Ab initio calculations are used to provide information on H(3)N...XY...HF triads (X, Y=F, Cl, Br) each having a halogen bond and a hydrogen bond. The investigated triads include H(3)N...Br(2)-HF, H(3)N...Cl(2)...HF, H(3)N...BrCl...HF, H(3)N...BrF...HF, and H(3)N...ClF...HF. To understand the properties of the systems better, the corresponding dyads are also investigated. Molecular geometries, binding energies, and infrared spectra of monomers, dyads, and triads are studied at the MP2 level of theory with the 6-311++G(d,p) basis set. Because the primary aim of this study is to examine cooperative effects, particular attention is given to parameters such as cooperative energies, many-body interaction energies, and cooperativity factors. The cooperative energy ranges from -1.45 to -4.64 kcal mol(-1), the three-body interaction energy from -2.17 to -6.71 kcal mol(-1), and the cooperativity factor from 1.27 to 4.35. These results indicate significant cooperativity between the halogen and hydrogen bonds in these complexes. This cooperativity is much greater than that between hydrogen bonds. The effect of a halogen bond on a hydrogen bond is more pronounced than that of a hydrogen bond on a halogen bond.

An ab initio study of the complexes formed by hypohalous acids (HOX, X = F, Cl and Br) with formaldehyde has been carried out at the MP2/aug-cc-pVTZ computational level. Two minima complexes are found, one with an H...O contact and the other one with an X...O contact. The former is more stable than the latter, and the strength difference between them decreases as the size of the X atom increases. The associated HO and XO bonds undergo a bond lengthening and red shift, whereas a blue shift was observed in the bond of the hypohalous acid not involved in the interaction. The interaction strength and properties in both complexes are analyzed with atoms in molecules (AIM) and natural bond orbital (NBO) theories. The energy decomposition analyses indicate that the contribution from the electrostatic interaction energy is larger in the hydrogen-bonded complexes than that in the halogen-bonded complexes.

The properties and applications of halogen bonds are dependent greatly on their strength. In this paper, we suggested some measures for enhancing the strength of the halogen bond relative to the hydrogen bond in the H(2)CS-HOX (X = F, Cl, and Br) system by means of quantum chemical calculations. It has been shown that with comparison to H(2)CO, the S electron donor in H(2)CS results in a smaller difference in strength for the Cl halogen bond and the corresponding hydrogen bond, and the Br halogen bond is even stronger than the hydrogen bond. The Li atom in LiHCS and methyl group in MeHCS cause an increase in the strength of halogen bonding and hydrogen bonding, but the former makes the halogen bond stronger and the latter makes the hydrogen bond stronger. In solvents, the halogen bond in the Br system is strong enough to compete with the hydrogen bond. The interaction nature and properties in these complexes have been analyzed with the natural bond orbital theory.

In the present paper, a new type of lithium bonding complex HMgHLiX (X = H, OH, F, CCH, CN, and NC) has been predicted and characterized. Their geometries (C(infinityv)) with all real harmonic vibrational frequencies were obtained using the second-order Møller-Plesset perturbation theory (MP2) with 6-311++G(d,p) basis set. For each HMgHLiX complex, a lithium bond is formed between the negatively charged H atom of an HMgH molecule and the positively charged Li atom of an LiX molecule. Due to the formation of the complexes, the Mg-H and Li-H bonds are elongated. Interestingly, the Li-X harmonic vibrational stretching frequency is blueshifted in the HMgHLiX (Y = CCH, CN, and NC) complexes and redshifted in the HMgHLiX (X = H, OH, and F) complexes. The binding energy of this type of lithium bond ranges from 12.18 to 15.96 kcal mol(-1), depending on the chemical environment of the lithium. The nature of lithium-hydride lithium bond has also been analyzed with natural bond orbital (NBO) and atoms in molecules (AIM).

AimsErectile dysfunction (ED) is a major care problem worldwide. Tadalafil and sildenafil are the two most common phosphodiesterase 5 inhibitors used to treat ED. This systematic review and meta-analysis were conducted to directly compare tadalafil with sildenafil for the treatment of ED.MethodsWe designed a strategy for searching the PubMed, Embase, EBSCO, Web of Science and Cochrane library databases; the reference lists of the retrieved studies were also investigated. A literature review was performed to identify all published randomized or non-randomized controlled trials that compared tadalafil with sildenafil for the treatment of ED and to assess the quality of the studies. Two investigators independently and blindly screened the studies for inclusion. The meta-analysis was performed using RevMan 5.0.ResultsA total of 16 trials that compared tadalafil with sildenafil for the treatment of ED were included in the meta-analysis. In the meta-analysis, tadalafil and sildenafil appeared to have similar efficacies and overall adverse event rates. However, compared with sildenafil, tadalafil significantly improved psychological outcomes. Furthermore, the patients and their partners preferred tadalafil over sildenafil, and no significant difference was found in the adherence and persistence rates between tadalafil and sildenafil. Additionally, the myalgia and back pain rates were higher and the flushing rate was lower with tadalafil than with sildenafil.ConclusionTadalafil shares a similar efficacy and safety with sildenafil and significantly improves patients’ sexual confidence. Furthermore, patients and their partners prefer tadalafil to sildenafil. Hence, tadalafil may be a better choice for ED treatment.

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We used two chemical modifiers, tetranitromethane (TNM) and acetic anhydride (Ac(2)O), which specifically target accessible tyrosine and lysine residues, respectively, to modify recombinant Syrian hamster PrP(90-231) [rSHaPrP(90-231)] and SHaPrP 27-30, the proteinase K-resistant core of PrP(Sc) isolated from brain of scrapie-infected Syrian hamsters. Our aim was to find locations of conformational change. Modified proteins were subjected to in-gel proteolytic digestion with trypsin or chymotrypsin and subsequent analysis by mass spectrometry (MALDI-TOF). Several differences in chemical reactivity were observed. With TNM, the most conspicuous reactivity difference seen involves peptide E(221)-R(229) (containing Y(225) and Y(226)), which in rSHaPrP(90-231) was much more extensively modified than in SHaPrP 27-30; peptide H(111)-R(136), containing Y(128), was also more modified in rSHaPrP(90-231). Conversely, peptides Y(149)-R(151), Y(157)-R(164), and R(151)-Y(162) suffered more extensive modification in SHaPrP 27-30. Acetic anhydride modified very extensively peptide G(90)-K(106), containing K(101), K(104), K(106), and the amino terminus, in both rSHaPrP(90-231) and SHaPrP 27-30. These results suggest that (1) SHaPrP 27-30 exhibits important conformational differences in the C-terminal region with respect to rSHaPrP(90-231), resulting in the loss of solvent accessibility of Y(225) and Y(226), very solvent-exposed in the latter conformation; because other results suggest preservation of the two C-terminal helices, this might mean that these are tightly packed in SHaPrP 27-30. (2) On the other hand, tyrosines contained in the stretch spanning approximately Y(149)-R(164) are more accessible in SHaPrP 27-30, suggesting rearrangements in α-helix H1 and the short β-sheet of rSHaPrP(90-231). (3) The amino-terminal region of SHaPrP 27-30 is very accessible. These data should help in the validation and construction of structural models of PrP(Sc).

An ab initio computational study of the regulating function of the methyl group in the strength of the CH...O hydrogen bond (HB) with XCC-H (X = H, CH3, F) as a HB donor and HOY (Y = H, CH3, Cl) as a HB acceptor has been carried out at the MP2/aug-cc-pVDZ and MP2/aug-cc-pVTZ levels. The bond lengths, interaction energies, and stretching frequencies are compared in the gas phase. The results indicate that the methyl substitution of the proton acceptor strengthens the CH...O HB, whereas that of the proton donor weakens the CH...O HB. NBO analysis demonstrates that the methyl group of the proton acceptor is electron-withdrawing and that of the proton donor is electron-donating in the formation of the CH...O HB. The electron-donation of the methyl group in the proton acceptor plays a positive contribution to the formation of the CH...O HB, whereas the electron-withdrawing action of the methyl group in the proton donor plays a negative contribution to the formation of the CH...O HB. The positive contribution of methyl group in the proton acceptor is larger than the negative contribution of methyl group in the proton donor.