Individual differences in the Wegner rebound effect: evidence for a moderator variable in thought rebound following thought suppression.

Wegner, Schneider, Carter, and White in 1987 found that attempts to suppress thoughts of a white bear produced even greater preoccupation with that stimulus--a rebound effect. This effect was investigated in Exp. 1 using both Wegner's white bear stimulus and a more personally meaningful stimulus (an upcoming test). The rebound effect was not observed with either stimulus. Exp. 2 was conducted to examine the hypothesis that this failure to replicate Wegner, et al.'s rebound effect reflected individual differences in the respective subject pools. A within-subjects design was used to classify subjects as rebounders or nonrebounders by comparing each subject's expression of a thought following suppression to their own baseline expression of that thought. Subjects classified as rebounders had significantly higher ACT Mathematics subtest scores than did the subjects classified as nonrebounders. This suggests that there is a moderator variable related to mathematics ability for the rebound effect.

UV filters for hair protection.

Synopsis Hair damage, caused by sunlight, and the possibility to protect hair against sunlight by means of cosmetic formulations was studied. For this, five UV-filters were tested: benzophenone-3 (UV-A/UV-B); benzophenone-4 (UV-A/UV-B); phenylbenzimidazole sulfonic acid (UV-B); butylmethoxydibenzoylmethane (UV-A); octyl dimethyl PABA (UV-B). The stability of the UV-filters was tested as pure substances as well as in two cosmetic formulations: a setting lotion and a shine spray. The degree of decolouration and stress strain behaviour were determined. The benzophenones had the best protection ability both on colour and on morphology. Stability data and UV-spectra are discussed.

Nucleosides. 114. 5'-O-Glucuronides of 5-fluorouridine and 5-fluorocytidine. Masked precursors of anticancer nucleosides.

5'-O-Glucuronides of anticancer nucleosides, 5-fluorouridine and 5-fluorocytidine, were synthesized by three different methods. The best preparative procedure was the one starting from benzyl 5-O-(methyl 2', 3', 4'-tri-O-acetyl-beta-D-glucopyranosyluronate)-2,3-O-isopropylidene-beta-D-ribof uranoside (15) that was obtained almost quantitatively by condensation of benzyl 2,3-O-isopropylidene-beta-D-ribofuranoside (8) with methyl (2,3,4-tri-O-acetyl-alpha-D-glucopyranosyl bromide)uronate (2). After de-O-isopropylidenation of 15, the crystalline product, benzyl 5-O-(methyl 2', 3', 4'-tri-O-acetyl-beta-D-glucopyranosyluronate)-beta-D-ribofuranoside (16), was de-O-benzylated catalytically to 5-O-(methyl 2', 3', 4'-tri-O-acetyl-beta-glucopyranosyluronate)-D-ribofuranose (17). Compound 17 was acetylated to crystalline 5-O-(methyl 2',3',4'-tri-O-acteyl-beta-D-glucopyranosyluronate)-1,2,3-tri-O-acetyl-beta-D-ribofuranose (18) and condensed with trimethylsilylated 5-fluorouracil of 5-fluorocytosine in the presence of SnCl4 to afford the corresponding protected nucleosides 5 and 19 in good yields. Saponification of these compounds gave 5'-O-beta-D-glucuronides of 5-fluorouridine and 5-fluorocytidine (20 and 21) isolated as their crystalline N salts. These glucuronides were substrates of both bacterial and bovine beta-glucuronidase. They were, as expected, much less toxic against several leukemia cell lines in tissue culture.

Nucleosides. 116. 1-(beta-D-Xylofuranosyl)-5-fluorocytosines with a leaving group on the 3' position. Potential double-barreled masked precursors of anticancer nucleosides.

Syntheses of five pairs of cytosine and 5-fluorocytosinexylofuranosyl nucleosides in which the 3'-hydroxyl group is replaced by Cl, Br, OMs, or OTs are described. Those xylosyl nucleosides with a good leaving group at the 3' position exhibit good inhibitory activity against L5178Y and P815 mouse leukemic cells in vitro at rather low concentrations, and like that of ara-C this cytotoxicity is reversed by 2'-deoxycytidine but not by thymidine. Xylosylcytosines are not active against ara-C resistant lines of L5178Y and P815 cells; however, the corresponding 5-fluorocytosine analogues exhibit significant cytotoxicity against these ara-C resistant leukemic cell lines, and this activity is reversed by thmidine but not by deoxycytidine. These data support the "double-barreled" masked precursor hypothesis in that xylosyl-5-fluorocytosines substituted at the 3' position by a good leaving group exhibit activity akin to that of ara-C in the ara-C sensitive lines, while these nucleosides act as 5-fluoropyrimidines in the ara-C resistant lines.

Nucleosides. 102. Synthesis of some 3'-deoxy-3'-substituted arabinofuranosylpyrimidine nucleosides.

The synthesis of some 3'-deoxy-3'-substituted arabinofuranosylcytosine (4a-d) and uracil (7a-d, 8a-d, X =Br, I, N3, SCN) nucleosides was accomplished by treatment of the requisite 2',3'-anhydrolyxofuranosylpyrimidine nucleoside (5,6a,b) with the appropriate ammonium salt in refluxing ethanol. Cleavage of the oxirane ring provided the desired 3'-deoxy-3'-substituted pyrimidine nucleosides (4a-d, 7a-d, and 8a-d). In vitro screening of compounds 4a-d, and 7a-d, with L5178Y cells in culture showed no significant inhibitory properties.

Acyloxy neighboring-group participation in the acid-catalyzed cleavage of methyl 2,3-anhydro-beta-D-ribofuranoside.

The reaction of methyl 2,3-anhydro-beta-D-ribofuranoside with hydrogen bromide in an acetic acid-acetic anhydride solution leads to the formation of methyl 2,3-di-O-acetyl-5-bromo-5-deoxy-alpha,beta-D-xylofuranoside. Similar treatment of methyl 2,3-anhydro-5-O-benzoyl-beta-D-robofuranoside provided methyl 2-O-acetyl-3-O-benzoyl-5-bromo-5-deoxy-alpha,beta-D-xylofuranosides. The position of halogen substitution was ascertained by hydrogenolysis to the resultant 5-deoxy sugars, which were characterized by their n.m.r. spectra. Confirmation of the structural assignment for methyl 2-O-acetyl-3-O-benzoyl-5-deoxy-alpha,beta-D-xylofuranoside was obtained by synthesis from 1,2-O-isopropylidene-alpha-D-xylofuranose. The formation of the 5-bromo derivatives under the reported conditions probably occurred through the intermediacy of the 3,5-acyloxonium ions. Similar conversions were observed when the starting compound was treated with hydrogen chloride, acetyl bromide, or acetyl chloride in acetic acid-acetic anhydride solutions.

Nucleosides LXXXIX. Synthesis of 1-(2-chloro-2-deoxy-alpha- and -beta-D-arabinofuranosyl)cytosines.

1-(2-Chloro-2-deoxy-beta-D-arabinofuranosyl)cytosine (16) and its alpha anomer (18) were synthesized by direct condensation of 3,5-di-O-acetyl-2-chloro-2-deoxy-alpha-D-arabinofuranosyl bromide with trimethylsilylated N-4-acetylcytosine in the absence of catalyst. A new and convenient method for the synthesis of 1,3,5-tri-O-acetyl-2-chloro-2-deoxy-alpha-D-arabinofuranose from methyl 3,5-di-O-benzyl-alpha,beta-D-ribofuranoside is described.