N.m.r. studies on aromatic compounds. I—13C n.m.r. spectra of some mono- and disulpho-substituted hydroxycarboxylic acids

Carbon-13 n.m.r. spectra of 3-hydroxy-4-sulpho-2-naphthoic, 3-hydroxy-5-sulpho-2-naphthoic, 3-hydroxy-7-sulpho-2-naphthoic, 5-sulphosalicylic, 3-hydroxy-5,7-disulpho-2-naphthoic, 1-hydroxy-4,7-disulpho-2-naphthoic, and 3,5-disulphosalicylic acids were recorded with and without proton noise-decoupling. Analyses of the spectra were carried out for all compounds except 3-hydroxy-5-sulpho-2-naphthoic acid which dimerized. The fine splitting caused by long-range coupling was used in identifying the lines of the ¹³C n.m.r. spectra.     

Komplexometrische Bestimmung von Calcium, insbesondere im Harn, mit 2-Hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-3-naphthoes?ure als Indicator

Zusammenfassung Die in der vorliegenden Arbeit empfohlene Methode der chelometrischen Calciumbestimmung verwendet 2-Hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-3-naphthoesäure als Indicator. Das Verfahren eignet sich gut zur Calciumbestimmung im Harn. Die gefundenen Werte für Calcium schwanken in reinen Lösungen, im Harn und auch in Gegenwart von Magnesium (0,1 mg Mg neben 0,4 mg Ca) um 0,1–0,2 mg-% Ca.

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Summary A procedure is described for the determination of calcium with EDTA using 2-hydroxy-1-(2-hydroxy-4-sulpho-1-naphthylazo)-3-naphthoic acid as an indicator. The method is well suitable for being-applied to urine. Errors are about 0.1 to 0.2 mg-% (for pure solutions, for urine, and also in presence of magnesium [0.1 mg of Mg to 0.4 mg of Ca]).

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Frl. mgr. Irena Nawrocka spreche ich für die im Laboratorium durchgeführten Analysen meinen Dank aus.     

Complex formation equilibria between 1-hydroxy-7-sulpho-2-naphthoic or 1-hydroxy-4,7-disulpho-2-naphthoic acid and iron(III) in 0.1M NaClO4 medium

The equilibria for formation of iron(III) complexes with 1-hydroxy-7-sulpho-2-naphthoic and 1-hydroxy-4,7-disulpho-2-naphthoic acids in aqueous 0.1M sodium perchlorate medium at 25 degrees have been studied by spectrophotometric and potentiometric methods. The data are well described in terms of a series of stepwise complexes, FeL((3-rn)+)(r) in both systems (L(n-) denotes the unprotonated ligand anion).     

Spectrophotometric determination of iron with 2-hydroxy-3-napthoic acid

2-Hydroxy-3-napthoic acid is presented as a new, highly sensitive and selective reagent for its colour reaction with ferric ion. The sensitivity of the reaction is 0.025 μg/cm² (SANDELL). The blue-coloured complex is maximally absorbed at 590 mμ and obeys Beer's law up to 24 p.p.m. of iron. The optimum range of concentration is from 4 to 20 p.p.m. of iron, where the percent relative analysis error per 1% absolute photometric error is 2.9. The composition of the complex, as evaluated by JOB's method and as verified by the Molar and Slope ratio methods, shows that in solution, the complex contains the iron and the reagent in a ratio of l : 1. The empirical formula of the complex is suggested to be [Fe(C₁₁H₇O₃)]⁺². The molar extinction coefficient is 2212 and the instability constant of the complex is about 4.29 ? 10^-4. Coloured ions or those ions that give coloured products are tolerated to a limited extent during the determination of iron.     

Complex formation between aluminium and 3-hydroxy-7-sulpho-2-naphthoic acid Potentiometric, absorption-spectrophotometric and spectrofluorometric studies in aqueous solution

The formation of chelates between aluminium(III) and 3-hydroxy-7-sulpho-2-naphthoic acid has been studied in aqueous solutions of various ionic strengths, at 298 K. The stability constants of AlL, AlL(2) and AlL(3) and the protonation constants of the ligand, obtained by potentiometry with the glass electrode, are compared with values found by absorption and fluorescence spectrophotometric methods.     

A rapid gas chromatographic method for the determination of chlorophenoxyisobutyric acid in plasma and urine.

A rapid gas chromatographic method is described for the determination of chlorophenoxyisobutyric acid (the active metabolite of clofibrate) in plasma and urine. The assay involves an extraction into toluene and back-extraction of the chlorophenoxyisobutyric acid and the internal standard (2-naphthoic acid) into the methylating reagent (trimethylanilinium hydroxide). Concentrations of 1 mug/ml in plasma and urine can easily be measured; the precision of the method is 3.3 +/- 0.7% for plasma and 2.7 +/- 0.4% for urine. There is no interference from endogenous compounds or from drugs commonly prescribed together with clofibrate.     

A highly selective spectrophotometric determination of niobium (V) using 3-hydroxy-2-[1'-phenyl-3'-(p-chlorophenyl)-4'-pyrazolyl]-4-oxo-4H-1-benzopyran as a complexing agent

3-Hydroxy-2-[1'-phenyl-3'-(p-chlorophenyl)-4'-pyrazolyl]-4-oxo-4H-1benzopyran (HPCPB) is used as an analytical reagent for the spectrophotometric determination of niobium in trace amounts with which it forms a yellow coloured complex (4:1) in perchloric acid medium. The complex is extractable into chloroform and shows absorption maximum at 407-418 nm with a molar absorptivity of 2.79 x 10(4) L mol(-1) cm(-1) and Sandell's sensitivity equal to 0.0033 microg Nb(V) cm(-2), respectively. Beer's law holds good in the range 0-1.2 microg Nb ml(-1), with a standard deviation of +/- 0.0015 absorbance units. The method is free from the interference of a large number of elements and handles satisfactorily the analysis of various samples of varying complexity.     

Extraction-spectrophotometric determination of trace iron (II) in sea water with 2-[2-(3,5-dibromopyridyl)azo]-5-diethylaminobenzoic acid

An extraction-spectrophotometric method is described for the determination of traces of iron(II) with 2-[2-(3,5-dibromopyridyl)azo]-5-diethyl-aminobenzoic acid. The reagent forms a stable and blue 12 iron/reagent complex that can be extracted into chloroform. The apparent molar absorptivity of the iron(II) complex is 1.09 × 10⁵ 1 mol^–1 cm^–1 at 624 nm in chloroform. The reagent is relatively selective; interferences from cobalt, copper, nickel and vanadium can be removed by using dimethylglyoxime and EDTA. The method is applied to the determination of iron (II) in sea water and aluminium alloys with good precision and accuracy.     

Extractive-spectrophotometric determination of trace iron(II) with di-2-pyridylmethanone 2-(5-nitro)pyridylhydrazone

The optimum conditions for the extractive-spectrophotometric determination of trace iron(II) with di-2-pyridylmethanone 2-(5-nitro)pyridylhydrazone have been established. Iron(II) reacts with this reagent at pH 2.0-7.5 to form an uncharged 1:2 (metal-to-ligand) complex, which can be extracted with toluene. Beer's law is obeyed over the range up to 0.84 mug/ml of iron(II) at 505 nm. The molar absorptivity of the extracted species is 5.83 x 10(4) 1.mole(-1).cm(-1). The proposed method is extremely sensitive and reproducible, and has been satisfactorily applied to the determination of total iron in freshwater samples by adding ascorbic acid to reduce iron(III).     

Spectrophotometric determination of iron with ferrozine by flow-injection analysis

Two methods for the determination of iron by normal FIA and reversed FIA were developed using sodium 3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-4',4'-disulphonate (ferrozine). The reagent formed a chelate with Fe(II) in hexamethylentetramine buffered medium at pH 5.5. In one previous reaction coil Fe(III) was reduced to Fe(II) by ascorbic acid and in the other reaction coil the complexation reaction was developed. The linear range of the determination was 0.5-6 and 0.1-5 mug ml(-1) of iron for normal FIA and reversed FIA respectively. The proposed method was sensitive (detection limit 0.012 and 0.010 mug ml(-1)), rapid and reproducible (RSD 0.3 and 0.28%). The method was satisfactorily applied to the determination of iron in waste water, toadstool tissue, potato leaves, human hair and bauxites at a sampling rate of 90 and 50 samples h(-1) for normal FIA and reversed FIA respectively.     

8-喹啉偶氮显色剂QADCB的合成及其分析性能的研究

报道了8-喹啉偶氮显色剂2-(8-喹啉偶氮)-5-二羧甲氨基苯甲酸(QADCB)的合成、提纯与鉴定,研究了其与Co(Ⅱ)、Ni(Ⅱ)、Fe(Ⅲ)的显色反应,对QADCB与Co(Ⅱ)的显色反应作了研究。在pH5.9的缓冲体系中,试剂与Co(Ⅱ)形成棕红色配合物,其最大吸收波长位于650nm,表观摩尔吸光系数为4.2×104L.mol-1.cm-1,钴量在0~20μg/25mL范围内符合比耳定律。方法简便、快速,选择性较好,已用于纯铜、维生素B12中微量钴的测定,结果满意。     

Simultaneous determination of four plant hormones in bananas by molecularly imprinted solid-phase extraction coupled with high performance liquid chromatography

A highly selective molecularly imprinted solid-phase extraction (MISPE) combined with liquid chromatography-ultraviolet detection was developed for the simultaneous isolation and determination of four plant hormones including indole-3-acetic acid (IAA), indole-3-propionic acid (IPA), indole-3-butyric acid (IBA) and 1-naphthaleneacetic acid (NAA) in banana samples. The new molecularly imprinted microspheres (MIMs) prepared by aqueous suspension polymerization using 3-hydroxy-2-naphthoic acid and 1-methylpiperazine as mimic templates performed with high selectivity and affinity for the four plant hormones, and applied as selective sorbents of solid-phase extraction could effectively eliminate the interferences of the banana matrix. Good linearity was obtained in a range of 0.04-4.00 μg g(-1) and the recoveries of the four plant hormones at three spiked levels ranged from 78.5 to 107.7% with the relative standard deviations (RSD) of less than 4.6%. The developed MISPE-HPLC protocol obviously improved the selectivity and eliminated the effect of template leakage on quantitative analysis, and could be applied for the determination of plant hormones in complicated biological samples.     

Spectrophotometric study of the reaction of the uranyl ion with 4-(2-thiazolylazo) resorcinol

The uranyl ion forms only 1:1 chelates with 4-(2-thiazolylazo) resorcinol (TAR) in solution, UO(2)(TAR)H(+) being formed below pH 3 and UOS(TAR) above pH 3-5. The latter complex may also be precipitated at pH > 3. The quantitative formation of UO(2)(TAR) at pH 7.5-7.8 in solutions containing a small excess of reagent and some triethanolamine as buffer can be used for the sensitive spectrophotometric determination of uranium. Several interfering ions can be masked with a mixture of sodium fluoride, cyclohexanediaminetetraacetic acid and 5-sulphosalicylic acid. TAR is slightly less sensitive than 4-(2-pyridylazo)resorcinol as a reagent for uranium but is more selective.     

STUDIES ON THE DISSOCIATION OF THE RARE-EARTH CHROMOGENIC REAGENT CHLOROPHOSPHONAZO-mA

Chlorophosphonazo-mA [2-(4-Chloro-2-phosphonobenzenenazo)-7-(3-ac-etylbenzenenazo)-1,8-dihydroxynaphthalene-3,6-disulfonic acid] is a derivative of unsyr.metrical bisazo chromotropic acid,with the following structureIn 1979,it was first reported that the title compound could be used in the spectro determination of the total amount of micro rare-earths existing in spherical graphite cast iron and weak alloy steel and direct spectro determination of the total amount of the rare-earths and the fractional amount of the light and heavy rare-earths when used together with chlophosphonazo-mN It is a rather ideal chromogenic reagent to determine the total amount of the rare-earths.It was also discovered in later work to be usefulin the spectro determination of the elements uranium(VI)and calciumetc[3,4]In order to make a further study for the thermodynamic properties and kinetic characteristics of the reagent when complexing with the rare-earths we have first investigated the ionization of the chlorophosphonazo     

新显色剂2-(2-噻唑偶氮)-5-二乙氨基苯甲酸分光光度法测定微量钴

近年来,杂环偶氮苯甲酸类显色剂取得了较快的发展。由于氨基取代结构对试剂性能有较大的影响^[1],因此本文合成了新显色剂2-(2-噻唑偶氮)-5-二乙氨基苯甲酸,(TAEB)并研究了它与钴的显色反应。     

2-Hydroxy-1-naphthaldoxime as an analytical reagent for titanium(IV)

2-Hydroxy-1-naphthaldoxime is proposed as a new selective and sensitive reagent for titanium. The oxime complex can be dried to constant weight at 105-110 degrees and the conversion factor is 0.1793. The method is sensitive and gives reproducible results. Quantitative separation of titanium(IV) from iron(III) and other metals by this method gives good results. The method has been applied to the gravimetric determination of titanium(IV) in ilmenite and the results are in good agreement with those obtained by the cupferron method. The dried complex has definite composition [TiO(OH)(C(11)H(8)O(2)N)](2) and is a non-electrolyte. The dimeric structure proposed for the complex is based on evidence from elemental analysis, molecular weight determination, magnetic susceptibility and infrared spectral data.     

A novel water-soluble fluorescent probe for the determination of methylamine

A novel water-soluble fluorescent probe, monosodium 7-(4,6-dichloro-1,3,5-triazinylamino)-1,3-naphthalenedisulfonic acid (DTND), was synthesized by reacting cyanuric chloride with 7-amino-1,3-naphthalenedisulfonic acid monopotassium salt at 0-5 degrees C. This new reagent was used for the determination of methylamine. The linear range is 3x10(-6)-2x10(-4) mol L(-1) with a detection limit (S/N=3) of 7.2x10(-8) mol L(-1), and the relative S.D. is 1.3% for ten replicate determinations of 1x10(-5) mol L(-1) CH3NH2. Common species in the aqueous environment have no or only slight influence on the determination. The method can be used to determine methylamine in real water samples.     

The effect of the solvent in the nitrate-selective electrode

An organoboron reagent, 2-[1(o-dihydroxyborylphenyl)-2-phenylethyl]-2-imidazoline hydrochloride, is used for the determination of tartaric acid in aqueous solution. The complex of tartaric acid with the organoboron reagent can be extracted into an organic solvent and determined spectrophotometrically in the concentration range 10^-5–lO^-4 M, with a relative standard deviation of ca. 5%. Alternatively, the complex can be determined turbidimetrically in the concentration range 2 × 10^-4–IO^-3 M with approximately the same precision.     

Spectrophotometric determination of trace molybdenum in plants and seeds with 3,5-dibromo-4-hydroxyphenylflurone

A novel spectrophotometric method based on a new reagent, 3,5-dibromo-4-hydroxyphenylflurone, was developed for the determination of molybdenum in plants and seeds. 3,5-Dibromo-4-hydroxyphenylflurone showed outstanding analytical characteristics for spectrophotometric determination of molybdenum. The reaction conditions are simple and stable. In 0.2 mol l(-1) phosphoric acid medium (which can combine with iron and other metal ions and greatly improves the selectivity of the color system), molybdenum(VI) reacts with 3,5-dibromo-4-hydroxyphenylflurone to form a 1:2 red complex with an absorption maximum at 530 nm, the color reaction can completed in 2 min and the absorbance of the molybdenum complex remains stable for at least 72 h at room temperature. Its stability constant is 1.21 x 10(28) at 25 degrees C. Beer's law is obeyed over the range 0-0.6 microg ml(-1) Mo(VI). The reagent has very high sensitivity and selectivity; the molar absorptivity of the complex is 1.35 x 10(5) 1 mol(-1) cm(-1) and the limit of quantification, the limit of detection and relative standard deviation (n = 10) were found to be 6.7 ng ml(-1), 2.2 ng ml(-1) and 1.01%, respectively. Cu (50000-fold), Fe (20000-fold), K (20000-fold), NH4+ (20000-fold), Mg (15000-fold), Zn (10000-fold), Na (10000-fold), Al (4000-fold), Ca (25000-fold), Mn (2000-fold), Ce (500-fold), Cr (400-fold) and Bi (200-fold) do not interfere with the determination of trace levels of molybdenum up to the excesses indicated. The selectivity is much superior to that of other published methods. The proposed method was applied to the direct determination of molybdenum in plants and seeds with satisfactory results. The synthesis of the reagent and conditions of color reaction were studied in detail.     

Spectrophotometric determination of iron with quinolinic acid

Quinolinic acid forms two complexes with ferrous ion. One is formed at pH 5.9 and has maximum absorption at 420 mμ; the metal to reagent ratio is 1:2 and the instability constant is about 7.10^-9. The other complex is formed with an excess of potassium cyanide and shows maximum absorption at 440 mμ; the metal to reagent ratio is 1:1 the instability constant is only 2.73?10^-5. The latter complex adheres to Beer's law from 1 to 16 p.p.m. of iron, and its optimum concentration range is 4^-16 p.p.m. of iron, where the percent relative error per 1% absolute photometric error is only 2.94.The reagent is highly specific and can be used spectrophotometrically for the determination of very small quantities of iron in presence of many cations.