research article effect of some substituents...

Research ArticleEffect of Some Substituents Increasing the Solubility of Zn(II)and Al(III) Phthalocyanines on Their Photophysical Properties

A A Chernonosov1 E A Ermilov2 B Roumlder2 L I Solovyova3 and O S Fedorova1

1 Institute of Chemical Biology and Fundamental Medicine Siberian Branch of the Russian Academy of SciencesLavrentiev Avenue 8 Novosibirsk 630090 Russia

2 Institut fur Physik Photobiophysik Humboldt-Universitat zu Berlin Newtonstraszlige 15 12489 Berlin Germany3 Institute of Organic Intermediates and Dyes B Sadovaya 14 Moscow 123995 Russia

Correspondence should be addressed to A A Chernonosov sandynibochnscru

Received 29 May 2014 Accepted 4 August 2014 Published 11 September 2014

Academic Editor Francesco P Fanizzi

Copyright copy 2014 A A Chernonosov et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Water solubility of phthalocyanines (Pcs) usually increases by the introduction of charged or carboxy substituents in the peripheralpositions of the macrocycle As a result such structural changes influence their photophysical and photochemical properties asphotosensitizers Phthalocyanines substituted with four or eight terminal carboxyl groups and having in some cases additionaleight positive charges (water soluble phthalocyanines) were studied in order to evaluate the spectroscopic and photophysical effectsof these side residues on the chromophore properties The quantum yield of singlet oxygen (1O

2) generation the triplet-triplet

absorption and the transient absorption spectra were measured and linked to the structure of the substituents It was shown thatcharged substituents did not change the quantum yields of 1O

2generation but decrease its lifetimesThe introduction of the charged

substituents not only increases the water solubility but also significantly changes absorption fluorescence and transient absorptionspectra of water soluble Pcs

1 Introduction

Phthalocyanines are purely synthetic analogues of por-phyrins They have a great potential as photosensitizers inphotodynamic therapy (PDT) for the treatment of malignan-cies and other diseases [1ndash4] As photosensitizers Pcs havethe advantage of high molar absorption [5 6] resistance tochemical and photochemical degradation and long lifetimesof 1O

2with high quantum yields [7] Moreover Pcs have

absorption and emission in the range of 660ndash750 nmmakingthem sensitive to the light which can penetrate deeply intoliving tissues [8] Propensity to aggregation due to molecularstacking resulting in low quantum yields of 1O

2[9 10] and

limiting solubility in aqueous media is the disadvantage ofthese dyes

The chemical structure of Pcs can be modified by theintroduction of substituents in the peripheral positionsof the tetraaza isoindole macrocycle [11] as well as bythe coordination of metal ions with the central nitrogen

atoms and the addition of axial ligands in the fifth andsixth coordinative positions of such molecules [12 13]Primary goal of such modifications of Pcs is to tune thewater solubility and aggregation [14 15] without significantchanges in the photophysical properties Introduction ofseveral identical groups for example carboxylic groups doesnot break significantly the symmetry of the Pc moleculesbut usually reduces their aggregation In this work wereport the spectroscopic and photophysical characteristicsof several new Pcs derivatives that can potentially serve asphotosensitizers for PDT with favorable water solubilityWe examined Al(III) tetra-4-carboxymethyl sulfanyl (1)Zn(II) tetra-4-carboxyhexylsulfamidophthalocyanine (2)having terminal carboxyl groups as well as Al(III) andZn(II) octakis-45-[2-(N-carboxymethyl-NN-dimethyl-ammonium)ethoxycarbonyl] phthalocyanine octachlorides(3 and 4) having eight charged substituents (Figure 1) inorder to evaluate the spectroscopic and photophysical effectsof these side residues on the chromophore properties

Hindawi Publishing CorporationBioinorganic Chemistry and ApplicationsVolume 2014 Article ID 952632 7 pageshttpdxdoiorg1011552014952632

2 Bioinorganic Chemistry and Applications

Y = ndashSO2NH(CH2)5ndash M = AlCl (1)

Y = ndashSCH2ndash M = Zn (2)

R+ = ndashCH2CH2N+(CH3)2CH2COOH

M = AlOH (3) Zn (4)

HOOC

HOOC

Y

Y

Y

Y

COOH

COOH

N

NN

N N

N

N

N

N

N

N

N

NN

N

N MM

ClminusR+OOC

ClminusR+OOC

COOR+ Clminus COOR+ Clminus

COOR+ Clminus

COOR+ Clminus

COOR+ ClminusCOOR+ Clminus

Figure 1 Structures of the Pc complexes 1ndash4

The quantum yield of 1O2generation the measurements

of the triplet-triplet absorption and the picosecond transientabsorption spectra (ps-TAS) which are crucial in determin-ing the feasibility of using these dyes for PDT are reportedand linked to the structure of the substituents

2 Materials and Methods

21 Chemicals and Reagents Dimethylformamide (DMFSigma Germany) D

2O and double-distilled water were used

as solvents

22 Al(III) Tetra-4-carboxymethylsulfanylphthalocyanine (1)This compound has been prepared by analogy with [16]The yield of compound 1 was about 30 UV-vis 120582maxnm (DMF) 680 613 353 (relative intensity 1 02 035)(water ethanol 1 1) 693 652 sh 618 sh 349 (relative inten-sity 085 065 05 1)

23 Zn(II) Tetra-4-carboxyhexylsulphamidophthalocyanine(2) This compound has been prepared by analogy with [16]The yield of compound 1 was about 30 UV-vis 120582maxnm (DMF) 690 622 363 (relative intensity 1 022 044)(water ethanol 1 1) 682 sh 637 344 (relative intensity059 078 085)

24 Hydroxyaluminum Octakis-45-[2-(N-carboxymethyl-NN-dimethylammonium)ethoxycarbonyl] Phthalocyanine Oct-achloride (3) To a solution of 01mmol hydroxyaluminumoctakis-4 5-(2-chloroethoxycarbonyl) phthalocyanine [17]in 15mL anhydrous N-methylpyrrolidone 18mmol NN-dimethylglycine and catalytic amount of sodium iodide wereadded and reaction mixture was stirred 6 h at 105ndash110∘Ccooled and poured in the mixture of petroleum ether-benzene (3 1) solvent was decanted the precipitate waswashed with benzene and ether and then dried in a vacuum

desiccator over phosphorus pentoxide The yield of com-pound 3 was about 90 UV-vis 120582max nm (water) 690 652350 (relative intensity 095 092 1) (ethanol) 691 682 617352 (relative intensity 197 195 072 1)

25 Zinc Octakis-45-[2-(N-carboxymethyl-NN-dimethylam-monium)ethoxycarbonyl] Phthalocyanine Octachloride (4)This was prepared analogously from zinc octakis-45-(2-chloroethoxycarbonyl) phthalocyanine [17] with yield of92 UV-vis 120582max nm (water) 685 sh 641 345 (relativeintensity 074 107 1) (ethanol) 676 643 344 (relative inten-sity 1 108 10)

Compounds 1 and 2 are soluble in polar solvents espe-cially DMSO and DMF as well as aqueous acetonitrile andalcohols Compounds 3 and 4 are soluble in water concen-trated mineral acids and their aqueous solutions alcoholsand polar aprotic solvents UV-vis absorption spectra of theiraqueous solutions show an aggregation to a lesser extent inthe case of aluminum complex 3

26 Absorption and Steady-State Fluorescence The groundstate absorption spectra were recorded using a spectropho-tometer Shimadzu UV-2501PC at room temperature Thesteady-state fluorescence spectra were measured using 1 cmtimes 1 cm quartz cells with a combination of a cw-Xenon lamp(XBO 150) and a monochromator (Lot-Oriel bandwidth10 nm) for excitation and a polychromator equipped with acooled CCDmatrix as a detector system (Lot-Oriel InstaspecIV) [18]

27 Time-Resolved Singlet Oxygen Luminescence Measur-ement These measurements were carried out using ananosecond Nd YAG laser (BM Industries Evry CedexFrance) coupled with an optical parametric oscillator (BMI)The 1O

2emission was detected using a liquid nitrogen

cooled Ge-diode (North Coast Inc Santa Rosa CA) For

Bioinorganic Chemistry and Applications 3

wavelength selection a combination of a silicon filter andan interference filter with the center wavelength of 1270 nmwas placed in front of the diode [19] The optical density ofthe sample was adjusted to 02 at the excitation wavelengthsin the 600ndash680 nm region Tetraphenylporphyrin served as areference standard for the determination of the singlet oxygenquantum yield (Φ1O

2

) with value 075 [20]

28 Laser Flash Photolysis In the triplet-triplet absorptionmeasurements the samples were excited using the sameinstrumentation as described above A continuous wavemonitoring beam was formed by light from XBO lamp thatpassed through a monochromator tuned to 488 nm Thebeam traversed through the solutions of studied compoundsperpendicular to the excitation beam The intensity of themonitoring beam was measured using an avalanche Si-photodiode equipped with an interference filter for 488 nmOxygen was removed by bubbling the samples with nitrogen(purity 990) for ca 40min at room temperature [21]

29 Picosecond Transient Absorption Spectroscopy To mea-sure ps-TAS a white light continuum generated in a cellwith a D

2OH2O mixture using intense 25 ps pulses from a

Nd3 YAG laser (PL 2143A Ekspla) at 1064 nm was used forthe monitoring beam Before passing through the samplethe monitoring beam was split to provide the referencespectrum The transmitted as well as the reference beamswere focused into two optical fibers and were recordedsimultaneously at different strips on a CCD-matrix (Lot-Oriel Instaspec IV) Tunable radiation from an OPGOPA(Ekspla PG 401SH tuning range 200ndash2300 nm) pumped bythird harmonic of the same laser was used as an excitationbeamThemechanical delay line allowed themeasurement oflight-induced changes of the absorption spectrum at differentdelays up to 15 ns after excitation The OD of all samples was10 at the maximum of the absorption band of the lowestenergy The analysis of the experimental data was performedusing the compensation method [22]

3 Results

In the present work the photophysical parameters of Zn(II)and Al(III) Pcs complexes 1ndash4 containing different sideresidues were studied All Pcs have terminal carboxyl groupswith spacers of different lengths and two of them (3 and 4)have eight positive charges in molecule

The chemical structures of the studied compounds areshown in Figure 1

The tetracarboxy-phthalocyanines 1 and 2 are not solublein water However the introduction in benzene rings ofmacrocycle of charged substituents leads to the increase inthe solubility of the resulting compounds 3 and4 To comparephotophysical properties of compounds 1 and 2 with water-soluble Pcs 3 and 4 in water-like solutions Pcs complexes1 and 2 were dissolved in 07 DMF in H

2O (or in D

2O)

mixture Such amount of DMF is appropriate to keep cellsalive that is important for further testing of compounds aspotential photosensitizers in PDT

Table 1 Quantum yields of 1O2generation and lifetimes of 1O

2

Compounds Solvent Φ1O2 119879 120583s1 DMF 012 199 plusmn 00

2 DMF 022 229 plusmn 00

1 07 DMF in D2O 016 100 plusmn 02

2 07 DMF in D2O 009 93 plusmn 02

3 D2O 011 69 plusmn 05

4 D2O 022 69 plusmn 04

31 Absorption and Steady-State Fluorescence Spectra Theabsorption spectra (see Figure 2) of the Pcs 1 and 2 and thecontaining charged residues 3 and 4 differ The changes inthe visible spectrum region are more significant for water-soluble Pc 4 the Q-band becomes broader and its maximumshifts are from 690 nm to 650 nm In the case of Pcs 1 and 3the Q-band at 610 nm disappears but the Q-band at 650 nmoccurs In case of Pc 3 the intensity of the Q-band at 690 nmdecreases relatively to that at 650 nm The Q-bands becomebroader for Pc 3 as well as for Pc 4

The fluorescence spectra of all compounds contain bandswith a maximum in the range of 680ndash730 nm and a shoulderat 750ndash770 nm (Figure 2) as well as a maximum of differentintensities in the range of 400ndash450 nm Blue shift is revealedin the fluorescence spectra in the 680ndash730 nm region for thePcs 3 and 4 in comparison to the Pcs 1 and 2 respectivelyCompounds 3 and 4 have low fluorescence intensity

32 SingletOxygenMeasurements Several solventswere usedin the measurement of the quantum yield of 1O

2generation

due to the different solubility of the studied compounds inaqueous media Pure DMF and 07 DMF in D

2O were

used for 1 and 2 samples D2O was used for Pcs 3 and

4 Tetraphenylporphyrin and tetraphenylporphyrin tetrasul-fonate were used as references in organic and water solutionsrespectively

The comparison of the quantum yields of 1O2allows

finding compounds with similar behaviours (Table 1) Firstthe value of Φ1O

2

for compounds 1 and 2 in DMF and 3 and4 in D

2O was 022 for Pcs 2 and 4 containing Zn(II) and

011-012 for Pcs 1 and 3 with Al(III) It could mean that theincrease in the solubility in water by charged side moietiesdoes not influence significantly theΦ1O

2

On the other hand 1 and 2 are not soluble in D

2O The

ldquo07DMF inD2Ordquo solvent was used tomodel the behaviour

of the photophysical properties of these compounds inaqueous solutions The Φ1O

2

decreased to 009 for 2 andincreased up to 016 for 1 compared with the results forthese compounds obtained in DMF The central metal seemsto affect the solubility also Aqueous-like solvents are moresuitable for compounds 1 and 3 with Al(III) due to thepresence of axial ligand

The other characteristic of the photophysical properties isthe lifetime of 1O

2 whose well-known value in D

2O is 60120583s

[23] But for all investigated compounds the lifetimes of 1O2

were significantly shorter 7 120583s for Pcs 3 and 4 The lifetime


350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(a)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(b)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence

Pc 2 in DMFPc 4 in D2O

(c)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(d)

Figure 2 Normalized absorption spectra of the compounds containing PcZn(II) 2 4 (a) and PcAl(III) 1 3 (b) Normalized fluorescencespectra of the compounds containing PcZn(II) 2 4 (c) and PcAl(III) 1 3 (d)

of 1O2for Pcs 1 and 2 was approximately 20 120583s in DMF and

10 120583s in 07 DMF in D2O Such difference in the lifetimes of

1O2from the well-known values could mean that quenching

of 1O2occurs The shortest lifetime of 1O

2was observed in

the case of Pcs 3 and 4 but the Φ1O2

for these compoundswas the same as that for 1 and 2 solved in DMFThe Pcs 2 and4 were chosen for additional experiments due to their betterfluorescence (compared to these with PcAl(III)) which wasrequired in some techniques

First the energy transfer from the first excited triplet state1198791tomolecular oxygen resulting in the generation of 1O

2was

characterized For this purpose we used laser flash photolysisfor the indirect detection of 1O

2formation via triplet lifetime

measurement which can be related to the 1O2generation

33 Laser Flash Photolysis The method of laser flash pho-tolysis was used for indirect determination of 1O

2formation

via triplet lifetime measurement This is possible because

the triplet lifetimes can be related to the singlet oxygengeneration After activation of the first excited singlet state1198781via light absorption a part of the molecules undergo

transition to the first excited triplet state 1198791with a quantum

yieldΦ119879[24]The subsequent deactivation could proceed via

phosphorescence (119896phos) or nonradiative (119896nonrad) transitionThe fraction of triplet states deactivated via interaction withmolecular oxygen is referred to as 119891

119879

The triplet lifetime in the presence of oxygen 120591O2

is givenby 120591O

2

= (119896phos + 119896nonrad + 119896O2

[O2])minus1 Removal of dissolved

oxygen by bubbling the solution with N2leads to an increase

of the triplet lifetime In this case the lifetime is calculated as120591N2

= (119896phos + 119896nonrad)minus1

In the presence of oxygen the triplet lifetime of Pc 2 inDMF was measured to be 120591

119879= 034 120583s the lifetime of Pc 4 in

D2O was 60 120583s (Table 2)After oxygen removal the triplet lifetimes of the com-

pounds dissolved in the same solvents increased to 120591119879=

526 120583s for Pc 2 and to 89 120583s for Pc 4 as seen in Table 2


Table 2 The first triplet state lifetime of the photosensitizers obtained by laser flash photolysis in the presence and absence of the O2

Compound Solvent 120591 with O2 120583s 120591 without O

2 120583s Without O

2with O

2119891119879

2 DMF 034 plusmn 000 526 plusmn 02 1527 0994 D2O 60 plusmn 01 89 plusmn 02 15 033

1 ns10 ns50 ns100 ns

150 ns200 ns250 ns

minus035

minus030

minus025

minus020

minus015

minus010

minus005

000

005

010

500 550 600 650 700 750 850800

Wavelength (nm)

PcZn 2

ΔA

(a)


150 ns200 ns250 ns

minus012

minus010

minus008

minus006

minus004

minus002

000

002

004

006

Wavelength (nm)

PcZn 4

ΔA

500 550 600 650 700 750 850800

(b)

Figure 3 Evolution-associated difference spectra that result from a global analysis on transient absorption experiments on compoundscontaining 2 and 4

The value of 119891119879can be obtained finally from 120591O

2

and 120591N2

119891119879=

119896O2

[O2]

119896phos + 119896nonrad + 119896O2

[O2]

=120591N2

minus 120591O2

120591N2

(1)

(see [24]) This parameter characterizes the efficiency ofthe energy transfer from the first excited triplet state 119879

1

to molecular oxygen Since in case of Pc 2 in DMF 119891119879

value is nearly unity this means that energy transfer to themolecular oxygen is predominant and takes place almostlossless For Pc 4 this value is only 03 However the 119891

119879

value is substantially lower for Pc 4 the Φ1O2

for 2 in DMFand 4 in D

2O are the same Therefore the charged side

moieties in compound 4 have no influence on the Φ1O2

butthesemoieties have influence on the photophysical propertiesresulting in the redistribution of the energy transfer Alsosuch a strong reduction of the triplet lifetime may resultfrom the interaction between Pc core and side moieties Todetermine the photophysical behavior of our compoundsmore details were investigated by ps-TAS method

34 Picosecond Transient Absorption Spectroscopy It wasshown that the ps-TAS of Pc 2 was different from the

spectrum of Pc 4 Spectra of Pcs 2 and 4 contain only onepeak at 690 and 629 nm respectively (Figure 3) Each peakwas characterized by an individual decay component

Compound 2 in DMF has two decay components at690 nm with lifetimes of 177 and 2183 ps also Pc 4 inD2O has two decay components at 629 nm with lifetimes

of 57 and 286 ps (Figure 3) The amplitude ratio of the firstand the second components (A1A2) for these compoundswas approximately the same 258 and 225 for Pcs 2 and4 respectively (Table 3) It means that the shorter decaycomponent makes primary contribution to the transientabsorption spectrum Presumably the blue shift of the peakmaximum and the significant decrease in the decay compo-nents lifetimes could be linked to the decrease of 1O

2lifetime

for water-soluble Pc 4

4 Conclusions

The introduction of the charged substituents not onlyincreases the water solubility but also significantly changesabsorption fluorescence and transient absorption spectra ofwater-soluble Pcs It was shown that charged substituentsdid not change the quantum yields of 1O

2generation but

they decreased its lifetimes It could mean that the increasein the solubility in water by charged side moieties doesnot influence significantly the Φ1O

2

which is important for


Table 3 Decay times amplitudes and their ratio and the quantum yield of intersystem crossing ΦISC

Compound Solvent 120582det nm 1205911 ps A1 1205912 ps A2 A1A2 ΦISC 2 DMF 690 177 plusmn 14 72 2183 plusmn 323 28 258 224 in (D2O) 629 57 plusmn 15 69 286 plusmn 144 31 225 8

using such compound in PDT Significant decreasing of 1O2

lifetime from the well-known value of 60 120583s to 7ndash20120583s couldmean that quenching of 1O

2occurs A strong reduction of

first triplet state lifetime of the Pc 4 may result from theinteraction between Pc core and sidemoietiesThus althoughthe charged side moieties have no influence on the Φ1O

2

they influence the photophysical proprieties resulting in theredistribution of the energy transfer

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgment

Theauthors are grateful to Professor Eugenii A Lukyanets forcritical reading of the paper

References

[1] H Ali and J E van Lier ldquoPorphyrins and phthalocyaninesas photosensitizers and radiosensitizersrdquo in Handbook of Por-phyrin Science with Applications to Chemistry Physics MaterialsScience Engineering Biology andMedicine K M Kadish K MSmith and R Guilard Eds World Scientific Singapore 2010

[2] E A Lukyanets ldquoPhthalocyanines as photosensitizers in thephotodynamic therapy of cancerrdquo Journal of Porphyrins andPhthalocyanines vol 3 no 6-7 pp 424ndash432 1999

[3] R BonnettChemical Aspects of PhotodynamicTherapy Gordonand Breach Science Publishers Amsterdam The Netherlands2000

[4] J G Levy ldquoPhotosensitizers in photodynamic therapyrdquo Semi-nars in Oncology vol 21 supplemen 15 no 6 pp 4ndash10 1994

[5] R Langlois H Ali N Brasseur J R Wagner and J Evan Lier ldquoBiological activities of phythalocyaninesmdashIV TypeII sensitized photooxidation of L-tryptophan and cholesterolby sulfonated metallo phthalocyaninesrdquo Photochemistry andphotobiology vol 44 no 2 pp 117ndash123 1986

[6] M Hu N Brasseur S Zeki Yildiz J E van Lier and C CLeznoff ldquoHydroxyphthalocyanines as potential photodynamicagents for cancer therapyrdquo Journal of Medicinal Chemistry vol41 no 11 pp 1789ndash1802 1998

[7] J D Spikes ldquoPhthalocyanines as photosensitizers in biologicalsystems and for the photodynamic therapy of tumorsrdquo Photo-chemistry and photobiology vol 43 no 6 pp 691ndash699 1986

[8] G Jori ldquoFar-red-absorbing photosensitizers their use in thephotodynamic therapy of tumoursrdquo Journal of Photochemistryand Photobiology A Chemistry vol 62 no 3 pp 371ndash378 1992

[9] H Abramczyk and I Szymczyk ldquoAggregation of phthalocya-nine derivatives in liquid solutions and human bloodrdquo Journalof Molecular Liquids vol 110 no 1ndash3 pp 51ndash56 2004

[10] N A Kuznetsova N S Gretsova V M Derkacheva O LKaliya and E A Lukyanets ldquoSulfonated phthalocyaninesaggregation and singlet oxygen quantum yield in aqueoussolutionsrdquo Journal of Porphyrins and Phthalocyanines vol 7 no3 pp 147ndash154 2003

[11] E A Lukyanets and V N Nemykin ldquoThe key role of peripheralsubstituents in the chemistry of phthalocyanines and theiranalogsrdquo Journal of Porphyrins and Phthalocyanines vol 14 no1 pp 1ndash40 2010

[12] N Brasseur R Ouellet C la Madeleine and J van LierldquoWater soluble aluminium phthalocyanine-polymer conjugatesfor PDT photodynamic activities and pharmacokinetics intumour bearing micerdquo British Journal of Cancer vol 80 no 10pp 1533ndash1541 1999

[13] M Soncin A Busetti R Biolo et al ldquoPhotoinactivation ofamelanotic and melanotic melanoma cells sensitized by axiallysubstituted Si-naphthalocyaninesrdquo Journal of Photochemistryand Photobiology B vol 42 no 3 pp 202ndash210 1998

[14] E A Cuellar and T J Marks ldquoSynthesis and characterizationof metallo and metal-free octaalkylphthalocyanines and uranyldecaalkylsuperphthalocyaninesrdquo Inorganic Chemistry vol 20no 11 pp 3766ndash3770 1981

[15] K Sakamoto T Kato E Ohno-Okumura M Watanabe andM J Cook ldquoSynthesis of novel cationic amphiphilic phthalo-cyanine derivatives for next generation photosensitizer usingphotodynamic therapy of cancerrdquo Dyes and Pigments vol 64no 1 pp 63ndash71 2005

[16] A M Sevim C Ilgun and A Gul ldquoPreparation of heteroge-neous phthalocyanine catalysts by cotton fabric dyeingrdquo Dyesand Pigments vol 89 no 2 pp 162ndash168 2011

[17] S A Mikhalenko L I Solov1015840eva and E A Luk1015840yanetsldquoPhthalocyanines and related compounds XXXVIII Synthesisof symmetric taurine- and choline-substituted phthalocya-ninesrdquo Russian Journal of General Chemistry vol 74 no 11 pp1775ndash1800 2004

[18] O Korth T Hanke I Ruckmann and B Roder ldquoHigh sensitiveand spatially resolved absorptionfluorescence measurementson ultrathin Langmuir-Blodgett-filmsrdquo Experimental Techniqueof Physics vol 41 no 1 pp 25ndash36 1995

[19] S Oelckers M Sczepan T Hanke and B Roder ldquoTime-resolved detection of singlet oxygen luminescence in red cellghost suspensionsrdquo Journal of Photochemistry and PhotobiologyB Biology vol 39 no 3 pp 219ndash223 1997

[20] W Spiller H Kliesch DWohrle S Hackbarth B Roder andGSchnurpfeil ldquoSinglet oxygen quantum yields of different photo-sensitizers in polar solvents and micellar solutionsrdquo Journal ofPorphyrins and Phthalocyanines vol 2 no 2 pp 145ndash158 1998

[21] A Paul S Hackbarth A Molich et al ldquoComparative study ofthe photosensitization of Jurkat cells in vitro by pheophorbide-a and a pheophorbide-a diaminobutane poly-propylene-iminedendrimer complexrdquo Laser Physics vol 13 no 1 pp 22ndash292003

[22] I Ruckmann A Zeug R Herter and B Roder ldquoOn the influ-ence of higher excited states on the ISC quantum yield of octa-aL-alkyloxy-substituted Zn-phthalocyanine molecules studied


by nonlinear absorptionrdquo Photochemistry and Photobiology vol66 no 5 pp 576ndash584 1997

[23] A A Gorman and M A J Rodgers ldquoLifetime and reactivity ofsinglet oxygen in an aqueous micellar system a pulsed nitrogenlaser studyrdquo Chemical Physics Letters vol 55 no 1 pp 52ndash541978

[24] M Regehly K Greish F Rancan H Maeda F Bohm andB Roder ldquoWater-soluble polymer conjugates of ZnPP forphotodynamic tumor therapyrdquo Bioconjugate Chemistry vol 18no 2 pp 494ndash499 2007

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Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


Y = ndashSO2NH(CH2)5ndash M = AlCl (1)

Y = ndashSCH2ndash M = Zn (2)

R+ = ndashCH2CH2N+(CH3)2CH2COOH

M = AlOH (3) Zn (4)

HOOC

HOOC

Y

Y

Y

Y

COOH

COOH

N

NN

N N

N

N

N

N

N

N

N

NN

N

N MM

ClminusR+OOC

ClminusR+OOC

COOR+ Clminus COOR+ Clminus

COOR+ Clminus

COOR+ Clminus

COOR+ ClminusCOOR+ Clminus

Figure 1 Structures of the Pc complexes 1ndash4

The quantum yield of 1O2generation the measurements

of the triplet-triplet absorption and the picosecond transientabsorption spectra (ps-TAS) which are crucial in determin-ing the feasibility of using these dyes for PDT are reportedand linked to the structure of the substituents

2 Materials and Methods

21 Chemicals and Reagents Dimethylformamide (DMFSigma Germany) D

2O and double-distilled water were used

as solvents

22 Al(III) Tetra-4-carboxymethylsulfanylphthalocyanine (1)This compound has been prepared by analogy with [16]The yield of compound 1 was about 30 UV-vis 120582maxnm (DMF) 680 613 353 (relative intensity 1 02 035)(water ethanol 1 1) 693 652 sh 618 sh 349 (relative inten-sity 085 065 05 1)

23 Zn(II) Tetra-4-carboxyhexylsulphamidophthalocyanine(2) This compound has been prepared by analogy with [16]The yield of compound 1 was about 30 UV-vis 120582maxnm (DMF) 690 622 363 (relative intensity 1 022 044)(water ethanol 1 1) 682 sh 637 344 (relative intensity059 078 085)

24 Hydroxyaluminum Octakis-45-[2-(N-carboxymethyl-NN-dimethylammonium)ethoxycarbonyl] Phthalocyanine Oct-achloride (3) To a solution of 01mmol hydroxyaluminumoctakis-4 5-(2-chloroethoxycarbonyl) phthalocyanine [17]in 15mL anhydrous N-methylpyrrolidone 18mmol NN-dimethylglycine and catalytic amount of sodium iodide wereadded and reaction mixture was stirred 6 h at 105ndash110∘Ccooled and poured in the mixture of petroleum ether-benzene (3 1) solvent was decanted the precipitate waswashed with benzene and ether and then dried in a vacuum

desiccator over phosphorus pentoxide The yield of com-pound 3 was about 90 UV-vis 120582max nm (water) 690 652350 (relative intensity 095 092 1) (ethanol) 691 682 617352 (relative intensity 197 195 072 1)

25 Zinc Octakis-45-[2-(N-carboxymethyl-NN-dimethylam-monium)ethoxycarbonyl] Phthalocyanine Octachloride (4)This was prepared analogously from zinc octakis-45-(2-chloroethoxycarbonyl) phthalocyanine [17] with yield of92 UV-vis 120582max nm (water) 685 sh 641 345 (relativeintensity 074 107 1) (ethanol) 676 643 344 (relative inten-sity 1 108 10)

Compounds 1 and 2 are soluble in polar solvents espe-cially DMSO and DMF as well as aqueous acetonitrile andalcohols Compounds 3 and 4 are soluble in water concen-trated mineral acids and their aqueous solutions alcoholsand polar aprotic solvents UV-vis absorption spectra of theiraqueous solutions show an aggregation to a lesser extent inthe case of aluminum complex 3

26 Absorption and Steady-State Fluorescence The groundstate absorption spectra were recorded using a spectropho-tometer Shimadzu UV-2501PC at room temperature Thesteady-state fluorescence spectra were measured using 1 cmtimes 1 cm quartz cells with a combination of a cw-Xenon lamp(XBO 150) and a monochromator (Lot-Oriel bandwidth10 nm) for excitation and a polychromator equipped with acooled CCDmatrix as a detector system (Lot-Oriel InstaspecIV) [18]

27 Time-Resolved Singlet Oxygen Luminescence Measur-ement These measurements were carried out using ananosecond Nd YAG laser (BM Industries Evry CedexFrance) coupled with an optical parametric oscillator (BMI)The 1O

2emission was detected using a liquid nitrogen

cooled Ge-diode (North Coast Inc Santa Rosa CA) For



2






3 Results




2O (or in D

2O)



2


2 DMF 022 229 plusmn 00

1 07 DMF in D2O 016 100 plusmn 02


3 D2O 011 69 plusmn 05

4 D2O 022 69 plusmn 04




2generation


2O were





2




2


2O The



2




2O is 60120583s




350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(a)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(b)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(c)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(d)






2was observed in




2was





2formation






119879


is givenby 120591O

2

= (119896phos + 119896nonrad + 119896O2













2 120583s Without O

2with O

2119891119879



150 ns200 ns250 ns

minus035

minus030

minus025

minus020

minus015

minus010

minus005

000

005

010

500 550 600 650 700 750 850800

Wavelength (nm)

PcZn 2

ΔA

(a)


150 ns200 ns250 ns

minus012

minus010

minus008

minus006

minus004

minus002

000

002

004

006

Wavelength (nm)

PcZn 4

ΔA

500 550 600 650 700 750 850800

(b)



2

and 120591N2

119891119879=

119896O2

[O2]

119896phos + 119896nonrad + 119896O2

[O2]

=120591N2

minus 120591O2

120591N2

(1)


1



119879










2lifetime


4 Conclusions


2generation but


2









2




Acknowledgment


References




































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



2






3 Results




2O (or in D

2O)



2


2 DMF 022 229 plusmn 00

1 07 DMF in D2O 016 100 plusmn 02


3 D2O 011 69 plusmn 05

4 D2O 022 69 plusmn 04




2generation


2O were





2




2


2O The



2




2O is 60120583s




350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(a)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(b)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(c)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(d)






2was observed in




2was





2formation






119879


is givenby 120591O

2

= (119896phos + 119896nonrad + 119896O2













2 120583s Without O

2with O

2119891119879



150 ns200 ns250 ns

minus035

minus030

minus025

minus020

minus015

minus010

minus005

000

005

010

500 550 600 650 700 750 850800

Wavelength (nm)

PcZn 2

ΔA

(a)


150 ns200 ns250 ns

minus012

minus010

minus008

minus006

minus004

minus002

000

002

004

006

Wavelength (nm)

PcZn 4

ΔA

500 550 600 650 700 750 850800

(b)



2

and 120591N2

119891119879=

119896O2

[O2]

119896phos + 119896nonrad + 119896O2

[O2]

=120591N2

minus 120591O2

120591N2

(1)


1



119879










2lifetime


4 Conclusions


2generation but


2









2




Acknowledgment


References




































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(a)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Abs

orpt

ion

Wavelength (nm)

(b)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(c)

350 400 450 500 550 600 650 700 750 800

00

02

04

06

08

10

Wavelength (nm)

Fluo

resc

ence


(d)






2was observed in




2was





2formation






119879


is givenby 120591O

2

= (119896phos + 119896nonrad + 119896O2













2 120583s Without O

2with O

2119891119879



150 ns200 ns250 ns

minus035

minus030

minus025

minus020

minus015

minus010

minus005

000

005

010

500 550 600 650 700 750 850800

Wavelength (nm)

PcZn 2

ΔA

(a)


150 ns200 ns250 ns

minus012

minus010

minus008

minus006

minus004

minus002

000

002

004

006

Wavelength (nm)

PcZn 4

ΔA

500 550 600 650 700 750 850800

(b)



2

and 120591N2

119891119879=

119896O2

[O2]

119896phos + 119896nonrad + 119896O2

[O2]

=120591N2

minus 120591O2

120591N2

(1)


1



119879










2lifetime


4 Conclusions


2generation but


2









2




Acknowledgment


References




































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




2 120583s Without O

2with O

2119891119879



150 ns200 ns250 ns

minus035

minus030

minus025

minus020

minus015

minus010

minus005

000

005

010

500 550 600 650 700 750 850800

Wavelength (nm)

PcZn 2

ΔA

(a)


150 ns200 ns250 ns

minus012

minus010

minus008

minus006

minus004

minus002

000

002

004

006

Wavelength (nm)

PcZn 4

ΔA

500 550 600 650 700 750 850800

(b)



2

and 120591N2

119891119879=

119896O2

[O2]

119896phos + 119896nonrad + 119896O2

[O2]

=120591N2

minus 120591O2

120591N2

(1)


1



119879










2lifetime


4 Conclusions


2generation but


2









2




Acknowledgment


References




































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of








2




Acknowledgment


References




































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

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