Exact helical polymer synthesis by a two-point-covalent-linking protocol between C2-chiral spirobifluorene and C2- or C(s)-symmetric anthraquinone monomers.

Two types of one-handed exact helical polymers, coil- and screw-shaped polymers, were synthesized by the two-point-covalent-linking protocol using C2-chiral spirobifluorene (SBF) and C2- or C(s)-symmetric anthraquinone spacers. Central to this protocol is a new aromatic ring-forming reaction based on the stepwise reductive cyclization of bis(aryloxy group)-substituted anthraquinone derivatives. The helical structures of the polymers annulated by aromatic skeletons exhibited high thermal stability attributed to the rigid C2-chiral SBF units and the covalently two-point-connected structure.

Reversible Transformation of a One-Handed Helical Foldamer Utilizing a Planarity-Switchable Spacer and C2-Chiral Spirobifluorene Units.

Polymeric quaterthiophenes containing optically active C2-chiral spirobifluorene skeletons were synthesized as a new type of helical foldamers, and their higher-order structures were investigated. Oxidization of quaterthiophene moieties caused the spacer units to be in planar structure, leading the conformation of the polymer to be a coil-shaped, rigid helix. This transformation was reversibly performed.

The role of carotenoid cleavage dioxygenases in the regulation of carotenoid profiles during maturation in citrus fruit.

To investigate the relationship between a carotenoid profile and gene expression for carotenoid cleavage dioxygenases, three citrus varieties that exhibit different 9-cis-violaxanthin levels in their juice sacs, Satsuma mandarin (Citrus unshiu Marc.; a variety accumulating a low level of 9-cis-violaxanthin), Valencia orange (Citrus sinensis Osbeck; variety accumulating a high level of 9-cis-violaxanthin), and Lisbon lemon (Citrus limon Burm.f.; a variety accumulating an undetectable level of 9-cis-violaxanthin) were used. Three cDNAs (CitCCD1, CitNCED2, and CitNCED3) were cloned. The recombinant CitCCD1 protein cleaved beta-cryptoxanthin, zeaxanthin, and all-trans-violaxanthin at the 9-10 and 9'-10' positions and 9-cis-violaxanthin at the 9'-10' position. The recombinant CitNCED2 and CitNCED3 proteins cleaved 9-cis-violaxanthin at the 11-12 position to form xanthoxin, a precursor of abscisic acid (ABA). The gene expression of CitCCD1 increased in the flavedos and juice sacs of the three varieties during maturation. In Satsuma mandarin, the gene expression of CitNCED2 and CitNCED3 increased noticeably, accompanying a massive accumulation of ABA in the flavedo and juice sacs. In Valencia orange, the gene expression of CitNCED3 increased with a slight elevation of the ABA level in the flavedo, whereas neither the gene expression of CitNCED2 nor the ABA level increased noticeably in the juice sacs. In Lisbon lemon, the gene expression of CitNCED2 increased remarkably, accompanying increases in the ABA level in the flavedo and juice sacs. These results suggest that, in the juice sacs, the efficient cleavage reaction for ABA synthesis reduces the 9-cis-violaxanthin level in Satsuma mandarin and Lisbon lemon, whereas the low cleavage reaction maintains the predominant 9-cis-violaxanthin accumulation in Valencia orange.

Physiological changes in gentian axillary buds during two-step preculturing with sucrose that conferred high levels of tolerance to desiccation and cryopreservation.

BACKGROUND AND AIMS: Induction of dehydration tolerance is a key to achieving high survival rates in cryopreservation of plant specimens. It has been reported previously that two-step preculturing with sucrose effectively increased desiccation tolerance in axillary buds of gentian (Gentiana scabra), which allow the buds to survive cryopreservation. This study is aimed at characterizing each step of this preculturing and to elucidate physiological changes induced during this preculturing. METHODS: In standard two-step preculture, excised gentian axillary buds were incubated for 11 d on MS medium with 0.1 m sucrose at 25 degrees C (first step: mild osmotic stress was given) and the subsequent incubation on MS medium with 0.4 m and 0.7 m sucrose for 1 d each (second step). The levels of abscisic acid (ABA), proline and soluble sugars in gentian buds during the preculture were determined. Effects of various combinations of two-step preculturing and of exogenous ABA and proline were studied. KEY RESULTS: During the first preculture step, there was a transient increase in ABA content peaking on day 4, which declined to a background level at the end of the first and second step preculturing. Proline level increased steadily during the first preculture step and increased further in the second preculture step. Incubating buds with medium containing proline, instead of the two-step preculturing, did not allow them to survive desiccation. Incubating buds with ABA instead of 0.1 m sucrose-preculturing effectively increased desiccation tolerance only when it was followed by the second preculture step. Fluridone, an ABA synthesis inhibitor included in the two-step preculture medium, reduced desiccation tolerance of the buds. The normal first-step preculture increased the levels of soluble sugars 2.4-fold, especially sucrose and raffinose. Buds treated with the second preculture step had greatly increased sucrose levels. CONCLUSIONS: These observations lead to the hypothesis that the first preculture step involves ABA-mediated cellular changes and the second step induces loading of sucrose in the gentian buds.

Irreducible dorsal subluxation of the first metatarsophalangeal joint: a case report.

We report a case of dorsal subluxation of the first metatarsophalangeal joint without dislocation of the sesamoids or destruction of the sesamoid complex. Closed reduction was unsuccessful. At surgery, the subluxation was found to be associated with locking of the abductor hallucis tendon onto the medial condyle of the metatarsal. After restoration of the tendon to its normal anatomic alignment, the joint was successfully reduced. One year after the injury, the patient was asymptomatic and had full range of motion of the metatarsophalangeal joint.