The synthesis and characterization of the first bismuth salicylate complexes, stabilized by chelating amine ligands, offers the possibility for detailed investigation of molecular precursors of the biologically significant compound bismuth subsalicylate (BSS).

Thianthrene cation radical salts, Th(*)(+) X(-)(X(-) = a, ClO(4)(-); b, PF(6)(-); c, SbF(6)(-)), add to cycloalkenes (C(5)-C(8)) in acetonitrile (MeCN) to form 1,2-bis(5-thianthreniumyl)cycloalkane salts and 1,2-(5,10-thianthreniumdiyl)cycloalkane salts, most of which have now been isolated and characterized. These are called bis- (3, 6, 9, 12) and monoadducts (4, 7, 10, 13). The proportional amount of the monoadduct obtained in the initial stage of the reaction varied with the cycloalkene in the order C(6) << C(5) < C(7) << C(8). Thus, the ratio bis:mono for C(5) and C(7) was, respectively, about 80/20 and 50/50. In contrast, only about 5% of the C(6) monoadduct (7a) and none of 7b,c was obtained, while for C(8) none of the bisadducts 12a-c was found. Bisadducts 3 and 9 lost thianthrene (Th) slowly in MeCN solution and changed into monoadducts 4 and 10. A comparable change from 6a into 7a was not observed. The monoadducts, themselves, lost a proton slowly in dry MeCN and opened into 1-(5-thianthreniumyl)cycloalkenes (5, 8, 11, 14). With 3 and 9, particularly, it was possible to follow with NMR spectroscopy the succession of changes, for example, 3 to 4 to 5. The opening of a monoadduct was made faster by adding a small amount of water to the solution. The bisadducts of 4-methylcyclohexene (15a) and 1,5-cyclooctadiene (17a) were isolated and characterized. Although a small amount of monodduct (16a) of 4-methylcyclohexene was found with NMR spectroscopy, it could not be isolated. Bis- and monoadducts were obtained also in additions of Th(*)(+) ClO(4)(-) to acyclic alkenes, in relative amounts that, again, varied with the alkene. From cis-2-butene the dominant product was the bisadduct (18), while the monoaduct (19) was characterized with NMR spectroscopy but could not be isolated. In contrast, trans-3-hexene gave mainly the monoadduct (21), while the bis adduct (20) could not be isolated. With 4-methyl-cis-2-pentene, both bis- (22) and monoadduct (23) were isolated, the former being dominant. The conversion of 18 into 19 was characterized with NMR spectroscopy. In all cycloalkene bisadducts, the configurational relationship of the two thianthrenium groups was trans, while in the monoadducts, the bonds to the single thianthrene dication were (necessarily) cis. In both bis- and monoadducts of acyclic alkenes, the configuration of the alkene was retained. The mechanisms of addition with retention of configuration, of conversion of a bis- into a monoadduct, and of opening of a monoadduct are discussed. Products were identified with a combination of NMR spectroscopy, X-ray crystallography, elemental analysis, and (for cycloalkene adducts) reaction with thiophenoxide ion.

Fumonisins are myocotoxins produced by Fusarium moniliforme and F. proliferatum, common molds of corn in North America. The toxin is at especially high concentrations in corn screenings. Fumonisins are toxic to swine and horses, but effects of these toxins in cattle have not been evaluated. This experiment was conducted to determine the effects in cattle of feeding fumonisins at levels known to be toxic to swine and horses. A total of 18 crossbred feeder calves were fed diets containing fumonisins at 15, 31, or 148 micrograms/g for 31 d. Feed consumption, weight gain, complete blood count, serum clinical chemistries, and an immune function profile were done on d -3, 4, 10, 17 and 31 relative to the start of fumonisin feeding. There was no treatment-related effect on feed intake or weight gain, but feed containing 148 micrograms/g of fumonisins seemed to be less palatable than other feeds. Significant increases in serum aspartate amino transferase, gamma glutamyl transpeptidase, lactate dehydrogenase, bilirubin, and cholesterol occurred from d 10 through 31. Mild microscopic liver lesions were present in two calves fed at the highest fumonisin level. Lymphocyte blastogenesis was significantly impaired at the end of the feeding period in the group given the highest dose. Other measures of immune function were not affected significantly. Fumonisins are capable of causing changes in liver function and in some measures of immune function. However, cattle seem to be relatively less susceptible to fumonisins present naturally in grains than either swine or horses.

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A new approach for the formation of bimetallic coordination complexes of bismuth containing a 1:1 ratio of the two metal species has been developed. The strategy exploits the Lewis acidic nature of bismuth and has been used to synthesize the new complexes BiV(O)(Hsal)(sal)(salen*)‚CH 2 Cl 2 (1), BiCu(Hsal) 3 (salen) (2), and BiNi(Hsal) 3 (salen)‚CH 2 -Cl 2 (3) (salen ) ethylenebis(salicylimine), salen* ) ethylenebis(3-methoxysalicylimine), salThe compounds have been characterized spectroscopically and, in the case of 2 and 3, by single-crystal X-ray diffraction. The decomposition of the bimetallic complexes by both thermal and hydrolytic routes has been investigated. The ability of the compounds to act as single-source precursors for the formation of bimetallic oxides has been explored. Oxide ion-conducting phases have been produced by direct pyrolysis of 1, which results in the formation of monoclinic BiVO 4 , and by pyrolysis of mixtures of 1 and 2 or 3, which results in isolation of the γ′-related Bi 2 V x M 1-x O 5.5-δ (M ) Cu, Ni). Thermal decomposition of the molecular compounds results in the formation of spherical oxide nanoparticles with diameters ranging from approximately 110 nm to 1 µm. Hydrolytic decomposition of the complexes results in the formation of nanoparticles with an average diameter of 40 nm. The materials produced in this manner have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and powder X-ray diffraction. Conservation of metal stoichiometry in converting the molecular precursor to the corresponding oxide has been confirmed by analysis of the materials by energydispersive X-ray spectroscopy.

The reactions between triphenylbismuth, salicylic acid, and the metal alkoxides M(OCH(2)CH(3))(5) (M = Nb, Ta) or Ti[OCH(CH(3))(2)](4) have been investigated under different reaction conditions and in different stoichiometries. Six novel heterobimetallic bismuth alkoxy-carboxylate complexes have been synthesized in good yield as crystalline solids. These include Bi(2)M(2)(sal)(4)(Hsal)(4)(OR)(4) (M = Nb, Ta; R = CH(2)CH(3), CH(CH(3))(2)), Bi(2)Ti(3)(sal)(8)(Hsal)(2), and Bi(2)Ti(4)(O(i)Pr)(sal)(10)(Hsal) (sal = O(2)CC(6)H(4)-2-O; Hsal = O(2)CC(6)H(4)-2-OH). The complexes have been characterized spectroscopically and by single-crystal X-ray diffraction. Compounds of the group V transition metals contain metal ratios appropriate for precursors of ferroelectric materials. The molecules exhibit excellent solubility in common organic solvents and good stability against unwanted hydrolysis. The nature of the thermal decomposition of the complexes has been explored by thermogravimetric analysis and powder X-ray diffraction. We have shown that the complexes are converted to the corresponding oxide by heating in an oxygen atmosphere at 500 degrees C. The mass loss of the complexes, as indicated by thermogravimetric analysis, and the resulting unit cell parameters of the oxides are consistent with the formation of the desired heterobimetallic oxide. The complexes decomposed to form the bismuth-rich phases Bi(4)Ti(3)O(12) and Bi(5)Nb(3)O(15) as well as the expected oxides BiMO(4) (M = Nb, Ta) and Bi(2)Ti(4)O(11).

In this manuscript, we describe the fabrication of photoactive biocidal or sporicidal films from urea-derived graphitic carbon nitride (u-g-C3N4). Co-deposited films of u-g-C3N4 and Escherichia coli O157:H7 (IC50 = 14.1 ± 0.2 mJ) or Staphylococcus aureus (methicillin resistant IC50 = 33.5 ± 0.2 mJ, methicillin sensitive IC50 = 42.7 ± 0.5 mJ) demonstrated significantly enhanced bactericidal behavior upon administration of visible radiation (400 nm ≤ λ ≤ 426 nm). In all cases, complete eradication of the microbial sample was realized upon administration of 100 mJ of visible radiation, while no antimicrobial activity was observed for non-irradiated samples. In contrast, Bacillus anthracis endospores were more resistant to u-g-C3N4 mediated killing with only a ca. 25% reduction in spore viability when treated with a 200 mJ dose of visible radiation. Characterization of u-g-C3N4 reveals that the improved activity results from enhancements of both the surface area and reduction potential of the material’s conduction band edge, coupled with fast injection of charge carriers into localized states and a decline in radiative recombination events. The results of this study demonstrate that g-C3N4-based materials offer a viable scaffold for the development of new, visible light driven technologies for controlling potentially pathogenic microorganisms.