Different Species In Solution Research Articles

Mining minerals and critical raw materials from bittern: Understanding metal ions fate in saltwork ponds

Seawater represents a potential resource for raw materials extraction. Although NaCl is the most representative mineral extracted other valuable compounds such as Mg, Li, Sr, Rb and B and elements at trace level (Cs, Co, In, Sc, Ga and Ge) are also contained in this “liquid mine”. Most of them are considered as Critical Raw Materials by the European Union. Solar saltworks, providing concentration factors of up-to 20 to 40, offer a perfect platform for the development of minerals and metal recovery schemes taking benefit of the concentration and purification achieved along the evaporation saltwork ponds.However, the geochemistry of these elements in this environment has not been yet thoroughly evaluated. Their knowledge could enable the deployment of technologies capable to achieve the recovery of valuable minerals. The high ionic strengths expected (0.5–7 mol/kg) and the chemical complexity of the solutions imply that only numerical geochemical codes, as PHREEQC, and the use of Pitzer model to estimate the activity coefficients of the different species in solution can be adopted to provide valuable description of the systems.In the present work, for the first time, PHREEQC Pitzer code database was extended to include the target minor and trace elements using Trapani saltworks (Sicily, Italy) as a case study system. The model was able to predict: i) the purity in halite and the major impurities contained, mainly Ca, Mg and sulphate species; ii) the fate of minor components as B, Sr, Cs, Co, Ge and Ga along the evaporation ponds. The results obtained pose a fundamental step in critical raw materials mining from seawater brine, for process intensification and combination with desalination.

Non‐Linear Effects in Asymmetric Catalysis: Impact of Catalyst Precipitation

AbstractNon‐linear effects between the enantiomeric excesses of both the ligand and the product are ubiquitous phenomena in asymmetric catalysis, allowing asymmetric amplification (or depletion) and are widely used tools for mechanistic investigations. Non‐linear effects are caused by catalyst aggregation; however, the effect of catalyst precipitation on NLEs has not been systematically investigated to date, except in special cases such as ternary phase systems. In this article, we show through simulations and with several literature cases at hand how precipitation affects shape and amplitude of NLE curves. The limit of solubility of the homo‐ or heterochiral dimeric species causes broken‐shaped NLE curves or very pronounced NLEs even though the equilibria between the different species in solution are not favorable, at first sight. Peculiar features such as horizontal segments, inverse S‐shaped curves and a strong effect of total catalyst concentration are also observed. Overall, this study allows to get a better understanding of chiral catalytic systems and gives an outlook at other types of phase separation leading to NLEs.

Optical Detection of Streptavidin-Biotin Binding on Nanoporous Anodic Alumina Pore Surface

Nanoporous anodic alumina (NAA) is a material with a high interest in nanotechnology[1]. Its physical and chemical properties combined with a cost-effective and scalable production process make it a good candidate in many nanotechnologically-related applications. Its high and tuneable surface-to-volume ratio as well as its interesting optical properties[2] have been used as the basis of different biosensing schemes[3]. Biosensing, and specifically optical biosensing is of great interest in health and environmental applications. The reflection interference spectroscopy (RIfS) method based on NAA has demonstrated its ability in detecting many kinds of molecules (proteins, antibodies[4]).One of the molecular systems with interest in biotechnological applications is the streptavidin-biotin system. The high affinity between both molecules is exploited in many applications for the binding of different biological species. For this reason, we have studied the streptavidin-biotin binding event with NAA-based RIfS, as part of a biosensing process. In our study we assess the optimal conditions for real time monitoring of the different steps (covalent streptavidin bonding, surface passivation, biotin complexation). In order to establish such optimal conditions, we have chosen the protein thrombin as a model molecule to be detected.We prepared NAA with the usual anodization conditions under oxalic acid electrolyte to obtain porous layers with uniform pore diameter and with a thickness that permits the measurement with RIfS in a flow-cell where the different species in solution can be introduced. The experiments consisted of monitoring the change in effective optical thickness (EOT, the quantitative characteristic parameter obtained from RIfS) in the different steps of the biosensing process. The NAA pore surfaces were initially functionalized with (3-aminopropyl)triethoxysilane (APTES) with the carboxyl groups activated in order to form later a peptide bond with the streptavidin.One of the parameters to be optimized was the pore diameter. Furthermore, in order to study the ability of RIfS to detect the covalent streptavidin binding to the NAA pore surface, different concentrations of streptavidin were tested. Finally, the biosensing capabilities were evaluated by detecting biotinylated thrombin at different concentrations.An example of a complete experiment with all the steps in the streptavidin-biotinylated molecule attachment detection can be seen in Figure 1. After establishing a baseline with a PBS flow, streptavidin at 50 µg/ml is introduced in the RIfS setup and its covalent attachment to APTES is detected as an increase in EOT. Following this first step, PBS is introduced to wash away the non-specifically bound molecules and a 3% Bovine Serum Albumin (BSA) solution is flowed to passivate the remaining activated carboxyl groups of APTES and the remaining hydroxyl groups on the NAA pore surface. Such steps are detected by the RIfS procedure. Then, after a subsequent PBS wash, biotinylated thrombin at a concentration of 20 µg/ml is introduced causing a steady increase in EOT reaching a value of 3.5 nm above the initial one. The experiment in Figure 1 was repeated for different NAA pore sizes revealing a higher change in EOT for bigger pore sizes.An important parameter in the detection of the biotinylated molecules binding is the concentration at the streptavidin immobilization step. Thus, different streptavidin concentrations were tested in 60 nm pore diameter NAA. Results are summarized in Figure 2: for the highest concentrations (50 µg/ml) the attachment of streptavidin shows a two-phase curve with an initial phase with a faster increase in EOT and a second phase with a slower increase after an inflection point in the EOT versus time curve. Instead, for a small concentration (1 µg/ml) an initial fast increase is followed by a stabilization of the EOT signal. These two behaviors are associated with the attachment of streptavidin to the activated carboxyl of APTES for the initial fast EOT increase, while the subsequent slower increase can be explained by the aggregation of streptavidin through amine group binding.Finally, in order to demonstrate the capability of quantifying the attachment of biotinylated molecules to the NAA surface, the process was carried out using thrombin as the model molecule and for increasing concentrations. Figure 3 shows the change in EOT as a function of the thrombin concentration. It can be seen that RIfS based on NAA sensing platforms is able to quantify such attachment.[1] Josep Ferré-Borrull, et al., Nanomaterials, vol. 7, p. 5225 (2014).[2] Josep Ferré-Borrull et al., in NANOPOROUS ALUMINA: FABRICATION, STRUCTURE, PROPERTIES AND APPLICATIONS, Springer Series in Materials Science, vol. 219, p. 185 (2015).[3] Chris Eckstein, ACS Applied Materials and Interfaces, vol. 10, p.10571 (2018).[4] Gerard Macías, Analyst, vol. 140, p. 4848 (2015). Figure 1

Optical Detection of Thrombin on Nanoporous Anodic Alumina with Aptamer-Modified Surface

Nanoporous anodic alumina (NAA) attracts interest in nanotechnology[1]. Its physical and chemical properties combined with a cost-effective and scalable production make it a good for nanotechnology-related applications. Its high and tuneable surface-to-volume ratio as well as its interesting optical properties[2] have been used as the basis of different biosensing schemes. Biosensing, and specifically optical biosensing is of great interest in health and environmental applications. The reflection interference spectroscopy (RIfS) method based on NAA has demonstrated its ability in detecting many kinds of molecules [3,4].Biosensors engineered with aptamers as a bioreceptor are called aptabiosensors. Thrombin Binding Aptamer (TBA) has a well-known binding process and high affinity and is one of the most studied aptamers. Thrombin is the key factor of blood coagulation, whose activity is important in wounds and in blood circulation. The free thrombin-binding aptamer remains as a random-coil state in the absence of thrombin, while in the presence of thrombin the protein attaches to the aptamer changing its conformation to quadruplex. In this study we assess the capabilities of NAA with the inner pore surfaces modified with TBA to detect specifically the thrombin protein by means of the RIfS method.We prepared NAA with the usual anodization conditions under oxalic acid electrolyte to obtain porous layers with uniform pore diameter and with a thickness that permits the measurement with RIfS in a flow-cell where the different species in solution can be introduced. The experiments consisted of monitoring the change in effective optical thickness (EOT, the quantitative characteristic parameter obtained from RIfS) in the different steps of the biosensing process. Figure 1 shows SEM pictures of the NAA platforms prepared.The NAA pore surfaces were initially functionalized with (3-aminopropyl)triethoxysilane (APTES) and then the surface mas modified in a three-step procedure monitored in real time thanks to the RIfS method. Figure 2 shows the change in EOT as a function of time during the surface functionalization of NAA: the covalent attachment of Sulfo-NHS-Biotin and subsequent streptavidin attachment (stages 1 and 2 in the figure) and the final immobilization of TBA in the pore walls of NAA (step 3 in the plot).. First, the flow of the Sulfo-NHS-Biotin solution produced a considerable increase in EOT. Then, a further increase in EOT is observed with the infiltration of streptavidin. Finally, EOT also shows clearly the immobilization of biotinylated TBA.The aptamer-functionalized NAA substrates were employed to detect human thrombin protein. For this purpose, different substrates were used in RIfS experiments with human thrombin protein at different concentrations. Figure 3 shows one example of the evolution of the EOT signal upon infiltration of a 1.35 µM thrombin solution. Results show that after obtaining a baseline with constant EOT corresponding to the flow of binding buffer, the thrombin solution is injected causing a rapid increase in EOT, at a rate of 0,05 nm/s. After this increase a stable value is reached after 3600 s, with an absolute change in EOT of ∆EOT = 28 nm. The experiment corresponding to Figure 3 has been repeated for a set of concentrations to obtain a sensitivity curve of the aptamer-functionalized NAA and to determine the lower limit of detection. With this, the dissociation constant of the aptamer-thrombin reaction is determined as Kd = 0,9 µM, the sensitivity to be m = 45.5 nm/µM and the LOD = 72 nM.Finally, in order to demonstrate the specificity of the NAA platform, experiments replacing the flow of thrombin by the flow of a different but similar protein, Bovine Serum Albumin (BSA) were conducted showing a much lower response. Furthermore, thrombin flow experiments with NAA lacking the aptamer functionalization step were also performed to demonstrate the protein does not bind non-specifically to the NAA inner pore walls.[1] Josep Ferré-Borrull, et al., Nanomaterials, vol. 7, p. 5225 (2014).[2] Josep Ferré-Borrull et al., in NANOPOROUS ALUMINA: FABRICATION, STRUCTURE, PROPERTIES AND APPLICATIONS, Springer Series in Materials Science, vol. 219, p. 185 (2015).[3] Laura Pol et al., Nanomaterials, vol. 9, p.478 (2019).[4] Laura Pol et al, Sensors, vol. 19, p. 4543 (2019). Figure 1

Rational Synthesis of 5,10-Diazaporphyrins via Nucleophilic Substitution Reactions of α,α′-Dibromotripyrrin and Dihydrogenation to Give 5,10-Diazachlorins

We report here the first rational synthesis of 5,10-diazaporphyrins via nucleophilic substitution reactions of α,α'-dibromotripyrrin. Uses of 1,3-diiminoisoindoline and 3,4-di(ethylsulfanyl)pyrrole-2,5-diimine as nucleophiles allowed for synthesis of 5,10-diazabenzoporphyrin (2) and 5,10-diaza-7,8-di(ethylsulfanyl)porphyrin (3). 3 was reduced to 5,10-diazaporphyrin (4), 5,10-diaza-2,3-dihydrogenated porphyrin (5), and 5,10-diaza-7,8-dihydrogenated porphyrin (6) with yields that were dependent upon reduction conditions. All the structures of these products were confirmed by X-ray crystallographic analysis. Their optical and electrochemical properties have been comparatively studied with those of 5,15-diazaporphyrin (7) and 5,15-diazachlorin (8). Furthermore, NH tautomers of 2 and 4 were observed as different species in solution, and the dynamic NH tautomeric behavior was studied in 4.

(Invited) Optical Detection of Streptavidin-Biotin Binding on Nanoporous Anodic Alumina Pore Surface

Nanoporous anodic alumina (NAA) is a material with a high interest in nanotechnology[1]. Its physical and chemical properties combined with a cost-effective and scalable production process make it a good candidate in many nanotechnologically-related applications. Its high and tunable surface-to-volume ratio as well as its interesting optical properties[2] have been used as the basis of different biosensing schemes[3]. Biosensing, and specifically optical biosensing is of great interest in health and environmental applications. The reflection interference spectroscopy (RIfS) method based on NAA has demonstrated its ability in detecting many kinds of molecules (proteins, antibodies[4]). One of the molecular systems with interest in biotechnological applications is the streptavidin-biotin system. The high affinity between both molecules is exploited in many applications for the binding of different biological species. For this reason, we have studied the streptavidin-biotin binding event with NAA-based RIfS, as part of a biosensing process. In our study we assess the optimal conditions for real time monitoring of the different steps (covalent streptavidin bonding, surface passivation, biotin complexation). In order to establish such optimal conditions, we have chosen the protein thrombin as a model molecule to be detected. We prepared NAA with the usual anodization conditions under oxalic acid electrolyte to obtain porous layers with uniform pore diameter and with a thickness that permits the measurement with RIfS in a flow-cell where the different species in solution can be introduced. The experiments consisted of monitoring the change in effective optical thickness (EOT, the quantitative characteristic parameter obtained from RIfS) in the different steps of the biosensing process. The NAA pore surfaces were initially functionalized with (3-aminopropyl) triethoxysilane (APTES) with the carboxyl groups activated in order to form later a peptide bond with the streptavidin. One of the parameters to be optimized was the pore diameter. Furthermore, in order to study the ability of RIfS to detect the covalent streptavidin binding to the NAA pore surface, different concentrations of streptavidin were tested. Finally, the biosensing capabilities were evaluated by detecting biotinylated thrombin at different concentrations. An example of a complete experiment with all the steps in the streptavidin-biotinylated molecule attachment detection can be seen in Figure 1. After establishing a baseline with a PBS flow, streptavidin at 50 µg/ml is introduced in the RIfS setup and its covalent attachment to APTES is detected as an increase in EOT. Following this first step, PBS is introduced to wash away the non-specifically bound molecules and a 3% Bovine Serum Albumin (BSA) solution is flowed to passivate the remaining activated carboxyl groups of APTES and the remaining hydroxyl groups on the NAA pore surface. Such steps are detected by the RIfS procedure. Then, after a subsequent PBS wash, biotinylated thrombin at a concentration of 20 µg/ml is introduced causing a steady increase in EOT reaching a value of 3.5 nm above the initial one. The experiment in Figure 1 was repeated for different NAA pore sizes revealing a higher change in EOT for bigger pore sizes. An important parameter in the detection of the biotinylated molecules binding is the concentration at the streptavidin immobilization step. Thus, different streptavidin concentrations were tested in 60nm pore diameter NAA. Results are summarized in Figure 2: for the highest concentrations (50 µg/ml) the attachment of streptavidin shows a two-phase curve with an initial phase with a faster increase in EOT and a second phase with a slower increase after an inflection point in the EOT versus time curve. Instead, for a small concentration (1 µg/ml) an initial fast increase is followed by a stabilization of the EOT signal. These two behaviors are associated with the attachment of streptavidin to the activated carboxyl of APTES for the initial fast EOT increase, while the subsequent slower increase can be explained by the aggregation of streptavidin through amine group binding. Finally, in order to demonstrate the capability of quantifying the attachment of biotinylated molecules to the NAA surface, the process was carried out using thrombin as the model molecule and for increasing concentrations. Figure 3 shows the change in EOT as a function of the thrombin concentration. It can be seen that RIfS based on NAA sensing platforms is able to quantify such attachment. [1] Josep Ferré-Borrull, et al., Materials, vol. 7, p. 5225 (2014). [2] Josep Ferré-Borrull et al., in NANOPOROUS ALUMINA: FABRICATION, STRUCTURE, PROPERTIES AND APPLICATIONS, Springer Series in Materials Science, vol. 219, p. 185 (2015). [3] Chris Eckstein, et al. ACS Appl Mater Interfaces, vol. 10, p.10571 (2018). [4] Gerard Macías, et al. Analyst, vol. 140, p. 4848 (2015). Figure 1

Conductivity of weak electrolytes for buffer solutions: Modeling within the mean spherical approximation

The purpose of this study is to predict the electrical conductivity of some weak electrolytes used in buffer solutions. The acid-base reactions occurring between the different species in solution are evaluated taking into account the activity coefficients. The deviations from ideality necessary to describe the equilibrium and transport properties are estimated within the mean spherical approximation (MSA). Results from theoretical expressions of the conductivity of electrolyte mixtures are compared with experimental results from the literature in the case of acetate, carbonate and bicarbonate solutions. In order to characterize all the ions that may be present, we also studied the ability of our theory to describe some strong alkaline or acid solutions.

Synthesis, characterization, DFT calculations and antibacterial activity of palladium(II) cyanide complexes with thioamides

Palladium(II) cyanide complexes of thioamides (or thiones) having the general formula PdL2(CN)2, where L = Thiourea (Tu), Methylthiourea (Metu), N,N′-Dimethylthiourea (Dmtu), Tetramethylthiourea (Tmtu), 2-Mercaptopyridine (Mpy) and 2-Mercaptopyrimidine (Mpm) were prepared by reacting K2[PdCl4] with potassium cyanide and thioamides in the molar ratio of 1:2:2. The complexes were characterized by elemental analysis, thermal and spectroscopic methods (IR, 1H and 13C NMR). The structures of three of the complexes were predicted by DFT calculations. The appearance of a band around 2100 cm−1 in IR and resonances around 120–130 ppm in the 13C NMR spectra indicated the coordination of cyanide to palladium(II). More than one resonances were observed for CN− carbon atoms in 13C NMR indicating the existence of equilibrium between different species in solution. DFT calculations revealed that in the case of the palladium(II) complex of Tmtu, the ionic dinuclear [Pd(Tmtu)4][Pd(CN)4] form was more stable than the dimer of mononuclear complex [Pd(Tmtu)2(CN)2] by 0.91 kcal mol−1, while for the complexes of Tu or Mpy ligands, the nonionic [Pd(L)2(CN)2] forms were more stable than the corresponding [Pd(L)4][Pd(CN)4] complexes by 1.26 and 6.49 kcal mol−1 for L = Tu and Mpy, respectively. The complexes were screened for antibacterial effects and some of them showed significant activities against both gram positive as well as gram negative bacteria.

Potentiometric, equilibrium studies and thermodynamics of novel thiosemicarbazones and their bivalent transition metal(II) complexes

Protonation constants of novel thiosemicarbazones including 2-(1-(2-phenyl-hydrazono)-propan-2-ylidene) hydrazine-carbothioamide (TPHP) and N-methyl-2-(1-(2-phenyl-hydrazono)-propan-2-ylidene)hydrazinecarbo-thioamide (MTPHP) ligands and their corresponding metal-ligand formation constants with Cu(II), Ni(II), Mn(II) and Co(II) ions were determined at 15°C, 25°C and 35°C in 50% DMSO solution at I=0.1mol·dm−3 NaNO3. The stability order of complexes with reference to the metal ions has been followed this order Cu(II)>Ni(II)>Co(II)>Mn(II) in concord with the Irving-Williams stability order. Also, chemical equilibrium studies indicated that substitution of hydrogen in thiosemicarbazone (TPHP) by methyl group causes lowering of acidity as a result of the electron-releasing effect of the methyl group in the substituted amino group of the thiosemicarbazide moiety. The speciation of different species in solution has been evaluated as a function of pH. Additionally, the effect of temperature on protonation of thiosemicarbazone ligands and formation of their M(II)-thiosemicarbazone complexes was investigated. The thermodynamic parameters (ΔH, ΔS and ΔG) were calculated and discussed. It was found that both log K1 and –ΔH1, for M(II)-thiosemicarbazone complexes are somewhat larger than log10 K2 and –ΔH2, indicating a change in the dentate character of these ligands from tridentate (SNN-donors) in 1:1 chelates to bidentate (SN-donors) in 1:2; M:L chelates. Also, the lower values of log10 K2 and –ΔH2 than log K1 and –ΔH1 may be attributed to steric hindrance produced by the entrance of a second molecule.

Potentiometric, Thermodynamics and Coordination Properties for Binary and Mixed Ligand Complexes of Copper(II) with Imidazole-4-acetic Acid and Tryptophan or Phenylalanine Aromatic Amino Acids

Binary and ternary complex formation equilibria of copper(II) with imidazole-4-acetic acid (IMA) and some aromatic amino acids such as tryptophan and phenylalanine have been studied from 15 to 45 °C by potentiometric titration. The pH-titrations of the reaction mixtures have shown 1:1:1 (Cu:IMA:amino acid) ternary complex formation. The stability of mixed-ligand complexes was quantitatively compared with the stability of the binary complexes as Δlog10 K, Δlog10 β and log10 X parameters. The speciation of different species in solution has been evaluated as a function of pH. The effect of temperature on protonation of the ligands and formation of mixed ligand complexes was investigated. Thermodynamic parameters were calculated and are discussed. The effect of solvent of the protonation of IMA and Cu–IMA complex formation was also investigated and discussed. Additionally, the stoichiometric protonation constants (log10 β) of imidazole-4-acetic acid and its binary Cu(II)–IMA complexes were determined potentiometrically over a wide range of solvent composition.

Thioflavin T templates amyloid β(1–40) conformation and aggregation pathway

Aβ(1–40) peptide supramolecular assembly and fibril formation processes are widely recognized to have direct implications in the progression of Alzheimer's disease. The molecular basis of this biological process is still unknown and there is a strong need of developing effective strategies to control the occurring events. To this purpose the exploitation of small molecules interacting with Aβ aggregation represents one of the possible routes. Moreover, the use specific labeling has represented so far one of the most common and effective methods to investigate such a process. This possibility in turn rests on the reliability of the probe/labels involved.Here we present evidences of the effect of Thioflavin T (ThT), a worldwide used fluorescent dye to monitor amyloid growth, on the Aβ(1–40) conformation, stability and aggregation. By combining experimental information and Molecular Dynamics simulation results, we show that the presence of ThT in solution affects peptide conformation inducing peculiar supramolecular association. In particular ThT interactions with specific Aβ(1–40) residues promote a rigid partially-folded conformation which shifts the balance between different species in solution toward a more aggregation-prone ensemble of peptides, leading to aggregation. Our findings suggest ways for developing strategies to reverse and block aggregation or to stimulate supramolecular assembly and consequently reduce the presence of transient oligomers. This investigation underlines the need of developing label-free techniques for unbiased quantitative studies of Aβ(1–40) aggregation processes.

Solid-State and Solution-State Coordination Chemistry of Lanthanide(III) Complexes with (Pyrazol-1-yl)acetic Acid

As a precursor of carboxyl-functionalized task-specific ionic liquids (TSILs) for f-element separations, (pyrazol-1-yl)acetic acid (L) can be deprotonated as a functionalized pyrazolate anion to coordinate with hard metal cations. However, the coordination chemistry of L with f-elements remains unexplored. We reacted L with lanthanides in aqueous solution at pH = 5 and synthesized four lanthanide complexes of general formula [Ln(L)3(H2O)2]·nH2O (1, Ln = La, n = 2; 2, Ln = Ce, n = 2; 3, Ln = Pr, n = 2; 4, Ln = Nd, n = 1). All complexes were characterized by single crystal X-ray diffraction analysis revealing one-dimensional chain formations. Two distinct crystallographic structures are governed by the different coordination modes of carboxylate groups in L: terminal bidentate and bridging tridentate (1-3); terminal bidentate, bridging bidentate, and tridentate coordination in 4. Comparison of the solid state UV-vis-NIR diffuse reflectance spectra with solution state UV-vis-NIR spectra suggests a different species in solution and solid state. The different coordination in solid state and solution was verified by distinctive (13)C NMR signals of the carboxylate groups in the solid state NMR.

The Metal/Electroactive Polymer Interface Studied by Surface Resistance

The experimental arrangement in this investigation was one in which a poly(o-aminophenol) (POAP) film was supported on a thin gold film electrode whose thickness is of the order of the mean free path of conduction electrons of gold. This arrangement allows one to apply the surface resistance technique to study the electrochemical processes occurring at the metal film surface coated with the polymer film. The dependence of the resistance change of the thin gold film electrode on the external electrolyte composition for polymer thickness lower than 0.25 mC.cm-2, was attributed to a competition, at the gold film surface, between the redox process of the polymer and adsorption of different ion species contained in the electrolyte. This competition reflects a discontinuous character of polymer thickness lower than 0.25 mC.cm-2 at the metal polymer interface. The resistance response of the metal film becomes independent of both the external electrolyte composition and polymer thickness for polymer thickness higher than 0.8 mC.cm-2. Then, POAP thicknesses higher than 0.8 mC.cm-2 seem to be compact enough at the metal polymer interface to prevent the interaction of the species contained in the supporting electrolyte with the gold film surface. The increase of the gold film resistance in going from the reduced to the oxidized state for POAP thicknesses higher than 0.8 mC.cm-2 was attributed to the redox conversion of poly(o-aminophenol) from amine to imine groups. This resistance increase was explained as a transition from specular to diffuse scattering of conduction electrons of gold at the gold poly(o-aminophenol) interface due to a less compact distribution of oxidised sites of POAP as compared with that of the reduced ones. An attenuation of the resistance response of the gold film was observed when the POAP films were deactivated either by contact with a ferric cation solution or prolonged potential cycling. The deactivation of the polymer film was attributed to the creation of inactive gaps within the redox sites configuration of POAP. The surface resistance technique allows one to detect different redox sites configurations of POAP on the gold film, according to the method used to deactivate the polymer films. In this work, it is demonstrated that the surface resistance technique can be employed to study not only the ability of a POAP film to inhibit the interaction of different species in solution with a metal surface but also the deactivation of the polymer film.

Synthesis and spectroscopic analysis of an extended series of hetero dinuclear complexes containing two different lanthanides in 1:1 stoichiometry

An extended series of air and moisture stable and thermally volatile hetero dinuclear complexes of general composition [Ln1Ln2(fod)6(μ-bpm)] (where Ln1–Ln2=Pr–Nd (1); Nd–Sm (2); Dy–Ho (3); Ho–Er (4); Er–Tm (5); Tm–Yb (6); Yb–Lu (7) and Eu–Tb (8); fod=6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate; bpm=2,2′-bipyrimidine) have been synthesized and characterised. To explore the stoichiometry of the two different lanthanides in these complexes, we performed a thorough analysis of the f–f absorption spectra of the complexes in solution and found that the hetero dinuclear complexes contain two different lanthanides in 1:1 stoichiometric ratio. Furthermore, the complexes display intense f–f hypersensitive transitions as compared to Ln3+ aqua-ions. In pyridine (a strong coordinating solvent) the oscillator strength and band shape of the f–f hypersensitive transitions show distinct variations as compared to the oscillator strength and band shape in chloroform (non-coordinating solvent). We attribute this change to a change in asymmetry of the field around Ln3+ ion due to the coordination of the solvent (pyridine). A thorough investigation of the steady-state emission and excitation spectra of the complexes 3 and 8 in chloroform and pyridine further establishes that pyridine competes for coordination with weak bpm bridge and eventually replaces it to generate two different species in solution, i.e. [Ln1(fod)3(py)n] and [Ln2(fod)3(py)n] (where py=pyridine).

Strain-driven self-rolling of hybrid organic–inorganic microrolls: interfaces with self-assembled particles

Strain driven micro and nanoroll fabrication is generally restricted to multilayer and multiprocessing systems, limiting the ability to exploit self-organization at different length scales. We have designed a hybrid organic–inorganic single-layered film with a surface that responds selectively to external stimuli, resulting in mechanical strain and self-rolling in one-step fabrication. The scrolling is initiated by water and any aqueous solution of molecules or colloidal particles. During scrolling, the different species in solution remain entrapped in the rolls; the constrained environment at the interface of the roll walls pushes the particles to organize into ordered structures. We used this rolling process to create self-assembled hybrid films with well-ordered layers of gold nanoparticles and opals of polystyrene nanospheres. These films also respond selectively to solvents, allowing the easy release of molecules/particles entrapped at the interface. Researchers from Japan and Italy have devised a one-step strategy to roll single-layer films into microtubes. Films of materials ranging from metals to semiconductors to polymers have previously been rolled up. They typically consist of two or more mismatched layers, so that the scrolling process relies on the strain between layers. The researchers have now prepared a self-rolling single-layer film by ‘sol–gel’ synthesis of a glycidoxy-organosilane derivative in basic conditions, spin-coating of the product obtained on a silica substrate and subsequent drying. The bottom part of the film formed, less condensed than its upper counterpart, takes up water preferentially. Simply dipping it in water creates a strain that is sufficient to provoke scrolling. Species such as molecules or particles can be trapped within the resulting microtubes, whose diameters are controlled by adjusting the processing conditions. This simple and convenient method may facilitate preparation of rolls for functional materials. Strain-driven micro- and nanorolls fabrication is generally restricted to multilayer and multiprocessing systems, which limit the possibility of exploiting the self-organization at different length scales. We have designed a hybrid organic–inorganic film whose surface shows a selective response to external stimuli, which induces mechanical strain and self-rolling in one-step–one-layer fabrication. The scrolling is initiated by water and any aqueous solution that also contains molecules or colloidal particles. During scrolling, the different species in solution remain entrapped in the rolls, giving rise to functional microrolls.

Structuration mechanism of β-lactoglobulin – acacia gum assemblies in presence of quercetin

The interactions of β-lactoglobulin (BLG) with total Acacia gum (TAG) in presence of quercetin have been investigated in aqueous solutions at pH 4.2 and 25 °C. Isothermal titration calorimetry (ITC) has been used to determine the type and magnitude of the energies involved in the complexation process. Dynamic light scattering (DLS), electrophoretic mobility (μE), turbidity measurements (τ), optical microscopy and Fourier transform infrared spectroscopy in total attenuated reflection mode (ATR-FTIR) were used as complementary methods to better understand the sum of complicated phenomena at the origin of thermodynamic behaviour.The first structuring stage was characterized by an exothermic signal and was mainly controlled by favourable enthalpy changes due to electrostatic interactions between biopolymers. The second structuring stage was largely endothermic and more entropy driven, probably due to the release of small counterions from the electrical double layer and hydrophobic contribution to the binding process, implying the release of water molecules. The population distribution of the different species in solution and their size were determined through DLS. Dispersion turbidity of particles markedly increased and reached a maximum at 0.013 TAGQ:BLG molar ratio corresponding to the appearance of coacervates. Above TAGQ:BLG molar ratio of 0.015, dispersions turbidity decreased, which might be due to an excess of negative charges onto particles as revealed by electrophoretic mobility measurements. FTIR experiments indicated that BLG–TAG interactions, in presence or in absence of quercetin, induced a change in the α-helical structure of BLG. The results also showed significant loss in β-sheets indicating a change in the environment of BLG hydrophobic amino acids and the formation of protein–flavonoid complexes stabilized by hydrophobic associations.The results presented in this study should provide information about thermodynamic mechanisms of TAG–BLG binding processes in presence of an antioxidant, quercetin and will facilitate the application of the formed supramolecular assemblies as functional ingredients in food and non food systems.

Binding of Biotin to Streptavidin: A combined fluorescence correlation spectroscopy and time-resolved fluorescence study

The Biotin-Streptavidin complex is a widely studied system in biology and biophysics, because of its extremely strong non-covalent binding affinity. The latter is often exploited to link molecules to substrates or to one another. However, the details of the Biotin-Streptavidin binding have not been fully elucidated so far. Particularly, the role of cooperative effects in enhancing the binding affinity has not been clarified. Our long-term aim is to investigate this point by implementing two complementary approaches, fluorescence correlation spectroscopy and time-correlated single-photon counting. As both methods rely on the analysis of fluorescence signals, biotin labeled with Atto-550-dye was used. In this work, in order to get a first overview of the system, we analyzed solutions in three paradigmatic ranges of Biotin-to-Streptavidin concentration ratio. Fluorescence correlation spectroscopy measurements allowed us to extract diffusion times of free biotin and of biotin-Streptavidin complexes, and also to gain information about the dynamics of the intersystem crossing between the first excited triplet and the first excited singlet states. Time-correlated single-photon counting made it possible to derive the lifetimes of the different species in solution, as well as to deduce relevant information about the relative abundance of Streptavidin-complexed and free Biotin.

Reactivity of [1],[1]Disilamolybdenocenophane toward Zerovalent Platinum Complexes

The results of studies of the reactivity of strained [1],[1]disilamolybdenocenophane toward zerovalent platinum complexes are reported. Whereas [Pt(PEt(3))(3)] underwent clean insertion into both Si-C(ispo) bonds of the twofold-bridged molybdenocene, the reaction with the tricyclohexylphosphine analogue is considerably more complex. Thus, treatment of the molybdenum compound with 2 equiv of [Pt(PCy(3))(2)] results in a trinuclear cluster. To gain insight into the mechanistic aspects, the reaction was performed in a 1:1 stoichiometry. Multinuclear NMR spectroscopy revealed the presence of different species in solution. Two constitutional isomers were identified by X-ray diffraction analyses, one presumably depicting an intermediate in the formation of the trinuclear cluster. The predominant isomer in solution was identified as the product of C-H oxidative addition to the platinum phosphine fragment. Its solid-state structure displays an unusual coordination mode of platinum, and structural parameters suggest the formulation as the sigma-complex of a Mo-Si bond.

Thermodynamic Characterization of Acacia Gum−β-Lactoglobulin Complex Coacervation

The interactions of beta-lactoglobulin (BLG) with total acacia gum (TAG) in aqueous solutions have been investigated at pH 4.2 and 25 degrees C. Isothermal titration calorimetry (ITC) has been used to determine the type and magnitude of the energies involved in the complexation process of TAG to BLG. Dynamic light scattering (DLS), electrophoretic mobility (mu(E)), turbidity measurements (tau), and optical microscopy were used as complementary methods on the titration mode to better understand the sum of complicated phenomena at the origin of thermodynamic behavior. Two different binding steps were detected. Thermodynamic parameters indicate a first exothermic step with an association constant K(a1) of (48.4 +/- 3.6) x 10(7) M(-1) that appeared to be mostly enthalpy-driven. A positive heat capacity change was obtained corresponding at the signature for electrostatic interactions. The second binding step, 45 times less affinity (K(a2) = (1.1 +/- 0.1) x 10(7) M(-1)), was largely endothermic and more entropy-driven with a negative value of heat capacity change, indicative of a hydrophobic contribution to the binding process. The population distribution of the different species in solution and their sizes were determined through DLS. Dispersion turbidity of particles markedly increased and reached a maximum at a 0.015 TAG/BLG molar ratio. Largely more numerous coacervates appeared at this molar ratio (0.015) and two different kinds of morphologies were noticed for the large coacervates. Above the TAG/BLG molar ratio of 0.015, dispersions turbidity decreased, which might be due to an excess of negative charges onto particles as revealed by electrophoretic mobility measurements. The results presented in this study should provide information about the thermodynamic mechanisms of TAG/BLG binding processes and will facilitate the application of the formed supramolecular assemblies as functional ingredients in food and nonfood systems.

Coordination of neutral, methylene bridged bis-guanidyls at palladium

The bis-guanidyl compound H(2)C{hpp}(2) (hppH = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine) coordinates to palladium(ii) as a neutral, chelating N,N'-bidentate ligand. Structural analysis of PdMeCl(H(2)C{hpp}(2)) shows a non-planar metallacycle that is twisted relative to the square plane of the metal and an "anagostic" interaction with a C-H from the bridging methylene group. Generation of the cationic palladium complex, [PdCl(H(2)C{hpp}(2))][OTf] was achieved by halide abstraction from the dichloride PdCl(2)(H(2)C{hpp}(2)) using NaOTf. The product was identified as a mixture of different species in solution; in the solid-state, the molecular structure is dimeric, consisting of the mu,mu'-dichlorobridged dication. The new bis-guanidyl compound H(2)C{tbo}(2) (Htbo = 1,4,6-triaza-bicyclo[3.3.0]oct-4-ene) was synthesized, and structurally characterized. Coordination of this compound at palladium dichloride was accompanied by ionization of the Pd-Cl bond, and formation of the dication [Pd(H(2)C{tbo}(2))(2)][Cl](2). Structural analysis shows a significant reduction in the twisting of this ligand.