Production of Acetone–Butanol–Ethanol (ABE) in Direct Fermentation of Cassava by Clostridium saccharoperbutylacetonicum N1-4

In this work, acetone–butanol–ethanol (ABE) fermentation characteristics of cassava starch and cassava chips when using Clostridium saccharoperbutylacetonicum N1-4 was presented. The obtained results in batch mode using a 1-L fermenter showed that C. saccharoperbutylacetonicum N1-4 was a hyperamylolytic strain and capable of producing solvents efficiently from cassava starch and cassava chips, which was comparable to when glucose was used. Batch fermentation of cassava starch and cassava chips resulted in 21.0 and 19.4 g/L of total solvent as compared with 24.2 g/L of total solvent when using glucose. Solvent productivity in fermentation of cassava starch was from 42% to 63% higher than that obtained in fermentation using corn and sago starches in the same condition. In fermentation of cassava starch and cassava chips, maximum butanol concentration was 16.9 and 15.5 g/L, respectively. Solvent yield and butanol yield (based on potential glucose) was 0.33 and 0.41, respectively, for fermentation of cassava starch and 0.30 and 0.38, respectively for fermentation using cassava chips.     

Chiroptical properties of an alternatingly functionalized cellotriose bearing two porphyrin groups

Right-handedness derived from bisporphyrins attached to a cellotriose backbone at O-6 and O'-6 positions is revealed for the first time. This cellotriose is proposed as a model of alternatingly functionalized cellulosics, which have promising properties for applications in optoelectronics and molecular receptors owing to the chirality and rigid backbone effects.     

On-line measurement of intramolecular carbon isotope distribution of acetic acid by continuous-flow isotope ratio mass spectrometry

Molecular and intramolecular carbon isotope measurements of acetic acid present in natural environments have been performed by off-line procedures. The off-line method is complicated and time-consuming and requires micromolar to millimolar amounts of sample. This limits geochemical isotopic studies, especially at the intramolecular level, on acetic acid present in natural samples. Here, we examine an on-line measurement of intramolecular carbon isotope distribution of acetic acid using continuous-flow isotope ratio mass spectrometry (CF-IRMS) coupled with an on-line pyrolysis system. This is achieved by measurement of the respective carbon isotope ratios of CH4 and CO2 produced by on-line pyrolysis of acetic acid. Results for authentic standards of pure acetic acid demonstrated the practicality of this on-line method, although the carbon isotope ratio of the methyl group could not be determined directly. The precision of the carbon isotope measurements was 0.4 per thousand (1sigma). The carbon isotope distribution determined by the on-line method was identical to that determined by the conventional off-line method within analytical error. The advantages of the on-line method compared with the conventional off-line method are that it is less laborious, requires less analytical time (less than one hour per sample) and, most importantly, uses smaller sample sizes (ca. 10 nanomole). An application of this on-line method to natural geochemical samples will provide an insight into the geochemical cycle of acetic acid.     

Bis(pentafluorophenyl) disulfide as a hydrogen abstractor and an electron acceptor from the resulting radical intermediate

The pentafluorobenzenethiyl radical is an efficient hydrogen abstractor from an activated methylene or methine group and bis(pentafluorophenyl) disulfide is an efficient electron acceptor from the resulting radical intermediate. Thus benzyl-OTBS ether was easily converted into the corresponding pinacol, and 2-phenyl-1,3-dioxanes are converted into the monobenzoates of diols.     

Synthesis of (±)‐Kempa‐6,8‐dien‐3‐ol (=(2aRS,3SR,4aSR,7RS,7aSR,10bSR,10cSR)‐2,2a,3,4,4a,5,6,7,7a,8,10b,10c‐Dodecahydro‐2a,7,10,10c‐tetramethylnaphth[2,18‐cde]azulen‐3‐ol)

The synthesis of kempa‐6,8‐dien‐3β‐ol ( 4a ), as a synthetic leading model of the natural product 4b , was carried out starting from intermediate 12 , the synthetic route of which has been developed previously (Scheme 1). The conversion of 12 to the model compound 4a involved the elaboration of three structure modifications by three processes, Tasks A, B, and C (see Scheme 2). Task A was achieved by epoxy‐ring opening of 41 with Me₃SiCl (Scheme 9), and Task B being performed by oxidation at the 13‐position, followed by hydrogenation, and then epimerization (Schemes 4 and 5). The removal of the 2‐OH group from 12 (Task C) was achieved via 30b according to Scheme 6, whereby 30b was formed exclusively from 30a / 31a 1 : 1 (Scheme 7). In addition, some useful reactions from the synthetic viewpoint were developed during the course of the present experiments.     

Facile formation of five-membered N-heterocyclic zirconacycloallenoids

The reaction of η(2)-iminozirconocene chloride complexes with trimethylsilylethynyl lithium leads to rapid C-C coupling at room temperature to yield the corresponding five-membered aza-zirconacycloallenoids. Such compounds were also obtained by trapping of in situ generated zirconocene with alkynyl imines.     

Synthesis of (zinc(II) phthalocyanine)-containing cellulose derivative using phthalocyanine-ring formation reaction

2,3-Di-O-myristyl-6-O-(zinc(II) phthalocyaninyl) cellulose (5) was synthesized from cellulose (1) by five reaction steps via 6-O-(3′,4′-dicyanophenyl)-2,3-di-O-myristyl cellulose (4). The key reaction was phthalocyanine-ring formation on a cellulose backbone, that is, the reaction of compound 4 with o-phthalodinitrile in the presence of hexamethyldisilazane and zinc acetate in DMF afforded to compound 5 in 35.4 % yield. Consequently, the degree of substitution with phthalocyanine moieties of compound 5 was 0.38. The LB monolayer film of compound 5 on an indium tin oxide (ITO) electrode was found to show photocurrent generation performance at 680 nm.     

Does B3LYP correctly describe magnetism of manganese complexes with various oxidation numbers and various structural motifs?

We assessed the applicability and basis set dependency of the B3LYP functional to investigate magnetic interactions of Mn complexes. For the purpose, we constructed a test set consisting of 16 Mn complexes with various oxidation states and structural motifs.The B3LYP results correctly reproduced magnetism and magneto–redox correlation of the standard μ-oxo motifs with superexchange paths, while it does not work for weak magnetic complexes. We also showed that a modest basis set yields results similar to those of triple-zeta plus diffuse-and-polarization functions. This basis set is expected to be a standard basis set for investigating magnetism of manganese complexes.