超临界流体干燥过程的分析

以ZrOCl2•8H2O为原料，采用超临界流体干燥（SCFD）法，在短时间内制备出大孔体积高比表面ZrO2气凝胶超细粉．该法具有良好的稳定性和可靠性．建立了醇凝胶中液相含水量的分析方法，为产品质量控制及确认体系是否处于超临界状态提供了依据．对抽提后的溶剂分析表明，SCFD过程是一物理过程．对水的抽提干燥过程亦进行了初步的理论探讨．     

Determination of stability constants of copper(II) complex of glycine in water + alcohol mixed solvents with ion selective electrode technique

The first stability constants (log beta(1)) of the copper(II) complex of glycine in water and in 13 water + alcohol (isopropanol, tert-butanol, 1,2-propylene glycol and glycerol) solvents have been determined at 25 degrees C and an ionic strength of 0.10, from pH and pCu measurements of cells containing copper(II) ion selective electrode. It has been shown that as the proportion of the alcohol increases, the stability constants become increasing positive in all of the mixed solvents examined. An almost linear relation between log beta(1) and the mole fraction of alcohol was found for the complex in aqueous solutions of isopropanol, tert-butanol and glycerol. The response of the copper(II) ion selective electrode in water and in water + alcohol mixed solvents was also investigated. The advantages of using an ion selective electrode to determine the stability constants in mixed solvents are discussed.     

Sigma-1 Receptor Agonist TS-157 Improves Motor Functional Recovery by Promoting Neurite Outgrowth and pERK in Rats with Focal Cerebral Ischemia

Sigma-1 (σ-1) receptor agonists are considered as potential treatment for stroke. TS-157 is an alkoxyisoxazole-based σ-1 receptor agonist previously discovered in our group. The present study describes TS-157 profile in a battery of tests for cerebral ischemia. Initial evaluation demonstrated the compound’s safety profile and blood–brain barrier permeability, as well as its ability to induce neurite outgrowth in vitro. The neurite outgrowth was shown to be mediated via σ-1 receptor agonism and involves upregulation of ERK phosphorylation (pERK). In particular, TS-157 also significantly accelerated the recovery of motor function in rats with transient middle cerebral artery occlusion (tMCAO). Overall, the results herein support the notion that σ-1 receptor agonists are potential therapeutics for stroke and further animal efficacy studies are warranted.     

TFA-sensitive arylsulfonylthiourea-assisted synthesis of N,N'-substituted guanidines

An efficient synthesis of N,N'-substituted guanidine derivatives was developed via an aromatic sulfonyl-activated thiourea intermediate. The use of certain aromatic sulfonamides, such as PbfNH(2), as the key reagent to incorporate a TFA-labile guanidine protection group greatly facilitates solid-phase synthesis of N,N'-substituted guanidine compounds.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.     

Oligomeric guanidine synthesis assisted by TFA-sensitive arylsulfonylthiourea

Through arylsulfonyl activation of thiourea, efficient synthesis of oligomeric guanidines can be achieved in either solution or solid-phase. Incorporation of TFA-sensitive arylsulfonyl groups, such as Pbf, during the synthesis greatly simplifies deprotection procedures for obtaining the final oligomeric guanidine products.     

Self-assembly of a series of novel metal-organic compounds containing ferrocenecarboxylate components

Using FcCOONa (Fc = (eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) as starting material, we obtained an unprecedented metal-organic coordination polymer containing ferrocenecarboxylate components [[Pb(2)(FcCOO)(eta(2)-FcCOO)(mu(2)-eta(2)-FcCOO)(mu(3)-eta(2)-FcCOO)(CH(3)OH)].1.5CH(3)OH.H(2)O](n) (1), tetramer [Zn(4)(mu(2)-FcCOO)(6)(mu(4)-O)] (2), and coordination polymers [Pb(FcCOO)(mu(2)-FcCOO)(bpe)](n) (3) (bpe = 1,2-bis(4-pyridyl)ethene), [[Zn(FcCOO)(2)(bpt)].2.5H(2)O](n) (4) (bpt = N,N'-bis(3-pyridylmethyl)thiourea), and [Zn(FcCOO)(eta(2)-FcCOO)(bbp)](n) (5) (bbp = 4,4'-trimethylene-dipyridine). Compounds 1 and 2 are formed by ferrocenecarboxylate units coordinating with Pb(II) or Zn(II). In polymer 1, ferrocenecarboxylate units have four kinds of coordinate modes; just these novel coordinate modes lead to the unprecedented one-dimensional polymer where two kinds of rhomboids are arranged alternatively along the chain. Compound 2 is a tetramer, in which a distinct connectivity of the six ferrocene units is established through the four Zn atoms. Compounds 3-5 are obtained by organic ligands bridging Pb(II) or Zn(II), leading to a new type of metal-organic coordination polymer.     

Eu1—xTbxBa2Cu3O7—δ中Tb离子价态的研究

研究了BaTbO_3、Tb_4O_7、TbFeO_3的Tb_(4d)XPS谱,找到了表征Tb~(3+)、Tb~(4+)的特征峰,得出的高、低结合能峰强之比与Tb~(4+)/Tb含量间的依赖关系,可用于确定Eu_(1-x)Tb_xBa_2Cu_3O_(7-δ)中“123”相的Tb离子混合价态,用常压高温烧结法,未能获得纯“123”单相,也不易获得纯利Tb~(3+)价态样品.在Eu_(1-x)Tb_xBa_2Cu_3O_(7-δ)中的Tb以Tb~(3+)、Tb~(4+)混合价态存在;当x=0.3时,Tb~(4+)/Tb=0.61.引入Tb~(4+)后“123”主相Cu(2)-O(2)平面上的O_(2p)空穴数降低,这是Tb~(4+)破坏超导电性的一种可能原因。     

中性芳烃稀土有机配合物的合成、结构及性能研究——Ⅲ.RE(C_6H_6)(AlCl_4)_3C_6H_6(RE=La,Nd)的合成及Nd(C_6H_6)(AlCl_4)_3C_6H_6的晶体结构

将加热活化的AlCl_3与三氯化稀土在苯溶液中反应,合成了2个新的轻稀土中性芳烃配合物RE(C_6H_6)(AlCl_4)_3C_6H_6(RE=La或Nd)。并用元素分析和红外光谱对其进行了表征。测定了含Nd配合物的晶体结构。对2个配合物结构的比较表明,中心金属离子对配合物的结构无明显影响,其键参数的差别主要来自“镧系收缩”。     

2020 Roadmap on two-dimensional nanomaterials for environmental catalysis

This roadmap demonstrates a series of two-dimensional nanomaterials, such as graphene, black phosphorus, oxides, layered double hydroxides, chalcogenides, bismuth-based layered compounds, MXenes, metal organic frameworks, covalent organic frameworks, and others, for environmental catalysis.