Non-heme iron(II) complexes containing tripodal tetradentate nitrogen ligands and their application in alkane oxidation catalysis

A series of iron(II) bis(triflate) complexes containing tripodal tetradentate nitrogen ligands with pyridine and dimethylamine donors of the type [N(CH(2)Pyr)(3-n)()(CH(2)CH(2)NMe(2))(n)] [n = 0 (tpa, 1), n = 1 (iso-bpmen, 3), n = 2 (Me(4)-benpa, 4), n = 3 (Me(6)-tren, 5)] and the linear tetradentate ligand [(CH(2)Pyr)MeN(CH(2)CH(2))NMe(CH(2)Pyr), (bpmen, 2)] has been prepared. The preferred coordination geometry of these complexes in the solid state and in CH(2)Cl(2) solution changes from six- to five-coordinate in the order from 1 to 5. In acetonitrile, the triflate ligands of all complexes are readily displaced by acetonitrile ligands. The complex [Fe(1)(CH(3)CN)(2)](2+) is essentially low spin at room temperature, whereas ligands with fewer pyridine donors increase the preference for high-spin Fe(II). Both the number of pyridine donors and the spin state of the metal center strongly affect the intensity of a characteristic MLCT band around 400 nm. The catalytic properties of the complexes for the oxidation of alkanes have been evaluated, using cyclohexane as the substrate. Complexes containing ligands 1-3 are more active and selective catalysts, possibly operating via a metal-based oxidation mechanism, whereas complexes containing ligands 4 and 5 give rise to Fenton-type chemistry.     

Dilatometric constant for polymerization of α-methylstyrene

By measurement of the specific volume of solutions of poly-α-methylstyrene in α-methylstyrene monomer at 25°C, the dilatometric constant was found to be K_D = (0.002007 ± 0.000030)%^?1. Estimation of the temperature dependence resulted in the equation (K_D)_t = 1.81 × 10^?3 + 7.82 + 10^?6 t, where t denotes temperature in °C.     

Nanosecond and picosecond laser flash photolysis studies of 2,2′-dinitrodiphenylmethanes

The transient absorption spectra of the 2,2′-dinitrodiphenylmethanes 1a–1c in solution were examined in the picosecond and nanosecond time ranges. The absorption bands, observed at 420–450 nm on 355 nm (18 ps) excitation of these compounds, were attributed to the nitronic acids 2a–2c, formed through the singlet-state- mediated intramolecular hydrogen abstraction and the triplet states of 1a–1c. Biradical intermediates, formed through the intramolecular abstraction of the benzylic hydrogen by the triplet excited state, were detected for 1a and 1b. Transient species produced following 355 nm (approximately 6 ns) pulse excitation of 1a–1c result in the formation of the corresponding nitronic acids 2a–2c, with absorption maxima around 415–430 nm. These nitronic acids are the precursors of the various products formed in the steady state irradiation of 1a–1c     

Conformational dependence of the electrostatic potential-derived charges of dopamine: Ramifications in molecular mechanics force field calculations in the gas phase and in aqueous solution

The electrostatic potential-derived charges for the catecholamine neurotransmitter dopamine were calculated at the STO-3G and 6-31G* basis sets for six different molecular conformations. The degree of variance of the charges with changing conformations was examined. The 6-31G* basis set produced charges that were more sensitive to changes in conformation than those derived from the STO-3G electrostatic potentials. The implication of the charge variations in molecular mechanics calculations was also investigated. The molecular mechanics results in the gas phase exhibited a variance depending upon the charge set used. The force field calculations varied much less when aqueous solvation was included in the calculations through a continuum model. © 1993 John Wiley & Sons, Inc.     

Quinazolines and 1,4-benzodiazepines. XLVI. Photochemistry of nitrones and oxaziridines

The cyclic nitrones 7-chloro-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one 4-oxide ( 5a ) and 1,3-dihydro-7-methylthio-5-phenyl-2H-1,4-benzodiazepin-2-one 4-oxide ( 5b ) are photoisomerized to readily isolable oxaziridines, 7-chloro-4,5-epoxy-5-phenyl-1,3,4–5-tetrahydro-2H-1,4-benzodiazepin-2-one ( 6a ) and 4,5-epoxy-5-phenyl-1,3,4,5-tetrahydro-7-methylthio-2H-1,4-benzo-diazepin-2-one ( 6b ). Oxaziridine 6b upon further irradiation gave ring expansion and ring contraction products, 4,6-dihydro-2-phenyl-9-methylthio-5H-1,3,6-benzoxadiazocin-5-one ( 7b ) and 4-benzoyl-3,4-dihydro-6-methylthioquinoxalin-2(1H)-one ( 8b ) respectively. The ring contraction product, 4-benzoyl-6-chloro-3,4-dihydroquinoxalin-2(1H)-one ( 8a ), was obtained from irradiation of oxaziridine 6a .     

What controls the melting properties of DNA-linked gold nanoparticle assemblies?

We report a series of experiments and a theoretical model designed to systematically define and evaluate the relative importance of nanoparticle, oligonucleotide, and environmental variables that contribute to the observed sharp melting transitions associated with DNA-linked nanoparticle structures. These variables include the size of the nanoparticles, the surface density of the oligonucleotides on the nanoparticles, the dielectric constant of the surrounding medium, target concentration, and the position of the nanoparticles with respect to one another within the aggregate. The experimental data may be understood in terms of a thermodynamic model that attributes the sharp melting to a cooperative mechanism that results from two key factors: the presence of multiple DNA linkers between each pair of nanoparticles and a decrease in the melting temperature as DNA strands melt due to a concomitant reduction in local salt concentration. The cooperative melting effect, originating from short-range duplex-to-duplex interactions, is independent of DNA base sequences studied and should be universal for any type of nanostructured probe that is heavily functionalized with oligonucleotides. Understanding the fundamental origins of the melting properties of DNA-linked nanoparticle aggregates (or monolayers) is of paramount importance because these properties directly impact one's ability to formulate high sensitivity and selectivity DNA detection systems and construct materials from these novel nanoparticle materials.     

Capillary electrophoresis separation of heterocyclic nitrosoamino acid-conformers at sub-ambient temperatures

The separation of a selected group of naturally occurring, heterocyclic nitrosoamino acids was achieved by capillary zone electrophoresis and the resolution of the syn and anti conformers improved as the temperature was lowered to 5 °C. The double peaks observed for each nitrosoamino acid are probably caused by the slow kinetics of conformational isomerism. The experimental setup consisted of a P/ACE 5510 electrophoresis system, a 57 cm polyacrylamidecoated capillary, and a 10 mM phosphate buffer, pH 7.2, containing 2 mM of 3-(N-N-dimethylmyristylammonio)propanesulfonate (DMMAPS) and 0.1% Tween 20. Our study shows that (a) the lower the temperature, the greater the resolution and the longer the migration times; and (b) different nitrosoamino acid conformers were resolved at different temperatures because of differences in the rate of isomerization. For example, the conformers of N-nitrosothiazolidine-4-carboxylic acid were partially resolved at 30 °C while those of N-nitrosoproline were well resolved at the same temperature.     

Scanning tunneling microscopy of prochiral anthracene derivatives on graphite: chain length effects on monolayer morphology

The morphology of monolayers formed upon adsorption of prochiral 1,5-substituted anthracene derivatives on highly oriented pyrolytic graphite is investigated using scanning tunneling microscopy at the liquid-solid interface. The adsorption orientation of these prochiral anthracene derivatives positions one of their enantiotopic faces in contact with the graphite. The molecules adsorb in rows with contact between adjacent anthracenes. The anthracene side chains extend perpendicular to the direction of the row repeat. All molecules within a single row adsorb via the same enantiotopic face. Anthracenes with side chains containing an even number of non-hydrogenic atoms (C, S) form monolayers in which molecules in adjacent rows adsorb via opposite enantiotopic faces. Anthracenes with side chains that contain an odd number of non-hydrogenic atoms form two-dimensional chiral domains in which all rows contain molecules adsorbed via the same enantiotopic face. This chain length effect on monolayer morphology represents a generalized example of structural effects previously observed in alkanoic acid monolayers formed on HOPG. The variation of the STM current with position in the vicinity of the anthracenes indicates that the highest occupied molecular orbital is the predominant mediator of tunneling for the aromatic group.     

The Neutral Part of the Bark of Pinus Luchuensis Mayer

The neutral part of the acetone extract from the bark of Pinus luchuensis Mayer has been investigated and found to consist of alkanes (C₂₂–C₃₄) and triterpenes of serratene type. The triterpenes are 3β–methoxyserrat–14–en–21–one, serrat–14–en–3, 21–dione, 3β–hydroxyserrat–14–en–21–one, 3β–21α–dimethoxyserrat–l4–ene and 3β–methoxyserrat–14–en–21α–ol.