Total synthesis of antifungal gamahonolide A

The first stereoselective total synthesis of gamahonolide A (1) has been accomplished using aminoxylation, Keck allylation, and ring-closing metathesis (RCM) reactions as key steps.     

Developing Intense Blue and Magenta Colors in α‐LiZnBO3: The Role of 3d‐Metal Substitution and Coordination

We describe the synthesis, crystal structures, and optical absorption spectra/colors of 3d‐transition‐metal‐substituted α‐LiZnBO₃ derivatives: α‐LiZn_1?xM^II_xBO₃ (M^II=Co^II (0<x<0.50), Ni^II (0<x≤0.05), Cu^II (0<x≤0.10)) and α‐Li_1+xZn_1?2xM^III_xBO₃ (M^III=Mn^III (0<x≤0.10), Fe^III (0<x≤0.25)). The crystal structure of the host α‐LiZnBO₃, which is both disordered and distorted with respect to Li and Zn occupancies and coordination geometries, is largely retained in the derivatives, which gives rise to unique colors (blue for Co^II, magenta for Ni^II, violet for Cu^II) that could be of significance for the development of new, inexpensive, and environmentally friendly pigment materials, particularly in the case of the blue pigments. Accordingly, this work identifies distorted tetrahedral MO₄ (M=Co, Ni, Cu) structural units, with a long M?O bond that results in trigonal bipyramidal geometry, as new chromophores for blue, magenta, and violet colors in a α‐LiZnBO₃ host. From the L*a*b* color coordinates, we found that Co‐substituted compounds have an intense blue color that is stronger than that of CoAl₂O₄ and YIn_0.90Mn_0.10O₃. The near‐infrared (NIR) reflectance spectral studies indicate that these compounds exhibit a moderate IR reflectivity that could be significant for applications as “cool pigments”.     

Coordination chemistry of chromium-Salen complexes studied by electrospray ionization mass spectrometry

The gas-phase coordination behavior of the [Cr(III)(Salen)]PF(6) complex at the free axial positions has been studied in the presence of amines as ligands (propylamine and a series of diamines) under electrospray ionization conditions. The [Cr(III)(Salen)](+) complex formed stable five- and six-coordinated complex ions, [Cr(III)(Salen)(L)](+) and [Cr(III)(Salen)(L)(2)](+), respectively, where L = solvent molecule or amine. When diamines were used as ligands, abundant [Cr(III)(Salen)(L)](+) ions were observed in which two axial positions of the [Cr(III)(Salen)](+) species are occupied by the two amino groups of the diamine ligand. The relative abundances of ligated complex ions, fragment ions, and solvent adducts of fragment ions in the ESI mass spectra, were found to depend on the cone voltage used to record the spectrum. The ESI mass spectra of [Cr(III)(Salen)](+) in the presence of diamines as ligands, and experiments on ligand-pickup in the collision cell, clearly demonstrated that the [Cr(III)(Salen)(L)](+) complex ion is stable for 1,2-diaminoethane and 1,3-diaminopropane. The stability of [Cr(III)(Salen)(L)](+) ions gradually decreased from 1,4-diaminobutane to 1,6-diaminohexane, and then showed a slight increase for 1,7-diaminoheptane and 1,8-diaminooctane. The collision-induced dissociation spectra of [Cr(III)(Salen)(L)](+) ions support the above observations.     

Mechanical characterization of unplasticised polyvinylchloride thick pipes by optical methods

In this work a number of techniques (electronic speckle pattern interferometry, holographic interferometry, strain gauge and finite element method) are brought to bear in order to establish consistency in the results of strain measurement. This is necessary if optical non-destructive testing methods, such as those used here, are to gain acceptance for routine industrial use. The FE model provides a useful check. Furthermore, ESPI fringe data facilitates the extension of FE models, an approach that is of growing importance in component testing.

The use of in-plane and out-of-plane sensitive electronic speckle pattern interferometry (ESPI) for non-destructive material characterization of thick unplasticised polyvinylchloride (uPVC) pipes is presented. A test rig has been designed for stressing pipes by internal pressure. ESPI gives a complete mapping of the displacement field over the area imaged by the video camera. The results for the strain of uPVC obtained from ESPI data and from strain gauges are in good agreement. The value of Young's modulus has been obtained from the fringe data and compared with results obtained using holographic interferometry and from strain gauge measurements. The FE model also produces fringe data that is consistent with the ESPI results.     

Synthesis, thermal, spectral and magnetic studies of complexes of Co(II), Ni(II), Cu(II), Ru(II), Pd(II) and Pt(II) with 2, 3-disubstituted quinazolin-(3H)-4-ones

A number of complexes of Co(II), Ni(II), Cu(II), Ru(II), Pd(II) and Pt(II) with 2-methyl-3-(carboxy methyl) quinazolin (3H)-4-one (MCMQ) and 2-phenyl-3-(carboxy methyl) quinazolin (3H)-4-one (PCMQ) have been synthesized and characterized by analytical, conductivity, thermal, magnetic, infrared, electronic, proton magnetic resonance and electron spin resonance spectral data. Based on analytical data, the stoichiometry and the association with other molecules of the complexes have been determined. Conductivity data show that all these complexes are nonelectrolytes. Infrared and PMR spectral data indicate that both the ligands are uninegative bidentate with all the metal ions. Based on electronic spectral data, the geometries of the complexes have been indicated. Electronic spectral parameters for Co(II) and Ni(II) and ESR parameters for Cu(II) complexes have been calculated and relevant conclusions have been drawn with respect to the nature of bonds present in them.     

The first stereoselective and the total synthesis of Leiocarpin C and total synthesis of (+)-Goniodiol

The synthesis of the styryl lactone Leiocarpin C has been achieved in a highly stereoselective manner using Jacobsen’s kinetic resolution, Sharpless asymmetric epoxidation and Sharpless asymmetric dihydroxylation as key steps. This is the first total synthesis of Leiocarpin C, and thus establishes for the first time the absolute stereochemistry of this natural product.     

Estimation of trace elements in some medicinal plants used in anti‐cancer drugs by PIXE

A trace elemental analysis was carried out in various parts of 12 anticancer medicinal plants, using the PIXE (particle‐induced X‐ray emission) technique. A 3‐MeV proton beam was used to excite the samples, and spectra were recorded using a Si (Li) detector. Data analysis was done using the GUPIX software. The elements Cl, K, Ca, Ti, V, Mn, Fe, Ni, Cu, Zn, Br and Sr were identified, and their concentrations estimated. The results of the present study provide justification for the usage of these medicinal plants in the development of anticancer drugs. Copyright © 2012 John Wiley & Sons, Ltd.