Magnetic properties of amorphous alloys

The magnetic properties of existing amorphous iron based materials, i.e., Fe--metalloid, Fe--early transition metals and Fe--rare earth alloys, are briefly discussed for some representative alloys. The spin orientation of amorphous Fe--metalloid alloys has been determined by the angular dependence of hyperfine interactions. It is shown that in iron--early transition metals ferromagnetic order is not long-ranged, but determined by magnetic clusters. The magnetic hyperfine field distributions of Fe-rich iron--early transition metals consist of a high and a low field tail. The magnetic structure has been investigated for two representative Fe--RE (RE = Er, Ce) amorphous alloys. For the first time, the magnetic coupling phenomenon in amorphous/crystalline multilayers has been discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Molybdenum (VI)‐functionalized UiO‐66 provides an efficient heterogeneous nanocatalyst in oxidation reactions

A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr₆ nodes in the structure of the well‐known UiO‐66 metal–organic framework (MOF). The structure of the UiO‐66 before and after Mo (VI) immobilization was confirmed with XRD, DR‐FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X‐ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H₂O₂ in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material.     

Studies on cryoprotectant toxicity to zebrafish (Danio rerio) ovarian tissue fragments

Cryopreservation of ovarian tissue is a viable alternative to cryopreservation of oocytes and embryos in many species but it has not been studied in fish. Selection of cryoprotectant is an important step in designing cryopreservation protocols. In order to identify the optimum cryoprotectant (CPA) in a suitable concentration for zebrafish ovarian tissue cryopreservation, studies on toxicities of five commonly used cryoprotectants methanol, ethanol, dimethyl sulfoxide (DMSO), ethylene glycol (EG) and propylene glycol (PG) were carried out. Experiments were conducted on ovarian tissue fragments consisting of stage I and stage II ovarian follicles. Ovarian tissue fragments were incubated in 90% L-15 medium (pH 9) containing 1-4M cryoprotectants for 30min at 22°C. Three different tests were used to assess ovarian tissue fragment viability: trypan blue (TB) staining, fluorescein diacetate (FDA) combined with propidium iodide (PI) staining and adenosine 5′- triphosphate (ATP) assay. Results from these tests showed that ATP assay was more sensitive than FDA+PI or TB staining for assessing cryoprotectant toxicity to follicles in tissue fragments. Methanol and ethanol were the least toxic cryoprotectants tested. Cryoprotectant toxicity increased in the order of methanol/ethanol, DMSO, PG and EG. Ethanol was used for zebrafish ovarian tissue for the first time and the results showed that the effect of methanol and ethanol on ovarian tissue fragments were comparable. As methanol has been shown to be the most effective cryoprotectant for zebrafish ovarian follicles in our laboratory, the use of ethanol will also be considered in assisting future freezing protocol design. The present study also showed that stage II ovarian follicles are more sensitive to cryoprotectant treatment than stage I follicles in tissue fragments. The results obtained in this study provided useful information for ovarian tissue fragment cryopreservation protocol design in the future.     

Mössbauer Studies of Nanosize CuFe2O4 Particles

⁵⁷Fe Mössbauer spectra of pulsed-laser deposited (PLD) films of CoFe₂O₄ of 0.3 µm thickness is investigated using transmission geometry is reported. Mössbauer parameters were determined for the tetrahedral (A) and octahedral (B) sites. The PLD processed films gave measurable spectra with no visible evidence of clustering or multiple phases present. Results on the films agreed with those of the bulk material. The films exhibited magnetic hyperfine and quadruple splittings similar to that of bulk CoFe₂O₄. This work demonstrates that measurable transmission Mössbauer spectra may be obtained for PLD deposited CoFe₂O₄ thick films.     

Identification of a higher-order organozincate intermediate involved in Negishi cross-coupling reactions by mass spectrometry and NMR spectroscopy

Negishi cross-coupling reactions were analyzed in solution by mass spectrometry and NMR spectroscopy to identify both the effect of LiBr as an additive as well as the purpose of 3-dimethyl-2-imidazolidinone (DMI) as a co-solvent. The results suggest that the main role of DMI is to facilitate a higher order bromozincate formation during the addition of LiBr.     

Mössbauer study of ultrafine amorphous Fe−B alloys

The chemical composition of ultrafine amorphous Fe−B powders prepared by a chemical reduction depends on the mixed molar ratio of KBH₄ to Fe ions. We propose the following reaction processes for the formation of ultrafine Fe−B powders: (1) 4Fe²⁺+2BH₄₋+6OH⁻→2Fe₂B+6H₂O+H₂ and (2) 4Fe²⁺+2BH₄₋+7OH⁻→2Fe₃B+Fe+BO₂+5H₂O+5/2H₂.     

Mössbauer study of amorphous Fe2RE (RE=Ce,Er) alloys

Among amorphous Fe₂RE (RE=Er, Ce, Gd, La, Pr, Sm, Dy, Ho) alloys, Fe₂Ce exhibits a tendency toward short range order, while the other Fe₂RE compounds show clustering. However, we have almost no information about environments around Fe atoms. Using Mössbauer spectroscopy we have determined the quadrupole splitting distributionsP(QS) of two representative amorphous Fe₂RE (RE=Ce, Er) alloys, leading to local environments of Fe atoms. The analysis of the mixed magnetic dipole and quadrupole interactions in Fe₂Er shows two kinds of electrical field gradients (EFT) with the positive and negative signs in the sample, indicating a random packing of Fe atoms. Furthermore, the analyzed quadrupole splitting distributionP(QS) of Fe₂Er also supports random packing in this amorphous alloy. On the other hand, the amorphous Fe₂Ce alloy shows two kinds of distributions of quadrupole splitting; the major component indicating random packing and the minor component Ce-rich Ce-Fe clusters.     

Pd-catalyzed aryl amination mediated by well defined, N-heterocyclic carbene (NHC)-Pd precatalysts, PEPPSI

Pd-N-heterocyclic carbene (NHC)-catalyzed Buchwald-Hartwig amination protocols mediated by Pd-PEPPSI precatalysts is described. These protocols provide access to a range of hindered and functionalized drug-like aryl amines in high yield with both electron-deficient and electron-rich aryl- and heteroaryl chlorides and bromides. Variations in solvent polarity, base and temperature are tolerated, enhancing the scope and utility of this protocol. A mechanistic rationalization for base strength (pKb) requirements is also provided.