Os(bipy)(CN)4]2- and its relatives as components of polynuclear assemblies: structural and photophysical properties

A series of diimine-tetracyanoosmate anions [Os(diimine)(CN)4]2- [diimine=2,2'-bipyridine (bipy), 2,2'-bipyrimidine (bpym), 1,10-phenanthroline (phen), and 4,4'-tBu2-2,2'-bipyridine (tBu2bpy)] were prepared and isolated as their Na+ salts (water soluble) or PPN+ salts (soluble in organic solvents). Several examples were crystallographically characterized; the Na+ salts form a range of 1D, 2D, or 3D infinite coordination polymers via coordination of the cyanide groups to Na+ cations in either an end-on or a side-on manner. The [Os(diimine)(CN)4]2- anions are solvatochromic, showing three MLCT absorptions, which are considerably blue-shifted in water compared to organic solvents, in the same way as is well-known for the analogous [Ru(diimine)(CN)4]2- anions. Luminescence in the red region of the spectrum is very weak but (following the expected solvatochromic behavior) is higher energy and more intense in water. However, by exploiting the effect of metallochromism (ref 4), the emission from [Os(tBu2bpy)(CN)4]2- in MeCN can be very substantially boosted in energy, intensity, and lifetime in the presence of Lewis-acidic metal cations (Na+, Ba2+, Zn2+), which, in a relatively noncompetitive solvent, coordinate to the cyanide groups of [Os(tBu2bpy)(CN)4]2-. This has an effect similar in principle to hydrogen bonding of the cyanides to delta+ protons of water, but very much stronger, such that in the presence of Zn2+ ions in MeCN the 1MLCT and 3MLCT absorptions are blue-shifted by ca. 7000 cm(-1), and the luminescence moves from 970 nm (vanishingly weak) to 610 nm with a lifetime of 120 ns (dominant component). Thus, the binding of metal cations to the cyanides provides a mechanism to incorporate [Os(diimine)(CN)4]2- complexes into polynuclear assemblies and simultaneously increases their 3MLCT energy and lifetime to an extent that makes them comparable to much-stronger luminophores such as Ru(II)-polypyridines.     

Structural and photophysical properties of coordination networks combining [Ru(bipy)(CN)4]2- anions and lanthanide(III) cations: rates of photoinduced Ru-to-lanthanide energy transfer and sensitized near-infrared luminescence

Co-crystallization of K2[Ru(bipy)(CN)4] with lanthanide(III) salts (Ln = Pr, Nd, Gd, Er, Yb) from aqueous solution affords coordination oligomers and networks in which the [Ru(bipy)(CN)4]2- unit is connected to the lanthanide cation via Ru-CN-Ln bridges. The complexes fall into two structural types: [{Ru(bipy)(CN)4}2{Ln(H2O)m}{K(H2O)n}] x xH2O (Ln = Pr, Er, Yb; m = 7, 6, 6, respectively), in which two [Ru(bipy)(CN)4]2- units are connected to a single lanthanide ion by single cyanide bridges to give discrete trinuclear fragments, and [{Ru(bipy)(CN)4}3{Ln(H2O)4}2] x xH2O (Ln = Nd, Gd), which contain two-dimensional sheets of interconnected, cyanide-bridged Ru2Ln2 squares. In the Ru-Gd system, the [Ru(bipy)(CN)4]2- unit shows the characteristic intense (3)metal-to-ligand charge transfer luminescence at 580 nm with tau = 550 ns; with the other lanthanides, the intensity and lifetime of this luminescence are diminished because of a Ru --> Ln photoinduced energy transfer to low-lying emissive states of the lanthanide ions, resulting in sensitized near-infrared luminescence in every case. From the degree of quenching of the Ru-based emission, Ru --> Ln energy-transfer rates can be estimated, which are in the order Yb (k(EnT) approximately 3 x 10(6) sec(-1), the slowest energy transfer) < Er < Pr < Nd (k(EnT) approximately 2 x 10(8) sec(-1), the fastest energy transfer). This order may be rationalized on the basis of the availability of excited f-f levels on the lanthanide ions at energies that overlap with the Ru-based emission spectrum. In every case, the lifetime of the lanthanide-based luminescence is short (tens/hundreds of nanoseconds, instead of the more usual microseconds), even when the water ligands on the lanthanide ions are replaced by D2O to eliminate the quenching effects of OH oscillators; we tentatively ascribe this quenching effect to the cyanide ligands.     

Structural characterization and spectroelectrochemical, anion sensing and solvent dependence photophysical studies of a bimetallic Ru(II) complex derived from 1,3-di(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)benzene

The X-ray crystal structure of a mixed-ligand bimetallic ruthenium(II) complex of composition [(bipy)(2)Ru(H(2)Impib)Ru(bipy)(2)](ClO(4))(4) (1), where H(2)Impib = 1,3-di(1H-imidazo[4,5-f][1,10]phenanthroline-2-yl)benzene and bipy = 2,2'-bipyridine, has been determined and showed that the compound crystallized in monoclinic form with the space group P2(1)/c. The absorption, steady state and time-resolved luminescence spectral properties of the complex were thoroughly investigated in different solvents. The compound displays strong luminescence at room temperature with lifetimes in the range of 140-470 ns, depending upon the nature of the solvent. Solvent-induced lifetime tuning makes the complex a suitable solvatochromic probe. The complex is found to undergo one simultaneous two-electron reversible oxidation in the positive potential window (0 to +1.6 V) and four quasi-reversible reductions in the negative potential window (0 to -2.2 V). Spectroelectrochemical studies have also been carried out for the bimetallic compound in the range of 300-1600 nm. With stepwise oxidation of the Ru(ii) centers replacement of MLCT bands by LMCT bands occur with the development of a broad band at λ(max) = 1260 nm, which is ascribed to inter-valence charge-transfer (IVCT) transition for the mixed-valence Ru(II)Ru(III) species. The anion sensing properties of the receptor were thoroughly investigated in acetonitrile solution using absorption, steady state and time-resolved emission spectroscopic studies. The anion sensing studies revealed that the receptor acts as sensor for F(-), AcO(-) and H(2)PO(4)(-). It is evident that in the presence of excess F(-) and AcO(-) ions, deprotonation of the imidazole N-H fragments of the receptor occurs, an event which is signaled by the change of color from yellow to orange visible to the naked eye. From the absorption and emission titration studies the binding/equilibrium constants of the receptor with the anions have also been determined. Anion-induced lifetime quenching by F(-) and AcO(-) and enhancement by H(2)PO(4)(-) makes the receptor a suitable lifetime-based sensor for selective anions. Cyclic voltammetry (CV) measurements of the compound carried out in acetonitrile have provided evidence in favor of anion-dependent electrochemical responses with F(-) and AcO(-) ions.     

Surface-modified CdSe quantum dots as luminescent probes for cyanide determination

Luminescent surface-modified CdSe semiconductor quantum dots (QDs), with nanoparticle (NP) size distribution in the order of 2-7 nm, have been synthesized for optical determination of cyanide ions. The nanoparticles have been functionalised with tert-butyl-N-(2-mercaptoethyl)-carbamate (BMC) groups and exhibit a strong fluorescent emission at about 580 nm with rather long fluorescence lifetimes (several hundred nanoseconds) in aerated methanolic solution. The observed luminescence emitted by the synthesized nanocrystals was tremendously increased by photo-activation under sunlight exposure. The functionalised QDs turned out to exhibit excellent long-term stability when stored in the dark (no significant changes in QDs luminescence emission intensity was observed even after two months from synthesis). The functionalisation of the NPs with carbamate ligand allowed a highly sensitive determination of free cyanide via analyte-induced changes in the photoluminescence (fluorescence quenching of intensity at 580 nm and lifetime changes) of the modified quantum dots (excited at 400 nm). A detection limit of 1.1 × 10⁻⁷ M (2.9 μg l⁻¹) of cyanide ions was obtained, while the interfering effect of other inorganic anions (including NO₃⁻, Cl⁻ or SCN⁻) was negligible even at 200-fold level concentrations in excess of cyanide.     

Fluorescence lifetime enhancement of organic chromophores attached to gold nanoparticles

We present for the first time experimental evidence of fluorescence lifetime enhancement of organic chromophores attached to metal nanospheres via radiative decay engineering. The hybrid system (HS) was a modified "diconjugated" molecular probe, 4-acetamido-4'-maleimidylstilbene-2,2'-dithiol (AMDT), covalently bound to the surface of 5-nm-diameter Au nanospheres by its two sulfur atoms, at a distance d < 1 nm and with its molecular axis parallel to the surface of the nanoparticle surface. We measured a fluorescence lifetime increase of a factor of 2 at room temperature (tau(AMDT) = (4.32 +/- 0.10) ns and tau(HS) = (8.73 +/- 0.23) ns) and a factor of 3.4 at 4.2 K (tau(AMDT) = (2.64 +/- 0.07) ns and tau(HS) = (7.96 +/- 0.14) ns). We also found that the fluorescence quantum yield of this hybrid system is not reduced, proof of a weak energy transfer between the molecular probe and the nanoparticle. These results demonstrate that a molecular dipole oriented parallel to the metal surface tends to be reduced by the coupling with its image.     

A highly fluorescent anthracene-containing hybrid material exhibiting tunable blue-green emission based on the formation of an unusual "T-shaped" excimer

A series of flexible bis(9-anthryldiamine) ligands (L1-L3) linked with alkyl spacers of different chain length was synthesized and characterized, in order to investigate the coordination behavior of these diamine ligands with metal ions (Zn2+, etc.) based on fluorescence measurements. The results showed that, in the case of anthryldiamine ligands bearing two- or four-carbon links, the zinc ion induced a chelation-enhanced fluorescence (CHEF) effect in aqueous media, while a trace amount of water could selectively quench the blue emission of the Zn(II) complex with a three-carbon-linked ligand (1). Meanwhile, the introduction of more water (concentration >11 %) resulted in the formation of a new green luminescent species; the luminescence intensity was enhanced stepwise to a maximum with addition of approximately 30 % water in THF solution. The peak position (centered at approximately 500 nm) and the lifetime measurement (tau=19.59 ns) indicated that the green luminescence was attributable to a novel edge-to-face dimeric conformation ("T-shaped" conformation) of anthracene, and not to the more common face-to-face dimeric conformation. Accordingly, 1H NMR spectroscopic studies in nonaqueous or aqueous solution confirmed this T-shaped conformation, which is consistent with the results of single-crystal X-ray structure analysis and solid-state photoluminescence studies.     

Monolayer dispersion of NiO in NiO/Al2O3 catalysts probed by positronium atom

NiO/Al(2)O(3) catalysts with different NiO loadings were prepared by impregnation method. The monolayer dispersion capacity of NiO is determined to be about 9 wt.% through XRD quantitative phase analysis. Positron lifetime spectra measured for NiO/Al(2)O(3) catalysts comprise two long and two short lifetime components, where the long lifetimes τ(3) and τ(4) correspond to ortho-positronium (o-Ps) annihilation in microvoids and large pores, respectively. With increasing loading of NiO from 0 to 9 wt.%, τ(4) drops drastically from 88 to 38 ns. However, when the NiO loading is higher than 9 wt.%, τ(4) shows a slower decrease. Variation of λ(4) (1/τ(4)) as a function of the NiO content can be well fitted by two straight lines with different slopes. The relative intensity of τ(4) also shows a fast decrease followed by a slow decrease for the NiO content lower and higher than 9 wt.%, respectively. The coincidence Doppler broadening measurements reveal a continuous increase of S parameter with increasing NiO loading up to 9 wt.% and then a decrease afterwards. This is due to the variation in intensity of the narrow component contributed by the annihilation of para-positronium (p-Ps). Our results show that the annihilation behavior of positronium is very sensitive to the dispersion state of NiO on the surface of γ-Al(2)O(3). When the NiO loading is lower than monolayer dispersion capacity, spin conversion of positronium induced by NiO is the dominant effect, which causes decrease of the longest lifetime and its intensity but increase of the narrow component intensity. After the NiO loading is higher than monolayer dispersion capacity, the spin conversion effect becomes weaker and inhibition of positronium formation by NiO is strengthened, which results in decrease of both the long lifetime intensity and the narrow component intensity. The reaction rate constant is determined to be (1.50 ± 0.04) × 10(10) g mol(-1) s(-1) and (3.43 ± 0.20) × 10(9) g mol(-1) s(-1) for NiO content below and above monolayer dispersion capacity, respectively.     

Direct observation of the luminescence from the (3)deltadelta excited state of Re(2)Cl(2)(p-OCH(3)form)(4)

There are only a few reports on the measurement of the energy of the low-lying (3)deltadelta state of quadruply bonded bimetallic complexes, and the direct observation of the (1)deltadelta excited electronic state was only recently reported. In the quadruply bonded bimetallic complexes reported to date, luminescence arises from their (1)deltadelta excited state, and the (3)deltadelta state is nonemissive. Here we report the luminescence of Re(2)Cl(2)(p-OCH(3)form)(4) [p-OCH(3)form = (p-CH(3)OC(6)H(4))NCHN(p-CH(3)OC(6)H(4))(-)] observed upon 400-460 nm excitation with maxima at 820 nm (CH(2)Cl(2), tau = 1.4 micros) and 825 nm (CH(3)CN, tau = 1.3 micros) at 298 K. From the large Stokes shift, the vibronic progression at 77 K, the quenching by O(2), the long lifetime, and the calculated energy of the (3)deltadelta state, the luminescence of Re(2)Cl(2)(p-OCH(3)form)(4) and the corresponding transient absorption signal are assigned as arising from the (3)deltadelta ((3)A(2u)) excited state of the complex.     

Selective anion encapsulation by a metalated cryptophane with a pi-acidic interior

Metalation of the exterior arene faces of the molecular capsule (+/-)-cryptophane-E with [Cp*Ru]+ moieties results in a pi-acidic cavity capable of encapsulating anions. The [CF3SO3]- and [SbF6]- salts have been crystallographically characterized and demonstrate the encapsulation of these anions by the metalated cryptophane. 1H and 19F NMR spectroscopy establish the binding of anions in NO2CD3 solution and reveal the relative affinity of the cavity for different anions (KX-/KOTf-): [BF4]- approximately 0, [PF6]- = 1.18, [CF3SO3]- identical with 1, [SbF6]- = 0.30. Variable temperature rate studies reveal the activation barrier for triflate encapsulation to be DeltaG298K = 18.0(8) kcal.mol-1 (DeltaH = 17.5(4) kcal.mol-1 and DeltaS = 2(1) cal.mol-1.K-1).     

Triplet formation involving a polar transition state in a well-defined intramolecular perylenediimide dimeric aggregate

A cofacially stacked perylenediimide (PDI) dimer with a xanthene linker was studied under a variety of conditions (solvent, temperature) and serves as a model for the molecular interactions occurring in solid films. Intrinsically, the PDI units have a fluorescence quantum yield (Phi F) close to unity, but Phi F is lowered by a factor of 6-50 at room temperature when two PDI moieties are held in a cofacial arrangement, while the decay time of the most emissive state is increased significantly (tau F = 27 ns in toluene) compared to a monomeric PDI molecule (tau F = 4 ns). Fluorescence measurements show a strong solvent and temperature dependence of the characteristics of the emissive excited state. In a glassy matrix of toluene (TOL) or 2-methyltetrahydrofuran (2-MeTHF), Phi F is high, and the decay time is long (tau F = approximately 50 ns). At higher temperature, both Phi F and tau F are reduced. Interestingly, at room temperature, Phi F and tau F are also reduced with increasing solvent polarity, revealing the presence of a polar transition state. Photoinduced absorption of the stacked molecules from the picosecond to the microsecond time scale shows that after photoexcitation reorganization occurs in the first nanoseconds, followed by intersystem crossing (ISC), producing the triplet excited state. Using singlet oxygen ( (1)Delta g) luminescence as a probe, a triplet quantum yield (Phi T) greater than 50% was obtained in air-saturated 2-Me-THF. Triplet formation is exceptional for PDI chromophores, and the enhanced ISC is explained by a decay involving a highly polar transition state.     

Time gating improves sensitivity in energy transfer assays with terbium chelate/dark quencher oligonucleotide probes

Lanthanides are attractive as biolabels because their long luminescence decay rates allow time-gated detection, which separates background scattering and fluorescence from the lanthanide emission. A stable and highly luminescent terbium complex based on a tetraisophthalamide (TIAM) chelate is paired with a polyaromatic-azo dark quencher (referred to as a Black Hole Quencher or BHQ) to prepare a series of 5'TIAM(Tb)/3'BHQ dual-labeled oligonucleotide probes with no secondary structure. Luminescence quenching efficiency within terbium/BHQ probes is very dependent on the terbium-BHQ distance. In an intact probe, the average terbium-BHQ distance is short, and Tb --> BHQ energy transfer is efficient, decreasing both the terbium emission intensity and lifetime. Upon hybridization or nuclease digestion, which spatially separate the Tb and BHQ moieties, the Tb luminescence intensity and lifetime increase. As a result, time-gated detection increases the emission intensity ratio of the unquenched probe/quenched probe due to the shorter lifetime of the quenched species. A 40-mer probe that has a 3-fold increase in steady-state luminescence upon digestion has a 50-fold increase when gated detection is used. This study demonstrates that time gating with lanthanide/dark quencher probes in energy transfer assays is an effective means of improving sensitivity.     

Photophysical behavior of a dimeric cyanine dye (BOBO-1) within cationic liposomes

This study is aimed at establishing optimal conditions for the use of 2,2'-[1,3-propanediylbis[(dimethyliminio)-3,1-propanediyl-1(4H)-pyridinyl-4-ylidenemethy-lidyne]]bis[3-methyl]-tetraiodide (BOBO-1) as a fluorescent probe in the characterization of lipid/DNA complexes (lipoplexes). The fluorescence spectra, anisotropy, fluorescence lifetimes and fluorescence quantum yields of this dimeric cyanine dye in plasmid DNA (2694 base pairs) with and without cationic liposomes (1,2-dioleoyl-3-trimethylammonium-propane [DOTAP]), are reported. The photophysical behavior of the dye in the absence of lipid was studied for several dye/DNA ratios using both supercoiled and relaxed plasmid. At dye/DNA ratios (d/b) below 0.01 the fluorescence intensity increases linearly, whereas lifetime and anisotropy values of the dye are constant (tau approximately 2.5 ns and = 0.20). By agarose gel electrophoresis it was verified that up to d/b = 0.01 DNA conformation is not considerably modified, whereas for d/b = 0.05-0.06 a single heavy band appears on the gel. For these and higher dye/DNA ratios the fluorescence intensity, anisotropy and average lifetime values decrease with an increase in BOBO-1 concentration. When cationic liposomes are added to the BOBO-1/DNA complex, an additional effect is noticed: The difference in the environment probed by BOBO-1 bound to DNA leads to a decrease in quantum yield and average lifetime values, and a redshift is apparent in the emission spectrum. For fluorescence measurements including energy transfer (FRET), a d/b ratio of 0.01 seems to be adequate because no considerable change on DNA conformation is detected, a considerable fluorescent signal is still measured after lipoplex formation, and energy migration is not efficient.     

Hydrogen bond breaking dynamics of the water trimer in the translational and librational band region of liquid water.

The effect of exciting each of the three classes of intermolecular vibrations on the hydrogen bond lifetime (tau(H)) of the isolated water trimer is investigated by far-infrared laser spectroscopy. Single excitation of a librational vibration decreases tau(H) by 3 orders of magnitude to tau(H) = 1-6 ps, comparable to the time scale of a number of important bulk water dynamical relaxation processes. In contrast, excitation of translational or torsional vibrations has no significant effect (tau(H) = 1-2 ns). Although such a dependence of tau(H) on intermolecular motions has also been proposed for liquid water via computer simulations, these are the first experiments that provide a detailed molecular picture of the respective motions without extensive interpretation.     

Characterization of carbon monoxide photodissociation from Fe(II)LPO with photoacoustic calorimetry

Lactoperoxidase belongs to a family of mammalian peroxidases that catalyze the oxidation of halides and small organic molecules in the presence of H2O2. We have used photoacoustic calorimetry to characterize thermodynamic parameters associated with ligand dissociation from bovine milk lactoperoxidase. Upon CO photorelease, a prompt (tau < 50 ns) exothermic volume contraction (DeltaH = -20 +/- 7 kcal mol-1 and DeltaH = -2 +/- 1 mL mol-1) was measured at pH 7.0 and 4.0, whereas an endothermic expansion (DeltaH = 30 +/- 13 kcal mol-1 and DeltaV = 9 +/- 2 mL mol(-1)) was observed at pH 10.0 and 7.0 in the presence of 500 mM NaCl. We attribute the observed volume and enthalpy changes to electrostriction arising from changes in the charge distribution associated with a reorganization of the heme binding pocket upon ligand dissociation. It is likely that cleavage of the Fe-CO bond is accompanied by distortion of a salt bridge between Arg557 and the heme propionate group, resulting in the observed electrostriction due to changes in charge distribution.     

Hydrogen-bonded assemblies of ruthenium(II)-biimidazole complex cations and cyanometallate anions: structures and photophysics

The complex cations [RuL2(H2biim)]2+ (L=bipy, 4,4'-tBu2-bipy) interact with cyanometallate anions via a chelating hydrogen-bonding interaction between the two N-H donors of the complex cation and the N lone pair of one cyanide ligand in the complex anion; the anion hexacyanoferrate(III) quenches the Ru(II)-based luminescence in CH2Cl2 solution by photoinduced electron-transfer within the H-bonded assembly, whereas hexacyanocobaltate(III) enhances the Ru(II)-based luminescence.     

Extreme fluorescence sensitivity of some aniline derivatives to aqueous and nonaqueous environments: mechanistic study and its implication as a fluorescent probe

Effects of solvent water on the photophysical properties of a series of meta- and para-substituted anilines have been investigated by means of time-resolved fluorescence, transient absorption, and photoacoustic measurements. Some aniline derivatives exhibit extremely short fluorescence lifetime (tau(f)) and small quantum yield (Phi(f)) in water (e.g., tau(f) = 45 ps and Phi(f) = 0.0019 for m-cyanoaniline (m-ANCN) in H(2)O), which is in marked contrast with their much larger values in nonaqueous solvents (tau(f) = 7.3 ns and Phi(f) = 0.14 for m-ANCN in acetonitrile). Photoacoustic and transient absorption measurements show that the remarkable fluorescence quenching of m-ANCN in water is attributed almost exclusively to fast internal conversion. The lifetime measurements of m-ANCN in H(2)O/acetonitrile binary solvent mixtures reveal that the quenching is related to variation of hydrogen-bonding interactions between the amino group and water molecules and the conformational change of the amino group upon electronic excitation. Similar fluorescence quenching due to solvent water is also found for N-alkylated m-ANCNs. The drastic differences in the fluorescence intensity and lifetime of m-ANCNs under hydrophobic and hydrophilic environments and also the large solvent polarity dependence of the fluorescence band position suggest the possibility that they can be utilized as fluorescent probes for investigating the microenvironment of biological systems. In suspensions of human serum albumin (HSA) in water, remarkable enhancement of the fluorescence intensity and lifetime is observed for m-ANCN and its N-alkylated derivatives, demonstrating that m-ANCNs can be a candidate for novel fluorescent probe with small molecular size.     

Metallocyclodextrins as building blocks in noncovalent assemblies of photoactive units for the study of photoinduced intercomponent processes

Cyclodextrin cups have been employed to build supramolecular systems consisting of metal and organic photoactive/redox-active components; the photoinduced communication between redox-active units assembled in water via noncovalent interactions is established. The functionalization of a beta-cyclodextrin with a terpyridine unit, ttp-beta-CD, is achieved by protection of all but one of the hydroxyl groups by methylation and attachment of the ttp unit on the free primary hydroxyl group. The metalloreceptors [(beta-CD-ttp)Ru(ttp)][PF(6)](2), [(beta-CD-ttp)Ru(tpy)][PF(6)](2), and [Ru(beta-CD-ttp)(2)][PF(6)](2) are synthesized and fully characterized. The [(beta-CD-ttp)Ru(ttp)][PF(6)](2) metalloreceptor exhibits luminescence in water, centered at 640 nm, from the (3)MLCT state with a lifetime of 1.9 ns and a quantum yield of Phi = 4.1 x 10(-)(5). Addition of redox-active quinone guests AQS, AQC, and BQ to an aqueous solution of [(beta-CD-ttp)Ru(ttp)](2+) results in quenching of the luminescence up to 40%, 20%, and 25%, respectively. Measurement of the binding strength indicates that, in saturation conditions, 85% for AQS and 77% for AQC are bound. The luminescence quenching is attributed to an intercomponent electron transfer from the appended ruthenium center to the quinone guest inside the cavity. Control experiments demonstrate no bimolecular quenching at these conditions. A photoactive osmium metalloguest, [Os(biptpy)(tpy)][PF(6)], is designed with a biphenyl hydrophobic tail for insertion in the cyclodextrin cavity. The complex is luminescent at room temperature with an emission band maximum at 730 nm and a lifetime of 116 ns. The osmium(III) species are formed for the study of photoinduced electron transfer upon their assembly with the ruthenium cyclodextrin, [(beta-CD-ttp)Ru(ttp)](2+). Time-resolved spectroscopy studies show a short component of 10 ps, attributed to electron transfer from Ru(II) to Os(III) giving an electron transfer rate 9.5 x 10(9) s(-)(1).     

Spectroscopic characterization of flavin mononucleotide bound to the LOV1 domain of Phot1 from Chlamydomonas reinhardtii

The absorption and emission behavior of flavin mononucleotide (FMN) in the light-, oxygen- and voltage-sensitive (LOV) domain LOV1 of the photoreceptor Phot1 from the green alga Chlamydomonas reinhardtii was studied. The results from the wild-type (LOV1-WT) were compared with those from a mutant in which cysteine 57 was replaced by serine (LOV1-C57S), and with free FMN in aqueous solution. A fluorescence quantum yield of phi(F) = 0.30 and a fluorescence lifetime of tau(F) = 4.6 ns were determined for FMN in the mutant LOV1-C57S, whereas these quantities are reduced to about phi(F) = 0.17 and tau(F) = 2.9 ns for LOV1-WT, indicating an enhanced intersystem crossing in LOV1-WT because of the adjacent sulfur of C57. A single-exponential fluorescence decay was observed in picosecond laser time-resolved fluorescence measurements for both LOV1-WT and LOV1-C57S as expected for excited singlet state relaxation by intersystem crossing and internal conversion. An excitation intensity dependent fluorescence signal saturation was observed in steady-state fluorescence measurements for LOV1-WT, which is thought to be because of the formation of a long-lived intermediate flavin-C(4a)-cysteinyl adduct in the triplet state (few microseconds triplet lifetime, adduct lifetime around 150 s). No photobleaching was observed for LOV1-C57S, because no thiol group is present in the vicinity of FMN for an adduct formation.     

Exploring 12'-apo-beta-carotenoic-12'-acid as an ultrafast polarity probe for ionic liquids

The ultrafast excited-state dynamics of the carbonyl-containing carotenoid 12'-apo-beta-carotenoic-12'-acid (12'CA) have been used for probing the microscopic environment in various ionic liquids (ILs). The following IL cations were investigated: 1,3-di-n-alkyl-imidazolium featuring different n-alkyl chain lengths and also additional methylation at the C2 position, triethylsulfonium, as well as two tetraalkylammonium ions. These were combined with different anions: [BF4]-, [PF6]-, ethyl sulfate ([EtOSO3]-), and bis(trifluoromethylsulfonyl)amide ([Tf2N]-). The probe molecule was excited via the S0 --> S2 transition at 425 or 430 nm, and the characteristic stimulated emission decay of the low-lying excited electronic S1/ICT (intramolecular charge transfer) state of 12'CA was monitored in the near IR (850 or 860 nm). Its lifetime tau1 is sensitive to the micropolarity-induced stabilization of S1/ICT relative to S0. The lifetime tau1 of the S1/ICT state varies only moderately in all ionic liquids studied here ( approximately 40-110 ps), which lies in the range between ethanol (109 ps) and methanol (49 ps). While organic solvents show an excellent correlation of tau1 with the solvent polarity function Deltaf = (epsilon - 1)/(epsilon + 2) - (n2 - 1)/(n2 + 2), where epsilon and n are the static dielectric constant and the refractive index of the solvent, respectively, this is not the case for ILs. This is due to dominant local electrostatic probe-cation interactions which cannot be easily quantified by macroscopic quantities. Methylation at the C2 position of 1,3-di-n-alkyl-imidazolium reduces the accessibility of the cation and therefore the electrostatic stabilization of the probe, resulting in an increase of tau1. A similar increase is observed upon extension of one of the n-alkyl chains from ethyl to n-decyl. Tetraalkylammonium ILs show an increased tau1 probably due to their more delocalized positive charge which cannot interact so favorably with the probe, in contrast to trialkylsulfonium ILs where the charge is more localized on the sulfur atom. The dependence of tau1 on the IL anion is much weaker, the only notable exception being [EtOSO3]-, where 12'CA experiences a less polar local environment than expected on the basis of extrapolated static dielectric constants. This is possibly due to the competition of the anion and probe for the cation interaction sites. Considerable electrostatic probe-cation interactions can be also introduced by addition of large amounts of LiClO4 salt to ethanol and diethyl ether. In this case, tau1 also strongly decreases, indicating an efficient coordination of Li+ cation(s) with the carbonyl oxygen at the negative end of the probe molecule. The S1/ICT --> S0 internal conversion of the 12'CA probe in ILs accelerates with increasing temperature, which can be characterized by an apparent activation energy of a few kJ mol-1, which is expected for energy-dependent nonradiative processes.     

Time-resolved fluorescence of tryptophans in yeast hexokinase-PI: effect of subunit dimerization and ligand binding

Time-resolved and steady-state fluorescence measurements have been performed on monomeric and dimeric forms of yeast hexokinase-PI. Observation of similar emission spectra and fluorescence decay parameters for both the forms of the enzyme suggests that tryptophan residue(s) are not likely to be present at the subunit-subunit interface and the process of dimerization does not perturb the local environment of tryptophan(s). The fluorescence decay of tryptophans in enzyme could be fitted to a bi-exponential function with two lifetime components, tau1 approximately 2.2 ns and tau2 approximately 3.9 ns. Binding of glucose, which is known to convert the 'open' conformation of the enzyme to a 'closed' active conformation, results in approximately 30% reduction in emission intensity and a selective decrease in tau1 from approximately 2.2 to approximately 1.1 ns. These effects can be reversed by the addition of trehalose 6-phosphate (an inhibitor of yeast hexokinase), suggesting that the trehalose 6-phosphate inhibits the enzyme by binding to its 'open' inactive conformation rather than competing with glucose to bind to the 'closed' active conformation. Binding of nucleotide ligands (ATP, ADP and adenyl-(beta,gamma-methylene)-diphosphate (AMPPCP)) to the monomeric or dimeric form of enzyme quenched the steady-state fluorescence by approximately 4-8%, but had no measurable effect on the distribution of lifetimes or on their magnitudes. Addition of nucleotides to the enzyme-glucose complex also did not produce any further change in fluorescence decay parameters. These results indicate that it is highly unlikely that the formation of a ternary enzyme-glucose-nucleotide complex from the binary enzyme-glucose complex is accompanied by a large conformational change in the enzyme, as has been surmised in some earlier studies.