Energetic origin of proton affinity to the air/water interface.

Recent experimental and theoretical studies showed the preference of the hydronium ion for the vapor/water interface. To investigate the mechanism responsible for the surface propensity of this ion, we performed a series of novel quantum chemical simulations combined with the theory of solutions. The solvation free energy of the H(3)O(+) solute placed at the interface was obtained as -97.9 kcal/mol, being more stable by 3.6 kcal/mol than that of the solute embedded in the bulk. Further, we decomposed the solvation free energies into contributions from the water molecules residing in the oxygen and the hydrogen sides of the solute to clarify the origin of the surface preference. When the solute was displaced from the bulk to the interface, it was shown that the free energy contribution from the oxygen side is destabilized by ∼10 kcal/mol because of a reduction of the number of surrounding solvent water molecules. It was observed, however, that the free energy contribution due to the hydrogen side of the solute is unexpectedly stabilizing and surpasses the destabilization in the opposite side. We found that the stabilization in the hydrogen side originates from the solute-solvent interaction in the medium range beyond the nearest neighbor. It was also revealed that the free energy contribution due to the solute's electronic polarization amounts to about the half of the total free energy change associated with the solute displacement from the bulk to the interface.

Endovascular management of ruptured pancreaticoduodenal artery aneurysms associated with celiac axis stenosis.

The purpose of this study was to assess the efficacy of transcatheter arterial embolization for ruptured pancreaticoduodenal artery (PDA) aneurysms associated with celiac axis stenosis (CS). Seven patients (four men and three women; mean age, 64; range, 43-84) were treated with transcatheter arterial embolization between 2002 and 2007. They were analyzed with regard to the clinical presentation, radiological finding, procedure, and outcome. All patients presented with sudden epigastric pain or abdominal discomfort. Contrast-enhanced CT showed a small aneurysm and retroperitoneal hematoma around the pancreatic head in all patients. The aneurysms ranged from 0.3 to 0.9 cm in size. In one patient, two aneurysms were detected. The aneurysms were located in the pancreaticoduodenal artery (n = 5) and the dorsal pancreatic artery (n = 3). Embolization was performed with microcoils in all aneurysms (n = 8). N-Butyl 2-cyanoacrylate (n = 1) and gelatine particle (n = 1) were also used. Complete occlusion was achieved in four patients. In the other three patients, a significantly reduced flow to the aneurysm remained at final angiography. However, these aneurysms were thrombosed on follow-up CT within 2 weeks. And there was no recurrence of the symptoms and bleeding during follow-up (mean, 28 months; range, 5-65 months) in all patients. In conclusion, transcatheter arterial embolization for PDA aneurysms associated with CS is effective. Significant reduction of the flow to the aneurysm at final angiography may be predictive of future thrombosis.

Pulmonary cryptococcosis with a solitary focal ground-glass opacity on high-resolution computed tomography.

We report a 74-year-old woman with cervical cancer who developed pulmonary cryptococcosis which presented as a solitary focal ground-glass opacity (GGO) on high-resolution computed tomography (HRCT). Serial HRCT showed the progression from the GGO to a discrete solid nodule. We hypothesize that the initial GGO may correspond pathologically to partial filling of air spaces with cryptococcal organisms and inflammatory cells. To our knowledge, this is the first report of pulmonary cryptococcosis with a solitary focal GGO on HRCT in the literature.