Impact of Structural Modification on the Photophysical Response of Benzoquinoline Fluorophores

Structural influence on the photophysical behavior of two pairs of molecular systems from the biologically potent benzoquinoline family, namely, dimethyl-3-(4-chlorophenyl)-3,4-dihydrobenzo[f]-quinoline-1,2-dicarboxylate, dimethyl-3-(2,6-dichlorophenyl)-3,4-dihydrobenzo[f]quinoline-1,2-dicarboxylate and their corresponding dehydrogenated analogues has been investigated exploiting experimental as well as computational techniques. The study unveils that dehydrogenation in the heterocyclic rings of the studied quinoline derivatives modifies their photophysics radically. Experimental observations imply that the photophysical behavior of the dihydro analogues is governed by the intramolecular charge transfer (ICT) process. However, the ICT process is restricted significantly by the dehydrogenation of the heterocyclic rings. Computational exertion leads to the proposition that the change in the electronic distribution in these molecular systems on dehydrogenation is the rationale behind the dramatic modification of their photophysics.     

1-(2′-Pyridylazo)-2-naphtholate complexes of ruthenium: Synthesis,characterization, and DNA binding properties

Reaction of 1-(2′-pyridylazo)-2-naphthol (Hpan) with [Ru(dmso)₄Cl₂] (dmso = dimethylsulfoxide), [Ru(trpy)Cl₃] (trpy = 2,2′,2″-terpyridine), [Ru(bpy)Cl₃] (bpy = 2,2′-bipyridine) and [Ru(PPh₃)₃Cl₂] in refluxing ethanol in the presence of a base (NEt₃) affords, respectively, the [Ru(pan)₂], [Ru(trpy)(pan)]⁺ (isolated as perchlorate salt), [Ru(bpy)(pan)Cl] and [Ru(PPh₃)₂(pan)Cl] complexes. Structures of these four complexes have been determined by X-ray crystallography. In each of these complexes, the pan ligand is coordinated to the metal center as a monoanionic tridentate N,N,O-donor. Reaction of the [Ru(bpy)(pan)Cl] complex with pyridine (py) and 4-picoline (pic) in the presence of silver ion has yielded the [Ru(bpy)(pan)(py)]⁺ and [Ru(bpy)(pan)(pic)]⁺ complexes (isolated as perchlorate salts), respectively. All the complexes are diamagnetic (low-spin d⁶, S = 0) and show characteristic ¹H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a Ru(II)–Ru(III) oxidation on the positive side of SCE. Except in the [Ru(pan)₂] complex, a second oxidative response has been observed in the other five complexes. Reductions of the coordinated ligands have also been observed on the negative side of SCE. The [Ru(trpy)(pan)]ClO₄, [Ru(bpy)(pan)(py)]ClO₄ and [Ru(bpy)(pan)(pic)]ClO₄ complexes have been observed to bind to DNA, but they have not been able to cleave super-coiled DNA on UV irradiation.     

Synthesis and characterization of zinc benzoate complexes through combined solid and solution phase reactions

A combined solid and solution phase methodology for the synthesis of a series of mononuclear and polynuclear zinc benzoate complexes is described. The substituent on the aromatic ring and the effect of solvent on deciding the composition of the complexes is presented. From the 4-substituted benzoic acids 4-methylbenzoic acid (ptolH), 4-nitrobenzoic acid (pnitrobenH) and 4-chlorobenzoic acid (pchlorbenH), the mononuclear complexes [Zn(ptol)₂(H₂O)₂], [Zn(pnitroben)₂(H₂O)(DMSO)₂] and [Zn(pchlorben)₂py)₂] (where DMSO = dimethylsulfoxide, py = pyridine) have been synthesized and structurally characterised. Zinc complexes from the reaction of zinc sulfate heptahydrate with 3-methylbenzoic acid (mtolH) and 2-methylbenzoic acid (otolH), the dinuclear complexes [Zn₂(μ²-mtol)₄(py)₂], [Zn₂(μ²-otol)₄(py)₂], pentanuclear complex [Zn₅(μ²-mtol)₆(mtol)₂(μ³-OH)₂ (py)₂] and tetranuclear complex [Zn₄(μ²-otol)₆(μ⁴-O) (DMSO)₂], have been prepared by varying the reaction conditions and the complexes have been structurally characterized.     

Binding of HgCl2 by tripodal ligands controlled by AgPF6: receptors for the PF6- anion

Mercuric chloride can readily enter into the biological cycle where it gets converted into other forms of mercury and causes severe neurotoxic, genotoxic and immunotoxic effects; a number of tripodal ligands have been synthesized that selectively bind mercuric chloride and in the presence of AgPF6, mercury can be removed and supramolecular complexes of the PF6- anion are formed.     

Development of cholesterol biosensor based on immobilized cholesterol esterase and cholesterol oxidase on oxygen electrode for the determination of total cholesterol in food samples

The development of a cholesterol biosensor by co-immobilization of cholesterol esterase (ChEt) and cholesterol oxidase (ChOX) on oxygen electrode is described. The electrode consists of gold cathode and Ag/AgCl anode. The enzymes were immobilized by cross-linking with glutaraldehyde and Bovine Serum Albumin (BSA). The immobilized enzymatic membrane was attached to the tip of the electrode by a push cap system. The optimum pH and temperature of the sensor was determined, these are 6 and 25 degrees C respectively. The developed sensor was calibrated from 1-75 mg/dl of cholesterol palmiate and found linear in the range of 2-50 mg/dL. The calibration curve was drawn with V(i) (ppm/min)(initial velocity) vs different concentrations of cholesterol palmiate (mg/dL). The application of the sensor to determine the total cholesterol in different real food samples such as egg, meat was investigated. The immobilized enzymatic layer can be reused over 30 times and the stability of the enzymatic layer was studied up to 9 weeks.     

A new methanol solvate and Hirshfeld analysis of π‐stacking in 2,3,6,7,10,11‐hexahydroxytriphenylene solvates

The structure of 2,3,6,7,10,11‐hexahydroxytriphenylene (hhtp) methanol monosolvate, C₁₈H₁₂O₆·CH₃OH, has triclinic symmetry (space group P). The compound has a three‐dimensional layered network structure formed by intermolecular hydrogen bonding. Structure analysis with Hirshfeld surfaces is shown to be a sensitive method for comparing π‐stacking effects in the five known solvates of hhtp. The title structure shows slightly weaker π‐stacking than the dihydrate, but stronger π‐stacking than the other three solvates.     

Direct crystallographic observation of catalytic reactions inside the pores of a flexible coordination polymer

A new flexible porous coordination polymer (PCP), {[Gd(2)(L)(3)(dmf)(4)]·4DMF·3H(2)O}(n) (1), was synthesized under solvothermal condition by reacting [Gd(NO(3))(3)]·6H(2)O with the ligand 2,6,2',6'-tetranitro-biphenyl-4,4'-dicarboxylic acid (H(2)L). Compound 1 had a 3D coordination polymeric structure with two types of 1D channels (A and B) that were occupied by DMF and water molecules. When crystals of 1 were separately exposed to vapors of various aromatic aldehydes, either the lattice or both the lattice and metal-bound solvent molecules were replaced by aldehyde molecules. The aldehyde molecules inside the pores spontaneously underwent cyanosilylation and Knoevenagel condensation reactions upon exposure to vapors of trimethylsilyl cyanide and malononitrile, respectively. These reactions took place at ambient temperature and pressure. Moreover, both the reactants and the products translocated from one cavity to another. The products that occupied the cavity were expunged upon exposure to the vapors of an aldehyde. Because crystallinity was maintained during these chemical transformations, direct crystallographic observation was possible. Herein, we showed that confinement of the reactants inside the void spaces of the PCP led to the products; we also assessed catalytic activities of this PCP in bulk quantities.     

Synthesis of zeolite ZSM‐5: Effect of emulsifiers

Zeolite ZSM‐5 has been synthesized in presence of various emulsifiers. Influence of types and proportions of cationic, anionic and non‐ionic emulsifier has been studied. Cationic emulsifier, cetyl trimethyl ammonium bromide resulted in an amorphous phase, whereas anionic emuisifier, sodium lauryl sulphate afforded crystalline phase, identified as magadiite. Non‐ionic emulsifiers, 1,2,3‐benzotriazole and sorbital mono‐stearate led to the formation of pure crystalline ZSM‐5 phase. Emulsifier concentration was found to affect the process of crystallization, and the crystal size and morphology of ZSM‐5. Emulsifier necessitated higher crystallization temperature and/or longer hydrothermal period. ZSM‐5 crystallization was observed to proceed through magadiite phase formation. In case of benzotriazole, unusual stacked square platelet type morphology and with sorbital monostearate, very small crystals were observed.     

Using Approximation Algorithms to Build Evidence Factors and Related Designs for Observational Studies

Abstract

Observational or nonrandomized studies of treatment effects are often constructed with the aid of polynomial-time algorithms that optimally form matched treatment-control pairs or matched sets. Because each observational comparison may potentially be affected by bias, investigators often reinforce a single comparison with an additional comparison that is unlikely to be affected by the same biases, for instance using multiple control groups or evidence factors or control?+?instrument designs. Use of two comparisons affected by different biases may detect bias if the two comparisons disagree, or may show that two comparisons with different weakness concur in their conclusions. Even this simplest addition—a second comparison—creates design problems without polynomial-time solutions. Faced with a problem that no polynomial-time algorithm can solve, a so-called approximation algorithm is a type of compromise: it provides a solution in polynomial time that is provably not much worse than the unattainable optimal solution. Building upon existing techniques for related problems in operations research, we develop an approximation algorithm for minimum distance matching with near-fine balance for three comparison groups. This algorithm is a practical approach to most observational designs that add a second comparison. The method is applied to an observational study of the effects of side airbags on injury severity in the U.S. Fatality Analysis Reporting System. For many car makes and models, side airbags were initially unavailable, then later available as optional equipment for an additional fee, then still later provided as standard equipment. Within sets matched for make and model of car, for safety belt use, for direction of impact, and other covariates, we compare crashes in these three periods, where each comparison has different limitations. The method is implemented in the R package approxmatch, whose example reproduces some of the calculations. Supplementary materials for this article are available online.     

On the temperature dependent frequency factor in thermoluminescence

In thermoluminescence (TL), frequency factor might not always be temperature independent. In the present article we consider a method of two heating rates for evaluation of temperature exponent for the case of temperature dependent frequency factor in TL. The method has been analysed by applying it both to numerical and experimental TL peaks.