Predictive factors of biochemical recurrence after radical prostatectomy for high-risk prostate cancer.

OBJECTIVE: To identify risk factors of biochemical recurrence after radical prostatectomy in high-risk patients. METHODS: A total of 191 high-risk prostate cancer patients according to the D'Amico classification treated with radical prostatectomy at a single institution between April 2000 and December 2013 were enrolled. The pathological evaluation including intraductal carcinoma of prostate was reassessed, and the clinical and pathological risk factors of biochemical recurrence were analyzed. RESULTS: The median follow up after radical prostatectomy was 49 months. The 5-year biochemical recurrence-free survival rate after radical prostatectomy in high-risk prostate cancer patients was 41.6%. Initial prostate-specific antigen, pathological Gleason score, seminal vesicle invasion, extraprostatic extension and intraductal carcinoma of the prostate were significantly associated with biochemical recurrence-free survival. The 5-year biochemical recurrence-free survival rates in patients with zero, one, two and three of these risk factors were 92.9%, 70.7%, 38.3% and 28.8%, respectively. In patients with four or more factors, the biochemical recurrence-free survival rate was 6.1% after 18 months. CONCLUSIONS: In D'Amico high-risk patients treated with radical prostatectomy, risk factors for biochemical recurrence can be identified. Patients with fewer risk factors have longer biochemical recurrence-free survival, even among these high-risk cases.

Phase and glass transitions observed by adiabatic calorimetry of host p-tert-butylcalix[4]arene and guest toluene inclusion crystal, suggesting the progress of the combined order-disorder process of the host-guest molecules.

Heat capacities of crystalline p-tert-butylcalix[4]arene·toluene host-guest compound were measured in a temperature range between 3 K and 345 K by adiabatic calorimetry. The crystal showed one second-order phase transition at 256.4 K accompanied by wide heat-capacity tails on both the high and low temperature sides and two first-order phase transitions with heat-capacity peaks at 127 K and 139 K. The total entropy of a sequence of the phase transitions was assessed experimentally to be 47 J K(-1) mol(-1), indicating that the number of allowed distinguishable molecular configurations is over 100 in the high-temperature disordered state. Many such distinguishable configurations are understood to be produced by a special intermolecular interaction of C-H···(π-electron) bonds formed between p-tert-butylcalix[4]arene and toluene molecules, and the transitions were interpreted as originating from orientational order-disorder of both the guest toluene molecule and the tert-butyl groups of host arene in their combination.

Effect of p-tert-butyl group substitution on the quantum tunneling rate in quadruple proton rearrangement of calix[4]arene.

Glass-transition behaviors concerning the quadruple proton/deuteron rearrangements in the crystalline p-tert-butylcalix[4]arene-toluene (BC4A·T) host-guest compound were studied by adiabatic calorimetry. The glass-transition temperatures (Tg's) of the hydrated BC4A·T-h and deuterated BC4A·T-d were found to be around 90 and 181 K, respectively. The difference of 90 K is too big to be recognized as the ordinary isotope effect, which is about 5 K in classical thermal activation processes. The temperature interval over which the enthalpy relaxation effect was observed was beyond 50 K, being too wide, in BC4A·T-h, while it was 20-30 K in BC4A·T-d; the latter is the one ordinarily observed in the classical processes. The associated equilibration rate in BC4A·T-h was evaluated from the enthalpy relaxation curve observed at 62 K to evidence the non-Arrhenius nature of the temperature dependence. The relaxation effect was detected even at 20 K. These are quite the same behaviors as observed in calix[4]arene, and the quantum tunneling rate in the quadruple proton rearrangement was concluded to be only a little affected by the substitution of the tert-butyl group at the para-position of each phenol moiety.

Quantum tunneling in the quadruple proton rearrangement on a hydroxyl hydrogen bond ring in calix[4]arene.

Proton rearrangement rates in hydrogen bond networks are dominated by classical activation and quantum tunneling at higher and lower temperatures, respectively. Calix[4]arene (C4A) has a square-ring network composed of four hydroxyl groups with the O···O length of ~0.265 nm. Calorimetry and dielectric relaxation measurements were applied to determination of the rates in the crystals of C4A and its deuteron analogue (C4A-d). The rearrangement rates in C4A-d exhibited Arrhenius dependence in the measured temperature range. On the other hand, the rates in C4A showed the same dependence as those in C4A-d above 200 K, deviated from this dependence at around 180 K, and became independent of temperature at around 10(-4) s(-1) below 100 K. This evidenced that the tunneling in the quadruple proton rearrangement proceeds at a very slow rate of 10(-4) s(-1). This is the first determination by calorimetry of the proton tunneling rate.