How Does Solvation Affect the Binding of Hydrophilic Amino Saccharides to Cucurbit[7]uril with Exceptional Anomeric Selectivity?

Cucurbit[7]uril (CB[7]) is known to bind strongly to hydrophilic amino saccharide guests with exceptional α‐anomer selectivities under aqueous conditions. Single‐crystal X‐ray crystallography and computational methods were used to elucidate the reason behind this interesting phenomenon. The crystal structures of protonated galactosamine (GalN) and glucosamine (GluN) complexes confirm the inclusion of α anomers inside CB[7] and disclose the details of the host–guest binding. Whereas computed gas‐phase structures agree with these crystal structures, gas‐phase binding free energies show preferences for the β‐anomer complexes over their α counterparts, in striking contrast to the experimental results under aqueous conditions. However, when the solvation effect is considered, the binding structures drastically change and the preference for the α anomers is recovered. The α anomers also tend to bind more tightly and leave less space in the CB[7] cavity toward inclusion of only one water molecule, whereas loosely bound β anomers leave more space toward accommodating two water molecules, with markedly different hydrogen‐bonding natures. Surprisingly, entropy seems to contribute significantly to both anomeric discrimination and binding. This suggests that of all the driving factors for the strong complexation of the hydrophilic amino saccharide guests, water mediation plays a crucial role in the anomer discrimination.     

Baeyer–Villiger oxidation of cyclohexanone by molecular oxygen with Fe–Sn–O mixed oxides as catalysts

Fe–Sn–O mixed oxides were synthesized and used as catalysts for Baeyer–Villiger oxidation of cyclohexanone, which showed both high catalytic activity and selectivity. X‐ray powder diffraction and scanning electron microscopy suggested that the Fe–Sn–O catalysts had a tetragonal structure with a grain size of 29.3 nm. An ε‐caprolactone yield as high as 98.8% was obtained in a small‐scale experiment (5 mmol of cyclohexanone). In a scale‐up test (20 mmol of cyclohexanone), the cyclohexanone conversion and ε‐caprolactone yield were 96.7 and 96.5%, respectively. In addition, the catalysts can be reused five times without any major decline in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Large‐Scale Synthesis of Enantiopure Molecular Cages: Chiroptical and Recognition Properties

A convenient and efficient gram‐scale synthesis for enantiopure hemicryptophane–tren (tren=tris(2‐aminoethyl)amine) derivatives has been developed. The four‐step synthesis is based on the optical resolution of a key intermediate, cyclotriveratrylene, for which the energy barrier for racemization has been measured to ensure that no racemization occurs during the two last steps of the synthetic pathway. The assignments of the absolute configurations have been performed by electronic circular dichroism and the enantiopurity was determined by NMR spectroscopy in the presence of enantiopure camphor sulfonic acid. To highlight the interest of such compounds, the recognition of norephedrine neurotransmitter was investigated and showed a remarkable enantioselectivity towards the C₃ symmetrical hosts. Finally, this highly modular synthetic pathway was used to provide eight enantiopure hemicryptophanes with different sizes, shapes, and functionalities. These results underline the high potential of this approach, which could lead to many applications in chiral recognition or asymmetric supramolecular catalysis.     

Molecular dynamic study of dielectric polarization and ferroelectricity in a model polar polymer

Molecular dynamics simulations are used to explore the polarization response of a lamellar crystal consisting of folded chains of a highly simplified model polar polymer. The system is based on a united atom model of polyethylene with constrained bond lengths and bond angles, and it is endowed with artificial partial charges placed on the united atoms to give it a simple polar character. Simulations performed with various temperatures, electric field directions, and electric field application histories reveal a complicated sequence of reorientation processes, including pronounced ferroelectric behavior. The sequence includes a weak, temperature‐independent prompt response, and a slow‐rising delay regime with stretched exponential behavior and thermally‐activated reorientation parameters consistent with trans‐gauche (TG) barrier crossings in the amorphous phase. When the delay regime has progressed sufficiently, a primary large‐amplitude response due to organized rotation of large subsegments in the crystalline phase occurs in a rapid manner that requires relatively few TG barrier crossings. A final, extremely slow rise in residual polarization completes the sequence. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 740–759     

Molecular dynamics simulation of DNA‐directed assembly of nanoparticle superlattices using patterned templates

DNA‐directed assembly is a well developed approach in constructing desired nano‐architectures. On the other hand, E‐beam lithography is widely utilized for high resolution nano‐scale patterning. Recently, a new technique combining these two methods was developed to epitaxially grow DNA‐mediated nanoparticle superlattices on patterned substrates. However, defects are observed in epitaxial layers which restricts this technique from building large‐scale superlattices for real applications. Here we use molecular dynamics simulations to study and predict defect formation on adsorbed superlattice monolayers. We demonstrate that this epitaxial growth is energetically driven by maximizing DNA hybridization between the epitaxial layer and the substrate and that the shape anisotropy of the DNA‐mediated template posts leads to structural defects. We also develop design rules to dramatically reduce defects on epitaxial layers. Ultimately, with the assist of the computational study, this technique will open the door to constructing well‐ordered, three‐dimensional novel nanomaterials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1687–1692     

Highly Selective Zeolite Topologies for Flue Gas Separation

The separation of carbon dioxide from flue gas is essential for the reduction of greenhouse gas emissions. In adsorptive methods, the challenge lies in the choice of suitable porous materials. Among all zeolite topologies, a number of adsorbents with pore dimensions in the range of the guest molecules were identified to allow an excellent separation by diffusion, and MRE and AFO zeolite topologies appear to be the best candidates based on equilibrium adsorption. Also, it was found that the behavior of this gas mixture in DFT and APD zeolites differed from the normal behavior.     

UHMWPE纤维的超临界CO_2辅助渗透预处理研究

利用Minitab软件设计实验,以超高分子量聚乙烯纤维(UHMWPE)为原料,研究了在不同的超临界CO_2流体状态下,处理压力、温度和时间等因素对三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)渗入率的影响,确定了最佳因素设置范围;通过单因子实验优化了超临界CO_2处理工艺,并对经过电子束辐照的UHMWPE纤维凝胶含量和蠕变率进行了测试。研究结果表明:处理温度对TMPTMA的渗入率影响最大,其次为压力,时间的影响最小,确定了最优工艺条件为处理压力25MPa,温度80℃,时间30min;TMPTMA渗入率越高,电子束辐照后UHMWPE纤维的增感辐照交联效应和抗蠕变效果越好。     

CL-20/TNT共晶炸药的分子动力学研究

运用分子动力学(MD)方法,选择凝聚态分子势能优化力场(COMPASS),对六硝基六氮杂异伍兹烷(ε-CL-20)、2,4,6-三硝基甲苯(TNT)晶体及其等摩尔比的CL-20/TNT混合炸药和共晶炸药进行不同温度下恒定粒子数等压等温(NPT)系综模拟研究.结果表明,CL-20/TNT共晶的内聚能密度(CED)和结合能随温度的升高逐渐减小;共晶的CED比混合炸药的大,结合能是混合炸药的2倍多,预示其稳定性明显增强.对相关函数和局部放大结构显示共晶中组分分子间作用主要来自TNT中H和CL-20中O以及CL-20中H和TNT中O之间形成的氢键.通过波动法求得的弹性力学性能结果表明,CL-20/TNT共晶的拉伸模量(E)、体积模量(K)和剪切模量(G)介于ε-CL-20和TNT晶体之间,且随温度的升高而下降,符合一般预期;但共晶炸药的柯西压(C12-C44,Cij弹性系数)、K/G和泊松比(ν)均比其组分炸药ε-CL-20和TNT高得多,预示该共晶具有异常高的延展性和弹性伸长,主要是二组分呈层状交替排列且之间存在较强相互作用所致.