Shu Yuanjie

Theoretical Investigation of the Relationship between Impact Sensitivity and the Charges of the Nitro Group in Nitro Compounds

ABSTRACT By means of density functional theory (DFT), the general gradient approximation method (GGA), and the Beck LYP hybrid functional and DNP basis set, nitro group Mulliken charges (Q NO 2 ) are calculated and defined to assess and correlate with the impact sensitivities (H 50 ) of nitro compounds: very negative Q NO 2 and high H 50 . By calculating, analyzing, and comparing, we find that Q NO 2 can be regarded as a structural parameter to estimate impact sensitivity and has more availability in almost all nitro compounds in contrast to the length of the C‒NO 2, N‒NO 2 , or O‒NO 2 bond R R ‒ NO 2 , molecular electrostatic potential (V mid ), and oxygen balance (OB). At the same time, it has good reliability and accuracy even though there are some exceptions. According to the data in this paper, the compound may be sensitive (H 50 ≤ 0.4 m) when its nitro group has fewer negative charges than about 0.23.

Theoretical calculation on permeation of gas molecules through crystalline poly (p-xylylene) (PPX) films

Molecular mechanics (MM) and the gradually reduced size (GRS) techniques were used to construct the crystalline poly-p-xylylene (PPX) films, including PPX N, PPX C and PPX D. The corresponding chain-end area of crystalline PPX films provides enough free volumes for adsorbing and transferring gas molecules. Then, the permeable properties of gases were calculated using Grand Canonical Monte Carlo (GCMC), NVT-Molecular Dynamics (MD) and cluster analysis methods. The calculated diffusion coefficients are in the same order of magnitude over a range of temperatures and pressures. And there is no permeation property of gases in the inner part of the crystalline PPX films.

Metallomicellar Catalytic Hydrolysis of NPP by CuIINiII Heterodinuclear Complexes Containing Diamine Groups in Brij35 Micellar Solution

The hydrolysis of p‐nitrophenyl phosphate (NPP) catalyzed by metallomicelles formed from four asymmetry CuIINiII heterodinuclear oxamido‐bridged complexes, whose ligands contain different diamine groups, and nonionic surfactant Brij35 has been investigated quantitatively at the pH range of 6.0–10.5 and 25°C, respectively. The results indicated that the rates of catalytic hydrolysis of NPP by four complexes in Brij35 micellar solution were all largely enhanced under the experimental conditions. The order of effectiveness of the four complexes in Brij35 micellar solutions toward hydrolysis of NPP was found to be: complex I>complex II>complex III>complex IV. The different catalytic function of four complexes may be attributed to the different activation abilities of coordinated water molecules induced by different polarities of ligands, which has been discussed in detail. Meanwhile, kinetic studies show that the active species in the catalytic hydrolysis of NPP may be the aquo‐hydroxy form and that the mechanism of the reaction involves intramolecular nucleophilic attack of the nickel‐bound hydroxide ion on phosphoryl of NPP. The studies suggested that the metallomicelle containing CuIINiII heterodinuclear oxamido‐bridged complexes with two coordinated H2O molecules may be a potential catalyst for the hydrolysis of NPP.

聚醚砜酮及其与ε-CL-20复合体系性能的分子动力学模拟

通过在二氮杂萘酮中引入叠氮基和氨基，设计了一种新型聚醚砜酮（PPESK），并研究了其对六硝基六氮杂异伍兹烷（e-CL-20）稳定性和力学性能的影响。应用COMPASS力场，构建PPESK无定型晶胞并研究了其密度和玻璃化转变温度；对e-CL-20的4个主要生长面与PPESK组成的界面晶体模型进行了分子动力学（MD）模拟，求得PPESK/e-CL-20复合体系的内聚能密度、结合能和力学性能。结果表明，与文献相比，计算所得的PPESK密度和玻璃化温度较为准确；e-CL-20与PPESK的溶度参数差值（Δδ）为8.512（J/cm3）1/2，两者具有一定相容性；PPESK与e-CL-20主要生长面的结合能大小依次为：（0 1 1）>（0 0 2）>（1 0 -1）>（1 1 0），其中（0 1 1）为最大生长面，所占比例为38.2%；4种复合体系的力学系数均大幅度减小，表明PPESK的加入有效降低了e-CL-20的刚性和各向同性，体系塑性增强。