Two‐Component Supramolecular Gels Derived from Amphiphilic Shape‐Persistent Cyclo[6]aramides for Specific Recognition of Native Arginine

A unique supramolecular two‐component gelation system was constructed from amphiphilic shape‐persistent cyclo[6]aramides and diethylammonium chloride (or triethylammonium chloride). This system has the ability to discriminate native arginine from 19 other amino acids in a specific fashion. Cyclo[6]aramides show preferential binding for the guanidinium residue over ammonium groups. This specificity was confirmed by both experimental results and theoretical simulations. These results demonstrated a new modular displacement strategy, exploring the use of species‐binding hydrogen‐bonded macrocyclic foldamers for the construction of two‐component gelation systems for selective recognition of native amino acids by competitive host–guest interactions. This strategy may be amenable to developing a variety of functional two‐component gelators for specific recognition of various targeted organic molecular species.     

PdII Complexes of [44]‐ and [46]Decaphyrins: The Largest Hückel Aromatic and Antiaromatic,and Möbius Aromatic Macrocycles

Reductive metalation of [44]decaphyrin with [Pd₂(dba)₃] provided a Hückel aromatic [46]decaphyrin Pd^II complex, which was readily oxidized upon treatment with DDQ to produce a Hückel antiaromatic [44]decaphyrin Pd^II complex. In CH₂Cl₂ solution the latter complex underwent slow tautomerization to a Möbius aromatic [44]decaphyrin Pd^II complex which exists as a mixture of conformers in dynamic equilibrium. To the best of our knowledge, these three Pd^II complexes represent the largest Hückel aromatic, Hückel antiaromatic, and Möbius aromatic complexes to date.     

Improving the Alkaline Stability of Imidazolium Cations by Substitution

Imidazolium cations are promising candidates for preparing anion‐exchange membranes because of their good alkaline stability. Substitution of imidazolium cations is an efficient way to improve their alkaline stability. By combining density functional theory calculations with experimental results, it is found that the LUMO energy correlates with the alkaline stability of imidazolium cations. The results indicate that alkyl groups are the most suitable substituents for the N3 position of imidazolium cations, and the LUMO energies of alkyl‐substituted imidazolium cations depend on the electron‐donating effect and the hyperconjugation effect. Comparing 1,2‐dimethylimidazolium cations (1,2‐DMIm⁺) and 1,3‐dimethylimidazolium cations (1,3‐DMIm⁺) with the same substituents reveals that the hyperconjugation effect is more significant in influencing the LUMO energy of 1,3‐DMIms. This investigation reveals that LUMO energy is a helpful aid in predicting the alkaline stability of imidazolium cations.     

Blue Luminescence of Dendrimer‐Encapsulated Gold Nanoclusters

Direct evidence for the blue luminescence of gold nanoclusters encapsulated inside hydroxyl‐terminated polyamidoamine (PAMAM) dendrimers was provided by spectroscopic studies as well as by theoretical calculations. Steady‐state and time‐resolved spectroscopic studies showed that the luminescence of the gold nanoclusters consisted largely of two electronic transitions. Theoretical calculations indicate that the two transitions are attributed to the different sizes of the gold nanoclusters (Au₈ and Au₁₃). The luminescence of the gold nanoclusters was clearly distinguished from that of the dendrimers.     

Combined use of hydroxypropyl‐β‐cyclodextrin and ionic liquids for the simultaneous enantioseparation of four azole antifungals by CE and a study of the synergistic effect

A CE method employing a dual system of hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) and ionic liquids (ILs) has been developed for the simultaneous enantioseparation of four azole antifungals for the first time. In this study, three different types of ILs were employed as modifiers and among them dodecyl trimethyl ammonium chloride was found to be the most effective. The effects of the concentration, cations, and anions of ILs on the enantioseparation were investigated. With the developed dual system, all the enantiomers were well separated in resolutions of 3.8, 3.5, 2.8, and 2.5 for miconazole, econazole, ketoconazole, and itraconazole, respectively. The interactions between dodecyl trimethyl ammonium chloride and HP‐β‐CD were also studied using a neutral polyacrylamide coated capillary and ¹H NMR spectroscopy to further explore the synergistic effect involved. It was found that ILs improved the enantioseparation not only by changing the EOF, but also by interactions with HP‐β‐CD that could change its ability of forming inclusion complex with the enantiomers.     

毛细管气相色谱法测定工作场所空气中3种多环芳烃

采用毛细管气相色谱法测定工作场所空气中3种多环芳烃(萘、萘烷和四氢化萘)的含量。样品采用活性炭管采集,二硫化碳解吸20min,用DB-FFAP毛细管气相色谱柱分离,火焰离子检测器检测。3种多环芳烃在一定的质量浓度范围内与其峰面积呈线性关系,方法的检出限(3S/N)在0.05~0.5 mg·L-1之间。以空白样品为基体进行加标回收试验,所得回收率在89.3%~97.5%之间,测定值的相对标准偏差(n=6)在2.2%~5.4%之间。     

污染物甲胺为电子给体可见光下Pt/ZnIn2S4光催化制氢

用水热法制备了ZnIn2S4固溶体,并通过XRD和UV-vis漫反射光谱进行了表征.研究了一甲胺、二甲胺和三甲胺为给电子体,在Pt/ZnIn2S4上的可见光光催化制氢及自身的降解反应.3种甲胺都能显著提高光催化分解水制氢活性,同时自身得到很好的降解.电子给体的放氢活性顺序为:TMADMAMMA.通过红外衰减全反射(ATR-IR)法检测电子给体在ZnIn2S4表面的吸附行为,吸附强度大小依次为MMADMATMA.光催化活性与分子结构和在催化剂表面的吸附行为有关.3种污染物浓度对放氢活性的影响都符合Langmuir-Hinshelwood动力学模型.讨论了可能的化学反应机理.     

固相萃取-气相色谱法测定饮用水中12种农药

提出了固相萃取-气相色谱法测定饮用水中12种农药残留量的方法。取水样250mL过固相萃取柱,用乙酸乙酯、正己烷各5mL洗脱,经无水硫酸钠脱水,采用DB-5MS毛细管色谱柱分离,电子捕获检测器检测。溴氢菊酯的线性范围为0.05~0.5mg·L-1,其他农药的线性范围均在0.01~0.1mg·L-1。溴氰菊酯的检出限为24.2ng·L-1,其他农药的检出限均低于10ng·L-1。12种农药的加标回收率在70.0%~110%之间,相对标准偏差(n=6)均小于10%。     

Bi_2O_3掺杂对Ag(Nb_(0.8)Ta_(0.2))O_3陶瓷结构和介电性能的影响(英文)

本文研究了Bi2O3掺杂对Ag(Nb0.8Ta0.2)O3陶瓷的结构和介电性能的影响。X射线衍射(XRD)结果表明,Bi2O3的掺杂可以使陶瓷中Ag+被还原并析出,且银析出的量随Bi2O3掺杂量的增加而不断增加,这可能源自于Bi3+对Ag+的取代。在一定范围内增大Bi2O3掺杂量可提高Ag(Nb0.8Ta0.2)O3陶瓷的室温介电常数,降低介电损耗,并使温度系数向负值方向移动。当Bi2O3的掺杂量约为3.5wt%时,样品具有较大的介电常数(ε=672)和较小的介电损耗(tanδ=7.3×10-4)。     

Evidence for a Bulky Unit of a Pillar[5]arene Flipping in the Solid State

It is well known that pillar[5]arenes have two most stable conformations (pS and pR) in their crystal structures. Because of the intramolecular H‐bonding interactions, substituents, temperature, solvent and so on, the rotational behaviors of the phenolic units on pillararenes are also common. This paper showed some other kinds of conformations in the functionalized pillar[5]arenes and gave evidence for a bulky unit (1,4‐methoxycarbonylmethoxybenzene unit) flipping in the solid state. The presence of hydrogen bonding facilitated the intermolecular self‐assembly in terms of energy‐minimized packing in the crystals. Thus, the main driving force for the flipping of this bulky unit might be both the intramolecular hydrogen bonding between the phenolic units on pillararenes and quadrupolar hydrogen bonding between the host and water. This paper helps us to have a better understanding on the conformations of pillar[5]arenes.