Carbazole-thiosemicarbazone-Hg(II) ensemble-based colorimetric and fluorescence turn-on toward iodide in aqueous media and its application in live cell imaging

A carbazole-thiosemicarbazone-Hg(2+) ensemble-based fluorogenic probe for detection of iodide in aqueous media is reported. The first fluorescent sensor for iodide anions was constructed based on the displacement approach. An 'ensemble' is able to selectively sense iodide over other anions followed by the release of 9-(butane-1-yl)-9H-carbazole-3,6-dihydrazinecarbothioamide to give a remarkable change of fluorescence turn-on signal at pH 7.4 under aqueous media. The practical use of an 'ensemble' was demonstrated by its application to the detection of iodide in the living cells.     

Iris segmentation using game theory

Robust segmentation of an iris image plays an important role in iris recognition. However, the nonlinear deformations, pupil dilations, head rotations, motion blurs, reflections, nonuniform intensities, low image contrast, camera angles and diffusions, and presence of eyelids and eyelashes often hamper the conventional iris/pupil localization methods, which utilize the region-based or the gradient-based boundary-finding information. The novelty of this research effort is that we describe a new iris segmentation scheme using game theory to elicit iris/pupil boundaries from a nonideal iris image. We apply a parallel game-theoretic decision making procedure by modifying Chakraborty and Duncan??s algorithm, which integrates (1) the region-based segmentation and gradient-based boundary-finding methods and (2) fuses the complementary strengths of each of these individual methods. This integrated scheme forms a unified approach, which is robust to noise and poor localization, and less affected by weak iris/sclera boundaries. The verification and identification performance of the proposed method are validated using the ICE 2005, the UBIRIS Version 1, WVU Nonideal, and the CASIA Version 3 data sets.     

Self and N2 collisional broadening of far-infrared methane lines measured at the SOLEIL synchrotron

Following our recent study devoted to measurements of intensities of pure rotation lines of methane, room temperature far infrared spectra of methane diluted in nitrogen at five total pressures between 100 and 800 hPa have been recorded at the AILES beamline of the SOLEIL synchrotron. One hundred and five N₂ broadening coefficients of methane pure rotation lines have been measured in the 83–261 cm^?1 spectral range using multi-spectrum non-linear least squares fitting of Voigt profiles. Pressure-induced line shifts were not needed to fit the spectra to the noise level and line mixing effects were neglected. One hundred and seventy-six self broadening coefficients have also been measured in the 59–288 cm^?1 spectral range using the pure methane spectra recorded in our previous work. The measured N₂ broadening coefficients were compared to semi-classical calculations.     

Metal ions as cofactors for aggregation of therapeutic peptide salmon calcitonin

The effects of multivalent metal ions (Cu(2+)/Zn(2+)/Al(3+)) on the aggregation of salmon calcitonin (sCT)--a therapeutic peptide used worldwide in the treatment of osteoporosis and Paget's disease--have been studied in vitro using NMR (both solution state and solid state), TEM, ThT-fluorescence, and FT-IR spectroscopy. Overall, the various results indicated that the metal-ions-induced conformational transitions in the peptide--mostly toward the β-sheet--facilitate the aggregation of sCT in solution. First, the solution NMR has been used to check the interaction between the peptide and the metal ions. Following this, the formation and characterization of calcitonin aggregates has been performed using TEM, solid state NMR, and FT-IR spectroscopy. The TEM and ThT-fluorescence results revealed that the sCT peptide incubated with Cu(2+) and Zn(2+) metal ions (in aqueous environment) forms globular aggregates, while that with Al(3+) ions forms fibrils. The solid state NMR and FT-IR studies revealed the presence of a substantial amount of β-sheet content in sCT aggregates (formed in the presence of these metal ions) compared to the monomeric sCT, indicating that the metal binding is concomitant with conformational changes. The present study becomes crucial while prescribing this drug peptide under physio-pathological conditions associated with an abnormal accumulation of metal ions (Cu(2+)/Zn(2+)/Al(3+)) in the body (i.e., abnormal metal ion homeostasis).     

A path-integral Langevin equation treatment of low-temperature doped helium clusters

We present an implementation of path integral molecular dynamics for sampling low temperature properties of doped helium clusters using Langevin dynamics. The robustness of the path integral Langevin equation and white-noise Langevin equation [M. Ceriotti, M. Parrinello, T. E. Markland, and D. E. Manolopoulos, J. Chem. Phys. 133, 124104 (2010)] sampling methods are considered for those weakly bound systems with comparison to path integral Monte Carlo (PIMC) in terms of efficiency and accuracy. Using these techniques, convergence studies are performed to confirm the systematic error reduction introduced by increasing the number of discretization steps of the path integral. We comment on the structural and energetic evolution of He(N)-CO(2) clusters from N = 1 to 20. To quantify the importance of both rotations and exchange in our simulations, we present a chemical potential and calculated band origin shifts as a function of cluster size utilizing PIMC sampling that includes these effects. This work also serves to showcase the implementation of path integral simulation techniques within the molecular modelling toolkit [K. Hinsen, J. Comp. Chem. 21, 79 (2000)], an open-source molecular simulation package.     

Direct synthesis of aqueous quantum dots through 4,4'-bipyridine-based twin ligand strategy

We report a new class of derivatized 4,4'-bipyridinium ligands for use in synthesizing highly fluorescent, extremely stable, water-soluble CdSe and CdTe quantum dots (QDs) for bioconjugation. We employed an evaporation-condensation technique, also known as solvated metal atom dispersion (SMAD), followed by a digestive ripening procedure. This method has been used to synthesize both metal nanoparticles and semiconductors in the gram scale with several stabilizing ligands in various solvents. The SMAD technique comprised evaporation condensation and stabilization of CdSe or CdTe in tetrahydrofuran. The as-prepared product was then digestively ripened in both water and dimethyl formamide, leading to narrowing of the particle size distributions. The ligands were synthesized by nucleophilic substitution (S(N)2) reactions using 4,4'-bipyridine as a nucleophile. Confocal microscopy images revealed the orange color of the nanocrystalline QDs with diameters of ~5 nm. The size has been confirmed by using transmission electron microscopy. As a part of our strategy, 85% of the 4,4'-bipyridinium salt was synthesized as propionic acid derivative and used to both stabilize the QDs in water and label basic amino acids and different biomarkers utilizing the carboxylic acid functional group. Fifteen percent of the 4,4'-bipyridinium salt was synthesized as N-propyl maleimide and used as a second ligand to label any protein containing the amino acid cysteine by means of a 1,4-Michael addition.     

How Accessible Is Atomic Charge Information from Infrared Intensities? A QTAIM/CCFDF Interpretation

Infrared fundamental intensities calculated by the quantum theory of atoms in molecules/charge-charge flux-dipole flux (QTAIM/CCFDF) method have been partitioned into charge, charge flux, and dipole flux contributions as well as their charge-charge flux, charge-dipole flux, and charge flux-dipole flux interaction contributions. The interaction contributions can be positive or negative and do not depend on molecular orientations in coordinate systems or normal coordinate phase definitions, as do CCFDF dipole moment derivative contributions. If interactions are positive, their corresponding dipole moment derivative contributions have the same polarity reinforcing the total intensity estimates whereas negative contributions indicate opposite polarities and lower CCFDF intensities. Intensity partitioning is carried out for the normal coordinates of acetylene, ethylene, ethane, all the chlorofluoromethanes, the X(2)CY (X = F, Cl; Y = O, S) molecules, the difluoro- and dichloroethylenes and BF(3). QTAIM/CCFDF calculated intensities with optimized quantum levels agree within 11.3 km mol(-1) of the experimental values. The CH stretching and in-plane bending vibrations are characterized by significant charge flux, dipole flux, and charge flux-dipole flux interaction contributions with the negative interaction tending to cancel the individual contributions resulting in vary small intensity values. CF stretching and bending vibrations have large charge, charge-charge flux, and charge-dipole flux contributions for which the two interaction contributions tend to cancel one another. The experimental CF stretching intensities can be estimated to within 31.7 km mol(-1) or 16.3% by a sum of these three contributions. However, the charge contribution alone is not successful at quantitatively estimating these CF intensities. Although the CCl stretching vibrations have significant charge-charge flux and charge-dipole flux contributions, like those of the CF stretches, both of these interaction contributions have opposite signs for these two types of vibrations.     

Two-warehouse production model for deteriorating inventory items with stock-dependent demand under inflation over a random planning horizon

This paper develops a production-inventory model for a deteriorating item with stock-dependent demand under two storage facilities over a random planning horizon, which is assumed to follow exponential distribution with known parameter. The effects of learning in set-up, production, selling and reduced selling is incorporated. Different inflation rates for various inventory costs and time value of money are also considered. A hybrid genetic algorithm is designed to solve the optimization problem which is hard to solve with existing algorithms due to the complexity of the decision variable. To illustrate the model and to show the effectiveness of the proposed approach a numerical example is provided. A sensitivity analysis of the optimal solution with respect to the parameters of the system is carried out.