Features of photoluminescence of biologically active drugs excited by ultraviolet laser radiation. Russia

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1 Fetures of photoluminescence of biologiclly ctive drugs excited by ultrviolet lser rdition Vldimir Semenovich Gorelik 1, Mksudjon Fyzuloevich Umrov 2, Anton Alexndrovich Sinitsyn 2 1 P.N. Lebedev Physicl Institute of the Russin Acdemy of Sciences, Leninsky Ave., 53, Moscow, GSP-1, , Russi 2 Vologd Stte University, Lenin str., 15, Vologd, , Russi Abstrct. A method of identifying biologiclly ctive drugs by mnufcturers hs been developed on the exmple of spirin, citrmonum, nlgin, prcetmol nd cffeine. The method is bsed on fiber-opticl detection of the photoluminescence spectr using opticl chnnels - photon trps, compct spectrometer nd dt processing system tht mkes it possible to compre nlyzed spectrum with the spectrum of reference substnce. Difference hs been estblished between photoluminescence spectr of queous solutions of phrmceuticl drugs nd their pill form. With tht, trnsition effect hs been observed in the spectr from the mode of spontneous photoluminescence to the superluminescence mode. It hs been found tht the nture of superluminescence is similr to the well-known mechnism in dye lsers. Bsed on the estblished superluminescence effect, it is possible to crete new types of lsers with tunble frequency of genertion in the ultrviolet region of the spectrum. [Gorelik V.S., Umrov M.F., Sinitsyn A.A. Fetures of photoluminescence of biologiclly ctive drugs excited by ultrviolet lser rdition. Life Sci J 2014;11(12): ] (ISSN: ).. 52 Keywords: photoluminescence, phrmceuticl objects, biologiclly ctive preprtions, lser, correltion function Introduction Functioning of n orgnism is ensured by two processes - ssimiltion nd dissimiltion - which re bsed on the metbolic process between the internl (body cells) nd the externl environment. Norml metbolic processes re ensured by mintining constnt chemicl composition nd physico-chemicl properties of the internl environment (homeostsis). [1] It depends on certin fctors, mong which n importnt role is plyed by Biologiclly Active Drugs (BAD) [2] coming with food (vitmins, enzymes, minerl slts, trce nutrients, etc.) nd ensuring hrmonicl interction nd interdependence of ll physiologicl nd biochemicl processes in the orgnism. By normlizing nd djusting ll vitl functions, biologiclly ctive drugs lso hve effective therpeutic ction. BAD physiologicl ctivity cn be regrded both in terms of their possible medicl use nd in terms of mintining norml functioning of humn orgnism, or giving specil properties to group of orgnisms [3]. Besides, BAD hve pronounced phrmcologicl ctivity, so they re lso clled cting drugs. Thus, BAD include lrge clss of substnces tht t the moleculr level hve strong influence on biologicl structures nd living orgnisms. These include, in prticulr, vrious phrmceuticl objects, stimulnts of life processes, mino cids, toxic substnces, etc. For efficient use of BAD it is necessry to ensure complince of their moleculr structure nd composition to nominl drugs whose effects on biologicl structures nd living orgnisms is well estblished. In this respect, there is the problem of estblishing t the quntittive level the extent of complince between moleculr structure nd composition of rel smples used in medicine, food industry, griculture nd other res, nd nominl BAD with chrcteristics known nd populted into the dtbse. To solve such problem, spectroscopic methods my be used, including fluorescence spectroscopy [4], the Rmn scttering method [5], methods of optic nlysis [6], etc. In this work we consider fetures of the photoluminescence spectr in BADs on the exmple of commercilly vilble phrmceuticl drugs from vrious mnufcturers in solid nd liquid stte. Experiment method The subjects of study were typicl phrmceuticl drugs (citrmonum, nlgin, spirin nd prcetmol) from vrious mnufcturers. Ech of them ws studied in form of pills nd in form of queous solution. Tble 1 shows chemicl nd structurl formul of the studied phrmceuticl drugs. As it cn be seen from this tble, the structure of ll investigted substnces includes benzene rings, which fct leds to fundmentl electronic bsorption in the middle UV bnd. Fiber-opticl method ws used for excittion nd recording fluorescence spectr [7]. Schemtic digrm of the experimentl setup is shown in Figure 1. The source of exciting ultrviolet rdition ws the fourth hrmonic ( nm) of the YAG lser tht 278

2 generted pulse-periodic rdition with 1064 nm wvelength. A smll mount of the substnce to be nlyzed (12, Fig. 1) in the form of tblet ws plced in cuvet (13, Figure 1). Tble 1. Chemicl nd structurl formul of the studied phrmceuticl drugs Phrmceuticl Drug Chemicl formul Structurl formul Aspirin C 9 H 8 O 4 Anlgin C 13 H 16 N 3 NO 4 S Citrmonum (spirin, cffeine, phencetin) C 9 H 8 O 4 + C 8 H 10 N 4 O 2 + C 10 H 13 NO 2 Prcetmol C 8 H 9 NO 2 Cffeine C 8 H 10 N 4 O 2 photoluminescence spectr ws trnsmitted to the computer. Fig.1. Experimentl setup lyout for recording photoluminescence spectr: 1, 2, 7-mirrors; 3 - ctive element; 4 - "pumping" LEDs; 5 - nonliner crystl; 6, 8, 9 - lenses; 10 - lightguide holder; 11 - lightguide; 12 - tested substnce; 13-1 mm dimeter cylindricl cuvet; 14 - miniture spectrometer FSD-8; 15 - computer. Qurtz lightguide (11, Figure 1) ws used for guiding ultrviolet rdition to the substnce nd for diverting fluorescence emission occurring in the smple to the FSD 8 miniture spectrogrph (14, Figure 1). From the FSD-8 miniture spectrometer digitl informtion bout rdition Min prt Photoluminescence spectr hve been recorded following phrmceuticl drugs: citrmonum, nlgin, spirin, prcetmol nd cffeine. Authors [8, 9] studied the ultrviolet nd infrred spectr of these drugs. After computer processing, normlized photoluminescence spectr of studied romtic compounds were built. Fig. 2((а)- (d)) shows normlized photoluminescence spectr of citrmonum in the form of pills obtined from four mnufcturers. Fig. 2 ((а)-(d)) shows tht in photoluminescence spectr of citrmonum there ws slight difference between nm nd nm. 279

3 446,8 344, , b 446,8 344,2 Similr mesurements were mde for other phrmceuticl drugs. Bsing on the photoluminescence spectr of ll the five objects structured fluorescence bnd in violet-red region of the spectrum ws found, shpe of which slightly differs. Similrity of fluorescence spectr for citrmonum nd spirin is cused by the presence of the sme component, nd the difference is cused by the fct tht citrmonum lso contins other components, beside spirin (see Tble 1), which generte n dditionl bnd between 400 nd 550 nm. Brodening of the fluorescence bnd for nlgin compred to prcetmol spectrum cn be ttributed to the more complex moleculr structure of nlgin [10]. For estblishing quntittive differences between photoluminescence spectr obtined from vrious phrmceuticl drugs, correltion coefficients of nlyzed drugs were clculted s compred to the reference one [10]. Reference substnces were normlized photoluminescence spectr of spirin (smple No.1), citrmonum (smple No. 1), nlgin (smple No. 1), prcetmol (smple No. 1) nd cffeine (smple No. 1). All clculted vlues of correltion coefficients in studied drugs re shown in Tble 2. As cn be seen from Tble 2, correltion coefficients of the phrmceuticl drugs studied were different for ech mnufcturer. In this regrd, the proposed method mkes it possible to identify mnufcturers of phrmceuticl drugs. c ,8 445,8 685 d Fig. 2. Normlized photoluminescence spectr of citrmonum solid phses: - citrmonum No. 1, b - citrmonum No. 2, c - citrmonum No. 3, d - citrmonum No.4. Tble 2. Phrmceuticl drugs correltion coefficients Substnce Smple Correltion Nme No. coefficient Aspirin Citrmonum Prcetmol Anlgin Cffeine

4 Now let us consider the results of nlyzing photoluminescence spectr of phrmceuticl drugs in queous solution [11]. Fig. 3 (() - (d)) shows photoluminescence spectr obtined from sturted queous solutions of the sme four smples of citrmonum. From the comprison in Figure 2 (() - (d)) nd 3 (() - (d)) we cn see tht in course of trnsition from solid smples to sturted queous solutions there is n increse in photoluminescence intensity in the short-wve re of the spectrum, nd its decy in the purple-blue re. Besides, similr effect is observed, most clerly defined for smples of citrmonum No. 1 nd No. 3: spectr revel n intense nrrow bnd with mximum t 330 nd 338 nm, respectively (see Fig. 3 (()-(d))). Similr effects were observed for other phrmceuticl drugs. The observed effects of intensity redistribution in the photoluminescence spectr of the romtic compounds studied cn be explined by trnsition from the spontneous photoluminescence mode to the superluminescence mode. This is due to effective popultion of excited singlet term of n romtic molecule cused by intense pulsed ultrviolet lser rdition [11]. Boost nture in this cse is similr to the well-known mechnism in dye lsers. Boost rte in this cse hs the form: b 338 K S ( N N ) S N. (1) s1 s0 s1 Provided tht effective cross section S cm2, nd molecules concentrtion in queous solution Ns cm -3, we find tht the boost K cm -1. In ccordnce with the Bouguer lw for ctive medium ( L mm), we hve: I ( L) I e I (2) K L Assessments mde explin the ppernce of photoluminescence spectrum in thin lyers of the solid phse nd in queous solutions of compounds tested. Chrcteristic of the effect observed is the effect of superluminescence in ultrviolet re of the spectrum tht corresponds to the position of the first excited electronic singlet term in studies romtic substnces. с 336 d Fig. 3. Normlized photoluminescence spectr of queous solutions of drugs: - citrmonum No. 1, b - citrmonum No. 2, c - citrmonum No. 3, d - citrmonum No.4 281

5 Conclusions It hs been shown tht correltion coefficients of the phrmceuticl drugs studied were different for ech mnufcturer. In this regrd, the proposed method mkes it possible to identify mnufcturers of phrmceuticl drugs. It hs been found tht in course of trnsition from solid smples to sturted queous solutions there is n increse in photoluminescence intensity in the short-wve re of the spectrum, nd its decy in the purple-blue re. The observed superluminescence effect cn be used for creting new types of lsers with tunble frequency of genertion in the ultrviolet region of the spectrum. Corresponding Author: Dr. Gorelik Vldimir Semenovich P.N. Lebedev Physicl Institute of the Russin Acdemy of Sciences Leninsky Ave., 53, Moscow, GSP-1, , Russi References 1. Tylor, D., N. Green nd W. Stout, Biology (in 3 volumes B.3: trnslted from English by / edited by R. Soper, 3rdedition). Moscow: Mir, pp: Glktionov, S.G., Biologiclly ctive. Moscow: Molody Gvrdiy, pp: Popkov, N.А., I.V. Yegorov, V.I. Fisinin et l., Food nd biologiclly ctive substnces. Belrus: Belrusky Nvuk, pp: Lkowicz, J.R., Principles of Fluorescence Spectroscopy (3rdEd). Springer Science, pp: Downes, A. nd A. Elfick, Rmn Spectroscopy nd Relted Techniques in Biomedicine. Journl Sensors, 10(3): Silverstein, R.M., F.X. Webster nd D.J. Kiemle, Spectrometric Identifiction of Orgnic Compounds (7thEd). New York Univ: John Wiley& Sons, pp: Gorelik, V.S., Yu.P. Voinov, V.D. Zvorykin, et l., Lser implnttion of sodium nitrite ferroelectric into pores of synthetic opl. Journl of Russin Lser Reserch, 31(1): Dibbern, H.-W., R.K. Muller nd E. Wirbitzki, UV nd IR Spectr Phrmceuticl Substnces (UV nd IR) nd Phrmceuticl nd Cosmetic Excipients (IR). Editio Cntor Verlg Aulendorf, pp: Pivonk, D, Applictions of Vibrtionl Spectroscopy in the Phrmceuticl Industry. Wiley, pp: Voinov, Y.P., V.S. Gorelik, M.F. Umrov nd S.V. Morozov, Difference fluorescence spectroscopy of the structure nd composition of bioctive preprtions. Bulletin of the Lebedev Physics Institute, 38(11): Voinov, Y.P., V.S. Gorelik, A.Y. Pytyshev, nd M.F. Umrov, Photoluminescence of romtic compounds in photon trps under resonnt pulse-periodic excittion. Bulletin of the Lebedev Physics Institute, 39(12): Svelto, O. nd D.C. Hnn, Principles of Lsers (4rdEd). Springer, pp: /13/

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