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Mesoporous manganese-porphyrinsilica
hybrid nanomaterial sensitive to H2O2
fluorescent detection

Article in Materials Research Bulletin October 2015

DOI: 10.1016/j.materresbull.2015.10.032

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Contents lists available at ScienceDirect

Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

1 Mesoporous manganeseporphyrinsilica hybrid nanomaterial

2 sensitive to H2O2 uorescent detection
3 Q1 Anca Lascua , Anca Paladea , Gheorghe Fagadar-Cosmab , Ionela Creangaa , Catalin Ianasia ,
4 Iuliana Sebarchievicic , Mihaela Birdeanua,c, Eugenia Fagadar-Cosmaa,*
5 a
Institute of Chemistry Timisoara of Romanian Academy, M. Viteazul Ave. 24, 300223-Timisoara, Romania
6 b
Politehnica University of Timisoara, Vasile Parvan Ave. 6, 300223 Timisoara, Romania
7 c
National Institute for Research and Development in Electrochemistry and Condensed Matter, 1 Plautius Andronescu Street, 300224 Timisoara, Romania

A R T I C L E I N F O A B S T R A C T

Article history: A novel hybrid mesoporous silicaMnporphyrin nanomaterial and its application for uorescent
Received 16 May 2015 detection of H2O2 is reported. The hybrid was obtained by solgel method in two steps acid-base catalysis
Received in revised form 2 October 2015 and was completely characterized by UVvis, FT-IR, uorimetric, DRX, BET, AFM, TEM and conductivity
Accepted 16 October 2015
investigations. The inuence of adding H2O2 to the silicaMnporphyrin hybrid generates major
Available online xxx
differences regarding the optical, textural and morphological properties of the material. The dependence
between H2O2 concentration and the uorescence intensity, measured at the emission maximum at the
Keywords:
wavelength 655 nm, is linear with an excellent correlation coefcient of 0.9945. The high sensitivity for
A. Nanostructures
A. Optical materials
hydrogen peroxide in wet media noticed for this hybrid, accompanied by changes in color, justies
B. Solgel chemistry further investigations towards design of uorimetric and colorimetric O2 gas sensors. The low
C. Atomic force microscopy conductivity of the manganese(III)porphyrinsilica hybrid (0.694
108 S/cm) can be improved, so that
D. Surface properties this material may become a promising one for electrochemical cells (batteries).
2015 Published by Elsevier Ltd.

8 1. Introduction [10] and the epoxidation of various alkenes [11,12]. The solgel 27

process is well-known in tailoring properties of silicaporphyrin 28

9 Hydrogen peroxide is known as a redox signaling agent due to hybrids, being recognized for producing highly homogeneous 29
10 its capacity to induce oxidative damage, and nally apoptosis. On materials [13] that exist as a single phase resulting from the 30
11 the other hand, Mn-porphyrins are subjected to increased incorporation of an organic dye into an inorganic matrix. Q2 31
12 attention due to their capacity to attenuate protein oxidation [1] The nanoscale combination of organic and inorganic compo- 32
13 and to reverse such damage [2]. An efcient protection against nents produces multifunctional materials exhibiting enhanced 33
14 oxygen quenching is essential for porphyrins involved in PDT properties, arising not only from the sole constituents, but also 34
15 applications [3,4]. Mn-porphyrins are also suitable compounds in from the interface between them. 35
16 catalyzing several biological phenomena [5]. Among the large Starting from the knowledge that in class I materials, 36
17 variety of metals used in complexes that are available for use in inorganic and organic components interact only weakly through 37
18 optical sensing of oxygen, manganese is considered one of the best hydrogen bonding, van der Waals contacts or electrostatic forces 38
19 oxygen carriers [6]. Besides, 5,10,15,20-tetraphenyl-21H, 23H- [14] the entrapped organic molecule usually retains its character- 39
20 porphyrin manganese(III) chloride was successfully applied for istic physical and chemical properties. On the other hand, it is 40
21 protein labeling by means of differential pulse voltammetry, UV always possible to control the texture of the material by varying 41
22 vis spectrophotometry and spectrouorimetry [7]. Hybrid gold, the experimental conditions. As a consequence optical applications 42
23 Fe3O4, silica, carbon nanotubes or polymeric nanomaterials of porphyrin-silica hybrids are the most developed due to this 43
24 grafting or incorporating Mn-porphyrins received great attention preservation or even enhancement of properties [15]. 44
25 due to the amazing applications as sensors for L-cysteine [8] or Our previous work concerning the inuence of H2O2 on 45
26 toxic gas detection [9] and as catalysts for the oxidation processes photophysical behavior of Mn(III) 5,10,15,20-tetra(4-methyl-phe- 46

nyl) porphyrin chloride revealed that this metalloporphyrin is 47

suitable for usage as sensitive material in O2 gas UVvis detection 48

[16]. It is already known that Mn porphyrins show negligible 49

* Corresponding author. Fax.: +40 256491824. 50
uorescence in their bare state [17]. Chromophore aggregation
E-mail address: efagadar@yahoo.com (E. Fagadar-Cosma).

http://dx.doi.org/10.1016/j.materresbull.2015.10.032
0025-5408/ 2015 Published by Elsevier Ltd.

Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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2 A. Lascu et al. / Materials Research Bulletin xxx (2015) xxxxxx

51 might generate aggregation-induced emission [18]. The emission using nitrogen as adsorbate at the temperature of liquid nitrogen 90
52 of bare Mn-porphyrin is non-luminescent when it is dissolved in 77.350K. The method for calculation was de Boers with software 91
53 THF, but emits intensely when its molecules are aggregated into Quantachrome NovaWin2Data Acquisition and Reduction for 92
54 silica matrix due to adopting a twisted conformation which NOVA instruments 19942003, Quantachrome Instruments, 93
55 prevents free movement between the molecules. version 2.1. X-ray powder diffraction (DRX) was performed on 94
56 The outcomes presented in this report refer to the obtaining of a powder samples to analyze the structure and phase using Cu Ka 95
57 hybrid silicaMnporphyrin nanomaterial and its application as radiation in the 2u range from 20 to 80 . AFM measurements were 96
58 uorescent molecule for the detection of H2O2. This established performed in contact mode with phase or frequency detection on 97
59 high sensitivity for oxygen in wet media is in connection with our Nanosurf1 EasyScan 2 Advanced Research AFM, with sample 98
60 efforts for validating novel materials able for O2 gas detection. The preparation onto silica plates. UVvis, uorimetric and AFM 99
61 obtaining of a novel hybrid, having optimal morphologic and measurements were done in ambient conditions (temperature: 100
62 structural properties was carried out based on our previous 22 2  C; relative humidity: 5070%). TEM analysis was performed 101
63 investigations [19]. on a Titan G2 80200 TEM/STEM (FEI Company, The Netherlands), 102
64 We focused only on the solgel approach (two steps acid base under accelerating voltage of 200 kV and using soft Digital 103
65 catalysis) in order to protect the manganese central metal ion and Micrograph v. 2.12.1579.0. The samples in powder form were 104
66 to ensure optimal dispersion of organic dye into the silica matrix. ultrasonically dispersed in EtOH for 20 min and deposited on 105
67 MnTTPClsilica hybrid was found to meet all the criteria in order to 300 mesh TEM copper grids covered with lacey carbon lm. The 106
68 be used both as uorimetric sensor for H2O2 detection and also as conductivity was determined based on the measurements on a 107
69 colorimetric indicator. Besides, the low determined conductivity potentiostat/galvanostat Autolab 302N, equipped with the 108
70 might be improved so that the material becomes promising for FRA2 impedance module, using the ZviewScribner Associated 109
71 electrochemical cells (batteries). Inc. program for simulation. The experimental conditions were: 110

brass electrodes having the working area A = 1.1 cm2 and the 111
72 2. Experimental distance between them d = 80 mm (thickness of the studied 112

material); the frequency range was from 0.1 Hz to 1 MHz; the 113
73 2.1. Reagents amplitude of the excitation voltage signal was 10 mV and was 114

applied near to the OPC (open circuit potential). 115

74 All reagents provided of purum analiticum quality by Merck,
75 Fluka and Sigma-Aldrich were used without further purication. 2.3. Solgel preparations 116
76 The aqueous solutions were prepared with doubled distilled water.
77 The porphyrin base, tetratolylporphyrin, was synthesized and fully Solgel preparations have been performed modifying a previ- 117
78 characterized in previous work [20]. 5,10,15,20-Tetra(4-methyl- ous recipe [22] and monitored by UVvis (Fig. 1) and FT-IR (Fig. 2) 118
79 phenyl) porphyrinato manganese (III) chloride was synthesized by spectroscopy. 119
80 Adlers method [21] modied procedures [19]. Pophyrin Mn(III) 5,10,15,20-tetratolyl-porphyrin chloride 120

(0.017 g, 0.02 mmol) was solved in 14 mL THF (c = 1.4
103 M) 121

81 2.2. Apparatus resulting in intense green solution. Under vigorous stirring a 122

solution of TEOS (7.9 g, 0.038 mol) solved in ethanol (6.98 g, 123

82 FT-IR spectra were carried out as KBr pellets, in the 4000 0.152 mol) was added dropwise. After 15 min intense stirring, a 124
83 400 cm1 range on JASCO 430 apparatus. UVvis spectra were solution comprised of 37% HCl solution (0.037 g, 1.01 mol) and H2O 125
84 investigated using classical 1 cm quartz cells on a JASCO UVvis (2.73 g, 0.152 mol), is again dropwise added to the mixture so that 126
85 spectrometer, V-650 model in THF. Fluorescence spectra were the nal molar ratio TEOS: EtOH:H2O is 1:4:4:0.01. After another 127
86 recorded in THF on a PerkinElmer Model LS 55 apparatus in a 1 cm 15 min of stirring, droplets of a basic 2.5% NH3 solution (0.38 g) 128
87 cuvette, exciting at 430 nm with constant slit widths, 5 nm for were added, so that the formed sol should not instantaneously turn 129
88 excitation and 10 nm for emission. Pore Size Data (BJH method) into gel, but remain stable. After 2 h the complete geliation was 130
89 were determined on QUANTACHROME Nova 1200 apparatus, by noticed and transparent green gels were formed. The gels were 131

Fig. 1. Monitoring of the solgel process for obtaining the silica porphyrin hybrid in two steps (acid-base catalysis). In detail the spectrum of the MnTTPCl solution in THF, at
the same concentration as in the nal hybrid, before gelation (c = 0.57
106 M). UVvis, THF (lmax (log e)): 370(4.89), 394(4.85), 475(5.20), 586(4.11), 622(4.20).

Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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A. Lascu et al. / Materials Research Bulletin xxx (2015) xxxxxx 3

Fig. 2. Overlapped FT-IR spectra of MnTTPCl and Mn-porphyrin-silica hybrid.

132 dried to lose the incorporated THF in ambient conditions followed hybrid, obtained in acid-base two steps solgel process, presents 149
133 by oven drying at 95  C for 2 days. The control sample was the best optical properties, its Soret band intensity being increased 150
134 identically synthesized without porphyrin adding and transparent more than twice in comparison with the initial porphyrin, 151
135 colorless gels were obtained. After washing the gels with water and although the concentration of the organic dye in the hybrid is in 152
136 alcohol no bleaching phenomenon was observed. the range of ppm. 153

137 3. Results and discussion 2.6. FT-IR spectroscopy 154

138 2.5. UVvis spectroscopy The FT-IR spectrum of the dry hybrid presents the most intense 155

bonding mode around 1100 cm1 that is broadened and is 156

139 As can be seen from Fig. 1 (detail), the MnTTPCl absorption attributed to the SiO cage stretching mode (Fig. 2). The broad 157
140 spectrum is belonging to d-hyper type class,having ve identica- band peaked at 3450 cm1 and the shoulder that appears at 158
141 tion peaks: VI band located at 370 nm, Va band at 394 nm, Soret 1620 cm1 are attributed to O H stretching and bending 159
142 band (called also V band) at 475 nm and two Q band of lower vibrations. The porphyrin characteristic intense ngerprint bands 160
143 intensity, namely: QIV band located at 586 nm and QIII band at located at 800 and around 950 cm1, attributed to wagging and 161
144 622 nm. twisting modes of the CH bonds in the pyrrole ring [23] are 162
145 Further analysis of Fig. 1 reveals that both the intermediates and engulfed in the broad bands of SiO Si and SiOC in the nal 163
146 the nal hybrid prezerve the shape and location of all peaks of the silica hybrid material, as expected [24]. 164
147 initial porphyrin dye and bring the benet of amplifying the This feature might indicate that silica component can be 165
148 intensity of absorption, that was one of our main goals. The nal bonded to the Mn-porphyrin, due to the great afnity of 166

Fig. 3. Superposed UVvis spectra of the MnTTPCl-silica hybrid when increasing H2O2 concentration.

Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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4 A. Lascu et al. / Materials Research Bulletin xxx (2015) xxxxxx

Osilica bonds ascribed in

indicates a possible existence of Mn 172

the literature to manganeseoxygen derivatives [25] 173

2.7. The inuence of H2O2 adding on optical spectroscopy 174

By continuously adding of H2O2 to the hybrid solution, the UV 175

vis spectra show a continuous decrease with respect to the 176

intensity of absorption of all bands (Fig. 3). 177

Both the emission bands of bare porphyrin (the lowest intensity 178

emission spectrum in Fig. 4) and of the hybrid material in THF 179

exhibit a strong intensity band at 655 nm assigned to Q (0,0) 180

transition accompanied by a weaker one at 719 nm representing 181

the and Q (0,1) transition. This feature includes the hybrid material, 182

emitting at superior wavelengths, in the category of second 183

generation photosensitizersand opens the possibility to be used in 184

photosensitizing techniques in non-invasive medicine. 185

From UVvis and uorescence data it can be observed that 186

positive Stokes shifts of 181 nm occur (wavelength values of Q (0,0) 187

Fig. 4. Superposed emission spectra of the MnTTPCl-silica hybrid when increasing emission bandwavelenght of Soret absorption band) giving 188
H2O2 concentration. 189
expectations to good emission properties because the large
positive shift allows easy separation of the emission from scattered 190
167 manganese to oxygen. This is also conrmed by the slight light. 191
168 broadening of the Soret band in the UVvis spectrum of the By increasing concentration of H2O2 (the rate of adding 33% 192
169 hybrid material, proving that the dye molecules tend to aggregate H2O2 to the THF solution is 1 mL/5 min) the uorescence behavior 193
170 by ppinteractions and possible MnO coordinative bonds. The of the porphyrin-silica hybrid solved in THF (Fig. 4) preserves the 194
171 shoulder from 550 cm1 in our FT-IR spectrum of the hybrid shape and location of initial MnTTPCl compound but produces a 195

Fig. 5. The dependence between H2O2 concentration and the uorescence intensity.

Fig. 6. Color changes of the MnTTPCl-silica hybrid before introducing H2O2, after introducing 18 mL of H2O2 and 24 h later.

Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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A. Lascu et al. / Materials Research Bulletin xxx (2015) xxxxxx 5

Fig. 7. DRX-ray powder pattern with characteristic peak of amorphous silica before and after H2O2 exposure. Q3

Fig. 8. AFM images show the surface of the hybrid material before (A and C) and after exposure to H2O2 (B and D).

Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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6 A. Lascu et al. / Materials Research Bulletin xxx (2015) xxxxxx

Table 1
Surface, morphological and textural characteristics, obtained from AFM and BET measurements (DFT and BJH methods)

Sample MnTTPCl-silica Average surface roughness (Sa, Maximum valley depth (Sv, Height distribution Dp [Ads] Dp [Des] SBET (m2/ VP (cc/g)
hybrid nm) nm) (nm) (nm) (nm) g)
(1) Bare 2.1 18 3040 4.88 3.8 467.3 0.34
(2) After H2O2 5.3 31 15.450 3,17 3.4 179.6 0.15
exposure

196 signicant increase regarding the intensity of the emission bands. the hybrid, is insignicant in comparison to that of the hybrid 224
197 This behavior is unexpected, in most cases a quenching of silicaporphyrin material and is not offering the requested 225
198 uorescence is taking place [2633]. sensitivity. 226
199 The dependence between H2O2 concentration and the uores-
200 cence intensity, measured at the emission maximum at the 2.8. DRX, AFM, TEM and BET analysis of the silicaporphyrin 227
201 wavelength 655 nm, is linear with an excellent correlation hybrid material 228
202 coefcient of 0.9945 (Fig. 5). Besides, colorimetric changes
203 (Fig. 6) are accompanying these uorimetric modications. DRX-ray powder pattern with characteristic peak of amorphous 229
204 Considering this behavior, MnTTPCl-silica hybrid was found to silica without displaying signicant differences was revealed for 230
205 meet all the criteria in order to be used both as uorimetric sensor both untreated and exposed to H2O2 hybrid material, as can be seen 231
206 for H2O2 detection and also as colorimetric indicator (Fig. 6). in Fig. 7. 232
207 The advantages of using a mesoporous porphyrin-silica hybrid AFM images show the surface of the hybrid material before 233
208 material instead of using the metalloporphyrin alone for sensitive (Fig. 8A and C) and after exposure to H2O2 (Fig. 8B and D) from THF 234
209 detection of H2O2 reside in: the preservation or in our case the solution. Analyzing the AFM images (4
4 mm), the most 235
210 amplication of sensitive material properties; the signicant important common feature is the organization of aggregates into 236
211 diminishing of costs as the expensive pure porphyrin dye is added triangular geometries and their constant orientation. J aggregates 237
212 to the mesoporous silica only in the range of ppm order of (edge-to-edge stacked) and H sandwich-type aggregates are 238
213 magnitude; the increased performance of the sensing properties accompanied by multiple H-bonding interactions to form the 239
214 by the creation of the hybrid. The correlation coefcients straw and shell like stacks [23,34]. The differences reside in the 240
215 presented: a value of 0.9945 for the uorescence sensor based sizes and the shape of the aggregates that are signicantly 241
216 on hybrid and only 0.9826 for the porphyrin alone used in the UV increased after H2O2 treatment. The AFM roughness parameters 242
217 vis detection, as reported in our previous research [16], justify our are presented in Table 1 together with morphological and textural 243
218 approach. With respect to the bare silica material, it has no BET characteristics. 244
219 uorescence so that solely it cannot be a candidate for this type of TEM analysis indicated that the silicagel matrix was amor- 245
220 sensors. Additionally, we have tested the porphyrin dye alone, that phous and uniformly distributed for the untreated hybrid (Fig. 9a) 246
221 exhibits very low intensity of emission [17]. The increase of but non-uniformly mesoporous for the H2O2 exposed material 247
222 uorescence of porphyrin alone due to exposure to increased H2O2 (Fig. 9b). Additionally, the mesoporous structure presented in 248
223 concentration, measured under the same conditions with that of

Fig. 9. (a) and (b) TEM images of porphyrin silica hybrid before (a) and after (b) H2O2 exposure.

Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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A. Lascu et al. / Materials Research Bulletin xxx (2015) xxxxxx 7

Fig. 10. (a) and (b) Nyquist and Bode diagrams of MnTTPCl-silica hybrid.

249 Fig. 9b clearly indicates that most of the pores were lled, a decreasing the free volume, which might result in less and smaller 282
250 situation similar with literature data [35]. hydrophilic pores and channels for hydrated proton transport [40]. 283
251 As in another similar case [36] we presume that a substantial
252 number of oxygen molecules, generated by the H2O2 decomposi- 4. Conclusions 284
253 tion penetrate the porous silica shell and nally diminish the
254 surface area as also BET measurements in Table 1 demonstrate. This report refers to the obtaining of a novel hybrid mesoporous 285
255 BET analysis of the hybrid material before and after exposure to silicaMnporphyrin nanomaterial and its application for uores- 286
256 H2O2 presents major differences regarding the values of specic cent detection of H2O2. The noticed high sensitivity for oxygen in 287
257 area and pore size diameters (Table 1). All these parameters have wet media of this material justies further investigations toward 288
258 decreased values after the H2O2 interaction, fact that is a proof for O2 gas detection. The hybrid was obtained by solgel method in 289
259 the physico-chemical inclusion of the liberated oxygen (2H2O2 two steps acid-base catalysis in order to protect the manganese 290

! 2H2O + O2) into the pores of the hybrid material. Oxygen is central metal ion and to ensure optimal dispersion of organic dye 291
260 allowed to diffuse to the Mn-metalloporphyrin grafted on the into the silica matrix. MnTTPCl-silica hybrid was completely 292
261 internal surface of the silica matrix [10]. It is documented that the characterized by FT-IR, UVvis, Fluorescence, X-ray powder 293
262 presence of oxygen improves silica matrices stability and preserves diffraction (DRX), BET, AFM, TEM microscopy and conductivity 294
263 its morphology (pores shape), but decreases porosity, pore investigations and we can conclude that major differences appear 295
264 diameter and as a consequence the surface area, as demonstrated regarding the optical, textural and morphological properties of the 296
265 in our case [37,38]. The hybrid material is mesoporous and capable material after being exposed to increased concentrations of H2O2. 297
266 of applications in gas sensing, catalysis, drug delivery and imaging. MnTTPCl-silica hybrid was found to meet all the criteria in order 298

to be used both as uorimetric sensor for H2O2 detection and also 299
267 2.9. Conductivity measurements as colorimetric indicator. The conductivity of the MnTTPCl-silica 300

hybrid is 0.694
108 S/cm, but further work can improve it so that 301
268 In order to explore other properties and possible electrochemi- this material may become a promising one for electrochemical 302
269 cal applications of the hybrid, the conductivity of the material was cells (batteries). 303
270 investigated by EIS (electrochemical impedance spectroscopy). The
271 Nyquist and Bode diagrams for MnTTPCl-silica hybrid are Acknowledgements 304
272 presented in Fig. 10a and b respectively.
273 The conductivity was calculated with the value of the electrical The authors from Institute of Chemistry Timisoara of Romanian 305
274 resistance (R = 1.0473
106 ohm) obtained from the simulation Academy are kindly acknowledging the support from Program 3- 306
275 program, using the equation: s = d/(RA). The obtained values for Porphyrins/2015 and STAR Programme, SAFEAIR Project 76/2013. 307
276 MnTTPCl-silica hybrid was s = 0.694
108 S/cm representing a
277 low conductivity. Further work using functionalized silica pre- References 308
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Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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Please cite this article in press as: A. Lascu, et al., Mesoporous manganeseporphyrinsilica hybrid nanomaterial sensitive to H2O2 uorescent
detection, Mater. Res. Bull. (2015), http://dx.doi.org/10.1016/j.materresbull.2015.10.032
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