Why calcium inhibits magnesium-dependent enzyme phosphoserine phosphatase? A theoretical study

Mechanisms for the formation of the Schiff base from acetaldehyde and butylamine, glycine and phosphatidylethanolamine based on Dmol3/DFT calculations were realized. For the case of phosphatidylethanolamine, calculations were done under periodic boundary conditions, in an amine-phospholipid monolayer model with two molecules of phosphatidylethanolamine by cell. All models contained explicit aqueous solvent. In the three cases, a neutral amino group is used to model the nucleophilic attack on the carbonyl group of acetaldehyde, and water molecules form hydrogen bond networks. These networks were involved in the reactions by performing as proton-transfer carriers, important in some steps of reactions, and stabilizing reaction intermediates. In all the studied reactions, they take place in two steps, namely: (1) formation of a carbinolamine and (2) its dehydration to the Schiff base, being the dehydration the rate-determining step of the process, consistent with available experimental evidence for similar reactions. The main difference between the studied reactions is found in the value for relative free energy for the intermediates and transition states in the second step; these values are lower in the cases of glycine and phosphatidylethanolamine in comparison with butylamine, due the influence of their molecular environments. Based on the results, the aminophospholipid surface environment and carboxylic group of glycine may boost Schiff base formation via a neighboring catalyst effect.     

Optical Properties of Neutral and Charged Low Band Gap Alternating Copolyfluorenes: TD-DFT Investigation

用含时的密度泛函(TD-DFT)方法研究了低带隙的中性和带电的交替共聚芴(Green 1),该化合物是由烷基取代芴和(1,2,5-噻吩基-3,4-硫重氮基)喹喔啉噻吩(T-TDQ-T)单元交替重复组成,对他们的激发态特性用二维(2D)和三维(3D)实空间分析方法做了进一步分析．对于中性的Green 1,分别得到其带隙、键能、激子结合能和核驰豫能．用3D跃迁密度方法对中性和带电的Green 1的跃迁偶极矩进行比较可显示出跃迁偶极矩的取向和强度;用3D电荷差异密度方法显示出激发后的中性和带电的Green 1电荷重新分布和比较,用2D实空间分析方法(跃迁密度矩阵)来研究中性和带电的Green1处于激发态时的电子空穴相干性．中性Green 1的激发态特性分别用TD-DFT和ZINDO两种方法进行了计算,比较得出电子-电子相互作用(在TD-DFT中)对激发态性质的重要影响．     

The isometric extension problem between unit spheres of two separable Banach spaces

In this article, we use some analytic and geometric characters of the smooth points in a sphere to study the isometric extension problem in the separable or reflexive real Banach spaces. We obtain that under some condition the answer to this problem is affirmative.     

Reductions on equivalence relations generated by universal sets

Let X, Y be Polish spaces, , . We say A is universal for Γ provided that each x‐section of A is in Γ and each element of Γ occurs as an x‐section of A. An equivalence relation generated by a set is denoted by , where . The following results are shown:

• (1) If A is a set universal for all nonempty closed subsets of Y, then is a equivalence relation and .
• (2) If A is a set universal for all countable subsets of Y, then is a equivalence relation, and
  • (i) and ;
  • (ii) if , then ;
  • (iii) if every set is Lebesgue measurable or has the Baire property, then .
  • (iv) for , if every set has the Baire property, and E is any equivalence relation, then .

     

Upper Bounds on Liouville First-Passage Percolation and Watabiki's Prediction

Given a planar continuum Gaussian free field h^𝒰 in a domain 𝒰 with Dirichlet boundary condition and any δ > 0, we let be a real-valued smooth Gaussian process where is the average of h^𝒰 along a circle of radius δ with center v. For γ > 0, we study the Liouville first-passage percolation (in scale δ), i.e., the shortest path distance in 𝒰 where the weight of each path P is given by . We show that the distance between two typical points is for all sufficiently small but fixed γ > 0 and some constant c^* > 0. In addition, we obtain similar upper bounds on the Liouville first-passage percolation for discrete Gaussian free fields, as well as the Liouville graph distance, which roughly speaking is the minimal number of euclidean balls with comparable Liouville quantum gravity measure whose union contains a continuous path between two endpoints. Our results contradict some reasonable interpretations of Watabiki's prediction (1993) on the random distance of Liouville quantum gravity at high temperatures.© 2019 Wiley Periodicals, Inc.     

One-Pot Synthesis and Fungicidal Activities of Derivatives of Imidazo [2,1-b]-1,3,4-thiadiazol-5(6H)-one

The isothiocyanates 2, obtained from aza-Wittig reactions of vinyliminophosphoranes 1 with CS ₂ , reacted with hydrazine to give 3-amino-2-thioxo-4-imidazolidinones 4. One-pot reactions of 4, aromatic isocyanates, Ph ₃ P, C ₂ Cl ₆ , and Et ₃ N generated imidazo[2,1-b]-1,3,4-thiadiazol-5(6H)-ones 7. Compound 7 exhibited good fungicidal activities, especially against Sclerotinia sclerotiorum de Bary and Botrytis Cinerea Pers.     

An approach to the Paal–Knorr pyrroles synthesis in the presence of β-cyclodextrin in aqueous media

An efficient and facile method for the synthesis of N-substituted pyrroles in moderate to good yields by the Paal–Knorr reaction of γ-diketones with amines in the presence of β-cyclodextrin in aqueous media has been developed.Moreover,this process tolerated diamines(e.g.,para-,meta- or orthophenylenediamine)to construct bis-pyrrole or mono-pyrrole derivates.β-Cyclodextrin can be recovered easily after the reactions and reused without evident loss in activity.