INTERNATIONAL RESEARCH JOURNAL OF PHARMACY ISSN Research Article
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1 Shekhar H et al. IRJP 0, 3 (5) INTERTIOL RESEARCH JOURL OF PHARACY ISSN Research Artcle THERODYICS OF PHARACEUTICAL ACTIVE NICOTIIDE BASED BIRY ALLOYS Shekhar H.* and Kant Vshnu Department of Chemstry, V. K. S. Unversty, Ara, 8030, Inda Artcle Receved on: 8/03/ Revsed on: 8/04/ Approved for publcaton: 09/05/ *Emal: hshe503@redffmal.com ABSTRACT The sold-lqud equlbrum data of Ncotnamde ()- β-naphthol (βn) and Ncotnamde()- Acetanlde (ACT) systems have been determned by Thaw- melt method whch suggest the formaton of smple eutectcs n both cases. Eutectc alloy E of -βn system acheved at 65 C and 0.6 mole fracton of βn, whereas the eutectc alloy E of -ACT system form at 93 C and mole fracton of ACT. The ecess thermodynamc quanttes have been determned by computng heat of fuson data and actvty coeffcent of the component n bnary m. These values hghlght the orderng, stablty and structure of eutectc and non-eutectc alloys. The thermodynamc mng functons descrbe about the nature of mng of the components durng alloyng. The Gbb s-duhem equatons gve the graphcal soluton of actvty, actvty coeffcent and partal mng thermodynamc quanttes. The thermodynamc stablty factors evaluated by graphcal method favour the stablty of eutectc and non-eutectc alloys. Keywords: Ncotnamde, Phase dagram, Thermodynamc ecess and mng functons, stablty factors INTRODUCTION Ncotnamde (nacnamde)/ncotnc acd (nacne) s well known for measurng pellagra preventve factors (PPF). It s a water soluble component of the vtamn B comple group. In vvo, ncotnamde s ncorporated nto ncotnamde adenne dnucleotde (D) and ncotnamde adenne dnucleotde phosphate (DP). The physologcal functon and pharmaceutcal acton of D and DP s to functon as enzymes n a wde varety of enzymatc odaton-reducton reactons essental for tssue respraton, lpd metabolsm and glycogenolyss. It s manly used n two prncple forms together wth nacn both as food nutrent and a drug -4. It may be of beneft n ptents wth nflammatory acne vulgars, ncludng but not lmted to, supperesson of antgen nducedlymphocytc transformaton and nhbton of 3 5 cycle AP phosphodestarase. It has demonstrated the ablty to block the nflammatory actons of oddes known to precptate or eacerbate nflammatory acne. It lacks the vasodlator, gastrontestnal, hepatc and hypolpemc acton of nacn. As such ncotnamde has not been shown to produce the flushng, tchng and burnng sensatons of the skn as s commonly seen when large doses of nacn are admnstrated orally. Ncam gel s most effectve when appled to the skn, whch helps to reduce the nflammaton and redness of nflammatory acne. -Naphthol (βn) s also employed n pharmaceutcal, agrcultural and rubber ndustres. Acetanlde(ACT) has been etensvely used as antpyretc and analgesc agents. Keepng ths vew n mnd ncotnamde() s used as basc materal for synthess of ts bnary m. In the present pece of our nvestgaton Ncotnamde() wth β-naphthol(βn) and Acetanlde (ACT) systems have been taken for detaled studes such as, Phase dagram, Thermodynamc ecess and mng functons and stablty factors. Epermental Procedure Ncotnamde (Thomas Baker, Bombey), -Naphthol (Loba, Inda) were drectly taken for nvestgaton and Acetanlde (Qualgen, Inda) was purfed by slow sublmaton method and repeated dstllaton under vacuum method. The meltng pont (epermental value) of ncotnamde, -naphthol and acetanlde was found to be 8 C, 9 C and 6 C respectvely. The sold-lqud equlbrum data of - and -ACT systems were determned by the Thaw-melt method 5-7. tures of dfferent composton were made n glass test tubes by repeated heatng and followed by chllng n ce. The meltng and thaw temperatures were determned n a Toshnwal meltng pont apparatus usng a precson thermometer whch could read correctly up to ± 0. C. The heater was regulated to gve above C ncrease n temperature n every fve mnutes. Heat of fuson of materals was measured by the DTA method 8-0 usng NETZSCH Smultaneous Thermal Analyzer, STA 409 seres unt. All the runs were carred out wth heatng rate C/mn, chart speed 0mm/mn and chart senstvty 00µv/0mv.The sample weght was 5 mg for all estmaton. Usng benzoc acd was a standard substance, the heat of fuson of unknown compound was determned usng the followng equaton: H s W s A H W A where H s the heat of fuson of unknown sample and H s s the heat of fuson of standard substance. W and A are weght and peak area, respectvely and suffces and s ndcate the correspondng quanttes for the unknown and standard substances, respectvely. RESULTS AND DISCUSSION Phase Dagram The phase dagram of - and -ACT systems determned by the thaw melt method, s reported n the form of temperature-composton curve (Fg.&). Both systems show the formaton of smple eutectc. Eutectc of - s formed at 65 C and 0.6 mole fracton of βn, whereas eutectc of -ACT s formed at 93 C and mole fracton of ACT. The meltng pont of (8 C) decreases on the addton of second component (.P., 9 C) and ACT (P, 6 C) and further attans mnmum and then s Page 8
2 Shekhar H et al. IRJP 0, 3 (5) ncreases. At the eutectc temperature two phases namely a lqud phase L and two sold phases (S and S ) are n equlbrum and the system s nvarant. In the regon ndcated by L a homogenous bnary lqud soluton ests whle the two sold phases ests below the horzontal lne. In the case, n regon located on the left sde of the dagram a bnary lqud and sold est whle n a smlar regon located on the rght sde of the dagram a bnary lqud and the second component of the system co-est. Coolng L S + S The chemcal nteracton between two components n a bnary system leads to an assocaton of molecules n defnte quanttes. Physcal as well as chemcal forces are nvolved n the formaton of eutectc and non-eutectc alloys. Thermodynamcal studes unfold the nature of mng as well as nature of nteracton between components durng bnary m. Heat of Fuson The values of heats of fuson of eutectc, noneutectc alloys and addton compound are calculated by the mture law usng equaton H) = H + H () ( e N N where and H are the mole fracton and the heat of fuson of the component ndcated by the subscrpt, respectvely. The value of heat of fuson of bnary alloys A - A, E s reported n Table. Actvty and Actvty Coeffcent The actvty coeffcent of components for the systems under nvestgaton has been calculated from the equaton 0- gven below H æ ö - ln ç R è Te T ø () Where s actvty coeffcent of the component n the lqud phase respectvely, s the heat of fuson of component at meltng pont T and R s the gas constant. T e s the meltng temperature of alloy. Usng the values of actvty and actvty coeffcent (Table ) of the components n alloys mng and ecess thermodynamcs functons have been computed. ng Functons Integral molar free energy of mng (G ), molar entropy of mng (S ) and molar enthalpy of mng (H ) and partal thermodynamc mng functons of the bnary alloys when two components are med together were determned by usng the followng equatons G RT ( ln a N ln a ) (3) S R ln ln ) (4) ( N H RT ln ln ) (5) G ( N RT ln a (6) where G - (μ - ) s the partal molar free energy of mng of component (mng chemcal potental) n bnary m. and and a s the actvty coeffcent and actvty of component respectvely. The negatve value -3 of molar free energy of mng of alloys (Table ) suggests that the mng n all cases s spontaneous. The ntegral molar enthalpy of mng value corresponds to the value of ecess ntegral molar free energy of the system favors the regularty n the bnary solutons. Ecess Thermodynamc Functons In order to unfold the nature of the nteractons between the components formng the eutectc, noneutectc alloys and addton compound, the ecess thermodynamc functons such as ntegral ecess ntegral free energy (g E ), ecess ntegral entropy (s E ) and ecess ntegral enthalpy (h E ) were calculated usng the followng equatons E l g RT( ln ln N ) (7) æ ö ç ln E ln s R ( ln ln T T è T T ø(8) æ ö ç ln E ln h RT è T T ø (9) and ecess chemcal potental or ecess partal free energy of mng E g RT ln (0) The values of l / lqudus curve near the alloys form n the phase dagram. The values of the ecess thermodynamc functons are gven n Table 3. The value of the ecess free energy s a measure of the departure of the system from deal behavor. The reported ecess thermodynamc data substantate the earler concluson of an apprecable nteracton between the parent components durng the formaton of alloys. The negatve value of ecess free energy ndcates the possblty of a stronger assocaton between unlke molecules whle the postve value n the present system suggests an assocaton of weaker nature between unlke molecules and of stronger nature between lke molecules. The mamum negatve g E value for eutectc 4-5 alloy E nfers stronger nteracton between and n the eutectc. The ecess entropy s a measure of the change n Confguratonal energy due to a change n potental energy and ndcates an ncrease n randomness. Gbbs-Duhem Equaton Further the partal molar quantty, actvty and actvty coeffcent can also be determned by usng Gbbs-Duhem equaton or or or [H - å dz y 0 y Usng equaton (4) a graph between ] ò () 0 H A (3) () (4) and / gves the soluton of the partal molar heat of mng of a consttuent n / alloy and plot between / vs Page 9
3 Shekhar H et al. IRJP 0, 3 (5) ln βn determnes the value of actvty coeffcent of component n bnary alloys. Stablty Functon Thermodynamc behavor of the present system n form of stablty and ecess stablty functons 6-7 can be determned by the second dervatve of ther molar free energy and ecess energy respectvely, wth respect to the mole fracton of ether consttuent: G ln a Stablty RT (5) ( ) E g ln Ecess Stablty RT (6) ( ) These values may be calculated by multplyng the slope(fg. 3&4) of lna vs ( ) and ln vs ( ) plots wth -RT. The best polynomal equaton of the curve generated s gven below: ln ( ).44( ) 8.99( ) 46.84( ) 6.( ) 4.47( ) (7) The slope of the curve shown n Fgs. as obtaned by dfferentatng the above equaton wth respect to ( ) may also be used to calculate the ecess stablty of the - ACT and -βn systems. The values of total stablty to the deal stablty and defned as RT Ideal Stablty (8) ( ) These values show the overall thermodynamc stablty n the alloy. CONCLUSION The sold-lqud equlbra of the systems -βn and - ACT nfer the formaton of smple eutectc n each case. The stablty functons favour the thermodynamc stablty n all the alloys of both systems. The mng functons suggests the spontaneous mng overall the alloys of both systems whle ecess functons descrbes the stronger assocaton between the two components n the eutectc melt. ACKNOWLEDGEENT Thanks are due to the Head Department of Chemstry, V K S Unversty Ara 8030, Inda for provdng research facltes. REFERENCES. Knp, Douek IF and oore WP. Safety of hgh-dose ncotnamde: a revew, Dabetologa 000; 43: Hakozak T, nwalla L and Zhung J. The effect of nacnamde on reducng cutaneous pgmentaton and suppresson of melanosome transfer, Br. J. Dermatol 00; 47: Akbulut S, Ocak Y, Kesloglu K and arasl N. Determnaton of Interfacal energes n the amnomethylpropanedol neopentyl glycol organc alloy, Appled Surface Scence, 009; 55: Kumar S, Ra SB Spectroscopc studes of L-argenne molecule, IJPAP 00; 48: Redd R. S. B., Kumar V S A Satulur, Ra U. S., Ra R. N. Thermal, physcochemcal and mcrostructural studes of bnary organc eutectc systems, J Therm Anal Calorm 0; 07: Shekhar H and Pandey KB Thermochemcal studes on alloys and compound Acetanlde-Salcylc acd system, J. Ind. Councl Chemsts 00; 7: Shekhar H. and Roy Y. Thermodynamc nteracton n alloys of Naphthalene-Imdazole system, Neper Ind. Adv. Res. Journal of Sc 00; 5: Shekhar H, Salm SS and Kumar N Thermodynamc Investgaton of alloys of Phenanthrene-Benzdne System, J. Int. Acad. Phy. Sc. 009; 3: Shekhar H, Pandey KB and Kant V Thermodynamc Characterstcs of : molecular comple of Phthalc anhydrde-camphene system, J. Nat. Acd. Sc. Letter 00; 33: Shekhar H and Salm SS Thermodynamc Characterstcs of Succnontrle-Cnnamc acd system, Nat. Journal of Jyot Res. Acad. 0; 5: Agrwal T, Gupta P, Das SS, Gupta A and Sngh NB Phase equlbra crystallzaton and mcrostructural syudes of Naphthalen--ol +,3- Dntrobenzene, J. Chem. Engg. Data 00; 55: Shekhar H and Salm SS olecular nteractons and stablty n bnary organc alloys, J. Nat. Acad. Sc Letter 0; 34: Dwved Y, Kant Shva, Ra SB, Ra RN Synthess, Physcochemcal and Optcal Characterzaton of Novel Fluorescng Comple: o- Phenylenedamne-Benzon, J Fluorescence 0; : Kumar S, Ra AK, Ra SB and Ra DK Infrared & Raman Spectra of Hstdne. A Ab-nto DFT calculatons of Hstdne molecule and ts dfferent protonated form, Ind. J. Phys. 00; 84: Shekhar H and Kant V Knetc and Interfacal Studes on Transparent Organc Alloys, I. J. Chem. Soc. 0; 88: Shamsuddn, Sngh SB and Nasar A Thermodynamc nvestgatons of lqud gallum-cadmum alloys, Thermochemca Acta 998; 36: Sharama BL, Tandon S and Gupta S Characterstcs of the bnary faceted eutectc: benzoc Acd-Salcylc Acd system, Cryst. Res. Technol 009; 44: 58. TABLE : PHASE COPOSITION, ELTING TEPERATURE, VALUES OF ENTHALPY OF FUSION(H), ENTROPY OF FUSION (S) AND ACTIVITY COEFFICIENT IN PLACE OF ROUGHNESS PARAETER (α) Alloy P S X (⁰C) (/K) βn A A A A E A A A A A A A A Page 30
4 Shekhar H et al. IRJP 0, 3 (5) TABLE : VALUE OF PARTIAL AND INTEGRAL IXING OF GIBBS FREE ENERGY(G ), ENTHALPY( ) AND ENTROPY(S ) OF - SYSTE Alloy G G G A H S /K S /K S /K A A A A E A A A A A A A A TABLE 3: VALUE OF PARTIAL AND INTEGRAL EXCESS GIBBS FREE ENERGY(g E ), ENTHALPY(h E ) AND ENTROPY(s E ) OF - SYSTE Alloy g E g E g E h E h E h E s E s E /K /K A A A A E A A A A A A A A Table 4: values of Stablty Ecess Stablty and Ideal Stablty of bnary alloys -βn System Alloy X Stablty Ecess stablty Ideal Stablty A A A E A A A A A ACT System A A A E A A A A A s E /K Page 3
5 Shekhar H et al. IRJP 0, 3 (5) Page 3
6 Shekhar H et al. IRJP 0, 3 (5) Source of support: Nl, Conflct of nterest: None Declared Page 33
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