Creation of Chiral Thixotropic Gels through a Crown–Ammonium Interaction and their Application to a Memory‐Erasing Recycle System

A unique class of oligothiophene‐based organogelator bearing two crown ethers at both ends was synthesized. This compound could gelatinize several organic solvents, forming one‐dimensional fibrous aggregates. From the observation of circular dichroism, it was confirmed that the helical handedness of the fibrous assembly is controllable by the chirality of 1,2bisammonium guests, thus suggesting that one guest molecule bridges two gelator molecules through the crown–ammonium interaction. Interestingly, we have found that such chirality is created by thermal gelation, whereas it disappears by thixotropic gelation. The new finding implies that the present organogel system is applicable as a reversible switching memory device, featuring memory creation by a heat mode and memory erasing by a mechanical mode.     

Synthesis and Self‐Association of Double‐Helical AADD Arrays

The design and syntheses of four self‐complementary oligomers that contain an underlying AADD hydrogen bond sequence are presented, and their self‐association was examined in the solution and solid state. The molecular recognition between the two strands is highly sensitive to substitutions of their component heterocycles. Substitution with electron‐donating and ‐withdrawing groups and the influence of preorganization has a large effect on the overall stabilities of the complexes studied. In particular, a wide range (>10⁵ M ^?1) of stabilities with respect to substitutions at various positions in the AADD oligomers was demonstrated. In the most extreme case, the dimerization constant measured (K_dimer≥4.5×10⁷ M ^?1) is comparable to the most stable homodimers of neutral AADD arrays reported to date.     

Multilayer Films with Nanocontainers: Redox‐Controlled Reversible Encapsulation of Guest Molecules

Stable multilayer films with cucurbit[8]uril have been fabricated on the basis of the alternating layer‐by‐layer assembly of a novel side‐chain pseudopolyrotaxane and a photoreactive polyanion. The as‐prepared multilayer films exhibit good properties as surface‐imprinted multilayers, because cucurbit[8]uril molecules that are locked inside the multilayers can act as nanocontainers with specific binding to certain guest molecules, and the loading and release of the guest is redox‐controllable and reversible.     

Production of palladium nanoparticles supported on multiwalled carbon nanotubes by gamma irradiation

Palladium nanoparticles were produced and supported on multiwalled carbon nanotubes (MWCNT) by gamma irradiation. A solution with a specific ratio of 2:1 of water-isopropanol was prepared and mixed with palladium chloride and the surfactant sodium dodecyl sulfate (SDS). The gamma radiolysis of water ultimately produces Pd metallic particles that serve as nucleation seeds. Isopropanol is used as an ion scavenger to balance the reaction, and the coalescence of the metal nanoparticles was controlled by the addition of SDS as a stabilizer. The size and distribution of nanoparticles on the carbon nanotubes (CNT) were studied at different surfactant concentrations and radiation doses. SEM, STEM and XPS were used for morphological, chemical and structural characterization of the nanostructure. Nanoparticles obtained for doses between 10 and 40 kGy, ranged in size 5-30 nm. The smaller nanoparticles were obtained at the higher doses and vice versa. Histograms of particle size distributions at different doses are presented.     

Growth characteristics of spherical titanium oxide nanoparticles during the rapid gaseous detonation reaction

The nanosize grain growth characteristics of spherical single-crystal titanium oxide (TiO₂) during the rapid gaseous detonation reaction are discussed. Based on the experimental conditions and the Chapman–Jouguet theory, the Kruis model was introduced to simulate the growth characteristics of spherical TiO₂ nanoparticles obtained under high pressure, high temperature and by rapid reaction. The results show that the numerical analysis can satisfactorily predict the growth characteristics of spherical TiO₂ nanoparticles with diameters of 15–300 nm at different affecting factors, such as concentration of particles, reaction temperature and time, which are in agreement with the obtained experimental results. We found that the increase of the gas-phase reaction temperature, time, and particle concentration affects the growth tendency of spherical nanocrystal TiO₂, which provides effective theoretical support for the controllable synthesis of multi-scale nanoparticles.     

Acetalization of poly(vinyl alcohol) by a fatty aldehyde in water medium: Model study,kinetics, and structure analysis

Acid catalyzed poly(vinyl alcohol) (PVA) acetalization was investigated in aqueous medium at 80 °C for a PVA concentration of 8 wt %. The reactant, 10‐undecenal, was composed of a long alkyl chain with a vinyl end group, and the functionalization reaction was studied in heterogeneous media for low reactant concentrations (from 0.33 to 2.0 mol % compared with PVA hydroxyl groups concentration). First, the reaction was scrutinized with pentane‐2,4‐diol, as a model compound of PVA. Besides the expected reaction, the oxidation of the aldehyde into 10‐undecenoic acid in the presence of water was evidenced. This carboxylic acid appeared unreactive toward esterification of pentane‐2,4‐diol and PVA in water. Characterization of acetal stereochemical structure formed on the PVA backbone was performed by NMR spectroscopy in accordance to the model approach. A protocol based on ¹H NMR analysis was developed to quantify grafted aldehyde, residual aldehyde, and created carboxylic acid through direct sampling of the reaction medium. Conversions and reaction rate constants were calculated for pH ranging from 1 to 3. Finally, the acetalization yield was found to be enhanced at low pH and, in such conditions, the oxidation reaction contribution was limited. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 661–671     

福建省首届大学生化学实验邀请赛无机及分析化学实验试题解析

介绍了福建省首届大学生化学实验邀请赛无机及分析化学实验的命题思路、试题原题及评分规则,并对实验中存在的问题及成绩进行了总结分析。