Synthesis of new dyes containing double tetrazole groups for sensitization of TiO<Subscript>2</Subscript> nanoparticles in dye-sensitized solar cells

Di(1H-tetrazol-5-yl)methane is employed as a new electron acceptor group in the synthesis of two metal-free organic dyes containing triphenylamine donor group. Dye-sensitized nanocrystalline TiO₂ solar cell (DSSC) applying these novel dyes is constructed for consideration of their photovoltaic properties. The electronic properties of the dyes are also considered with the aid of theoretical calculations. The DSSC constructed from 4-(2,2-di(1H-tetrazol-5-yl)vinyl)-N,N-diphenylaniline (T1) shows a short-circuit photocurrent density of 13.38 mA cm^?2, an open circuit voltage of 578 mV, and a fill factor of 0.54, with a resulted solar energy-to-electricity conversion efficiency of 4.18% under simulated 1 sun irradiation (100 mW cm^?2). This result reveals that the dye with the di(1H-tetrazol-5-yl)methane anchoring group injects more electrons to the conduction band of TiO₂ in comparison with its analogs with single tetrazole ring in their anchoring group. It is found that in spite of a red-shift of the absorption spectrum resulted from the lengthening of the molecule, the dye with two di(1H-tetrazol-5-yl)methane groups gives lower performance than the dye with a single electron acceptor.     

Investigation on the self-association of an inorganic coordination compound with biological activity (Casiopeína III-ia) in aqueous solution

From studies using different experimental techniques employed to determine the presence of aggregates e.g. isothermal titration calorimetry, surface tension, electrical conductivity, UV–Vis spectrophotometry, dynamic and static light scattering, it is clearly demonstrated that the compound [Cu(4, 4′-dimethyl-2, 2′-bipyridine)(acetylacetonato)H₂O]NO₃ (Casiopeína III-ia), promising member of a family of new generation compounds for cancer treatment, is able to auto associate in aqueous media. Physicochemical properties associated with the formation of the aggregates were determined in pure water and in phosphate buffer media in order to simulate physiological conditions. From isothermal titration calorimetry and electrical conductivity measurements we calculated the dissociation constant of the aggregates, K _D . For pure water the values obtained in both techniques are 2.73 × 10^?4 and 5.93 × 10^?4 M respectively while for the buffer media we obtained 4.61 × 10^?4 and 1.57 × 10^?3 M. The enthalpy of dissociation, ?H _D , calculated from the calorimetric data shows that the presence of the phosphate ions has an energetic effect on the aggregate stability since in pure water a value of 18.79 kJ mol^?1 was obtained in comparison with the buffer media where a value 4 times bigger was found (70.48 kJ mol^?1). With the data collected from these techniques the number of monomers calculated which participate in the formation of the aggregates is around two. From our surface tension, electrical conductivity and UV–Vis spectrophotometry measurements the critical aggregate concentration, cac, was determined. For each technique specific concentration ranges were obtained but we can summarize that the cac in pure water is between 3 and 3.5 mM and for the buffer media is between 3.5 and 4 mM. Dynamic light scattering measurements provide us with the hydrodynamic diameter of the aggregates and from static light scattering measurements we determined the molecular weight of the Casiopeína III-ia aggregates to be of 1000.015 g mol^?1 which is two times the molecular weight of the Casiopeína III-ia molecule. This value is in agreement with the number of monomers which participate in the formation of the aggregates obtained from isothermal titration calorimetry and electrical conductivity data analysis.     

Evaluation of the stability of dye heteroassociates formed in aqueous solutions

The additive tetraphenylarsonium-tetraphenylborate model of interactions was found to be applicable to the problem of “preexperimental” evaluation of the stability of associates formed by dye cations (Ct⁺) and anions (An^?) in aqueous solutions. The possibility of predicting equilibrium association constants K _as from preliminarily calculated ΔG(Ct⁺) and ΔG(An^?) and of solving the inverse problem was analyzed. The invariability of the ΔG(Ct⁺) and ΔG(An^?) values and the problem of bringing calculation results in consistency with the experimental K _as values are discussed.     

The Effect of Simulation Cell Size on the Diffusion Coefficient of an Ionic Surfactant Aggregate

Results of all-atom molecular dynamics simulation have been presented for salt-free aqueous solutions of sodium dodecyl sulfate at its fixed total concentration in a simulation cell containing one to four preliminarily formed quasi-stable ionic aggregates with equal aggregation numbers n = 32. The obtained molecular dynamics trajectories have been used to study the structural and transport properties of the micellar solution. The value of the counterion diffusion coefficient obtained using the Green–Kubo relation has turned out to be somewhat higher than the corresponding value calculated by the Einstein equation. The diffusion coefficients of the aggregates in the systems containing from two to four aggregates have appeared to be higher than the diffusion coefficient of a single aggregate in a cell. The mean force potential obtained for the interaction between the aggregates having aggregation number n = 32 as a function the distance between the aggregate centers of mass has a local minimum in the system containing four such aggregates.     

Conducting materials prepared by the oxidation of <Emphasis Type="Italic">p</Emphasis>-phenylenediamine with <Emphasis Type="Italic">p</Emphasis>-benzoquinone

p-Phenylenediamine was oxidized with p-benzoquinone in the aqueous solutions of methanesulfonic acid (MSA). The conductivity of the products increased with increasing concentration of MSA from 1.5?×?10^?12 S cm^?1 in 0.1 M MSA up to 3.4?×?10^?4 S cm^?1 in 5 M MSA. The low-molecular-weight products are basically composed of one p-benzoquinone and two p-phenylenediamine molecules. Their molecular structure is discussed on the basis of mass, Fourier-transform infrared, Raman, NMR and electron paramagnetic resonance (EPR) spectroscopies. The formation of 2,5-di(p-phenylenediamine)-p-benzoquinone protonated with methanesulfonic acid best complies with the information provided by spectroscopic techniques. Its conversion to hydroquinone tautomer explains the formation of unpaired spins observed by EPR and their potential contribution to the conduction.     

Premicellar aggregation in water–salt solutions of sodium alkyl sulfonates and dodecyl sulfate

The features of premicellar aggregation in aqueous solutions of sodium n-octyl, n-nonyl, and n-decyl sulfonate, as well as sodium n-dodecyl sulfate, at a constant ionic strength maintained by adding NaCl are studied by potentiometry using modified ion-selective electrodes reversible with respect to the ions of these surfactants. For the studied surfactants, the critical micelle concentrations are refined, the compositions of the products of premicellar aggregation are determined, and the stability constants of aggregates are evaluated.     

Phthalocyanines and Related Compounds: XL. Synthesis of β-Diethylaminoethyl-substituted Octa-4,5-carboxyphthalocyanine Tetraimides and Their Quaternary Salts

Cobalt, zinc, hydroxoaluminum, and iron complexes of N,N′,N″,N?-tetrakis(β-diethylaminoethyl) phthalocyanine-2,3 : 9,10 : 16,17 : 23,24-tetrakis(dicarboxamide) were synthesized and were converted into the corresponding water-soluble quaternary salts by treatment with methyl iodide, methyl p-toluenesulfonate, diethyl and dimethyl sulfates, and trimethyl phosphate. The electronic absorption spectra of the quaternary salts indicated their considerable aggregation in aqueous solution; the degree of aggregation decreases in going to solutions in ethanol and disappears in DMSO.     

Electrophoretic and spectrophotometric determination of triiodides of sulfur-containing organic cations

Trimethylsulfonium triiodide (I) and p-xylylene-bis-(tetrahydrothiophenium) triiodide (II) were identified and determined by capillary electrophoresis with the resolution R _s = 4.86 using an unmodified quartz capillary. The procedure ensures the determination of sulfur-containing organic compounds in a concentration range of 1.0 × 10^?5–5.0 × 10^?4 M RSD ≤ 5%). The high stability of trimethylsulfonium triiodide and p-xylylene-bis-(tetrahydrothiophenium) triiodide in chloroform and acetonitrile solutions was found by spectrophotometry. A procedure was proposed for the spectrophotometric determination of compounds I and II as ion associates of sulfur-containing cations with a sulfophthalein dye, Bromocresol Purple (c _min (I) = 1.32 × 10^?5 M, c _min (II) = 7.1 × 10^?6 M, RSD = 5%), and by the characteristic absorption of the triiodide anion in acetonitrile (c _min (I) = 3.18 × 10^?6 M, c _min (II) = 2.76 × 10^?6 M, RSD <-3%).     

Application of chemometric methods in modeling of competitive multidye biosorption from ternary system

Simultaneous biosorption properties of three cationic dyes (Methylene blue, Crystal violet and Safranin) on Sargassum glaucescens were studied. In the most of previous papers in the field of dye biosorption, one dye or dyes with nearly separate spectra were used and dye concentration was determined by Beer’s law at different λ _max. Significant of this study is application of dyes with highly overlapped spectra (as many real situations) that their concentrations can be determined by chemometric methods. Plackett–Burman design was applied to identify the most significant factors, Box–Behnken design was used to determine optimal conditions, and principal component-wavelet neural network was used for the simultaneous determination of dye concentrations in ternary solutions. The optimum biosorption conditions were determined as dye concentration 10^?4 mol L^?1, biosorbent dosage 0.1 g L^?1 and biosorbent particle size 0.188 µm. At this condition, maximum biosorption capacity was 0.80 mmol g^?1. The biosorption process was slightly slower in the ternary system comparing with single system which was related to competition phenomena between dyes. It was found that the overall biosorption data were described by the pseudo-second-order kinetic model. Fourteen isotherm models were applied to experimental data, and it was concluded that Hill model had the best correlation.     

Apparent Molar Volumes of Aqueous Solutions of Magnesium Tetraborate from 283.15 to 363.15 K and 0.1 MPa

Densities for aqueous solutions of magnesium tetraborate MgB₄O₇(aq) at the molalities of (0.00556–0.03341) mol·kg^?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V _? ) of MgB₄O₇(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB₄O₇(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a₀?+?a₁?×?T?+?a₂?×?T ²?+?a₃/T?+?a₄?×?ln(T)?+?a₅?×?T ³ (where T is temperature in Kelvin, a _i are model parameters) for MgB₄O₇ were obtained for the first time.     

Thermodynamic characteristics of the dissolution of glycine,glycylglycine, and glycylglycylglycine in aqueous solutions of sodium dodecyl sulfate at <Emphasis Type="Italic">Т</Emphasis> = 298.15 K

the enthalpies of dissolution of glycine (Gly), glycylglycine (GlyGly), and glycylglycylglycine (GlyGlyGly) are measured in aqueous solutions of sodium dodecyl sulfate (SDS) at SDS concentrations m = 0–0.7 mol kg^?1 and Т = 298.15 K by means of calorimetry. The obtained data are used to calculate the standard values of enthalpies of dissolution (Δ_sol H ^m ) and enthalpies of transfer (Δ_tr H ^m ) of glycine and its oligomers from water to SDS aqueous solutions. The dependences of Δ_sol H ^m and Δ_tr H ^m on SDS concentration in an aqueous solution at a constant concentration of glycine and its oligomers are determined. A comparative analysis of the thermodynamic characteristics of Gly, GlyGly, and GlyGlyGly transfer within the studied range of SDS concentrations is performed. The results are interpreted in terms of ion–ion, ion–polar, and hydrophobic interactions between SDS and molecules of glycine and its oligomers.     

New phosphonate-substituted tricarbocyanines and their interaction with bovine serum albumin

New tricarbocyanine dyes with phosphonate groups (2, 3) were synthesized and their binding constants to bovine serum albumin (BSA) were determined. The binding constants of the synthesized tricarbocyanines and cardiogreen (1) (K_b ~ 10⁵ M^–1) are similar, indicating an insignificant contribution of the Coulomb interaction to the complex formation, which is determined by the polymethine chain interaction with BSA. The fluorescence lifetimes attest to the formation of two types of complexes: the lifetime of the dye complex with BSA with a major contribution (~80%) is 740–800 ps, and a lifetime of ~210 ps corresponds to the complex of dye aggregates with BSA.     

Stability of gold(I) glycinate complexes in aqueous solution

The stepwise substitution equilibrium AuCl ₂ ^? +iX^?=AuCl_2?i X _i ^? +iCl^?, β_i, where X^? is the glycinate ion (H₂N-CH₂-COO^?), i = 1 or 2, at 25°C in an aqueous solution with I = 1.0 mol/L (NaCl) has been studied pH-metrically. The corresponding constants are logβ₁ = 3.60 ± 0.10, and logβ₂ = 6.2 ± 0.2.     

Kinetics of thermal reaction HOCl ⇄ H(<Superscript>2</Superscript><Emphasis Type="Italic">S</Emphasis>) + OCl(<Emphasis Type="Italic">X</Emphasis><Superscript>2</Superscript>Π<Subscript><Emphasis Type="Italic">i</Emphasis></Subscript>) in gas phase

The kinetics of gas reaction \(HOCl\underset{{k_r }}{\overset{{k_f }}{\longleftrightarrow}}H(^2 S) + OCl(X^2 \Pi _i )\) was analyzed by the MP4 method. In the temperature range of 100–373 K the rate constants k _f and k _r and equilibrium constant K were changed from 1.10 × 10^?220 to 1.17 × 10^?52 s^?1, from 2.89 × 10^?16 to 1.68 × 10^?5s^?1 and from 3.80 × 10^?205 to 6.96 × 10^?48 respectively. In the above temperature range, the activation energy of the forward reaction (E _f) is 105.05 kcal/mol. In the same temperature interval there are two kinetic domains for the reverse reaction with activation energies (E _r1 = 5.53 kcal/mol when T is 100–273 K and E _r2 = 14.50 kcal/mol when T is 273–373 K, respectively.     

Ro-vibrating energy states of a diatomic molecule in an empirical potential

An approximate analytical solution of the Schrödinger equation is obtained to represent the rotational–vibrational (ro-vibrating) motion of a diatomic molecule. The ro-vibrating energy states arise from a systematical solution of the Schrödinger equation for an empirical potential (EP) V _±(r) = D _e {1 ? (?/δ)[coth (ηr)]^±1/1 ? (?/δ)}² are determined by means of a mathematical method so-called the Nikiforov–Uvarov (NU). The effect of the potential parameters on the ro-vibrating energy states is discussed in several values of the vibrational and rotational quantum numbers. Moreover, the validity of the method is tested with previous models called the semiclassical (SC) procedure and the quantum mechanical (QM) method. The obtained results are applied to the molecules H₂ and Ar₂.     

Simulation of copper(II) cations sorption on goethite from aqueous solutions of complexons

Effect of complexons of polyaminopolycarboxylic acid series (IDA, NTA, EDTA, and DTPA) and polyphosphonic acid series (HEDP, NTP, and EDTP) on Cu(II) cations sorption on goethite (α-FeOOH) from aqueous solutions has been studied. Obtained results have been considered in the context of complexation reactions in bulk solution and on sorbent surface. It has been found that all complexons (except for EDTA), depending on nature, produce on goethite surface (≡FeOH) triple complexes of type A (surface–metal–complexon) of composition ≡FeOCuLH _i ^1+i?n and ≡FeOCuL(OH) _j ^1?j?n or type B (surface–complexon–metal) of composition ≡FeLH _i Cu^3+i-n and ≡FeLCu(OH) _j ^3?j?n . pH-Ranges for complex existence and stability constants for the surface complexes have been determined. Factors affecting the character of complexon effect (immobilization/remobilization) on the sorbed metal have been analyzed.     

Antimicrobial Property of Nanosilver Colloid Prepared by Electrical Spark Discharge Method on <Emphasis Type="Italic">Aspergillus niger</Emphasis>

This study employed an electrical spark discharge method (ESDM) to prepare a nano-Ag colloid as an antifungal solution. The solution was diluted to two concentrations, and the fungal medium prepared in this study was coated with Aspergillus niger. The nano-Ag colloid solution was mixed with A. niger in various concentrations and dripped onto 3M Petrifilm plates. Inhibited growth observed after several days confirmed the antifungal effect of the nano-Ag colloid on A. niger. Because direct washing produced inaccurate quantitation and yielded A. niger in an excessively high concentration, this study employed an inoculation loop method for A. niger quantitation. The concentrations of A. niger ranged from 10^?2 to 10^?7%. The optimal colony count was observed on day 2. During an experiment regarding the antifungal effect of the ESDM-prepared nano-Ag colloid on A. niger, 3M Petrifilm plates were employed to observe the growth of A. niger. The colony count of 10^?2% A. niger without nano-Ag colloid was approximately 60. After the nano-Ag colloid was added, the colony count substantially decreased to approximately 10. The colony count of 10^?7% A. niger was reduced to 11 or lower after the nano-Ag colloid was added. The results confirmed the antifungal effect of the nano-Ag colloid on the growth of A. niger.     

Dissolution kinetics of silver metal nanoparticles in their reaction with nitric acid in an reverse micelle solution of AOT

The dissolution of silver nanoparticles in their reaction with aqueous HNO₃ solubilized to an reverse micelle solution of sodium bis(2-ethylhexyl)sulfosuccinate in decane is studied spectrophotometrically. A physicochemical model is advanced for quantifying the process kinetics on th basis of the following autocatalytic scheme: Ag⁰ + H⁺ + NO ₃ ^? → Ag⁺ + products (k ₁), and Ag⁰ + Ag⁺ + NO ₃ ^? → 2Ag⁺ + products (k ₂). The effective rate constant k ₂ decreases with decreasing solubilization capacity V _S/V _O (where V _S is the volume of the solubilized dispersed aqueous phase and V _O is the volume of the micelle solution); the solubilization capacity determines the size of the micelle cavities in which the reaction between Ag⁰ and HNO₃ occurs: k ₂ = 74 (V _S/V _O) · 100% ≈ 3.8%), 41 (2.9), and 35 (2.0) L/(mol s). The effective constant k ₁ is determined with a high uncertainty; the effect of V _S/V _O on k ₁ has the opposite tendency.     

Noncovalent columnar structures based on β-cyclodextrin

A new method for the synthesis of associates of cyclodextrins (CDs) of the columnar type consisting of the precipitation of CDs from aqueous solutions into acetone at lowered temperatures is developed. It is shown that columnar structures exist in both a crystalline state and in aqueous solutions. Hydrodynamic radii and molecular masses of noncovalent columnar structures (NCSs) in aqueous solutions are determined by the dynamic and static light scattering methods. The degree of association of noncovalent columnar polymers is ～40. It is revealed the NCS associates based on β-CD are stable and their hydrodynamic radius R _h is equal to 100 ± 10 nm. The kinetics of interactions of initial β-CD and NCS with poly(propylene oxide) (PPO) is studied. The pattern of kinetic curves of R _h growth upon interaction between NCS and PPO indicates that the aggregation of the particles of polymer inclusion complex proceeds in the regime of reaction-limited cluster-cluster aggregation. Kinetic curves describing the interaction processes between β-cyclodextrin and PPO are characterized by the presence of induction period t ₀. At t > t ₀, R _h ∞ t ^0.56 which is typical for the diffusion-limited cluster-cluster aggregation. Schemes of the formation of polymer inclusion complexes between initial β-CD or NCS and poly(propylene oxide) are proposed. Comparison of kinetic data on the complexation of β-CD in solution in the form of associates of two types with PPO demonstrates that columnar forms of associates are reactive species acting as macroreceptors.     

Thermochemistry of the Dissolution of Dipeptides Containing DL-α-Alanine in Aqueous Solutions of Sodium Dodecyl Sulfate at 298.15 K

Enthalpies of the dissolution of DL-α-alanylglycine (AlaGly), DL-α-alanyl-DL-α-alanine (AlaAla), DL-α-alanyl-DL-α-valine (AlaVal), and DL-α-alanyl-DL-norleucine (AlaNln) in an aqueous solution of sodium dodecyl sulfate (SDS) at SDS concentration of m = 0–0.07 mol kg^?1 and temperature Т = 298.15 K are measured via calorimetry. The standard values of the enthalpy of dissolution (Δ_solH ^m ) and the transfer of dipeptides (Δ_trH ^m ) from water to aqueous SDS solutions are calculated using the experimental data. The dependences of Δ_solH ^m and Δ_trH ^m the SDS concentration at a constant concentration of dipeptide are established. Thermochemical characteristics of the transfer of AlaGly, AlaAla, AlaVal, and AlaNln in the investigated range of SDS concentrations are compared. The results are interpreted by considering ion–ion, ion–polar, and hydrophobic–hydrophobic interactions between SDS and dipeptide molecules.