THE ISOMERIZATION OF 3-PHOSPHOLENS IN DEUTERIOCHLOROFORM

Abstract

Cis-1-alkyl (or aryl)-2,5-dimethyl-3-phospholens isomerize to the trans-isomers in deuteriochloroform and the isomerization is probably due to small quantities of phosgene in the solvent.     

Fully Protected Glycosylated Zinc (II) Phthalocyanine Shows High Uptake and Photodynamic Cytotoxicity in MCF‐7 Cancer Cells

Phthalocyanine photosensitizers are effective in anticancer photodynamic therapy (PDT) but suffer from limited solubility, limited cellular uptake and limited selectivity for cancer cells. To improve these characteristics, we synthesized isopropylidene‐protected and partially deprotected tetra β‐glycosylated zinc (II) phthalocyanines and compared their uptake and accumulation kinetics, subcellular localization, in vitro photocytotoxicity and reactive oxygen species generation with those of disulfonated aluminum phthalocyanine. In MCF‐7 cancer cells, one of the compounds, zinc phthalocyanine {4}, demonstrated 10‐fold higher uptake, 5‐fold greater PDT‐induced cellular reactive oxygen species concentration and 2‐fold greater phototoxicity than equimolar (9 μm ) disulfonated aluminum phthalocyanine. Thus, isopropylidene‐protected β‐glycosylation of phthalocyanines provides a simple method of improving the efficacy of PDT.     

Antennal morphology, structure and sensilla distribution in Microplitis pallidipes (Hymenoptera: Braconidae)

Microplitis pallidipes (Hymenoptera: Braconidae) is an important larval parasitoid of noctuid larval pests. In this study, we describe the morphology, ultrastructure and distribution of sensilla on the antennae of both male and female adults using scanning electron microscopy; complemented with transmission electron microscopy. Observations determined that the antennae of M. pallidipes were threadlike and the flagella were composed of 16 sub-segments. Totally, there were six types of sensilla found on the antennae. They were identified as Sensilla trichodea, Sensilla chaetica, Sensilla basiconica type I, S. basiconica type II, Sensilla coeloconicum, and elongated Sensilla placodea, respectively. The S. trichodea were the most abundant sensilla and distributed over the entire antennae, while S. basiconica I and II, S. coeloconicum, and elongated S. placodea were limited to the flagellum. S. chaetica were found on the scape and pedicle in very low numbers. The S. basiconica II and elongated S. placodea walls were full of pores as evident in transmission electron micrographs. Though the shape and structure of antennae between male and female adults were not basically different, the length and width of the antennae on male wasps were significantly greater than that of females. Also, the number, size and density of S. placodea of the male were significantly greater than those of females. The morphology and structure of these sensilla were compared with that found in other braconid wasps. Their possible functions are discussed in light of previously published literature.     

Thermal analysis characterization of isosorbide-containing thermosets

Sugar-based new monomers, polymers, and low molar mass additives have emerged as an exciting topic on green chemistry research, due to the worldwide focus on sustainable material. Isosorbide and its isomers, as ??Generally Recognized as Safe?? GRAS materials, possess unique stereochemistry and molecular geometry suitable for making cost-effective chemicals and polymers. With growing awareness of bisphenol A (BPA) as a xenoestrogen, isosorbide and its isomers holding the remarkable chemical properties and attractive price can be attached to glycidyl ether to make crosslinkable epoxy resin monomers with similar properties to BPA diglycidyl ether. By adding the hydrophobic functional group into the backbone of isosorbide epoxy or adjusting the amount and type of crosslinker, the mechanical properties and the water uptake ratios (from <1 to >50?wt%) of the isosorbide-derived epoxies could be optimized for different applications. The high water uptake epoxy with controllable biodegradation rate could be used as a drug delivery system or extracellular matrix for biomedical applications while the low water uptake epoxy with strong mechanical properties could be used for can coatings, bone cements, and other industrial additives and adhesives. The chemical structures and properties of the synthesized epoxy monomers and polymers were characterized by DSC, TG, and ¹H NMR.     

The giant magnetoresistance of Co/Cu superlattices grown by MBE

We report the first observation of a giant magnetoresistance (MR) in Co/Cu superlattices grown by MBE. The maximum value of the MR is - 26% and this is found in a specimen for which the copper layers are about 7 Å thick and which includes a thin 10 Å layer of gold in the buffer region between the substrate and the superlattice. From RHEED and X-ray diffraction it is shown that the metallic layers in the specimens grown in this way are extremely flat and that the orientation of the copper is (111).     

The attention filter for tones in noise has the same shape and effective bandwidth in the elderly as it has in young listeners

Listeners asked to detect tones masked by noise hear frequent signals but miss infrequent probes, suggesting that they attend to spectral regions where they expect the signals to occur. The narrow detection pattern centered on the frequent target approximates that obtained in notched noise, indicating that attention is focused on the auditory filter. We measured attention bands in young and elderly listeners (n=5, 4; 20-25 and 62-82 years of age) for targets (800 or 1200 Hz) and infrequent probe signals (target +/-25-100 Hz) masked in wideband noise. We anticipated that their width would increase with age, as has been reported for auditory filters. A yes-no single-interval procedure provided detection probabilities and detection response speeds. Both measures showed near-linear declines with decreasing signal level, and graded decay functions as probe frequency deviated from the target frequency. Probes deviating from the target by 25 to 50 Hz were equivalent to a 2-dB reduction in signal level for both measures. The equivalent rectangular bandwidth (ERB) for detection approximated 11% of the signal frequency for each age group. Confidence intervals (95%) showed that the elderly ERB could be at most only about 20% larger than that of younger listeners.     

Functionalization of monofluoroallene and the synthesis of aryl-substituted conjugated fluorodienes

[reaction: see text] 4-Fluoroallenol 3a, prepared from 1, cyclized easily to 4 but preserved its fluoroallenyl integrity under oxidation and S(N)2 displacement to yield aldehyde, amine, mesylate, and halide 6. Allylic isomerization yielded 2-halo-1-fluoro-1,3-butadiene 7, which underwent a Suzuki coupling to give aryl-substituted conjugated diene 8.     

Regiospecific synthesis of bicyclo- and heterobicyclo-gem-difluorocyclobutenes using functionalized fluoroallenes and a novel Mo-catalyzed intramolecular [2 + 2] cycloaddition reaction

The first synthesis of functionalized gem-difluoroallenes 4 served as platform for an unprecedented molybdenum-catalyzed intramolecular allene-alkyne [2 + 2]-cycloaddition that produced 6, a hitherto unknown class of bicyclo- and heterobicyclo-CF2-containing cyclobutenes.     

In-beam spectroscopy of 253, 254No

In-beam conversion electron spectroscopy experiments have been performed on the transfermium nuclei ^{253, 254}No using the conversion electron spectrometer SACRED in nearly collinear geometry in conjunction with the gas-filled separator RITU at the University of Jyv?skyl?. The experimental setup is discussed and the spectra are compared to Monte Carlo simulations. The implications for the ground-state configuration of ²⁵³No are discussed. Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002 RID="a" ID="a"e-mail: rdh@ns.ph.liv.ac.uk RID="b" ID="b"Present address: GANIL, F-14021 Caen, France. RID="c" ID="c"Permanent address: IReS Strasbourg, IN2P3-CNRS, F-67037-Strasbourg, France. RID="d" ID="d"Present address: CEA/DIF DCRE/SDE/LDN F-91680 Bruyeres-le-Chatel. RID="e" ID="e"Present address: Daresbury Laboratory, Daresbury WA4 4AD, UK. RID="f" ID="f"Permanent address: IPN Lyon, IN2P3-CNRS, F-69037 Lyon, France.