Absolute configuration of arylglycerol-β-aryl ethers obtained by asymmetric reduction of the correspondingα-ketonic compound with intactFusarium solani cells

When (±)--oxo-guaiacylglycerol--(vanillic acid) ether (1) is degraded byFusarium solani M-13-1, the-ketone is initially reduced to giveerythro andthreo guaiacylglycerol--(vanillic acid) ethers (2), arylglycerol--aryl ethers, both of which are enantiomerically pure. The absolute configuration in each2 was determined by Mosher's method; the products were converted to,-di-(R)--methoxy--trifluoromethylphenylacetates (MTPA esters) (3) oferythro (-)- andthreo (+)-veratrylglycerol--(methyl vanillate) ethers (3), whose¹H nuclear magnetic resonance (NMR) spectra were examined and compared with those of four di-(R)-MTPA ester (3) diastereomers from chemically synthesizederythro (±)-3 andthreo (±)-3. To assign the- and-MTPA-OCH₃ peaks, the¹H NMR scans of several compounds that have substructures of 3 and their 3,4,5-trimethoxyphenyl analogues were examined. When a racemic alcohol reacts with (R)-MTPA to give a pair of (R)-MTPA ester diastereomers, the value was defined as the absolute value of the difference in the¹H chemical shifts of the peak between the diastereomers. It was found that the values of-MTPA-OCH₃ were larger than those of-MTPA-OCH₃ owing to a shielding effect of the veratryl ring located on the-MTPA-OCH₃, and that the-MTPA-OCH₃ peaks in the 3,4,5-trimethoxyphenyl compounds shifted downfield relative to those in the veratryl compounds. On the basis of the¹h NMR data of (R)-MTPA esters, the absolute configuration of the four chemically prepared diastereomers (3) were determined. The catabolicerythro 3 [fromerythro (-)-3] andthreo 3 [fromthreo (+)-3] were identical to (R, S, R)-erythro 3 and (R, S, S)- threo 3, respectively. An hydrogen species in the fungal reduction would attack the-ketone fromre-face of both (R)-1 and (S)-1, givingerythro (S, R)-2 andthreo (S, S)-2, respectively.Part of this paper was presented at the 33rd Lignin Symposium, Tsukuba, November 1988     

Novel plasmodesmata association of dehydrin-like proteins in cold- acclimated Red-osier dogwood (Cornus sericea)

Dehydrins are proteins associated with conditions affecting the water status of plant cells, such as drought, salinity, freezing and seed maturation. Although the function of dehydrins remains unknown, it is hypothesized that they stabilize membranes and macromolecules during cellular dehydration. Red-osier dogwood (Cornus sericea L.), an extremely freeze-tolerant woody plant, accumulates dehydrin-like proteins during cold acclimation and the presence of these proteins is correlated with increased freeze tolerance (Karlson 2001, Sarnighausen et al. 2002, Karlson et al. 2003). Our objective was to determine the location of dehydrins in cold-acclimated C. sericea stems in an effort to provide insight into their potential role in the freeze tolerance of this extremely cold hardy species. Abundant labeling was observed in the nucleus and cytoplasm of cold-acclimated C. sericea stem cells. In addition, labeling was observed in association with plasmodesmata of cold-acclimated vascular cambium cells. The unique association of dehydrin-like proteins with plasmodesmata has not been reported previously.     

Polymorphism analysis of Fagaceae and DNA-based identification ofFagus species grown in Japan based on therbcL gene

Fagaceae species in Japan were identified by restriction fragment length polymorphism (RFLP) and sequence comparison of a region ofrbcL. Of nine restriction endonucleases used for digestion, three (MspI,RsaI,HaeIII) produced different restriction patterns in Fagaceae. Digestion byMspI yielded four patterns: Fagus species,Castanea crenata, Pasania glabra, and others. Digestion byRsaI andHaeIII afforded two patterns:Fagus species and others. These facts indicate thatCastanea crenata andPasania glabra can be identified byMspI restriction patterns ofrbcL. Sequence comparison of a region of therbcL gene among 20 species of Fagaceae showed that: (1) they could be divided into seven groups; (2) there is a site mutation betweenFagus crenata andF. japonica. The latter indicates that the wood of both Fagus species are identifiable at the species level, which is not the case using conventional methods. This result indicates the possibility of wood identification based on DNA polymorphism in Fagaceae at the intrageneric level.Part of this paper was presented at the 46th annual meeting of the Japan Wood Research Society, Kumamoto, April 3–5, 1996 and the 47th annual meeting of the Japan Wood Research Society, Kochi, April 3–5, 1997     

A rubberlike stretchable active matrix using elastic conductors

By using an ionic liquid of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, we uniformly dispersed single-walled carbon nanotubes (SWNTs) as chemically stable dopants in a vinylidene fluoride-hexafluoropropylene copolymer matrix to form a composite film. We found that the SWNT content can be increased up to 20 weight percent without reducing the mechanical flexibility or softness of the copolymer. The SWNT composite film was coated with dimethyl-siloxane-based rubber, which exhibited a conductivity of 57 siemens per centimeter and a stretchability of 134%. Further, the elastic conductor was integrated with printed organic transistors to fabricate a rubberlike active matrix with an effective area of 20 by 20 square centimeters. The active matrix sheet can be uniaxially and biaxially stretched by 70% without mechanical or electrical damage. The elastic conductor allows for the construction of electronic integrated circuits, which can be mounted anywhere, including arbitrary curved surfaces and movable parts, such as the joints of a robot's arm.     

Microbial reduction mechanism of ferric iron in paddy soils (Part I)

In the previous paper¹⁾ the authors proved that the ferric iron reduction in submerged paddy soils is entirely or mostly effected by the activities of microorganisms in the soil. Prior to the study on the ferric iron reducing microorganisms isolated from the soil, the present paper reports the research for the microbial mechanism of iron reduction. working with the soil itself.     

Changes in allergenicity and digestibility of squid tropomyosin during the Maillard reaction with ribose

The effect of the Maillard reaction on the allergenicity of squid tropomyosin (TM) was investigated. When TM was reacted with ribose (TM-ribose), its human-specific IgE-binding ability decreased markedly and alpha-chymotryptic digestibility of TM was also altered at the early stage of the Maillard reaction. On the other hand, the modification of the lysine residues in TM using 2,4,6-trinitrobenzenesulfonic acid had no effect on the allergenicity and alpha-chymotryptic digestibility of TM. Therefore, the structural change in TM induced by the Maillard reaction would cause the reduction of the allergenicity, rather than the block of lysine residues. Although peptic digestion diminished the specific IgE-binding ability of TM, the reduction of the allergenicity by the Maillard reaction remained after peptic digestion. These results suggest that hypersensitive reaction of TM-ribose in the human body might be lower than that of native TM.     

Analysis of strigolactones,germination stimulants for striga and orobanche,by high-performance liquid chromatography/tandem mass spectrometry

A simple and rapid analytical method for strigolactones, germination stimulants for the root parasitic weeds witchweed (Striga spp.) and broomrape (Orobanche spp.), has been developed using high-performance liquid chromatography connected to tandem mass spectrometry (LC/MS/MS). The natural strigolactones (strigol, sorgolactone, orobanchol, and alectrol) were clearly separated and identified by LC/MS/MS. As low as 0.1 pg/microL of strigol and 0.5 pg/microL of sorgolactone could be quantified, whereas 1 pg/microL was needed for the quantification of orobanchol (S/N > 10). Using this method, it was found that red clover produces orobanchol and alectrol but not strigol. The roots of red clover seedlings were found to produce 13, 70, 58, and 65 pg of orobanchol/plant 1, 2, 3, and 4 weeks after germination, respectively.