Computational and dynamic NMR investigation of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane

The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by ¹H- and ¹³C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C₂ symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a C_s transition state with a calculated relative free energy of 11.0 kcal mol⁻¹. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol⁻¹ at 298 K.     

Perturbative manifolds and the Noether generators of nth-order Poisson equations

A manifold that contains small perturbations will induce a perturbed partial differential equation. The partial differential equation that we select is the Poisson equation – in order to explore the interplay between the geometry of the manifold and the perturbations. Specifically, we show how the problem of symmetry determination, for higher-order perturbations, can be elegantly expressed via geometric conditions.     

Boundedness of semilinear Duffing equations at resonance in a critical situation

In this paper, we propose a sufficient and necessary condition for the boundedness of all the solutions for the equation $\ddot{x}+n^{2}x+g(x)=p(t)$ with the critical situation that $|{\int }_0^{2\pi }p(t)e^{?int}dt|=2|g(+\infty )?g(?\infty )|$ on g and p, where $n\in {\mathbb{N}}^{+}$, $p(t)$ is periodic and $g(x)$ is bounded.     

Monte Carlo simulation of electric conductivity for pure and doping fullerene (C60)

In this paper, we have used Monte Carlo (MC) method to simulate and study the temperature and doping effects on the electric conductivity of fullerene (C60). The results show that the band gap has reduced by the doping and the charge carrier transport is facilitated from valence band to conduction band by the temperature where is touched a 300 K. In this case, the conductivity reached a value of $4\times {10}^{-7}\text{S}{\text{cm}}^{-1}$. The electric conductivity of C60 can increase by the triphenylmethane dye crystal violet (CV) alkali metal to reach $4\times {10}^{-3}\text{S}{\text{cm}}^{-1}$ at 303 K. Our results of MC simulation have a good agreement with those extracted from literature [10], [33].     

PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Directing-Group-Free C7-Alkylations of N-Alkylindoles Mediated by Cationic Zirconium Complexes: Role of Brønsted Acid for Catalytic Manifold

Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold.     

Et2Zn-mediated stoichiometric C(sp)-H silylation of 1-alkynes and chlorosilanes

A first example of an Et₂Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis.     

Rigidity and flexibility of virtual polytopes

All 3-dimensional convex polytopes are known to be rigid. Still their Minkowski differences (virtual polytopes) can be flexible with any finite freedom degree. We derive some sufficient rigidity conditions for virtual polytopes and present some examples of flexible ones. For example, Bricard's first and second flexible octahedra can be supplied by the structure of a virtual polytope.     

非线性互补问题的一种全局收敛的显式光滑Newton方法

本针对Po函数非线性互补问题，给出了一种显式光滑Newton方法，该方法将光滑参数μ进行显式迭代而不依赖于Newton方向的搜索过程，并在适当的假设条件下，证明了算法的全局收敛性。     

On the Moments of Overflow and Freed Carried Traffic for the GI/M/C/0 System

In circuit-switched networks call streams are characterized by their mean and peakedness (two-moment method). The GI/M/C/0 system is used to model a single link, where the GI-stream is determined by fitting moments appropriately. For the moments of the overflow traffic of a GI/M/C/0 system there are efficient numerical algorithms available. However, for the moments of the freed carried traffic, defined as the moments of a virtual link of infinite capacity to which the process of calls accepted by the link (carried arrival process) is virtually directed and where the virtual calls get fresh exponential i.i.d. holding times, only complex numerical algorithms are available. This is the reason why the concept of the freed carried traffic is not used. The main result of this paper is a numerically stable and efficient algorithm for computing the moments of freed carried traffic, in particular an explicit formula for its peakedness. This result offers a unified handling of both overflow and carried traffics in networks. Furthermore, some refined characteristics for the overflow and freed carried streams are derived.