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Photo-acoustic response of active biological systems
Available online at www.sciencedirect.com
Optical Materials 30 (2008) 814–816 www.elsevier.com/locate/optmat
Photo-acoustic response of active biological systems N. Guskos
a,b,* ,
K. Aidinis a, G.J. Papadopoulos a, J. Majszczyk b, J. Typek b, J. Rybicki c, M. Maryniak b
a
Department of Physics, University of Athens, Panepistimiopolis 15 784 Zografos, Athens, Greece Institute of Physics, Szczecin University of Technology, Al. Piastow 17, 70-310 Szczecin, Poland Department of Solid State Physics, Faculty of Technical Physics and Applied Mathematics, Gdansk University of Technology, Narutowicza 11/12, 80-952 Gdansk, Poland b
c
Available online 21 March 2007
Abstract Two samples from a biologically active system, Trunculariopsis trunculus, were used in thick film form: one damp and the other dry. In both cases intense and broad absorption bands appeared in the visible region of the electromagnetic spectrum near yellow, as well as below 330 nm, attributed to charge transfer transitions. The damp sample produced a higher response signal at about 570 nm. The Photo-acoustic spectra contain all the bands of radiation vital for maintenance of activity in a living system with a distinctive prominence of the yellow part of the spectrum. Ó 2007 Elsevier B.V. All rights reserved.
1. Introduction The Photo-acoustic (PA) effect plays a very important role in biogenic and evolutionary processes in the living matter, especially those involving solar radiation, in energy balancing and in intermolecular energy relaxation processes [1–4]. Polyamines (spermidines) are natural elements present in most of the living organisms that play a major role in many biological processes, including structural conformation and stabilization of nuclei acids [5–7]. Some copper(II) complexes of polyamines are constricted bridges for information transfer to DNA. Two main regions in the visible part of the electromagnetic spectrum of the Photoacoustic reaction were recorded for copper(II) complexes, a more intense one in the blue region, arising from the p ! p* and n ! p* charge transfer transitions, and another with a peak in the yellow region, due to the d ! d transitions [8,9]. It has been suggested that d-d transitions of metal complexes could play an important role in the so-
*
Corresponding author. Address: Department of Physics, University of Athens, Panepistimiopolis 15 784 Zografos, Athens, Greece. E-mail address: [email protected] (N. Guskos). 0925-3467/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.optmat.2007.02.004
called ‘‘channel selector processes’’ of a living system’s thermodynamic balance [10,11]. Other important components of living matter, such as magnetite or rare earth(III) organic complexes, display their radiative and non-radiative transitions in the yellow region, [3]. The aim of this report is to study radiative and non-radiative processes in tissue specimens from Trunculariopsis trunculus, the descendant of a prehistoric water gastropod, using Photo-acoustic spectroscopy (PAS) and shed some light on the related physics between polyamines and iron oxides. 2. Experimental PA spectra of samples were obtained using a modification of the PAS method initially proposed by Papadopoulos and Mair [12]. A 1 kW Xenon arc lamp and a 1/4 m ORIEL monochromator were used as a light source, with a bandpass width of 5 nm (at 500 nm). Light of intensity modulated with a chopper at a frequency of 10 Hz was directed onto a Photo-acoustic cell equipped with a TREVI EM27 microphone. A dual SR830 lock-in amplifier measured the amplitude and phase of the PA signal detected by the microphone. Data acquisition ensured that each
N. Guskos et al. / Optical Materials 30 (2008) 814–816
value was the average of 20 runs at the same wavelength of incident light. A carbon-black sample was used as a standard to calibrate the final spectrum. The PA spectra of all the complexes were recorded at room temperature in the range of 300–700 nm. Two samples (damp sample I and dried sample II) of the active biological organism, T. trunculus, were prepared by attaching tissue on cutouts of plotting paper 3 cm in diameter. 3. Results and discussion
PAS signal intensity [Arb.units]
Spectra obtained for the two investigated samples are shown in Fig. 1. In both cases, an intense and broad absorption band was registered near the yellow region of the spectrum. An even more intense absorption was observed in both samples below 330 nm, attributable to charge transfer transitions. Sample I produced a more intense PAS signal than sample II. The presence of an intense peak at about 570 nm was registered in sample I (see Fig. 1a), while only an extended peak in the yellow region was recorded for sample II (see Fig. 1b). Furthermore, in the background of the low energy part of the main PA signal of sample II an intense signal appeared at 650 nm—an absorption wavelength important in the processes of photosynthesis. The observed PA spectra com-
2
1
300
400
500
600
700
PAS signal intensity [Arb.units]
Wavelength [nm]
1.2 1 0.8 0.6
0.4 300
400
500
600
700
Wavelength [nm] Fig. 1. Photo-acoustic spectra of Trunculariopsis trunculus at room temperature for (a) sample I and (b) sample II.
815
prise all bands of radiation important in maintenance of an active state in a living system, with distinctively pre-eminent intensity in the yellow region. Iron(III) and copper(II) complexes are some of the most important compounds for living systems’ functionality and their PAS study has shown a very intense absorption signal at 576 nm [3,8– 11]. The PA spectra of the copper(II) complex of polyamine Spm323 and the iron(III) oxide (hematite) are shown a very intense PA absorption spectra were recorded in both samples, with an intense peak in the yellow region of the electromagnetic spectrum [8,11]. The similarity with the organic tissue samples is especially distinct for the copper(II) complex of polyamine Spm323. Copper(II) complexes of polyamines, can be very important for the activity of living systems. Important electron d–d transitions in the yellow region of radiation and their extended wave functions may have important connections with dynamic processes taking place in active biological systems [10]. PA absorption spectra are produced by heat through non-radiative relaxation released by a sample absorbing incident light. PA intensity (I) can be expressed as [12]: I ¼ ckAabs ;
ð1Þ
where c is a coefficient related to the sample’s thermal properties and the spectrometer’s characteristic, k is the probability of a non-radiative transition from an excited state, and Aabs is the sample’s absorbance. The parameters for sample I may be assumed to be similar to those of spermidine Spm323 [9], which is apparent from a comparison of their PA d–d transition absorption intensities. For sample II, the intensities of electron d–d transitions are drastically decreased, whereas the charge transfer transition intensities remain almost the same. The main part of T. trunculus body does not react anti-bondingly, but a majority of water molecules are removed. Some of them may change the molecules electronic structure and thus significantly influence the intensities of electron d–d transitions [8,9,13]. Magnetic interactions of copper(II) bioactive complexes are strongly dependent on the concentration of water molecules [14]. The presence of water may significantly modify the PA reaction to incoming radiation and involve magnetic interactions. The water molecular process had been especially important for living systems millions of years ago and in consequence could have influenced the evolutionary processes by gradually modifying the electronic structure of copper(II) complexes. Other PA absorptions below the blue region of the spectrum, the so-called charge transfers, are connected with p ! p* and n ! p* electron transitions. Transitions observed for active biological copper(II) complexes are similar to those of T. trunculus [8,9], where iron(III) oxides are absent in the PA signal below 300 nm [11]. Biologically active copper(II) complexes show two very important PA absorption bands, a very intense one below 300 nm and a very broad one in the yellow region of radiation.
816
N. Guskos et al. / Optical Materials 30 (2008) 814–816
4. Conclusions
References
A physical explanation has been attempted for the first time for n ! p* electron transitions in a living system, which play an essential role in its thermal processes [4]. In the case of d–d electron transitions, where the wave functions are extended the so-called ‘‘channel selector’’ mechanism could be activated for transferring very important information to the DNA system [10]. This preliminary report demonstrates that the PA reaction may produce evidence that yellow solar radiation plays a very important role in the dynamical processes of living mater. Already the ancient Greeks and Romans considered solar radiation an important healing agent, while colors yellow and blue are found throughout the history of religion to symbolize divine powers. Today, the discovery of a special role of yellow radiation for living organisms, if confirmed, could also be of utmost relevance to applications closely related to physics. A better understanding of these processes may have important consequences in:
[1] A. Lachaine, R. Pottieer, D.A. Russel, Spectrochim. Acta Rev. 15 (1993) 125. [2] R. Wu, Q. Su, J. Mol. Struc. 559 (2001) 195. [3] N. Guskos, J. Typek, G.P. Papadopoulos, M. Wabia, J. Majszczyk, E.A. Anagnostakis, M. Maryniak, Mol. Phys. Rep. (Poland) 39 (2004) 66. [4] N. Guskos, J. Typek, E.A. Anagnostakis, M. Maryniak, D.G. Paschalidis, Spectrosc. Lett. 39 (2006) 21. [5] C.W. Tabor, H. Tabor, Rev. Biochem. 53 (1984) 749. [6] A. Verma, R.K. Boutwell, in: P.P. McCann, A.E. Pegg, A. Sjoredsma (Eds.), Inhibition of Polyamine Metabolism, Biological Significance and Basis for New Therapies, Academic, Orlando, 1987, p. 113. [7] L. Lomzik, in: Berton (Ed.), Handbook of Metal-Ligand Interactions in Biological Fluids, vol. I, Dekker, New York, 1995, p. 686. [8] N. Guskos, G.P. Papadopoulos, V. Likodimos, G.L. Mair, J. Majszczyk, J. Typek, M. Wabia, E. Grech, T. Dziembowska, T.A. Perkowska, J. Phys. D: Appl. Phys. 33 (2000) 2664. [9] N. Guskos, G.P. Papadopoulos, V. Likodimos, J. Majszczyk, J. Typek, M. Wabia, E. Grech, T. Dziembowska, T.A. Perkowska, K. Aidinis, J. Appl. Phys. 90 (2001) 1436. [10] N. Guskos, G.P. Papadopoulos, J. Majszczyk, J. Typek, M. Wabia, D.G. Paschalidis, I.A. Tossidis, K. Aidinis, Acta Phys. Pol. A 103 (2003) 301. [11] N. Guskos, G.P. Papadopoulos, V. Likodimos, S. Patapis, D. Yarmis, A. Przepiera, K. Przepiera, J. Majszczyk, J. Typek, M. Wabia, K. Aidinis, Z. Drazek, Mat. Res. Bull. 37 (2002) 1051. [12] M.J. Adams, J.G. Highfield, G.F. Kirkbright, Anal. Chem. 52 (1980) 1260. [13] N. Guskos, J. Typek, G.J. Papadopoulos, M. Maryniak, K. Aidinis, Materials Science-Poland 25 (2005) 955. [14] N. Guskos, S. Glenis, V. Likodimos, J. Typek, H. Fuks, M. Wabia, R. Szymczak, C.L. Lin, T.A. Perkowska, J. Appl. Phys. 93 (2003) 9834.
– Medicine, where photo–thermal and Photo-acoustic phenomena have been employed for many years, but the importance of yellow radiation has not been studied (A new generation of thermal systems for living matter based on yellow radiation and relaxation processes could be used for direct generation of heat in the body). – Technology, where understanding the mechanism of intermolecular energy transfer may allow realization of advanced intelligent machines. – Nanotechnology, where it could help in the construction of systems with greater information storage capacity.
Optical Materials 30 (2008) 814–816 www.elsevier.com/locate/optmat
Photo-acoustic response of active biological systems N. Guskos
a,b,* ,
K. Aidinis a, G.J. Papadopoulos a, J. Majszczyk b, J. Typek b, J. Rybicki c, M. Maryniak b
a
Department of Physics, University of Athens, Panepistimiopolis 15 784 Zografos, Athens, Greece Institute of Physics, Szczecin University of Technology, Al. Piastow 17, 70-310 Szczecin, Poland Department of Solid State Physics, Faculty of Technical Physics and Applied Mathematics, Gdansk University of Technology, Narutowicza 11/12, 80-952 Gdansk, Poland b
c
Available online 21 March 2007
Abstract Two samples from a biologically active system, Trunculariopsis trunculus, were used in thick film form: one damp and the other dry. In both cases intense and broad absorption bands appeared in the visible region of the electromagnetic spectrum near yellow, as well as below 330 nm, attributed to charge transfer transitions. The damp sample produced a higher response signal at about 570 nm. The Photo-acoustic spectra contain all the bands of radiation vital for maintenance of activity in a living system with a distinctive prominence of the yellow part of the spectrum. Ó 2007 Elsevier B.V. All rights reserved.
1. Introduction The Photo-acoustic (PA) effect plays a very important role in biogenic and evolutionary processes in the living matter, especially those involving solar radiation, in energy balancing and in intermolecular energy relaxation processes [1–4]. Polyamines (spermidines) are natural elements present in most of the living organisms that play a major role in many biological processes, including structural conformation and stabilization of nuclei acids [5–7]. Some copper(II) complexes of polyamines are constricted bridges for information transfer to DNA. Two main regions in the visible part of the electromagnetic spectrum of the Photoacoustic reaction were recorded for copper(II) complexes, a more intense one in the blue region, arising from the p ! p* and n ! p* charge transfer transitions, and another with a peak in the yellow region, due to the d ! d transitions [8,9]. It has been suggested that d-d transitions of metal complexes could play an important role in the so-
*
Corresponding author. Address: Department of Physics, University of Athens, Panepistimiopolis 15 784 Zografos, Athens, Greece. E-mail address: [email protected] (N. Guskos). 0925-3467/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.optmat.2007.02.004
called ‘‘channel selector processes’’ of a living system’s thermodynamic balance [10,11]. Other important components of living matter, such as magnetite or rare earth(III) organic complexes, display their radiative and non-radiative transitions in the yellow region, [3]. The aim of this report is to study radiative and non-radiative processes in tissue specimens from Trunculariopsis trunculus, the descendant of a prehistoric water gastropod, using Photo-acoustic spectroscopy (PAS) and shed some light on the related physics between polyamines and iron oxides. 2. Experimental PA spectra of samples were obtained using a modification of the PAS method initially proposed by Papadopoulos and Mair [12]. A 1 kW Xenon arc lamp and a 1/4 m ORIEL monochromator were used as a light source, with a bandpass width of 5 nm (at 500 nm). Light of intensity modulated with a chopper at a frequency of 10 Hz was directed onto a Photo-acoustic cell equipped with a TREVI EM27 microphone. A dual SR830 lock-in amplifier measured the amplitude and phase of the PA signal detected by the microphone. Data acquisition ensured that each
N. Guskos et al. / Optical Materials 30 (2008) 814–816
value was the average of 20 runs at the same wavelength of incident light. A carbon-black sample was used as a standard to calibrate the final spectrum. The PA spectra of all the complexes were recorded at room temperature in the range of 300–700 nm. Two samples (damp sample I and dried sample II) of the active biological organism, T. trunculus, were prepared by attaching tissue on cutouts of plotting paper 3 cm in diameter. 3. Results and discussion
PAS signal intensity [Arb.units]
Spectra obtained for the two investigated samples are shown in Fig. 1. In both cases, an intense and broad absorption band was registered near the yellow region of the spectrum. An even more intense absorption was observed in both samples below 330 nm, attributable to charge transfer transitions. Sample I produced a more intense PAS signal than sample II. The presence of an intense peak at about 570 nm was registered in sample I (see Fig. 1a), while only an extended peak in the yellow region was recorded for sample II (see Fig. 1b). Furthermore, in the background of the low energy part of the main PA signal of sample II an intense signal appeared at 650 nm—an absorption wavelength important in the processes of photosynthesis. The observed PA spectra com-
2
1
300
400
500
600
700
PAS signal intensity [Arb.units]
Wavelength [nm]
1.2 1 0.8 0.6
0.4 300
400
500
600
700
Wavelength [nm] Fig. 1. Photo-acoustic spectra of Trunculariopsis trunculus at room temperature for (a) sample I and (b) sample II.
815
prise all bands of radiation important in maintenance of an active state in a living system, with distinctively pre-eminent intensity in the yellow region. Iron(III) and copper(II) complexes are some of the most important compounds for living systems’ functionality and their PAS study has shown a very intense absorption signal at 576 nm [3,8– 11]. The PA spectra of the copper(II) complex of polyamine Spm323 and the iron(III) oxide (hematite) are shown a very intense PA absorption spectra were recorded in both samples, with an intense peak in the yellow region of the electromagnetic spectrum [8,11]. The similarity with the organic tissue samples is especially distinct for the copper(II) complex of polyamine Spm323. Copper(II) complexes of polyamines, can be very important for the activity of living systems. Important electron d–d transitions in the yellow region of radiation and their extended wave functions may have important connections with dynamic processes taking place in active biological systems [10]. PA absorption spectra are produced by heat through non-radiative relaxation released by a sample absorbing incident light. PA intensity (I) can be expressed as [12]: I ¼ ckAabs ;
ð1Þ
where c is a coefficient related to the sample’s thermal properties and the spectrometer’s characteristic, k is the probability of a non-radiative transition from an excited state, and Aabs is the sample’s absorbance. The parameters for sample I may be assumed to be similar to those of spermidine Spm323 [9], which is apparent from a comparison of their PA d–d transition absorption intensities. For sample II, the intensities of electron d–d transitions are drastically decreased, whereas the charge transfer transition intensities remain almost the same. The main part of T. trunculus body does not react anti-bondingly, but a majority of water molecules are removed. Some of them may change the molecules electronic structure and thus significantly influence the intensities of electron d–d transitions [8,9,13]. Magnetic interactions of copper(II) bioactive complexes are strongly dependent on the concentration of water molecules [14]. The presence of water may significantly modify the PA reaction to incoming radiation and involve magnetic interactions. The water molecular process had been especially important for living systems millions of years ago and in consequence could have influenced the evolutionary processes by gradually modifying the electronic structure of copper(II) complexes. Other PA absorptions below the blue region of the spectrum, the so-called charge transfers, are connected with p ! p* and n ! p* electron transitions. Transitions observed for active biological copper(II) complexes are similar to those of T. trunculus [8,9], where iron(III) oxides are absent in the PA signal below 300 nm [11]. Biologically active copper(II) complexes show two very important PA absorption bands, a very intense one below 300 nm and a very broad one in the yellow region of radiation.
816
N. Guskos et al. / Optical Materials 30 (2008) 814–816
4. Conclusions
References
A physical explanation has been attempted for the first time for n ! p* electron transitions in a living system, which play an essential role in its thermal processes [4]. In the case of d–d electron transitions, where the wave functions are extended the so-called ‘‘channel selector’’ mechanism could be activated for transferring very important information to the DNA system [10]. This preliminary report demonstrates that the PA reaction may produce evidence that yellow solar radiation plays a very important role in the dynamical processes of living mater. Already the ancient Greeks and Romans considered solar radiation an important healing agent, while colors yellow and blue are found throughout the history of religion to symbolize divine powers. Today, the discovery of a special role of yellow radiation for living organisms, if confirmed, could also be of utmost relevance to applications closely related to physics. A better understanding of these processes may have important consequences in:
[1] A. Lachaine, R. Pottieer, D.A. Russel, Spectrochim. Acta Rev. 15 (1993) 125. [2] R. Wu, Q. Su, J. Mol. Struc. 559 (2001) 195. [3] N. Guskos, J. Typek, G.P. Papadopoulos, M. Wabia, J. Majszczyk, E.A. Anagnostakis, M. Maryniak, Mol. Phys. Rep. (Poland) 39 (2004) 66. [4] N. Guskos, J. Typek, E.A. Anagnostakis, M. Maryniak, D.G. Paschalidis, Spectrosc. Lett. 39 (2006) 21. [5] C.W. Tabor, H. Tabor, Rev. Biochem. 53 (1984) 749. [6] A. Verma, R.K. Boutwell, in: P.P. McCann, A.E. Pegg, A. Sjoredsma (Eds.), Inhibition of Polyamine Metabolism, Biological Significance and Basis for New Therapies, Academic, Orlando, 1987, p. 113. [7] L. Lomzik, in: Berton (Ed.), Handbook of Metal-Ligand Interactions in Biological Fluids, vol. I, Dekker, New York, 1995, p. 686. [8] N. Guskos, G.P. Papadopoulos, V. Likodimos, G.L. Mair, J. Majszczyk, J. Typek, M. Wabia, E. Grech, T. Dziembowska, T.A. Perkowska, J. Phys. D: Appl. Phys. 33 (2000) 2664. [9] N. Guskos, G.P. Papadopoulos, V. Likodimos, J. Majszczyk, J. Typek, M. Wabia, E. Grech, T. Dziembowska, T.A. Perkowska, K. Aidinis, J. Appl. Phys. 90 (2001) 1436. [10] N. Guskos, G.P. Papadopoulos, J. Majszczyk, J. Typek, M. Wabia, D.G. Paschalidis, I.A. Tossidis, K. Aidinis, Acta Phys. Pol. A 103 (2003) 301. [11] N. Guskos, G.P. Papadopoulos, V. Likodimos, S. Patapis, D. Yarmis, A. Przepiera, K. Przepiera, J. Majszczyk, J. Typek, M. Wabia, K. Aidinis, Z. Drazek, Mat. Res. Bull. 37 (2002) 1051. [12] M.J. Adams, J.G. Highfield, G.F. Kirkbright, Anal. Chem. 52 (1980) 1260. [13] N. Guskos, J. Typek, G.J. Papadopoulos, M. Maryniak, K. Aidinis, Materials Science-Poland 25 (2005) 955. [14] N. Guskos, S. Glenis, V. Likodimos, J. Typek, H. Fuks, M. Wabia, R. Szymczak, C.L. Lin, T.A. Perkowska, J. Appl. Phys. 93 (2003) 9834.
– Medicine, where photo–thermal and Photo-acoustic phenomena have been employed for many years, but the importance of yellow radiation has not been studied (A new generation of thermal systems for living matter based on yellow radiation and relaxation processes could be used for direct generation of heat in the body). – Technology, where understanding the mechanism of intermolecular energy transfer may allow realization of advanced intelligent machines. – Nanotechnology, where it could help in the construction of systems with greater information storage capacity.