Stereoselective syntheses of (+)-goniodiol, (-)-8-epigoniodiol,and (+)-9-deoxygoniopypyrone via alkoxyallylboration and ring-closing metathesis

A convenient synthesis of (+)-goniodiol, (-)-8-epigoniodiol, and (+)-9-deoxygoniopypyrone has been developed via asymmetric alkoxyallylboration and ring-closing metathesis pathways.     

The carbosilane unit as a stable building block for liquid crystal design: a new class of ferroelectric switching banana-shaped mesogens

New banana shaped liquid crystals with a carbosilane unit at one end were synthesised and depending on the number of Si-atoms either antiferroelectric (AF) or ferroelectric (FE) switching polar smectic C phases have been obtained.     

Metal-assisted red light-induced efficient DNA cleavage by dipyridoquinoxaline-copper(II) complex

Complete cleavage of double stranded pUC19 DNA by the complex [Cu(dpq)2(H2O)](ClO4)2 (dpq, dipyridoquinoxaline) has been observed on irradiation at 694 nm from a pulsed ruby laser, assisted by the metal d-band transition as well as the quinoxaline triplet states in the absence of any external additives.     

A facile one step synthesis of 1,6 ‐dihydro‐7H‐pyrazolo[4,3‐d]‐pyrimidin‐7‐ones

A general synthetic approach to pyrazolo[4,3‐d]pyrimidines is reported. Aldehydes, arylideneanilines, carboxylic acids and orthoesters are used as one‐carbon units for bridging the two amino functions of 4‐amino‐1‐alkyl‐3‐propylpyrazole‐5‐carboxamides.     

Instrumental neutron activation analysis of ferromanganese oxide encrustations of Indian Ocean by the k0 NAA method

Hot electron injection into aqueous electrolyte solution was studied with electrochemiluminescence and electron paramagnetic resonance (EPR) methods. Both methods provide further indirect support for the previously proposed hot electron emission mechanisms from thin insulating film-coated electrodes to aqueous electrolyte solution. The results do not rule out the possibility of hydrated electron being as a cathodic intermediate in the reduction reactions at cathodically pulse-polarized thin insulating film-coated electrodes. However, no direct evidence for electrochemical generation of hydrated electrons could be obtained with EPR, only spin-trapping experiments could give information about the primary cathodic steps.     

Determination of 4-aminophenol using the quartz crystal microbalance sensor

In this paper we report a method for the determination of 4-aminophenol (4-AP) in solution using a quartz crystal microbalance (QCM) sensor. 4-AP reacts with (para-unsubstituted) phenols to form hydrophobic indophenol dye species that precipitate out and adsorb to the surface of the crystal to produce a shift in the crystal resonant frequency. This frequency change, due to in-situ indophenol mass adsorption, can be related to the initial 4-AP concentration. A range of phenols (namely o-cresol, 1-naphthol, resorcinol, catechol and 8-hydroxyquinoline) and their reaction with 4-AP were tested. Ammonium persulfate (APS) and potassium periodate were used as initiators to improve the speed of the reaction and the rate of formation of the precipitate. APS elicited improved signal in terms of response times and frequency shifts compared with KIO4. Of the phenols studied, resorcinol gave the best response time of 6 min for 4-AP determination. The reaction of resorcinol with 4-AP gave extended response times and signal size with decreasing concentration of 4-AP (in the range 2-5 mM).     

Ion chemistry of anti-o,o dibenzene

The ion chemistry of anti-o,o'-dibenzene (1) was examined in the gaseous and the condensed phase. From a series of comparative ion cyclotron resonance (ICR) mass spectrometry experiments which involved the interaction of Cu+ with 1, benzene, or mixtures of both, it was demonstrated that 1 can be brought into the gas phase as an intact molecule under the experimental conditions employed. The molecular ions, formally 1*+ and 1*- , were investigated with a four-sector mass spectrometer in metastable-ion decay, collisional activation, charge reversal, and neutralization-reionization experiments. Surprisingly, the expected retrocyclization to yield two benzene molecules was not dominant for the long-lived molecular ions; however, other fragmentations, such as methyl and hydrogen losses, prevailed. In contrast, matrix ionization of 1 in freon (77 K) by gamma-radiation or in argon (12 K) by X-irradiation leads to quantitative retrocyclization to the cationic dimer of benzene, 2*+. Theoretical modeling of the potential-energy surface for the retrocyclization shows that only a small, if any, activation barrier is to be expected for this process. In another series of experiments, metal complexes of 1 were investigated. 1/Cr+ was formed in the ion source and examined by metastable ion decay and collisional activation experiments, which revealed predominant losses of neutral benzene. Nevertheless, comparison with the bis-ligated [(C6H6)2Cr]+ complex provided evidence for the existence of an intact 1/Cr+ under these experimental conditions. No evidence for the existence of 1/Fe+ was obtained, which suggests that iron mediates the rapid retrocyclization of 1/Fe+ into the bis-ligated benzene complex [(C6H6)2Fe]+.     

Stereoselective synthesis of polyketide precursors containing an anti-1,3-diol system via a Prins cyclisation and reductive cleavage sequence

A new approach for the stereoselective synthesis of polyketide precursors containing anti-1,3-diol units flanked by a variety of alkyl branches and functional groups through a Prins cyclisation and reductive cleavage sequence is described.     

First example of molecular iodine-catalyzed allylation and alkynylation of cyclic allylic acetates

Cyclic allylic acetates undergo smooth allylation and alkynylation with allyltrimethylsilane and alkynyl silanes in the presence of molecular iodine under mild conditions to afford the corresponding allylated and alkynylated cyclohexene derivatives in good yields with high selectivity.     

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.