Temperature variation of DC conductivity of poly(3-alkyl thiophenes) and their cocrystals

The dc conductivity of poly(3-alkyl thiophenes) (P3ATs) and their cocrystals are measured in the temperature range of -130 to 150 degrees C. Both solvent-cast films and the melt-cooled films are used. The former exhibit a sharp increase followed by a decrease in conductivity, whereas the latter show only a sigmoidal increase in conductivity with temperature. The sigmoidal increase of the melt-cooled samples is dependent on the regioregularity and alkyl chain length of the samples and is explained from the solid-state transformation of the interdigited type-II crystal to a noninterdigited type-I crystal. The type-I crystal itself has lower conductivity than type-II crystals, and the samples exhibit a blue shift in UV-vis absorption spectra with an increase in temperature. So the sigmoidal increase of conductivity is attributed to the increase in carrier mobility with temperature in the type-I crystals. The X-ray and DSC results suggest that during the transformation of type-II to type-I crystals with increasing temperature, localized crystallites of smaller dimensions separated by narrower amorphous portions are produced throughout the whole matrix. But in the type-II polymorph, the crystallites are large with a wider gap in between. The sigmoidal increase is attributed to the easier hopping of the charge carrier among the localized crystallites of the type-I crystal with increasing temperature. In the cocrystals, the smaller sigmoidal increase with increasing irregular sample concentration is valid for a lower concentration of such localized crystallites. The same is true for cocrystals with longer alkyl chain lengths. The interfibrillar contribution of conductivity through the network junctions together with the carrier hopping between the localized crystallites might be a possible reason for the metallic-type behavior of solvent-cast samples after a certain temperature. The melt-cooled films do not exhibit metallic-type behavior because of the absence of a fibrillar network morphology.     

Controlling J aggregation in fluorescein by bile salt hydrogels

Aggregation of the well-known xanthene dye, fluorescein has been studied in the restricted environment of a bile salt hydrogel and in the bile salt micelles. It has been observed that the hydrogel can be used to some extent “control” the type of aggregation in fluorescein, since J-aggregate formation is favored at the expense of H-aggregates in the gel. In contrast to the hydrogel, the effect of normal bile salt micelles is less dramatic, i.e., bile salt micelles do not lead to significant change in the type of dye aggregation.     

Environmental effects on the aggregation of some xanthene dyes used in lasers

The effect of solvents, halo substituents and surfactants on the aggregation of xanthene dyes (fluorescein and eosin Y) has been investigated. It has been found that polar protic solvents promote the aggregation of both the dyes while polar aprotic solvents hinder the aggregation process. Apolar solvents can disintegrate the aggregates previously formed in aqueous medium. The nature of the driving forces for aggregation in the two dyes is different. Surfactants bearing charge opposite to the dye molecules facilitate aggregation. These observations bear direct relevance to the possible use of fluorescein and eosin Y as quantum yield standards, photosensitizers, laser dyes and biological labels.     

Detection of miRNA in Live Cells by Using Templated RuII‐Catalyzed Unmasking of a Fluorophore

Reactions templated by cellular nucleic acids are attractive for nucleic acid sensing or responsive systems. Herein we report the use of a photocatalyzed reductive cleavage of an immolative linker to unmask a rhodamine fluorophore, and its application to miRNA imaging. The reaction was found to proceed with a very high turnover (>4000) and provided reliable detection down to 5 pM of template by using γ‐serine‐modified peptide nucleic acid (PNA) probes. The reaction was used for the selective detection of miR‐21 in BT474 cells and miR‐31 in HeLa cells following irradiation for 30 min. The probes were introduced by using reversible permeation with streptolysin‐O (SLO) or a transfection technique.     

Copper(II)‐Catalyzed Nitroaldol (Henry) Reactions: Recent Developments

Self‐assembled copper(II) complexes are described as effective catalysts for nitroaldol (Henry) reactions on water. The protocol involves a heterogeneous process and the catalysts can be recovered and recycled without loss of activity. Further, C2‐symmetric N,N′‐substituted chiral copper(II) salan complexes are found to be more effective catalysts than chiral copper(II) salen complexes for reactions in homogeneous catalysis, with high enantioselectivities. The reactions involve bifunctional catalysis, bearing the properties of a Brønsted base, as well as a Lewis acid, to effect the reaction in the absence of external additives.     

Effect of emergent carrying capacity in an eco‐epidemiological system

The paper explores an eco‐epidemiological model of a predator–prey type, where the prey population is subject to infection. The model is basically a combination of S‐I type model and a Rosenzweig–MacArthur predator–prey model. The novelty of this contribution is to consider different competition coefficients within the prey population, which leads to the emergent carrying capacity. We explicitly separate the competition between non‐infected and infected individuals. This emergent carrying capacity is markedly different to the explicit carrying capacities that have been considered in many eco‐epidemiological models. We observed that different intra‐class and inter‐class competition can facilitate the coexistence of susceptible prey‐infected prey–predator, which is impossible for the case of the explicit carrying capacity model. We also show that these findings are closely associated with bi‐stability. The present system undergoes bi‐stability in two different scenarios: (a) bi‐stability between the planner equilibria where susceptible prey co‐exists with predator or infected prey and (b) bi‐stability between co‐existence equilibrium and the planner equilibrium where susceptible prey coexists with infected prey; have been discussed. The conditions for which the system is to be permanent and the global stability of the system around disease‐free equilibrium are worked out. Copyright © 2015 John Wiley & Sons, Ltd.     

Solution of the “Classical” Schrödinger equation for a driven symmetric triple well: A comparison with its classical counterpart

The behavior of a driven symmetric triple well potential has been studied by developing an algorithm where the well‐established Bohmian mechanics and time‐dependent Fourier Grid Hamiltonian method are incorporated and the quantum theory of motion (QTM) phase space structures of the particle are constructed, both in “nonclassical” and “classical” limits. Comparison of QTM phase space structures with their classical analogues shows both similarity as well as dissimilarities. The temporal nature and the spatial symmetry of applied perturbation play crucial roles in having similar phase space structures. © 2016 Wiley Periodicals, Inc.     

A theoretical study on the mechanism of boron metathesis

The mechanism of the boron metathesis reaction of the transition-metal-aminoborylene complex Cp(CO)(2)FeBN(CH(3))(2+) (8) with EX, where EX = H(3)PO (9ap), H(3)AsO (9bp), H(3)PS (9aq), H(3)AsS (9bq), CH(3)CHCH(2) (9cr), (NH(2))(2)CCH(2) (9dr), H(2)CO (9ep), and (NH(2))(2)CO (9dp) is investigated at the B3LYP/LANL2DZ level. The analysis of bonding and charge distribution shows that the Fe-borylene complex (8) is a Fischer-type carbene analogue. The attack of the olefin takes place at the metal end of the M=C bond of the metal-carbene complex in olefin metathesis and proceeds via [2 + 2] cycloaddition, while in boron metathesis, the initial attack of the substrates takes place at the positively charged B atom of the Fe-borylene complex and forms the preferred acyclic intermediate. The energetics of boron metathesis is comparable to that of the olefin metathesis. Substrates that are polar and a have low-lying sigma* molecular orbital (weak sigma bond) prefer the boron metathesis reaction. The relative stability of the metathesis products is controlled by the strength of the Fe-E and B-X bonds of the products 13 and 14, respectively. We have also investigated the possibility of a beta-hydride-transfer reaction in the Fe-borylene complex.     

Adsorptive accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from water on montmorillonite: influence of acid activation

The present work investigates the influence of acid activation of montmorillonite on adsorption of Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) from aqueous medium and comparison of the adsorption capacities with those on parent montmorillonite. The clay-metal interactions were studied under different conditions of pH, concentration of metal ions, amount of clay, interaction time, and temperature. The interactions were dependent on pH and the uptake was controlled by the amount of clay and the initial concentration of the metal ions. The adsorption capacity of acid-activated montmorillonite increases for all the metal ions. The interactions were adsorptive in nature and relatively fast and the rate processes more akin to the second-order kinetics. The adsorption data fitted both Langmuir and Freundlich isotherms, indicating that strong forces were responsible for the interactions at energetically nonuniform sites. The Langmuir monolayer capacity of the acid-activated montmorillonite is more than that of the parent montmorillonite (Cd(II): 32.7 and 33.2 mg/g; Co(II): 28.6 and 29.7 mg/g; Cu(II): 31.8 and 32.3 mg/g; Pb(II): 33.0 and 34.0 mg/g; and Ni(II): 28.4 and 29.5 mg/g for montmorillonite and acid-activated montmorillonite, respectively). The thermodynamics of the rate processes showed the adsorption of Co(II), Pb(II), and Ni(II) to be exothermic, accompanied by decreases in entropy and Gibbs free energy, while the adsorption of Cd(II) and Cu(II) was endothermic, with an increase in entropy and an appreciable decrease in Gibbs free energy. The results have established the potential use for montmorillonite and its acid-activated form as adsorbents for Cd(II), Co(II), Cu(II), Ni(II), and Pb(II) ions from aqueous media.     

Efficient Low-Cost Procedure for Microextraction of Estrogen from Environmental Water Using Magnetic Ionic Liquids

In this study, three magnetic ionic liquids (MILs) were investigated for extraction of four estrogens, i.e., estrone (E1), estradiol (E2), estriol (E3), and ethinylestradiol (EE2), from environmental water. The cation trihexyl(tetradecyl)phosphonium ([P₆₆₆₁₄]⁺), selected to confer hydrophobicity to the resulting MIL, was combined with tetrachloroferrate(III), ferricyanide, and dysprosium thiocyanate to yield ([P₆₆₆₁₄][FeCl₄]), ([P₆₆₆₁₄]₃[Fe(CN)₆]), and ([P₆₆₆₁₄]₅[Dy(SCN)₈]), respectively. After evaluation of various strategies to develop a liquid–liquid microextraction technique based on synthesized MILs, we placed the MILs onto a magnetic stir bar and used them as extracting solvents. After extraction, the MIL-enriched phase was dissolved in methanol and injected into an HPLC–UV for qualitative and quantitative analysis. An experimental design was used to simultaneously evaluate the effect of select variables and optimization of extraction conditions to maximize the recovery of the analytes. Under optimum conditions, limits of detection were in the range of 0.2 (for E3 and E2) and 0.5 μg L⁻¹ (for E1), and calibration curves exhibited linearity in the range of 1–1000 μg L⁻¹ with correlation coefficients higher than 0.998. The percent relative standard deviation (RSD) was below 5.0%. Finally, this method was used to determine concentration of estrogens in real lake and sewage water samples.