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Theoretical Model to Study the Effect of Concentration and Impurities on the Fluorescence Spectrum of Fluorescein Solution in Ethanol using Fourier Series “3× 2

Authors:
  • Mustansiriyah University
  • Mustansiriyah University

Abstract

E-mai I : dr m a h a s i nf @St aho o. c om dr. a I i al z ulq, @4t ah o o. c om, i81J54@tahoo.com Abstract In this reseilch. we study the fluorescence spec_tm of fluorescein solution in ethmol for dilTerent concentrarions (10'r-l0-5) mol4irer in rhe cme of rhe presence ofoxygen md non existetrce. Increding corcentation led to shift fte flwrescence spectrum to longer wavelengths (low energies). A table cwe 2D vereion 5.01 softwae was used to find fitting cwe dd fitting eqMtions for all fluorescence spectms. Fouier series (3 x2) was used to be the befter frfting cwe for fluores@nce spectm for all concentration in the existence of oxygen md its absence. We foud that the intmsity of fluorescence spectu of fluorescein in ethmol wm affected in the presence of molecula oxygen. This is evident from the theoretical flttitrg cwes of fluorescence spectrm io the case ofpresence md abrence ofO:. Kewords: fluorescence spectnm, fluorescien dye, theorctical model, concentation effect, impuities effect.
lnt€@tioMl Joual of Materials Physics
ISSN 0974-309X Volme 2, Nmber I (201l), pp. 75-86
O IntematioMl Reseech Publication House
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Theoretical Model to Studv the Effect of
Concentration and Impurities on the Fluorescence
Spectrum ofFluorescein Solution in Ethanol using
Fourier Series "3x2"
Dn Mahssin F. d-Kadhemy, Dr, Ali A. Al-Zuky
and Israa F. Alsharuee
Physics DepaftmehL Al-Mustansiriyah Uniwtsity, College of Science, Iraq
E - mai I : dr m a h a s i nf
@St aho o. c om dr. a I i al z ulq, @4t ah o o. c om,
i81J54@tahoo.com
Abstract
In this reseilch. we study the fluorescence spec_tm of fluorescein solution in
ethmol for dilTerent concentrarions (10'r- l0-5) mol4irer in rhe cme of rhe
presence ofoxygen md non existetrce. Increding corcentation led to shift fte
flwrescence spectrum to longer wavelengths (low energies). A table cwe 2D
vereion 5.01 softwae was used to find fitting cwe dd fitting eqMtions for
all fluorescence spectms. Fouier series (3 x2) was used to be the befter
frfting cwe for fluores@nce spectm for all concentration in the existence of
oxygen md its absence. We foud that the intmsity of fluorescence spectu
of fluorescein in ethmol wm affected in the presence of molecula oxygen.
This is evident from the theoretical flttitrg cwes of fluorescence spectrm io
the case ofpresence md abrence ofO:.
Kewords: fluorescence spectnm, fluorescien dye, theorctical model,
concentation effect, impuities effect.
Introduction
A dye laser consists ofm orgmic dye mixed with a solvent, tlese dyes contain rather
lrge orgmic molecules which fluoresce when exposed to the proper fiequency of
light then the molecules emit fluorescmce md the dye is quite cled to the lasing
wavelength [l, 2]- The photo physical ploperties of dye solution is very importmt to
sfudy @d all effects otr the fluorescence spectm such as concentatiotr effects,
solvent effects, impwities effects, tempe€Ne effects,....etc must be studied. Itr ou
work we srudy the effect of concentation md impuities (molecule oxygetr) on the
76 Dt. Mahasin F. Al-Kadhemy et al
fluorescence spectm of fluorescein solution in ethool experimentally ed we use
table cwe 2D softwde to estimate a theoretical model for these effects.
The concentration effects were cled in high concentrated solution by foming
dimer ed trimer which decrease the lasing effects [3,4]. Some rcsedch [5] w6
showed that the increasing of concenhation fomed ilimers $omd sate which
fomed from tow uexcited monomer molecules that led to chmge of the shape of
absorption sp@tnm of dye solution, these molecules will be non-fluorescent. The
aggregation cled in concenffate fluorescein glution where the monomet molecules
fowd with dimer md fimmer ; thus aggregates have no emission in temperatre
20.c[6].
The effect of impuities embodied by dissolved oxygen (O2) tlEt effect otr the
inteNity ofoutput laser dye 6 that the oxygen either helps or stops the inJlwrce of
loer action. This explains that 02 inffeases intelsystem cmssing operations from the
ftiplet states to the grcmd states, which increase the nMber of excited molecules, or
it quench the excited singlet state by increding inteNystem cmssing to triplet levels
which decrede the intensity of lder action, by decreding the nmber of atoms in the
high- level of lmer md the fomation of tiplet level may be added to compute with
the absorption ofexcitation energy [7, 8].
Experimental work
Fluorercein is a s)athetic orgmic compomd available o a dak ormge/red powder
soluble in water dd alcohol. It is widely sed d a fluoresc@t hcer for mdy
applications. It is a fluorophor comonly ued in microscopy, in a type of dye laser as
the gain mediu, in forensics md serology detect latent blmd saim, dd in dye
tncing [9-11]. The chemical fom of fluorescein is C2oHr2Ori md its moleculd
weight is 332.30 gn/mol. The solvent was Ned ethmol. Its chemical form CzHsOH,
molecula weight 46.07 gnlmol, refractive index 1.364, dd fieezing point -
I 14.1'CU2l. In this study, prepdation bf dye solution was prepaed rccording b the
equationi m:CVM
Where:
m=weight ofthe dye needed to obtain the desired concenhation in uit (gm).
C= the coocenffaflon needed to preptred in uit mov liter.
V=the volume ofsolvent in liter necessary to add to the dye.
M:the moleculm weight ofthe dye Eed.
The effect of concentratior on the fluorescence sDecm will be studied. The
solulion concentradons (l l0r l'10i. I l0{. l.lOJ mol,4iter; were used in rhis
The instuent used in this work to measue the fluorescence spectus is
"Jerelash grating 82-410, lmetff Gzemy- Tmer Spectumeter Spectogmph".
Fitting cwes for fluorescence slrectu werc taken by the progrm "Table Cwe 2D
veEion 5.01".
(1)
Theoletical Model to Study the Efect ofconcefration and Impwities
Results and Discussions
The results in this study clssified inlo two parts practical model md modeling part:
Practical Port
In this pafr we will study tro effects
Coacenbation Elfecls
It is important to study the effect of @ncmtration otr the chdeteristics of the
absorption md fluorescence specha of dyes, with the reasons that it cr€ates rclating to
the prrctical me ofthese dyes to gdeEte stimulated emission. Fig.(1) represents the
fluorescen@ spectm offluorcscein solution ia ethdol at differcnt concentation (10-
2- 10-5) mol,4iter. It was foud that the incrembg @ncenfatiotr led to shift the
specm to longer waveleng*r (smalla energies) as cled fiom fig.(2).
Figure (l): Fluorescence spectu of fluorescein solution in etheol (a) with O, (b)
without O:.
12
9
510
go
ea
Dr. Mahxin F. Al-Kadhemy et al
E5x
I sre
P 513
i"'
gs6
514
0 0.m2 o.oq 0006 0.012
cone nhrion (nourib D
Figure (2): The reLation between waveletglh of fluorescence spectnm dd
concentration of fluorescein solution in etlmol.
Wherc some rcsetrchem [13] demonstrate that the shape of the fluorescence
spechum of fluorescein depends on the concentEtion of dre dye @d the cell Ned.
With fixed cell ed experimental mmgement used in ou reseuch, there was a
subshtial chege in the specm when increasing conceDtation. Note that the
shifting of the md. fluorescence specM rowilds longer wavelmgrh in diluted
solutioE {10_r - l0'5) molliEr. ADd in concenmted solutions lgreaLer rhm 10'J
movlibr), the increse in concentation ofthe dye produces a slightly chdge in the
fluorescence spectu which trises from the effect of abslption that decreasing the
highest energy pd of flmrcscence specm ed increases the inteNity of the other
pff belonging to the re-emission. This includes shifting mx. fluorescence towdds
longa wavelengths (lower energies).This effect is evid€nt in all molecules with high
quem efficiency.
Impufilies Ellecls
The ability of oxygen b qwnch the singlet md tiplet cases for molecules is well
know. We hav€ studied rhe effect ofmoleculd oxygen on fluorescence specua ofLhe
fluoresein solution in ethmol ar different conenradons (c=10-'z- l0_5 movliter).6
shoM in fig.t I ) in lhe cse oI fte presence md absence oforygen. We lmd that the
intmsity ofthe fluorescence specm ofthe dye elution affected by smll ratio as in
the case of presence of oxygen. Some reseachen have sted [14] that the oxygen
dose uot quenches the fluorescence spstm of xmthenes dd the others regleded
extut oxygen liom the solution.
3-2 Modeling Pail
For e\perjmenEl cwes. first we lake the finhg cwe for fluorescence specm of
fluoresein solution in elhmol for conceDbation ( I 0-2 - I 0-') mol,4iler in lhe exisEnce
ofor, as shoM in fig. (3).
Theoretical Model to Stody the Effect of Concetuotion md ltupeities
Figurc (3): Fluoresence specffi of fluorescein solulon in ethmol at alillerent
coientration ir exisrence ofor 1a.l I ^ l0-']1b.1 l. l0r (c) I'10" (d) I '10'5 mol,4itq
Where, we us€d Fouier sries polynomial (3x2) for these fitting pscess, this
Fouier soies eqution giv6 as follows:
v = a + n c o s (v) + c "i" (v) + a " o " (tz) + " " i" (:z) + r " o " (!) +
gsh(4) e)
Where the values of these pilmetds (4 b, c, d, e, f, md g) m shom in able (l)
for each fluorescence spectm. The pMeter f is corelation coefficient.
80 Dr. Mah6ihF. Al-Kadhenyetal
Table I : The pMeters of Fouier ssies eqution for each concedtration in
existence of 02.
The vanations of eeh pMder with concenhtiotr de plotted in figs. (4-
I 0).The fifting cwe for erch spectm ws uken, dd the flting eqution is
ill$hted above the cwe. Where, we used different frfiing equtiom for ihe*
pdmete$.
t
Fi9(4) he r.lali6 beeil a-pdleetq lad
@etrtatior h exist*e of O: Fis.{s) k rebt@ l'*q b-gdmeis
d @{@5dion ia edsioce of O,
Pemebr C=1x 10''
mol,4iter C=1x l0''
mol/liter C=lx10-
mol/liter C=1 x10''
mol,4iter
0.9956596263 o.9972404459 0.9980138318 0 .9965127 502
16.96925976 tt .720'71 1 37 3.t23422225 3.892411125
b2.706460502 I .OtJ9299230 o.555934t79 o.2t96
o4
7747 i14691114
4 64)310011 1 696149962 1 271160179 1 529271391
Theoretical Model to Stubr the Effect ofcohcilfrdion Md Impulities 8l
,ttns-a'atb ftrms-q,^tb
i *-,*,,, -",1-'".!!+- " : otus.h/a/ +:r!15n' .h_'.eil1."r.'
Fig.{6) ft€ rehdo! b*e* c-Feerer ed
oeahadoa iE.n$e* otq
.-_____ 773.Sr3rr r5i*017
tig.{7) *e reb{od hrs d-l)fuder @d
ce.4ladon h dsi@e oJ O,
,=-Gffi'+zilu.-b, 4#a
lis8:krel"tidktu ryru* lige9: &e rel.liohnv.d f-Fee€!
dd @(dadoD h abrsce of q ed concennaton h exisia.e o{ o.
,,....-,.___
Figure 10: The relation betueen g-pdmeter md concenuation in existerce of 02
E2 Dr. Mahasin F. Al-Kadhemy et al
After that, for the eq.(2) we calculated the fmal pemeters(a, b, c. d, e, f, md g)
&om the abore modeling equalions as Fsr to find the Lheoretical eqMrion for
fluorescein solution in elhilol specrM al C - 0.5. 10{ moL4irer in lhe exisrence of
02. So, the esti@ted Fowiet series eqution co be givm by:
8.78808s2 + 0.s37862es cos (I1) - ro.oor s67 sin(X) -
7.80t176s cos ff*) - 0.11s87613 sin (311i - 1,0274e38 cos (33:J +
:.r+sorsza sin (ff) (3)
Also, we make fiting curue for the florcscence spectu of fluorescein solution in
ethmol for all concentratioD in the absence of 02 as in fig.(11). The best fifiing
eqMtion is also Fouier series polynomial (3x2) (eq. (2)), md the pmeters of this
eqMtion is illustrated in table (2).
(c)
Figure 11: Fluorescence spectu of fluorescein solution in ethmol at differcnt
concentration inthe absence ofo, (a) lx10-2O) lxl0r (c) lxl0{ (d) lxl0-5 mol/liter
(d)
Theoretical Model to Stody the Effect ofconcehftation and Impurities
Trble 2: The p{metqs ofFouiq series eqution for each concenudion in absence
Oz.
Figs.(12-18) defronsfated the fiting cwes for eeh pdmehr with concentation
md its fitting equation.
Fis.(u) fte rehnctu a-pdede.
ad offitatio! h abeee O: Fig.(13) fte relatiqbd\rcea bpa,edtrad
c.*tuti@io$g*eG
Ptrmeter u:lxtu'
mol/libr C:l xl0-'
mol/libr C=1 x 10-
mol.{iter C:l x l0-"
mol/liter
0.9940607109 0.9945924765 0.99t
t4.72945E49 9.170852160
b2.505629839 0.75698639 -7 66)1RaO1 1T1617J7
o1419q176 -i oql t5Rl60
o 54499947i 0 758054884
T-0 q7RRlr r6 -0.201 1 1997 -0.033008679
3 I 15755085 t.401 801980 t.336450967
r = -a lres;;r-
Fis.(14) *e i&donbetwed c-pm6etd
ed corcadto! ia absdce q
'= 0*769m -23?379'&:5 +0,e0*0905'd
tig.(15) &e rclandbs=ea d-pde&.ed
c@d*aior in abe O:
, = 0l7r?5$3 -36.36s4a7,--94@t9'_"
Fis.(16) ne Elador*lre! e-pdd*r Fis.(r7) ft. retrrio,k@ f-@merd
d @!@ffitor b cbs@ Q U ocdEdm in,bsce o,
Figure 18: The relatiotr beffieen c-pmeter &d codcenuation in absence 02
Theoretical Model to Study the Efect ofcoacentation and Impvities 85
The estimated theoretica.l modeling equation^ for fluorescence spectrum in the
absence of Oz md also we will Ne C=0.5 . l0-' mol,4iter s lest comentrarion as
follow:
s.ss4e677 + o.ssTssss cos (ff) - e .ur+462 sin(x) -
sl2os3sl cos (4!*) + o.als7 aTaa sin(3!!\ - 0.6a31e3s3 cos (14) +
z);2aes+ sin(!z) (4)
The estimted theoretical fluorescence spectrm 6 firnction of concentration ee
plotted itr fig. (19) for both c6es (existence ad absence of molecula oxygen)
ecording to eq. (3) ed eq.(4).
3D
:2t
;1t
4An 42C 40 40 430 510 520 540 560 580 800
w.vdengh{nn)
l:ma *ffi;E
F'igure 19: Thmretical fluorescence slFctm offluorescien solution in ethmol in the
eristence md absen@ of02.
These theoretical flmresoence spectlms of fluorescein solution in ethmol give u
the ability of dBwing the fluorescence spectm of this dye in my concentration we
wdt in the existetrce md absence of 02. The effect of Oz is cleoly increasing the
intensity of flmrescence spectrm which will help to incrcase the nmber of re-
excited molecules by increasing the ideNystem clossing from triplet state to singlet
state, so that the l6er rction emitted fiom this dye will increme.
Conclusions
We w benefit ftom the contolling of cotrcentration of molecula fluorescen€
spectrum, which the tming of lcer dye is done by chage of concentration of dye
solution that is a pue fom of tuning without intoducing my other dispersion
elemmt. Where we able to get longer wavelength of fluorescein dye solution in
86 D/. Mahasin F. Al-Kadhemy et al
ethmol by increasing the concenfation fiom I x10-5 mol4iter (1, = 513.8m) to I x 10'2
mol/liter (7, =522 m).
From lable cwe 2D vereion 5.01 softwre. ue deremined the fining cwe for a)l
fluorescence specMs for fluorescein soludoB in ethsol (10_2 l0-',) moU lirer in
the existence and absence of oxygen. Fouier series polynomial (3x2) is the best
fifting eqMtion to detemine the theoretical model for fluorescence specM of
fluorescein dye. The effect of 02 for this solution was that 02 ircreded the intensity
of fluorescence specM. This is evident ftom the cwes of theoretical model. This
will increoe the lser etion emired fiom fluorescein dye laser by increasing nmber
of excited molecules.
References
[1] F. P. Schdfer (Ed.), (Dye Laser), Springer- Verlage, Berlin, (1990).
[2] F. J. Dume md L. W. Hillnm (Eds.), (Dye lasff Finciples) Academic, New
York, (1990).
K.K. Rohatgi- frukherjee, Indid J.Chefr .,3 lA(1992)500.
F. L6pez Arbeloa, A. Costela md I. L6pez Arbelo4 J- Photochem.
Photobiolog., 55 (1990) 97.
A.Peukofer md W.Leupacher, J.LM., 37(1987)61.
I. L6pez Arbeloa, J. Photochem., 14(1980)97.
J.R.MMay, (L6er's spectioscopy ed its applications), ed. By (
L.J.Radzienski, R.W.Solaz md J.A.Pmso), Mucel DeLker, INC.,(1987), 91.
A.Jantowski, S. Jankowski, A.Mironczyk, md J.Niedbrc\ Polish Joumal of
Microbiology 54(4X2005)323.
Yuichiro Ueoo; Jim, G.-S.; Bugess, K., Prutical Slnthetic Procedues 31,
o5) (2004) 2s91-2s93.
[10] U.Brrckmm, (L6er Dyes), 3rd edition, LmMa physics, (2000).
ull A.Costela, [.Gacia- Moreno, md R Sastoe, (Tunable lder applications), ed.
By FJDwte, CRC press, Taylor dd frdcis goup, 2nd edition, pp.(227-
244),Q009).
12- R.C. Wetrt, M.J.Astle dd W.H.Begel, (Hodbook of chemistry md
physics), RS piess INC, (1989).
[12] I. L6peztubeloa, J. Photochem., 18(1982)161.
[13] H.E.LessiDg, E.Lippen md W. Rapp, Chem.Phys.Left. 7(1970)247.
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t4l
tsl
t6l
tll
t8l
tel
... Laser dyes doped with nanoparticles can be used also for inspecting the optical properties of scattering media as in laser action [5,6]. In 2012, Al-Kadhemy, et al. [7], studied the absorption spectra of Styrene-butadiene in Toluene using the Table curve 2D program, which initiates the using curve fitting software in the spectral calculations. Quenching of the fluorescence by FRET has examined for nanoparticles with xanthene dyes by Zeinidenov, et al. [8], and by Barzan and Hajiesmaeilbaigi [9]. ...
Article
Full-text available
In this study, a novel theoretical method for the absorption and fluorescence spectral estimations has been presented. These estimations have been based on experimental measurements of absorption and fluorescence spectra for the solutions of Fluorescein laser dye with Silver (Ag) nanoparticles in distilled water. The used concentration was (1x10-5 M) for Fluorescein dye, while the mass amounts were (0.003g, 0.005g, 0.0065g, 0.008g and 0.0085g) for Silver nanoparticles. A spectral absorption enhancement was detected in the case of increased Silver nanoparticle masses, which specify that the doped Fluorescein dye with Ag nanoparticles has an important effect on the dye absorption spectra. On the other hand, each fluorescence emission spectrum for the dye has quenched as Ag nanoparticle's mass amounts have increased. The related amounts of mass increase as a consequence of Förster resonance energy transfer (FRET). The novel approach of theoretical estimations has been based on curve fitting using Logistic Power Peak (LPP) function to estimate theoretical models for the absorption and fluorescence spectra of these samples. These rated models have excellent matching profiles with the experimental profiles so that the estimated models can replace the experimental measurements.
Thesis
The present work includes a description of some photophysical effects (absorption and fluorescence spectra) for the solutions of two laser dyes (Fluorescein and Rhodamine 6G) with three types of nanoparticles (Silver, Titanium dioxide, and Silica) in distilled water. The used concentrations were (1x10-5 M, 2x10-5 M, 4x10-5 M, 6x10-5 M and 8x10-5 M) for Fluorescein dye and (1x10-5 M, 2x10-5 M, 2.5x10-5 M, 3x10-5 M and 4x10-5 M) for Rh6G dye. Whereas the amounts of masses for the nanoparticles were (0.003g, 0.005g, 0.0065g, 0.008g and 0.0085g) for Silver nanoparticles, (0.0005g, 0.0008g, 0.001g and 0.002g) for Titanium dioxide nanoparticles, and (0.001g, 0.002g, 0.003g and 0.004g) for Silica nanoparticles. This work showed that, absorption and fluorescence spectra can be enhanced or quenched according to the type and amount of the added nanoparticles. Best enhancement was from adding 0.001g of Titanium dioxide nanoparticles to the Fluorescein dye of 8x10-5 M, whereas the best quenching was from adding 0.008g of silver nanoparticles to the Fluorescein dye of 1x10-5 M and adding 0.0085g of silver nanoparticles to the Rh6G dye of 1x10-5 M). The enhancement of the fluorescence spectra can be from either local field enhancement of surface plasmon (Silver and Titanium dioxide nanoparticles), or from high scattering of electromagnetic field by dielectric nanoparticles (Silica nanoparticles). The quenching of the fluorescence spectra can be from electron transfer (Titanium dioxide nanoparticles), or from Förster Resonance Energy Transfer (FRET) or other non-radiative energy transfer (Silver and Silica nanoparticles). A curve fitting for samples of (fixed concentration of dyes with varying the nanoparticles amount of masses) has been made using Logistic Power Peak (LPP) function, which is another form of Gaussian function, to estimatetheoretical models for the absorption and fluorescence spectra for these samples, so that the estimated models can replace the experimental measurements. The obtained results of this work, proved that adding (0.005g of Ag and 0.001g of TiO2) nanoparticles to the Fluorescein dye of (8x10-5 M), can enhance the photostability of this dye, and also adding (0.005g of Ag, 0.001g of TiO2, and 0.004g of SiO2) nanoparticles, to the (8x10-5 M) of Fluorescein dye can produce random laser of reasonable intensities of (4.76 mW, 5.44 mW and 4.42 mW), respectively.
L6er's spectioscopy ed its applications)
  • J R Mmay
J.R.MMay, (L6er's spectioscopy ed its applications), ed. By (
  • L J Radzienski
L.J.Radzienski, R.W.Solaz md J.A.Pmso), Mucel DeLker, INC.,(1987), 91.
Taylor dd frdcis goup
  • By Fjdwte
By FJDwte, CRC press, Taylor dd frdcis goup, 2nd edition, pp.(227244),Q009).
  • H E Lessidg
  • E Lippen
  • W Rapp
H.E.LessiDg, E.Lippen md W. Rapp, Chem.Phys.Left. 7(1970)247.
Costela md I. L6pez Arbelo4 J-Photochem. Photobiolog
  • F Arbeloa
F. L6pez Arbeloa, A. Costela md I. L6pez Arbelo4 J-Photochem. Photobiolog., 55 (1990) 97.
Prutical Slnthetic Procedues 31, o5
  • G.-S Jim
  • K Bugess
Jim, G.-S.; Bugess, K., Prutical Slnthetic Procedues 31, o5) (2004) 2s91-2s93.