Double Suzuki cross‐coupling reaction of pyrimidine boronic acid: synthesis of new versatile dielectrophile

The double Suzuki cross‐coupling reaction has successfully been applied for the synthesis of 5,5′‐(5‐butoxy‐1,3‐phenylene)bis(2‐chloropyrimidine) with two reactive chloro groups and an alkoxy side chain starting from 2‐chloropyrimidin‐5‐ylboronic acid and 1,3‐dibromo‐5‐butoxybenzene. The reactivity of this dielectrophile was tested by reaction with aniline and phenol, a nitrogen and oxygen nucleophile, respectively. The new dielectrophile would further provide an ideal platform for the construction of large hetero‐atom bridged macrocycles for desired properties and functions in supramolecular and material chemistry. Copyright © 2012 John Wiley & Sons, Ltd.     

Determination of Arsenic as the Oxidate by Ion Chromatography

Abstract

An ion chromatographic procedure is described for the analysis of arsenic as the oxo anion. The procedure involves oxidations of the arsenic to arsenate in an aqueous solution and injection onto an anion separator column, Comparison is made with a standard wet chemical procedure, and data is presented on reproducibility. In addition, there is a brief discussion of the applicability of this method to the determination of other oxo anions.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Fluorescence Signal Enhancement Using Double Pass Cell Configurations

Abstract

A simple and reproducible method for increasing the sensitivity of fluorescence measurements by a factor of 2.0–2.5 is presented. Data are presented to explain: the deviation from the expected theoretical increase in sensitivity of 4.0; wavelength dependency and subsequent problems arising from enhanced inner filtering effects.     

Stripping Voltammetric Determination of Uranium Traces in Sea Water Samples: Effect of Surfactants on the Measurements

The variables affecting determination of ultra trace levels of uranium (VI) in aqueous samples by differential pulse cathodic stripping voltammetry using chloranilic acid as the complexing agent have been examined in detail. Effect of organic surfactants on the voltammetric behavior has been studied. Electrochemical impedance measurements reveal the effect of adsorption of different surfactants on the adsorption pre-concentration step of uranium-chloranilic acid complex. Additionally, to better understand the analytical feature of the method, physicochemical aspects of the preconcentration process has been studied. Adsorption of uranium-chloranilic acid complex follows the Langmuir adsorption isotherm. Analysis results on sea water samples from India are reported.     

Triphenylphosphane Oxide Complexes of Lanthanide Nitrates: Polymorphs and Photophysics

A series of mer‐[Ln(NO₃)₃(Ph₃PO)₃] complexes were prepared from Ln(NO₃)₃ · xH₂O and Ph₃PO in chloroform (Ln = La, Nd, Sm, Eu, Gd, Tb, Dy, and Er). The La and Nd complexes were 0.25 CHCl₃ solvates, whereas the others were solvent‐free. The identical reaction using Yb(NO₃)₃ · xH₂O produced the unique salt trans‐[Yb(NO₃)₂(Ph₃PO)₄][Yb(NO₃)₄(Ph₃PO)] · Et₂O. All nitrate ions in all complexes are η²‐chelating. A comparison of the various [Ln(NO₃)₃(Ph₃PO)₃] structures, including those in the literature, reveals at least four common polymorphs, each of which is represented by isomorphic structures of multiple Ln ions. Luminescence of mer‐[Ln(NO₃)₃(Ph₃PO)₃] (Ln = Y, La, Nd, Sm, Eu, Gd, Tb, and Dy), trans‐[Yb(NO₃)₂(Ph₃PO)₄][Yb(NO₃)₄(Ph₃PO)] and Ph₃PO assignments are reported. Latva's empirical rule allows for the antenna effect, in which energy is transferred from the triplet state of the Ph₃PO ligand, to occur only for Tb³⁺. Excitation via Ph₃PO results in strong green luminescence for Tb³⁺ having twice the intensity as that which results from direct excitation of the f‐f transitions.     

Protein dielectrophoresis: Key dielectric parameters and evolving theory

Globular proteins exhibit dielectrophoresis (DEP) responses in experiments where the applied field gradient factor ∇E² appears far too small, according to standard DEP theory, to overcome dispersive forces associated with the thermal energy kT of disorder. To address this a DEP force equation is proposed that replaces a previous empirical relationship between the macroscopic and microscopic forms of the Clausius–Mossotti factor. This equation relates the DEP response of a protein directly to the dielectric increment δε⁺ and decrement δε⁻ that characterize its β-dispersion at radio frequencies, and also indirectly to its intrinsic dipole moment by way of providing a measure of the protein's effective volume. A parameter Γ_pw, taken as a measure of cross-correlated dipole interactions between the protein and its water molecules of hydration, is included in this equation. For 9 of the 12 proteins, for which an evaluation can presently be made, Γ_pw has a value of ≈4600 ± 120. These conclusions follow an analysis of the failure of macroscopic dielectric mixture (effective medium) theories to predict the dielectric properties of solvated proteins. The implication of a polarizability greatly exceeding the intrinsic value for a protein might reflect the formation of relaxor ferroelectric nanodomains in its hydration shell.     

Quantitative study of cellular heterogeneity in doxorubicin uptake and its pharmacological effect on cancer cells

Cellular heterogeneity in doxorubicin (DOX) uptake and its relationship with pharmacological effect on cancer cells were quantitatively investigated for the first time. An in vitro experimental model was established by treating human leukemia K562 and breast cancer MCF‐7 cells with different schedules of DOX with or without surface P‐glycoprotein (P‐gp) inhibitor verapamil (VER). The cellular heterogeneity in DOX uptake was quantitatively examined by single‐cell analysis using capillary electrophoresis coupled with laser‐induced fluorescence detection. The corresponding cytotoxic effect was tested by cellular morphology, 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl‐tetrazolium and flow cytometry assays. The expression of cellular membrane surface P‐gp was determined by flow cytometry. Results showed that the cellular heterogeneity exists in DOX uptake. The single‐high DOX schedule leads to lower uptake heterogeneity and higher mean drug uptake. The cellular heterogeneity in DOX uptake was found to be negatively correlated with drug cytotoxicity and surface P‐gp expression, with r = ?0.7680 to ~ ?0.9587. VER reduces the cellular variation in DOX uptake, suggesting that surface P‐gp may be one of the causes of the cellular heterogeneity in DOX uptake. This research demonstrates the importance of quantitative study of cellular heterogeneity in drug uptake and its potential application in drug schedule design, response prediction and therapy modulation. Copyright © 2014 John Wiley & Sons, Ltd.     

Dual emission of singlet and triplet states boost the sensitivity of pressure-sensing

Pressure-related sensing materials in mechanochromic luminescent materials have received wide attention. However, at present, most piezochromic luminescence (PCL) materials have problems such as aggregation-caused quenching (ACQ) effect due to the presence of powder form, complicated preparation methods and fluorescence quenching effect under high pressure. To solve these problems, we employ three components containing carbon dots (CDs), layered double hydroxides (LDHs) and polyvinyl alcohol (PVA) to construct the CDs-LDHs/PVA film. The LDHs can provide a rigid environment for CDs and improve the luminescent efficiency of CDs. The film shows high sensitivity, stability and reversibility. Moreover, the compressed film can recover to its original state by heating. Therefore, the PCL film with dual emission (fluorescence and phosphorescence) characteristic is constructed, which boosts the sensitivity of pressure-sensing.