Pretreatment of yellow poplar sawdust by pressure cooking in water

The pretreatment of yellow poplar wood sawdust using liquid water at temperatures above 220°C enhances enzyme hydrolysis. This paper reviews our prior research and describes the laboratory reactor system currently in use for cooking wood sawdust at temperatures ranging from 220 to 260°C. The wood sawdust at a 6–6.6% solid/liquid slurry was treated in a 2 L, 304 SS, Parr reactor with three turbine propeller agitators and a proportional integral derivative (PID) controller, which controlled temperature within ±1°C. Heat-up times to the final temperatures of 220, 240, or 260°C were achieved in 60–70 min. Hold time at the final temperature was less than 1 min. A serpentine cooling coil, through which tap water was circulated at the completion of the run, cooled the reactor’s contents within 3 min after the maximum temperature was attained. A bottoms port, as well as ports in the reactor’s head plate, facilitated sampling of the slurry and measuring the pH, which changes from an initial value of 5 before cooking to a value of approx 3 after cooking. Enzyme hydrolysis gave 80–90% conversion of cellulose in the pretreated wood to glucose. Simultaneous saccharification and fermentation of washed, pretreated lignocellulose gave an ethanol yield that was 55% of theoretical. Untreated wood sawdust gave less than 5% hydrolysis under the same conditions.     

Proton control of oxidation and spin state in a series of iron tripodal imidazole complexes

Reaction of iron salts with three tripodal imidazole ligands, H(3)(1), H(3)(2), H(3)(3), formed from the condensation of tris(2-aminoethyl)amine (tren) with 3 equiv of an imidazole carboxaldehyde yielded eight new cationic iron(III) and iron(II), [FeH(3)L](3+or2+), and neutral iron(III), FeL, complexes. All complexes were characterized by EA(CHN), IR, UV, M?ssbauer, mass spectral techniques and cyclic voltammetry. Structures of three of the complexes, Fe(2).3H(2)O (C(18)H(27)FeN(10)O(3), a = b = c = 20.2707(5), cubic, I3d, Z = 16), Fe(3).4.5H(2)O (C(18)H(30)FeN(10)O(4.5), a = 20.9986(10), b = 11.7098(5), c = 19.9405(9), beta = 109.141(1), monoclinic, P2(1)/c), Z = 8), and [FeH(3)(3)](ClO(4))(2).H(2)O (C(18)H(26)Cl(2)FeN(10)O(9), a = 9.4848(4), b = 23.2354(9), c = 12.2048(5), beta = 111.147(1) degrees, monoclinic, P2(1)/n, Z = 4) were determined at 100 K. The structures are similar to one another and feature an octahedral iron with facial coordination of imidazoles and imine nitrogen atoms. The iron(III) complexes of the deprotonated ligands, Fe(1), Fe(2), and Fe(3), are low-spin while the protonated iron(III) cationic complexes, [FeH(3)(1)](ClO(4))(3) and [FeH(3)(2)](ClO(4))(3), are high-spin and spin-crossover, respectively. The iron(II) cationic complexes, [FeH(3)(1)]S(4)O(6), [FeH(3)(2)](ClO(4))(2), [FeH(3)(3)](ClO(4))(2), and [FeH(3)(3)][B(C(6)H(5))(4)](2) exhibit spin-crossover behavior. Cyclic voltammetric measurements on the series of complexes show that complete deprotonation of the ligands produces a negative shift in the Fe(III)/Fe(II) reduction potential of 981 mV on average. Deprotonation in air of either cationic iron(II) or iron(III) complexes, [FeH(3)L](3+or2+), yields the neutral iron(III) complex, FeL. The process is reversible for Fe(3), where protonation of Fe(3) yields [FeH(3)(3)](2+).     

Photochemical properties of mixed-metal supramolecular complexes

We have prepared a series of mixed-metal trimetallic complexes of the form {[(bpy)₂Ru(BL)]₂MCl₂}ⁿ⁺(bpy 2,2′-bipyridine; BL 2,3-bis(2-pyridyl)pyrazine (dpp), 2,3-bis(2-pyridyl)quinoxaline (dpq) or 2,3-bis(2-pyridyl)-benzoquinozaline (dpb); M Ir(III), Rh(III) or Os(II). This new class of trimetallic complexes can be prepared with a good yield, often as high as 95%, using our building block strategy. The central rhodium and iridium fragments of these trimetallic, namely [M(BL)₂Cl₂]⁺, have been shown in our laboratory to be capable of delivering multiple electrons, “stored” on the bridging ligand π* orbitals, to a substrate as they functioned as electrocatalysts for the reduction of carbon dioxide to formate. The two terminal ruthenium metals are good light absorbers designed to give rise to photochemical activity. These bichromophoric systems should be capable of absorbing two photons of light, each giving rise to a desired photochemical reaction, namely excited-state electron transfer. Thus these systems form the basis of a molecular device for photoinitiated electron collection. The properties of these supramolecular complexes have been tuned by variation in the central metal and bridging ligand. Comparison of this array of nine complexes is described herein.     

Reactions of transition-metal carbonyls with anhydrous HF

The reactions of a wide range of transition-metal carbonyls with anhydrous HF are described. In particular, Ru₃(CO)₁₂, Os₃(CO)₁₂ and Ir₄(CO)₁₂ give the solution stable [Ru₃(CO)₁₂H]⁺, [Ru(CO)₅H]⁺, [Os₃(CO)₁₂H]⁺, [Os(CO)₅H]⁺ and [Ir₄(CO)₁₂H₂]²⁺ respectively, which have been characterised by a combination of ¹H and ¹³C NMR spectroscopy.     

Method for improved secondary ion yields in cluster secondary ion mass spectrometry

A method to increase useful yields of organic molecules is investigated by cluster secondary ion mass spectrometry (SIMS). Glycerol drops were deposited onto various inkjet‐printed arrays and the organic molecules in the film were rapidly incorporated into the drop. The resulting glycerol/analyte drops were then probed with fullerene primary ions under dynamic SIMS conditions. High primary ion beam currents were shown to aid in the mixing of the glycerol drop, thus replenishing the probed area and sustaining high secondary ion yields. Integrated secondary ion signals for tetrabutylammonium iodide and cocaine in the glycerol drops were enhanced by more than a factor of 100 compared with an analogous area on the surface, and a factor of 1000 over the lifetime of the glycerol drop. Once the analyte of interest is incorporated into the glycerol microdrop, the solution chemistry can be tailored for enhanced secondary ion yields, with examples shown for cyclotrimethylenetrinitramine (RDX) chloride adduct formation. In addition, depositing localized glycerol drops may enhance analyte secondary ion count rates to high enough levels to allow for site‐specific chemical maps of molecules in complex matrices such as biological tissues. Published in 2010 by John Wiley & Sons, Ltd.