Probing solute distribution and acid-base behaviour in water-in-oil microemulsions by fluorescence techniques

The distribution and acid-base behaviour of the four solutes harmine, chromotropic acid (4,5-dihydroxynaphthalene-2,7-disulfonate, disodium salt), 2-naphthol and 5,10,15,20-tetrakis [4-trimethylammonium)phenyl]-21H,23H-porphine tetra-p-tosylate (TTMP) have been studied in water-in-oil (w/o) microemulsions using fluorescence and absorption spectroscopy. Carbon tetrachloride is a quencher of fluorescence of these compounds, and studies using this as oil phase in microemulsions show that chromotropic acid is located in the water domain, TTMP at the surfactant-water interface, while the distribution of harmine or 2-naphthol depends on the degree of protonation. Detailed studies have been made on harmine. In water/AOT/cyclohexane microemulsions the cationic form is observed up to much higher apparent pH than in aqueous solutions. An important factor is shown to be the compartmentalisation of hydroxide ions between water pools. Similar effects are observed with the other probes, and it is suggested that compartmentalisation of hydrogen or hydroxide ions is a major effect in many acid-base reactions in microemulsions. The validity of the concept of pH in microemulsions under these conditions is questioned. Fluorescence lifetime measurements are also shown to provide information on the dynamics of the processes, and demonstrate the importance of diffusion of solutes from organic solvent to the microemulsion pool. A comparison is made of the behaviour of harmine in water/AOT/cyclohexane and water/lecithin/cyclohexane microemulsions.http://www.sciencedirect.com/science/article/B6TFR-416K8BS-12/1/1e48ace7f73afe3996e2e8a782a190d

Theoretical and experimental insights into the complexation of 8-hydroxyquinoline-5-sulfonate with divalent ions of Group 12 metals

The complexation of 8-hydroxyquinoline-5-sulfonic acid with cadmium(II) and mercury(II) has been studied in aqueous solutions using UV/visible absorption, fluorescence and 1H NMR spectroscopy, accompanied by DFT calculations. Results are compared with the behavior of zinc(II) and show in all cases the dominant formation of a 1:2 (metal:ligand) complex. DFT calculations under PCM (water) conditions indicate a preference for hexacoordinated metal centers with two ligands and two water molecules. However, while the zinc(II) complex has a square bipyramidal geometry, with the two 8-HQS ligands and metal in the same plane and two coordinated water molecules mutually trans, with cadmium(II) and mercury(II), the isomers in which the water molecules are in the cis geometry are more stable. Changes in UV–Vis absorption, fluorescence spectra and fluorescence intensity are observed on complexation. Fluorescence quantum yields follow the order Zn/8-HQS Hg/8-HQS. We believe two competing factors may be involved: an increase in fluorescence on going from Zn(II) to Cd(II) due to increased stability, and a decrease on going increasing atomic number of the metal ion due to the heavy atom effect which increases intersystem crossing. Triplet state quantum yields were measured for the Zn(II) and Cd(II) complexes, and the value for the cadmium(II) complex is higher, in agreement with the heavy atom effect. However, the sum of fluorescence and triplet quantum yields in these cases is less than unity. It is suggested that there is a competing non-radiative route for deactivation of the excited state through ligand or solvent exchange. This provides a ready explanation of increased fluorescence yields when metal/8-HQS complexes are immobilized in solid matrices

Permeation of water as a tool for characterizing the effect of solvent, film thickness and water solubility in cellulose acetate membranes

Cellulose acetate membranes have been used in many applications; of particular interest are reverse osmosis systems, and as a neutral matrix for incorporation of different polymers (e.g., conducting polymers), inorganic ions (e.g., lanthanides) and organic (e.g., pharmaceutical) compounds. The properties of the new polymers derived from cellulose acetate or blends depend on those of cellulose acetate. This work presents an attempt to find links between thermodynamic and kinetic properties of cellulose acetate membranes in equilibrium with water. Water diffusion coefficients in cellulose acetate membranes are reported, measured with a simple water permeation technique. The comparison of these values with the percentage of water uptake and polymer thickness leads to interesting conclusions related with different polymer properties.http://www.sciencedirect.com/science/article/B6TWW-4DVBFCN-7/1/63e48f8aac1513c35feeaa6c746621e

Kinetics and thermodynamics of poly (9,9-dioctylfluorene) beta-phase formation in dilute solution

Poly(9,9-dioctylfluorene) (PFO) adopts a particular type of conformation in dilute solutions of the poor solvent methylcyclohexane (MCH) below 273 K, which is revealed by the appearance of a red-shifted absorption peak at 437−438 nm. The formation of this ordered conformation depends on the temperature but is independent of polymer concentration over the range studied (3−25 μg/mL). On the basis of absorption, steady-state, and time-resolved fluorescence data, the new absorption peak at 437−438 nm is assigned to a highly ordered conformation of PFO chains, analogous to the so-called β-phase first identified in PFO films. From the study of PFO solutions in MCH as a function of temperature, we conclude that these ordered segments (β-conformation) coexist with less ordered domains in the same chain. When the ordered domains are present, they act as efficient energy traps and the fluorescence from the disordered regions is quenched. The transition between the disordered and the ordered PFO conformations is adequately described by a mechanism that involves two steps:  a first, essentially intramolecular, one from a relatively disordered (α) to an ordered conformation (β), followed by aggregation of chains containing β-conformation into anisotropic ordered domains. From the temperature dependence of the 437−438 nm peak intensity, the transition temperature Tβ = 261 K, enthalpy ΔHβ = −18.0 kcal mol-1, and entropy ΔSβ = −68.4 cal K-1 mol-1 were obtained. The formation of the β-conformation domains were also followed as a function of time at 260 K. The rate constants at 260 K were determined, showing an order of magnitude around 10-3 s-1 (kα→β = 5.9 × 10-4 s-1; kβ→α = 9 × 10-4 s-1; kagg = 2.3 × 10-3 M-1 s-1; kdiss = 4.4 × 10-4 s-1). This small magnitude explains the long times required for a “complete” conversion to the β-conformation

Probing solute distribution and acid-base behaviour in water-in-oil microemulsions by fluorescence techniques

The distribution and acid-base behaviour of the four solutes harmine, chromotropic acid (4,5-dihydroxynaphthalene-2,7-disulfonate, disodium salt), 2-naphthol and 5,10,15,20-tetrakis [4-trimethylammonium)phenyl]-21H,23H-porphine tetra-p-tosylate (TTMP) have been studied in water-in-oil (w/o) microemulsions using fluorescence and absorption spectroscopy. Carbon tetrachloride is a quencher of fluorescence of these compounds, and studies using this as oil phase in microemulsions show that chromotropic acid is located in the water domain, TTMP at the surfactant-water interface, while the distribution of harmine or 2-naphthol depends on the degree of protonation. Detailed studies have been made on harmine. In water/AOT/cyclohexane microemulsions the cationic form is observed up to much higher apparent pH than in aqueous solutions. An important factor is shown to be the compartmentalisation of hydroxide ions between water pools. Similar effects are observed with the other probes, and it is suggested that compartmentalisation of hydrogen or hydroxide ions is a major effect in many acid-base reactions in microemulsions. The validity of the concept of pH in microemulsions under these conditions is questioned. Fluorescence lifetime measurements are also shown to provide information on the dynamics of the processes, and demonstrate the importance of diffusion of solutes from organic solvent to the microemulsion pool. A comparison is made of the behaviour of harmine in water/AOT/cyclohexane and water/lecithin/cyclohexane microemulsions.http://www.sciencedirect.com/science/article/B6TFR-416K8BS-12/1/1e48ace7f73afe3996e2e8a782a190d

Using Lanthanides as Probes for Polyelectrolyte-Metal Ion Interactions. Hydration Changes on Binding of Trivalent Cations to Nucleotides and Nucleic Acids

http://www.sciencedirect.com/science/article/B6TFM-4SWFNW8-1/1/aadd2972e76576ca7bf5c347abd5a68

Synthesis and characterization of new aromatic polyamides bearing crown ethers and acyclic ethylene oxide units in the pendant structure. III. Benzo-18-crown-6 systems and their open-chain counterparts

We report the synthesis and characterization of 10 novel polyamides containing the benzo-18-crown-6 subunit and its dipodal counterpart, along with their properties, and a comparison with homologous polyamides bearing benzo-12-crown-4, benzo-15-crown-5, and the corresponding dipodal systems. The anomalous polymerization of some of the diacid monomers, that leads to insoluble gels under standard Yamazaki polymerization conditions, is described. The gel formation has been attributed to the threading of cyclic oligoamides with a growing polyamide chain to yield rotaxanes, polyrotaxanes, catenanes, or polycatenanes. Polyamide macrocycles have been characterized with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. A route to avoid gel formation, consisting of a lower initial monomer concentration, is also described, along with the polymer properties of the polyamides obtained, including the chemical characterization, mechanical behavior, water sorption, morphology, diffusion data, and permeability of membranes prepared with these polymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6252-6269, 200

Optical and photovoltaic properties of thieno[3,2-b]thiophene-based push–pull organic dyes with different anchoring groups for dye-sensitized solar cells

The effect of anchoring groups on the optical and electrochemical properties of triphenylamine-thienothiophenes, and on the photovoltaic performance of DSSCs photosensitized with the prepared dyes, was studied using newly synthesized compounds with cyanoacetic acid or rhodanine-3-acetic acid groups. Precursor aldehydes were synthesized through Suzuki cross-coupling, whereas Knoevenagel condensation of these with 2-cyanoacetic acid or rhodanine-3-acetic acid afforded the final push–pull dyes. A comprehensive photophysical study was performed in solution and in the solid state. The femtosecond time-resolved transient absorption spectra for the synthesized dyes were obtained following photoexcitation in solution and for the dyes adsorbed to TiO2 mesoporous films. Information on conformation, electronic structure, and electron distribution was obtained by density functional theory (DFT) and time-dependent DFT calculations. Triphenylamine–thienothiophene functionalized with a cyanoacetic acid anchoring group displayed the highest conversion efficiency (3.68%) as the dye sensitizer in nanocrystalline TiO2 solar cells. Coadsorption studies were performed for this dye with the ruthenium-based N719 dye, and they showed dye power conversion efficiencies enhanced by 20–64%. The best cell performance obtained with the coadsorbed N719 and cyanoacetic dye showed an efficiency of 6.05%.The authors thank Fundacao para a Ciencia e Tecnologia (FCT) for PhD grants to S.S.M.F. (SFRH/BD/87786/2012) and M.C.R.C. (SFRH/BD/78037/2011) and postdoctoral grants to L.L.G.J. (SFRH/BPD/97026/2013) and J.P. (SFRH/BPD/108469/2015). The authors also thank FEDER-COMPETE for the financial support through the CQ/UM PEst-C/QUI/UI0686/2013 (FCOMP-01-0124-FEDER-037302). The NMR spectrometer Bruker AVANCE III 400 is part of the National NMR Network and was purchased within the framework of the National Program for Scientific Re-equipment, contract REDE/1517/RMN/2005 with funds from POCI 2010 (FEDER) and FCT. The group in Coimbra are grateful for funding from "Centro de Quimica de Coimbra," which is supported by the Fundacao para a Ciencia e a Tecnologia (FCT), Portuguese Agency for Scientific Research, through the programs UID/QUI/UI0313/2013 and COMPETE. The authors also thank the Laboratory for Advanced Computing at the University of Coimbra for providing computing resources that have contributed to the research results reported in this paper (URL http://www.lca.uc.pt). This work was performed under the project "SunStorage. harvesting and storage of solar energy,"with reference POCI-01-0145-FEDER-016387, funded by the European Regional Development Fund (ERDF), through COMPETE 2020. Operational Programme for Competitiveness and Internationalization (OPCI), and by national funds through FCT. The research leading to these results has received funding from Laserlab-Europe (grant agreement no. 284464, EC's Seventh Framework Programme). A.I.P. would like to acknowledge the European Commission through the Seventh Framework Programme, the Specific Programme "Ideas" of the European Research Council for research and technological development as part of an Advanced Grant under grant agreement no. 321315, which also partially funded this work. The authors would also like to acknowledge L. Andrade and I. Mesquita for their valuable contribution for the article.info:eu-repo/semantics/publishedVersio

Exploring excited states of Pt(ii) diimine catecholates for photoinduced charge separation

The intense absorption in the red part of the visible range, and the presence of a lowest charge-transfer excited state, render Platinum(II) diimine catecholates potentially promising candidates for light-driven applications. Here, we test their potential as sensitisers in dye-sensitised solar cells and apply, for the first time, the sensitive method of photoacoustic calorimetry (PAC) to determine the efficiency of electron injection in the semiconductor from a photoexcited Pt(II) complex. Pt(II) catecholates containing 2,2′-bipyridine-4,4′-di-carboxylic acid (dcbpy) have been prepared from their parent iso-propyl ester derivatives, complexes of 2,2′-bipyridine-4,4′-di-C(O)OiPr, (COOiPr)2bpy, and their photophysical and electrochemical properties studied. Modifying diimine Pt(II) catecholates with carboxylic acid functionality has allowed for the anchoring of these complexes to thin film TiO2, where steric bulk of the complexes (3,5-ditBu-catechol vs. catechol) has been found to significantly influence the extent of monolayer surface coverage. Dye-sensitised solar cells using Pt(dcbpy)(tBu2Cat), 1a, and Pt(dcbpy)(pCat), 2a, as sensitisers, have been assembled, and photovoltaic measurements performed. The observed low, 0.02–0.07%, device efficiency of such DSSCs is attributed at least in part to the short excited state lifetime of the sensitisers, inherent to this class of complexes. The lifetime of the charge-transfer ML/LLCT excited state in Pt((COOiPr)2bpy)(3,5-di-tBu-catechol) was determined as 250 ps by picosecond time-resolved infrared spectroscopy, TRIR. The measured increase in device efficiency for 2a over 1a is consistent with a similar increase in the quantum yield of charge separation (where the complex acts as a donor and the semiconductor as an acceptor) determined by PAC, and is also proportional to the increased surface loading achieved with 2a. It is concluded that the relative efficiency of devices sensitised with these particular Pt(II) species is governed by the degree of surface coverage. Overall, this work demonstrates the use of Pt(diimine)(catecholate) complexes as potential photosensitizers in solar cells, and the first application of photoacoustic calorimetry to Pt(II) complexes in general

Diffusion Coefficients of Copper Chloride in Aqueous Solutions at 298.15 K and 310.15 K

Mutual diffusion coefficients (interdiffusion coefficients) and molar conductivities have been measured for copper(II) chloride in water at 298.15 K and 310.15 K at concentrations between 0.005 mol·dm-3 and 0.05 mol·dm-3. The diffusion coefficients were measured using a conductometric cell. The experimental data are discussed on the basis of the Onsager−Fuoss model. The Nernst diffusion coefficients derived from diffusion (1.297 × 10-9 and 1.690 × 10-9) m2·s-1 and from conductance (1.282 × 10-9 and 1.663 × 10-9) m2·s-1 at two temperatures (298.15 K and 310.15 K, respectively) are in good agreement