Commercialization of biomass ethanol technology

Applied Biochemistry and Biotechnology - With the recent commissioning of the National Renewable Energy Laboratory’s (NREL) process development unit, through the support of the US Department...     

[η2-(E)-But-2-enedi­nitrile](N,N′-di­phenyl-1,7,7-tri­methyl­bi­cyclo­[2.2.1]heptane-2,3-diimine-N,N′)palladium(0)

The zero-valent palladium in [Pd(C₄H₂N₂)(C₂₂H₂₄N₂)] is coordinated to two imine N atoms of a derivatized camphor ligand, and to the olefinic C atoms of a π-bonded fumaro­nitrile group. The N—Pd—N bite angle of 77.31 (9)° is similar to angles observed in other zero-valent palladium di­iminoalkene species. The asymmetry of the camphor moiety leads to two different orientations of the N-aryl groups relative to the PdN₂ plane [C=N—C—C torsion angles of 102.4 (4) and 39.4 (4)°].     

Complexation with diol host compounds. Part 1. Structures of the 1:2 molecular complexes oftrans-9, 10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone and with 3-methylcyclopentanone

The structures of the 1:2 molecular complexes of trans -9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone (1), (C₂₆H₂₀O₂·2 C₈H₈O) and with 3-methylcyclopentanone (2), (C₂₆H₂₀O₂·2C₆H₁₀O) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P ,a =8.979(5) Å,b =9.316(3) Å,c = 11.12(1) Å, =94.40(6)°, = 106.53(6)°, = 109.92(5)°,V = 822.94 ų,Z = 1,R = 0.097 for 2549 unique reflections. Compound (2):P ,a = 8.958(7) Å,b =9.815(4) Å,c = 9.807(4) Å, = 96.88(3)°, = 109.21(8)°, = 103.33(7)°,V = 774.10 ų,Z = 1,R = 0.059 for 2494 unique reflections. The intermolecular arrangements in both structures are characterised by host-to-guest hydrogen bonding interactions. The thermal properties of compound (2) have been characterised by DTA and TGA thermograms.     

Complexation with diol host compounds. Part 2. Structures of 1,1,2,2-tetraphenylethane-1,2-diol and its 1∶2 molecular inclusion complex with dimethylsulphoxide

The structures of 1,1,2,2-tetraphenylethane-1,2-diol and its 12 molecular inclusion complex with dmso have been elucidated by X-ray crystallography from single crystal diffraction data. Crystals of the host, compound I, are monoclinic, space groupP2₁/n, witha=17.669(6) Å,b=6.144(6) Å,c=17.873(6) Å,=92.67(3)°,z=4. Crystals of the clathrate, compound II, are triclinic,P¯1, witha=9.138(5) Å,b=18.384(6) Å,c=18.496(3) Å,=61.16(2)°,=83.22(3)°, =88.06(3)°,Z=4. Both structures were solved by direct methods and refined to finalR values of 0.072 and 0.107, respectively. Compound I is partially disordered and its packing is governed by strong intermolecular hydrogen bonds. Compound II is characterized by crossing channels which accommodate the guest dmso molecules. The thermal properties of the latter compound have been characterized by DTA and TGA thermograms.     

3‐(1‐Hydroxy­ethyl­idene)‐1‐phenyl­pyrrolidine‐2,4‐dione

Analysis of C₁₂H₁₁NO₃ revealed a coplanar N‐substituted phenyl group on a pyrrolidine ring with two keto moieties and a hydroxy­ethyl­idene functionality. The hydroxy group forms part of a hydrogen‐bonding network characterized by a short intramolecular H?O distance of 1.81 (3) Å, and a longer intermolecular interaction with an H?O distance of 2.38 (3) Å. Both keto groups form additional intra‐ and intermolecular C—H?O contacts with H?O distances ranging from 2.26 to 2.41 Å.     

Oxidative atom-transfer to a trimanganese complex to form Mn6(μ6-E) (E = O, N) clusters featuring interstitial oxide and nitride functionalities

Utilizing a hexadentate ligand platform, a trinuclear manganese complex of the type ((H)L)Mn(3)(thf)(3) was synthesized and characterized ([(H)L](6-) = [MeC(CH(2)N(C(6)H(4)-o-NH))(3)](6-)). The pale-orange, formally divalent trimanganese complex rapidly reacts with O-atom transfer reagents to afford the μ(6)-oxo complex ((H)L)(2)Mn(6)(μ(6)-O)(NCMe)(4), where two trinuclear subunits bind the central O-atom and the ((H)L) ligands cooperatively bind both trinuclear subunits. The trimanganese complex ((H)L)Mn(3)(thf)(3) rapidly consumes inorganic azide ([N(3)]NBu(4)) to afford a dianionic hexanuclear nitride complex [((H)L)(2)Mn(6)(μ(6)-N)](NBu(4))(2), which subsequently can be oxidized with elemental iodine to ((H)L)(2)Mn(6)(μ(6)-N)(NCMe)(4). EPR and alkylation of the interstitial light atom substituent were used to distinguish the nitride from the oxo complex. The oxo and oxidized nitride complexes give rise to well-defined Mn(II) and Mn(III) sites, determined by bond valence summation, while the dianionic nitride shows a more symmetric complex, giving rise to indistinguishable ion oxidation states based on crystal structure bond metrics.     

A Novel Synthesis of 3-Amido-5-phenyl-benzazepin-2-one via an Intramolecular Amidoalkylation

A synthesis of N-(8-Methyl-2-oxo-5-phenyl-2,3-dihydro-1H-benz[b]azepin-3-yl)-benzamide 2 via an intramolecular amidoalkylation is described.     

LONG-WAVELENGTH UVA RADIATION INDUCES OXIDATIVE STRESS,CYTOSKELETAL DAMAGE and HEMOLYSIS*

Abstract— We investigated the ability of the different wavelength regions of UV radiation, UVA(320–400 nm), UVB(290–320 nm) and UVC(200–290 nm), to induce hemolysis. Sheep erythrocytes were exposed to radiation from either a UVA1 (>340 nm) sunlamp, a UVB sunlamp, or a UVC germicidal lamp. The doses used for the three wavelength regions were approximately equilethal to the survival of L5178Y murine lymphoma cells. Following exposure, negligible hemolysis was observed in the UVB- and UVC-irradiated erythrocytes, whereas a decrease in the relative cell number (RCN), indicative of hemolysis, was observed in the UVA 1-exposed samples. The decrease in RCN was dependent on dose(0–1625 kj/m²), time(0–78 h postirradiation) and cell density (10⁶-10⁷ cells/mL). Hemolysis decreased with increasing concentration of glutathione, hemoglobin or cell number, while the presence of pyruvate drastically enhanced it. Because scanning spectroscopy(200–700 nm) showed that hemoproteins and nicotinamide adenine dinucleotides were oxidized, cytoplasmic oxidative stress was implicated in the lytic mechanism. Further evidence of oxidation was obtained from electron micrographs, which revealed the formation of Heinz bodies near the plasma membrane. The data demonstrate that exposure of erythrocytes to UVA1, but not UVB or UVC, radiation causes oxidation of cytoplasmic components, which results in cytoskeletal damage and hemolysis.