NMR and potentiometric determination of the high pK values and protonation sequence of dipyridino-hexaaza-28-crown-8 and its interactions with selenate,sulfate and nitrate ions in aqueous solution

The aqueous protonation and anion-binding SeO ₂ ^–/4 SO _2– ⁴ , and NO _– ³ ) constants of the macrocyclic polyamine ligand, dipyridino-hexaaza-28-crown-8(L), were measured in 0.1M KCl using a potentiometric titration technique. The protonation sequence of the aza groups of L was studied in D₂O from the chemical shifts of the nonlabile protons so as to find the charge distribution geometry as a function of pD. The study indicates that in 0.1M KC1 fully protonated L forms stable l: 1 complexes with SeO _2– ⁴ (logK=3.68) and SO _2– ⁴ (logK=3.55), but not with NO _– ³ (logK < l.5). All of the amine pK values were above 6.3, thus allowing the use of the protonated form of this ligand over a wide pH range.     

Qualitative properties of pulsating fronts for reaction–advection–diffusion equations in periodic excitable media

In this paper, we study the pulsating fronts of reaction–advection-diffusion equations with two types of nonlinear term in periodic excitable media. Firstly, for the case with combustion nonlinearity, the unique front is proved to decay exponentially when it approaches the unstable limiting state. Secondly, for the degenerate monostable type nonlinearity, it is shown that the front with critical speed is unique, monotone and decays exponentially at negative end, while the fronts of noncritical speeds decay to zero non-exponentially.     

Asymptotic stability of the Degasperis–Procesi antipeakon–peakon profile

The aim of this paper is to prove that the Degasperis–Procesi antipeakon–peakon profile is asymptotically stable for all time. We start by proving the asymptotic stability of a single Degasperis–Procesi peakon and antipeakon with respect to perturbations having a momentum density that is first negative and then positive. Then this result is extended towards a well-ordered trains of antipeakons–peakons under such perturbations. In particular, the asymptotic stability of the antipeakon–peakon profile holds.     

Minimax principles for elliptic mixed hemivariational–variational inequalities

In this paper, minimax principles are explored for elliptic mixed hemivariational–variational inequalities. Under certain conditions, a saddle-point formulation is shown to be equivalent to a mixed hemivariational–variational inequality. While the minimax principle is of independent interest, it is employed in this paper to provide an elementary proof of the solution existence of the mixed hemivariational–variational inequality. Theoretical results are illustrated in the applications of two contact problems.     

Limit cycles of a class of Liénard systems derived from state-dependent impulses

Discontinuous phenomena, in which objects may behave continuously and sometimes discretely are not only found in nature and under laboratory conditions but also in simple, familiar contexts. For example, this phenomenon is skillfully incorporated into the internal structure of mechanical wristwatches. Unless an extremely small amount of state-dependent impulse is applied intermittently, the reciprocating rotational movement of the balance and hairspring, which is the heart of the mechanical wristwatch, cannot be maintained. The small amount of state-dependent impulse, which is often overlooked, can make a significant difference; however, very few studies have examined this subject. This study assumes the underlying cause of discontinuous behaviors as impulses generated when an object reaches a particular state, assuming that the continuous behavior follows the Liénard system, which is widely studied in the field of electrical circuits. The main theorem provides the conditions under which the effect of the impulses causes a stable limit cycle in the Liénard system, even if no limit cycle exists when there are no impulses. The Poincaré–Bendixson theorem for discontinuous dynamical systems and phase plane analysis are used to prove the main theorem. Several examples and their simulations are provided to illustrate the main theorem.     

Synthetic strategies and functional reactivity of versatile thiophene synthons

Abstract

Thiophenes are a highly important group of heterocycles and have been of great interest to researchers due to their various reactivities. Many synthetic strategies are used to generate functionalized thiophene derivatives. Several reactions are described, depending on the reactivity of the substituents attached to the thiophene nucleus toward different nucleophiles to yield the versatile thiophene products. Many diverse applications have been utilized for thiophenes from medicinal chemistry to material science.     

无机纳米管材料合成进展

无机材料的微观结构决定了材料的许多特性,如传输行为、催化活性、分离效率、粘附、储存和释放动力学。具有管状结构纳米尺度的材料由于其特殊的结构及由此带来的特殊性能正成为一个令人兴奋的化学研究领域。文章综述了近年来无机纳米管材料的合成途径和进展。     

CePO_4/Ce-ZrO_2可加工陶瓷性能与断裂机制研究

以Ce ZrO2为基体,通过复合不同加入量的第二相CePO4颗粒,研究了陶瓷材料力学性能的变化,并借助加载能谱仪(EDS)的扫描电子显微镜(SEM)对材料弯曲断口及压痕裂纹扩展方式进行分析。当CePO4加入量为25%时,虽然材料力学性能有一定下降,但已经能用WC刀具进行加工。材料的弯曲断口显示,CePO4在两相体系中的断裂呈层片状形式;加入CePO4后,由于两相之间弱结合界面的存在,压痕裂纹扩展形式发生明显变化,由连续扩展机制过渡为不连续扩展。由这两种机制形成的材料断裂过程是阶段性的,在实际中可以用作材料最终破坏前的预报。     

A Polymeric Iodiplumbate(Ⅱ) Templated by Conjugated Quaternary Ammonium: Synthesis, Band Structure and Optical Properties

A new lead(Ⅱ) iodide coordination polymer [(npq)(PbI3)]n 1 (npq = N-propyl- quinolinium) has been synthesized in the presence of npq as structure-directing reagent (SDA). Compound 1 crystallizes in the orthorhombic system, space group Pbca, with a = 19.158(4), b = 7.9909(16), c = 22.929(5) (A), V = 3510.2(12) (A)3, Z = 8, Dc = 2.877 g/cm3, F(000) = 2672, C12H14I3NPb, Mr = 760.14, μ(MoKα) = 14.872 mm-1, the final R = 0.0431 and wR = 0.1021 for 3678 observed reflections with I＞2σ(I). Structure determination indicates that the [PbI3]-n infinite chains in each unit cell shape the sketch of 1, which could be described as the result of face-sharing distorted PbI6 octahedra running along the b axis. Electrostatic interaction between conjugated organic counter-cations and inorganic moieties presents and contributes to the crystal packing. 1 was further characterized with IR and elemental analysis. Based on the crystal structure data, quantum chemical calculation with DFT method was used to reveal the electronic structure and optical property of 1.     

Electrooxidative C–H thiocyanation of hetarenes: voltammetric assessment of thiocyanogen reactivity

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