Photochromism and dynamic holographic recording in a rigid solution of fluorescein

An investigation was made of the spectra, the kinetics of induction and thermal decay and the dichroism of the photoinduced triplet absorption band in a rigid solution of fluorescein in orthoboric acid. Dynamic holographic recording was possible on this material. An experimental study was conducted into the polarizing properties of the volume transmission holograms. The experiments on four-wave mixing with continous laser light revealed a very high resolution for this rigid solution when used as a medium for optical recording. As a result of the investigations, some possible applications of the rigid solution of fluorescein are pointed out.     

A new generation of cyanide ion-selective membranes for flow injection application: part II. Comparative study of cyanide flow-injection detectors based on thin electroplated silver chalcogenide membranes

Using induced cathodic electrodeposition a number of silver chalcogenide thin layer membranes of non-trivial composition have been synthesized and their performance as ion-selective flow-injection potentiometric detectors (FIPDs) for free cyanide has been critically estimated in the context of the stringent requirements for toxic cyanide environmental monitoring. AgSCN/Ag₂S, Ag₂S, Ag_2+δSe, Ag_2+δSe_1−xTe_x (0 < δ < 0.25 and x ≈ 0.13), Ag₂Se and Ag₂Se_1−xTe_x electroplated membranes were selected for the present performance-based comparative study in order to obtain a feedback information about the effect of membrane composition. Both silver selenide and Te-doped silver selenide membranes, irrespective of their stoichiometry with respect to silver, exhibit the lowest detection limit for CN⁻ (52 ppb) with linear double-Nernstian response down to 130 ppb. The type of chalcogene anion in the membrane composition proves to exert dominant effect on the general performance characteristics of the newly developed FIPDs. The silver stoichiometry (intrinsic defects factor) and the inclusion of Te-dopant (extrinsic defects factor) have more pronounced effect on the profile of the output signal and exert moderate control on the detectors selectivity and baseline stability. This new generation of CN⁻—ion-selective membranes for FIPDs exhibits high selectivity against the common interferents present in cyanide effluents such as SCN⁻, S₂O₃²⁻, Cl⁻ and do not get poisoned in the presence of S²⁻. Moreover, their long-term stability and signal reproducibility, which make redundant the regular day-to-day calibration, coupled with the cost-effective technology for membranes preparation and easy re-generation make them attractive candidates for incorporation into automated in-field devices for in situ cyanide toxic species monitoring.     

Direct Red 28 Adsorption on Amosil and <Emphasis Type="Italic">Avena sativa </Emphasis> L.: Mass Transfer and Kinetics Modelling on the Solid/Solution Interface

Adsorption kinetics is a key issue for successful sorbent selection and the proper design of batch and fixed-bed adsorption systems. The aim of the present study was to determine the kinetics, mass transfer and diffusion coefficients and to establish the rate-controlling mechanism/s during Direct Red 28 adsorption on Amosil and Avena sativa L. biomass. Five kinetic models (pseudo-second order, Blanchard, Avrami, Ritchie and power function) and and four mass transfer (external diffusion, film diffusion, particle diffusion, intraparticle diffusion) mathematical models were applied to the experimental data. To confirm the best-fitting model(s), error analyses were conducted. The integrative comparative analyses of the values of the predicted model parameters, coefficients and error functions established that the intraparticle diffusion model best represented the experimental results of the dye sorption on dried A. sativa L. biomass, while for the Direct Red 28/Amosil system, the kinetic behavior is the best described by either the pseudo-second or Blanchard’s model. Boyd’s effective intraparticle diffusion coefficient (D _i ), characterizing the dye sorption on Amosil, is significantly lower than that for the system Direct Red 28/A. sativa L. biomass. The low values of the Bi number (Bi < 0.5) suggests that the mass transfer resistance, for both systems, is concentrated at the fluid/solid phase surface.     

Microwave assisted synthesis and X-ray structure of a novel anthracene-derived aminophosphonate. Enantioseparation of two α-aminophosphonates and genotoxicity in vivo

A novel anthracene-derived α-aminophosphonate has been synthesized through a classical addition reaction of dimethyl phosphite to a Schiff base and via a microwave assisted Kabachnik–Fields reaction. The compound has been characterized by elemental analysis, TLC, IR, NMR, and fluorescent spectra. The X-ray analysis showed that the compound crystallizes in the orthorhombic space group Pbca (N° 61) with one molecule per asymmetric unit. The enantioseparation of two racemic aminophosphonates (5 and 6) into enantiomers (5a, 5b and 6a, 6b, respectively) has been performed. Data about genotoxicity and antiproliferative activity in vivo of the racemic compounds and their enantiomeric forms is also presented. The studied racemic α-aminophosphonates 5 and 6 and their enantiomers have weak genotoxic effect. Both pairs of enantiomers did not show a significant inhibition of cell dividing processes in the bone marrow cells compared to 5 and 6. The hematopoietic function of the bone marrow will not be discontinued after exposure of the tested compounds.     

Controlled Tautomeric Switching in Azonaphthols Tuned by Substituents on the Phenyl Ring

A series of new tautomeric azonaphthols are synthesized and the possibilities for molecular switching are investigated using molecular spectroscopy, X‐ray analysis and density functional theory quantum chemical calculations. Two opposite effects that influence switching are studied: attaching a piperidine sidearm, and adding substituents to the phenyl ring. On the one hand, the attached piperidine moiety stabilizes the enol form leading to a controlled shift of the equilibrium upon protonation. On the other hand, the relative stability of the azonaphthol tautomers strongly depends on the effects of the substituents on the phenyl ring: electron donors tend to stabilize the enol tautomer, whereas electron acceptors lead to stabilization of the keto form. However, these effects do not shift fully the equilibrium towards either of the tautomers. Nevertheless, the effect of the substituents can be an additional tool to affect the switching between “on” and “off” states. Electron‐withdrawing substituents stabilize the keto form and impede switching to the off state, whereas electron donors stabilize the enol form. The effect of the piperidine unit is dominant overall, and with strongly electron‐withdrawing substituents at the phenyl ring, the enol form exists as a zwitterion.     

Low-temperature graft copolymerization of triethylene glycol dimethacrylate with oligomeric butadiene rubber

The kinetics of low-temperature graft copolymerization of triethylene glycol dimethacrylate with Krasol LBH-3000 oligobutadiene rubber was studied in relation to the initial mixture composition at 20°C. The experimental kinetic data were compared with the results of calculation by the suggested equation. The copolymer compositions were calculated from the extraction data in relation to the initial mixture compositions. The binary copolymerization constants were calculated by the analytical and graphical methods.     

Probing transient Hoogsteen hydrogen bonds in canonical duplex DNA using NMR relaxation dispersion and single-atom substitution

Nucleic acids transiently morph into alternative conformations that can be difficult to characterize at the atomic level by conventional methods because they exist for too little time and in too little abundance. We recently reported evidence for transient Hoogsteen (HG) base pairs in canonical B-DNA based on NMR carbon relaxation dispersion. While the carbon chemical shifts measured for the transient state were consistent with a syn orientation for the purine base, as expected for A(syn)?T(anti) and G(syn)?C(+)(anti) HG base pairing, HG type hydrogen bonding could only be inferred indirectly. Here, we develop two independent approaches for directly probing transient changes in N-H···N hydrogen bonds and apply them to the characterization of transient Hoogsteen type hydrogen bonds in canonical duplex DNA. The first approach takes advantage of the strong dependence of the imino nitrogen chemical shift on hydrogen bonding and involves measurement of R(1ρ) relaxation dispersion for the hydrogen-bond donor imino nitrogens in G and T residues. In the second approach, we assess the consequence of substituting the hydrogen-bond acceptor nitrogen (N7) with a carbon (C7H7) on both carbon and nitrogen relaxation dispersion data. Together, these data allow us to obtain direct evidence for transient Hoogsteen base pairs that are stabilized by N-H···N type hydrogen bonds in canonical duplex DNA. The methods introduced here greatly expand the utility of NMR in the structural characterization of transient states in nucleic acids.     

Spectrophotometric study of competitive complexation equilibria involving overlapped spectral responding species: Determination of the stability constant of bismuth-pyrophosphate complex

Spectrophotometric study of competitive complex formation equilibria involving overlapped spectral responding species applying a simple and versatile algorithm was carried out. The algorithm involves multivariable regression for calculation of equilibrium concentrations from multiwavelength data and mass action law for the stability constant calculation. The used regression functions are part of common statistical software. Stability constants and complex stoichiometry of competing equilibria were simultaneously determined. The species concentration profiles at several spectral overlapping and ??-coefficient of competing reaction were obtained. Non-absorbing bismuth ?? pyrophosphate (PPh) system was studied as a competitive reaction of bismuth ?? 4-(2-Pyridylazo) resorcinol (PAR) complex. The formation of Bi-PPh complex with 1:1 stoichiometry was proved in the studied concentration region (C_Bi = 1×10^?5 mol L^?1; C_PPh = 5×10^?6 ? 1×10^?4 mol L^?1). The stability constant of the complex at pH 1 and ?? = 1.0 have been determined: log?? = 4.2±0.2.      

Novel pyridyl‐substituted coumarin and its perchlorate salt–crystal structure and spectroscopic properties

The novel pyridyl‐substituted coumarin ( 1 ) and its perchlorate salt ( 2 ) have been synthesized and their structure and properties elucidated in detail spectroscopically, thermally and structurally, using single crystal X‐ray diffraction for 2 , linear‐polarized solid state IR‐spectroscopy, UV‐spectroscopy, TGA, DSC, DTA, and positive and negative ESI MS. Quantum chemical calculations were used to obtain the electronic structure, vibrational data and electronic spectra. The studied compound crystallizes in the centrosymmetric space group P‐1 and exhibits an infinite layered structure with the ions linked by means of the intermolecular N⁺H…OClO₃ (2.795 Å) interactions. The cations are disposed in a manner leading to a significant π‐stacking effect with a distance of 2.980 Å. The effects of N_py protonation on the optical and magnetic properties are elucidated by comparing the data of the protonated and neutral compounds. Copyright © 2009 John Wiley & Sons, Ltd.