The Synthesis and Antitumor Activity of the Sodium Salt and Copper (II) Complex of N-[(Trimethylamineboryl)-Carbonyl]-L-Phenylalanine Methyl Ester

Sodium N-[(trimethylamineboryl)-carbonyl]-L-phenylalanine 2 and {N-[(trimethylamineboryl)-carbonyl]-L-phenylalanyl- carbxylato}-bis-{N-[(trimethylaminebryl)-carbonyl]-L-phenylalanine} dicopper (II) 3 were successfully synthesized. The agents blocked L(1210) leukemic cell DNA and RNA syntheses by inhibiting multiple enzyme activities for nucleic acid synthesis, e.g. PRPP amido transferase, IMP dehydrogenase, DNA polymerase alpha, thymidine kinase, and TMP kinase. The copper (II) complex 3 demonstrated improved ability to inhibit L(1210) partially purified DNA topoisomerase II compared to the parent compound while the sodium salt was inactive at 100 muM.     

<Superscript>1</Superscript>H NMR characterization of milk lipids: A comparison between cow and buffalo milk

Characterization of the lipid fraction of raw cow and buffalo milk samples, collected in different breeding areas in Apulia, a region of southern Italy, were performed by means of ¹H NMR. The aim of this work was to establish whether FA composition data obtained by ¹H NMR can be used in the differentiation of buffalo and cow milk samples according to species. A complete assignment of the signals present in the spectrum was attempted by COSY, heteronuclear coherence spectra. Quantification of FA was carried out by inserting the integrals of particular peaks in suitable calculations. Multivariate statistical analysis, conducted on the results of the quantification, permitted buffalo and cow milks to be distinguished.     

On the preparation and properties of CuZSM-5 catalysts for NO decomposition

Equilibrium exchange isotherms were determined for the exchange of Cu²⁺ with NaZSM-5 at varying Cu(Ac)₂ concentrations in solutions of constant volume and zeolite weight. At low Cu²⁺ levels the solid scavenged all the copper ions. When copper could be detected in the equilibrated solutions, overexchange was observed. The extent of overexchange was higher at pH 6 than at pH 4. These results were analyzed in relation to catalytic activity.On leave from the Central Institute for Chemistry, Hungarian Academy of Sciences, H1525 Budapest, Hungary.     

Alumina-, niobia-, and niobia/alumina-supported NiMoS catalysts: Surface properties and activities in the hydrodesulfurization of thiophene and hydrodenitrogenation of 2,6-dimethylaniline

The activity of NiMoS catalysts supported on niobia, alumina, and niobia/alumina was compared for the thiophene hydrodesulfurization (HDS) and 2,6-dimethylaniline (2,6-DMA) hydrodenitrogenation (HDN) reactions. To evaluate the acidity of the supports and identify the nature of the sulfide sites, adsorption of 2,6-dimethylpyridine, pyridine, and CO was performed and followed by IR spectroscopy. This study has shown that with niobia as a support, the activity of NiMoS catalysts in thiophene HDS and in HDN of 2,6-DMA was no longer promoted by the synergy between Ni and Mo. The absence of synergy between molybdenum and nickel on niobia can be explained by the strong interaction of each metal with niobia at the expense of interaction with each other. Moreover, it has been shown that on a niobia/alumina support, the formation of the NiMoS phase can be directly linked to the presence of alumina not covered by niobia. However, niobia is an interesting support for the HDN of 2,6-DMA, because it favors the formation of xylene through direct ammonia elimination involving low H₂ consumption. The activity for xylene formation on niobia is linked to the electron-deficient nature of the Mo sulfide site, as demonstrated by CO adsorption followed by IR.     

Separation of kinetics and mass-transfer in a batch alkoxylation reaction

The quantitative aspects of the role of interfacial mass-transfer and reaction kinetics in ethoxylation of lauryl alcohol were examined in a batch recirculation reactor. The liquid droplets falling through a gas column were obtained by utilizing a recirculation loop and a set of spray nozzles. The CO₂/NaOH reaction was employed to characterize the interfacial area. The alkoxylation reaction was studied at temperatures between 124°C and 171°C, at catalyst levels between 0.09 and 0.50 weight percent and at ethylene oxide partial pressures between 68 kPa and 204 kPa. A model was developed which permits the prediction of reactor performance at various operating conditions. The mass-transfer during free fall dominates the interfacial mass-transfer and the contributions during the drop formation and coalescence stages are small. The rate of ethylene oxide (EO) addition to lauryl alcohol was constant during the batch run, indicating similar activity for the unreacted lauryl alcohol and the lauryl alcohol ethoxylated to varying extents. The rate of ethoxylation is first-order in both catalyst and ethylene oxide concentrations. The liquid-phase reaction kinetics and interfacial mass-transfer occur in series, with kinetics dominating the overall ethoxylation rate. As expected, an increasing role of mass transfer is observed at higher temperatures, and/or higher catalyst concentrations where the kinetic rate becomes significantly high. The intrinsic activation energy for the ethoxylation of lauryl alcohol is 55.2 kJ/mole.     

Characterization of rubber particle size distribution of high-impact polystyrene using low-angle laser light scattering

A new application of low-angle laser light scattering has led to a new instrument capable of characterizing the rubber particle size distribution of high-impact polystyrene (HIPS) containing particles as small as 0.1 μ. Rubber particle size distributions of several HIPS resins have been characterized, and the particle size ranking of resins using light scattering parallels the ranking of resins using photomicroscopy. Several solvents have been employed to suspend the HIPS rubber particles for the scattering determination. Swelling of the rubber phase has been found to be relatively insensitive to variations in rubber phase crosslinking when methyl ethyl ketone is used to suspend the rubber particles. Particle swelling in methyl ethyl ketone does not detract from the usefulness of the light scattering method for HIPS rubber particle size characterization.     

The effects of bleached and unbleached rosemary oleoresins on light-sensitized oxidation of soybean oil

Bleached and unbleached forms of a rosemary oleoresin (RO) in stripped and nonstripped soybean oil behave both as antioxidant and prooxidant in a light-induced oxidative system. At 0.02 and 0.05% levels, RO had the greatest antioxidant activity, while at 0.01 and 0.5% levels it had the highest prooxidant activity in both stripped and nonstripped soybean oil. Treatment of both soybean oil systems with tertiary butylhydroquinone controlled light-induced oxidation of the oil better than did the oleoresin treatments. The prooxidant activity of the 0.5% RO level was probably due to an excess of prooxidant components being carried into the oil at that level, whereas the reduced antioxidant activity at 0.01% was probably due to the low initial level of active antioxidant components being added to the oil. Published as Journal Series No. 10072, Nebraska Agricultural Research Division, Department of Food Science and Technology, University of Nebraska, Lincoln, NE 68583-0919.     

Attraction of Male European Tarnished Plant Bug, <Emphasis Type="Italic">Lygus rugulipennis</Emphasis> to Components of the Female Sex Pheromone in the Field

Previous work showed that females of the European tarnished plant bug, Lygus rugulipennis Poppius (Heteroptera: Miridae), produced three chemicals, hexyl butyrate, (E)-2-hexenyl butyrate, and (E)-4-oxo-2-hexenal, and that these were suspected to be components of the female sex pheromone. In field experiments, traps baited with blends of these chemicals dispensed from polyethylene vials and sachets failed to catch significant numbers of males. Here, we report more recent field experiments in which the chemicals were released from glass microcapillary tubes. A blend of hexyl butyrate and (E)-4-oxo-2-hexenal was significantly attractive to male L. rugulipennis. In addition, whereas the mixture of all three components attracted fewer L. rugulipennis males, this tertiary blend captured significantly greater numbers of males of the congeneric species Lygus pratensis than the binary mixture. The possible reasons for the success of the microcapillaries compared with other dispensers are discussed.     

Minor components in the sex pheromone of legume podborer: Maruca vitrata development of an attractive blend

The legume podborer, Maruca vitrata (syn. M. testulalis) (F.) (Lepidoptera: Pyralidae) is a pantropical pest of legume crops. Sex pheromone was collected by gland extraction or trapping of volatiles from virgin female moths originating in India, West Africa, or Taiwan. Analysis by GC-EAG and GC-MS confirmed previously published findings that (E,E)-10,12- hexadecadienal is the most abundant EAG-active component with 2–5% of (E,E)-10,12-hexadecadienol also present. At least one other EAG response was detected at retention times typical of monounsaturated hexadecenals or tetradecenyl acetates, but neither could be detected by GC-MS. Laboratory wind-tunnel bioassays and a field bioassay of blends of (E,E)-10,12-hexadecadienal with (E,E)-10,12-hexadecadienol and a range of monounsaturated hexadecenal and tetradecenyl acetate isomers indicated greatest attraction of males was to those including (E,E)-10,12-hexadecadienol and (E)-10-hexadecenal as minor components. In subsequent trapping experiments in cowpea fields in Benin, traps baited with a three-component blend of (E,E)-10,12-hexadecadienal and these two minor components in a 100:5:5 ratio caught significantly more males than traps baited with the major component alone, either two-component blend, or virgin female moths. Further blend optimization experiments did not produce a more attractive blend. No significant differences in catches were found between traps baited with polyethylene vials or rubber septa, or between lures containing 0.01 and 0.1 mg of synthetic pheromone. Significant numbers of female M. vitrata moths, up to 50% of total catches, were trapped with synthetic blends but not with virgin females. At present there is no clear explanation for this almost unprecedented finding, but the phenomenon may improve the predictive power of traps for population monitoring.     

A Flavanone and Two Phenolic Acids from Chrysanthemum morifolium with Phytotoxic and Insect Growth Regulating Activity

Leaves of Chrysanthemum morifolium cv. Ramat were extracted sequentially with hexane, ethyl acetate, and methanol. The methanol fraction, when incorporated into artificial diet was found to reduce the growth of cabbage looper (Trichoplusia ni Hubner) larvae at concentrations between 500 and 5000 ppm of diet. Fractionation of the methanol extract on a Sephadex column yielded five fractions, three of which reduced the weight of larvae relative to the control. One fraction was analyzed using high performance liquid chromatography (HPLC) and found to contain three main constituents. These compounds were purified using a combination of gel permeation chromatography on Sephadex LH20 and HPLC, and analyzed by 1H and 13CNMR as well as undergoing chemical and physical analyses. The compounds were identified as: 1, chlorogenic acid (5-O-caffeoylquinic acid); 2, 3,5-O-dicaffeoylquinic acid; and 3, 3', 4',5-trihydroxyflavanone7-O-glucuronide (eriodictyol7-O-glucuronide). At concentrations between 100 to 1000 ppm these compounds reduced both growth and photosynthesis of Lemna gibba L. with the order of efficacy being: flavanone > chlorogenic acid > 3,5-O-dicaffeoylquinic acid. Furthermore, when incorporated separately into artificial diet these compounds, at 10 to 1000 ppm, enhanced or reduced growth of the cabbage looper (Trichoplusia ni) and gypsy moth (Lymantria dispar L.).