Tgp chi phdn tich Hda, Ly vd Sinh hgc - Tdp 19, Sd 3/2014
TONG HOP, NGHIEN CUtl PHlfC CHAT CUA Zn(II) VOl
THIOSEMICACBAZON BENZANBEHIT VA DAN XUAT N(4)- PHENYL CUA NO
Din tda sogn 14-2 — 2014
Trjnh Ngoe Ch$u
Khoa Hda hoc, Tru&ng Dgi hqc Khoa hgc Tu nhien, Dgi hgc Quoc gia Hd Noi Nguyin Thj Bich Hirdng
Khoa Khoa hgc co bdn. Hoc vien Hgu cdn Nguyen Thi Quyen
Tru&ng Trung hoc phd thong Hodng Quoc Viet, Thdnh pho Bdc Ninh
SUMMRY
SYNTHESIS, STUDIES ON THE COMPLEXES OF ZnClI] WITH THIOSEMICARBAZONE BENZALfiEHYDE AND N(4)- PHENYL ITS DERIVATIVE Thiosemicarbazone benzaldehyde (Hthbz) arui N(4) phenyl thiosemicarbazone benzaldehyde (Hpthbz) react with zinc(II) in solution and present ofNHs to afford the complexes inform [ZnL2f (L is thbz or pthbz). These ligands and their complexes were synthesized characterized by means of elemental analysis, MS, 'H- NMR and "C - NMR. IR. UV- Vis spectroscopy. The obtained results showed that Hthbz and Hpthbz coordinated to zinc(II) over N, S - donor atoms and two ligands are bidentate The antibacterial activities ofthe ligands and their complexes were tested in vitro against three of positive bacteria types: Lactobacillus fermentum. Bacillus subtilis.
Staphylococcus aureus and three of negative bacteria types: Salmonella enterica, Escherichia coll Pseudomonas aeruginosa and one type of fungus, that is Candida albican.
Keywords: thiosemicarbazone; Zn(II) complex: benzaldehyde.
1. MO DAU cua cac ti bao ung thu [1, 9]. Cac tac gia Hoat tinh sinh hpc cua cac [3, 6] da su dung phiic chit cua thiosemicacbazon va phiic chat cua thiosemicacbazon di phan tich phan chiing vdi kim loai chuyen tiip da dugc tach ham lugng kim loai trong cdc miu nghien ciiu tir rat lau [7, 8]. Nhiiu hgp .hue nhu tac gia [3] da sir dung phirc chat loai nay cd kha nang khang khuin chit cuaZn(II) vdi N-etyl-3- [1, 10], kha nang iic che su phat triin cacbazolecacboxandehit-3-
thiosemicacbazon de xac dinh Zn(II) trong thiic an... Nhieu tac gia da che tao dugc cac dien cue chgn lpc ion tren ca sd cac thiosemicacbazon hay sit dung lam chat uc che, an mdn kim loai [2, 5].... De ddng gdp vao hudng nghien Cliu nay, chiing tdi nghien ciiu phuong phap tdng hgp, xac lap cau tao va tham dd boat tinh sinh hpc cac phiic chat cua Zn(ll) vdi thiosemicacbazon benzandehit (Hthbz) vaN(4) phenyl thiosemicacbazon benzandehit.
2. THI/C NGHIEM
2.1. Tong hgp phoi tir Hthbz vii Hpthbz
Hdn hgp gdm 30 ml nudc cat da dugc axit hoa bang dung djch HCI (pH: 1 - 2) chira 0,01 moi (0,91 g thiosemicacbazit hay l,67g N(4)- metyl thiosemicacbazit va 20 ml dung djch etanol chiia 0.01 moi benzandehit (1,2 ml) dugc khuiy diu tren may khuay tir d nhiet dp phdng. Sau mgt thdi gian thay tach ra ket tua man trang min, tiep tuc khuSy them 2 gid niia. Lpc, nia ket tiia fren pheu lpc day thuy tinh xdp, bing nudc, hdn hgp etanol - nudc, etanol va cudi cimg bang dietyl ete. San pham dugc lam khd ttong binh hut im din khdi lugng khdng ddi.
2.2. Tdng hop cic phirc chat Zn(thbz)2 va Zn(pthbz)2
Phiic chit Zn(thbz)2 dugc tong hgp bing each khuiy deu hdn hpp cua 0,001 moi (5 ml) dung dich mudi ZnCl2 0,2M da
dugc dieu chinh mdi truimg bang dung djch NH3 (pH = 9 - 10) va 40 ml etanol cd hoa tan 0,002 moi (0,358 g Htiibz hay 0,51 g Hpthbz fren may khuay tir d nhiet dp phdng. Sau mdt thdi gian thay tir dung djch tach ra ket tua mau frang ddi vdi Zn(thbz)2 va tting nga vdi Zn(pthbz)2, tiep tuc khuay hdn hgp nay trong vdng 2 gid. Sau dd, tien hanh lgc tren pheu lpc thuy tinh xdp, nia bang nudc cit, hdn hgp etanol - nudc va cudi cimg bing etanol. Sau khi lgc, rira va lam khd trong binh hiit am.
Ket qua phan tich ham lugng kim loai trong cac phirc chat theo thuc te lan lugt nhu sau: Zn(thbz)2 15,69 %, Zn(pthbz)2 - 11,24 %. Theo ly thuyit lin lugt vdi cdng thiic ZnCi6Hi6N6S2- 15,44
%, ZnC28H24N6S2 -11,19%.
3. KET QUA VA THAO LUAN 3.1. Ket qua phan tich pho khoi lirpng Tren phd MS ciia tit ca cac phiic chat cua Zn(II) deu cd pic vdi cudng do ldn nhat va ti sd m/z tuong iing bang 421 va 573 cd trj sd iing diing bing khdi lugng phan tli cita cac phirc chat cdng them 1 don vj. Dieu dd chirng td day la cac manh ion phan tii do phiic chat bi proton hda ([M+H]*). Nhu vay, cdng thiic phan tir du kien cua cac phiic chat dugc dua ra la hoan toan dung, cac phiic chat deu la don nhan. Hinh 1 la phd khdi lugng ciia phiic chat Zn(thbz)2.
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Hinh 1. Phd khdi lugng ciia phiec chdt Zn(thbz)2
Mdt bang chiing khac cho thay cdng thiic phan tu gia djnh dua ra la dung,tbe hien su tuong ddng giiia cuimg do tuong ddi ciia cac pic ddng vi tinh ly thuyet theo cdng thiic phan hi cua cac phirc chat bing phan mem "Isotope disttibution caculator' va tten phd thuc nghiem (bieu dd 1).
Biiu dd I. Cuong dg tuang ddi cia pic dong vi giiea ly thuyet vd thiec nghiem vol
phuc chdt Zn(thbz)2 3.2. Kit qua phan tich pho c$ng hirdng tir h^t nhan ' H va " C cua cac phoi tu va phirc chat
Phd cdng hudng tir hat nhan ' H va "C ciia phiic chit Zn(pthbz)2 dugc dua ra tren hinh 2 va 3.
O i l L
Hinh 2. Phd 'H-NMR ciia phirc chdt Zn(pthbz)2
Tin hieu ciia proton nhdm N'^'H cdng hudng d 11.41 va 11.81 ppm vdi tich phan la I trong phi 'H- NMR cua Hflibz
\ a Hpthbz, do phdi hi tdn tai d trang thai tiiion [4, 11]. Trong phd ciia ca hai phiic chat deu khdng thiy xuit hien tm hieu cpng hudng cua proton nhdm nay do xay ra su thiol hda \ a phdi tri dugc thuc hien qua nguyen hi S. BSng chiing la C nhdm CS cpng hudng d trudng cao hon khi chuyen hi Hpthbz sang Zn(pthbz)2. Mat khac. tin hieu cdng hudng ciia C nhdm
Hinh 3. Phi'^C-NMR ciia phiic chit Zn(pthbz)2
CN xuit hien tren pho "C - NMR ciia Hpthbz d 142,85 ppm nhung trong phi ciia phuc chat nd cdng hudng d 150 ppm.
Dieu nay dugc giai tiiich do hinh thanh lien kit phdi tti giua Zn(II) vdi S, N<".
Proton nhdm N ' ^ trong phd ' H - NMR tten phd Hthbz xuit hien vdi hai tm hieu singlet d 8,177; 7,969 ppm vdi tich phan la 1 va thay ddi khdng dang ki ve vi tri khi chuyin vao phirc chit Zn(thbz)2 (8,19; 7,99 ppm) [4, 9, 10].
Trong pho ' H NMR ciia phoi Ui
Hpthbz proton nay cdng hudng vol 1 pic singlet d 10,10 ppm, tich phan la 1 cdn trong phiic Zn(pthbz)2 cpng hudng d 9,38 ppm. Tin hieu singlet d 8,05; 8,17 ppm trong phd ' H - NMR ciia Hthbz dugc gan cho proton nhdm CHN va tin hieu nay khdng thay ddi khi chuyin vao
phiic chat Zn(thbz)2 va thay ddi khdng dang ke trong phiic chat Zn(pthbz)2. Cac tin hieu cdng hudng ciia cac proton va cacbon cdn lai thay ddi khdng dang ke khi chuyen tir phdi tit tu do vao phirc chat tuang ling va dugc liet ke diy dii tren bang I.
Bdng 1. Cdc tin hieu cgng hu&ng tren pho H, C - NMR cia phoi tir vd phitc chdt tucmg img
N « H
N''"H CS
HC = N Ho (I) Ho (II) Hp(I)
(I) Hm (II) Hp (II)
1 d
Vj tri, ppm Hthbz
11,41 (s, I) 8,18;
7,97 (s, I) 8,05 (s,
1) 7,79;
7,79 (d, 2)
7,403 (chap, 3)
177,98
142,21
134,14;
128,59;
127,24;
129,76
Zn(thbz)2
8,19;
7,99 (s, 1) 8,05 (s,
1) 7,80 (t,
2)
7,40 (t, 3)
Hpthbz 11,81 (s,l) 10,10 (s,l) 8,17 (s,
1) 7,91;
7,90 (d, 2) 7,58 (d,
2) 7,43 (chap,
3) 7,37 (t,
2) 7,21 (t,
1)
176,00
142,85
139,03;
127,99;
125,80;
129,98;
133,97;
127,58;
125,27;
128,59
Zn(pthbz)2
9,38 (s, 1) 8,15 (s,
1) 7,87 (m,
2) 7,67 (t, 2) 7,61 (t, 1) 7,55 (t, 2) 7,48 (m,
2) 7,20 (t, 1)
172,95
150,00
140,43;
132,10;
131,49;
131,37;
130,70;
128,75;
128,37;
128,31
3.3. Nghien ctiu phoi tir va cac phirc chat bing phirong phap pho hap thu hdng ngoai
Tren phd IR ciia cac phdi tli va phitc chat deu khdng thay xuat hien dai dao ddng hda trj dac tnmg cho nhdm C = O va SH lin lugt d khoang 1650 -1860 va 31
2550 - 2600 cm''. Su ving mat nay cho fliiy phan img ngung tu da xay ra va
\ 2
/
N -//
phdi tu tdn tai d trang thai thion d dieu kien ghi phd.
\=_ /
= \J
Dang thion
Xet vi hinh dang, phd ciia phdi tii va phiic chit cd su khac biet rd ret, chiing td phiic chit da dugc tao thanh. Su thay ddi rd ret nhit la vimg tten 3000 cm', cd cac dai hip tiiu dac trung cho nhdm NH va su xuit hien dai dao ddng hda trj dac trung cho nhdm N'^' = C d 1590 va 1591 cm'' fren phd IR ciia phirc chat Zn(thbz)2 va Zn(pthbz)2. Su chuyin dich vi phia sd sdng thap ban cua dai dao ddng hda trj dac trung cho nhdm CS (til 947 cm' frong Hthbz ve 700 cm'' ttong Zn(thbz)2 va tir 943 cm'' frong Hpthbz vi 706 cm'' frong Zn(pthbz)2) la do xay ra su thiol hdaafphoois tu khi tao phiic va lien ket phdi tri dugc tao thanh qua nguyen tu S. Su chuyen djch ve sd sdng thap hon ciia dai dao ddng hda trj dac trung cho nhdm C N ' " ttr 1596 cm'' frong Hthbz vi 1541 cm'' trong Zn(thbz)2 va 1592 cm'' frong Hpthbz ve 1570 cm'' trong Zn(pthbz)2, C N N ' " tit 1446 cm'' frong Hthbz vi 1379 cm'' frong Zn(thbz)2 \a 1444 cm'' trong Hpthbz \e 1385 cm'' frong Zn(pthbz)2 la bing chung cho thiy phdi tri dugc thuc hien qua nguyen tu N^''.
Tir tat ca cac phan tich fren cd the dua ra cdng thiic cau tao cua cac phiic chit nhu sau:
/ ; > \ . \
N = C H
\ (2) / RH.C,JI, ~ ' ^ \ i 4 > ' ' '
NH
3.4. Kit qua thir hoat tinh siuh hoc ciia phoi tir vii cac phirc chat Hoat tinh khang khuin va khang nam cua 02 phdi tu va 02 phitc chat frong cdng trinh nay dugc nghien ciiu dua tten phuang phap pha loang da ndng do.
Mirc do khang vi sinh vat kiim djnh va nim cua cac mau thir dugc danh gia qua gia tri IC50 {50% inhibitor concentration - ndng dp ire chi 50%) frSn 3 ddng vi khuin Gram (+): Lactobacillus fermentum. Bacillus subtilis, Staphylococcus aureus, 3 ddng vi khuan Gram (-): Sahnonella enterica, Escherichia coli, Pseudomonas aeruginosa va I ddng nam la:Candida albican. Ndng do cac chat thu nghiem diu la 128 ^i g/ml.
Ket qua thii cho thay cac mau dem thir deu chua the hien boat tinh khang sinh d ndng dp va cac chiing khuan dem thir.
Ket qua nay la du kien thuc nghiem cung cap cho Hnh vuc nghien cira mdi quan he giira ciu tao va hoat tinh smh hpc ciia cac hgp chit tren co sd thiosemicacbazon sau nay.
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4. KET LUAN
Da tdng hgp va dua ra cdng thiic ciu tao, nghien ciiu hoat tinh sinh hgc ciia 02 phdi tu Hthbz, Hpthbz va 02 phiic chit Zn(thbz)2, Zn(pthbz)2. Kit qua nghien cuu hoat tinh sinh hgc cho thiy cac hgp chit tdng hgp dugc chua thi hien hoat tmh sinh hpc vdi cac ddng khuan va nam d ndng dp dem thu.
Cong liinh nay ttiac hodn thdnh nha stf tai tra kinh phi cua di tai QG 12.04, DHQG Ha Npi
TAI LIEU THAM KHAO 1. Duraippandi Palanunuthu, Ashoka G.
Samuelson, "Dinuclear zinc bis(thiosemicarbazone) complexes:
Synthesis, in vitro anticancer activity, cellular uptake and DNA mteraction study", Inorganica Chimica Acta, 408, pp. 152-161(2013).
2. K. Stanly Jacob, Geetha Parameswaran, "Corrosion inhibition of mild steel in hydrochloric acid solution
by Schiff base fiirointhiosemicarbazone". Corrosion Science, 52 (1), pp. 224 - 228(2010).
3.K. Janardhan Reddy, J. Rajesh Kumar, C. Ramachandraiah, T. Thriveni, '"Specfrophotometric determination of zinc m foods using iV-ethyl 3- carbazolecarboxaldehyde-3 -
thiosemicarbazone: Evaluation of a new analytical reagent", Food Chemistry,
101, pp. 585-591(2007).
4. Mohammad Akbar Ali, Aminul H.
Muza, Jy D. Charfres, Paul V.
Bernhardt, ''Synthesis, characterization and X-ray crystal structures of seven-
coordinate pentagonal-bipyramidal zmc(II). cadmium(II) and tin(IV) complexes of a pentadentate N3S2 thiosemicarbazone". Polyhedron, 30 (2), pp. 299-306(2011).
5. S.I. Orysyk, V.V. Bon, 0 . 0 . Obolentseva, Yu. L. Zborovskii, V.V.
Orysyk, V.I. Pekhnyo, V.I. Staninets, V.M. Vovk, "Corrosion inhibition of mild steel in hydrochloric acid solution
by Schiff base fiirointhiosemicarbazone", Inorganica Chimica Acta, 382, pp. 127 - 138(2010).
6. S. Adi Narayana Reddy, K. Janardhan Reddy, Lee Kap Duk, A. Varada Reddy,
"Evaluation of 2,6-diacetylpyridinebis- 4-phenyl-3-thiosemicarbazone as complexing reagent for zinc in food and environmental samples". Journal of Saudi Chemical Society, In Press, Co/recfedProo/, pp. 215-220(2012).
7. Subhash Padhye, Ge orge B.
Kauf&nan, "Transitation metal complexes of semicarbazone and thiosemicarbazone". Coordination Chemistry Reviews, 63, pp. 127 — 160 (1985).
8. Suryanarayana R.V. and Brahmaji R.S., "Polarographic and specfrophotometric studies of cobalt(II) thiosemicarbazide system'', Journal of Electroanalytical chemistry, 96, pp. 1 0 9 - 1 1 5 (1979).
9. P. S. Tatjana, Dimifra Kovala- Demertzi, Alexandra Primikyri,
"Zmc(II) complexes of 2-acetyl pyridine l-(4-fluorophenyl)-piperazinyl
thiosemicarbazone: Synthesis, spectroscopic study and crystal
33
smicnu-es - Potential anticancer drugs", Joumal of Inorganic Biochemistry, 104, pp. 467-476 (2010).
10. T.A. Yousef, G.M. Abu El-Reash, M. Al-Jahdali, El-Bastawesy R. El- Rakhawy, "Structural and biological evaluation of some metal complexes of vanillm-'^-(2-
pyridyl)thiosemicarbazone". Journal of Molecular Structure, 1053, pp. 15 -
21(2013).
II. Tulay Bal-Demirci, "Synthesis, spectral characterization of the zinc(II) mixed - ligandcomplexes of N(4)-all)|
thiosemicarbazones and N,N,N',N' teframethyl ethylene diamme, and crystal structure of the novel [ZnL2(tmen)]" compound". Polyhedron, 27, pp. 4 4 0 - 4 4 6 (2008).
NGHIEN c i r u CHE TAO HE XUC TAC AXIT RAN....(tiip theo tr.I5)
biodiesel from Jattopha oil catalyzed by nanosized solid basic catalyst. Energy 1-8 (2011).
5. Yan S. Salley SO, Simon Ng KY.Simultaneous transesterification and esteriiication of unrefined or waste oils over ZnOlLaiOi catalysts. AppI Catal A 353 .H)203-212(2009).
6.Qianhe Liu,Lei Wang. Congxm Wang, Wei Qu. Zhijian Tian. The effect of lanthanum doping on activity of Zn-Al spinel for ttansesterification. Applied Catalysis B: Environmental Volumes 136-137. 5 June 2013. Pages 210-217 (2013).
7. Zong. M.H.. Duan, Z.Q.. Lou, W.Y., Smitii, T.J.. Wu, H. Preparation of a sugar catalyst and its use for highly
efficient production of biodiesel. Green Chemistry, Vol.7, pp.434-437 (2007) 8. Bharatkumar Z. Dholakiya. Super Phosphoric Acid Catalyzed Biodiesel Production from Low Cost Feed StockArchives of Applied Science Research, 4 (1):551-561 (2012).
9. Maria L Martins*, Ricardo F. Pires, Magno J. Alves, Carla E. Hori, Muia R M. Reis, Vicelma L. Cardoso.
Transesterification of Soybean Oil for Biodiesel Production Using Hydrotalcite as Basic Catalyst.Ctemmfca/ engineering transactions \o\.31. 817-822(2013).
10. M. Canakci, J. Van Gerpen.
Biodiesel production via acid catalysis. American Society of Agricultural Engineers! 203-
1210(1999).
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