynthetic intermediates to high enough levels to support steady rates of CO2 fixation. There was no evidence that Rubisco inactivation contributed towards delayed CO2 uptake (under measurement conditions of low light). However, we obtained evidence that an enzyme in the reaction path between triose phosphates and RuBP must become completely inactivated in the dark. As a consequence, in dark-adapted leaves, a large amount of triose phosphates were exported from the chloroplast over the first minute of light rather than being converted to RuBP for CO2 fixation. That pattern was not observed if the pre-incubation light level was increased to just 3-5 micromol quanta m(-2) s(-1). The findings from this work underscore that there are fundamental differences in enzyme activation between complete darkness and even a very low light level of only 3-5 micromol quanta m(-2) s(-1) which predispose leaves to different gas exchange patterns once leaves are transferred to higher light levels.

Carbon Dioxide↗

PubMed1989

Turbulent transfer in a deciduous forest.

Carbon dioxide, water vapor and other passive scalars are physically transferred between a plant canopy and the atmosphere by turbulence. Intense and intermittent sweep and ejection events transfer most of the mass. Although the capacity for turbulence to transfer material is high, mass transfer is coupled to the diffusive source or sink strength of the foliage and soil and is ultimately limited to a minimum level set by the supply of material, or the demand for it. The diffusive source/sink strength of material leaving or entering leaves and the soil is a function of many physical, biological and chemical attributes and processes. These attributes and processes include the amount and distribution of foliage, the leaf boundary layer and surface resistances, the turbulence and radiative regimes in the canopy, biochemical and photochemical reactions and the scalar concentration field within and above the canopy and inside leaves and the soil. Here we discuss how these factors contribute to turbulent transfer in a deciduous forest.

Journal Article↗

PubMed1998

Demonstration of a Directly Photopatternable Spin-On-Glass Based on Hydrogen Silsesquioxane and Photobase Generators.

A commercially available spin-on-glass material, hydrogen silsesquioxane, has been rendered photopatternable to micrometer dimensions by the introduction of a photobase generator at concentrations of <5 wt %. The cure process proceeds via hydrolysis of the silyl hydride linkage by residual water in the film, as activated by a photogenerated base catalyst. Subsequent reaction of the generated silanol with neighboring silyl hydride groups yields a thermally stable siloxane cross-link. The photochemical cross-linking of hydrogen silsesquioxane shows high sensitivity (<40 mJ/cm2) and is not inhibited by molecular oxygen. The resultant oxide films can be further cured at elevated temperature either under an inert atmosphere to minimize the dielectric constant or heated in an air atmosphere to complete the conversion to silica glass. The oxidative nature of both the photo and thermal cure processes and the release of only traces of hydrogen as byproduct results in minimal weight loss in the film during processing.

Journal Article↗

PubMed2005

Investigation on the photochemical stability of lercanidipine and its determination in tablets by HPLC-UV and LC-ESI-MS/MS.

The photostability of lercanidipine, a dihydropyridine calcium-channel blocker used in the treatment of the hypertension, was studied. Drug substance and its solutions and formulations were exposed to UV-A radiations (solar simulator) and the photodegradation process was monitored by UV spectrophotometry, HPLC and HPLC-mass spectrometry. The effect of the solvent (ethanol and ethanol/PBS 1:1 v/v) on the photodegradation pathway and kinetic was evaluated. Lercanidipine and its photodegradation products were separated by a selective reversed-phase HPLC method and the main photoproducts were characterized by HPLC-MS/MS analysis, using an electrospray ionization source (ESI) and an ion trap analyzer. Photochemical reactions, involved in the photodegradation of lercanidipine, include aromatisation of the dihydropyridine moiety, formation of nitrosoderivatives and N-dealkylation in the side chain. The developed stability-indicating HPLC method was then applied to the quality control of commercially available lercanidipine formulations (tablets).

Calcium Channel Blockers↗

PubMed2001

UDFT and MCSCF descriptions of the photochemical Bergman cyclization of enediynes.

Several singlet and triplet potential energy surfaces (PES) for the Bergman cyclization of cis-1,5-hexadiyne-3-ene (1a) have been computed by UDFT, CI, CASCI, CASSCF, and CASMP2 methods. It is found that the first six excited states of 1a can be qualitatively described as linear combinations of the configurations of weakly interacting ethylene and acetylene units. Although the symmetry relaxation from C2nu to C2 makes cyclization of the 13B state Woodward-Hoffmann allowed, it also increases the probability of competing cis-trans isomerization. Hydrogen atom abstraction is another plausible pathway because the terminal alkyne carbons possess a large radical character. In view of the competing processes, we conclude that the Bergman cyclization along the 13B path is unlikely despite its exothermicity (Delta = -42 kcal/mol). Calculations on cyclic analogues of 1a lead to similar conclusions. A less exothermic, but more plausible pathway for photochemical cyclization lies on the 2(1)A PES (Delta = -18 kcal/mol). Compared to the 1(1)A(1) and 1(3)B states, the 2(1)A state has less in-plane electron repulsion which may facilitate cyclization. The resulting p-benzyne intermediate has an unusual electronic structure combining singlet carbene and open-shell diradical features. Deactivation of the 2(1)A state of 1a is a competing pathway.

Journal Article↗

PubMed2002

Ozonation of chlorophenylurea pesticides in water: reaction monitoring and degradation pathways.

The degradation of mono- and dichlorophenylureas under ozone/hydrogen peroxide conditions was investigated in order to establish the effect of the structural parameters. The N-dimethyl phenylureas (mono- and dichloro) appear to differ strongly from the corresponding N-methyl N-methoxy analogues in terms of disappearance of the parent pesticide and evolution of the by-products identified by MS and MS-MS. The degradation rate of the latter is slower by a factor of 2.5 giving rise to additional pathways (hydroxylation of the phenyl ring and carbinolamine intermediate). Experiments with 14C-labelled compounds allow a complete determination of the mass balances obtained after solid-phase-extraction (SPE). This study demonstrates the interest of SPE for reaction monitoring and compares the performances of different types of phases for this purpose used alone or in combination. Mineralisation is also evaluated regarding 14CO2 production and found to contribute up to 20% in the degradation process.

Biodegradation, Environmental↗

PubMed2001

Comparison of advanced oxidation processes in flow-through pilot plants (part I).

The advanced oxidation processes (AOPs) UV/H2O2, UV/O3 and O3/H2O2 were optimised to achieve a 90% degradation of the micropollutant atrazine in continuous-flow reactors. The experiments were performed with spiked Berlin tap-water. The comparison of mechanistically different oxidation systems needs a non-specific figure-of-merit to avoid influences by system-inherent parameters. The chosen figure-of-merit consists of the electrical energy per order of magnitude in oxidation per m3, EE/o. The combination O3/H2O2 proved to be the most efficient process by means of energy consumption.

Atrazine↗

PubMed1977

Light collection and harvesting processes in bacterial photosynthesis investigated on a picosecond time scale.

Fluorescence lifetimes have been determined for four strains of Rhodopseudomonas sphaeroides. Chromatophore samples were excited with a single picosecond flash, and the fluorescence was detected with a streak camera. The decay times are 100 psec in strains 2.4.1 and Ga, and 300 psec in the carotenoidless strain R-26. These times are related to the transfer of energy from the light-harvesting antenna pigment molecules to the photochemical reaction center. In strain PM-8 dpl, which lacks reaction centers, the lifetime is 1.1 nsec. In addition, we have obtained curves relating the quantum yield of fluorescence to the photon density of the excitation pulse. These curves can be fit with a simple model that relates excitonic processes to properties of the photosynthetic unit and that qualitatively describes differences between the mutant strains.

Journal Article↗

PubMed2004

Effect of binary and ternary polyethyleneglycol and/or beta-cyclodextrin complexes on the photochemical and photosensitizing properties of Naproxen.

The effect of the polyethylene glycol and/or beta-cyclodextrin on the photolability of aqueous solutions of the anti-inflammatory drug Naproxen was studied. In all systems studied, the photodegradation process followed zero-order kinetics, leading to the same photoproducts as in the absence of these additives. Kinetic studies revealed that the presence of polyethylene glycol (PEG) reduced drug photodegradation (phi=0.11 in water and phi=0.045 in the presence of 1% of PEG). By contrast, the binary inclusion complex, Naproxen:beta-CD, did not protect the drug from degradation, phi=0.11. However, the ternary complex, Naproxen:beta-CD:PEG, reduced the efficiency of the photodegradative process to a considerable extent, with phi=0.022 in this system. In all cases the presence of the different additives elicited a change in the photomixture composition, the alcoholic derivative being the major photoproduct formed. Nevertheless, the change in the efficiency of the process and the amount of the photoproducts formed in the different systems were not related with the biodamage produced by the drug. In this sense, the presence of free Naproxen clearly sensitized the photoperoxidation of linoleic acid. The photosensitizing effect decreased as the PEG concentration increased and was completely abolished by both the binary (Naproxen:beta-CD) and ternary (Naproxen:beta-CD:PEG) complexes. In light of these observations, it is possible to speculate that in these systems the prevention of biodamage would be due to a decrease in the contact between the short-lived species generated during Naproxen photodegradation and biological structures, rather than to the nature or amount of the photoproducts.

Kinetics↗