Luminescent multifunctional biocellulose membranes

J.M.A. Caiuta, H.S. Barudb M.V. Santosb, U.L. Oliveirac, J.F.S. Menezesc, Y. Messaddeqb,d, S.J.L. Ribeirob
a b

Dept. of Chemistry- FFCLRP- University of So Paulo- USP

Instititute of Chemistry- So Paulo State University- UNESP- CP 355, Araraquara-SP, 14801-970, Brazil
c

CFP- Universidade Federal do Reconcavo da Bahia, Amargosa- BA, 45300-000, Brazil

d

Univ Laval, COPL, Quebec City, PQ G1K 7P4, Canada

ABSTRACT
Luminescent biocellulose membranes were obtained by incorporation of ethanolic solutions of the europium compounds
[Eu(BTFAC)3(H2O)2], [Eu(BTFA)3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] (BTFAC- 4,4,4-Trifluoro-1-

phenyl-1,3-butanedione DBSO- dibenzyl sulfoxide, PTSO- p-Tolyl sulfoxide and FSO phenyl sulfoxide). Selfsustainable semi-transparent composite membranes were obtained showing strong emission under UV exctiation. The antenna hole played by the ligands was observed to be more efficient in the composite membranes than in the precursor complexes which by themselves are also strong red emitter compounds. These new multifuctional membranes could find application in different areas as phosphors and UV Visible energy converting devices. Keywords- biocellulose,luminescent membranes, europium, -diketonates, sulfoxides

1. Introduction

Cellulose is the most abundant natural biopolymer on Earth, being synthesized by plants and also by some bacteria species. However, polluting liquid and gaseous residues resulting from the industrial process of cellulose extraction have been an important international concern1. While cellulose extraction doesn't go greener, the polluting process can be overcome with the employment of bacterial cellulose or biocellulose (BC)2,3. In particular, Gluconacetobacter xylinus bacteria produce cellulose with properties markedly different from plant cellulose (PC). From a carbohydrate rich culture medium, a pure-cellulose network free of lignin and hemicellulose is obtained as highly hydrated pellicles. The pellicles as observed in electron

microscopy are composed of a random assembly of ribbon-shaped fibers less than 100nm wide, denominated nanocelluloses2-5. The resulting particular supramolecular structure of hydrated BC leads to higher molecular weight, higher cellulose crystallinity (60-90%) and higher mechanical strength when compared to PC2-5. The almost endless possibilities of functionalization displayed by cellulosic polymers have lead to new BC based multifunctional materials, including biomedical applications as temporary skin substitution or new antimicrobial dressings6,7, fuel cell membranes8, diaphragms for high quality headphones9, organic-inorganic hybrids involving BC-silica10 or BC-laponite clay11, optoelectronic devices (electronic paper, flexible OLEDs)4,12,13, among others. Luminescence properties have been described for BC-silica composites where broad emission bands originating from the siliceous counterpart could be observed 10. As far as we know no result is reported concerning the preparation of lanthanide ions based luminescent membranes. Such membranes could find specific applications in opto-electronics and solar areas. In fact lanthanide containing organic-inorganic hybrids are versatile materials with many different photonic appplications14-16. Lanthanide luminescent complexes with strongly UV absorbing ligands are excelent UV VIS converters and in this sense, besides phosphors with many dfferent applications14-16, could also find applcation in UV converters in order to improve light harvesting in silicon based solar cells17,18. In this contribution we show preliminary luminescence results for Eu 3+ containing biocellulose membranes. Highly efficiently UV-excited red photoluminescent Eu3+ complexes of -dilketonates19 an sulphoxide ligands20 were incorporated to BC membranes. As it will be shown, the final composite membranes display strong red emission with improved quantum efficiency under UV excitation.

2. Experimental

Hydrated BC membranes (5x6cm, 5 mm thick) were obtained from cultures of wild strains of Gluconacetobacter xylinus isolated in our laboratory. Membranes are composed of approximately 1% celulose and 99% water. Cultivation was conducted for 96h at 28oC in trays 30x50 cm, containing the sterile medium which was composed of glucose 50g.L-1, yeast extracts 4g.L-1, anhydrous disodium phosphate 2g.L-1, heptahydrated magnesium sulphate 0.8 g.L-1, ethanol 20g.L-1. After 96 h, highly hydrated BC pelicles with an average thickness of 5 mm were obtained. The pelicles were washed sequentially in water, 1wt% aqueous NaOH at 70oC in order to remove bacteria and water until neutral pH. The -diketonate complex [Eu(BTFAC)3(H2O)2] (BTFAC- 4,4,4-Trifluoro-1-phenyl-1,3-butanedione or benzoyltrifluoroacetone) is well known from literature21,22 and was prepared following Ismail et al.22. A water-ethanol (50% v/v) solution of Eu3+ nitrate and the ligand (1:3.1 molar ratio) was prepared. A second ethanol-water solution of sodium hydroxide was added dropwise. After 2h under agitation the ethanol was evaporated and the resulting solid recrystallised from chloroform. Complexes with sulfoxide ligands DBSO (dibenzyl sulfoxide) (PTSO) p-Tolyl sulfoxide and (FSO) phenyl sulfoxide were prepared from the [Eu(BTFAC)3(H2O)2] and the specific sulfoxide ligand both dissolved in ethanol in 1:2

(Eu3+:ligand) molar ratio. Solutions were allowed to stand at 4oC until the formation of a pale-yellow precipitated. The solid products were recrystallized from acetone and dried under vacuum over anhydrous calcium chloride in a desiccator at room temperature overnight. The Eu3+ content was obtained by complexometric titration with EDTA, where the compounds were dissolved in methanol using xylenol orange as an indicator. C and H contents were determined by microanalytical procedures. FTIR spectra were measured at room temperature in a Perkin Elmer 1750-FTIR spectrophotometer in the 4000-400 cm-1 spectral range by using the KBr pellet. Composite BC membranes were obtained by incorporation from ethanol solutions with hydrated membranes first submmited to a solvent exchange. Ethanol was substituted for water by several ethanol swelling-pressing cicles. Once in ethanol, membranes were immersed in ethanolic solutions of the complexes.for 24 hours. After that time membranes were removed from the solutions and dried at 40 oC for 2 days. Photoexcitation and photemission spectra were obained in a Fluorolog FL3-22 Jobin-Yvon spectrometer equipped with a R928 Hammamatsu photomultiplier and a 450-W Xe excitation lamp. Measurements of emission decay versus time were performed with the same equipment by using a pulsed Xe lamp (5J/pulse, 3 s bandwidth).

3. Results and Discussion

Molar conductivities results (not shown here) of acetonitrile solutions of the complexes were indicative of nonelectrolyte behavior. That observation together with the analytical data are consistent with the stoichiometric formula [Eu(BTFA)3L2] (L=DBSO, PTSO an FSO). The shift of the S=O stretching vibrational mode from the value of 1033 cm1

observed the free sulfoxides ligand to ~1007 cm-1 observed for the 3 sulfoxide compounds, provides good evidence that

the Eu3+ ion is coordinated to the sulfoxide ligands. The absence of IR absorption bands around 3500 cm-1 in the spectra obtained for the sulfoxide compounds confirms that they are anhydrous, that is, the 2 water molecules present in the betadiketonate precursor were subtituted by the sulfoxide ligands. The substitution was further confimed by thermogravimetric curves (not shown here) showing two water molecules loss at 120oC for [Eu(BTFAC)3(H2O)2] whereas a plateau was observed in the temperature region from 30 o to 140oC for [Eu(BTFA)3L2] sulfoxide complexes. Figure 1 shows excitation spectra obtained for the solid complexes. A broad band covering the UV range with maxima disserned at 284, 327 and 380 nm is observed for the [Eu(BTFAC) 3(H2O)2] compound in Figure 1(a). This band is attributed to the process of absorption of the ligand followed by energy transfer to Eu 3+ excited state levels. From upper levels non-radiative decay populates the 5D0 emmiting level. This is the so-called antenna role played by the ligand. Characteristic intra-4f6 Eu3+ narrow lines are observed at 464.9 nm ( /F0,15D2) and 525.9, 534.8 and 538.7 ( /F0,15D1). The relative intensities ratio between the broad ligand band and the narrow Eu 3+ gives an idea of the efficiency of the antenna effect. Figures 2(b-d) shows spectra obtained for [Eu(BTFA) 3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] respectively. The main picture is the same for all complexes, that is, a broad ligand band in the UV together with the narrow Eu3+ lines. It must be observed that in the 3 spectra the intensities ratio between the broad band

and the narrow lines increases with respect to the [Eu(BTFAC) 3(H2O)2] compound. Therefore, the presence of the sulfoxide ligand substituting for water leads to an increase in the antenna effect.

(d)
Intensity (a.u.)

(c))

(b) (a)
300 400 500

Wavelength (nm)

Figure 1- Solid compounds. Excitation spectra (Em=612 nm). (a) [Eu(BTFAC)3(H2O)2] (b) [Eu(BTFA)3(DBSO)2], (c) [Eu(BTFA)3(PTSO)2] and (d) [Eu(BTFA)3(FSO)2]

Figure 2 shows emission spectra obtained for the solid compounds. Characteristic Eu3+ lines were observed and J numbers in the figure denote trasitions from the 5D0 excited state to the 7FJ lower levels of the Eu3+ 4f6 electronic configuration. Spectra are dominated by the hypersensitive transition 5D07F2 occurring in 610 nm region denoting the highly polarizing ligand field neighbouring Eu3+ ions. The polarizing nature of the ligand field can also be evaluated by the intensities ratio between the electric dipolar 5D07F2 transition and the magnetic dipolar 5D07F1 (R21=I02/I01). Table 1 shown the results for R21 which are larger for the compounds where sulfoxides substitute for water in the Eu 3+ first coordination sphere. Sulfoxide ligands are in fact known to enhance Eu 3+ electric dipolar transitions20. Decay curves (not shown here) could be fitted with a single exponential decay. Values obtained for experimental lifetime ( EXP) and also for the purely radiative decay time ( RAD) are presented in Table 1. RAD values were calculated from the emission spectra by taking the magnetic dipolar 5D07F1 transtion as an internal reference. Details on the metholodology used can be found in Carlos et al15. The 5D0 level quantum efficiency values, q, as defined by the ratio between EXP and RAD are also shown together with the non-radiative decay rate that can be obtained considering that the experimental decay (kEXP=1/EXP) is composed only by the radiative decay (kRAD=1/RAD) and the non-radiative decay (kNRAD).

2 0 1

(d)
3 4

Intensity (a.u.)

(c)

(b)

(a)
550 600 650 700

Wavelength (nm)

Figure 2 - Solid compounds. Emission spectra (Exc=360 nm). (a) [Eu(BTFAC)3(H2O)2] (b) [Eu(BTFA)3(DBSO)2], (c) [Eu(BTFA)3(PTSO)2] and (d) [Eu(BTFA)3(FSO)2]

Experimental lifetime values are observed to increase with sulfoxide substitution for water. The value of 0.33 ms was obtained for the [Eu(BTFAC)3(H2O)2 in agreement with literature values23. Results between 0.45 and 0.67 ms are obtained for the sulfoxide containing compounds. As Table 1 clearly shows the increase in the experimental lifetime is due to an increase in the radiative decay (1/ RAD) together with a decrease in the non-radiative decay. Both effects are a direct consequence of 1- removing of water ligand from Eu3+ coordination sphere, since water vibrational modes are known to strong quench the 5D0 Eu3+ state through non-radiative paths15 and 2- the strong coordination ability of sulfoxides20. Among sulfoxide ligands used here DBSO seems to lead to more pronounced effects. Concerning composites, paper-like homogeneous semi-transparent membranes were obtained that show strong red luminescence under UV excitation. Figure 3 shows excitation spectra. In this case only the broad UV band is observed. Eu3+ ff lines are no longer observed and in fact this feature is due to the higher intensity of the antenna band. Incorporation of the complexes in the BC membrane leads to an increase in the efficiency of the antenna effect which may be very interesting concerning potential photonic applications of these composite membranes.

Table 1- Values obtained for R21 (I02/I01), experimental lifetime (EXP), radiative lifetime (RAD), and quantum efficiency (q) for the solid compounds and BC composite membranes

_________________________________________________________________________________________________ compound R21 (0.5) [EXP] (0.05ms) [RAD] kNRAD(s-1) q

_________________________________________________________________________________________________ [Eu(BTFAC)3(H2O)2] [Eu(BTFA)3(DBSO)2] [Eu(BTFA)3(PTSO)2] [Eu(BTFA)3(FSO)2] BC-[Eu(BTFAC)3(H2O)2] BC- Eu(BTFA)3(DBSO)2] BC-[Eu(BTFA)3(PTSO)2] BC-[Eu(BTFA)3(FSO)2] 7.4 11.8 11.3 12.7 9.4 10.3 9.8 9.2 0.33 0.67 0.45 0.47 0.35 0.61 0.41 0.45 2.00 1.40 1.40 1.23 1.86 1.71 1.80 1.64 2546 762 1495 1315 2319 1056 1881 1610 0.16 0.48 0.32 0.38 0.19 0.36 0.23 0.27

_________________________________________________________________________________________________

(d)

Intensity (a.u.)

(c)

(b)

(a)
300 400 500

Wavelength (nm)

Figure 3- Excitation spectra obtained for composite membranes (EM= 610 nm). (a) BC-[Eu(BTFAC)3(H2O)2] (b) BC[Eu(BTFA)3(DBSO)2], (c) BC-[Eu(BTFA)3(PTSO)2] and (d) BC-[Eu(BTFA)3(FSO)2]

Figure 4 shows emission spectra.. Comparing figures 2 and 4, broadening is observed for the composite membranes with respect to the precursor complexes, denoting changes in the Eu3+ coordination shell with the

incorporation in the cellulose host. Moreover, similar spectra are obtained for the 4 membranes suggesting an interesting coordination role played by the host. Table 1 also gathers the results obtained for R 21 (I02/I01), experimental lifetime (EXP), radiative lifetime (RAD), and quantum efficiency q for the composite membranes.

(d)

Intensity (a.un.)

(c)

(b)

(a) 600 650 700

Wavelength (nm)

Figure 4- Emission spectra obtained for composite membranes (EXC= 360 nm). (a) BC-[Eu(BTFAC)3(H2O)2] (b) BC[Eu(BTFA)3(DBSO)2], (c) BC-[Eu(BTFA)3(PTSO)2] and (d) BC-[Eu(BTFA)3(FSO)2]

Considering the [Eu(BTFAC)3(H2O)2] compound, the incorporation in the biocellulose host leads to improvement on the luminescence characteristics. R21 and EXP values slightly increase and RAD and kNRAD values are almost the same for the precursor complex and the biocellulose composite. Concerning the -diketone-sulfoxide complexes and taking into account the experimental errors, the overall experimental lifetime values (EXP) are not altered with the incorporation. The radiative decay rate value (1/RAD) increases with the incorporation showing a positive effect due to the biocellulose host. However the non-radiative decay path values (kNRAD) also increase with the incorporation and as a consequence, the quantum efficiency values decrease with respect to the precursor complexes. The resulting effects observed on luminescence characteristics are not negative since, as shown by figure 3, the antenna effect is more pronounced in the composite membranes despite the overall decrease in quantum efficiency. In addition it must be stressed that from the potential applications point of view the precursor compounds could hardly being applied unless some additional processing method should be employed for the preparation of thin films on a given substrate for example. The composite membranes gather the positive properties of the biocellulose itself, being obtained as self-sustainable membranes, with the additional strong luminescence functionality.

4. Conclusion
Eu3+ complexes were prepared by using the -diketone BTFAC (BTFAC- 4,4,4-Trifluoro-1-phenyl-1,3butanedione or benzoyltrifluoroacetone) and the sulfoxides DBSO (dibenzyl sulfoxide) (PTSO) p-Tolyl sulfoxide and (FSO) phenyl sulfoxide ligands. Compounds with general formula [Eu(BTFAC)3(H2O)2], [Eu(BTFA)3(DBSO)2], [Eu(BTFA)3(PTSO)2] and [Eu(BTFA)3(FSO)2] were characterized. Preliminary spectroscopic properties were obtained and strong red emission was observed under UV excitation. With the substitution of sulfoxides for water in the Eu 3+ coordination sphere, improvement on the luminescence characteristics was observed, taking into account emission and excitation spectra, experimental lifetimes and emission quantum efficiency. The complexes were incorporated in biocellulose membranes by using ethanolic solutions. Self-sustainable semi-transparent composite membranes were obtained showing strong emission under UV exctiation. The antenna role played by the ligands was observed to be more efficient in the composite membranes than in the precursor complexes, showing the importance of the biocellulose host. These new multifuctional membranes could find application in different areas as phosphors and UVVisible energy converting devices.

Acknowledgements
Brazilian funding agencies FAPESP, CNPq and CAPES are acknowledged. The Photonics Institute (INFO) (National Institute of Science and Technology- CNPq- Brazil) is also acknowledged for financial support.

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