Advances in Anion Supramolecular Chemistry: From Recognition to Chemical Applications

Since the start of this millennium, remarkable progress in the binding and sensing of anions has been taking place, driven in part by discoveries in the use of hydrogen bonding, as well as the previously under‐exploited anion–π interactions and halogen bonding. However, anion supramolecular chemistry has developed substantially beyond anion recognition, and now encompasses a diverse range of disciplines. Dramatic advance has been made in the anion‐templated synthesis of macrocycles and interlocked molecular architectures, while the study of transmembrane anion transporters has flourished from almost nothing into a rapidly maturing field of research. The supramolecular chemistry of anions has also found real practical use in a variety of applications such as catalysis, ion extraction, and the use of anions as stimuli for responsive chemical systems.     

Sponge Phase Producing Porous CeO2 for Catalytic Oxidation of CO

The aggregation behavior of mixtures of the alkaline amino acid L ‐Arginine (L ‐Arg) and bis(2‐ethylhexyl)phosphoric acid (DEHPA) in water was studied in detail. At a fixed L ‐Arg concentration, a phase sequence of micellar phase (L₁ phase), vesicle phase (L_αv phase), planar lamellar phase (L_αl phase), and sponge phase (L₃ phase) was obtained with increasing DEHPA concentration due to changes in the packing parameter. The phase transition of the lamellar structures was determined by freeze‐fracture TEM and ²H NMR spectroscopy. Rheological measurements reflected the phase transition through significant variations of both the elastic modulus and the viscous modulus. Porous CeO₂ materials were produced by utilizing the L₃ phase as template, and the porous CeO₂ exhibited excellent catalytic oxidation activity toward CO due to its high surface area, which provides more active sites for CO conversion.     

A Study on the Growth of Cr2O3 in Ordered Mesoporous Silica and Its Replication

A systematic study on the growth of Cr₂O₃ in three‐dimensional cubic ordered mesoporous silica (KIT‐6) and its replication through nanocasting is reported. By changing the loading time and amount of precursor, the size and shape of the obtained replica could be controlled to some extent. More interestingly, in contrast to previously published studies, when KIT‐6 with an aging temperature of 100 °C, which has a high degree of interconnectivity, was used as a hard template, a cubic ordered mesoporous Cr₂O₃ replica with an open uncoupled subframework structure and reduced symmetry was obtained. Formation of a replica with different symmetry and uncoupled subframework structure is not only related to the degree of interconnectivity of the parent, but also strongly depends on the type of metal oxide and its growth mechanism in the silica template. Nanocasting of Cr₂O₃ with a low loading results in a replica with monomodal pore size distribution that has same symmetry as the hard template, whereas increasing the loading amount alters the symmetry of the replica and yields a replica with bimodal distribution.     

Polysaccharide‐Based Oleogels Prepared with an Emulsion‐Templated Approach

The preparation and characterization of oleogels structured by using a combination of a surface‐active and a non‐surface‐active polysaccharide through an emulsion‐templated approach is reported. Specifically, the oleogels were prepared by first formulating a concentrated oil‐in‐water emulsion, stabilized with a combination of cellulose derivatives and xanthan gum, followed by the selective evaporation of the continuous water phase to drive the network formation, resulting in an oleogel with a unique microstructure and interesting rheological properties, including a high gel strength, G′>4000 Pa, shear sensitivity, good thixotropic recovery, and good thermostability.     

Interconnected sandwich structure carbon/Si-SiO2/carbon nanospheres composite as high performance anode material for lithium-ion batteries

In the present work,an interconnected sandwich carbon/Si-SiO2/carbon nanospheres composite was prepared by template method and carbon thermal vapor deposition（TVD）.The carbon conductive layer can not only efficiently improve the electronic conductivity of Si-based anode,but also play a key role in alleviating the negative effect from huge volume expansion over discharge/charge of Si-based anode.The resulting material delivered a reversible capacity of 1094 mAh/g,and exhibited excellent cycling stability.It kept a reversible capacity of 1050 mAh/g over 200 cycles with a capacity retention of 96%.     

分子生物学手段检测转Bt基因棉花中Cry杀虫蛋白的定性和定量方法

建立了转Bt基因棉花中Cry杀虫蛋白的提取、样品前处理以及酶联免疫(ELISA)定量分析方法,并使用凝胶电泳、普通聚合酶链式反应(PCR)和实时荧光定量PCR等分子生物学手段对转基因棉花中的Bt基因进行定性和定量检测.所建立的苏云金芽孢杆菌杀虫晶体蛋白(Cry1Ab蛋白和Cry1Ac蛋白)标准曲线线性关系良好,相关系数r2均大于0.999,相对标准偏差RSD均小于2.0%.方法简单、快速、重现性和精密度好,可为农业食品行业和环境领域科研人员提供一种简便快速地从转基因棉花中检测Bt毒蛋白的分析方法.     

基于MCM-41硬模板的镍铁磁性纳米管的合成及其磁性研究

以Si-MCM-41为硬模板,利用介孔材料的吸附作用,将Fe3+和Ni 2+按一定比例定量吸附组装到介孔材料的孔壁上;然后通过程序升温在900℃条件下高温焙烧,并经氢氟酸处理,得到直径大约为3.0nm的中空铁氧体纳米管.分别利用傅立叶变换红外光谱仪、扫描电镜、透射电镜、X射线衍射仪分析了合成材料的结构、组成、形貌;采用振动样品磁强计测定了其磁性能.结果表明,合成的镍铁氧体纳米管具有良好的管状形貌,其结构与分子筛MCM-41的结构相似,并具有良好的磁学性能.这说明MCM-41分子筛孔道结构具有可复制性,本研究可望为制备具有适当长径比的一维纳米磁性材料打下良好基础.     

T-symmetric 40-nucleus silver clusters assembled by hetero-anions

We report two anion-templated Ag₄₀ clusters, [Ag₄₀(E)₄(SO₄){S₂P(OEt)₂}₂₄](PF₆)₆ (E = S, 1 ; Se, 2 ). The anionic templates were generated in situ from the decomposition of dithiophosphate (dtp) ligands. The extrusion of sulfur undergoes disproportionation reactions to generate sulfide and sulfate anions, which provide the source of templates in the subsequent cluster assembly reactions. Two Ag₄₀ clusters display high similarity in their structures. The sulfide (selenide) anions and the central sulfate anion reveal a six-coordinate and a rare dodecametallic dodecaconnective pattern, respectively. Four near-equivalent [Ag₁₀(E){S₂P(OEt)₂}₆]²⁺ motifs were assembled via the connection of central sulfate anion to construct Ag₄₀ clusters. The cluster cation, [Ag₄₀(E)₄(SO₄){S₂P(OEt)₂}₂₄]⁶⁺, displayed in T symmetry, is unprecedented in anion-templated silver clusters.     

一步制备高比表面积介孔Co3O4-CeO2及其表征

以有序介孔二氧化硅KIT-6为硬模板,硝酸钴、硝酸铈为金属源,分别在真空辅助条件和普通搅拌条件下制备了介孔CoCeOx复合氧化物。采用XRD、SEM、TEM、N2吸脱附等技术表征了复合氧化物的物化性质,并评价其氧化甲苯的性能。结果表明,在真空辅助和搅拌条件下制备的CoCeOx氧化物是由Co3O4和CeO2组成的介孔Co3O4-CeO2复合氧化物,其比表面积分别为141和89 m^2·g^-1,平均孔径分别为8.7和9.6 nm。真空辅助纳米复制过程有利于金属盐的前驱体充分填充到模板的孔隙中,去除模板后,可以得到有序的介孔复合金属氧化物。所制备介孔钴铈复合氧化物具有孔道有序性好、比表面积大的特点,在挥发性有机化合物的氧化去除方面具有一定的应用前景。     

含骨架铁ZSM-5的合成及其负载Pt催化剂在正十二烷脱氢反应中的催化性能

采用水热合成法使铁进入分子筛MFI骨架结构,成功合成出含骨架铁的分子筛Na-[Fe]-ZSM-5,并通过离子交换法负载Pt制备脱氢催化剂Pt/Na-[Fe]-ZSM-5。通过正十二烷脱氢反应,研究了该催化剂对长链烷烃脱氢制单烯烃反应的催化性能。采用N2吸附-脱附测试、X射线衍射(XRD)、傅立叶变换红外光谱(FT-IR)、氨气程序升温脱附(NH3-TPD)、吡啶吸附的红外光谱(Py-IR)、CO化学吸附、透射电子显微镜(TEM)等不同方法对催化剂进行了表征。结果表明,通过控制骨架铁含量可调控催化剂表面酸性;含骨架铁的ZSM-5分子筛载体具有抑制负载金属晶粒长大,保持金属高分散度的作用;其负载铂催化剂Pt/Na-[Fe]ZSM-5-50具有表面弱酸中心(0.69 mmol·g^-1)和高分散Pt中心,因而具有良好的长链烷烃脱氢活性、稳定性和单烯烃选择;在转化率稳定在~20%时,TOF为4.56 s^-1,单烯烃选择性为92.7%;在实验范围内,Pt/Na-[Fe]ZSM-5催化剂表面弱酸量和脱氢反应的本征活性(TOF)均随催化剂铁含量的增加而增加。