Preparation and application of trimethylamine amination polychloromethyl styrene nanolatex coated capillary column for the determination of bromate by field‐amplified sample stacking open‐tubular capillary electrochromatography

A new trimethylamine amination polychloromethyl styrene nanolatex (TMAPL) and TMAPL coated capillary column (ccc‐TMAPL) were successfully prepared. The TMAPL coating was characterized with reversed steady EOF values of ca. ?16.8 × 10^?5 cm² V^?1 s^?1. It was applied to establish open‐tubular (OT) CEC and field‐amplified sample stacking (FASS) OT‐CEC methods for the determination of bromate in tap water. Compared to OT‐CEC, the LOD with FASS‐OT‐CEC was improved from 80 to 8 ng/mL. The developed FASS‐OT‐CEC method was practically used for the analysis of bromate in tap water samples with recoveries ranging from 93.6 to 103.5%.     

Gadolinium(III)‐Hydroxy Ladders Trapped in Succinate Frameworks with Optimized Magnetocaloric Effect

Two kinds of inorganic gadolinium(III)‐hydroxy “ladders”, [2×n] and [3×n], were successfully trapped in succinate (suc) coordination polymers, [Gd₂(OH)₂(suc)₂(H₂O)]_n ? 2n H₂O ( 1 ) and [Gd₆(OH)₈(suc)₅(H₂O)₂]_n ? 4n H₂O ( 2 ), respectively. Such coordination polymers could be regarded as alternating inorganic–organic hybrid materials with relatively high density. Magnetic and heat capacity studies reveal a large cryogenic magnetocaloric effect (MCE) in both compounds, namely (ΔH=70 kG) 42.8 J kg^?1 K^?1 for complex 1 and 48.0 J kg^?1 K^?1 for complex 2 . The effect of the high density is evident, which gives very large volumetric MCEs up to 120 and 144 mJ cm^?3 K^?1 for complexes 1 and 2 , respectively.     

Expanded Organic Building Units for the Construction of Highly Porous Metal–Organic Frameworks

Two new organic building units that contain dicarboxylate sites for their self‐assembly with paddlewheel [Cu₂(CO₂)₄] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU‐35 and ZJU‐36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST‐1. Because the organic linkers in ZJU‐35 and ZJU‐36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST‐1 to 14.4 Å in ZJU‐35 and 16.5 Å in ZJU‐36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m² g^?1 for ZJU‐35 and ZJU‐36, respectively. High‐pressure gas‐sorption isotherms indicate that both ZJU‐35 and ZJU‐36 can take up large amounts of CH₄ and CO₂, and are among the few porous MOFs with the highest volumetric storage of CH₄ under 60 bar and CO₂ under 30 bar at room temperature. Their potential for high‐pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU‐35 and ZJU‐36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH₄ under 60 bar and CO₂ under 30 bar at room temperature are those self‐assembled from organic tetra‐ and hexacarboxylates that contain m‐benzenedicarboxylate units with the [Cu₂(CO₂)₄] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self‐assembly with [Cu₂(CO₂)₄] units has provided great promise for the exploration of a large number of new tetra‐ and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future.     

Efficient and Rapid Method for the Oxidation of Electron‐Rich Aromatic Aldehydes to Carboxylic Acids Using Improved Basic Hydrogen Peroxide

An efficient and rapid method for oxidation of electron‐rich aromatic aldehydes to their corresponding carboxylic acids in excellent yields was developed. It is based on the oxidation of methoxy‐substituted benzaldehydes in methanol with an improved aqueous basic hydrogen peroxide system. Benzaldehydes with electron‐withdrawing substituents are oxidized to the corresponding carboxylic acid in excellent yields under mild reaction conditions.     

Facile Preparation and Molecular Structure of a Novel Metacyclophane

Abstract

A novel 1,1,10,10,19,19-hexamethyl-5,14,23-trimethoxy[3.3.3]metacyclophane (2) was prepared in 25% yield by Friedel–Crafts cyclization of 4-(2-methoxyphenyl)-2-methylbutan-2-ol (1) at ? 78 °C using TiCl₄ as Lewis acid catalyst in anhydrous dichloromethane. The structure of cyclophane 2 was determined by single-crystal X-ray diffraction, and the impact of substrate concentration on the yield of macrocycle 2 was also examined. The study on the effect of substituents at the phenyl ring showed that the methoxy group in 1 is crucial for its trimerization to give the hexamethyl[3.3.3]metacyclophane derivative. Demethylation of 2 with BBr₃ gave 1,1,10,10,19,19-hexamethyl-5,14,23-trihydroxy[3.3.3]metacyclophane (4) in 96% yield, and its three hydroxyl groups provide the possible modification sites for further construction of supramolecular assemblies.     

Syntheses of Novel Chiral Calix[4]crown: Lariat Calix[4]-1,3-aza-crowns with Chiral Amino Acid Groups as Branched Chains

The first examples of lariat calix[4]-1,3-aza-crowns with chiral amino acid groups as branched chains (5a and 5b) were designed and synthesized via a 1 + 1 addition reaction of calix[4]-1,3-substituted benzaldehyde derivative (4) and amino acid hydrazide derivatives (3a and 3b) in yields of 70% and 75%, respectively. The preliminary extraction experiments suggested that hosts 5a and 5b possessed good complexation abilities for α-amino acids.      

Stereoselective Synthesis of 1,3-Dienes from Propargylic Alcohols by LiAlH4/AlCl3

Herein we report that LiAlH₄/AlCl₃ is a very efficient reagent for the reductive dehydration of aryl propargylic alcohols in tetrahydrofuran solvent at reflux to give 1,3-dienes with good yields and high E selection. The reaction conditions are mild and easy to operate, and a variety of aryl functional groups, such as bromo, fluoro, butyl, and methoxyl groups, are tolerated. With our protocol, useful (E,E)-1,3-dienes can be synthesized.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

The (100) orientation evolution and temperature-dependent electrical properties of Bi(Zn1/2Ti1/2)O3–PbTiO3 ferroelectric films

The 0.2Bi(Zn_1/2Ti_1/2)O₃–0.8PbTiO₃ (0.2BZT–0.8PT) ferroelectric thin film was successfully fabricated on Pt(111)/Ti/SiO₂/Si substrates by a sol–gel method. The result indicates that the film exhibits the (100) preferred orientation and has a relatively dense and uniform microstructure with a thickness of ~230 nm. The formation mechanism of the oriented films was ascribed to the growth of the (100) oriented PbO layer at ~450 °C during a layer-by-layer crystallization process. Temperature-dependent electrical properties of the 0.2BZT–0.8PT films were investigated, showing that the film has a potential for high temperature applications.     

十三氟辛基修饰的疏水有机-无机杂化二氧化硅膜孔结构、氢气分离及水热稳定性

采用1,2-双（三乙氧基硅基）乙烷（BTESE）和十三氟辛基三乙氧基硅烷（PFOTES）为前驱体,在酸性条件下通过溶胶-凝胶法制备了十三氟辛基修饰的有机-无机杂化SiO₂膜材料。利用接触角测量、红外光谱、动态光散射和N₂吸附等测试技术分别对膜材料的疏水性、溶胶粒径和孔结构进行表征,并深入研究有支撑膜材料的氢气渗透、分离性能以及长期水热稳定性。结果表明,十三氟辛基修饰后的膜材料由亲水性变成了疏水性,当n_PFOTES/n_BTESE=0.6时膜材料对水的接触角达到（110.4±0.4）°,膜材料还保持微孔结构,孔径分布在0.5~0.8nm。氢气在修饰后的膜材料中的输运遵循微孔扩散机理,在300℃时,氢气的渗透率达到8.5×10^-7mol·m^-2·s^-1·Pa^-1,H₂/CO₂,H₂/CO和H₂/SF₆的理想分离系数分别为5.49,5.90和18.36,均高于相应的Knudsen扩散分离因子。在250℃且水蒸气物质的量分数为5%水热环境下陈化250h,氢气渗透率和H₂/CO₂的理想分离系数基本保持不变,膜材料具有良好的水热稳定性。     

MIL-101/P25复合材料的制备及光催化性能

本文采用水热法,将MIL-101负载到预处理过的P25表面,制得MIL-101/P25复合光催化材料,通过X射线衍射（XRD）、傅里叶变换红外（FTIR）、低温N₂物理吸附-脱附（BET）、热重（TG）、场发射透射电镜（FETEM）和光致发光光谱（PL）等对催化剂进行结构表征,同时考察MIL-101及复合材料的稳定性,并且提出协同因子指标来定量评价复合带来的协同效应。结果表明MIL-101呈片状,与P₂₅部分结合。复合后,MIL-101的稳定性得到提高。在适当的配比下,复合具有协同效应,当Cr（NO₃）₃·9H₂O与P25的物质的量之比为1：1时,复合材料对罗丹明B的可见光催化活性最高,协同因子达到1.64。复合材料对无色有机污染物水杨酸同样表现出良好的光催化效果。