All patients receiving > 15 Gy to the ovaries developed hormone failure. In one case of a patient receiving an ovarian dose of 15 Gy, hormone failure was not found. In case of pelvic irradiation excluding at least one ovary, approximately half of the patients developed ovarian dysfunction, probably also due to the effects of polychemotherapy.
p-Dioxane is non-polar, hence its rotational constants cannot be determined by microwave rotational coherence spectroscopy (RCS). We perform high-resolution gas-phase rotational spectroscopy of para-dioxane-h and -d using femtosecond time-resolved Raman RCS in a gas cell at T = 293 K and in a pulsed supersonic jet at T∼130 K. The inertial tensor of p-dioxane-h is strongly asymmetric, leading to a large number of asymmetry transients in its RCS spectrum. In contrast, the d-isotopomer is a near-oblate symmetric top that exhibits a much more regular RCS spectrum with few asymmetry transients. Fitting the fs Raman RCS transients of p-dioxane-h to an asymmetric-top model yields the ground-state rotational constants A = 5084.4(5) MHz, B = 4684(1) MHz, C = 2744.7(8) MHz, and (A + B)/2 = 4884.5(7) MHz (±1σ). The analogous values for p-dioxane-d are A = 4083(2) MHz, B = 3925(4) MHz, C = 2347.1(6) MHz, and (A + B)/2 = 4002.4(6) MHz. We determine the molecular structure with a semi-experimental approach involving the highly correlated coupled-cluster singles, doubles and iterated triples method and the cc-pCVXZ basis set series from double- to quadruple-zeta (X = D, T, Q). Combining the calculated vibrationally averaged rotational constants A(X),B(X),C(X) for increasing basis-set size X with non-linear extrapolation to the experimental constants A,B,C allows to determine the equilibrium ground state structure of p-dioxane. For instance, the equilibrium C-C and C-O bond lengths are r(CC) = 1.5135(3) Å and r(CO) = 1.4168(4) Å, and the four axial C-H bond lengths are 0.008 Å longer than the four equatorial ones. The latter is ascribed to the trans-effect (anomeric effect), i.e., the partial delocalization of the electron lone-pairs on the O atoms that are oriented trans, relative to the axial CH bonds.
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