'Magic blue'--subtle reagent for EPR studies on H-abstraction from various substrates.

This paper is an EPR study on the generation of new 'magic blue' (MB) reagent containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide 2 and perfluoro[1-nitroso-1-(2-fluorosulfonyl)ethoxy]ethane 3, both bearing chemically convertible terminal omega-fluorosulfonyl group -SO2F, and its H-abstraction reactions from arylalkanes, alcohols, aldehydes and polymers, leading to a large number of new fluorinated nitroxides (FN).

The antioxidative function of lutein: electron spin resonance studies and chemical detection.

In the present study, both electron spin resonance (ESR) and chemical detection confirmed that lutein [extracted from alfalfa (Medicago sativa L.)], the most abundant xanthophyll in thylakoids of chloroplasts, could serve as an antioxidant to scavenge reactive oxygen species (ROS) in vitro. Lutein exhibited a greater capacity for scavenging hydroxyl (OH·) and superoxide (O2·-) radicals than ß-carotene at the same concentration, whereas the opposite trend was observed in the capacity for scavenging singlet oxygen (1O2). The capacity of lutein for scavenging ROS from high to low is OH· > O2·- > 1O2. We hypothesise that lutein plays an important photoprotective role in scavenging O2·- and OH· under severe stress. This hypothesis is consistent with our previous report that the lut2 (lutein-deficient) Arabidopsis mutant is more susceptible to damage than the npq1 (lutein-replete but violaxanthin de-epoxidase-deficient) Arabidopsis mutant under severe stress during exposure to high light intensity at low temperature (Peng and Gilmore 2003).

Recognition through self-assembly. A quadruply-hydrogen-bonded, strapped porphyrin cleft that binds dipyridyl molecules and a [2]rotaxane.

Quadruply-hydrogen-bonded porphyrin homodimer Zn1.Zn1 has been designed, assembled, and evaluated as a supramolecular cleft-featured receptor for its ability to bind dipyridyl guests in chloroform-d. Monomer Zn1 consists of a 2-ureidopyrimidin-4(1H)-one unit, which was initially reported by Meijer et al., and a zinc porphyrin unit. The zinc porphyrin is strapped with an additional aliphatic chain for controlling the atropisomerization of porphyrin. The 2-ureidopyrimidin-4(1H)-one unit dimerizes exclusively in chloroform even at the dilute concentration of 10(-)(4) M, while the two "strapped" zinc porphyrin units of the homodimer provide additional binding sites for selective guest recognition. (1)H NMR studies indicate that the new homodimer Zn1.Zn1 adopts an S-type conformation due to strong donor-acceptor interaction between the electron-rich porphyrin units and the electron-deficient 2-ureidopyrimidin-4(1H)-one unit. (1)H NMR, UV-vis, and vapor pressure osmometry investigations reveal that Zn1.Zn1 could function as a new generation of assembled supramolecular cleft, to be able to not only efficiently bind linear dipyridyl molecules 14-17, resulting in the formation of stable termolecular complexes, with K(aasoc) values ranging from 3.8 x 10(6) to 8.9 x 10(7) M(-)(1), but also strongly complex a hydrogen-bond-assembled [2]rotaxane, 18, which consists of a rigid fumaramide thread and a pyridine-incorporated tetraamide cyclophane, with K(aasoc) = 1.2 x 10(4) M(-)(1). (1)H NMR competition experiments reveal that complexation to the dipyriyl guests also promotes the stability of the quadruply-hydrogen-bonded dimeric receptor.

Self-assembly of novel [3]- and [2]rotaxanes based on donor-acceptor and hydrogen-bonding interactions. Intensified inter-ring repulsion interaction and shuttling behavior.

Three novel hetero[3]rotaxanes, which comprise one neutral tetraamide cyclophane, one tetracationic cyclophane, and one linear component, have been assembled by utilizing hydrogen-bonding and donor-acceptor interactions, through three neutral [2]rotaxanes as intermediates. Three tetracationic [2]rotaxanes are also prepared for property comparison. For all three linear components, diamide subunits, the hydrogen-bonding templating moieties, are introduced at the center of the molecules, while the electron-rich hydrogquinone subunits, the donor-acceptor interaction templates, are incorporated between the diamides and the triphenylmethyl stoppers. Compared with the reported [3]rotaxanes, the novel hetero[3]rotaxanes exhibit remarkably intensified spatial interaction between the two ring components, which had been proved by (1)H NMR and UV study. For the first time, inter-ring NOEs are observed for interlocked [3]rotaxanes.

Self-Assembling Calix[4]arene [2]Catenanes. Preorganization, Conformation, Selectivity, and Efficiency.

A novel class of preorganized U-shape calix[4]arene clefts, dicationic salts 3a,c,e.2Cl, 3b.2PF(6)(), and 3f.2Br, consisting of one cone calix[4]arene and two bipyridine residues being linked by an aliphatic chain, have been designed and synthesized as precursors for self-assembly of calix[4]arene [2]catenanes by utilizing pi-stacking interactions between the hydroquinone and bipyridinium units. Conformationally flexible 6.2PF(6)() and cone 10.2Cl, whose conformation is fixed by two propyloxy groups on the lower rim, were also prepared in order to explore the effects of conformation and hydrogen bonding of the calix[4]arene moiety on self-assembly. For all reactions, bis-p-phenylene-34-crown ether-10 (11) was employed as the donor component. Alternate cone [2]catenane 13.4Cl is obtained in 8% yield from reaction of ethylene-incorporating 3a.2Cl and 1,4-bis(bromomethyl)benzene (12a). Three cone and one conformationally flexible [2]catenanes were obtained in moderate to good yields from reactions of propylene-incorporating 3b.PF(6)() and 3c.2Cl with 12a, 1,3-bis(bromomethyl)benzene (12b) or 4,4'-(bromomethyl)biphenyl (12c). Both cone and partial cone [2]catenanes were generated in moderate yields from butylene-incorporating 3c.2Cl with four tert-butyl groups on the calix[4]arene moiety and with 12a. In contrast, only cone [2]catenane was obtained from similar tert-butyl-free cleft 3d.2Cl. Cone and conformationally flexible [2]catenanes were obtained in moderate yields, respectively, from the reactions of 3d.2Cl and 3e.2Cl with 12c. No catenanes were isolated from reaction of phenylene-incorporating 3f.2Br or 6.2Cl, whereas reaction of 10.2Cl afforded cone [2]catenane in low yield. It was demonstrated that hydrogen bonding, which may be destroyed after catenation, within the calix[4]arene moiety is crucial for efficient self-assembly of the [2]catenanes. The dynamic (1)H NMR and absorption spectra and luminescent properties of the [2]catenanes were investigated, which reveal that incorporation of calix[4]arene into the tetracationic cyclophane reduces pi-stacking interactions between the donor and acceptor units and catenation has substantial influence on conformational distributions of the calix[4]arene moiety. The results demonstrate the versatility of calix[4]arene derivatives as building blocks in the construction of supramolecular structures.