Toward the total synthesis of a lagunamide B analogue

Lagunamides, isolated from a marine cyanobacterium Lyngbya majuscule found in Singapore, showed very potent activities against Plasmodium falciparum and murine leukemia cell line (P388). Herein, a concise synthetic approach toward the total synthesis of a lagunamide B analogue is discussed. Macrolactonization, HWE-olefination, and modified Crimmin’s aldol are some of the key reactions featured in this synthesis.     

Application of ultra performance liquid chromatography-tandem mass spectrometry to the analysis of priority pesticides in groundwater

Ultra performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UPLC-MS/MS) has been applied for the accurate and rapid analysis of nine trace level priority pesticides in water. The UPLC technology, based on the use of columns packed with 1.7 microm porous particles combined with higher pressures than those conventionally applied in HPLC, enabled to improve in peak resolution, sensitivity and speed of analysis. UPLC chromatograms showed very sharp peaks with less than 2 s wide at the base, except for alachlor. This enhanced efficiency resulted in an increased separation speed of the whole UPLC-MS/MS procedure that required less than 5 min. Limits of detection, determined for 300 ml water samples after SPE preconcentration were in the range between 0.1 and 20 ng/L. The presence of matrix effects or ion suppression was checked by the obtaining of calibration curves in both pure solvent and matrix matched standards. Other performance characteristics of the method, such as linearity and precision were also satisfactory. Finally, the method was successfully applied to the analysis of two water samples from an inter-laboratory exercise.     

Regulation of the extent and dynamics of excited-state proton transfer in 2-(2'-pyridyl)benzimidazole in nafion membranes by cation exchange

The effect of the microenvironment of a Nafion membrane on the excited-state proton transfer (ESPT) of 2-(2'-pyridyl)benzimidazole (2PBI) has been investigated by steady-state and time-resolved fluorescence spectroscopy. The mechanism of the ESPT is found to depend remarkably on the water content of the membrane. In the protonated form of the membrane, ESPT is found to involve the dicationic (D) form of the fluorophore, whereas in cation-exchanged membranes, it is found to involve the monocation (C). The change in the mechanism and extent of ESPT in cation-exchanged membranes can be explained by considering dehydration of the membrane as well as the less acidic environment around the 2PBI molecules. The slow dynamics is found to result from two factors, namely, slow and incomplete solvation of the transition state, leading to a slowing down of the proton-transfer process, and a slow solvation of the polar tautomeric excited state.     

Donor-acceptor interaction promoted gelation: visual observation of color change

An anthrylidene derivative of arjunolic acid could immobilize varieties of organic solvents at low concentrations in the presence of an electron-deficient guest. Gelation in the presence of picric acid in organic solvents could be observed visually with concomitant color change. Electron micrographs of the xerogels showed a fibrous structure having fibers of submicron diameters. [structure: see text].     

Calculation of electric dipole intensity parameter to explore some interaction between hard metal ions Pr(III) and Nd(III) with pi-electron density of butene-1,4 and butyne-1,4-diols in non-aqueous solutions: an absorption spectral study

Pr(III) and Nd(III) are hard acceptors in HSAB (hard and soft acid base) sense and hence are known to exhibit practically a little affinity towards electrons. At the same time these metal ions show strong preference for oxygen donor chelating ligands. The ligands chosen for this study are structurally related diols, viz. butane-1,4, butene-1,4 and butyne-1,4-diols which form identical seven membered chelate ring by coordinating to metals in a bidentate manner through oxygen on 1 and 4 positions of the diol molecules. Complexation of these diols with Pr(III) and Nd(III) was carried out in DMF, CH3OH, CH3CN and their equimolar binary mixtures using comparative absorption spectrophotometry of 4f-4f transitions. The variation of oscillator strengths (P) of different 4f-4f bands as well as the magnitude and variation of Judd-Ofelt electric dipole intensity parameters (T lambda, lambda = 2, 4, 6) was discussed. They correlate the interaction between the metal 4f-orbitals of Pr(III) and Nd(III) with the pi-electron densities of the double and triple bonds present in butene-1,4 and butyne-1,4-diols, respectively. The value of empirical intensity parameter [T lambda(complex)/T lambda (aquo)] was calculated and its plot against oscillator strength (P) is drawn.     

Phosphorus-supported multidentate coumarin-containing fluorescence sensors for Cu

Phosphorus hydrazides PhP(O)[N(Me)NH₂]₂, (S)P[N(Me)NH₂]₃, and N₃P₃[N(Me)NH₂]₆ were condensed with 7-diethylaminocoumarin-3-aldehyde (RCHO) to afford the corresponding hydrazones PhP(O)[N(Me)NCHR]₂ (1), (S)P[N(Me)NCHR]₃ (2), and N₃P₃[N(Me)NCHR]₆ (3). The structural characterization of 1-3 was carried out by their HRMS, ¹H and ³¹P{¹H} NMR spectra. The molecular structure of 2 was established by a single-crystal X-ray analysis. Interaction of 1 and 2 with various transition metal ions revealed substantial fluorescence enhancement upon interaction with Cu²⁺ enabling a selective detection mechanism for this metal ion. However, such a fluorescence enhancement was not observed in the case of 3. A 1:1 complex [2·Zn][ClO₄]₂·4CH₂Cl₂ was isolated in the reaction of 2 with Zn(ClO₄)₂·6H₂O. The molecular structure of this complex revealed that the Zn^II is encapsulated by the ligand utilizing a 3N, 3O coordination set.     

A variable-wavelength-based approach of phase retrieval for contrast transfer function based methods

X-ray phase-contrast imaging has emerged as an important method for improving contrast and sensitivity in the field of X-ray imaging. This increase in the sensitivity is attributed to the fact that, in the hard X-ray regime, the phase shift is more prominent as compared with the attenuation for materials having a low X-ray absorption coefficient. Among all the methods using the X-ray phase-contrast technique, in-line phase-contrast imaging scores over the other methods in terms of ease of implementation and efficient use of available X-ray flux. In order to retrieve the projected phase map of the object from the recorded intensity pattern, a large number of algorithms have been proposed. These algorithms generally use either the transport of intensity or contrast transfer function based approach for phase retrieval. In this paper it is proposed to use multiple wavelengths for phase retrieval using the contrast transfer function based formalism.     

Capabilities of using white x-rays for the reconstruction of surface morphology from coherent reflectivity

We present a new method to reconstruct the surface profile of a sample from coherent reflectivity data of a white x-ray beam experiment. As an example the surface profile of a laterally confined silicon wafer has been reconstructed quantitatively from static speckle measurements using white coherent x-rays from a bending magnet in the energy range between 5 < E < 20 keV. As a consequence of using white radiation, speckles appear in addition to the Airy pattern caused by scattering at the entrance pinhole. Nevertheless, the surface profile of a triangularly shaped specimen was reconstructed considering sufficient oversampling between the beam-footprint and the effective sample width. For the profile reconstruction the Error-Reduction phase retrieval algorithm was modified by including the spectral illumination function and a Fresnel propagator term. The simultaneous use of different x-ray energies having different penetration depth provides information on the evolution of the surface profile from the near-surface towards the bulk. The limitations of present experiment can be overcome using white or pink radiation from a source with higher photon flux.