The acidity-enhancing effect of BH(3) in gas-phase phosphineboranes compared to the corresponding free phosphines is enormous, between 13 and 18 orders of magnitude in terms of ionization constants. Thus, the enhancement of the acidity of protic acids by Lewis acids usually observed in solution is also observed in the gas phase. For example, the gas-phase acidities (GA) of MePH(2) and MePH(2)BH(3) differ by about 118 kJ mol(-1) (see picture).The gas-phase acidity of a series of phosphines and their corresponding phosphineborane derivatives was measured by FT-ICR techniques. BH(3) attachment leads to a substantial increase of the intrinsic acidity of the system (from 80 to 110 kJ mol(-1)). This acidity-enhancing effect of BH(3) is enormous, between 13 and 18 orders of magnitude in terms of ionization constants. This indicates that the enhancement of the acidity of protic acids by Lewis acids usually observed in solution also occurs in the gas phase. High-level DFT calculations reveal that this acidity enhancement is essentially due to stronger stabilization of the anion with respect to the neutral species on BH(3) association, due to a stronger electron donor ability of P in the anion and better dispersion of the negative charge in the system when the BH(3) group is present. Our study also shows that deprotonation of ClCH(2)PH(2) and ClCH(2)PH(2)BH(3) is followed by chloride departure. For the latter compound deprotonation at the BH(3) group is found to be more favorable than PH(2) deprotonation, and the subsequent loss of Cl(-) is kinetically favored with respect to loss of Cl(-) in a typical S(N)2 process. Hence, ClCH(2)PH(2)BH(3) is the only phosphineborane adduct included in this study which behaves as a boron acid rather than as a phosphorus acid.

Therapy of neurocysticercosis with cysticidal drugs is frequently complicated by the exacerbation of symptoms that follows the inflammation triggered by the acute destruction of cysticerci. Treatment of such adverse reactions with dexamethasone is highly effective. However, it has been shown that dexamethasone lowers the plasma levels of praziquantel, thus reducing its cysticidal efficacy. We measured plasma levels of albendazole, another strong cysticidal drug, when dexamethasone was given simultaneously. We found that dexamethasone increased the plasma levels of albendazole by about 50% (P less than 0.002); hence, it seems that cysticercosis and the ensuing inflammation can be treated simultaneously with albendazole and dexamethasone without diminishing the efficacy of the cysticidal drug.

Dissolution profiles of four carbamazepine immediate-release generic products (200 mg tablets) and the reference product Tegretol® were evaluated using the USP paddles method and an alternative method with the flow-through cell system, USP Apparatus 4. Under official conditions all products met the Q specification, dissolution profiles of generic products were similar to the dissolution profile of the reference product (f 2 > 50) and model-independent parameters showed non significant differences to the reference product except mean dissolution time for product A (p < 0.05). On the other hand, when the flow-through cell system was used, none of the products met the pharmacopeial specification at 15 min and product A did not reach dissolution criteria at 60 min, dissolution profiles of all generic products were not similar to the reference product profile (f 2 < 50) and all model-independent parameters showed significant differences compared to the reference product (p < 0.05). Weibull's model was more useful for adjusting the dissolution data of all products in both USP apparatuses and Td values showed significant differences compared to the reference product (p < 0.05) when USP Apparatus 4 was used. These results indicate that the proposed method, using the flow-through cell system, is more discriminative in evaluating both, rate and extent of carbamazepine dissolution process from immediate-release generic products.

Gas-phase interactions between Pb(2+) ions and cytosine (C) were studied by combining tandem mass spectrometry, infrared multiple photon dissociation spectroscopy, and density functional theory (DFT) calculations. Both singly and doubly charged complexes were generated by electrospray. The [Pb(C)-H](+) complex was extensively studied, and this study shows that two structures, involving the interaction of the metal with the deprotonated canonical keto-amino tautomer of cytosine, are generated in the gas phase; the prominent structure is the bidentate form involving both the N1 and O2 electronegative centers. The DFT study also points out a significant charge transfer from the nucleobase to the low-lying p orbitals of the metal and a strong polarization of the base upon complexation. The various potential energy surfaces explored to account for the fragmentation observed are consistent with the high abundance of the [PbNH2](+) fragment ion.

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