Bromination of N-phenyloxypropyl-N'-ethyl-4,4'-bipyridium in cucurbit[8]uril molecular reactor

CB[n](n=6-8) is a family of synthetic macrocyclic host molecules composed of n glycoluril units, which can be employed as molecular reactor. N-phenyloxypropyl-N'-ethyl-4,4'-bipyridium (1) was designed to form a host-guest inclusion complex with CB[n](n=6-8), subsequently, the bromination reaction of 1 and its corresponding inclusion complexes was investigated in this work. In the case of 1/CB[8], the folded including mode is quite helpful to acquire 1-bormination product completely through intramolecular charge transfer (ICT), and CB[8] can provide a safe bromination environment for 1.     

Strukturelle Charakterisierung der Dicyanamid-Komplexe von Kupfer(II), Nickel(II) bzw. Kobalt(II) mit Aminopyridinen

Summary New dicyanamide complexes of the typeM[N(CN)₂]₂ L ₂ (M=Cu or Ni;L=2-, 3-, 4-aminopyridine, 2-amino-5-nitropyridine) and Co[N(CN)₂]₂ (2-amino-5-nitropyridine)₂ were prepared and studied by spectroscopic methods as well as by room-temperature magnetic moments. The results show that the Cu(II) complexes have elongated pseudooctahedral structures while the Ni(II) and Co(II) complexes are octahedral. In most cases the N(CN)₂ groups are in bridging function and through their cyanide nitrogens, or-more rarely-amide and cyanide nitrogens connect the basic structure units into polymeric conglomerates. In the Cu(II) systems exchange coupling is seen from the _eff value or ESR spectrum.

Professor Viktor Gutmann zum 70. Geburtstag gewidmet     

聚甲醛自然老化的SEM研究

对户外曝晒3～36个月的聚甲醛(POM)老化形态进行了研究,讨论了老化层厚度,裂纹宽度、裂纹深度及断口形态与老化时间的关系。结果表明:POM的老化导致了材料内部结构由韧性变成脆性而几乎完全丧失物理机械性能。     

测接触角法确定偶联剂的最佳用量

偶联剂是一类能在无机填料和聚合物基材之间形成“分子桥”、改善两者之间相容性或提高两者之间相互作用能力的化合物。将经偶联剂改性的无机填料填充到聚合物中可以制得成本低、性能好的复合材料。由于偶联剂用量多少将对复合材料的性能产生较大影响,因此建立一种准确、简便地确定偶联剂最佳用量的方法有着十分重要的理论和实际应用意义。     

漆树漆酶的催化氧化作用——Ⅳ.二茂铁及其衍生物的酶促氧化

In phosphate buffer-diethylene glycol monobutyl ether(DGBE), the oxidations of ferrocene and 15 derivatives were investigated in the presence of Rhus vernicifera laccase. The results showed that ferrocene and 11 derivatives can be oxidized. The mechanism of Laccase catalyzed oxidation of ferrocene was put forward.     

The spin delocalization substituent parameter σ˙. 7. Meta-substituent effects on the cyclodimerization of trifluorostyrenes. A test for the σ˙JJ approach

Rate constants (k's) of the thermal cyclodimerization of ten meta-substituted trifluorostyrenes (m-Y-TFS's) have been measured in the temperature range 110–160°C. On the basis of these k's and the σ_mb values derived from ¹⁹F NMR data the spin-delocalization substituent constant σ^˙_m values of these ten meta-substituents have been calculated. The averaged σ^˙_m values are: m-Et, 0.09; m-t-Bu, 0.11; m-F, 0.03; m-Cl,?0.05; m-Br, 0.12: m-CF₃, ?0.07; m-OMe, 0.10; m-NO₂, ?0.002; m-CN, 0.11 and m-CO₂Me, 0.08. Both the smallness of these values and the nonexistence of correlation between Hammett-Type polar σ^X and these σ^˙_m values support our belief that the σ_j?J approach is reliable and trustworthy.     

铽(Ⅲ)-1,4-双(1′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4]体系荧光性质的研究及应用

本文研究了Tb(Ⅲ)-1,4-双(′-苯基-3′-甲基-5′-氧代吡唑-4′-基)丁二酮-[1,4](BPMPBD)-溴化十六烷基三甲胺(CTMAB)体系的荧光性质,探讨了响影体系荧光性质的诸因素,确定了最佳实验条件。该体系中Tb(Ⅲ)浓度以2.0×10~(-5)～1.0×10~(-10)mol/L范围内与其荧光强度呈线性关系,检测限可达到5.0×10~(-11)mol/L。应用于合成样品中微量Tb(Ⅲ)的分析,结果令人满意。     

Chemical Analyses and Antimicrobial Activity of Nine Kinds of Unifloral Chinese Honeys Compared to Manuka Honey (12+ and 20+)

Honey has good antimicrobial properties and can be used for medical treatment. The antimicrobial properties of unifloral honey varieties are different. In this study, we evaluated the antimicrobial and antioxidant activities of nine kinds of Chinese monofloral honeys. In addition, headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) technology was used to detect their volatile components. The relevant results are as follows: 1. The agar diffusion test showed that the diameter of inhibition zone against Staphylococcus aureus of Fennel honey (21.50 ± 0.41 mm), Agastache honey (20.74 ± 0.37 mm), and Pomegranate honey (18.16 ± 0.11 mm) was larger than that of Manuka 12+ honey (14.27 ± 0.10 mm) and Manuka 20+ honey (16.52 ± 0.12 mm). The antimicrobial activity of Chinese honey depends on hydrogen peroxide. 2. The total antioxidant capacity of Fennel honey, Agastache honey, and Pomegranate honey was higher than that of other Chinese honeys. There was a significant positive correlation between the total antioxidant capacity and the total phenol content of Chinese honey (r = 0.958). The correlation coefficient between the chroma value of Chinese honey and the total antioxidant and the diameter of inhibition zone was 0.940 and 0.746, respectively. The analyzed dark honeys had better antimicrobial and antioxidant activities. 3. There were significant differences in volatile components among Fennel honey, Agastache honey, Pomegranate honey, and Manuka honey. Hexanal-D and Heptanol were the characteristic components of Fennel honey and Pomegranate honey, respectively. Ethyl 2-methylbutyrate and 3-methylpentanoic acids were the unique compounds of Agastache honey. The flavor fingerprints of the honey samples from different plants can be successfully built using HS-GC-IMS and principal component analysis (PCA) based on their volatile compounds. Fennel honey, Agastache honey, and Pomegranate honey are Chinese honey varieties with excellent antimicrobial properties, and have the potential to be developed into medical grade honey.     

The atomic-level structure of bandgap engineered double perovskite alloys Cs2AgIn1−xFexCl6

Although lead-free halide double perovskites are considered as promising alternatives to lead halide perovskites for optoelectronic applications, state-of-the-art double perovskites are limited by their large bandgap. The doping/alloying strategy, key to bandgap engineering in traditional semiconductors, has also been employed to tune the bandgap of halide double perovskites. However, this strategy has yet to generate new double perovskites with suitable bandgaps for practical applications, partially due to the lack of fundamental understanding of how the doping/alloying affects the atomic-level structure. Here, we take the benchmark double perovskite Cs₂AgInCl₆ as an example to reveal the atomic-level structure of double perovskite alloys (DPAs) Cs₂AgIn_1−xFe_xCl₆ (x = 0–1) by employing solid-state nuclear magnetic resonance (ssNMR). The presence of paramagnetic alloying ions (e.g. Fe³⁺ in this case) in double perovskites makes it possible to investigate the nuclear relaxation times, providing a straightforward approach to understand the distribution of paramagnetic alloying ions. Our results indicate that paramagnetic Fe³⁺ replaces diamagnetic In³⁺ in the Cs₂AgInCl₆ lattice with the formation of [FeCl₆]³⁻·[AgCl₆]⁵⁻ domains, which show different sizes and distribution modes in different alloying ratios. This work provides new insights into the atomic-level structure of bandgap engineered DPAs, which is of critical significance in developing efficient optoelectronic/spintronic devices.

Through Fe³⁺-alloying, the bandgap of benchmark double perovskite Cs₂AgInCl₆ can be tuned from 2.8 eV to 1.6 eV. The atomic-level structure of Cs₂AgIn_1−xFe_xCl₆ was revealed by solid-state nuclear magnetic resonance (ssNMR).