低温和低压下水热合成Na4Zr2(SiO4)3

以ZrOCl_2·8H_2O,Na_2SiO_3·9H_2O和NaOH为原料,在250℃约100bar的条件下,水热晶化合成出Na_4Zr_2(SiO_4)_3,并生长相应的单晶。讨论了水热反应及其条件.产物借助于XRD,Raman,~(29)Si MAS NMR以及阻抗谱技术进行了研究.结果表明产物具有与其他方法制备的Na_4Zr_2(SiO_4)_3相同的性质.     

Biradicals/zwitterions from thermolysis of enyne-isocyanates. Application to the synthesis of 2(1H)-pyridones, benzofuro[3,2-c]pyridin-1(2H)-ones, 2,5-dihydro-1H-pyrido[4,3-b]indol-1-ones, and related compounds

Thermolysis of benzannulated enyne-isocyanates 13 and enyne-isocyanates 36 and 37 promoted the cycloaromatization reactions to generate in situ O,4-didehydro-2-hydroxyquinolines and O,4-didehydro-2-hydroxypyridines, respectively, as reactive intermediates. These cycloaromatized intermediates could be captured either as biradicals and/or as zwitterions depending on the nature of the substituent at the alkynyl terminus. The intermediate derived from cycloaromatization of 13a bearing a phenyl substituent could be regarded as biradical 14, which then abstracts hydrogen atoms from gamma-terpinene leading to 2(1H)-quinolinone 15. Alternatively, the same intermediate could also be regarded as zwitterion 14', which then undergoes an initial hydride abstraction from gamma-terpinene followed by protonation to produce 15. The presence of a 2-phenylethyl substituent in 13b and 37a or a 2-methylphenyl substituent in 37b also allowed the resulting intermediates to be captured intramolecularly either as biradicals or as zwitterions, producing 2(1H)-quinolinone 19, 2(1H)-pyridone 39, and benzopyranopyridine 43, respectively. On the other hand, with a 2-methoxyphenyl, a 2-(dimethylamino)phenyl, or a 3-methoxypropyl substituent, the chemical behavior of the cycloaromatized adduct could be best accounted for in terms of a zwitterionic intermediate leading to benzofuro[3,2-c]quinolin-6(5H)-one (20), 5,11-dihydro-11-methyl-6H-indolo[3,2-c]quinolin-6-one (25), benzofuro[3,2-c]pyridin-1(2H)-one 44, 2,5-dihydro-2,5-dimethyl-1H-pyrido[4,3-b]indol-1-one 46, and related compounds. Interestingly, thermolysis of 37f bearing a 2-(methoxymethyl)phenyl substituent at the alkynyl terminus produced the unexpected benzopyranopyridine 56 as the major product in a process involving the cleavage of the bond between the methoxyl oxygen and the adjacent methylene carbon. The efficiency and selectivity of the cycloaromatization reaction could also be enhanced by the introduction of 1.1 to 10 equiv of dimethylphenylsilyl chloride to the reaction mixture to capture the resulting zwitterion.     

Hydrothermal Synthesis and Structural Characterization of a Tubular Arsenic-Vanadate: [CoII(2,2′-bpy)2]2[AsIII8VIV14O42(H2O)]·H2O

The hydrothermal reaction of VOSO₄, As₂O₃, CoC₂O₄·2H₂O and 2,2-bipy yields a novel arsenic-vanadate [Co^II(2,2-bpy)₂]₂[As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O (1), which is characterized by IR, elemental analysis, TGA, magnetic susceptibility and single crystal X-ray diffraction analysis. X-ray diffraction shows that compound 1 is the first example of tubular arsenic–vanadium cluster containing infinite {[Co(2,2-bpy)₂]₂[As₈V₁₄O₄₂(H₂O)]} chain constructed from [As₈V₁₄O₄₂(H₂O)] clusters interconnected through [Co(2,2-bpy)]²⁺ units. Crystal data: 1, orthorhombic, P 2₁2₁2₁, a=12.1401(2) Å, b=15.8722(1) Å, c=39.9533(5) Å, Z=4.Graphical Abstract: A novel polyoxoarsenicvanadate, [Co^II(2,2-bipy)₂]₂ [As^III₈V^IV ₁₄O₄₂(H₂O)]·H₂O, is depicted along with a tubular hybrid solid with a rhombic tube formed within the chain.     

Highly efficient nitration of phenolic compounds in solid phase or solution using Bi(NO3)3.5H2O as nitrating reagent

[reaction: see text] Bi(NO(3))(3).5H(2)O was used as an efficient nitrating reagent in the nitration of phenolic compounds to give nitrated phenols in good to high yields. The nitration reaction proceeded smoothly by grinding 1 equiv of phenol, 2-methylphenol, 4-methylphenol, or 4-chlorophenol and Bi(NO(3))(3).5H(2)O, and the nitration of other phenolic compounds could be performed in acetone at ambient temperature (22-30 degrees C).     

A Novel Oxidative N-Demethylation of 12-Membered Macrolide with Lead Tetraacetate

Erythromycin has been extensively used in the treatment of bacterial infections for over 50 years1. In addition to the antimicrobial effect, the quite unique antiinflammatory activity of the erythromycin derivatives has attracted much attention as new the…     

Synthesis, Characterization and Conductivity of α-Keggin-type Nanoparticles, Co(en)_3PMo_(12)O_(40)·8H_2O with Optical Activity

IntroductionChirality is ubiquitous in the nature.Chiralcompounds have many applications in the areas ofmedicine,catalysis and materials,etc. Polyox-ometallates are inorganic polymers,which have at-tracted much interest since they have electri-cal[1_ 3 ] ,magnetic[4] ,optical properties[5_ 7] ,andsome characters as liquid crystals[8,9] .In this workwe report theα- Keggin structural polyoxometallatenanoparticles with optical activities.The opticalactivities of the samples are [α]13 D =+ 1 7…     

Ion-induced CO adsorption on polycrystalline nickel. Secondary ion mass spectrometry study

In the process of ion-induced CO adsorption (Ar⁺, 4 keV, 4 A/cm²) on polycrystalline Ni at room temperature and P=(1–40)×10^–6 Pa the emission of Ni⁺, NiCO⁺, CO⁺, NiO⁺ and C⁺ ions is observed. The emission of the last three ions is due to the ion-stimulated dissociation of weakly bound CO state and NiO formation. The weakly bound state is formed owing to surface defects produced by ion bombardment. The cross sections of the ion-induced desorption are 1.8 and 0.8×10^–14 cm², respectively, for weakly bound and strongly bound states.     

Ω型分子筛脱铝的核磁共振研究

在不同投料比（ＳｉＯ２／Ａｌ２Ｏ３＝１３．８，１９及２１）条件下，合成了三种Ω型分子筛原粉．对投料比为１３．８的原粉样品进行了四种不同方式的脱铝处理，即水热、ＳｉＣｌ４、ＥＤＴＡ和（ＮＨ４）２ＳｉＦ６处理，而形成了系列脱铝Ω型分子筛样品．对原粉及其脱铝样品进行了２９Ｓｉ和２７ＡｌＭＡＳＮＭＲ测试，确定出样品骨架硅铝比和铝在两种晶体学不等价Ｔ位上的占据比率，以探索四种脱铝方法的效果．实验结果与分析表明：在所有样品中，铝原子的占据具有择优Ｂ位的倾向；且铝在ＴＡ与ＴＢ位上的占据比率与合成条件有关；四种处理方式对Ω型分子筛的脱铝效果不尽相同．     

Chromatographic studies of corrosion sites in metallic materials

Many types of corrosion phenomena are controlled by the ionic composition of a small volume of solution at the surface. Localized corrosion and atmospheric corrosion are two examples in which < 1 μl of solution can cause dramatic damage. Ion chromatographic (IC) techniques have been used to analyze these solutions in order to gain a better understanding of the mechanisms which govern them. Two examples are presented. The presence of minor alloying elements at localized corrosion sites in two aluminum alloys has been demonstrated, indicating non-stoichiometric dissolution of the alloy during localized corrosion. In addition, IC analysis allowed the determination of the species responsible for the atmospheric corrosion failure of electrical connectors, including their likely origin.     

Simultane Ionen-Chromatographie von Kationen und Anionen mit Komplexonen als Elutionsmittel und selektiver UV-Detektion

Summary The complexones EDTA, DCTA and EGTA were investigated as eluting agents at various pH-values for the simultaneous separation of 9 cations and 6 anions using ion chromatography on a silica gel based anion exchanger (Nucleosil 10-Anion II). 1,2-Diaminocyclohexanetetraacetic acid (DCTA) proved to be the best eluting agent. UV spectrophotometry was used for both direct and indirect detection of the anions and anionic metal complexes and a detailed study was carried out with respect to selectivity of detection. This was facilitated by referring to the UV absorption spectra of the anions and metal complexes involved. By choice of a suitable wavelength between 203 and 270 nm and taking into account pH effects, a number of selective determinations were possible. Examples include Pb and Cu in the presence of excess of Ca and Mg as well as nitrate, nitrite and bromide in a large excess of chloride and sulphate. Some examples of detection limits are (g/l) nitrate 2, Fe(III) 3, Cu 9 and Pb 12 (sample volume 20 l, direct UV-detection). The Chromatographie behaviour of Fe(II) and Fe(III) was studied and discussed. Drinking water was analysed for chloride, nitrate and sulphate as well as Ca and Mg using DCTA in the eluent. Complete analyses can be carried out in less than 15 min.

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Herrn Prof. Dr. R. Neeb zum 60. Geburtstag gewidmet