analytical applications of 1, io-anthraquinones: a review

Talanra, Vol 38, No 6, pp 571-588, 1991 Prmted m Great Brltam All nghts reserved

0039-9 140/9 I $3 00 + 0 00 Pergamon Press plc

ANALYTICAL APPLICATIONS OF 1, IO-ANTHRAQUINONES: A REVIEW

AURORANAVAS DIAZ

Department of Analytlcal Chemistry, Faculty of Saences, Umverslty of MBlaga, 29071-Mblaga, Spam

(Recewed 7 March 1988 Rewed 19 November 1990 Accepted 24 January 1991)

Summary-AnalytIcal aspects of the chemistry m solution of I,lO-anthraqumone (AQ) derlvatlves IS revlewed The mformatlon about photometric and fluonmetnc determmatlon of morgamc species has been condensed and presented m tabular form

Although technological advances m mstrumen- tation have shifted the emphasis of analytical research towards Improvement of methods by means of new and more powerful Instruments or by modification of the Instrumental configur- ation, the prmcrple of chemical analysis still remains chemical reaction between the sub- stance to be determined and an auxiliary sub- stance to be added, the reagent. The extensive but widely dispersed amount of mformation on reaction chemrstry makes a comprehensive and sufficiently critical review of great value for choosmg a reagent for a particular application.

This review deals with anthraqumone (AQ) dertvatlves, a group of reagents widely used m analytical chemistry, but not hitherto surveyed.

The chemistry of anthraqumones has received much attention1-5 because of its relevance to some important technological processes. Anthraqumone derivattves have also been widely used m analytical chemistry, mainly as strong chelatmg agents and chromophores. The major focus of this paper is on their optical properties, which are extensively used in analytical practice, mainly photometry and fluor- tmetry, and m the study of acid-base, redox, complexatton and photochemical reactions. These compounds also display Interesting electrochemical behavtour but its analytical use 1s more limited

The basic chemical structure of anthraqumones is shown m Fig 1, with the posttion and nomenclature of the substituents. The trade names used by the dyestuff manufacturers can be obtained from the Colour Index6 and the chemical structures and properties can be found m the book by Venkataraman ’

In dyes obtained by chemical synthesis, only substances which have formed during manufac-

ture, together with small amounts of electrolytes obtained during neutralization, will appear In the commercial dyes different types of impurittes may be present 7 Separation of anthraqumone dyes has been dtscussed’ and various chromato- graphic procedures are available for analytt- ca17-12 and preparative scale’3s’4 separations

The properties of anthraqumone and Its de- nvatlves that are of mam interest m analytical chemistry are related to their spectral features Theoretical and experimental studies of the absorption 1s-25 and emtssion25-30 electromc spectra have been reported. The spectral characteristics of AQ compounds are related to the molecular structure and to the nature and relative positions of the electronic states AQ is character- ized by the electronic states S,, T, ,+, T,,. , S,,,, , s . The weak long-wavelength dti to the &,

absorption is transition Phosphorescence

occurs from the T,,=. transition Both transitions are mainly due to the carbonyl group, which ensures minimum energy difference between the lowest excited and ground (SO) electronic levels.3’ S n,n. transitions are responsible for the intense short-wavelength absorptions.** 3’

The optical properties of AQ derlvattves are modified by various factors. the nature and posttions of the substituents, the formation of hydrogen bonds, and other mtermolecular and mtramolecular Interactions. The spectral, photochemtcal and photophystcal properties of the AQs have recently been reviewed 32

ACID-BASE PROPERTIES

Studies have been made of the effect of pH on the spectra of AQ derivatives, m terms of the acid-base equtllbrta,33-36 which depend on the nature, number and posttion of the substituents

571

572 AURORA NAVAS DIAZ

Fi, 0 4 Fig 1 Basic chemical structure of l,lO-anthraqumone

Although the agreement between the various reports of pK, values is generally quite good, there are some discrepancies, which may be attributed to differences m the solvent system and the method of calculation.

In strong acid media, the nitrogen atom of I- and 2-ammoanthraqumone is protonated3’ and m suffictently acidic media so are the sulphomc groups m 1,5- and 1 ,S-dihydroxyanthraqumone- dtsulphomc acid (pKAr(sO,njH+ = -6.03 and - 3.90 respecttvely).38 At pH < 4-6 the immo- nitrogen atom m arylammoanthraquinones 1s protonated 33

The acidity of a derivative depends on the electron-donor or acceptor nature of the substituent and on the conlugation effects mvolved

Generally, the pK value for the ammo group is higher for the non-sulphonated compounds than the corresponding sulphonated derivatives 33*34,39-4’ This is usually attributed to the mductive effect of the sulphonate group leading to easier ionization of the ammo group.

1,4-Diammoanthraqumone and 1 ,Cdihy- droxyanthraqumone have higher pK, values than those for the imine groups of Qumizarm Green and its non-sulphonated derivative. For the diammoanthraqumone this is attributed to the greater electron-donor power of the aryl- ammo substituents m the latter compounds, and for the dihydroxyanthraquinones to the effect of intramolecular hydrogen bonding 33 The effect of different substituents can be observed m the pK value of the ammo group for some 1-ammoanthraqumone derivatives. for I-ammoanthraqumone-2-sulphonic acid pK, = 3 79, for 1-ammoanthraqumone-2-carboxyhc acid pK, = 5 74, for 1-ammo-4-hydroxyanthraqumone pK, = 9.10, and for I-amino-2-bromo- 4-hydroxyanthraqumone pK, = 9.93 23

Changes m the posttion of substitution can affect the pK values. For example, the values for I-hydroxyanthraqumone are about two units greater than those for the 2-hydroxy compound,35 but the dissociation constants of 1,2- dihydroxyanthraqumone are similar to those of the 2,3-dihydroxy derivative 42

Intramolecular hydrogen bonding also affects the acidity of AQ derivatives The markedly higher pK values of the 2- than the 1 -derivatives have been attributed to mtramolecular hydrogen bonding. ” Taking as examples ahzarm (1,2-dihydroxyanthraqumone) and qumahzarm (1,2,5,8-tetrahydroxyanthraqumone), the hydrogen bond of the 8-hydroxyl group with the carbonyl group should affect the stability of the hydrogen bond of the 1-hydroxyl group with the same carbonyl group, this reduces the bastctty of the 1-hydroxyl group.43

In methanol, the ammo- and N-substituted 2-ammoanthraqumones are markedly more basic than the correspondmg l-ammo derivatives. Hydroxyanthraqumones show a similar effect.” The basic strength of l-dimethylammo- anthraqumone is higher than that of either ammo- or methylammoanthraqumone, because m the former the ammo group is out of the plane of the aromatic nucleus, so the comu- gation is reduced and the group tends to exert its normal basictty.”

The pK values measured m pure aqueous solutions are mostly higher than those obtained m mixed solvents (~40% v/v water/organic solvent), the latter leading to increased iomz- atton,33*34*37*44 but pK values have been reported for 1,4-dihydroxyanthraqumone,42 1,8-dihy- droxyanthraquinone45 and 1,2,7-trihydroxyanthraqumone‘@ m water which are greater than those obtained m mixed solvents (>30% v/v water/ethanol).

The ionization of AQ derivatives is Influenced by the nature and concentration of the solvent system. The changes m pK, with organic solvent concentration, though mamly governed by the dielectric constant, are also affected by the solvent basictties 33*34

The pK of AQ derivatives increases as the dielectric constant of the medium decreases, e g., in the presence of high proportions of alcohols,33*34’46 acetone33,34 or dioxan33 47 but decreases with increase m amount of ethylene glycol or glycerol. This is explained on the basis that the latter solvents act as proton- acceptors rather than donors, leadmg to easier dissociatton.33*”

The acidity constants of hydroxy- and ammo- anthraquinones m 1.2 v/v dioxan-water are always higher for the excited smglet3748 and triplet49 states than for the ground state, but the triplet state constant lies much closer to the ground state value than does that for the singlet state

Analytlcal apphcatlons of l,lO-anthraqumones A rewew 573

Some AQ derivatives, mainly the hydroxyanthraqumones, change colour with pH and have been used as acid-base indicators. For analytical purposes the most suitable transition of HAQs is that between yellow and red. Qumizarm (1,4-dihydroxyanthraquinone) and Alizarm S (1,2-dihydroxyanthraqumone sulphonate) are very good mdicators with a colour change quality similar to that of Bromocresol Green; ahzarm is also a good indicator but with shghly lower colour change quality, and the colour change of qumahzarm (1,2,5,8-tetrahydroxyanthraqumone) IS still poorer.sO

Diaminoanthraquinones, which do not show such marked colour changes with pH as do various ammohydroxyanthraqumones m aqueous medium, have been used as indicators m the titration of weak bases such as urea and sodium acetate, benzoate or sahcylate with perchloric acid m glacial acetic acid alones’” and mixed with other solvents,56~s7 but are not applicable m the titration of weaker bases with perchloric acid.‘*

COMPLEXATION REACTIONS

Anthraqumones have long been used as analytical reagents and particularly as chromogenic and fluorogemc hgands for various metal ions.

The co-ordmation reactions of AQ derivatives characteristically display moderate selectivity and large absorbance changes.‘* The absorption and emission properties of these compounds and their complexes give great fluonmetric potential, but the relatively high blank signal and the comparatively small spectral shifts due to complexation impair the analytical performance 58

The optical characteristics of the anthraqumone co-ordmation compounds are due to mtrahgand transitions, so the complexation results m modification of only the position of the absorption and emission maxima, and non- fluorescent derivatives do not generate fluorescent complexes. It has been shown that, depending on the acidity, the solvent and the metal ion, the same reagent may give erther excellent or poor analytical response s9

When a more highly acidic reagent, such as Quimzarm Green m comparison with 1,4- dihydroxyanthraqumone,a is used, the stability of the complexes of the more acidic reagent will be lower than that of the complexes of the less acidic compound, and also the formation of its

complexes should be affected less by the pH of the solution.60

When the colour contrast IS due to differences in the positions of the absorption band maxima of the various acid-base forms, to make full use6’ of the contrast it is essential to adjust the acidity or choose a solvent so that the free reagent will be in its molecular form, but the anionic form will be present m the metal complex.

As regards the influence of the solvent m the complexanon, it has been shown46 that it IS necessary to consider the influence of the di- electnc constant of the medium An mcrease m the dielectric constant causes6* a decrease m the relative fluorescence intensity m both reagent and complex The absorption maxima of both the reagent and the complex are shifted to longer wavelengths with mcreasmg solvent polarity The pH for maximum difference in absorbance between 1,2,7-trihydroxyanthraqumone and its Cu(I1) complex as a function of the dielectric constant of the medium, shifts m parallel to the correspondmg pK value for the reagent.&

The nature of the metal, its position m the Periodic Table, the iomc charge, radius and potential, cation-field energies etc., all affect the properties of the complexes.

It has been shown43 that the molar absorptiv- ity and luminescence intensity of alizarm and its complexes with group IIIa and IIIb elements are inversely related to the cation-field energy The higher the field energy of the cation introduced into the complex, the higher the degree of localtzation of the n-electrons of the hetero- atom, and the greater the electron-density deficiency m the ring. This affects the optical properties of the molecules Hence reagents such as ahzarin have been recommended43 for determmation of elements with cations which have a lower cation-field energy or iomc potential, z.e , cations with large radius and small charge

Mixed-hgand complexes of elements of subgroup IIIb with hydroxyanthraqumones and auxiliary ligands have been widely studied The auxiliary hgands mclude 8-hydroxyqumo- line,63*6( ethylenediamme,64*65 phenazone,66*67 benzoic acid,6s N-phenylbenzohydroxamic acid@ and sulphosahcyhc acid.” It has been shown that auxiliary hgands contammg mtrogen donor atoms form the most stable ternary complexes.70 The order of stability of the ternary Th(IV) complexes of 3-ammo- 1,2-dihydroxyanthraqumone is as follows, for the auxihary hgands


named: l,lO-phenanthrolme > 2,2’-bipyridyl > sahcyhc acid > 5-sulphosahcyhc acid = 5-mtro- sahcyhc acid. This order 1s explamed” as due to mteraction between the n-systems of the two hgands bound to Th(IV) These ternary complexes are more stable than the binary complex.

For the mixed-hgand complexes of the rare- earth metals with 1,2,5,8,-tetrahydroxyanthraqumone and 8-hydroxyqumohne the molar absorptivtty depends directly on the ionic potential (cation-field energy) 43 Addition of boric acid to the system increases the linear range 63

The reported complexation reactions of AQ derivatives generally show moderate sensitivity and selectivity, but m some cases the variables were not optimized for modern mstrumen- tation Also, recent approaches62,7’-73 have improved the general performance of the analytical methods, especially sensitivity and selectivity For example, a sigmficant improvement m sensitivity and selectivity m the determmation of Be(I1) 1s achieved by use of its mcluston complex m cyclodextrms 58 Again, develop- ments m the treatment of spectral signals allow analysis of mixtures of lanthamdes at trace levels, which is otherwise difficult because of interelement interferences ” ”

The most important mformation on the use of anthraqumones m determmation of elements by complexation reactions is given m Table 1 at the end of the paper The most widely used reagents and their types of co-ordmation are summarized below

Hydroxy-, polyhydroxy- and carboxyanthraqumones have two oxygen donor-atoms, some typical configurations are shown m Fig 2. Thus chelation by the qumonoid oxygen atom and the hydroxy group occurs m the Ahzarm S complexes with Th(IV), Hf(IV) and Cr(III), and chelation by the two hydroxyl groups of the same reagent occurs with Pb(II), V(V), W(VI), UOz(II)74 and with Zr(IV) ”

It has been reported that with l-hydroxyanthraqumone an ML, chelate is formed with Mg(I1) whereas with 1 ,Cdihydroxyanthra-

Fig 2 Configuratlons of (a) hydroxy-. (b) polyhydroxy- and (c) carboxyanthraqumones

quinone a 1.1 complex is formed.76 The latter was reported to be polymeric.

Some complexes are polymers. For example, the fluorescent product formed between 1,2,4- trihydroxyanthraqumone-3-carboxyhc acid and Cu(I1) 1s said to have a polymeric complex structure.” Polymeric characteristtcs have also been assigned78 to the lakes that are often formed by AQ derivatives and metal tons

(Fig 3). The ahzarm-Co(II)-Co(III) complex shows

a similar structure, with partictpatton of the 2-hydroxy group m the polymerization.” It has been reported that chain co-ordination polymers of 1,4-dthydroxyanthraqumone and biva- lent metal ions with co-ordmation number 4 can be formed from the metal acetylacetonates.76 Alcohol solutions of o-hydroxyanthraqumones form internal complex salts when treated with magnesium acetate. *’ Because of its polarity, N,N-dimethylformamide is very often used as the medium for obtammg polymers “q8’

The formation of msoluble hydroxyanthraqumone complexes of ion metals has long been used m quahtattve analysts. Thus, Al(II1) is identified by means of the red lake formed with ahzarm m baste medium Qumahzarm IS used for the identification of magnesium and various bt-, ter- and quadnvalent cations by means of lake formation.

Amino-, polyammo- and ammohydroxyanthraqumones are compounds with N,N or 0,N donor-atom configurations, as shown m Fig 4

Fig 3 SchematIc formula of the lakes m which M:’ IS a tervalent metal and M, IS hydrogen, or a umvalent, blvalent

or quadrlvalent metal

AnalytIcal apphcations of I,lO-anthraqumones A review 515

Fig 4 ConfiguratIons of (a) ammo-, (b) polyammo- and (c) ammohydroxyanthraqumones

The co-ordmatton sites of the complexes of these AQ derivatives may be the carbonyl and ammo groups, but the structure of the chelates may be due not only to the donor character of the carbonyl group and the displacement of a proton from the ammo group by a metal but also to the donor character of the ammo mtrogen atom. Furthermore, several of the reactions with metal ions may be attributed to redox processes.

Ammoanthraqumones, m contrast to the “broad spectrum” reacttvity of the hydroxyanthraqumones, exhibit selectivity m their reactions, particularly m ethanohc medium.82 This selectivity is decreased m sulphurtc acid medium, however.8384 Thus m ethanohc media ammoanthraqumones react with the transition metal tons Pd(II), Cu(I1) and Co(II), which tend to prefer mtrogen donor atoms The Cu(I1) complex wtth 1,2-diammoanthraqumone has been used as a metallochromic mdicator m the complexometnc titration of calcmm and strontium 85

In contrast, m concentrated sulphuric acid medium, ammoanthraqumones co-ordinate with Se(IV), boric acid, calcium, strontium and barium Selenmm(IV) reacts with aromatic compounds contammg ammo and carbonyl groups. Of the monoammo anthraquinones only the l-isomer reacts to form the dimer (Se),( 1 -AAQ), 86 Similarly, 4,5-dtamino- 1,8- dihydroxyanthraqumone has an ammo group adlacent to the qumone oxygen and reacts with Se(IV) to give both an SeL and an SeL, complex *’

Ammohydroxyanthraqumones form metal co-ordmation compounds which have the characteristics of both the ammo- and hydroxyanthraqumone complexes With metals such as Be, Th and the lanthamdes they react in a similar manner to the hydroxyanthraqumones, and with Pd and Cu similarly to ammoanthraqumones The stability constant of the 1.1 complexes of some rare-earth metals with 1 -ammo-4-hydroxyanthraqumone are very stmilar, mcreasmg as the size of the cation decreases ‘*

The anthraquinone-complexan reagents are derivatives which possess an iminodiacetic group, and have been applied for the photometric determination of several tons and as complexometnc mdicators 89.90 Ahzarm Com- plexan (Ahzarm Fluorme Blue) forms red complexes with Ce(III), La(II1) and Pr(II1) When fluoride is present tt replaces a molecule of water in the co-ordination sphere of the metal ion and a blue ternary complex 1s formed (Ftg. 5).*9-92

Other anthraqumone derivattves used m complexation reactions are mtroanthraqumones and arylaminoanthraqumones. It has been re- porteds9 that the reaction between Tt(IV) and mtroahzarin gives a colour contrast comparable with that of the reaction of Al(II1) and alrzarm l,CDiamino-5nitroanthraqumone is not itself fluorescent, but gives an orange fluorescence with tons such as Au(II1) and V(V).93 The complexanon eqmhbna of La(III)94 and Y(III)@’ wtth 1,4-bts(4’-methylamlmo)anthraqumone (Qumrzarm Green) have been studied spectro- photometrtcally.

Among the coloured chelates of anthraquinone derivatives and transition metal ions, the most widely studied and used is that of Zr with Ahzarm Red S m strong acrd medium This reaction has been applied m the photometric determmation of Zr rn various materials, such as plutomum-uranium fisston alloys95.96 and other alloys97*98 and mmerals.9~‘@’

The most widely studied of the reacttons of AQs with subgroup IIIa elements are those of aluminium with Ahzarm Red S, which is smt- able for determination of alummmm m various matertals,‘0’-‘03 and those of boron with carmmlc acid’“-‘lo and qumalizarm.‘“~“‘-“4

The reaction between fluoride and Alizarm Complexans9-92 is one of the few colour reactions of the fluoride ion. It has been widely studied and applied.“4-‘20

/\ 0

*

H2: lF I ’ ocdCe~c02

’ &L~/CIH, 2

0

Fig 5 Chemical structure of the ternary complex Ahzarm Complexan-Ce(III)-F-


0 NH2 0 NH

0 0

0 1; II

0 0

Fig 6 Oxldatlon react’on of p-ammohydroxyanthraqu’none

REDOX REACTIONS

Chemical oxldatlon

Anthraqumone derivatives readily undergo reduction-oxidation reactions under proper condittons of acidity. Ammo-, hydroxy- and ammohydroxyanthraqumones are capable of further oxidation to a variety of amon radicals, qumones and qumone-immes. Oxidatton of o- or p-ammo- and ammohydroxyanthraqumone results m the correspondmg o- or p-qumone through the mtermediate ammo- or di-immo- qumone”‘~‘** (e g , Fig 6)

The colour or fluorescence change accom- panying their oxtdation facilitates the use of a number of these AQ derivattves as redox mdicators m titration of reducing agents such as ascorbic acid,‘*’ ‘23-‘27 phenazone,‘*’ arsenic(III),‘2’~‘23-‘27 hydrazme sulphate,‘*’ Fe(II),‘*’ but the reagents decompose m the presence of an excess of oxidizmg agent and hence cannot be used’** m titrations of oxidants.

There appear to be two stages of oxidation,‘28 the first (perhaps a one-electron oxidation to an amon radical) producing a hypsochromtc shift, and the second (perhaps a further one-electron oxidation to give the qumone) producing a bathochromic shift to restore the original colour

The redox reactions of AQ derivatives have been used for kmetic determmation of the oxi- dant, the reductant or a catalyst Catalytic methods give very high sensitivity ‘2g-‘33 Their mechanisms have been reviewed by Bontchev.‘34

AQ derivatives provide good indicator reactions for kinetic photometric and fluorimetric methods of analysis, because they give pronounced colour”’ ‘34 and fluorescence”* ‘34-‘37 changes m their redox transformation, and extremely low concentrations of the species involved can be determmed.

Kinetic determmations based on the redox reactions of AQ derivatives show a greater selectivity ‘22 ‘30-132 ‘34 '36'37 than those based on

the complexation reactions.

Various AQ derivatives have been used m indicator reactions Thus, o-dihydroxyanthra- qumones are oxidized by hydrogen peroxide m the presence of traces of cobalt,13) ‘38-‘40 m borate buffer. The ahzarm-hydrogen peroxide mdicator reaction““’ permits the determmation of cobalt m a range of about l-7 ng/ml, Zn, Cd and Ni interfere

The quinahzarm-H,O, (or sodium perborate) reaction is quoted as an indicator reaction with which the sensitivity for Co at 100” is 20 and 0 2 pg/ml with H,O, and NaBO, respectively as oxidizmg agents. I38 After a detailed optimiz- ation study ‘33 the same reaction has been used at 25” to determine Co (sensitivity 0 5 ng/ml) A mechanism similar to that for enzymatic reactions was postulated to explain the optimal conditions found. Tartrate, citrate and oxalate have an mhtbttmg effect.

The reaction between 1 -ammo-4-hydroxyanthraqumone and V(V)‘36 to yield an oxtdation product of the reagent allows a sensitive (loo-530 ng/ml) and selective [only Ce(IV) interferes seriously] kmettc fluonmetric deterrm- nation of V(V)

Fluorimetric’4’ and kmetic-fluorimetric’37 methods have been proposed for the determt- nation of Fe(I1) and Tl(III), based on the intense green fluorescence that appears when these cations react with 1,4-diammo-2,3-dthydro- anthraqumone. The fluorescence is due to the oxtdative transformatton of the reagent m the presence of these cations.

The blue non-fluorescent reagent 4&diammo- 1,5-dihydroxyanthraqumone-2,6-disulphomc acid is transformed mto a pink, highly fluorescent, product by oxidation m acid medium This reaction is slow, but m the presence of certain morgamc oxidants tt is accelerated and completed m about 30 mm This allows the kmetic determmation of V(V),12* Fe(III),14* Ce(IV),‘43 Au(III)13* and Mn(I1) ‘35 The com- bined action of Fe(II1) and V(V) notably m- creases the sensitivity of either or both determmations, and concentrations as low as

AnalytIcal appkatlons of l,lO-anthraqumones A review 577

1 ng/ml V(V)“’ and 2 ng/ml Fe(III)13’ can be determined

Oxidation of 1,2,4-trihydroxyanthraquinone- 3-carboxylic acid by bromatelM or iodate’4S in hydrochloric acid medium has served as the basis for their spectrophotometnc determination and for a fluonmetric method for iodate’34 which is more selective and 10 times more sensitive than the spectrophotometric method.

Electrochemrcal reduction

Polarographic studies of analytically important anthraqumones have been made, to investi- gate their redox characteristics.39 Because of their qumonoid structure, anthraquinones display mterestmg electrochemical behaviour.39 When reduced I46 by taking up a smgle electron, they form semiqumones, and the uptake of a further electron results m the formation of hydroqumones In all the redox processes of AQs these three oxidation states are expected to be involved. Whether under given experimental circumstances a single two-electron polarographic wave or two one-electron waves will be observed, depends on the stability of the semiqumone Additionally, each oxidation state can mvolve different degrees of protonation.”

The polarographic behaviour of anthraqumones depends as much on the nature of the derlvatlve39,146-'58 as on the p~,39,146,147.'50,'5Z,lS7,158

the solvent3’ ‘48~‘49,‘53 and the supportmg electro- lyte solution

For the complexes of Alizarm Red S with Be and Al information has been obtained on the structure of the complexes by polarographic reduction of the llgand.‘s9 Similarly, from voltametric and spectrophotometnc studies it has been deduced that the two adjacent hydroxyl groups are involved m formation of the highly stable Zr-Ahzarm Red S complex.7s

It has also been estabhshedlm that the half- wave potential for the polarographic reduction of some AAQs is correlated with the wavelength of maximum absorption m the visible region and also with the polarizabihty of the carbonyl groups. Each AAQ can be determined m the range 0.1-O 5 mg/ml.

Redox photochemrcal properties

The excited states of some AQ derivatives are very reactive chemical species The photochemical reactions mvolvmg these species can compete with lummescence for deactivation of the excited electronic states. The photo-

chemistry of AQs has been useful m analytical chemistry, from the point of view of photo- reaction and of deactivation of excited states The absorption and fluorescence spectra of some AQs have been studied m relation to the photochemical properties.2*‘6’ “*

The photochemical oxidation of anthraquinones is confined to oxidation of the side- chain, which is characteristic of p-qumones ’

Photochemtcal reduction is the simplest photochemical reaction of anthraqumones. It mvolves3*4*3’ the addition of an electron or a hydrogen atom to the oxygen atom of the carbonyl group under conditions where the analogous dark reactions are imposs’ble The facile reduction of AQs to anthrahydroqumones under the influence of light has long been recog- mzed4 as one of the major causes of the photo- mstabihty and photoreactivity of these dyes

The photochemical reactivity of an AQ derivative depends critically upon the nature of the lowest excited electronic state Anthraqumones m which this lowest state is n,rr* are assocl- ated3A*3’*‘63 with high photochemical activity, because m that state the oxygen atom of the carbonyl group is electron-deficient, which ren- ders it4 extremely reactive towards the hydrogen atom or electron abstraction. In the case of x,x * states, and more particularly charge-transfer (C-T) states, photoexcitation causes an electron shift towards the oxygen atom, which lessens ‘ts affinity for the hydrogen atom and electron abstraction. Anthraqumones which possess low- lying x,x* or C-T states are therefore comparatively unreactive

Anthraqumone derivatives vary widely m their photochemical reactivity They are divided into “strong” and “weak” sensitizers’ ‘63 I64 m the oxidatton of the environment The former give phosphorescence emission and semi- quinone radical formation, while the latter give only fluorescence emission ‘64

AQ and its derivatives with electron-accept- ing substituents (-HS03, -N02, halogens) are very photochemtcally reactive, but the position of the substrtuents can have a profound effect on their photochemical behaviour.4 ‘63 Sodium anthraqumone-2-sulphonate, and 2,6- and 2,7- disulphonates are more active sensitizers than the l- and 1,5-sulphonates, and the 1,8-disulphonate is mactive.‘63.‘65

Powerful electron-donating groups (-OH, -NH,, -NRR’) diminish the sensit’zmg power of AQs in the photochemical pro- cess ‘.3~‘63 a substituent m the l-position gener- 3

Tab

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I Ph

otom

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an

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met

rlc

met

hods

fo

r de

term

mat

lon

of m

orga

mc

soec

les

with

ant

hraq

umon

e de

rlva

tlves

,_

Ion

Rea

gent

T

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of

Inte

rfer

ence

s,

3

met

hod

Con

dltlo

ns

Ran

ge

rem

arks

R

efer

ence

Al(

II1)

1,

2DH

AQ

-3S

I ,4D

HA

Q-2

S

1,2,

4TH

AQ

-3s

1,2,

7TH

AQ

A

hzan

n C

ompl

exan

c/Ph

pH

4

8, d

490

nm

0

08-O

76

ngjm

l c/

Ph

MeO

H,

1560

nm

<

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pgf

ml

c/F

pH 4

76,

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500,

I,

558

nm

1 l-5

4 ng

/ml

c/Ph

pH

5

5. i

58

0 nm

0

5-3

fig/

ml

c/Ph

Z

500

nm

, st

andm

g tim

e 2

4 hr

O

-2 &

ml

c/Ph

pH

4 I

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, he

at

at 7

0”, s

tand

mg

l-12

fi

g/m

l

Mn,

Fe

, C

a B

e, S

C, T

h, T

I, Y

, Z

r,

F-,

PO:-

, la

ntha

mde

s

Det

n in

pre

senc

e of

Fe

and

T

I

171

172

173

174

175

176

Au(

III)

IA

DA

AQ

-2JD

S c/

Ph

pH

9,14

25

nm

5-30

~g/

mI

Man

y to

ns

177

B(I

I1)

4,8D

A-I

,jD

HA

Q-2

,6D

S k/

F

I ,4D

HA

Q

c/F

I ,4D

HA

Q-2

S c/

F

I ,8D

HA

Q

c/Ph

1,

2,5,

8TT

HA

Q

c/Ph

C

arm

mlc

ac

ed

c/Ph

1,

8DA

-4,5

DH

AQ

c/

ph

ISD

H-4

,8D

AA

Q

c/Ph

b 15

M H

CI,

t,,

525,

i,

585

nm

91-9

6%

H,S

O,,

A,,

365,

1,

595

nm

cone

H

2S04

, A

,, 52

2, &

, 57

8 nm

, st

andm

g tim

e >

15

mm

co

ne

H,S

O,,

1 58

0 nm

93

%

H,S

O,,

1615

nm

92

-94%

H

ZS

04,

1610

nm

96

%

H&

, 1

525

nm

96%

H-$

0,,

Iz 6

00 n

m

46-2

65

peg

Fe,

Ce,

V

132

4 x

lo-+

-8

x Io

-jM

I-

, C

IO;,

Sb,

Fe

178

25-2

50 n

g/m

l N

O;,

F-

179

0 l-

3 pg

/mI

H,B

O,

Fe,

NI,

Co,

Cr

180

OO

I-O

1%

G

e, A

s, F

- 11

1 0

15-I

6 r

g/m

l 10

5 2-

7 Pg

O

xida

nt

amon

s,

F-,

TI

181

2-10

I.r

g 18

2

NO

1,

2DH

AQ

-3S

1,4D

HA

Q-2

S

I PD

HA

Q-2

,6D

S

1 A-4

HA

Q

1 H-2

CA

Q

4,8D

A-

1,5D

HA

Q2,

6DS

C

arm

mlc

ac

td

Ahz

ann

Com

plex

an

c/F

c/F

c/Ph

c/

F c/

Ph

c/ph

c/

Ph

PhO

z-D

S c/

Ph

c/Ph

c/

Ph

c/F

c/Ph

pH

54-5

6,11

8O

nm

pH 6

, i

575

nm

8 x

IO-l

M

HA

c,

2,

475,

&,,5

75 n

m

pH

7, 1

530

nm

, 7%

Na,

S,O

,, he

at

5 m

m a

t 60

-70”

0

02M

NaO

H,

&

540,

&,,,

620

nm

pH

10

2,

IO-*

M b

-cyc

lode

xtrm

4

x IO

-‘M

N

aOH

, t

4704

80

nm

A,

470,

&,,,

580

nm

00

2N

NaO

H,

i 64

5 nm

pH

4,

1580

nm

pH

7 2

, L 4

80 n

m,

extn

w

ith

Ado

gen

soln

m

tol

uene

D

H 6

. Z

550

nm

0 2-

4 7

pg/m

i I-

20

yg

l-7

ng/m

l 0

I fi

g/m

l

Pb,

Zn,

Cu,

Ce,

Co,

N

I, V

(V),

MO

PO

:-,

F-,

Al

183

184

185

186

0 2

&m

l 10

-70

ng/m

I 0

4-l

2 jig

/ml

3&I

30 n

g/m

l 04

-I

13 &

ml

0 4-

I 6

pg/m

i 0

09-O

36

pg/m

l

Lar

ge a

mts

of

Cu

and

smal

l am

ts

of A

l an

d Fe

Int

erfe

re

LI,

Cr(

VI)

Mg,

AsO

:-

Zn,

A

l, Y

C

u, C

r, C

o, V

(V),

Ag,

Ge,

AI,

NI

Seve

ral

ions

Se

vera

l Io

ns

187

58

188

189

190

191

192

5-35

lie

19

3

1 H-2

CA

Q

c/Ph

50

% E

tOH

, pH

I I

, d

463

nm f

or M

g 0

I-I

5 pg

/ml

Mg

Be

up t

o 0

4 jig

/ml

194

1492

nm

for

Be

004-

04

ue/m

l B

e M

E U

D to

1

5 up

/ml

194

1,2,

4TH

AQ

-3C

rx

/Ph

I 92

M H

CI,

1 5

20 n

m

I-8

pug/

ml

Oxi

dant

s an

d ot

her

Ions

14

4

Ca(

l1)

1,2D

HA

Q-3

S 1,

8DH

AQ

1,

2,4T

HA

Q-3

S 1,

2,3T

HA

Q

1,2,

7TH

AQ

1,

4DA

AQ

Abz

arm

C

ompl

exan

A

nthr

apu~

unn

Com

plex

an

c/Ph

c/

F c/

Ph

c/Ph

c/

Ph

c/Ph

pH

102,

1509

nm

0 O

lM N

H,,

A,,

485,

1,

615

nm

pH

11

pH

10 5

, 80

% D

MF

EtO

H,

1 56

0 nm

50

% H

2SO

d, A

: 400

nm

<O

1.5

mgj

ml

50-5

50 n

g/m

l 0

5-4

5 pg

fml

2-12

fig

/ml

l-6

jig/m

l 14

-35f

lg/m

l

c/P

50%

H,S

O,,

AX

410

, &

,,, 5

80 n

m

150-

400

ng/m

l c/

Ph

pH

10 3

1,1

610

nm

2-10

p&

ml

c/Ph

pH

IO

58,

R 5

80 n

m

2-10

@g/

ml

195

Seve

ral

mns

19

6 19

7 M

any

eons

19

8

No

Inte

rfer

ence

by

Mg,

Sr,

Ba,

PO

:-,

ED

TA

if

201

Ba,

Sr

caus

e po

sitiv

e er

rors

20

2 20

3

Cd(

H)

CeW

)

Co(

H)

Cr(

II1)

Cuf

ll)

F-

Ahz

arm

C

ompl

exan

1,2D

HA

Q-3

S

4,8D

A-1

,5D

HA

Q-2

,6D

S

1,2D

HA

Q

1,2D

HA

Q-3

S 1,

2,5,

8,T

TH

AQ

1,2,

4TH

AQ

-3S

t ,Z

DA

AQ

1,

2DA

AQ

-3S

1,2D

HA

Q-3

S

1,2,

7TH

AQ

1,2,

4TH

AQ

-3C

1 ,Z

DA

AQ

4,

8DA

-1,5

DH

AQ

-2,6

DS

Ant

hrap

urpu

nn

Com

plex

an

1,2D

HA

Q-3

S

1,2D

HA

Q-3

S f

Th

1,4D

HA

Q-3

S +

Zr

1,2,

3,5,

6,7H

HA

Q +

Zr

Abz

arm

C

ompl

exan

c/Ph

pH

8,

i,

620

nm,

stan

dmg

time

30 m

m

2-11

jig

/ml

204

cfPh

pH

9 9

-10

10, L

500

nm

00

7-O

15

%

Impu

ntIe

s ca

n be

ext

ract

ed

at

205

pH 4

-5

with

oxm

e m

chl

orof

orm

k/

P 0

2M &

SO,,

1,

525,

&,,

585

nm

0 02

-O 3

7 /I

glm

l H

g, V

, C

r(V

I)

143

k/ph

pH

9 4

, 0

035M

H,0

2 2

x lo

-‘-2

x

1O-4

fig/

ml

Zn,

Cd,

NI

140

k/Ph

15

10

nm

0 05

&m

l 20

6 k/

Ph

pH

I2,1

56

5 nm

, 25

”, H

,O,

I x

10-s

-2

x lo

-7M

C

N-,

ta

rtra

te,

titra

te,

C,O

$-

133

lOO

”, H

,O,

c20

pg/m

l 13

8 IO

O”,

Na5

B0,

C

O 2

pg/

ml

138

c/Ph

pH

538,

IZX

Wnm

O

-2 5

&m

l N

l 20

7 c/

Ph

0 32

M N

aOH

, d

690

nm

l-3

&m

l St

abdt

zed

with

po

ly(v

my1

alc

ohol

) 20

8 c/

Ph

pH

7 8,

I

580

nm,

stan

dmg

15 m

m

0 95

-3 8

@g/

ml

209

c/Ph

pH

3-

6,15

25

nm

0 2-

10 4

&g/

ml

210

c/Ph

pH

8,

1 52

0 nm

, ex

tn

with

O

-7 ,

g/m

l 21

1 ls

oam

yl

alco

hol

c/Ph

0

02M

NaO

H,

1750

nm

0

l-l

0 &

g/m

l M

any

Ions

21

2 c/

F O

OIl

w N

aOH

, 80

% D

MF,

A

,, 51

5 nm

50

-250

ng/

ml

213

c/Ph

0

32M

NaO

H,

1 65

0 nm

l-

7 pg

/ml

Stab

lhze

d w

ith

poly

(vm

y1 a

lcoh

ol)

214

c/Ph

pH

7

13, 1

690

nm

3-9

jig/m

l 21

5 c/

Ph

pH 4

6,

1 51

5 nm

l-

20

pg/m

l 21

6

c/Ph

pH

2 9

-3 0

.1,

415

nm,

1 14

-l 9

0 m

g/g

217

F-

titra

ted

wtth

0 O

lM Z

r(IV

) ic

/Ph

1% N

H,O

H

HC

l, L

525

nm

0

05-l

fi

g/m

l A

l, SO

;-

218

i 52

5 nm

0

4-4

fig/

m1

D~f

fe~n

tl~I

met

hod

s/Ph

0

1M H

Cl,

1545

nm

O

-3 5

pg/

ml

~25

&g/

ml

SOi-

21

9 Ic

/Ph

IM H

Cl,

1560

nm

G

-7 p

gjm

l 22

0 c/

Ph

pH 4

6,

1. 5

74 n

m,

0 08

-l

2 m

g/l

Flow

-mje

ctio

n de

term

mat

ton

221

Na

dode

cyl

sulp

hate

---c

ontm

ued

Ion

F-

Fe(I

I1)

Ga(

II1)

Tab

le

I-co

ntm

ued

i?

Typ

e of

in

terf

eren

ces,

R

eage

nt

met

hod

Con

dmon

s R

ange

re

mar

ks

Ref

eren

ce

Abz

ann

Com

plex

an

f L

a tc

/Ph

La

com

plex

~r

nrno

b~l~

~d o

n 95

0 pg

N

H:,

Mg,

Ca,

Al.

Fe(I

lI)

222

Am

berh

tc

CG

-400

or

IRA

-938

A

bzar

m

Com

plex

an-S

S +

La

tc/P

h L

a co

mpl

ex

lmm

oblh

zed

on

0 00

3-l

pg/m

l 22

3 A

mbe

rhte

C

G-4

00 o

r IR

A-9

38

Alu

arm

C

ompl

exan

tc

/Ph

pH 5

O-5

2,

i 61

0-62

0 nm

O

-60

pg

Al,

Fe,

Sn,

Ca,

Mg

59-6

1, 2

24

+C

e(IV

) or

La

F’O

i- ,

SO;-

, C

z(Y

4-, o

xrda

nts

1,2D

HA

Q-3

S c/

Ph

pH >

4 2

, I

570

nm,

extn

w

ith

0 02

-l

5 fi

g/m

l 22

5 A

hqua

t 33

6 so

ln

m C

HC

I,

t ,2,

4TH

AQ

-F-

c/Ph

pH

8 1

, il

595

nm,

extn

m

to

MIB

K

0 02

5-O

250

pg/

ml

Mas

ked

with

CN

- 22

6 1,

4DA

-2,3

DH

yAQ

=

JF

pH49

0

28-O

6 &

ml

Au,

Tl,

Ce,

Pt

141

k/F

pH

3 4,

1,40

0,

&,

470

nm

0 O

S-0

6 pg

/ml

Au,

Tl,

Ce,

Pt,

V(V

) I3

7 4,

8DA

-l,S

DH

AQ

-2,6

DS

k/F

0012

M

HC

I, ,I_

525

, &

,,, 5

85 n

m

2 5-

25 f

ig

Au,

C

e, V

(V),

Th,

F-

142

k/F

25 p

ug V

(V)

I 5-

25 j

Lg

BrO

;,Tb

131

2

1,2D

HA

Q3S

c,

lPh

pH

3-5,

Z 4

90 n

m

0 55

-14

pgfm

l 22

7 8

1,2D

HA

Q-3

S c/

Ph

pH

3 3,

20%

EtO

H,

1 50

5 nm

, 0

28 c

g/m

I N

o In

terf

eren

ce

by A

l, C

u, I

n,

228

0 04

M h

exad

ecyl

pynd

mm

m

brom

ide

Sb,

Tl,

Ce,

Zn

; 1,

2,5,

8’IT

HA

Q

c/P

h

pH

5, N

H,O

Ac,

N

aF,

heat

at

80”

0 l-

10

fig

Man

y Io

ns

229

2 G

e(IV

) i,2

DH

AQ

3S

c/Ph

pH

7,

A 4

70 n

m,

extn

m

to

CC

&

!%-4

fl Pcc

g I ,

2,3T

HA

Q

c/Ph

90

%

MeO

H,

4 x

IO”‘

*M, 1

490

nm

1-5

jfg/

ml

1,2,

4TH

AQ

c/

Ph

40%

E

tOH

, pH

l-

4,

I, 4

90 n

m

0 4-

12 7

pg/

ml

1,2,

7TH

AQ

A

hzan

n C

ompl

exan

Ahz

arm

C

ompl

exan

+

Rh~

amln

e 6G

A

hzar

m

Red

S (

II)

+D

PhG

(I

) O

~ina

ll~rl

n +

DPh

G

. H

NIV

I

c/Ph

c/

Ph

c/Ph

c/

Ph

tc/P

h tc

/F

tc/P

b

tc/P

h

cone

H

,SO

., 90

%

EtO

H,

4 x

10v4

M N

H,,

k 47

0 nm

pH

7,

d 4

45

pH 8

, A

450

nm

pH

S-6,

A 5

20 n

m

A,._

543

nm

pH 4

, I

475

nm,

extn

m

to

CH

CI,

ac

eton

e (1

4)

at p

H

7-8

oH 4

. A

500

nm

. ex

tn

with

CH

Cl,

0 4-

15 f

ig/m

l 0

5-4

pg/m

l 0

2-4

jig/m

l G

eG,

0 5-

6 pg

/ml

Ge

0 02

-l

@g/

ml G

eO,

2-10

0 ng

/ml

GeO

, O

OIW

63

pg/

ml

0 l-

2 u&

ml

-

BO

;, S@

-, N

O;,

OA

c-,

PO:-

do

not

in

terf

ere

4 1

(R

Ge)

com

plex

fo

rmed

4 1

(R

Ge)

com

plex

fo

rmed

C

l-,

Br-

, I-

, N

O;,

ClO

;

230

231

232

233

234

235

236

237

Ion

asso

c w

ith G

e (I

) (I

I)

ratlo

1

2 2

238

239

$ l-4

-

1,2D

HA

Q-3

S c/

Ph

O-8

0 m

gjl

Hm

z 24

0

i ,2R

HA

Q-3

S

c/P

h

pH

3 8-

4 5,

L 5

30 n

m

0 23

-27

pg/m

l 24

1 A

hzar

m

Com

plex

an

c/Ph

pH

4 3

, A

520

nm

l-

9 fi

g/m

l Se

vera

l io

ns

242

1,2-

DH

AQ

-3S

+ D

PhG

tc

/Ph

pH

5 3-

5 9,

,l

525

nm,

extn

m

to C

HC

I?

0 3-

2 8

@g/

ml

243

10;

1,2,

4TH

AQ

-2C

rx

/Ph

70%

EtO

H,

1 !%

A4 H

CI,

i:

520

nm

50-3

50 /

Jg

Oxi

dant

s an

d ot

her

ions

14

5 rx

/F

1 20

M H

CI,

ii,,

515

, &

, 62

5 nm

S-

50 p

g O

xida

nts

and

othe

r Io

ns

244

Laf

III)

1 H

AQ

-2C

c/

Ph

pH 4

9,8

0%

EtO

H,

&,,

465,

1,,

520

nm

0 1-

1 jig

/ml

Seve

ral

ions

1,

2DH

AQ

-3S

45

C/P

h pH

35_6

5,15

20nm

0

42-1

0 fi

g/m

l M

any

Ions

1,

2,5,

8TT

HA

Q

246

c/Ph

pH

6-8

, 1

570

nm

0 08

-l

6 fig/ml

1,2D

HA

Q-3

S +

phe

nazo

ne

In p

rese

nce

of b

one

acid

24

7 tc

/Ph

pH

5, I

540

nm

, ex

tn

mto

I-

6 j&

W

66

buta

nol

or r

sobu

tyl

alco

hol

1,2D

HA

Q-3

S tc

/Ph

rl 5

30 n

m,

extn

m

to b

utan

ol

30.-

-so

pg

64

f I-

hydr

oxyq

umoh

ne

W

c/Ph

pH

7

6,40

%

DM

F,

,? 6

00 n

m

2 x

10-5

-J

x 10

-4M

94

LI(

I)

1,8D

HA

Q

c/F

90%

E

tOH

, /1

, 49

5, &

,, 62

5 nm

10

0-70

0 ng

/mf

Sepa

ratio

n of

LI

IS re

com

men

ded

248

>

c/F

90%

ace

tone

, 2

5 x

10s4

M N

aOH

50

-450

ng/

ml

$ A

,, 52

5, &

,, 61

5 nm

4

Lu(

III)

/Pr(

II~)

iii

.

1,4D

HA

Q

c/F

90

%

MeO

H,

pH 4

5,

A 5

60 n

m f

or L

u I-

100

mg

Lu

Pr t

oler

ance

fr

om

1 5

to 5

1

71

pl

1 56

4 fo

r Pr

3

Mg(

W

L

D

1,4D

HA

Q-2

S ‘d

F

g

pH

10, 6

0% E

tOH

, E

.,, 5

45,

a,,,

610

nm

20-2

00 n

g/m

l 1 ,

SDH

AQ

Fe

(H),

B

e 24

9 c/

F Z

? p

H

9 1-

9 6,

A,,

490,

&,

610

nm

I ,SD

HA

Q

10-1

00 n

g/m

l M

any

tons

25

0 c/

Ph

90%

EtO

H,

8 x

IW’M

N

H,,

I 51

0 nm

0

25-2

00

p&/m

l 0,

1,2,

7TH

AQ

M

any

fan

s 25

1 c/

Ph

40%

E

tOH

, 4

x 10

s3M

NaO

H,

l-6

fig/

ml

Man

y Io

ns

252

em

L 5

40 n

m

e

lH-2

CA

Q

c/Ph

90

%

EtO

H,

0 04

M N

H,,

1 53

0 nm

9-

45 j

fgfm

l M

n, Z

n, C

o, C

a 25

3 $

Mn(

I1)

B

i: A

hzan

n C

ompl

exan

c/

Ph

pH

11 I

-116

,157

Onm

l-

8 @

g/m

l 9

Ant

hrap

urpu

rm

Com

plex

an

254

E

c/Ph

pH

11

4-ll8

,n55

Onm

l-

-7 ,

ug/m

l %

4,

g-D

A-l

,SD

HA

Q-2

,6D

S 25

5 0

016M

NaO

H,

0 16

M H

CI,

i!

k/

Ph

1518

or

560

nm

3-

11 j

4g

Oxd

n ,

redn

an

d co

mpl

exm

g ag

ent

k/F

135

L,

525,

&,,

585

nm

0 16

-O 5

4 /~

g 9

Mo

(V1)

2 <

1,2D

HA

Q-3

S

c/Ph

pH

5,

I

525

nm,

extn

w

ith

0 2-

6 5

jig/m

l F-

an

d E

DT

A

adde

d to

25

6 A

4

I,2-

d~hl

oroe

than

e I,

2,5,

8TT

HA

Q

c/Ph

m

ask

Co,

Z

n, C

u, T

h, U

(W)

pH

5, i

54

0 nm

l-

10

yg/m

l uo

:+

Car

mnu

c ac

id

257

c/Ph

pH

4-5

, /,

336

nm

4-11

fig

/ml

258

1 56

5 nm

I

5-8

fig/

ml

c/F

pH

5 2,

E,,

560,

&,,

590

nm

0

1-O

9 p

g/m

l Pr

evto

us

sepa

ratio

n IS

reco

mm

ende

d 2.

59

Nb(

V)

I ,2D

HA

Q-3

S c/

Ph

2M H

?SO

,, A

cn 49

9, A

,,,, 5

62 n

m,

~32

erg

260

hexa

decy

ltr~m

ethy

lam

mon

lum

br

omtd

e,

stan

dmg

time

2 hr

Ni(

II)

I .2,

4TH

AQ

c/

‘Ph

pH 8

5,

A 5

25 n

m,

extn

m

to

MIR

K

o-25

pg

M

any

ions

1,

2,4T

HA

Q-3

S 26

1 ej

Ph

pH

8

1, A

520

nm

O-3

pgi

ml

co

205

Tab

le

I-ro

ntm

ued

Ion

Rea

gent

Ty

pe

o

f In

terf

eren

ces,

ii

met

hod

Con

dltlo

ns

Ran

ge

rem

arks

R

efer

ence

Nl(I

1)

I H-Z

CA

Q

Abz

ann

Com

olex

an

+ L

a c/

Ph

50%

EtO

H,

8 x

10-‘

M

NN

, e/

Ph

DH 45. ,? 5%

nm

2 66

6

fig/

ml

O-1

0-5&

4 Se

vera

l 10

ns

Co.

Cu.

Zn.

Th.

Ce.

Fe

262

263

PdfI

I)

1,2D

HA

Q-3

S 1,

2,4T

HA

Q-J

C

1,5D

AA

Q-2

,6D

S 4,

8DA

-I ,

5DH

AQ

-2,6

DS

I A

DA

-SN

AQ

C

arm

mlc

ac

id

1.2D

~~ph

e~yl

hydr

azon

e

c/Ph

c/

Ph

c/Ph

c/

Ph

c/P

h

c/F

c/Ph

pH 4

, I

450

nm

04-1

1 /I

g/m

l 26

4 80

% E

tOH

, 16

70

nm

0 30

-2 4

0 @

g/m

l M

any

ions

26

5 pH

2

5, A

6.5

0 nm

4-

20 p

g/m

l M

any

Ions

pH

10

5,

1 72

0 nm

4

8-18

2 I

;cg/

ml

ii:

0 64

M

NaO

H,

I 64

0 nm

2-

10 p

g/m

l St

abrh

zed

with

po

ly(v

my1

alc

ohol

) 26

8 pH

5 3

, ac

eton

e,

2,

$46,

&,,

580

nm

0 1-

1 pg

In

terf

eren

ces

rem

oved

by

ppt

n of

Pd

269

0 4M

NH

3, A

675

nm

0

5-2

&m

l 27

0

Rh(

II1)

1,

2DH

AQ

-3S

c/Ph

pH

4,1

45O

nm

, he

at

at

100”

for

1 5

hr

1 5-

8 6

pg/m

l Pd

, C

u, R

u 27

1

I ,5D

HA

Q-2

,6D

S 1,

4DH

AQ

1,2,

7TH

AQ

pH35

-51,

149S

nm

0 3-

4 rg

/ml

272

0 02

M N

aOH

, a,

, 54

5, J

., 60

0 nm

, 3-

4 @

g O

nly

Be

Inte

rfer

es

seno

usly

72

lO

-2 M

B-c

yclo

dext

rm

?Y

DM

F,

&

48.5

, &,,

563

nm

12-2

25 n

g/m

l 62

8 ”

sefW

4

5DA

-1 ,S

DH

AQ

c/

Ph

99 W

OO

%

H2S

04,

2 61

0 nm

O

-4 3

&m

l 87

;; gr

he

at

at 9

0” f

or 2

1 hr

$

Sr(I

1)

3A- 1

,2D

HA

Q i

- eo

sm

Altz

arm

C

ompl

exan

tc/P

h pH

65-7

2,iW

nm

0 14

-2 0

fig

/ml

Al,

CN

- A

dd

ED

TA

to

mas

k A

l 27

3

M

cjPh

pH

10

9, I

610

nm

2-12

pg/

ml

Man

y so

ns

274

-wlV

f

T@

V)

Tl(

II1)

1,2D

HA

Q-3

S 1,

2,7T

HA

Q

1,2,

5,8T

TH

AQ

1,

2,3,

5,6,

7HH

AQ

4,

8DA

- I ,

5DH

AQ

-2,6

DS

BM

AnA

Q

3A-1

,2D

HA

Q

+ S

-sul

phos

ahcy

hc

acid

1,2D

HA

Q-3

S 1,

2DH

AQ

-3S

1,4D

A-2

,3D

HyA

Q

c/Ph

c/

Ph

c/Ph

c/

Ph

c/Ph

c/‘P

h tc

/Ph

c/Ph

c/

Ph

k/F

rx

jF

pH

3 2-

-8

0 23

-16

7 pg

/ml

256

EtO

H,

I 54

0 nm

, st

andm

g tim

e 2

hr

7-21

p&

/ml

275

1 57

0 nm

25

-250

/ig

27

6 1

530

nm,

lOM

HC

I 5-

12 j

ig/m

l 27

7 pH

3 5

, ,l

68.5

nm

7 5-

22 5

jig

/m!

As,

Au,

Al,

Fe,

Cr,

Zn

278

UO

g*,

Ba

F-

pH 4

6,4

0%

DM

F,

I 62

0 nm

4

7-18

5 k

g/m

1 27

9 pH

4 6

-S 5

, 1

580

nm,

20%

EtO

H

60-5

60 /

_tg

CN

-,

NO

;, H

PO

;- ,

F-

70

i, 66

0 nm

10

-100

/Ig

28

0 p

H

3 5,

/

51.5

nm

, st

andi

ng

time

1.5 m

m

~24

/rg

260

hexa

de~y

ltr~m

ethy

lam

mon

~um

br

omid

e

pH

3 4,

J.,,

400

, ie

m 4

70 n

m

0 05

-O 4

jfg

jml

Au,

F

e, C

e 13

7 pH

3

6, s

tand

mg

90 m

m

0 l-

3 #g

/ml

Au,

Fe,

Ce,

V

141

;!

r T

m(l

l~)/

Nd(

Il~)

IP

DH

AQ

c/

F M

eOH

, pH

4 5

, i

557

nm f

or N

d 0

4-12

0 #g

/ml

Tm

T

m

Nd

tole

ranc

e 73

I

559

nm f

or T

m

0 4-

l 20

pg/

ml

Nd

from

2

5 1

to 1

2 5

Wi)

I ,

2DH

AQ

-3S

c/Pb

pH

4 5

-5 5

, L

550

nm

40

-250

p&

ml

Cl-

, N

O,,

SO;-

28

1 1,

4DH

AQ

-3S

c/P

h

I 55

0-59

0 nm

50

fig

C

e an

d T

h m

ust

be a

bsen

t 28

2 1,

2,5,

8TT

HA

Q

c/Ph

pH

5

5,L

63

0660

nm

3

5-21

p&

ml

MO

and

ot

hers

25

7, 2

83

V(V

) 1,

2DH

AQ

-3S

C/P

h pH

35_5

8,R

455n

m

0 l-

3 67

/@

/ml

Var

ious

io

ns

284

iA4H

AQ

k/

F 0

Ski

HC

I, 1

,480

, ;I

, 57

5 nm

0

l-o

5 fi

g/m

l C

e 13

6 1,

4DA

-SN

AQ

c/

F 2M

HC

I, ;

len 4

75,

E.,

550

nm

100-

800

ng/m

l 93

4,

8DA

- 1,

5DH

AQ

-2,6

DS

k/F

04M

H

Cl,

A,,

524,

&,,

582

nm

0 04

-a 5

lrg

/ml

Ce,

Fe,

I-

122

4,8D

A-1

,5D

HA

Q-2

,6D

S k/

F 0

4M H

Cl,

il,

524,

&,,,

582

nm

l-

10

ng/m

l C

e, F

e(B

),

I-

130

5 ue

fml

Fe(I

II1

1,2D

HA

Q-3

S

I ,2D

HA

Q-3

S

Car

mnu

c ac

td

c/Ph

C

/F

c/Ph

c/F

pH

3 5-

5 8,

147O

nm

pH

48-

62

pH 4

, L

483

at

30”

, nm

, he

xad~

yltn

met

hyla

mm

on~u

m

pH 4

6,

,$,,

515,

rZ

, 58

5 nm

0 4-

13 3

jig

/ml

Man

y Io

ns

285

0 5-

4 fi

g/m

l A

l m

ust

be a

bsen

t <

: 10

pg/m

l 28

6

0 04

-O 3

6 p&

/ml

Prev

ious

se

para

tton

IS re

com

men

ded

259

Y(I

I1)

w

c/Ph

pH

7 7

,40%

D

MF

7 12

-28

5 pg

/ml

60

Zn(

II)

Zr(

IV)

Ahz

ann

Com

plex

an

I A4H

AQ

4,

8DA

-1 ,S

DH

AQ

-2,6

DS

c/Ph

c/Ph

c/

Ph

pH 4

3,

d 50

0 nm

, st

andi

ng

ttme

30 m

m

0 13

-O 5

pg/

mI

287

pH35

,16W

nm

24-l

13

pg

lnte

rfer

ents

m

aske

d w

tth C

N-

288

0 17

M H

CI,

J. 7

00 n

m

20-2

00 p

g PO

:-,

F-,

BrQ

;, H

,PQ

;, 28

9 E

DT

A,

Fe,

C,C

@

l,ZD

HA

Q-F

- tc

/Ph

pH 8

9,1

556

nm,

MB

K

<20

iu

g In

terf

eren

ts

mas

ked

wtth

ED

TA

29

0 1,

2DH

AQ

-3S

c/

Ph

0 1M

HC

I, A

510

nm

01

-03m

g 75

, 97

c/

Ph

O-8

0 m

g/l

ZrQ

, 24

0 I ,

2,4-

TH

AQ

-3S

c/Ph

pH

O75

_093

,160

9nm

n-

7 lr

glm

l 20

7 1,

2,3,

5,6,

7HH

AQ

c,

!Ph

IM

HC

I, d

560

nm

3-

9 pg

/ml

220

Abb

revt

atto

ns

used

A

liza

rin

Com

plex

an,

[(3,

4-dl

hydr

oxy-

2-an

thra

quln

olyl

)met

hyl]

lmln

odla

cetlc

ac

td,

Ant

hrap

urpu

rin

Com

plex

an,

[(1,

2,7-

trth

ydro

xy-3

-ant

hraq

umyl

)met

hyl]

tmm

o-

dtac

etrc

acr

d, 3

A-1

,2R

HA

Q,

3-am

ino-

1,2-

dihy

drox

yant

hraq

uIno

ne,

lA-4

HA

Q,

I-am

ino-

~hyd

roxy

anth

raqu

lnon

e,

BM

AnA

Q,

I,~B

~~~m

ethy

lanl

Ilno

)ant

hraq

utno

ne,

e, c

ompl

ex

form

atto

n,

Car

min

ic a

cid,

7-a

-a-g

luco

pyra

nosy

l-3,

5,6&

tetr

ahyd

roxy

- I-

met

hyla

nthr

aqum

one-

2-ca

rbox

yhc

actd

, 1,

2DA

AQ

, 1,2

-dta

mm

oant

hraq

umon

e,

1,2D

AA

Q-p

heny

kyd

razo

w,

1,2-

d~am

lnoa

nthr

aqul

none

ph

enyl

hydr

azon

e,

1,2D

AA

Q-3

%

1,2-

d~am

inoa

nthr

aqu~

none

-3-~

ulph

on~c

ac

td,

1,4D

AA

Q2,

3DS,

l,~

dlam

inoa

nthr

aq~l

none

-2,3

-dls

ulph

onlc

ac

td,

1,5D

AA

Q_2

,6D

S,

1,5-

dtam

moa

nthr

aqum

one-

2,6-

dtsu

lpho

mc

acid

, 1,

4DA

-2,3

DH

yAQ

, I ,

4-dt

amm

o-2,

3-dt

hydr

oant

hraq

umon

e,

1,8D

A-&

SDH

AQ

, I,8

dtam

tno-

4,5-

dthy

drox

y-

anth

raqu

Inon

e,

4,8D

A-l

,5D

HA

Q-2

,6D

~,

4.8-

dtam

mo-

i,5-d

~hyd

roxy

anth

raqu

mon

e-2,

6-d~

sulp

hon~

~ ac

td,

1,4D

A-S

NA

Q,

1,4-

diam

lno-

5-nl

troa

nthr

aqui

none

, df

, d~

~ere

ntla

l m

etho

d,

1,2D

HA

Q,

1,2d

lhyd

roxy

anth

raqu

lnon

e,

1,4D

HA

Q-2

,6D

S,

l.~!h

ydro

xyan

thra

quin

one-

2,6-

d~su

lpho

ntc

acid

, 1,

2DH

AQ

GS

, 1,

2-dl

hydr

oxya

nthr

aqui

none

-3-s

ulpb

onlc

an

d,

1,4D

HA

Q-2

S,

I ,4-

drhy

drox

yant

hraq

umon

e-2-

sulp

hom

c ac

td,

1,5D

H-4

,8 D

AA

Q,

I ,5-

dthy

drox

y4,8

_dta

mm

oant

hraq

mno

ne,

DPh

G,

drph

enyl

guam

dmru

m,

F, f

luon

met

nc

met

hod,

IH

-ZC

AQ

, I-

hydr

oxy-

2car

boxy

anth

raqu

mon

e,

1,2,

3,5,

6,7H

HA

Q, 1

,2,3

.5,6

-hex

ahyd

roxy

anth

raqu

mon

e,

ic, m

dtre

ct m

etho

d,

k, k

met

tc m

etho

d,

Ph,

phot

omet

rrc

met

hod,

Ph

QrD

S,

2-ph

enox

yqui

n~za

~n-3

,4-d

~sul

phon

~c

acid

, Q

G,

1,4-

bls-

(~-s

ulph

o-4-

met

hyla

nll~

no)a

nthr

aqul

none

, Q

uina

lizar

in,

1,4,

5,8t

etra

hydr

oxya

nthr

aqm

none

, T

X, re

dox

reac

tron

, tc

, te

rnar

y co

mpl

ex.

1,2,

3TH

AQ

, 1,

2,3-

t~hy

drox

yant

hraq

uin~

ne,

1,2,

4TH

AQ

-2C

, 1,

2,4-

trlh

ydro

xy-2

~arb

oxya

nthr

aqut

none

, I,

2,4T

?iA

Q-3

S,

1,2,

4-tr

lhyd

roxy

anth

raqu

inon

e-3-

sulp

honl

c ac

id,

1,2,

5$T

’lM

AQ

, 1,

2,5,

8~et

rahy

drox

yant

hraq

urno

ne

584 AURORA NAVM DIAZ

ally having a much more pronounced effect than one m the 2-position.‘q4

In the absence of a hydrogen donor, photo- excited AQs can undergo photoreduction by the abstraction of an electron. Aminoanthra- qumones that are relatively unreactive towards hydrogen-atom abstraction, because of the C-T character of the lowest excited state, can undergo photoreduction by electron transfeP2 from hydroxide ions m solutions of high pH.

The photochemistry of anthraquinone-Zsul- phonate and anthraqumone-2,6-disulphonate has received much attention2” and various reaction mechanisms have been proposed. These photoreactions have been used in ltqutd chro- matography to detect compounds’66-168 that do not absorb ultraviolet-visible radiation at all. An anthraqumone-sensitized photo-oxygen- ation reaction produces hydrogen peroxide during the oxidation of the analytes (alcohols, aldehydes, ethers and saccharides) by hydrogen- atom abstraction Once formed, the hydrogen peroxide is measured by a chemilummescence reaction. The photoreduction of anthraquinone- 2,6-disulphonate to dihydroxyanthracene-2,6- disulphonate has been used for the determmation of several herbicides.“’

Anthraqumone-2-sulphonates which have been reduced photochemically can serve as electron donors, and thus can behave as sensitizers of the reduction of electron acceptors.13

Another aspect of the photochemistry of anthraqumones is concerned with the gener- ation of singlet oxygen. Energy transfer between the triplet state of a dye and molecular oxygen occurs as follows

sens* + 302(3Z) + sens + ‘02(‘A)

Anthraqumones which posses relatively long- lived triplet states are likely candidates as sensitizers for the formation of singlet oxygen. 1-Ammo-4-hydroxyanthraqumone and its 2- methoxy derivative are extremely efficient sensitizers of singlet oxygen production. Seven of the components of the dye C I. Disperse Blue 35 are efficient producers of singlet oxygen under the influence of light, the most photoactive component being 1 &diammo-4,5dihydroxy- anthraqumone.4

CONCLUSION

The anthraqumones are very versatile reagents A summary of their prmctpal analytical applications is given m Table 1.

Acknowledgement-The Comtston Asesora de Investtgacton Ctenttfica y Tbmca IS thanked for supportmg thts study (kOJC!Ct 3007/83 CO24l2)

5

6

7

8

9 10 11 12

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REFERENCES

K Venkataraman, The Chemistry of Synthetic Dyes, Vol II, Academtc Press, New York, 1952 J F McKellar, Radraf Res Rev, 1971, 3, 141 A V El’tsov, 0 P Studzmsku and U M Grebenkma, Russ Chem Rev, 1977, 46, 93 I H Leaver, m Photochemrstry of Dyed and Pigmented Polymers, N S Allen and J F McKellar (eds ), Applied Sctence Pubhshers, Barking, 1980 J M Bruce, m The Chemlsrry of Qumold Compounds, S Patar (ed ), Wtley, New York, 1974 Cofour Index, Soctety of Dyers and Colourtsts, and American Assoctatton of Texttle Chemtsts and Colortsts, Bradford, 2nd Ed, 1956 G S Egerton, J M Gleade and N N Uffindell, J Chromatog , 1967, 26, 62 A M Arsov, B K Mesrob and A B Gateva, lbld, 1973, 81, 181 P P Rat and T D Turner, rbrd, 1975, 104, 196 J Franc and M HaJkova, rbrd, 1964, 16, 345 P Wollenweber, rbzd, 1962, 7, 557 R J Passaraelh and E S Jacobs, J Chromarog Scr , 1975, 13, 153 I B Rubm, M V Buchanan and G Olertch, Anal Chon Acta, 1982, 135, 111 I B Rubm and M V Buchanan, rbrd, 1982,135,121 H Labhart, Helu Chum Acta, 1957, 40, 1410 R A Morton and W T Earlam, J Chem Sot, 1941, 159 R H Peters and H H Sumner, lbrd, 1953, 2101 2 Yoshtda and F Takabayasht, Tetrahedron, 1968. 24,913 G S Egerton and A G Roach, J Sot Dyers Col- ores, 1958, 74, 401 H Hartmann and E Lorenz, 2 Narurforsch , 1952, 71, 360 M S El-Ezaby, T M Salem, A H Zewatl and R Issa, J Chem Sot B, 1970, 1293 A Novik, M Tltz and M NepraS, CoNectlon Czech Chem Commun , 1974, 39, 1532 S H Etatw, M M Abou Sekkma, G B El-Hefnawey and S S Assar, Can J Chem , 1982, 60, 304 H Inoue, M Hosht, J Yoshma and Y Tamzakt, Bull Chem Sot Japan, 1972, 45, 1018 N A Shcheglova, D N Shlgorm and N S Dokumkhm, Russ J Phys Chem , 1964, 38, 1067 Idem, Zh Az Khlm , 1968, 2, 2724 N A Shcheglova, D N Shtgorm, R A Nezhel’skaya, L V. Gahtsma and N S Dokumkhm, Russ J Phys Chem, 1974, 48, 163 N A Shcheglova, R A Nezhel’skaya, D N Shtgorm, L V Gahtsma and N S Dokumkhm, ibid, 1974, 48, 166 M NepraS, J Fabian, M Tltz and B GaS, Collecrlon Czech Chem , Commun , 1982, 47, 2569 K R Popov, N V Platonova and L V Smlrnov, Opt Spektrosk, 1972, 32, 1097 D N Shlgorm, Russ J Phys Chem , 1970, 44, 1527 A Navas Diaz, J Pholochem Photobrol A, Chem ,

1990, 53, 141

Analyttcal apphcatrons of 1, IO-anthraqmnones A revtew 585

33 K A Idrtss and M M Seletm, Indian J Chem, 1980, 65 L S Serdyuk and L I Avramenko, lbrd, 1972, 27,

19A, 771 464

34 I M Issa, R M Issa, K A Idrtss and A M Hamman, rbld , 1976, 14B, 117

35 K A Idrtss, I M Issa and M M Seletm, Rev Roum

Chum , 1979, 24, 555

36 K A Idrtss, A Awad, M M Seletm and M S Abu-Bakr, Bull Sot Chrm Fr, 1981, I-180

37 H H Rtchtol and B R Fetch, Anal Chem, 1974,46,

1749 38 J Horyna, Collection Czech Chem Commun , 1959,

24, 2637

39 G Ah Qureshl, G Svehla and M A Leonard, Analyst,

1979, 104, 705

40 C K Laud and M A Leonard, Talanta, 1970, 17,

173

41 M A Leonard, Analyst, 1975, 100, 275

42 M Roman, A Fernandez Gutterrez and C Marin, Ajintdad, 1977, 34, 481

66 L S Serdyuk, V F Sthch and U S Smtrnaya, Tr

Komls po Anaht Khlm , Akad Nauk SSSR, Inst

Geokhlm I Anaht Khim , 1963, 14, 271

67 M K Akhmedh, A A Mehkov, Uch Zap Azerb

Gos Univ. Ser Khrm Nauk, 1968, No 1, 18

68 N S Poluektov, 0 P Makrenko, A 1 Kutllov and R S Lauer, Zh Anaht Khlm , 1973, 28, 285

69 N S Poluektov, L A Ovchar, S F Potapova and R S Latter, zbbrd, 1975, 30, 235

70 K A Idnss, M M Seletm, M K Hassan, M S Abu-Bakr and H Sedatra, Analyst, 1985, 110, 705

71 F Garcia Sanchez, M Hernlndez Lopez and J C Mdrquez Gomez, Talanta, 1987, 34, 639

72 Idem, Analyst, 1987, 112, 1037

73 F Garcia Sanchez, M Hernandez, J C Marquez, A L Ramos, C Cruces and C Carnero, Inorg Chum

Acta, 1987, 140, 249

43 A V Karyakm, T S Sorokma, V M Ivanov, T G Aktmova, N A Lebedeva and A A Karyakm, Zh

Anabt Khlm , 1982, 37, 1171

44 R M Issa, M S El-Ezaby and A H Zewatl, Z Phys

Chem , L.elpzrg, 1970, 244, 155 45 M Roman, A Fernandez Gutterrez and M C

Mahedero, An Quzm , 1978, 74, 439

46 D V Gonzalez Garcia, A Arrebola Ramuez and M Roman Ceba, J Inorg Nucl Chem, 1980, 42,

1453

74 A K Dey and S K BanerJt, Proc Symp Chem

Coord Compounds, Agra, India, 1959, Part 2. 198 75 H E Ztttel and T M Florence, Anal Chem , 1967,39,

321

76 R Suemttsu, Agr Wol Chem , 1963, 27, 1 77 M Roman, A Fernandez Gutterrez and A Mufioz de

la Petia, An Qulm , 1983. 79B, 128

78 E G Keel and P M HeertJes, J Sot Dyers Colourws,

1963, 79, 363

47 H Gtllet and J Ch Panaud, Bull Sot Chum Fr , 1966, 2624

79 J Laszlovszky, Acta Chum Acad Scz Hung, 1964.41,

133

48 F Sahnas, A Muiioz de la Petia and J A Murtllo, Talanta, 1986, 33, 923

80 S Shtbata, M Taktto and 0 Tanaka, J Am Chem

Sac , 1950, 72, 2789

49 H H Rtchtol and B R Fetch, Anal Chem , 1974,46, 1860

50 J Barbosa, E Bosch and R Carrera, Talanta, 1985,

32, 1077

81 V V Korshak, S V Vmogradova, V S Artemova, Vysokomolekulyarnye Soedmemya, 1960, 2, 492

82 F Capttan, M Roman and F Garcia Sanchez, If

Qulm Anal, 1973, 27, 7

51 F Capnan, E de Manuel and F Sahnas, Qurm Anal,

1974, 28, 153

52 F Cap&n, E de Manuel and M J Ruedas, ibid,

1975, 29, 27

83 M Roman, A Femandez Gutterrez and F Cardenas, An Qulm , 1980, 76B, 442

84 K Em], K Toet and K Harada, Nippon Kagaku Zasshl, 1957, 78, 1299

53 F Cap&n, F Garcia Sanchez and A Gomez Hens, Bol Sot Chrl Qurm, 1978, 23, No 2, 16

54 F Garcia Sanchez and A Navas Diaz, Ajinrdad, 1979, 36, 133

55 F Capttan, F Garcia Sanchez and A Gbmez Hens, Qulm Anal (Barcelona), 1982, 1, 178

56 I Krausz and A E Havas, Magy Kern Foly , 1967,

73, 135

85 M Roman, F Garcia Sanchez and L F Cap&n Vallvey, Bol Sot Qwm Peru, 1976, 42, 192

86 I Dahl and J A Myrstad, Acfa Chem Stand, 1966,

20, 1758

87 R S Brown, Anal Chum Acla, 1975, 74, 441

88 A K Jam, V P Aggarwala, P Chand and S P Garg, Talanfa, 1972, 19, 1481

57 I Krausz, A E Havas, M Kaldy and E Fodor, Ann

Unrv SCI Budapest, Roland0 Eotvos Nommatae, Sect

Chum, 1968, 10, 77

58 F Garcia Sanchez, M Hernandez Lopez and A Heredta, Anal Chrm Acta, 1986, 187, 147

59 A T Rhpenko and L I Savranskn, Zh Anahr Khlm , 1977, 32, 421

60 K A Idrtss, M K Hassan, M S Abu-Bakr and H Sedatra, Analyst, 1984, 109, 1389

61 A T Pthpenko and L I Savransku, Izv Vyssh Ucheb

Zaved , Khlm Khlm Tekhnol , 1973, 16, No 1, 32 62 F Garcia Sanchez, C Cruces Blanc0 and A Heredta

Bayona, Talanta, 1987, 34, 345

63 M K Akhmedh, P B Granovskaya and R A Nelmatova, Zh Anabt Khlm , 1976, 31, 298

64 L S Serdyuk and S M Lazorma, rbrd, 1966, 21,

561

89 R Belcher, M A Leonard and T S West, J Chem

Sot, 1958, 2390

90 M A Leonard and T S West, lbtd, 1960, 4477

91 R Belcher, M A Leonard and T S West, rbtd, 1959, 3577

92 Idem, Talanta, 1959, 2, 92

93 M Roman, F Garcia Sanchez and A Gomez Hens, Qulm Anal, 1974, 28, 191

94 K A Idnss, A A Harfoush, A S El-Shahawy and H Sedatra, Analyst, 1985, 110, 709

95 R F Buchanan, J P Hughes and C A A Bloomqutst, Talanta, 1960, 6, 100

96 H B Evans, A M Hrobar and J H Patterson, Anal

Chem , 1960, 32, 481

97 G B Wengert, rbrd, 1952, 24, 1449

98 D F Wood and R H McKenna, Analyst, 1962, 87,

880

99 N B Stanton, rbld, 1968, 93, 802

100 H Degenhardt, Z Anal Chem, 1956, 153, 327

586 AURORA N AVAS DIAZ

101 J A Corbett and B D Guerm, Analyst, 1966,91,490 102 H G C Kmg and G Pruden, zbrd, 1968, 93, 601 103 L A Lancaster and R Balasubramamam, J Scr Food

Agr , 1974, 25, 381 104 G W Goward and V R Wtederkehr, Anal Chem ,

1963, 35, 1542 105 D L Calhcoat and J D Wolzon, rbrd, 1959,31, 1434 106 D G Htggs, Analyst, 1960, 85, 897 107 F Rbb, Collecrron Czech Chem Commun 1959, 24, ,

3654 108 R S Brown, Anal Chum Acta, 1970, 50, 157 109 J T Hatcher and L V Wdcox, Anal Chem , 1950,22,

567 110 E N Pollock and L P Zopattt, Talanta, 1963,10, 118 111 K C Berger and E Truog, Ind Eng Chem , Anal Ed,

1939, 11, 540 112 A H Jones, Anal Chem 1957, 29, 1101 , 113 F J Langmyhr and A Holme, Anal Chzm Acra,

1966, 35, 220 114 H K L Gupta and D F Boltz, Mtkrochzm Acra,

1971, 577 115 R Greenhalghand J P Rtley, Anal Chum Acra, 1961,

25, 179 116 S S Yamamura, M A Wade and J H Stkes, Anal

Chem , 1962, 34, 1308 117 M Hanocq and L Molle, Anal Chum Acra, 1968, 40,

13 118 H Kubota, Mzcrochem J , 1967, 12, 525 119 H N S Schafer, Anal Chem, 1963, 35, 53 120 J P S Haarsma and J Agterdenbos, Talanfa, 1971,

18, 747 121 I Krausz and A Endrot-Havas, Proc S A C Confer-

ence, Nottingham, 1965, p 568 122 F Garcia Sanchez, A Navas Diaz, M Santiago and

F Grases, Talanta, 1981, 28, 833 123 F Capttan, M Roman and F Garcia Sanchez, Inf

Quzm Anal, 1973, 27, I 124 F Capttan, F Garcia Sanchez and A Gomez Hens,

Ajinzdad, 1977, 34, 755 125 Idem, An Quzm, 1978, 74, 272 126 F Garcia Sanchez and A Navas Diaz, Rev Sot Quzm

Mex, 1982, 26, No 2, 80 127 F Sahnas, F Garcia Sanchez and C Genestar,

Ajinzdad, 1982, 39, 261 128 E Bishop (ed ), Indzcators, Pergamon Press, Oxford,

1972 129 K B Yatstmtrskn, Kznetzc Methods of Analyszs,

Pergamon Press, Oxford, 1966 130 A Navas Diaz, M Santiago, F Grases, J J Laserna

and F Garcia Sanchez, Talanta, 1982, 29, 615 131 A Navas Diaz and F Sanchez RoJas, Analyst, 1984,

109, 1435 132 A Navas Diaz and F Sanchez RoJas, Qutm Anal

(Barcelona), 1983, 2, 112 133 Gh Ionescu, Al Duca and F Mate], Mzkrochzm Acta,

1980 1, 329 134 P R Bontchev, Talanta, 1970, 17, 499 135 A Navas Diaz and F Sanchez RoJas, zbzd, 1984, 31,

437 136 F Salmas, F Garcia Sanchez, F Grases and

C Genestar, Anal Left, 1980, 13, 473 137 F Sahnas, C Genestar and F Grases. Anal Chzm

Acta, 1981, 130, 337 138 J BognPr and 0 Jelhnek, Mag Kern Fe/y , 1961, 67,

147 139 J Bognar, Mzkrochzm Acra, 1961, 901

140 N V Parkhomenko, G A Prtk and K B Yatstmtrskn. Zh Anahf Khzm , 1961, 16, 599

141 F Salmas, F Garcta Sanchez and C Genestar, Anal Lerr , 1982, 15, 747

142 A Navas Diaz and F Sanchez RoJas, Mzcrochem J , 1985, 31, 50

143 A Navas Diaz and F Sanchez RoJas, Mzkrochzm Acta, 1982 1, 175

144 M Roman, A Fernandez Gutterrez and A Mufioz de la Petia, Mzcrochem J, 1984, 29, 19

145 Idem, An Quzm 1984, 80, 332 ,

146 N H Furman and K G Stone, J Am Chem Sot, 1948, 70, 3055

147 F Capnan, A Gmraum, J L Vtlchez and J F Arenas, Can J Chem , 1979, 57, 3243

148 L A Wales, J Chem Sot, 1952, 1358 149 R Jones and T McL Spotswood, Ausr J Chem ,

1962, 15, 492

150 F Capttan, E Alvarez Manzaneda and J L Vtlchez, Proc Indzan Acad Scz (Chem Scr ), 1984, 93, 59 ,

151 M Roman Ceba, A Sanchez Mtstego, A Femandez Gutterrez and A Muiioz de la Pefia, Ann Chzm Roma, 1984, 74, 837

152 R G111 and H I Stonehill, J Chem Sot 1952, 1845 ,

153 V D Bezuglyt, V A Shapovalov and V Ya Fain, Zh Obshch Khzm , 1976, 46, 696

154 A D Broadbent and R J Melanson, Can J Chem ,

1975, 53, 3757 155 A D Broadbent and E F Sommermann, J Chem

Sot, B, 1967, 376

156 Idem, zbzd. 1968, 519 157 F Capttln, J L Vtlchez and A Navalon, Analysf,

1982, 107, 953 158 F Capttan, A Gutraum and J L Vtlchez, Can J

Chem, 1981, 59, 1201 159 F Umland, Zh Anaht Khzm, 1978. 33, 612 160 S D Popescu and E Barbacaru, Anal Let?, 1985, 18,

947 161 N S Allen, P Bentley and J F McKellar, J Photo-

them , 1976, 5, 225 162 A K Davtes, J F McKellar and G 0 Phtlhps, Proc

Roy Sot Ser A, 1971, 323, 69 163 F Wtlkmson, J Phys Chem 1962, 66, 2569 , 164 H H Dearman and A Chart, J Chem Phys, 1966,

44, 416 165 H R Cooper, Trans Faraday Sot, 1966, 62, 2865

166 M S Gandelman and J W Barks, J Chromatog ,

1982, 242, 21

167 Idem, Anal Chem, 1982, 54, 2131 168 J R Poulsen and J W Barks, zbzd, 1989, 61, 2267 169 Idem, zbzd, 1990, 62, 1242 170 S Traore and J J Aaron, Anal Lezt, 1987, 20,

1995 171 W Oelschlager, Z Anal Chem, 1957, 154, 321 172 E G Owens and J H Yoe, Anal Chem, 1959, 31,

384 173 F Capttan, M Roman and A Guuaum, An Quzm ,

1974, 70, 508

174 F Cap&n-Garcia, M Roman and E Alvarez Manzaneda, Bol Sot Quzm Peru, 1973, 39, 125

175 F Capttin and M Roman, Rev Unzr Ind Santander, 1967, 9, No 314, 17

176 F Ingman, Talanra, 1973, 20, 999 177 F Capttln, F Garcia Sanchez and A G6mez Hens,

Afinzdad, 1977, 34, 467 178 A Holme, Acta Chem Stand, 1967, 21, 1679

Analyttcal apphcatrons of I,lO-anthraqumones A revtew 587

179 F Salmas, A Muiioz de la Petia, J A Murtllo and J C Jtmenez Sanchez, Analysr, 1987, 112, 913

180 R Ruggtert, Anal Chum Acra, 1961, 25, 145

181 E C Cogbtll and J H Yoe, Anal Chem , 1957, 29, 1251

182 G Wunsch, Z Anal Chem, 1972, 258, 30 183 P K Govtl and S K BanerJi, J Insr Chem , Calcutta,

1972, 44, 128

184 M W CUCCI, W F Neuman and B J Mulryan, Anal

Chem, 1949, 21, 1358 185 A Gmraum and J L Vdchez, Quzm Anal, 1975, 29,

265

186 L 0 Matveev and I S Mustafin, Tr Komzs po Analzt

Khzm , Akad Nauk SSSR, Inst Geokhzm Anal Khzm ,

1960, 11, 217 187 M H Fletcher, C E White and M S Sheftel, Ind

Eng Chem , Anal Ed, 1946, 18, 179 188 F Capttln, F Sahnas and L M Franquelo, An

Quzm , 1976, 72, 529

189 Idem, Anal Lett , 1975, 8, 753

190 A Navas Diaz and F Garcia Sanchez, An Quzm , 1979, 75, 514

191 P Kaur and V K Gupta, Z Anal Chem , 1989,334, 447

192 F Sahnas, J J Berzas Nevado, A Espmosa Manctlla and T Roman Galan, Bull Sot Chzm Belg , 1987, %,

71

193 E G Owens and J H Yoe, Anal Chem, 1960, 32, 1345

194 F Salmas, A Mufioz de la Petia and J A Munllo, zbzd, 1987, 112, 1391

195 H V Connerty and A R Briggs, Clzn Chem , 1965, 11, 716

196 M C Mahedero, M Roman Ceba and A Femandez Gutterrez, Anal L.ett , 1986, 19, 1725

197 M Roman, A Fernandez Gutterrez and F Cardenas, Rezl Sot Quzm Mex, 1977, 21, No 3, 89

198 Idem, Bol Sot Chzl Quzm 1980, 25, No I, 1 199 F Caprdn and M Roman, Inf Quzm Anal, 1968,22,

134, Ars Pharm , 1968, 9, 65

200 M Roman, A Fernandez Gutterrez and F Cardenas, Ajnzdud, 1981, 38, 253

201 Idem, Mzcrochem J, 1980, 25, 576

202 F Cap&n, A Gmraum and J BUkJos, Ajnzdad,

1975, 32, 461

203 F Capttan, M Roman and A Gunaum, An Quzm , 1972, 68, 989

204 F Capnan, M Roman and A Fernandez Gutrerrez, Bol Sot Chzl Quzm , 1971, 17, No 2, 29

205 E Illner, Z Chem , Lerpzrg, 1965, 5, 389

206 V I Vershmm, V T Chutko and B E Rezmk, Zh

Analzr Khzm, 1971, 26, 1710

207 M Roman and E Alvarez Manzaneda, Quzm Anal,

1975, 29, 253

208 F Cap&n, M Roman and F Garcia Sanchez, Rev

Unzr Ind Santander, 1978, 8, No 8, 43

209 F Garcia Sanchez, F Bosch Rerg and J M Estela, An Quzm , 1980, 76B, 273

210 S P Sangal. Chzm Anal, Pans, 1964, 46, 492

211 M Roman, A Arrebola and F Perera, Afinzdad, 1979,

36, 27

212 M Roman, A Fernandez Gutterrez and A Mmioz de la Pefia, zbzd, 1983, 40, 355

213 Idem, An Quzm, 1983, 79B, 128

214 F Capttan, M Roman and F Garcia Sanchez, Inf

Quzm Anal, 1973, 27, 179

215 A Navas and F Garcia Sanchez, An Quzm , 1979,7S,

506

216 F Capttan, A Gutraum and J L Vtlchez, Ajinzdad,

1980, 37, 129

217 R I Sptrma and K V Lyakhova, ZavodFk Lab , 1989, 55, No 4, 6

218 J M Icken and B M Blank, Anal Chem, 1953, 25, 1741

219 F Cap&m and A Gmraum, Ars Pharm, 1971, 12,

397

220 F Caprtdn, F Salmas and J Cobo, Rev Sot Venez

Quzm 1972, 8, No 415, 163

221 M E Le6n Gonzalez, M J Santos-Delgado and L M Polo Diez, Anal Chum Acta, 1989, 219, 329

222 M Chtkuma, Y Okabayashr, T Nakagawa, A Inoue and H Tanaka, Chem Pharm Bull, 1987, 35, 3734

223 Y Okabayasht, R Oh, T Nakagawa, H Tanaka and M Chtkuma, Analyst, 1988, 113, 829

224 M M Ferns, B Bmgham and M A Leonard, Anal

Proc , 1988, 25, 58

225 S Przeszlakowskt, Chem Anal, Warsaw, 1988, 33,

617

226 M Roman Ceba, A Arrebola Ramtrez and J J Berzas Nevado, Talanra, 1982, 29, 142

227 Ch D Dwtvedt, K N Munshr and A K Dey, Mzcrochem J , 1965, 9, 218

228 A T Pthpenko and E G Makstmyuk, Ukr Khzm

Zh , 1987, 53, 58

229 0 Engel and S Kdl, Hutn Lzsty, 1970, 25, 432

230 M K Akhmedh, D G Gasanov and R A Aheva, Acerb Khzm Zh, 1965, No 4, 92

231 M Roman and A Femandez Gutterrez, Bol Sot

Quzm Peru, 1975, 41, No 1, I 232 M Fmkel’shtematte and J GarJonyte, Zh Vses Khzm

Obshch , 1968, 13, 593

233 M Fmkel’shtemarte, J GarJonyte and V Skommatte, Lzet TSR Auks1 Mokykhu Mkslo Darb Chem Chem

Technol, 1970, 11, 69 234 M Roman and A Fernandez Gutterrez, Quzm Anal,

1975, 29, 203

235 V A Nazarenko, G V Flyanttkova, L I Korolenko and Yu N Amsrmov, Zh Analzt Khzm , 1975, 30,

1354

237 G V Flyanttkova and L I Korolenko, Zh Analzt

Khzm , 1975, 30, 1349

236 M Roman and A Fernandez Gutterrez, Qurm Anal,

1975, 29, 281

238 D I Zul’fugarly, I K Gusemov and Kh N Kuheva, Azerb Khrm Zh , 1972, No 2, 173

239 G V Flyantrkova, V A Nazarenko and I G Kostenko, Zh Analzt Khzm , 1975, 30, 814

240 E Crepaz, L Marchesma and G Mazzohm, Met Ital, 1962, 54, 373

241 M Otomo and K Tonosakt, Tulanta, 1971, 18,

438

242 M Roman, A Fernandez Gutlerrez, M C Mahedero and A Muiioz de la Pefia, Rev Port Quzm , 1983,2S, 41

243 E A Btryuk and V A Nazarenko, Zh Analzt Khzm , 1975, 30, 1720

244 A Fernandez Gutterrez, A Mutioz de la Peiia and J A Murillo, Anal Lerr , 1983, 16, 759

245 F Sahnas, A Muiioz de la Peiia and J A Murtllo, Mzcrochem J, 1987, 36, 79

246 L S Serdyuk and U F Sthch, Izv Vyssh Ucheb

Zaved , Khzm Khzm Tekhnol , 1962, 5, 38


247 K C Snvastava and S K BanerJi, J Prakt Chem, 1968, 38, 327

248 M Roman Ceba, A Fernandez Gutterrez and M C Mahedero, Anal Lert , 1981, 14, 1579

249 F Sahnas, A Mutioz de la Peiia and F Mutioz de la Pefia, Mzkrochzm Acta, 1985 III, 361

250 M Roman Ceba, A Fernlndez Gutterrez and C Marin Sanchez, Anal Letf , 1982, 15, 1621

251 Idem, Mrcrochem J, 1982, 27, 339 252 M Roman Ceba, A Fernandez Gutrerrez and A

Palomera, Anal Lert , 1977, 10, 907 253 F Cap&n, F Sahnas and L M Franquelo, Qurm

Anal, 1977, 31, 275

254 F Capstan, M Roman and A Gutraum, Qurm Ind, 1971, 17, 15

255 Idem, An Qurm, 1971, 67, 147 256 S N Smha and A K Dey, Z Anal Chem , 1963,195,

416 257 S Ram and S K BanerJt, Mtcrochem J, 1973, 18,

636 258 A Lee and D F Boltz, rbld, 1972, 17, 380 259 G K Ktrkbrtght, T S West and C Woodward,

Talanta, 1966, 13, 1637 260 E Blanc0 Gonzalez, J I Garcia Alonso, M E Dtaz

and A Sanz-Medel, Qurm Anal (Barcelona), 1986, 5, 428

261 T Roman Galan, A Arrebola Ramirez and M Roman Ceba, Mzcrochem J, 1982, 27, 210

262 F Sahnas and L M Franquelo, Qurm Anal, 1975,29, 319

263 M A Leonard and F I Nagl, Talanta, 1969,16, 1104 264 S P Sangal, Chtm Anal , Parzs, 1968, 50, 131 265 M Roman, A Fernandez Gutterrez and A Muiioz de

la Petia, Mlcrochem J , 1984, 29, 275 266 F Capttln, F Garcia Sanchez and A Gomez Hens,

Bol Sot Chrl Qulm , 1979, 24, No 1, 1 267 A Navas and F Garcia Sanchez, Ajinrdad, 1979, 36,

161 268 M Roman, F Garcia Sanchez and A Gomez Hens,

tbtd, 1977, 34, 118 269 A T Pthpenko, T L Shevchenko, Zh Analrr Khlm ,

1989, 44, 1262

270 F Garcia Sanchez, F Bosch Retg and J M Estela. Ajmdad, 1979, 36, 156

271 K K Saxena and B V Aganvala, Indian J Chem , 1976, 14A, 634

272 J C MacDonald and J H Yoe, Anal Chrm Acta, 1963, 28, 264

273 K A Idnss, M M Seletm, M S Abu-Bakr and M S Saleh, Analyst, 1982, 107, 12

274 M Roman Ceba, A Fernandez Gutterrez and F Cardenas, An Qutm , 1980, 76B, 447

275 F Captdn and M Roman, Ars Pharm , 1967,

8, 7 276 T Barra and B Seeger, Rev Real Acad CIenc

Exactas, Fls Natur Madrzd, 1967, 61, 827

277 F Capttan, F Sahnas and J Cobo, Ral Sot Vene: Qulm 1971, 8, No 1, 33

278 A Navas Diaz and F Garcia Sanchez, An Qurm , 1979, 75, 511

279 M M Selelm, K A Idnss, M S Abu-Bakr and M S Saleh, An Qurm, B, 1988, 84, 168

280 V I Kuznetsov and A I Zabelm, Zh Anahf Khrm , 1962, 17, 318

281 A K MukherJt and A K Dey, Z Anal Chem, 1958, MO,98

282 I M Issa, R M Issa and Y Z Ahmed, Mlcrochem J, 1973, 18, 569

283 J M Ramtrez de Verger and F Pmo Perez, Inf Qurm Anal, 1963, 17, 39

284 S N Smha and A K Dey, J Prakr Chem , 1963.20, 225

285 I&m, Z Anal Chem , 1961, 183, 182 286 T Perez Rmz, C Martmez Lozano and A C&novas

Garcia, Ajimdad, 1987, 44, 273

287 F Burnel Marti, A Cabrera Martin and C Fuentes Gutrerrez, If Quzm Anal, 1965, 19, 165

288 K A Idrtss, M M Seletm, M S Saleh, M S Abu-Bakr and H Sedana, Analyst, 1988, 113, 1643

289 F Sanchez RoJas, Ajinrdad, 1988, 45, 222 290 R Lopez Nuiiez, M CalleJon Monchon and

A Gutraum Perez, Anal Chum Acta, 1987, 192, 119

analytical applications of 1, io-anthraquinones: a review

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