Melting points and thermal expansivities of proton-disordered hexagonal ice with several model potentials

A method of free energy calculation is proposed, which enables to cover a wide range of pressure and temperature. The free energies of proton-disordered hexagonal ice (ice Ih) and liquid water are calculated for the TIP4P [J. Chem. Phys. 79, 926 (1983)] model and the TIP5P [J. Chem. Phys. 112, 8910 (2000)] model. From the calculated free energy curves, we determine the melting point of the proton-disordered hexagonal ice at 0.1 MPa (atmospheric pressure), 50 MPa, 100 MPa, and 200 MPa. The melting temperatures at atmospheric pressure for the TIP4P ice and the TIP5P ice are found to be about T(m)=229 K and T(m)=268 K, respectively. The melting temperatures decrease as the pressure is increased, a feature consistent with the pressure dependence of the melting point for realistic proton-disordered hexagonal ice. We also calculate the thermal expansivity of the model ices. Negative thermal expansivity is observed at the low temperature region for the TIP4P ice, but not for the TIP5P ice at the ambient pressure.     

一氧化氮选择还原锡锆固溶体催化剂的结构特性

采用双股并流共沉淀方法制备了SnO2含量从10％至90％的锡锆体系DeNOx催化剂,用XRD、微区电子衍射、FT-Raman及FT-IR等技术深入研究了锡锆体系氧化物的结构及其随组成的变化规律.结果表明，由于Sn4＋与Zr4＋离子半径接近,SnO2与ZrO2易于形成固溶体,并随组成变化表现出不同的结构特征.纯ZrO2为单斜相,当少量Sn4＋（SnO2 ≤ 20％）进入ZrO2晶格时形成四方相富锆固溶体,Sn4＋起到稳定ZrO2四方相的作用;随着SnO2含量的增大,结构从无定形或微晶态的富锆固溶体(含SnO2 30～50％)经富锆固溶体与金红石结构的富锡固溶体在55％ SnO2含量的共存状态变化到具有金红石结构的富锡固溶体（SnO2 ≥ 60％）.FT-Raman和FT-IR光谱测试证明,Zr进入SnO2晶格使得Sn－O键的结合减弱,Sn离子上的有效正电荷减小,降低了SnO2对丙烯的燃烧能力,从而提高了对NO的还原活性.     

Hydrogen bonding and π–π stacking in 6‐hydroxy­biochanin A monohydrate

In the lattice of the title compound (systematic name: 5,6,7‐trihydroxy‐4′‐meth­oxy­isoflavone monohydrate), C₁₆H₁₂O₆·H₂O, the isoflavone mol­ecules are linked into chains through R₄³(17) motifs composed via O—H⋯O and C—H⋯O hydrogen bonds. Centrosymmetric R₄²(14) motifs assemble the chains into sheets. Hydrogen‐bonding and aromatic π–π stacking inter­actions lead to the formation of a three‐dimensional network structure.     

Charge-charge and cation-<Emphasis Type="Italic">π</Emphasis> interactions in ligand binding to G protein-coupled receptors

To study the importance of charge–charge and cation-π interactions for the binding of positively charged amine ligands to their receptors, the energies of interaction between [(CH₃)₄–N]⁺, [(CH₃)₃–NH]⁺, and [(CH₃)₄–NH₃]⁺ and acetate, as a model of Asp and Glu, and with benzene, as a model of aromatic side chains, were obtained at the MP2/aug-cc-pVDZ level of theory. The free energies of solvation in water were also calculated for the different amines. It was found that, although primary amines form stronger charge–charge interactions with acetate than tertiary or quaternary amines, the difference is not large enough to compensate their higher solvation energy. Quaternary amines show the weakest interaction with acetate. However, their alkyl groups can interact with various aromatic groups, enhancing ligand binding to the receptor. The analysis was completed with MD calculations on amine binding to the G protein-coupled receptors β₂AR and CCR5. The calculations on the model systems were found to be in good agreement with the simulations of the ligand-receptor complexes. Contribution to the Serafin Fraga Memorial Issue.     

Fragmentation mechanisms of oligodeoxynucleotides: Effects of replacing phosphates with methylphosphonates and thymines with other bases in T-rich sequences

This article reports another step in an ongoing effort to understand the fragmentation of T-rich oligodeoxynucleotides. We extended an earlier investigation of T-rich 4-mers to T-rich 6-mers, 8-mers and 10-mers by using four different tandem mass spectrometric methods. The methods include low-energy collisionally activated decomposition (CAD) of electrospray ionization (ESI)-produced ions, source-CAD of ESI-produced ions, post-source decay (PSD), and CAD of matrix assisted laser desorption ionization (MALDI)-generated ions. The most abundant fragment ions produced from [M - 2H]2- precursors upon low-energy CAD in an ion trap are the [a - B]- and their complementary w ions. The predominant cleavage sites for T-rich oligodeoxynucleotides are always the 3' C-O bonds adjoining a non-T nucleobase (i.e., a base with a higher proton affinity (PA) than that of T). The relative abundance of [a - B]- correlates with the PAs of the nucleobases, underscoring the importance of proton transfer to the base. The propensity to form [a - B]- ions falls in the order of G > C approximately A > T. Structural isomers up to 10-mers can be readily sequenced and distinguished with each of the four tandem mass spectrometric methods applied. The fragmentation of oligodeoxynucleotides in which various phosphates were replaced with methylphosphonate is a measure of the participation of the phosphate proton in the formation of [a - B] ions. For 4 and 5-mers, transfer of an acidic proton from the 5'-phosphate to the departing base is the initiating step in the formation of [a - B]- ions.     

Synthesis of chiral hydroxyl phospholanes from D-mannitol and their use in asymmetric catalytic reactions

Chiral hydroxyl monophosphane 3 [(2S,3S,4S,5S)-3,4-dihydroxy-2, 5-dimethyl-1-phenylphospholane] and bisphospholanes 5a [1,2-bis[(2S, 3S,4S,5S)-3,4-dihydroxy-2,5-dimethylphospholanyl]benzene] and 5b [1, 2-bis[(2S,3S,4S,5S)-2,5-diethyl-3,4-dihydroxyphospholanyl]benzene] were synthesized from readily available D-mannitol in high yields. Strategies for protection and deprotection of OH-groups in the presence of phosphines have been explored. Rate acceleration in the Baylis-Hillman reaction was observed when a hydroxyl phosphine was used as the catalyst. Rhodium complexes with chiral bisphospholanes are highly enantioselective catalysts for the asymmetric hydrogenation of various kinds of functionalized olefins such as dehydroamino acid derivatives, itaconic acid derivatives, and enamides. An interesting feature of the hydroxyl phospholane system is that hydrogenation of some substrates can be carried out in water with >99% ee and 100% conversion (e.g., itaconic acid).     

Synthesis,Separation, and Theoretical Studies of Chiral Biphenyl Lignans (α‐ and β‐DDB)

Two biphenyl lignans, α‐ and β‐DDB ( 1 and 2 , respectively) were efficiently synthesized without contamination by other regio‐isomers. The different yields of the Ullmann coupling reactions for the synthesis of 1 and 2 were rationalized by calculating steric hindrance, stability, entropy change, and heat‐of‐formation values. The enantiomers of 1 and 2 were readily separated by HPLC on a chiral stationary phase. Their configurations were assigned based on the Cotton effect of the authentic natural products.     

Dinuclear and heteropolynuclear complexes containing Mo2(4+) units

The quadruply bonded compound Mo2(DpyF)4 (1), where DpyF- is the anion of N,N'-di(2-pyridyl)formamidine, has been prepared by ligand substitution reactions of Mo2(OOCCF3)4 and either the neutral ligand, HDpyF, at ambient temperature or its lithium salt, LiDpyF, under refluxing conditions. An X-ray structural analysis shows that 1 has a paddlewheel structure with a [symbol: see text] distance of 2.1108(6) A. Reaction of 1 with CoCl2 in methanol produces the paramagnetic compound [Mo2Co(DpyF)4][CoCl4].2MeOH (2). The Co(II) atom in the cation [Mo2Co(DpyF)4]2+ resides on a low-spin hexacoordinate environment (S = 1/2) with a Co...Mo separation of 2.979(6) A, suggesting there is no direct bonding interaction between the Co and Mo atoms. The Mo-Mo distance of 2.1096(5) A is similar to that in 1. Reaction of 1 and CuCl in methanol yields [Mo2Cu4(DpyF)4Cl2][CuCl2]2.2MeOHxEt2O (3). In the cation there are two copper atoms on each side of the Mo2 core. Each is coordinated to two pyridyl nitrogen atoms of the cis DpyF- ligands and loosely bridged to the other by a chloride ion. As a result, the Cu(I) atoms are not aligned with the Mo2 unit. The Cu to Mo separations are in the range 3.003(1)-3.015(1) A, and the Mo-Mo distance of 2.127(1) A is comparable to those in 1 and 2.     

Systems-based design of bi-ligand inhibitors of oxidoreductases: filling the chemical proteomic toolbox

Genomics-driven growth in the number of enzymes of unknown function has created a need for better strategies to characterize them. Since enzyme inhibitors have traditionally served this purpose, we present here an efficient systems-based inhibitor design strategy, enabled by bioinformatic and NMR structural developments. First, we parse the oxidoreductase gene family into structural subfamilies termed pharmacofamilies, which share pharmacophore features in their cofactor binding sites. Then we identify a ligand for this site and use NMR-based binding site mapping (NMR SOLVE) to determine where to extend a combinatorial library, such that diversity elements are directed into the adjacent substrate site. The cofactor mimic is reused in the library in a manner that parallels the reuse of cofactor domains in the oxidoreductase gene family. A library designed in this manner yielded specific inhibitors for multiple oxidoreductases.