Raman based pH measurements with polyaniline

The reversible acid–base equilibrium between the emeraldine salt (ES) and the emeraldine base (EB) form of thin electropolymerized films of polyaniline (PANI) has been studied between pH 2 and 9 with in situ Raman spectroscopy using the 514, 633 and 780 nm laser excitation wavelengths. The electropolymerization of PANI was done with cyclic voltammetry in a flow cell from a solution consisting of 50 mM aniline and 1.0 M HCl. It is shown that the Raman signal of the CN stretching vibration at 1439 cm⁻¹, originating from the quinoid units of the EB form, can be used for pH measurements between pH 3 and 6 with the 633 nm laser. This vibration is strongly resonance enhanced by the 633 nm laser and its intensity grows therefore considerably in the pH interval where the ES–EB transition mainly takes place (pH 3–6). The influence of the film conditioning pH was also studied as well as the reproducibility of the Raman spectra when pH was changed several times from pH 6 to 3.     

Polyketide stereotetrads in natural products

Natural products (or secondary metabolites) remain as the most important source for discovery of new and potential drug molecules. With high resolution data of their structures, and the advancement of synthesis possibilities, analysis of the natural products based on their specific structural features is valuable to those entering the field. In this tutorial review we attempt such an analysis indicating the salient features of the structural classes with examples of the synthesis of each one of them. As the particular class of natural products, we have chosen polyketides.     

p<Emphasis Type="Italic">K</Emphasis><Subscript>a</Subscript> measurements for the SAMPL6 prediction challenge for a set of kinase inhibitor-like fragments

Determining the net charge and protonation states populated by a small molecule in an environment of interest or the cost of altering those protonation states upon transfer to another environment is a prerequisite for predicting its physicochemical and pharmaceutical properties. The environment of interest can be aqueous, an organic solvent, a protein binding site, or a lipid bilayer. Predicting the protonation state of a small molecule is essential to predicting its interactions with biological macromolecules using computational models. Incorrectly modeling the dominant protonation state, shifts in dominant protonation state, or the population of significant mixtures of protonation states can lead to large modeling errors that degrade the accuracy of physical modeling. Low accuracy hinders the use of physical modeling approaches for molecular design. For small molecules, the acid dissociation constant (pK_a) is the primary quantity needed to determine the ionic states populated by a molecule in an aqueous solution at a given pH. As a part of SAMPL6 community challenge, we organized a blind pK_a prediction component to assess the accuracy with which contemporary pK_a prediction methods can predict this quantity, with the ultimate aim of assessing the expected impact on modeling errors this would induce. While a multitude of approaches for predicting pK_a values currently exist, predicting the pK_as of drug-like molecules can be difficult due to challenging properties such as multiple titratable sites, heterocycles, and tautomerization. For this challenge, we focused on set of 24 small molecules selected to resemble selective kinase inhibitors—an important class of therapeutics replete with titratable moieties. Using a Sirius T3 instrument that performs automated acid–base titrations, we used UV absorbance-based pK_a measurements to construct a high-quality experimental reference dataset of macroscopic pK_as for the evaluation of computational pK_a prediction methodologies that was utilized in the SAMPL6 pK_a challenge. For several compounds in which the microscopic protonation states associated with macroscopic pK_as were ambiguous, we performed follow-up NMR experiments to disambiguate the microstates involved in the transition. This dataset provides a useful standard benchmark dataset for the evaluation of pK_a prediction methodologies on kinase inhibitor-like compounds.     

Adsorption of polycyclic aromatic hydrocarbons from aqueous solutions by modified periodic mesoporous organosilica

A novel procedure was developed for the synthesis of a periodic mesoporous organosilica (PMO), which was used to remove polycyclic aromatic hydrocarbons (PAHs) from aqueous solutions. Adsorption equilibrium isotherms and adsorption kinetics experiments were carried out in solutions of PAHs (2-60 mg L(-1)), using the PMO as adsorbent. Adsorption models were used to predict the mechanisms involved. The adsorption kinetics data best fitted the pseudo-first-order kinetic model for naphthalene, and to the pseudo-second-order model for fluorene, fluoranthene, pyrene, and acenaphtene. The intraparticle model was also tested and pointed to the occurrence of such processes in all cases. The isotherm models which best represented the data obtained were the Freundlich model for fluoranthene, pyrene, and fluorene, the Temkin model for naphthalene, and the Redlich-Peterson model for acenaphtene. PAHs showed similar behavior regarding kinetics after 24 h of contact between adsorbent and PAHs. FTIR, XRD, BET, and SEM techniques were used for the characterization of the adsorbent material.     

Impedance study of thiolated polyaniline

Covalent attachment of thiolated probes to conducting polymers such as polyaniline (PANI) is a promising approach towards the development of electrochemical sensors and biosensors. However, thiolation alters the conjugated polymer backbone and influences the electrochemical behavior of the conducting polymer. PANI studied in this work was electropolymerized on glassy carbon (GC) electrodes from a solution of 0.1 M aniline in 0.5 or 1.0 M H₂SO₄. The GC/PANI electrodes were then functionalized by covalent attachment of 2-mercaptoethanol to the PANI backbone. The progress of thiolation was studied by cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Thiolation of PANI was found to cause an initial decrease in electroactivity at 0–0.25 V and an increase in electroactivity at 0.25–0.6 V. However, prolonged thiolation caused a loss of electroactivity of PANI, which could be seen from EIS measurements as a dramatic decrease in the bulk redox capacitance of PANI.     

Weyl Type Asymptotics and Bounds for the Eigenvalues of Functional-Difference Operators for Mirror Curves

We investigate Weyl type asymptotics of functional-difference operators associated to mirror curves of special del Pezzo Calabi-Yau threefolds. These operators are \({H(\zeta) = U + U^{-1} + V + \zeta V^{-1}}\) and \({H_{m,n} = U + V + q^{-mn}U^{-m}V^{-n}}\), where \({U}\) and \({V}\) are self-adjoint Weyl operators satisfying \({UV = q^{2}VU}\) with \({q = {\rm e}^{{\rm i}\pi b^{2}}}\), \({b > 0}\) and \({\zeta > 0}\), \({m, n \in \mathbb{N}}\). We prove that \({H(\zeta)}\) and \({H_{m,n}}\) are self-adjoint operators with purely discrete spectrum on \({L^{2}(\mathbb{R})}\). Using the coherent state transform we find the asymptotical behaviour for the Riesz mean \({\sum_{j\ge 1}(\lambda - \lambda_{j})_{+}}\) as \({\lambda \to \infty}\) and prove the Weyl law for the eigenvalue counting function \({N(\lambda)}\) for these operators, which imply that their inverses are of trace class.     

The homogeneity of the ball inR 3 and special relativity

Einstein's velocity addition formula ofspecial relativity (SR) defines a transformation _v of the ballB _c of radiusc inR ³, representing all possible velocities in an inertial systemK, onto identical ballB _c , which represents the velocities in another systemK, moving with velocity v relative toK. Since _v maps the zero velocity ofB _c into arbitrary vector v ofB _c ,B _c is homogeneous under all possible _v.A similar homogeneity of the unit ballB inL(G, H) under a set of maps _a, a B, arises also in theLine Transmission Theory (TLT) for a lossless line. HereL(G, H) is the space of all linear operators between Hilbert spacesG,H, representing the signals on the line in the two directions. The explicit form of _a is obtained naturally in TLT.     

Study on the reflectivity properties of spherically bent analyser crystals

Theoretical and experimental studies are presented on properties of spherically bent analyser crystals for high‐resolution X‐ray spectrometry. A correction to the bent‐crystal strain field owing to its finite surface area is derived. The results are used to explain the reflectivity curves and anisotropic properties of Si(660) and Si(553) analysers in near‐backscattering geometry. The results from the calculation agree very well with experimental results obtained using an inelastic X‐ray scattering synchrotron beamline.     

Rapid detection and characterization of reactive drug metabolites in vitro using several isotope‐labeled trapping agents and ultra‐performance liquid chromatography/time‐of‐flight mass spectrometry

Reactive metabolites are believed to be one of the main reasons for unexpected drug‐induced toxicity issues, by forming covalent adducts with cell proteins or DNA. Due to their high reactivity and short lifespan they are not directly detected by traditional analytical methods, but are most traditionally analyzed by liquid chromatography/tandem mass spectrometry (LC/MS/MS) after chemical trapping with nucleophilic agents such as glutathione. Here, a simple but very efficient assay was built up for screening reactive drug metabolites, utilizing stable isotope labeled glutathione, potassium cyanide and semicarbazide as trapping agents and highly sensitive ultra‐performance liquid chromatography/time‐of‐flight mass spectrometry (UPLC/TOFMS) as an analytical tool. A group of twelve structurally different compounds was used as a test set, and a large number of trapped metabolites were detected for most of them, including many conjugates not reported previously. Glutathione‐trapped metabolites were detected for nine of the twelve test compounds, whereas cyanide‐trapped metabolites were found for eight and semicarbazide‐trapped for three test compounds. The high mass accuracy of TOFMS provided unambiguous identification of change in molecular formula by formation of a reactive metabolite. In addition, use of a mass defect filter was found to be a usable tool when mining the trapped conjugates from the acquired data. The approach was shown to provide superior detection sensitivity in comparison to traditional methods based on neutral loss or precursor ion scanning with a triple quadrupole mass spectrometer, and clearly more efficient detection and characterization of reactive drug metabolites with a simpler test setup. Copyright © 2009 John Wiley & Sons, Ltd.     

Efficiency enhancement in a microcavity solid-state dye laser with Bragg grating reflectors

Bragg grating reflectors placed along microcavity facets can improve the efficiency of a polymer dye laser built with such a microcavity. The impact of different reflector designs on the mode pattern and resonance frequencies of the microcavity is numerically simulated and analyzed. This rigorous physical model is based on solving the Maxwell equations and includes such material properties as absorption, dispersion, fluorescence and optical gain. In certain cases, an asymmetrical layout of the reflectors can be more preferable than the pair of reflectors located on opposite sides of the microcavity as it is implemented for typical design.