三辛胺分离富集荧光光度法测定废渣中微量铬

本文研究了三辛胺三氯甲烷分离富集，在硫－磷混酸介质中，８－羟基喹啉－５－磺酸荧光光度法测定带钢酸洗废渣中微量铬。方法灵敏简便，准确度高。     

Preparation and chelating properties of polychalcones derived from 8-hydroxyquinoline-5-aldehyde

The polychalcones designated as poly(7-acetyl-8-hydroxyquinoline-5-aldehyde) (PAHQ) were prepared by Friedel-Crafts (F.C.) acetylation of 8-hydroxyquinoline-5-aldehyde (HQA) in nitrobenzene using AlCl₃ as F.C. catalyst. The polycondensation was carried out in a single step and under different experimental conditions. It was shown that the most likely mechanism of the reaction is F. C. acetylation of HQA followed by condensation of the acetyl and aldehyde groups leading to polychalcones. The polychalcone samples, designated as PAHQ, were characterized by determining nitrogen and hydroxy content, by IR spectroscopy, by bromination reactions, by number average molecular weights, by viscometric study, and by thermogravimetry. Polymeric chelates of selected PAHQ polychalcone samples with various metal ions have been prepared and characterized. Ion exchanging properties of PAHQ polychalcones were also studied by employing the batch equilibration method.     

一种新偶氮胂酸型试剂及荧光法测定铍的研究

新试剂７－（２＇－胂酸基－５＇－羧基）苯偶氮－８－羟基喹啉－５－磺酸的基本性能。详细研究了此试剂荧光法测定铍的条件，并用于水及铜中铍的测定。     

Reimer-Tiemann反应合成8-羟基喹啉-7-醛的研究

采用Reimer Tiemann反应合成杂环醛是一种简便易行的方法,在相转移催化剂AOT(2 乙基己基磺酸基琥珀酸钠)存在下,8 羟基喹啉通过Reimer Tiemann反应制备8 羟基喹啉 7 醛,该方法操作简单,收率较高且稳定,尚未见文献报道。     

Lutetium-177 and iodine-131 loaded chelating polymer microparticles intended for radioembolization of liver malignancies

We describe the synthesis, characterization and radiochemical studies on macroporous chelating polymer beads as carriers of beta-emitters lutetium-177 and iodine-131 intended for radioembolization of liver tumors. The starting poly(glycidyl methacrylate-co-ethylene dimethacrylate) (bead size 20–40 μ) was reacted with ammonia or methylamine to introduce primary and secondary amino groups, respectively. The primary amino groups containing polymer was used for the attachment of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) moieties, while quinoline-8-ol or 8-hydroxyquinoline-5-sulfonic acid moieties, respectively, were introduced onto the secondary amino groups containing polymer. All the polymers were labeled quantitatively by lutetium-177 in ammonium acetate buffer, DOTA containing beads however required heating to 80 °C while the quinoline-8-ol or 8-hydroxyquinoline-5-sulfonic acid moieties containing polymers were quantitatively radiolabeled within 1 h at room temperature. The quinoline-8-ol groups containing polymer was radioiodinated in 95% yield by a chloramine method. Both lutetium-177 and iodine-131 radiolabels were stable in an in vitro study in rat blood plasma. Quinoline-8-ol or 8-hydroxyquinoline-5-sulfonic acid moieties are thus more suitable for the radiolabeling of macroporous beads with lutetium-177 for radioembolization purposes than well-established DOTA moieties and in addition, quinoline-8-ol also allows radiolabeling with iodine-131.     

Preparation of cellulose filters with covalently bound dithiocarbamate, 8-hydroxyquinoline,and aminocarboxylic acid functional groups

Filter papers with covalently bound chelating groups are produced with the aim to enrich metal ions simultaneously for measurement by X-ray fluorescence spectrometry. The selectivity of the chelating groups to transition elements is of utmost importance. Some analytically important chelating groups dithiocarbamate-, 8-hydroxyquinoline-derivatives, and aminocarboxylic acid (EDTA analogue) are immobilized on cellulose filter papers. These filters are produced in a flow reactor, filled with commercially prefabricated analytical grade filter papers. They are synthesized in a three-step-reaction. First, an epoxyactivated cellulose is produced which in the second step is converted into an aminocellulose. This aminocellulose is the starting material for the dithiocarbamate-, the 8-hydroxyquinoline, and EDTA-analogue cellulose. The immobilization of 8-hydroxyquinoline or 8-hydroxyquinoline-5-sulfonic acid is accomplished through an aminomethylation. The analytically useful capacity of the various chelating filter papers is for dithiocarbamate, 8-hydroxyquinoline, 8-hydroxyquinoline-5-sulfonic acid, and EDTA-analogue derivatives 600, 700, 400, and 600 μmol/g, respectively.     

The acid catalysed condensation of phenol-4-sulphonic acid with formaldehyde

The reaction products formed when phenol-4-sulphonic acid reacts with formaldehyde have been investigated using ¹H and ¹³C nuclear magnetic resonance. It is shown that the reaction does not proceed readily at high phenol-4-sulphonic acid: formaldehyde ratios. As the ratio is decreased evidence of reaction is observed and further decreases lead to crosslinking. The crosslinking reaction is explained in terms of desulphonation and electrophilic substitution of the sulphonic acid group by a hydroxymethylene carbonium ion.     

对Fe3+和草酸具有荧光“关-开”功能的喹啉衍生物

通过8-羟基喹啉-2-甲醛与水杨酰肼的缩合反应,合成了一种喹啉席夫碱衍生物荧光分子探针(L)。经FT-IR、1H NMR、13C NMR、ESI-MS表征,确定了探针L的分子结构。利用吸收和荧光光谱研究了探针L的识别性能。在DMSO溶液中,探针L与Fe3+能够形成1:1型配合物L-Fe,表观结合常数为4.6 × 104 L/mol。利用该配合物的形成导致的探针荧光猝灭,能够在常见金属离子中高选择性识别Fe3+,检出限为6.8 × 10-8 mol/L。进一步以L-Fe复合物为探针,实现了对草酸的高选择性荧光增强识别,检出限为1.3 × 10-7 mol/L。该方法可用于蔬菜中草酸的检测。     

Studies on the base-catalyzed Solvolysis of Propane-2-sulphonic Acid p-Cresylester

Products of the reaction of propane-2-sulphonic acid p-cresylester with sodium butoxide in butanol are the sodium salt of propan-2-sulphonic acid, di-n-butyl ether, p-cresyl-n-butyl ether and p-cresol. The reaction proceeds via propane-2-sulphonic acid n-butylester which is formed from the starting compound by an elimination-addition (sulphene) mechanism. The elimination step is an E1-cB reaction.     

Comportement électrique des interfaces polyéthylène-métal en liaison avec l'adhésion

Some routes to synthetize covalently bound chelating groups as 8-hydroxyquinoline or 8-hydroxyquinoline-5-sulfonic acid to cellulose are given. The products show a capacity of 500–800 μmol/g, fast kinetics of exchange and good stability against the eluent. The apparent stability constant of the complexes with Zn²⁺ are around 2 · 10⁵ mol^?1 dm³.     

Substitutes for 1-naphthylamine. Part 3-disazo direct dyes with 3-amino-4-methoxyacetanilide and 1-naphthylamine components

A parallel series of dyes using 3-amino-4-methoxy acetanilide and 1-naphthylamine as intermediate components, and 6-(N-phenyl)-amino-1-naphthol-3-sulphonic acid as a coupling component, together with some well known disazo components, have been synthesised and compared in order to identify effective substitutes for 1-naphthylamine.     

Enzyme-catalyzed polymerization of 8-hydroxyquinoline-5-sulfonate by in situ nuclear magnetic resonance spectroscopy

In this report, we describe the use of in situ NMR spectroscopy to elucidate the mechanism of horseradish peroxidase-catalyzed oxidative free-radical coupling of phenols. We demonstrate the potential of the technique for the polymerization of 8-hydroxyquinoline-5-sulfonate (HQS). Based on the structural changes, we establish the involvement of ortho- and para-position protons (to the hydroxyl group) in the oxidative free-radical coupling polymerization with their relative preferences. For example, in HQS, we establish that the positions 2, 4, and 7 are involved in the chemical bonding with the order of preference being 7 ≥ 2 > 4. Analyses of ¹³C-NMR data suggest the formation of C—C- and C—O—C-type coupling bonds during enzymatic polymerization. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1257–1264, 1998     

Substitutes for 1-naphthylamine. Part 1-a comparative study of monoazo anionic dyes from 5-acetaniidoaniline-2-sulphonic acid and 1-naphthylamine

5-Acetamidoaniline-2-sulphonic acid has been evaluated as a substitute for 1-naphthylamine by synthesising and evaluating a parallel series of monoazo dyes derived from both components.     

A novel approach for improving the light fatigue resistance of spiropyrans

Photochromic behaviour is a common characteristic in spiropyrans and spiro-oxazines as well as other photochromic materials. From a commercial point of view, the fatigue resistance of these compounds is the key property that largely determines whether they are likely to find any practical application. Various potential metal complexes were synthesised to improve the light fatigue resistance of spiropyrans. The protective effect of these compounds against the dark or photofading of photocoloured species was examined on the solid state. The zinc or nickel salts of 8-hydroxyquinoline-2-carboxylic acid and its derivatives were found to be very effective in stabilising the coloured form of spiropyran.     

6-羟基-2,3,5-吡啶三甲酸的合成

采用2-羟基-3-喹啉甲醛为原料,以高锰酸钾为氧化剂,水为溶剂,经过氧化、浓缩、浓盐酸酸化、抽滤、干燥,合成了6-羟基-2,3,5-吡啶三甲酸,产率62.2%。     

Limits of Application of the Spectrophotometric Method for the Determination of Association Equilibria: Substituted 4-Phenylazo-1-naphthol-6-Sulphonic Acids*

The equilibrium constants for the dimerization of four 4-(p′-X-phenylazo)-1-naphthol-6-sulphonic acids (X = H, CH₃, n-C₄H₉, NO₂) have been determined in water by evaluation of the visible and ultraviolet spectra. The evaluation is complex owing to superimposed acid-base, tautomeric (i.e. hydroxyazo and quinonehydrazone) and oligomerization (trimers, tetramers etc.) equilibria. These factors make it impossible to obtain meaningful data for equilibrium enthalpies and entropies even when the results are put through an iteration procedure.     

Degradation of polycyclic aromatic hydrocarbons by hydrogen peroxide catalyzed by heterogeneous polymeric metal chelates

Chelating sorbents with 8-hydroxyquinoline (IVa), 8-hydroxyquinoline-5-sulfonic acid (IVb), and tris(2-aminoethyl)amine (VI) ligands immobilized on macroporous methacrylate matrix were prepared and saturated with Co(II), Cu(II), and Fe(II). All these chelates catalyze cleavage of H₂O₂ yielding highly reactive hydroxyl radicals. All were able to degrade by this mechanism polycyclic aromatic hydrocarbons (anthracene, benzo[a]pyrene and benzo[k]fluoranthene). The most effective catalysts IVa-Fe, IVb-Fe, and VI-Cu (25 mg with 100 μmol H₂O₂) performed complete decomposition of 33 μg anthracene and benzo[a]pyrene during one 7-day catalytic cycle at 25 °C. The fastest decomposition proceeded during the 1st day of incubation; 75% of anthracene and 74% of benzo[a]pyrene were decomposed by IVb-Co within the first 24 h. More than 25% decomposition within the 1st day was also achieved with IVb-Fe, VI-Cu, IVa-Cu, and VI-Co for anthracene and more than 30% benzo[a]pyrene was decomposed by IVb-Fe, VI-Cu, IVa-Cu, and IVb-Cu during the same period. 1,4-Anthracenedione was the main product of anthracene oxidation by all catalysts. The catalysts were stable at pH 2–11 depending on their structure and able to perform sequential catalytic cycles without regeneration.     

Water invaded micelles of some liquid cation-exchangers

The liquid ion exchangers 2,6-dinonylnaphthalene-4-sulphonic acid (HD) and corresponding lithium and sodium dinonylnaphthalenesulphonates in solution in n-heptane when equilibrated with an aqueous solution imbibe a considerable amount of water and form hydrous micelles. Further knowledge concerning the nature of the hydration of these micelles has been gleaned from infrared and nmr spectroscopic measurements and from a comparison with structural information for aqueous solutions obtained by neutron diffraction.     

Chelating polymeric particles intended for the therapy of Wilson’s disease

Wilson’s disease is a genetic disorder that leads to a high accumulation of copper in multiple organs with subsequent toxic effects. In this paper, a gentle therapy to eliminate harmful copper concentrations in patients with Wilson’s disease is proposed using an oral administration of insoluble polymeric sorbents containing selective chelating groups for copper(II). The sorbents contained triethylenetetramine, N,N-di(2-pyridylmethyl)amine, 8-hydroxyquinoline or 8-hydroxyquinoline-5-sulfonic acid chelating groups bound to a methacrylate-based macroporous support. Nearly quantitative copper(II) uptake within minutes was achieved in buffers modeling the pH range present in the gastric environment (pH 2.0 and 4.0). The sorbents demonstrated chelating selectivity for copper(II) against zinc(II) with ratios of up to 1321. The sorbents demonstrated sufficient stability of the copper complexes against rechelation using studies in a model environment for the small intestine (the presence of chelating amino acids, pH 6.8).     

PAN-6S和次甲基蓝作配合滴定混合指示剂--连续测定铜和镉的应用研究

研究了PAN-6S和次甲基蓝混合指示剂配合滴定连续测定镉和铜的行为。在pH值5．4的六次甲基四胺-HCI介质中,以PAN-6S和次甲基蓝为混合指示剂,EDTA为滴定剂连续滴定镉和铜,滴定终点变化敏锐,准确度高,铜和镉在一定的比例范围内相互无干扰。方法可用于合金和废水的测定,结果满意。