Aville online www.jocpr.com Journl of Chemicl nd Phrmceuticl Reserch, 2017, 9(4):250-255 Reserch Article ISSN : 0975-7384 CODEN(USA) : JCPRC5 ABSTRACT Effect of EDTA Doping on Urcil Crystls V Beul Premvthi 1*, G Mdhurml 2 nd B Kvith 1 1 TBML College, Poryr, Tmil Ndu, Indi 2 ADM College for Women, Ngpttinm, Tmil Ndu, Indi Ethylenedimine tercetic cid (EDTA) doped Urcil were grown y slow evportion method t room temperture with doule distilled wter s solvent. The grown crystls hve een sujected to spectroscopic nd structurl properties. FTIR nlysis hs een crried out to chrcterize the grown crystls. The rnge nd percentge of opticl trnsmission s well s sorption re determined y recording UV-Vis spectrum. From the UV dt, Bnd gp determintion is lso crried out. Fluorescence spectr hs lso een crried out to chrcterize the grown crystls to study the sorption nd emission spectr. The powder X-ry diffrction methods re used for identifying the structurl prmeters of grown crystls. The effect of the influence of dopnt on the surfce morphology of Urcil-EDTA crystl fces re nlyzed y SEM Elementl composition were lso confirmed y EDAX method. Keywords: Bnd gp; EDAX; FTIR; SEM INTRODUCTION Crystl growth is mjor stge of crystlliztion process, nd consists in the ddition of new toms, ions (or) polymer strings into the chrcteristic rrngement of crystlline Brvis lttice. Urcil is common nd nturlly occurring pyrimidine derivtive compounds, which re worth to study for mny resons, chief mong them eing their prevlence mong iologiclly ctive molecules [1-4]. It is plnr, unsturted compound tht hs the ility to sor light. Urcil s use in the ody is to help crry out the synthesis of mny enzymes necessry for cell function through onding with rioses nd phosphtes [5]. Urcil serves s llosteric regultor nd coenzymes for rections in the humn ody nd in plnts [6]. Urcil lso hs the cpility to rect with elementl hlogens ecuse of the presence of more thn one strongly electron-donting group [7]. The dopnt Ethylenedimine tetrcetic cid is typicl chelte lignd, which hs ttrcted much ttention over the pst five decdes ecuse of its usefulness for industril pplictions s well s sic study pplictions. Nowdys, orgnic crystls re highly recognized s the mterils of the future ecuse their moleculr nture cn e used to mximize the non-liner properties. In this pper, we report the results of our work on the growth of new Urcil-EDTA crystls for the first time long with the chrcteriztion of powder XRD, Fourier trnsform infrred trnsmission (FITR) spectrum, UV-Vis nlysis, Bnd Gp determintion, Fluorescence spectr, SEM nd EDAX nlysis studies. EXPERIMENTAL SECTION Crystl Growth The Selection of the solvent is n importnt step in the growth of crystls from solution y slow evportion method. In this method, wter is used s solvent. Commercilly ville Urcil nd EDTA were used for the Crystl growth. Initilly, the mteril ws purified y repeted recrystlliztion then, the sturted solutions of Urcil nd EDTA t room temperture were prepred. Then the solution is filtered. The filtered solution ws tken in eker which ws seled with smll size hole to control the evportion of the solvent. The welldefined crystls re otined within period of 15 dys. 250
VB Premvthi et l J. Chem. Phrm. Res., 2017, 9(4):250-255 Crystl Chrcteriztion FTIR spectrl nlysis: The fourier trnsform infrred spectrl nlysis is technique in which lmost ll functionl groups in molecule sor chrcteristic frequencies. The FTIR spectrum ws recorded in the rnge 400-4000 cm -1 y perkin-elmer Spectrometer (KBR Pellect Technique). The FTIR spectrum of Urcil nd doped Urcil re shown in Figures 1 nd 1 nd the fundmentl virtions nd the ssigned frequencies re shown in the Tle 1. It is seen from the spectrum tht the Urcil nd doped Urcil is hving different peks with different frequencies. In ll the heterocyclic compounds, the N-H stretching virtion occur in the region 3500-3000 cm -1. Hence the FT- IR nd oserved t 3099 cm -1, 3059.60 cm -1, 3022.81 cm -1 in pure Urcil correspond to N-H stretching virtions which is completely sent in doped Urcil. This shows tht EDTA my form vnderwl s ond with Urcil in this re. The FT-IR nds oserved t 1234.87 cm -1 in pure Urcil corresponds to C-N virtions is sent in doped Urcil. Similrly, the nd occurred t 1615.67 cm -1 ssigned to C-C stretching virtions modes in pure Urcil is sent in doped Urcil. But the stretching ssignments proposed in this study, for OH out-of-plne ending group re identified t 767.29 cm -1 in the doped Urcil which is completely sent in pure Urcil. The two C=O groups of Urcil re chemiclly in different positions; they seem to e intercting with ech other within the Urcil molecule. The interction of the cronyl group with hydrogen-donor group does not produce drstic nd chrcteristic chnges in the frequency of the C=O stretch s does y interction of N-H stretch. It gret del of structurl informtion cn e derived from the exct position of the cronyl stretching sorption pek. The cronyl frequency otined t 1678.28 cm -1 in pure Urcil my e shifted to 1684.34 cm -1 in doped Urcil which confirms the presence of C=O ond with djcent C-C ond increses the energy required for C=O stretching nd thus increses the cronyl stretching frequency in doped compounds. The C=C stretching virtions of 1648.69 cm -1 nd C-C stretching virtions of 1615.67 cm -1 re completely sent in doped Urcil which confirms the EDTA my e entered into the crystl lttice of Urcil. Further the O-H in plne ending of 1391.48 cm -1 re found in doped crystl which re completely sent in pure Urcil. The N-H ending virtions of 858.59 cm -1, 818.95 cm -1 in pre Urcil re completely sent in doped crystl. This virtions my e the further evidence for incorportion of EDTA into the host molecule [8,9]. Figure 1: ) FTIR spectrum of pure urcil; ) FTIR spectrum of doped urcil UV spectrl nlysis: The UV-Vis sorption spectrum of the grown crystl were recorded in the wvelength rnge of 200 nm nd 1100 nm using lmd 35 UV-Vis spectrophotometer in order to determine the trnsmission rnge nd hence the suitility of the crystls for opticl pplictions. The UV-Vis sorption spectrum of pure Urcil nd doped Urcil re shown in Figures 2 nd 2. 251
VB Premvthi et l J. Chem. Phrm. Res., 2017, 9(4):250-255 Tle 1: Virtionl frequencies of pure nd doped urcil Wve Numer(cm -1 ) Urcil Doped EDTA Assignment 30993.51 - O-H Stretching 3120.67 3083.81 3059.6 3022.81 2993.56 2933.51 N-H Stretching C-H Stretching 1678.28 1684.34 C=O Stretching 1648.69 C=C Stretching 1615.67 C-C Stretching - 1391.48 In plne O-H ending 1234.87 C-N 858.59 818.95 N-H ending - 767.29 OH-out-of-plne ending It is seen tht there is slight chnge in the UV trnsprency cut off wvelength in pure Urcil nd lso in doped Urcil nd there is residul sorption in the entire UV-Visile region in oth Urcil nd doped Urcil. Regrding the electronic sorption, the pek in the rnge is 258.8 nm is ttriuted to n-π * trnsition of the cronyl group. Usully, the C=O group show nd in the higher region, ut when the cronyl group is sustituted y n urochrome, the n-π * trnsition in this compound is shifted to lower wvelength region. When the EDTA entered into the Urcil crystl, the n-π * trnsition of imide group, mde thochromic shift from 258.8 nm to 260.1 nm considering the trnsition of imide. Bthochromic shift is lso oserved in the rnge of 200.8 nm to 203.3 nm. All these fcts suggested tht the doped crystls hs wide rnge of ppliction in optoelectronic files [8,9]. Figure 2: ) UV-Vis spectrum of pure urcil; ) UV-Vis spectrum of doped urcil Bnd gp energy determintion: The nd gp mesurement ws lso crried out for Urcil nd doped Urcil crystls. The plot of (αh ) 2 ginst h is shown in Figures 3 nd 3, trend line ws dded to extrpolte nd it cut the X-xis of 5.64 ev in Urcil nd 5.73 ev in doped crystl which is tken s the direct nd gp of the crystl. Due to the ddition of EDTA with Urcil, chnge in nd gp is oserved. As result of wide nd gp the doped crystls possess wide trnsmittnce window in the UV-visile region. 252
VB Premvthi et l J. Chem. Phrm. Res., 2017, 9(4):250-255 Figure 3: ) Bnd gp energy of pure urcil; ) nd gp energy of doped urcil Fluorescence spectr: The Fluorescence spectrum of Urcil nd doped crystl re mesured in the rnge of 320.00 nm to 750 nm re shown in Figures 4 nd 4. It hs een oserved tht fluorescence spectr oserved t excittion sorption of slight rod nd t 335.49 cm -1 nd emission of shrp nd t 606.68 cm -1 in pure Urcil. When the EDTA entered into the Urcil Crystl, the fluorescence slightly chnges in the sorption of rod nd t 337.49 cm -1 nd the excittion process confirms the presence of rod nd t 611.75 cm -1. All these fcts suggested tht oth Urcil nd doped Urcil hs fluorescence ctivity. Figure 4: ) Fluorescence spectr of pure urcil; ) fluorescence spectr of doped urcil Powder X-ry diffrction nlysis: X-ry diffrction technique is used to investigte the inner rrngement of toms (or) molecules in crystlline mteril. The grown Urcil nd EDTA doped Urcil crystl were sujected to powder X-ry diffrction studies nd the oserved ptterns re shown in Figures 5 nd 5 respectively. Well defined peks t specific 2 vlues shown high crystlline nture of the grown crystls. The powder XRD ptterns of doped Urcil re compred 253
VB Premvthi et l J. Chem. Phrm. Res., 2017, 9(4):250-255 with tht of pure mterils. The XRD profiles show tht ll the smples were of single phse without detectle impurities. The slight shift of the reflection peks in the powder XRD ptterns of the doped smples indictes tht the dopnt hs entered into the lttice of the host crystl XRD ptterns of doped crystls re not similr to tht of pure Urcil. Additionl peks re present in the XRD ptterns of doped crystls. This shows tht doped crystls hve different crystlline structure s tht of pure Urcil [10-12]. Figure 5: ) Powder XRD spectr of pure urcil; ) powder XRD spectr of doped urcil Scnning electron microscopic nlysis: SEM nlysis provided informtion out the nture nd lso it is used to check the presence of imperfections. The SEM imge of pure Urcil nd doped crystl re shown in the Figures 6 nd 6. It is found tht Urcil crystl hs well developed morphology exhiiting severl fces nd then ll the units re rrnged in different lyers. But the doped crystl hs entirely different morphology. Due to this fct, it my e reveled tht the EDTA cts s growth modifier [13]. Figure 6: ) SEM imge of pure urcil; ) SEM imge of doped urcil Figure 7: ) EDAX Spectrum of pure urcil; ) EDAX spectrum of doped urcil 254
VB Premvthi et l J. Chem. Phrm. Res., 2017, 9(4):250-255 Energy dispersive X-ry nlysis: In order to confirm the presence of the elements in the grown Urcil nd doped crystl, the smple of grown crystls were sujected to Energy dispersive X-ry nlysis nd shown in Figures 7 nd 7. The otined spectrum confirms the presence of C,O nd N nd the corresponding tomic percentges re 44.32, 26.84, 28.85 respectively. When the EDTA entered into the host crystl, the tomic percentge chnged into 57.37, 21-44 nd 21.18 respectively. These fcts reveled the sence of imperfections in the crystllistion. CONCLUSION EDTA doped Urcil were synthesized t room temperture y slow evportion method. Good opticl qulity single crystls were grown. The functionl groups present in the grown crystl hve een confirmed y FTIR spectrl nlysis. UV-Vis spectr show tht the crystl hs wide rnge of ppliction in opto-electronic field. Bnd gp mesurement indicted tht the doped crystls possess wide trnsmittnce window in the UV-Visile region. Fluorescence spectr confirm the fluorescence ctivity of grown crystls. Powder X-ry diffrction confirms the crystllinity nture of the smple. SEM nlysis confirms the morphology of the grown crystls nd EDAX nlysis shows the elementl nlysis of the crystl nd confirms the sence of ny impurities nd imperfection in the crystl. REFERENCES [1] J Chn; Hillig; WG Sers. Act Metll Mter. 1964, 12(12), 1421. [2] WK Burton; N Crer; FC Frnk. Philos T Roy Soc A. 1951, 243, 299. [3] KA Jckson. Growth nd perfection of crystls, RH Doremus; BW Roerts; D Turnull (eds), Wiley, New York, USA, 1958. [4] J Chn. Act Metll Mter. 1960, 8(8), 554. [5] RH Grrett, CM Grishm. Principles of iochemistry: with humn focus. Thomson Brooks/Cole, 2001. [6] EG Brown. Ring nitrogen nd key iomolecules: The iochemistry of N-heterocycles. Springer Science & Business Medi, 2012. [7] DJ Brown. Heterocyclic compounds, The pyrimidines. Inter Science, New York. 1994, 52. [8] RM Silverstein; GC Bssler; TC Morrill. Spectrometric identifiction of orgnic compounds. John wiley & sons, 2014. [9] YR Shrm. Elementry orgnic spectroscopy. S Chnd Pulishing, Indi, 2000. [10] H Senhil Pndin; P Rmsmy. J Cryst Growth. 2008, 310, 2563-2568. [11] T Blkrishnn; K Rmmurthi, Cryst Res Technol. 2006, 41, 1184. [12] R Murlidhrn; R Mohnkumr; PM Ushsree; R Jyvel; P Rmsmy. J Cryst Growth. 2002, 234, 545. [13] N Blmurugn; M Lenin; G Bhgvn Nryn; P Rmsmy. Cryst Res Technol. 2007, 42, 151. 255