Bran is an effective treatment for constipation but its use is often limited by heartburn and bloating. This study examined the effect of fine and coarse bran (15 g) on the gastric emptying and small bowel transit of a 325 kcal rice test meal. Twelve healthy volunteers underwent a three way cross over study, ingesting the technetium-99m labelled rice meal with or without 15 g of indium-l1lm labelled fine or coarse bran, in random order. Serial scintigraphic images were obtained to define gastric emptying and colonic arrival of label. Compared with control values (99 (9) minutes) (mean (SEM)), the time to 50% gastric emptying was significantly delayed by coarse but not fine bran, being 121 (6) and 104 (9) minutes respectively, p<0 05, n=12. Fundal emptying was unchanged but both brans seemed to increase the proportion of isotope in the antrum at 90 minutes. Small bowel transit was slightly faster with both bran types but in this study the difference was not significant. Both the bran and rice labels moved down the gut without significant separation. Fine bran causes less disturbance of gastric physiology than coarse bran.
The first observations of oxidation of palladium(II) by water
are reported. The pallada(II)cyclic complex ion
[Pd(CH2CH2CH2CH2){(pz)3BH}]-
[(pz)3BH = tris
(pyrazol-1-yl)borate)]
is oxidized by water in acetone or tetrahydrofuran to form
Pd(CH2CH2CH2CH2)(OH){(pz)3BH} and hydrogen, and oxidation by hydrogen peroxide gives the same
complex. Oxidation
by halogens results in the formation of
Pd(CH2CH2CH2CH2)(X){(pz)3BH}
(X = Cl, Br, I),
and these complexes, together with the hydroxopalladium(IV)
complex, represent the
first examples of stable dihydrocarbylpalladium(IV) complexes.
The octahedral complex
Pd(CH2CH2CH2CH2)(OH){(pz)3BH}
forms adducts with phenol, 3-methylphenol, and pentafluorophenol with an overall composition of
Pd(CH2CH2CH2CH2)(OH){(pz)3BH}·2ArOH
(5 and 6) and
Pd(CH2CH2CH2CH2)(OH){(pz)3BH}·C6F5OH
(7). Complex hydrogen-bonding
interactions occur in the adducts, consistent with the assignment of
the phenol and
3-methylphenol adducts as hydroxopalladium(IV) complexes and the
pentafluorophenol
adduct as an aquapalladium(IV) complex. Complexes
5 and 6 are considered to contain
the
hydrogen-bonding motifs
H−O(Pd)···HO(Ph)···HOPh and
Ar(H)O···H−O(Pd)···HOAr, respectively, and 7 to contain an aquapalladium(IV) cation
in which both hydrogen atoms of
the aqua ligand act as hydrogen-bond donors to pentafluorophenoxide
ions in a centrosymmetric dimer,
[Pd(CH2CH2CH2CH2)(OH2){(pz)3BH}·C6F5O]2.
The complex ions
[PdMeR{(pz)3BH}]- (R = Me, Ph)
react with water or halogens to form the
PdMe2R{(pz)3BH} and PdIIR species, and in the case of water as the
oxidant, hydrogen is also formed.
These reactions occur via initial oxidation to form undetected
palladium(IV) species,
presumably PdMeR(X){(pz)3BH} (X = OH, Cl,
Br, I), which undergo rapid methyl group
exchange reactions with
[PdMeR{(pz)3BH}]- to form
PdIIR species and
PdMe2R{(pz)3BH}.
The oxidation of palladium(II) by water and the structural
analysis of hydroxo- and
aquapalladium(IV) complexes represent the first examples of
organopalladium(IV) chemistry
in aqueous media.
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