二维层状配位聚合物{[Cd(p-CMSP)(Him)(H2O)]·3H2O}n

The novel coordination polymer {[Cd(p-CMSP)(Him)(H₂O)]·3H₂O}_n ( p-CMSP^2-=p-(carboxymethoxy)phenylthioacetate, Him=imidazole) was synthesized by the reaction of Cd(NO3)₂, imidazole and p-(carboxymethoxy)phenylthioacetic acid in an aqueous solution, and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The crystal structure is of monoclinic, space group P2₁/c with a=1.144 0(2) nm, b=1.876 7(4) nm, c=0.877 89(18) nm, β=106.31(3)° and V=1.808 9(7) nm³, Z=4, R=0.023 2, wR=0.051 4. Each Cd(II) atom displays a distorted octahedral coordination geometry, defined by three carboxyl O atoms from different p-CMSP^2- ligands, one S atom from thioether, one N atom from imidazole and one water molecule. Adjacent Cd(II) ions are bridged by p-CMSP^2- groups, resulting in a 2D layer structure. The adjacent Cd…Cd distances are 0.492 7 nm and 1.144 0 nm. Furthermore, such layers are linked through hydrogen bonds to form supramolecular network. CCDC: 269474.     

一维链状的2-氧-1(4H)-吡啶氮乙酸钴配位聚合物{[Co(2-OPA)2(4,4''-bipy)(H2O)2]·6H2O}n的合成、结构及性能研究

由于吡啶氮羧酸及其衍生物具有多种键合模式和广泛的生物学特性,近10年来由其与金属离子所形成的配合物研究已引起了人们的极大关注[1].作为吡啶氮羧酸衍生物之一的2-氧-1(4H)-吡啶氮乙酸,是合成抗生素的重要医药中间体[2],而且同时具有羰基和羧基两个配位活性基团,具有灵活多样的配位方式、可塑性强和空间构型多变等结构特点,从而为构筑具有新颖拓扑网络结构和性能的超分子聚合物体系提供了丰富多彩的识别和组装方式.     

4-溴-2-环戊烯砜酯化衍生物的合成

以3,4-二溴环戊砜(1)为原料, 在无水吡啶作用下发生消除反应, 得到反应中间体4-溴-2-环戊烯砜(2), 再分别与一系列取代苯甲酸盐3a～3c以及茜素黄GG (3d)发生酯化反应, 合成出4种新环戊烯砜衍生物4a～4d, 并用IR, ¹H NMR, MS, 元素分析等表征了它们的结构.     

β-环糊精季铵化的吡啶类离子液体的合成与表征

通过单-6-碘-β-环糊精(mono-6-I-β-CD)与吡啶反应合成吡啶衍生的β-环糊精碘化季铵盐作为中间体,将其与无机银盐(AgBF4,AgPF6)经过阴离子交换合成了两种新型的β-环糊精季铵化的吡啶类离子液体,并通过1HNMR,IR和MS对它们的结构进行了表征.     

Synthesis and Characterization of a One-dimensional Chain Polymer {[Cu(4-CPOA)(3-PyOH)2(H2O)2](H2O}n

A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]·H2O}n (4-CPOA2- = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The complex C19H22N2O10Cu crystallizes in triclinic system, space group P-1with a = 7.672(2), b = 18.490(4), c = 13.271(3) (A), α = 72.81(3), β ＝ 84.64(3), γ = 87.28(3)°, V = 1026.3(4) (A)3, Z = 2, Mr = 501.94, Dc = 1.624 g/cm3, μ = 1.126 mm-1, F(000) = 518, the final R = 0.0580 and wR = 0.1310 for 3364 observed reflections with I > 2σ(I). Each Cu(II) ion is coordinated with two different carboxyl O atoms from two 4-carboxyphenoxyacetate groups, two N atoms from two 3-PyOH ligands and two water molecules, residing in a distorted octahedral environment. Adjacent Cu(II) atoms are linked by bi-monodentate 4-CPOA2- groups into an one-dimensional chain along the b axis. A three-dimensional supramolecular network is constructed by O-H…O hydrogen bonds.     

Self-assembly of a [2]Pseudorotaxane Composed of Cucurbit[6]uril into Linear Pseudopolyrotaxanes by N–H···O, C–H···O and π···π Interactions

The [2]pseudorotaxane of cucurbit[6]uril (Q6) with 1,6-bis(imidazol-1-yl)hexane dihydrobromide was synthesized and its crystal structure was described. The structure of [2]pseudorotaxane was mainly stablized by host–guest C–H···O interactions. Self-assembly of the [2]pseudorotaxane produces infinite one-dimensional chains with intermolecular N–H···O, C–H···O, and π···π interactions; thus, a linear non-covalent pseudopolyrotaxane is formed.     

一维链状4-硝基-3-羧甲基苯异丙酸镉配位聚合物{[Cd(3-CNPP)(Py)3]·2H2O}n的合成、晶体结构及热稳定性研究

A novel one-dimensional coordination polymer, {[Cd(3-CNPP)(Py)₃]·2H₂O}_n (3-CNPP^2-=2-(3-carboxymethyl-4-nitrophenyl)propionate dianion, Py=pyridine) was synthesized and characterized by the element analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in monoclinic system with space group P2₁/ n, a=0.974 81(19) nm, b=1.992 3(4) nm, c=1.459 8(3) nm, β=95.92(3)°, and V=2.820 0(10) nm³ Z=4, R=0.037 3, wR=0.083 8. Each cadmium(Ⅱ) atom is seven-coordinated by four oxygen atoms from two different 3-CNPP^2- groups and three nitrogen atoms from three pyridine ligands, forming a distorted pentagonal bipyramindal coordination geometry. The cadmium(Ⅱ) atoms are bridged by the tetradentate 3-CNPP^2- groups, constructing a one-dimensional zigzag chain structure along c axis. The adjacent distance of Cd…Cd atoms is 0.979 6 nm. The two-dimensional hydrogen-bonding supramolecular network was formed via the hydrogen bond interactions. CCDC: 254257.     

纳米Mn-Zn铁氧体的制备和研究

Nanosize manganese zinc ferrites were fabricated by hydrothermal precipitation route using Fe₂(SO₄)₃, ZnSO₄·7H₂O, MnSO₄·H₂O as material, then some calcinated at 500 ℃ and studied by XRD, TEM, IR and VSM. The results showed that the products were spinel crystal structure and uniformly sized nanoparticles (15～25 nm) with little aggregation. The analysis of IR showed that the superficial water can be eliminated, but that was embedded in crystal lattice can not be removed by calcinating. The effect Zn content x on the lattice (a) of nanosize Mn_1-xZn_xFe₂O₄ was also discussed. The lattice of nanosize Mn_1-xZn_xFe₂O₄ decreases with x increasing; and its value deviated the standard lattice (a₀) of normal size manganese zinc ferrites. A lot of water was absorbed during the hydrothermal process owing to the large surface of nanosize particles. The change of magnetic properties of Mn_xZn_1-xFe₂O₄ with x increasing was studied: nanosize Mn_xZn_1-xFe₂O₄ particles synthesized by us exhibited peculiar magnetic properties curve with Zn content (x) increasing, Superparamagnetic behaviors of the synthesized ZnFe₂O₄ samples were confirmed by magnetic characterization, which can be explained by the difference between the distribution of the metal ions (Mn²⁺, Zn²⁺ and Fe³⁺) among the tetrahedral (A) and the octahedral (B) sites of nanosize ferrite and that of bulk ferrite.     

华泽兰的七个新的倍半萜

Seven new sesquiterpenoids, namely eupatochinilides Ⅰ-Ⅶ （1-7）, together with eight known compounds, euponin （8）, mollisorin A （9）, niveusin B （10）, 8β-（4＇-acetoxy-tiglyloxy）-3β-hydroxy-6Hβ,7Hα-germacra-1（10）E,4E,11（13）-trien-6,12-olide （11）, eupalinifide B （12）, 8β-（4＇-hydroxytigloyloxy）-5-desoxy-8-desacyleuparotin （13）, 3-deacetyeupalinin A （14）, and 15-hydroxyleptocarpin （15）, were isolated from the ethanolic extract of the whole plant of Eupatorium chinense L. Their structures and stereochemistry were established by spectroscopic methods and GIAO based ^13C NMR chemical shift calculations.     

High active amorphous Co(OH)2 nanocages as peroxymonosulfate activator for boosting acetaminophen degradation and DFT calculation

Acetaminophen (ACE) is commonly used in analgesic and antipyretic drug, which is hardly removed by traditional wastewater treatment processes. Herein, amorphous Co(OH)₂ nanocages were explored as peroxymonosulfate (PMS) activator for efficient degradation of ACE. In the presence of amorphous Co(OH)₂ nanocages, 100% of ACE removal was reached within 2 min with a reaction rate constant k₁ = 3.68 min^?1 at optimum pH 5, which was much better than that of crystalline β-Co(OH)₂ and Co₃O₄. Amorphous materials (disorder atom arrangement) with hollow structures possess large specific surface area, more reactive sites, and abundant vacancies structures, which could efficiently facilitate the catalytic redox reactions. The radicals quenching experiment demonstrated that SO₄^? radicals dominated the ACE degradation rather than OH radicals. The mechanism of ACE degradation was elucidated by the analysis of degradation intermediates and theoretical calculation, indicating that the electrophilic SO₄^? and OH tend to attack the atoms of ACE with high Fukui index (f ^?). Our finding highlights the remarkable advantages of amorphous materials as heterogeneous catalysts in sulfate radicals-based AOPs and sheds new lights on water treatment for the degradation of emerging organic contaminants.