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Quantum Yield (quantum + yield)
Kinds of Quantum Yield Selected AbstractsFLUORESCENCE-BASED MAXIMAL QUANTUM YIELD FOR PSII AS A DIAGNOSTIC OF NUTRIENT STRESSJOURNAL OF PHYCOLOGY, Issue 4 2001Jean-Paul Parkhill In biological oceanography, it has been widely accepted that the maximum quantum yield of photosynthesis is influenced by nutrient stress. A closely related parameter, the maximum quantum yield for stable charge separation of PSII, (,PSII)m, can be estimated by measuring the increase in fluorescence yield from dark-adapted minimal fluorescence (Fo) to maximal fluorescence (Fm) associated with the closing of photosynthetic reaction centers with saturating light or with a photosynthetic inhibitor such as 3,-(3,4-dichlorophenyl)-1,,1,-dimethyl urea (DCMU). The ratio Fv/Fm (= (Fm, Fo)/Fm) is thus used as a diagnostic of nutrient stress. Published results indicate that Fv/Fm is depressed for nutrient-stressed phytoplankton, both during nutrient starvation (unbalanced growth) and acclimated nutrient limitation (steady-state or balanced growth). In contrast to published results, fluorescence measurements from our laboratory indicate that Fv/Fm is high and insensitive to nutrient limitation for cultures in steady state under a wide range of relative growth rates and irradiance levels. This discrepancy between results could be attributed to differences in measurement systems or to differences in growth conditions. To resolve the uncertainty about Fv/Fm as a diagnostic of nutrient stress, we grew the neritic diatom Thalassiosira pseudonana (Hustedt) Hasle et Heimdal under nutrient-replete and nutrient-stressed conditions, using replicate semicontinuous, batch, and continuous cultures. Fv/Fm was determined using a conventional fluorometer and DCMU and with a pulse amplitude modulated (PAM) fluorometer. Reduction of excitation irradiance in the conventional fluorometer eliminated overestimation of Fo in the DCMU methodology for cultures grown at lower light levels, and for a large range of growth conditions there was a strong correlation between the measurements of Fv/Fm with DCMU and PAM (r2 = 0.77, n = 460). Consistent with the literature, nutrient-replete cultures showed consistently high Fv/Fm (,0.65), independent of growth irradiance. Under nutrient-starved (batch culture and perturbed steady state) conditions, Fv/Fm was significantly correlated to time without the limiting nutrient and to nutrient-limited growth rate before starvation. In contrast to published results, our continuous culture experiments showed that Fv/Fm was not a good measure of nutrient limitation under balanced growth conditions and remained constant (,0.65) and independent of nutrient-limited growth rate under different irradiance levels. Because variable fluorescence can only be used as a diagnostic for nutrient-starved unbalanced growth conditions, a robust measure of nutrient stressed oceanic waters is still required. [source] A Molecular Brush Approach to Enhance Quantum Yield and Suppress Nonspecific Interactions of Conjugated Polyelectrolyte for Targeted Far-Red/Near-Infrared Fluorescence Cell ImagingADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Kan-Yi Pu Abstract A red-fluorescent conjugated polyelectrolyte (CPE, P2) is grafted with dense poly(ethylene glycol) (PEG) chains via click chemistry and subsequently modified with folic acid to form a molecular brush based cellular probe (P4). P4 self-assembles into a core,shell nanostructure in aqueous medium with an average size of 130 nm measured by laser light scattering. As compared to P2, P4 possesses not only a substantially higher quantum yield (11%), but also reduced nonspecific interactions with biomolecules in aqueous medium due to the shielding effect of PEG. In conjunction with its high photostability and low cytotoxicity, utilization of P4 as a far-red/near-infrared cellular probe allows for effective visualization and discrimination of MCF-7 cancer cells from NIH-3T3 normal cells in a high contrast, selective, and nonviral manner. This study thus demonstrates a flexible molecular brush approach to overcome the intrinsic drawbacks of CPEs for advanced bioimaging applications. [source] A Molecular Brush Approach to Enhance Quantum Yield and Suppress Nonspecific Interactions of Conjugated Polyelectrolyte for Targeted Far-Red/Near-Infrared Fluorescence Cell ImagingADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Kan-Yi Pu Abstract A red-fluorescent conjugated polyelectrolyte (CPE, P2) is grafted with dense poly(ethylene glycol) (PEG) chains via click chemistry and subsequently modified with folic acid to form a molecular brush based cellular probe (P4). P4 self-assembles into a core,shell nanostructure in aqueous medium with an average size of 130 nm measured by laser light scattering. As compared to P2, P4 possesses not only a substantially higher quantum yield (11%), but also reduced nonspecific interactions with biomolecules in aqueous medium due to the shielding effect of PEG. In conjunction with its high photostability and low cytotoxicity, utilization of P4 as a far-red/near-infrared cellular probe allows for effective visualization and discrimination of MCF-7 cancer cells from NIH-3T3 normal cells in a high contrast, selective, and nonviral manner. This study thus demonstrates a flexible molecular brush approach to overcome the intrinsic drawbacks of CPEs for advanced bioimaging applications. [source] Effect of the Media on the Quantum Yield of Singlet Oxygen (O2(1,g)) Production by 9H -Fluoren-9-one: Solvents and Solvent MixturesHELVETICA CHIMICA ACTA, Issue 2 2003Claudia We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O2(1,g), denoted as 1O2) by 9H -fluoren-9-one (FLU). The normalized empirical parameter E derived from ET(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of 1O2 production (,,) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (,ISC). Values of ,, of unity have been found in alkanes. In nonprotic solvents of increasing polarity, ,ISC and, therefore, ,, decrease due to solvent-induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor 1O2 sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing ,, to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of ,, upon addition of increasing amounts of the latter. [source] Effects of the Interaction Between , -Carboline-3-carboxylic acid N -Methylamide and Polynucleotides on Singlet Oxygen Quantum Yield and DNA Oxidative DamagePHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 6 2007Iñigo X. García-Zubiri The complexation of , -carboline-3-carboxylic acid N -methylamide (,CMAM) with the sodium salts of the nucleotides polyadenylic (Poly A), polycytidylic (Poly C), polyguanylic (Poly G), polythymidylic (Poly T) and polyuridylic (Poly U) acids, and with double stranded (dsDNA) and single stranded deoxyribonucleic acids (ssDNA) was studied at pH 4, 6 and 9. Predominant 1:1 complex formation is indicated from Job plots. Association constants were determined using the Benesi,Hildebrand equation. ,CMAM-sensitized singlet oxygen quantum yields were determined at pH 4, 6 and 9, and the effects on this of adding oligonucleotides, dsDNA and ssDNA were studied at the three pH values. With dsDNA, the effect on ,CMAM triplet state formation was also determined through triplet,triplet transient absorption spectra. To evaluate possible oxidative damage of DNA following singlet oxygen ,CMAM photosensitization, we used thiobarbituric acid-reactivity assays and electrophoretic separation of DNA assays. The results showed no oxidative damage at the level of DNA degradation or strand break. [source] Tuning the Singlet Oxygen Quantum Yield of Near-IR,absorbing PorphyrazinesPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 6 2003Sangwan Lee No abstract is available for this article. [source] Quantum Yield of the Iodide,Iodate Chemical Actinometer: Dependence on Wavelength and Concentration,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2003Ronald O. Rahn ABSTRACT The quantum yield (QY) of the iodide,iodate chemical actinometer (0.6 M KI,0.1 M KIO3) was determined for irradiation between 214 and 330 nm. The photoproduct, triiodide, was determined from the increase in absorbance at 352 nm, which together with a concomitant measurement of the UV fluence enabled the QY to be calculated. The QY at 254 nm was determined to be 0.73 ± 0.02 when calibration was carried out against a National Institute of Standards and Technology traceable radiometer or photometric device. At wavelengths below 254 nm the QY increased slightly, leveling off at ,0.80 ± 0.05, whereas above 254 nm the QY decreases linearly with wavelength, reaching a value of 0.30 at 284 nm. In addition, the QY was measured at different iodide concentrations. There is a slight decrease in QY going from 0.6 to 0.15 M KI, whereas below 0.15 M KI the QY drops off sharply, decreasing to 0.23 by 0.006 M KI. Calibration of the QY was also done using potassium ferrioxalate actinometry to measure the irradiance. These results showed a 20% reduction in QY between 240 and 280 nm as compared with radiometry. This discrepancy suggests that the QY of the ferrioxalate actinometer in this region of the spectrum needs reexamination. [source] Effect of the Media on the Quantum Yield of Singlet Oxygen (O2(1,g)) Production by 9H -Fluoren-9-one: Solvents and Solvent MixturesHELVETICA CHIMICA ACTA, Issue 2 2003Claudia We have investigated the effect of a series of 18 solvents and mixtures of solvents on the production of singlet molecular oxygen (O2(1,g), denoted as 1O2) by 9H -fluoren-9-one (FLU). The normalized empirical parameter E derived from ET(30) has been chosen as a measure of solvent polarity using Reichardt's betaine dyes. Quantum yields of 1O2 production (,,) decrease with increasing solvent polarity and protic character as a consequence of the decrease of the quantum yield of intersystem crossing (,ISC). Values of ,, of unity have been found in alkanes. In nonprotic solvents of increasing polarity, ,ISC and, therefore, ,, decrease due to solvent-induced changes in the energy levels of singlet and triplet excited states of FLU. This compound is a poor 1O2 sensitizer in protic solvents, because hydrogen bonding considerably increases the rate of internal conversion from the singlet excited state, thus diminishing ,, to values much lower than those in nonprotic solvents of similar polarity. In mixtures of cyclohexane and alcohols, preferential solvation of FLU by the protic solvent leads to a fast decrease of ,, upon addition of increasing amounts of the latter. [source] Red Emitting Diphenylpyrrolopyrrole (DPP)-Based Polymers Prepared by Stille and Heck CouplingMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 23 2006Yu Zhu Abstract Summary: Six new soluble conjugated polymers are described, which were prepared by Stille and Heck polycondensation reactions. They alternately consist of dialkylated 1,4-diketo-3,6-diphenyl-pyrrolo[3,4-c]pyrrole (DPP) units and divinylbenzene or thiophene-based units. The polymers were prepared from 1,4-diketo-2,5-dialkyl-3,6-di(4-bromophenyl)-pyrrolo[3,4-c]pyrrole with alkyl being hexyl (1a), methyl (1b), and 2-ethylhexyl (1c) and 2,5-bis(tributylstannyl)thiophene (2), 5,5,-bis(tributylstannyl)bithiophene (3), 3,4-ethylenedioxythiophene (4) and divinylbenzene (5). The new polymers exhibit brilliant red purple color and strong photoluminescence in common organic solvents. The DPP-phenylenevinylene copolymers exhibit molecular weights up to 41,000 Da, and the poly(DPP-thienylene)s up to 12,200 Da. In chloroform, the poly(DPP-thienylene)s exhibit absorption and photoluminescence maxima up to 560 and 624 nm, respectively, the corresponding maxima of the poly(DPP-phenylenevinylene)s are at 529 and 640 nm, respectively. Quantum yields of fluorescence up to 36% were determined. Cyclic voltammetric studies indicate quasi-reversible oxidation (p -doping) of the poly(DPP-thienylene)s and irreversible reduction (n -doping) of all polymers. Molecular structure of polymers. [source] NMR in photoinduced chemical exchange systems: Theoretical basis of double-resonance inverse fractional population transferCONCEPTS IN MAGNETIC RESONANCE, Issue 4 2006S.P. Babailov Abstract The analytical expression describing dynamics of the nuclear magnetization with the use of double-resonance NMR in the transfer of inverse fractional population under photoinduced chemical exchange is obtained. An experimental procedure for the definition of effective rate constants and quantum yield of responses is considered. The technical approach created allows for planning experimental strategies for the study of photoinduced chemical exchange in any solvable substances. © 2006 Wiley Periodicals, Inc. Concepts Magn Reson Part A 28A: 299,305, 2006 [source] Design, characterization, and utilization of a fast fluorescence derivatization reaction utilizing o -phthaldialdehyde coupled with fluorescent thiolsELECTROPHORESIS, Issue 7 2007Suminda Hapuarachchi Abstract We have developed a chemical derivatization scheme for primary amines that couples the fast kinetic properties of o -phthaldialdehyde (OPA) with the photophysical properties of visible, high quantum yield, fluorescent dyes. In this reaction, OPA is used as a cross-linking reagent in the labeling reaction of primary amines in the presence of a fluorescent thiol, 5-((2-(and-3)- S -(acetylmercapto)succinoyl)amino)fluorescein (SAMSA fluorescein), thereby incorporating fluorescein (,,=,78,000,M,1, quantum yield of 0.98) into the isoindole product. Detection is based on excitation and emission of the incorporated fluorescein using the 488,nm laser line of an Ar+ laser rather than the UV-excited isoindole, thereby eliminating the UV light sources for detection. Using this method, we have quantitatively labeled biologically important primary amines in less than 10,s. Detection limits for analysis of glutamate, glycine, GABA, and taurine were less than 2,nM. We present the characterization of OPA/SAMSA-F reaction and the potential utility of the derivatization reaction for dynamic chemical monitoring of biologically relevant analytes using CE. [source] Comparison of Cd, Cu, and Zn toxic effects on four marine phytoplankton by pulse-amplitude-modulated fluorometryENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2005Ai-Jun Miao Abstract The toxic effects of Cd, Cu, and Zn on four different marine phytoplankton, Dunaliella tertiolecta, Prorocentrum minimum, Synechococcus sp., and Thalassiosira weissflogii, were examined by comparing the cell-specific growth rate, pulse-amplitude-modulated (PAM) parameters (maximum photosystem II quantum yield ,M and operational quantum yield ,'M), chlorophyll a content, and cellular metal concentration, over a 96-h period. The calculated no-observed-effect concentration (NOEC) based on both cell-specific growth rate and two PAM parameters (,M and ,'M) were mostly identical. Thus, these PAM parameters and cell-specific growth rate were comparable in their sensitivities as the biomarkers for trace metal toxicity to marine phytoplankton. The cyanobacteria Synechococcus sp. was the most sensitive species among the four algal species tested because of its higher cell surface to volume ratio. The toxicity of the three tested metals followed the order of Cd > Cu > Zn based on the cellular metal concentration of the four algae at the NOEC. The cellular metal bioaccumulation followed the same Freundlich isotherm for each metal regardless of the algal species, indicating that the metal accumulation was a nonmetabolic process under high ambient metal concentrations and that the cell surface metal binding was comparable among the different species. For all the algae examined in our study, the bioaccumulation potentials of Cu and Zn were similar to each other, while the Cd bioaccumulation was much lower under environmentally realistic metal concentration. [source] Changes in the potential quantum yield of photosystem II and the integrity of cell membranes relative to the elemental content of the epilithic desert lichen Ramalina maciformisENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 4 2002Jacob Garty Abstract The present study used the epilithic fruticose lichen Ramalina maciformis to investigate the occurrence of mineral elements, including heavy metals, at a distance of up to 50 km from the industrial region in Ramat Hovav in the Negev Desert, Israel. The major objective of this study was an analytical comparison of elemental content and physiological parameters of lichen vitality, apart from a test of the applicability of this specific lichen in investigations of air pollution. The Ca, Cr, Cu, K, Mg, Na, Pb, S, Sr, and Zn content of thalli from the unpolluted Tellalim site collected in August 1997, transferred to 24 biomonitoring sites, and retrieved in April 1998 was analyzed in comparison with the following parameters: The potential quantum yield of photosystem II (PSII), and the integrity of cell membranes. Transplanted thalli in several sites at Ramat Hovav accumulated large amounts of most of the elements. The K content of the transplants located in the polluted sites indicated a leakage of this element, because this content was lower than that of thalli in unpolluted sites. Calcium, Cu, Mn, and Na showed an inverse correlation with the K content of the lichen. Calcium, Cu, and Sr showed an inverse correlation with the Fv/Fm ratio expressing the potential quantum yield of PSII. Calcium, Cr, Cu, Mg, Na, S, and Sr showed a positive correlation with the electrical conductivity corresponding with cell-membrane disintegration. The present study demonstrated a meaningful connection between enlarged concentrations of certain elements and physiological phenomena. The capability of the lichen to detect air pollution was found to be satisfactory. The dispersion of airborne heavy metals was found, however, to be local and limited to a few hundred meters from the source of pollution. [source] Synthesis and Photophysical Properties of LnIII,DOTA,Bipy Complexes and LnIII,DOTA,Bipy,RuII Coordination ConjugatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2010Miguel Vázquez López Abstract The synthesis and the systematic and comparative photophysical study of a series of visible (EuIII, TbIII) and NIR-emitting (NdIII, YbIII) lanthanide complexes (Ln2L) and ruthenium,lanthanide coordination conjugates (Ln2LRu) are reported. The GdIII complex, the GdIII,RuII coordination conjugate, as well as the RuII complex of the ligand H6L have also been synthesized and photophysically studied as control systems. The ligand H6L, composed of a central bipyridine binding unit and functionalized on each 5,-position with a DOTA macrocycle, has been successfully synthesized from cyclen, 5,5,-dimethyl-2,2,-bipyridine and 1,2-ethylendiamine in a nine-step process. Detailed luminescence studies of all complexes, including the determination of the quantum yield and lifetime, were carried out on finely powdered microcrystalline samples as well as in water, deuterated water and [D6]DMSO at ambient (295 K) and low temperature (77 K). The photophysical data corroborate the existence of energy transfer in the Ln2L complexes and in the Nd2LRu coordination conjugate. However, no (or at most, very little) energy transfer is takes place from the Ru(bipy)3 chromophore to the LnIII ion in the other Ln2LRu heteropolymetallic complexes. Moreover, the photophysical studies reveal that all the complexes and coordination conjugates adopt different conformations and hydration states in solution and in the solid state, which influences the efficiency of the energy transfer between the bipy and/or Ru(bipy)3 antennae and the LnIII ions. [source] Strong Circularly Polarized Luminescence from Highly Emissive Terbium Complexes in Aqueous SolutionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2010Amanda P. S. Samuel Abstract Two luminescent terbium(III) complexes have been prepared from chiral ligands containing 2-hydroxyisophthalamide (IAM) antenna chromophores and their non-polarized and circularly-polarized luminescence properties have been studied. These tetradentate ligands, which form 2:1 ligand/TbIII complexes, utilize diaminocyclohexane (cyLI) and diphenylethylenediamine (dpenLI) backbones, which we reasoned would impart conformational rigidity and result in TbIII complexes that display both large luminescence quantum yield (,) values and strong circularly polarized luminescence (CPL) activities. Both TbIII complexes are highly emissive, with , values of 0.32 (dpenLI-Tb) and 0.60 (cyLI-Tb). Luminescence lifetime measurements in H2O and D2O indicate that while cyLI-Tb exists as a single species in solution, dpenLI-Tb exists as two species: a monohydrate complex with one H2O molecule directly bound to the TbIII ion and a complex with no water molecules in the inner coordination sphere. Both cyLI-Tb and dpenLI-Tb display increased CPL activity compared to previously reported TbIII complexes made with chiral IAM ligands. The CPL measurements also provide additional confirmation of the presence of a single emissive species in solution in the case of cyLI-Tb, and multiple emissive species in the case of dpenLI-Tb. [source] EuIII -Doping of Lamellar Bilayer and Amorphous Mono-Amide Cross-Linked Alkyl/Siloxane HybridsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2010Silvia C. Nunes Abstract Two structurally different but chemically similar families of alkyl/siloxane mono-amidosil hosts, represented by m-A(x) [where x = 14 or 8 represents the number of CH2 groups of the pendant alkyl chains directly bonded to the carbonyl group of the amide cross-link] have been doped with a wide range of concentrations of Eu(CF3SO3)3. Mono-amidosils m-A(x)nEu(CF3SO3)3 with n,,,10 (where n is the molar ratio of carbonyl groups per Eu3+ ion) have been analyzed. The m-A(8)nEu(CF3SO3)3 mono-amidosils are transparent and amorphous films, in which the alkyl chains adopt gauche conformations. In contrast, the m-A(14)nEu(CF3SO3)3 mono-amidosils are solid powders; here the lamellar bilayer hierarchical structure of m-A(14) coexists with a new lamellar phase in which the Eu3+ ions are bonded to carbonyl oxygen atoms of the amide groups. At n = 10 the hydrogen-bonded associations formed are highly ordered and considerably stronger than those found in the less concentrated hybrids and in the nondoped matrices. "Free" and weakly coordinated triflate ions occur in all the mono-amidosil samples. The hybrids are white light emitters (maximum quantum yield: 0.08,±,0.01), presenting a broad emission band in the blue/purplish-blue spectral region (ascribed to the hybrid host) superimposed on the 5D0,7F0,4 Eu3+ intra-4f6 transitions. Two Eu3+ local coordination sites (named A and B) have been discerned in both systems. Site A is attributed to weakly coordinated Eu3+/CF3SO3, ion pairs, whereas site B involves Eu3+ coordination to the oxygen atoms of the C=O groups, of the CF3SO3, ions and of the water molecules. For site B, the long-range order of the hybrid host induces distinct features in the energy of the 5D0,7F0,4 transitions, the 5D0 lifetime and the degree of covalency of the Eu3+,first-ligand bonds. [source] Synthesis and Functionalization of Germanium Triphenylcorrolate: The First Example of a Partially Brominated CorroleEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2007Sara Nardis Abstract Ge complexes of 5,10,15-triphenylcorrole were prepared in refluxing dry DMF using GeCl4 as the source of Ge. Chromatographic separation of the crude reaction mixture afforded the ,-oxo dimer 1 and the methoxy derivative 2a. The corresponding chloride 2b can be obtained by treatment of 1 or 2a with HCl. The reaction of 2a with Br2 in CHCl3/py afforded the hexabromo derivative 3 as the main product, giving the first indication of the regioselective substitution of pyrroles B and C on the corrole ring. The fully brominated open-chain tetrapyrrole 4 was also characterized as a reaction by-product. Different partially brominated Ge complexes 5 and 6 have been obtained by variation of reaction conditions, while the heptabromo derivative was obtained in a mixture with the corresponding fully brominated Gecorrole. Photophysical characterization of Ge corrolates confirmed the high fluorescence quantum yield of such complexes, and also led to the first observation of phosphorescence emissions from corrole complexes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Lanthanide Chelates Based on Diethylenetriamine Fitted with O -Benzoic Acid Pendant ArmsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 7 2003Daniel Imbert Abstract A new polycarboxylate ligand H5L has been synthesized by the attachment of five benzoate subunits onto a diethylenetriamine framework. Seven pKa values have been determined by potentiometry, spectrophotometry and NMR spectroscopy as 1.9(2), 2.8(2), 3.87(5), 4.58(6), 4.87(6), 9.19(6) and 11.68(5), the first four corresponding to the carboxylic functions and the last three to amine sites. The interaction between H5L and LnIII ions in dilute aqueous solution has been examined by UV/Vis absorption and emission spectrometries, and has been found to result in monometallic complexes that are moderately stable in the pH range 3.7,7.5. Conditional stability constants at pH 5.3 are logK11 = 5.3(2), 6.6(1), 6.5(1) and 7.2(3) for La, Eu, Tb and Lu, respectively. In the case of TbIII, the stability constants for [Tb(HL)], and [Tb(H2L)] are log,111 = 22.0(2) and log,121 = 29.8(1), giving a pTb of 10.0. In the pH range 4,7, more than 90% of the TbIII ions are in the form of the neutral species [Tb(H2L)]. Lifetime determinations of the Eu(5D0) and Tb(5D4) excited levels in both H2O and D2O at pH 5.3 indicate 4.8 ± 0.5 (Eu) and 4.5 ± 0.5 (Tb) water molecules being bound in the inner coordination sphere of the LnIII. The triplet state of the ligand in water lies at around 26000 cm,1, resulting in a sizeable sensitisation of the Tb-centred luminescence (absolute quantum yield: ,abs = 10.3%), while the luminescence of EuIII is only poorly sensitised (,abs = 1.5%). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Synthesis, Crystal Structure, and Photoluminescent Properties of a Tetracarbonyl(naphthyridylcarbamoyl)rhenium(I) Complex and a Highly Emissive Tetracarbonyl(naphthyridylamido)rhenium(I) ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2003Jing-Lin Zuo Abstract The reactions of Re(CO)5X (X = Cl, Br) with 7-amino-2,4-dimethyl-1,8-naphthyridine (H2L1) and 7-[2-(6-chloropyridyl)amino]-2,4-dimethyl-1,8-naphthyridine (HL2) in the presence of tBuOK afforded the ,1 -naphthyridylcarbamoyl complex [Re(CO)4(HL1CO)] (1) and the naphthyridylamido complex [Re(CO)4(L2)] (2), respectively. The structures of HL2, 1·CHCl3, 1·HL3·2CH2Cl2 [HL3 = (7-chloronaphthyridyl)(5,7-dimethylnaphthyridyl)amine], and 2 have been determined by X-ray crystallography. Complex 1 displays a weak emission at 453 nm in an EtOH/MeOH (1:4, v/v) glassy solution at 77 K; complex 2 exhibits an intense (quantum yield: 0.22 in CH2Cl2) and long-lived emission (46 ,s in CH2Cl2), with a solvent-sensitive ,max, in degassed solutions at room temperature. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2003) [source] Visualization of local Ca2+ dynamics with genetically encoded bioluminescent reportersEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 3 2005Kelly L. Rogers Abstract Measurements of local Ca2+ signalling at different developmental stages and/or in specific cell types is important for understanding aspects of brain functioning. The use of light excitation in fluorescence imaging can cause phototoxicity, photobleaching and auto-fluorescence. In contrast, bioluminescence does not require the input of radiative energy and can therefore be measured over long periods, with very high temporal resolution. Aequorin is a genetically encoded Ca2+ -sensitive bioluminescent protein, however, its low quantum yield prevents dynamic measurements of Ca2+ responses in single cells. To overcome this limitation, we recently reported the bi-functional Ca2+ reporter gene, GFP-aequorin (GA), which was developed specifically to improve the light output and stability of aequorin chimeras [V. Baubet, et al., (2000) PNAS, 97, 7260,7265]. In the current study, we have genetically targeted GA to different microdomains important in synaptic transmission, including to the mitochondrial matrix, endoplasmic reticulum, synaptic vesicles and to the postsynaptic density. We demonstrate that these reporters enable ,real-time' measurements of subcellular Ca2+ changes in single mammalian neurons using bioluminescence. The high signal-to-noise ratio of these reporters is also important in that it affords the visualization of Ca2+ dynamics in cell,cell communication in neuronal cultures and tissue slices. Further, we demonstrate the utility of this approach in ex-vivo preparations of mammalian retina, a paradigm in which external light input should be controlled. This represents a novel molecular imaging approach for non-invasive monitoring of local Ca2+ dynamics and cellular communication in tissue or whole animal studies. [source] Switchable Fluorescent and Solvatochromic Molecular Probes Based on 4-Amino- N -methylphthalimide and a Photochromic DiaryletheneEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2008Sergey F. Yan Abstract New fluorescent photochromic compounds (1 -H and 1 -Boc) have been synthesized and characterized in different solvents. The fluorescence emission can be switched "on" and "off" with visible light and UV, respectively, by means of the photochromic reaction. The emission wavelength and efficiency strongly depend on the polarity of the solvent. The compounds show a positive solvatochromic effect in the emission maxima, and their fluorescence quantum yield decreases as the solvent's polarity increases (from cyclohexane to dioxane). In solvents more polar than dioxane the emission is too weak and therefore undetectable, and thus 1 -H and 1 -Boc behave as "normal" photochromic compounds. The photochromic reaction is also sensitive to the environment. A decrease of more than an order of magnitude was found for the quantum yield of the colouring reaction (,OF,CF) for 1 -H in ethanol compared with cyclohexane, and an about threefold decrease in ,OF,CF was observed for the compound 1 -Boc in polar solvents (compared with apolar solvents). For both compounds the ring-opening reaction was found not to dependent on the solvent. The novel fluorescent molecular switches 1 -H and 1 -Boc are able to probe the polarity of their microenvironment. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Efficient Photosensitized Splitting of Thymine Dimer by a Covalently Linked Tryptophan in Solvents of High PolarityEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2005Qin-Hua Song Abstract Tryptophan-thymine dimer model compounds used to mimic the repair reaction of DNA photolyase have been synthesized. The photosensitized cleavage of the dimer by the covalently linked tryptophan is strongly solvent-dependent with the reaction rates increasing in increasingly polar solvents, for example, the quantum yield , = 0.004 in THF/hexane (5:95) and 0.093 in water. The fluorescence of the tryptophan residue is quenched by the dimer moiety by electron transfer from the excited tryptophan to the dimer. Fluorescence-quenching studies indicated that the electron transfer was efficient in polar solvents. The splitting efficiency of the dimer radical anion within the tryptophan·+,dimer·, species is also remarkably solvent-dependent and increases with the polarity of the solvents. The back-electron-transfer reaction in the charge-separated species, which competes with cleavage, was suppressed in polar solvents. These results are in contrast to those of earlier solvent-dependent studies of indole-dimer systems, but they can be rationalized in terms of the differences in the distances between the chromophore unit and the attached dimer. The pH-dependent measurements of the splitting reaction and the deuterium isotope effect showed that the tryptophan radical cation within the charge-separated species does not deprotonate prior to the cleavage of the dimer radical anion. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] The Synthesis of the Dimethyl Ester of Quino[4,4a,5,6- efg]-Annulated 7-Demethyl-8-deethylmesoporphyrin and Three of Its Isomers with Unprecedented peri -Condensed Quinoline Porphyrin Structures.EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2004Molecules with Outstanding Properties as Sensitizers for Photodynamic Therapy in the Far-Red Region of the Visible Spectrum Abstract The mesoporphyrin dimethyl ester nickel complex has been formylated via the Vilsmeier method. The four possible mono meso-formyl derivatives were isolated and characterized. Wadsworth,Emmons coupling with the anion of (diethylphosphono)acetonitrile converted these aldehydes into the four novel meso acrylonitriles. Brief treatment of these acrylonitrile systems in hot trichloroacetic acid resulted in the formation of four achiral porphyrin derivatives with unprecedented nickel complexes of quino-fused porphyrins. Subsequent removal of the nickel gave four quino-porphyrin free bases: quino[4,4a,5,6- efg]-annulated 7-demethyl-8-deethylmesoporphyrin dimethyl ester 6a, 2,-(methoxycarbonyl)quino[4,4a,5,6- jkl]-annulated 12-demethyl-13-de[2,-(methoxycarbonyl)ethyl]mesoporphyrin dimethyl ester 6b, 2,-(methoxycarbonyl)quino[4,4a,5,6- qrs]-annulated 18-demethyl-17-de(2,-methoxycarbonylethyl)mesoporphyrin dimethyl ester 6c and quino[4,5,6,7- abt]-annulated 2-demethyl-3-deethylmesoporphyrin dimethyl ester 6d. The structures of these systems were unambiguously determined via mass spectroscopy and a plethora of NMR techniques. In the same way, etioporphyrin and octaethylporphyrin were converted into the corresponding peri -condensed quinoporphyrins as products, which shows that the formation of novel pericondensed quino-porphyrins is a general reaction in the porphyrin series and will have a wide scope in this field. Also, a plausible reaction mechanism for the formation of the quinoporphyrin systems was derived. As a first test for the use of these systems as sensitizers in far-red phototherapy, the quantum yield of singlet oxygen generation by 6a in toluene was studied. This quantum yield is 0.77, which is even higher than the singlet oxygen generation by sensitized meso-tetraphenylporphyrin. Secondly, when Chinese Hamster ovary (CHO) cells were incubated in medium which contained up to 15 ,g/ml of 6a, the survival rate of the cells in the dark is complete within experimental error, showing that under these conditions, 6a is not toxic to CHO cells. When CHO cells incubated in medium containing 6a in concentrations of 1 ,g/ml and higher were treated with white light of intensity 30 mW/cm2 for 15 minutes, complete cell death was observed. Based on these facts, we expect that all four achiral systems will show very promising properties to form the basis of a photodynamic therapy in far-red light. The fact that these systems are achiral is an additional bonus for medical applications. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] A Molecular Brush Approach to Enhance Quantum Yield and Suppress Nonspecific Interactions of Conjugated Polyelectrolyte for Targeted Far-Red/Near-Infrared Fluorescence Cell ImagingADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Kan-Yi Pu Abstract A red-fluorescent conjugated polyelectrolyte (CPE, P2) is grafted with dense poly(ethylene glycol) (PEG) chains via click chemistry and subsequently modified with folic acid to form a molecular brush based cellular probe (P4). P4 self-assembles into a core,shell nanostructure in aqueous medium with an average size of 130 nm measured by laser light scattering. As compared to P2, P4 possesses not only a substantially higher quantum yield (11%), but also reduced nonspecific interactions with biomolecules in aqueous medium due to the shielding effect of PEG. In conjunction with its high photostability and low cytotoxicity, utilization of P4 as a far-red/near-infrared cellular probe allows for effective visualization and discrimination of MCF-7 cancer cells from NIH-3T3 normal cells in a high contrast, selective, and nonviral manner. This study thus demonstrates a flexible molecular brush approach to overcome the intrinsic drawbacks of CPEs for advanced bioimaging applications. [source] A Molecular Brush Approach to Enhance Quantum Yield and Suppress Nonspecific Interactions of Conjugated Polyelectrolyte for Targeted Far-Red/Near-Infrared Fluorescence Cell ImagingADVANCED FUNCTIONAL MATERIALS, Issue 17 2010Kan-Yi Pu Abstract A red-fluorescent conjugated polyelectrolyte (CPE, P2) is grafted with dense poly(ethylene glycol) (PEG) chains via click chemistry and subsequently modified with folic acid to form a molecular brush based cellular probe (P4). P4 self-assembles into a core,shell nanostructure in aqueous medium with an average size of 130 nm measured by laser light scattering. As compared to P2, P4 possesses not only a substantially higher quantum yield (11%), but also reduced nonspecific interactions with biomolecules in aqueous medium due to the shielding effect of PEG. In conjunction with its high photostability and low cytotoxicity, utilization of P4 as a far-red/near-infrared cellular probe allows for effective visualization and discrimination of MCF-7 cancer cells from NIH-3T3 normal cells in a high contrast, selective, and nonviral manner. This study thus demonstrates a flexible molecular brush approach to overcome the intrinsic drawbacks of CPEs for advanced bioimaging applications. [source] Highly Emissive and Electrochemically Stable Thienylene Vinylene Oligomers and Copolymers: An Unusual Effect of Alkylsulfanyl SubstituentsADVANCED FUNCTIONAL MATERIALS, Issue 10 2010Shehzad Jeeva Abstract The synthesis, unexpected efficient photoluminescence, and reversible electrochemical p- and n-doping of new conjugated thienylene vinylene materials functionalized with alkylsulfanyl substituents poly(trithienylene vinylene) (PTTV) and poly(dithienylvinyl- co -benzothiadiazole) (PDTVB) along with dithienylvinylene-based oligomers is reported. The materials are studied by thermal and X-ray diffraction analysis, optical spectroscopy, cyclic voltammetry, and spectroelectrochemistry. Organic field-effect transistors (OFETs) are fabricated with PTTV and PDTVB. The polymers, prepared by Stille polycondensation, exhibit good thermal stability and a photoluminescent quantum yield in the range 34%,68%. Low bandgaps (1.5,1.8,eV), estimated by optical and electrochemical measurements along with high stability of both redox states, suggest that these structures are promising materials for photovoltaic applications. OFETs fabricated with PDTVB reveal a hole mobility of 7,×,10,3,cm2 V,1 s,1 with on/off ratio 105, which are comparatively high values for completely amorphous polymer semiconductors. [source] Enhancement of Aggregation-Induced Emission in Dye-Encapsulating Polymeric Micelles for BioimagingADVANCED FUNCTIONAL MATERIALS, Issue 9 2010Wen-Chung Wu Abstract Three amphiphilic block copolymers are employed to form polymeric micelles and function as nanocarriers to disperse hydrophobic aggregation-induced emission (AIE) dyes, 1,1,2,3,4,5-hexaphenylsilole (HPS) and/or bis(4-(N -(1-naphthyl) phenylamino)-phenyl)fumaronitrile (NPAFN), into aqueous solution for biological studies. Compared to their virtually non-emissive properties in organic solutions, the fluorescence intensity of these AIE dyes has increased significantly due to the spatial confinement that restricts intramolecular rotation of these dyes and their better compatibility in the hydrophobic core of polymeric micelles. The effect of the chemical structure of micelle cores on the photophysical properties of AIE dyes are investigated, and the fluorescence resonance energy transfer (FRET) from the green-emitting donor (HPS) to the red-emitting acceptor (NPAFN) is explored by co-encapsulating this FRET pair in the same micelle core. The highest fluorescence quantum yield (,62%) could be achieved by encapsulating HPS aggregates in the micelles. Efficient energy transfer (>99%) and high amplification of emission (as high as 8 times) from the NPAFN acceptor could also be achieved by spatially confining the HPS/NPAFN FRET pair in the hydrophobic core of polymeric micelles. These micelles could be successfully internalized into the RAW 264.7 cells to demonstrate high-quality fluorescent images and cell viability due to improved quantum yield and reduced cytotoxicity. [source] High-Performance Phototransistors Based on Organic Microribbons Prepared by a Solution Self-Assembly ProcessADVANCED FUNCTIONAL MATERIALS, Issue 6 2010Yunlong Guo Abstract Oligoarenes as an alternative group of promising semiconductors in organic optoelectronics have attracted much attention. However, high-performance and low-cost opto-electrical devices based on linear asymmetric oligoarenes with nano/microstructures are still rarely studied because of difficulties both in synthesis and high-quality nano/microstructure growth. Here, a novel linear asymmetric oligoarene 6-methyl-anthra[2,3- b]benzo[d]thiophene (Me-ABT) is synthesized and its high-quality microribbons are grown by a solution process. The solution of Me-ABT exhibits a moderate fluorescence quantum yield of 0.34, while the microribbons show a glaucous light emission. Phototransistors based on an individual Me-ABT microribbon prepared by a solution-phase self-assembly process showed a high mobility of 1.66,cm2,V,1 s,1, a large photoresponsivity of 12,000 A W,1, and a photocurrent/dark-current ratio of 6000 even under low light power conditions (30,µW cm,2). The measured photoresponsivity of the devices is much higher than that of inorganic single-crystal silicon thin film transistors. These studies should boost the development of the organic semiconductors with high-quality microstructures for potential application in organic optoelectronics. [source] Photochromic Polymers Based on the Photoinduced Opening and Thermal Closing of [1,3]Oxazine RingsADVANCED FUNCTIONAL MATERIALS, Issue 24 2009Massimiliano Tomasulo Abstract Two macromolecular constructs incorporating a single polymer backbone with multiple photochromic side chains are developed. Both systems are prepared from preformed photochromic [1,3]oxazines after the ring-opening polymerization of their norbornene appendages. In solution, UV illumination of these polymers opens the [1,3]oxazine rings in their side chains in less than 6,ns and with a quantum yield of 0.09 in both instances. The photogenerated species incorporate a 4-nitrophenolate chromophore, and hence, their formation is accompanied by the appearance of an intense band in the visible region of the absorption spectrum. The photoproducts revert spontaneously to the original state with first-order kinetics in microseconds. Furthermore, both photochromic polymers tolerate hundreds of switching cycles with no sign of degradation, even in the presence of molecular oxygen. Thus, this design logic and choice of functional building blocks can translate into the realization of innovative photoresponsive materials with excellent photochromic performance. [source] Enhanced Optical Properties and Opaline Self-Assembly of PPV Encapsulated in Mesoporous Silica SpheresADVANCED FUNCTIONAL MATERIALS, Issue 23 2009Timothy L. Kelly Abstract A new poly(p -phenylenevinylene) (PPV) composite material has been developed by the incorporation of insoluble PPV polymer chains in the pores of monodisperse mesoporous silica spheres through an ion-exchange and in situ polymerization method. The polymer distribution within the resultant colloidal particles is characterized by electron microscopy, energy dispersive X-ray microanalysis, powder X-ray diffraction, and nitrogen adsorption. It was found that the polymer was selectively incorporated into the mesopores of the silica host and was well distributed throughout the body of the particles. This confinement of the polymer influences the optical properties of the composite; these were examined by UV,vis and fluorescence spectroscopy and time-correlated single-photon counting. The results show a material that exhibits an extremely high fluorescence quantum yield (approaching 85%), and an improved resistance to oxidative photobleaching compared to PPV. These enhanced optical properties are further complemented by the overall processability of the colloidal material. In marked contrast to the insolubility of PPV, the material can be processed as a stable colloidal dispersion, and the individual composite spheres can be self-assembled into opaline films using the vertical deposition method. The bandgap of the opal can be engineered to overlap with the emission band of the polymer, which has significant ramifications for lasing. [source] | ||||||||||||||||||||||||||||||||||