Pro fessor Aleksander Koll

Transcription

1 Pol ish J. Chem., 83, (2009) Pro fessor Aleksander Koll Dr Aleksander Koll is pro fes sor of chem is try at the Fac ulty of Chem is try of Wroc³aw Uni ver sity. His ba sic re search in ter ests are con nected with hy dro gen bond stud ies, par tic u larly intramolecular hy dro gen bonds and the struc ture-prop erty re la - tion ships of or ganic mol e cules. Aleksander Koll was born on June 3, 1939, in Wilno. He spent the sec ond world war in Orany (Varena) in Lith u a nia, where his fa ther was an of fi cer in the post of fice. Af ter the war, the fam ily moved to G³ogów in Lower Silesia in 1945, where he fin - ished pri mary and sec ond ary school. In 1957 he started his stud ies at the Fac ulty of Math e mat ics, Phys ics, and Chem is try of Wroc³aw Uni ver sity, and grad u ated in 1962 with a Mas ter of Sci ence in chem is try. He be gan his re search work un der the su per vi - sion of Prof. Lucjan Sobczyk, study ing the po lar ity of hy dro gen bonds be tween phe - nols and amines. In 1962 he started his Ph.D. stud ies at the De part ment of Phys i cal Chem is try of Wroc³aw Uni ver sity. His dis ser ta tion was de voted to the cor re la tion be tween the struc tures of bipyridineamines and their physicochemical prop er ties. In 1968 he has

2 re ceived his Ph.D. de gree for the dis ser ta tion en ti tled Struc ture and prop er ties of (pyridil) 2 Y com pounds. The su per vi sor of the dis ser ta tion was Prof. Lucjan Sobczyk. Si mul ta neously he stud ied the po lar ity of the hy dro gen bonds in ortho-sub - sti tuted phe nols. He dem on strated that in com pounds, which may form a che late ring with -elec tronic cou pling, the vec tor of the hy dro gen bond po lar ity is mainly de - ter mined by res o nance ef fects. The 1969/1970 ac a demic year he spent as a post doc toral re searcher at Le nin grad State Uni ver sity in the De part ment of Mo lec u lar Spec tros copy. He was in volved to - gether with Pro fes sors V.E. Borisenko, D.N. Shchepkin and G.S. Denisow in quan ti - ta tive stud ies of the in te grated in ten sity of HCl stretch ing vi bra tional bands in the com plex with acetonitrile in CCl 4. Af ter re turn ing to Wroclaw Uni ver sity he con tin ued stud ies on the complexation of HCl as well as DCl, HBr, and DBr with ox y gen bases in CC1 4 so lu tions by mea sur - ing IR spec tra, di pole mo ments, and for ma tion con stants. The stud ies were car ried out in co op er a tion with Prof. M. Rospenk and Prof. L. Sobczyk. The sec ond post grad u ate stud ies, in 1975 and 1976 at Guelph Uni ver sity, Can - ada, un der the su per vi sion of Prof. C.A. Fyfe, were de voted to NMR ki netic stud ies of nucleophilic sub sti tu tion of nitroaromatic com pounds with the use of con tin u ous flow method. Since 1978 he has been in ten sively en gaged in stud ies of the intramolecular hy - dro gen bond in ortho-hydroxy N-dialkyl benzyl amines (Mannich bases). On the ba - sis of di pole mo ment mea sure ments he sug gested that in nonpolar sol vents the mol e cules ex ist ex clu sively in nonplanar closed intramolecular forms. He con - structed the Mo lec u lar Force Field (MM) with the Lippincott-Schroeder po ten tial for a de scrip tion of the hy dro gen bond ing in ter ac tions. He dem on strated that the con for - ma tion of the che late ring formed by an intramolecular hy dro gen bond is re ally nonplanar. With in creas ing strength of the hy dro gen bond the mol e cules be come more pla nar, but even for the stron gest hy dro gen bonds they ap proach some limit of nonplanar struc tures. In de pend ent crys tal lo graphic de ter mi na tions per formed later pos i tively ver i fied this hy poth e sis. Cal cu lated di pole mo ments gave the same de - pend ence of the hy dro gen bond po lar ity on pka as in intermolecular com plexes, sug gest ing the same na ture of the inter- and intramolecular hy dro gen bond. UV-Vis spec tros copy was ap plied to de ter mine the ther mo dy namic pa ram e ters of the intramolecular pro ton trans fer re ac tion. It was shown that in all com pounds the enthalpy of this pro cess was neg a tive and en tropy changes were also neg a tive and rel - a tively high, sug gest ing a strong par tic i pa tion of sol vent mol e cules in the pro ton trans fer pro cess. Such an ef fect was later dem on strated by us ing mo lec u lar dy nam ics in the dis ser ta tion of one of his Ph.D. stu dents, Dr. Adam Fedorowicz. The change in the ar range ment of sol vent mol e cules re sult ing from intramolecular pro ton trans fer was clearly dem on strated. The po lar ity and struc ture of intramolecular hy dro gen bonds were the top ics of Prof. Koll s ha bil i ta tion dis ser ta tion, com pleted in In 1988 he was pro moted to

3 the po si tion of do cent, in 1992 he be came as so ci ate pro fes sor, and in 1996 he re - ceived the ti tle of pro fes sor. As Mannich bases were used by Prof. Koll as model com pounds in the study of the na ture of hy dro gen bond ing, biphenyl-type mol e cules were ap plied as a model for the study of conformational equi lib ria. A sub tle bal ance be tween steric and res o - nance ef fects in this type of mol e cules makes them es pe cially sen si tive to the sur - round ings and the in flu ence of tem per a ture. De riv a tives sub sti tuted not on the ro ta tional axis po si tions were ap plied in conformational stud ies with the use of di - elec tric meth ods. Prof. Koll per formed ex per i men tal mea sure ments in the lab o ra - tory of Dr. L. Hellemans at the De part ment of Bi o log i cal Dy nam ics of Leuven Cath o lic Uni ver sity. Prof. Koll spent two months there as a vis it ing pro fes sor and vis ited this lab o ra - tory many times for shorter pe ri ods. Prof. Koll pro posed the mo lec u lar force field model for cal cu lat ing the po ten tial for in ter nal ro ta tion in such mol e cules. A par tic u - lar achieve ment was in tro duc ing the res o nance cou pling ef fects to the force field. In or der to ob tain better con sis tency be tween the o ret i cal cal cu la tions and ex per i - ments done on nonpolar sol vents, Mo lec u lar Dy nam ics cal cu la tions were per formed in Prof. Koll s group by Dr. A. Szymoszek. It was dem on strated that, in agree ment with the ex per i ment, the nonpolar sol vent CCl 4 ex erts in flu ence on the sol ute mol e - cules to make them more pla nar. A spe cific fea ture of these cal cu la tions was in tro duc - ing the quan tum me chan i cal po ten tial for the sol ute mol e cules to gether with clas si cal mo lec u lar me chan ics for other move ments in so lu tion. Semiempirical quan tum me chan i cal meth ods were ap plied in cal cu la tion of the po ten tial en ergy sur face for mol e cules such as diphenylguanidine, dimesitil sul fone, and Mannich and Schiff bases. The re sults were ver i fied by ex per i men tally de ter - mined val ues of the di pole mo ments. To gether with Dr. hab. A. Filarowski, he per - formed anal y sis of the struc ture and strength of intramolecular hy dro gen bonds in Mannich bases and struc tur ally re lated Schiff bases. It was found that Schiff bases form stron ger intramolecular hy dro gen bonds, but with lower in ten sity of the (OH) stretch ing band. The in ter pre ta tion of such an ef fect was made on the ba sis of cal cu - lat ing de riv a tives of the di pole mo ments with re spect to the OH bond dis tance. An - har mon ic ef fects were dis cussed on the ba sis of the po ten tial for the stretch ing of the O H dis tance. In this study a sterically en hanced class of hy dro gen bonds was dis - cov ered. It was dem on strated that such hy dro gen bonds are shorter, but also re veal all fea tures of stron ger hy dro gen bonds. Wide-rang ing the o ret i cal stud ies on the struc - tural and en er getic ef fects of the for ma tion of intramolecular hy dro gen bonds were per formed in co op er a tion with Prof. P. Wolschann and Prof. A. Karpfen of the In sti - tute of The o ret i cal Chem is try of Vi enna Uni ver sity. Prof. Koll vis ited Vi enna Uni ver - sity many times and was the co or di na tor of joint bi lat eral pro grams un der an agree ment for sci en tific co op er a tion be tween Aus tria and Po land sup ported by the OAD. Ten orig i nal pub li ca tions were pre pared within the frame work of this co op er a - tion. Im por tant top ics of these stud ies are the res o nance in ter ac tions within

4 intramolecular hy dro gen bonds in Schiff bases as well as the ther mo dy namic cy cle type scheme for es tab lish ing the en ergy of intramolecular hy dro gen bond. In co op er a tion with the Vi enna Uni ver sity Cen ter and with Prof. G. Koehler, stud ies on the prop er ties of bi o log i cally im por tant bilayers im ple mented by biologically ac tive lig ands were in tro duced in Prof. Koll s group. The o ret i cal and ex per i - men tal stud ies were per formed in which IR-ATR has be come one of the most prom is - ing method. The ex ten sive co op er a tion be tween St. Pe ters burg and Wroc³aw Uni ver si ties, par tic u larly with Pro fes sors S.M. Melikova and K.S. Rutkowski, re sulted in a set of pub li ca tions on blue-shift ing im proper hy dro gen bonds. An in stal la tion for IR mea - sure ments in liq ue fied no ble gases was built in the De part ment of Chem is try of Wroc³aw Uni ver sity. These stud ies were sup ported by two grants of the Pol ish Com - mit tee for Sci en tific Re search (KBN). The fol low ing vis i tors have worked in his lab o ra tory: Pro fes sors S.M. Melikova, S.F. Bureiko, and K. Rutkowski from St. Pe ters burg Uni ver sity, Prof. V.E. Borisenko from Tyumen Uni ver sity, and Prof. S. Mukherjee from the In dian As so ci a tion for the Cul ti va tion of Sci ence of Cal cutta. Prof. Koll was pro moted to or di nary pro fes sor po si tion of Chem is try in Wroc³aw Uni ver sity in He served as a Vice-Dean of the Fac ulty of Chem is try of this Uni - ver sity in He has been head of the Struc ture and Mo lec u lar In ter ac tions group in this Fac ulty since 1998 and head of the De part ment of Phys i cal Chem is try since He is the au thor or co-au thor of 180 orig i nal re search pub li ca tions and one text book on ex per i men tal phys i cal chem is try to gether with L. Sobczyk, A. Kisza, and K. Gatner. He has been the su per vi sor of more than sixty mas ter s the ses and nine Ph.D. dis - ser ta tions. Two more dis ser ta tions are be ing com pleted un der his su per vi sion. He has taught phys i cal chem is try in the lab o ra tory, sem i nars, cal cu la tions, and lec tures as well as in more ad vanced mono graph lec tures and sem i nars on phys i cal or ganic chem is try and mo lec u lar in ter ac tions. He also de liv ers the lec tures on mo lec u lar mod el ing and phys i cal or ganic chem is try for Ph.D. stu dents. He is one of the or ga niz - ers of the an nual Schools of Phys i cal Or ganic Chem is try. Ed i tor

5 Pol ish J. Chem., 83, (2009) 2 -Hydroxybenzylideneanilines and 2-Hydroxyazobenzenes. The Role of Intramolecular O H N Res o nance As sisted Hy dro gen Bonds by P. Majewska, M. Rospenk ** and L. Sobczyk Fac ulty of Chem is try, Uni ver sity of Wroc³aw, Joliot-Cu rie 14, Wroc³aw, Po land ** mr@wchuwr.pl (Re ceived Oc to ber 22nd, 2008; ac cepted De cem ber 28th, 2008) A short re view on the ef fect of the OH groups in the ortho po si tion on the liq uid crys tal - line prop er ties of benzylideneanilines and azo ben zenes is pre sented. Nu mer ous ex am - ples show that there are no gen eral rules gov ern ing the be hav iour of these com pounds. How ever one finds most fre quently a broad en ing of the ex is tence range of mesophases both due to a de crease of freez ing tem per a ture and an in crease of the isotropisation tem - per a ture. In con trast, the pres ence of strongly po lar groups such as NO 2 and CN leads to a re verse be hav iour that can be ex plained by as sum ing a strong -elec tron con ju ga tion of these groups with the con ju gate-che late ring formed by intramolecular O H N hy - dro gen bond. These rings are an a lyzed by us ing data re lated to the struc ture of mol e cules and in fra-red spec tra in the re gion of the stretch ing (OH) and bend ing (OH) and (OH) modes. Key words: liq uid crys tals, Schiff bases, azo ben zenes, res o nance-as sisted OH N H-bonds

6 Pol ish J. Chem., 83, (2009) Hy dro gen Bonds and Elec tro static In ter ac tions in N-(Ethoxycarbonylmethyl)-quinuclidinium Chlo ride Dihydrate by Z. Dega-Szafran**, A. Katrusiak and M. Szafran Fac ulty of Chem is try, Adam Mickiewicz Uni ver sity, Grunwaldzka 6, Poznañ, Po land ** (Re ceived No vem ber 12th, 2008; ac cepted De cem ber 28th, 2008) N-(Ethoxycarbonylmethyl)-quinuclidinium chlo ride crys tal lizes as dihydrate, QNBE Cl 2H 2 O. The crys tals are monoclinic, space group C2/c. Wa ter mol e cules in ter - act with the chlo ride an ions and form a cy clic oligomer, through the O H Cl and O H O hy dro gen bonds. The chlo ride an ions and wa ter mol e cules ad di tion ally in ter act electrostically with the pos i tively charged ni tro gen atom of the quinuclidinium moi ety. The op ti mized struc ture of QNBE Cl 2H 2 O by the B3LYP/6-31G(d,p) level of the ory re - pro duces well the mo lec u lar ag gre ga tion ob served in the crys tal. The FTIR spec trum of the solid com pound is con sis tent with the X-ray struc ture. Key words: 1-azabicyclo[2.2.2]oc tane; quinuclidinium salts, X-ray dif frac tion, FTIR, Raman, NMR spec tra, DFT cal cu la tions, hy dro gen bond, elec tro static in ter ac tion

7 Pol ish J. Chem., 83, (2009) Time-Re solved In fra red Spec tros copy of Wa ter. Re la tion be tween the OH Stretch ing Fre quency and the OO Dis tance by S. Bratos 1,**, J.-C. Leicknam 1 and S. Pommeret 2,3,4 1 Laboratoire de Phy sique Théorique de la Matiére Condensée, Université Pi erre et Ma rie Cu rie-paris 6, Case Courrier 121, 4 Place Jussieu, Paris Cedex 05, France ** bratos@lptmc.jussieu.fr 2 CEA, IRAMIS, Laboratoire de Radiolyse, Gif-sur-Yvette Cedex, France 3 CNRS, IRAMIS, Laboratoire Claude Fréjacques, Gif-sur-Yvette Cedex, France 4 Pres ent ad dress: CEA, DPG, Gif-sur-Yvette Cedex, France (Re ceived No vem ber 12th, 2008; ac cepted Jan u ary 7th, 2009) It is shown how in fra red pump-probe spec tros copy can be used to mea sure sub pi co sec - ond vari a tions of the ox y gen-ox y gen dis tri bu tion func tion in liq uid wa ter. A di luted so lu - tion HDO/D 2 O rather than pure H 2 O is con sid ered to switch off res o nant vi bra tional in ter ac tions be tween wa ter mol e cules; the lo cal struc ture re mains un changed in this sub - sti tu tion. The pres ent study is lim ited to times su pe rior to fs. This per mits to avoid prob lems gen er ated by hard sphere type col li sions be tween wa ter mol e cules, as well as the in ter fer ence be tween ultrafast pump and probe pulses. It is then shown that the Novak-Mikenda type re la tions be tween the OH stretch ing fre quency and the OO dis tance largely sur vive when go ing from stan dard to ultrafast in fra red spec tros copy. More over, the in fra red pump-probe pro files of OH stretch ing bands closely par al lel the ox y gen-ox y - gen dis tri bu tion func tions in this time do main. In fra red pump-probe spec tros copy is thus a use ful sub sti tute of time-re solved X-ray dif frac tion in this ex cep tional case. Key words: time-re solved spec tros copy, wa ter, hy dro gen bond ing, OO dis tance vs streching fre quency

8 Pol ish J. Chem., 83, (2009) Struc ture of a New Schiff Base of Gossypol with Ethyl 4-Amino-1-piperidine Carboxylate in the Solid and in the So lu tion by P. Przybylski, K. Pyta, M. Ratajczak-Sitarz, A. Katrusiak and B. Brzezinski ** Fac ulty of Chem is try, A. Mickiewicz Uni ver sity, Grunwaldzka 6, Poznan, Po land ** bbrzez@amu.edu.pl, Tel: , Fax: (Re ceived No vem ber 25th, 2008; ac cepted De cem ber 28th, 2008) Crys tals of the Schiff base de riv a tive of gossypol with ethyl 4-amino-1-piperidine carboxylate (GSPC) have been grown and sub se quently ex am ined by X-ray dif frac tion, FT-IR and NMR meth ods. The crys tal space group is P2 1 /n with a = (1) Å, b = (1) Å, c = (1) Å, = 91.22(1) and Z = 4. In the crys tal GSPC ex ists in the enamine-enamine tau to meric form. The intramolecular N(16) H(16) O(2), N(16 ) H(16 ) O(2 ) hy dro gen bonds as sisted by the res o nance of the -elec trons in the ar o matic sys tem are the stron gest. The FT-IR spec tral fea tures of the crys tals are in agree - ment with the X-ray data in di cat ing that both parts of the mol e cule are sim i larly intramolecular hy dro gen-bonded but dif fer ent intermolecular hy dro gen-bonded, al - though the mol e cule is sym met ri cally sub sti tuted. The FT-IR as well as 1 H and 13 C NMR spec tra have shown that in chlo ro form so lu tion the enamine-enamine tau to meric form is pre served and the whole struc ture of GSPC be comes more sym met ri cal. Key words: gossypol, Schiff base, X-ray, FT-IR, 1 H, 13 C NMR

9 Pol ish J. Chem., 83, (2009) DFT Stud ies of H 3 N X (X = Li, Na, K, Rb, Cs and Fr) Sys tems by R. Wieczorek, P. Durlak and Z. Latajka** Fac ulty of Chem is try, Uni ver sity of Wroc³aw, F. Joliot-Cu rie 14, Wroc³aw, Po land ** latajka@wchuwr.chem.uni.wroc.pl (Re ceived No vem ber 26th, 2008; ac cepted Jan u ary 6th, 2009) Com plexes of al kali at oms with am mo nium have been stud ied us ing the Den sity Func - tional The ory with nonlocal and quasi-rel a tiv is tic cor rec tions. The sta ble com plexes were found for all al kali atom am mo nia com plexes. The cal cu lated in ter ac tion en er gies de crease as one pro gresses down the pe ri odic ta ble and are in range from 18.9 kcal/mol for lith ium sys tem up to 6.5 kcal/mol for the frans com plex. Sim i lar ten dency is noted for the cal cu lated val ues of charge trans fer. The in flu ence of cal cu lated quasi-rel a tiv is tic (QR) cor rec tions on val ues of in ter ac tion en er gies is de ter mined. The QR cor rec tions have no ef fect on lith ium com plexes whereas re duce the bind ing en ergy from 0.1 kcal/mol for Na sys tem up to 0.9 kcal/mol for Fr com plex. The DFT cal cu lated IR har - monic fre quen cies are com pared with ex per i men tal val ues and dis cussed. The cal cu lated vi bra tional fre quen cies of am mo nia in com plexes ex hibit trends that for all sys tems they are par al lel to the strength of the bind ing en er gies. For the H 3 N Li com plex the vi bra - tional anal y sis was sup ported by an har mon ic cal cu la tions at the MP2 level. It has been shown that there is a dis crep ancy be tween the ex per i men tal as sign ment and MP2 har - monic and an har mon ic low fre quency intermolecular modes. Key words: den sity func tional meth ods, MP2 method, mo lec u lar com plexes, al kali at oms, am mo nia, rel a tiv is tic ef fects, vi bra tional fre quen cies, an har mon ic vibrational spectra

10 Pol ish J. Chem., 83, (2009) Mo lec u lar In ter ac tions and Struc ture of H-Bonded Com plexes of Bifunctional Ni tro gen-con tain ing Mol e cules by S.F. Bureiko**, S.Yu. Kucherov and V.M. Schreiber Department of Physics, St. Petersburg State University, Ulianovskaya 1, Petrodvorets, St. Pe ters burg , Rus sia ** boureiko@paloma.spbu.ru (Re ceived De cem ber 1st, 2008; ac cepted De cem ber 29th, 2008) The re sults of ex per i men tal stud ies and quan tum chem i cal cal cu la tions of vi bra tional spec tra and struc ture of H-bonded com plexes formed by N-con tain ing bases 3,5-dimethylpyrazole, diphenyltriazene and diphenylformamidine with carboxylic ac ids and HHal are dis cussed. The IR spec tra of so lu tions in CH 2 Cl 2 and CCl 4 and low tem per a - ture NMR spec tra show the ex is tence of equi lib rium be tween mono mers and cy clic selfassociates of the mol e cules stud ied. Un der the in ter ac tion with weak carboxylic ac ids the com plexes have mo lec u lar struc ture with two H-bonds NH O=C and OH N, and the in ter ac tion with strong ac ids re sults in for ma tion of cy clic H-bonded ionic pairs with pro ton trans fer to the N atom of the base. The pro ton trans fer in so lu tion was ob served also for open com plexes with HHal. The quan tum chem i cal DFT cal cu la tions in har - monic and an har mon ic ap prox i ma tions con firm the for ma tion of cy clic com plexes, while the pro ton trans fer along the OH N bridge was sup ported for the com plexes with stron - gest ac ids. It was shown that the use of variational mul ti di men sional an har mon ic ap - proach is the most pref er a ble for cal cu la tions of the high-fre quency XH stretch in sys tems where the cor re spond ing nor mal mode is less char ac ter is tic and in volves mo - tions of many at oms. Key words: hy dro gen bond ing, so lu tions, pro ton trans fer, ionic pairs, IR ab sorp tion spec tra, quan tum chem i cal cal cu la tions

11 Pol ish J. Chem., 83, (2009) How Does the Bent Walsh Rule Work in Mol e cules of para-disubstituted Ben zene De riv a tives? The Case of para-nitrophenol and para-nitrophenolate by T.M. Krygowski 1** and H. Szaty³owicz 2 1 De part ment of Chem is try, War saw Uni ver sity, Pasteura 1, War saw, Po land ** tmkryg@chem.uw.edu.pl 2 Fac ulty of Chem is try, War saw Uni ver sity of Tech nol ogy, Noakowskiego 3, War saw, Po land (Re ceived De cem ber 4th, 2008; ac cepted Jan u ary 7th, 2009) DFT (B3LYP/6-311+G**) op ti mi za tion of nitrobenzene, 4-nitrophenol and 4-nitro - phenolate with the con straints for the ro tat ing ni tro group, with an in ter val of 15, al - lowed us to show how the Bent Walsh rule works in a whole range of vari a tion of ge om e try in the vi cin ity of both sub sti tuted car bon at oms, C1 and C4. For scat ter plots of ge om e try pa ram e ters in the vi cin ity of the C1 car bon atom the gen eral view is in line with the Bent Walsh rule. The re la tion ship be tween the mean value of C1C2 and C1C6 bond lengths and the CO bond length has a neg a tive slope, as ex pected. Two other dependences, this is the above men tioned bond lengths on C6 C1 C2 an gle, have also ra - tio nal slopes but pres ent a re la tion ship be tween two clus ters, for 4-nitrophenol and 4-nitrophenolate, and within these clus ters the slopes are op po site, due to the dom i nant res o nance ef fect over the electronegativity one. In the case of scat ter plots of ge om e try pa ram e ters in the vi cin ity of the C4 car bon atom the gen eral view is again in line with the Bent Walsh rule, but ir reg u lar i ties are of dif fer ent shape: they re sult from strong in ter ac - tions be tween ox y gen at oms of the ni tro group and both CH in ortho po si tions. These in - ter ac tions be come the stron gest for pla nar con for ma tion of the ni tro group and de crease in strength with an in crease of the ro ta tion an gle. This re sults in a per tur ba tion in the res o - nance/electronegativity blend lead ing to sub stan tial de vi a tions from lin ear dependences of the CN bond length vs. the mean value of C4C3 and C4C5 bond lengths, and the CN bond length vs. C3 C4 C5 an gle. Key words: ni tro group, substituent ef fect, electronegativity, Bent Walsh rule, hy dro gen bond

12 Pol ish J. Chem., 83, (2009) The Na ture of Hy dro gen Bond ing in Se lected Hydrazide De riv a tives Investigated via Static Mod els and Car-Parrinello Molecular Dynamics by A. Jezierska 1,2**, M. Noviè 1 and J.J. Panek 2 1 Na tional In sti tute of Chem is try, Hajdrihova 19, SI-1001 Ljubljana, Slovenia 2 Uni ver sity of Wroc³aw, Fac ulty of Chem is try, ul. F. Joliot-Cu rie 14, Wroc³aw, Po land ** anetka@elrond.chem.uni.wroc.pl, phone: , fax: (Re ceived De cem ber 5th, 2008; ac cepted Jan u ary 13th, 2009) The geo met ric and spec tro scopic prop er ties of 2-hydroxy-thiobenzhydrazide and 2-hydroxy-benzhydrazide were in ves ti gated within the frame work of Den sity Func tional The ory (DFT). Spe cial at ten tion was de voted to the de scrip tion and anal y sis of intra- and intermolecular hy dro gen bonds. The choice of the com pounds was dic tated by their struc - tural sim i lar ity and the pres ence of two types of hy dro gen bridges: O H...S (in 2-hydroxy-thiobenzhydrazide, less com mon) and O H...O (in 2-hydroxy-benzhy - drazide). The lat ter could be clas si fied as a low-bar rier hy dro gen bond (LBHB). First the DFT method was used to ob tain the geo met ric pa ram e ters for the monomeric and dimeric forms of the com pounds at var i ous lev els of the ory. Then the bind ing en ergy was cal cu - lated for the dimeric forms to es ti mate the strength of the intermolecular hy dro gen bonds. At oms in Mol e cules (AIM) the ory was ap plied to show quan ti ta tively how the for ma tion of the intermolecular hy dro gen bonds af fects the strength of the intramolecular hy dro gen bonds. The elec tron den sity and its Laplacian were cal cu lated for the bond crit i cal points de fin ing the H-bridges. Car-Parrinello mo lec u lar dy nam ics (CPMD) was then used to in ves ti gate the changes in the geo met ric pa ram e ters as a func tion of sim u la tion time. This part of the com pu ta tional study was per formed in vacuo and in the solid state. The vi bra - tional prop er ties of the in ves ti gated hydrazides were ob tained via Fou rier trans form of the autocorrelation func tions of the di pole mo ment and atomic ve loc ity. It was found that the for ma tion of the intermolecular H-bonds does not sig nif i cantly af fect the strength of the intramolecular H-bonds. There fore in duc tive and steric ef fects out side the im me di - ate vi cin ity of the intramolecular bridge have mi nor in flu ence on its in ves ti gated prop er - ties. The ap pli ca tion of CPMD gave a more de tailed pic ture of the bridged pro tons dy nam ics. The com pu ta tional re sults agree with avail able ex per i men tal data. The in flu - ence of the intermolecular hy dro gen bond ing net work and non-bonded crys tal field in - ter ac tions on the vi bra tional fea tures of the in ves ti gated mol e cules is dem on strated and dis cussed. Key words: hy dro gen bond, BSSE, AIM, CPMD, gas phase, solid state

13 Pol ish J. Chem., 83, (2009) Change of Prototropic Equi lib ria for Ura cil when Go ing from Neu tral Mol e cule to Charged Rad i cals. Quan tum-chem i cal Stud ies in the Gas Phase by E.D. Raczyñska **1, K. Zientara 2, K. Kolczyñska 2 and T.M. Stêpniewski 2 1 Department of Chemistry, 2 Interdisciplinary Department of Biotechnology, War saw Uni ver sity of Life Sci ences, Warszawa, Nowoursynowska 159c, Po land ** ewa_raczynska@sggw.pl (Re ceived De cem ber 11th, 2008; ac cepted Jan u ary 8th, 2009) To un der stand var i ous sub sti tu tion, ox i da tion or deg ra da tion re ac tions for ura cil, quan - tum-chem i cal cal cu la tions were per formed for two classes of charged rad i cals (cat ions and an ions) of ura cil (U + and U - ) and model com pounds: phe nol (P + and P - ) and hydroxyazines (HP1-4 + and HP1-4 - ). In cal cu la tions, all pos si ble eigh teen prototropic tautomers-rotamers of U and all pos si ble five prototropic tautomers-rotamers of P and HP1-4 were con sid ered. Sta bil i ties, in ter nal ef fects and ar o matic char ac ter, es ti mated for charged rad i cals, were com pared with those ob served pre vi ously for neu tral mol e cules. The great est changes of the tau to meric pref er ences take place for rad i cal an ions. One-elec tron re duc tion sta bi lizes the keto and am ide func tions in stud ied com pounds, whereas one-elec tron ox i da tion fa vors the enol func tion for phe nol and the am ide func - tion for ura cil and hydroxyazines. Key words: ura cil, hydroxyazines, charged rad i cals, prototropic equi lib ria, gas phase, AM1, DFT

14 Pol ish J. Chem., 83, (2009) Struc tural and Vi bra tional In ves ti ga tion of 2-Amino-5-nitropyridine. A Com bined Ex per i men tal and The o ret i cal Stud ies by J. Oszust 1, J. Baran 2, A. Pietraszko 2 and M. Drozd 2** 1 De part ment of Bioorganic Chem is try, Uni ver sity of Eco nom ics, 118/120 Komandorska str., Wroc³aw, Po land 2 In sti tute of Low Tem per a ture and Struc ture Re search of the Pol ish Acad emy of Sci ences, 2 Okólna str., Wroc³aw, Po land ** m.drozd@int.pan.wroc.pl (Re ceived De cem ber 16th, 2008; ac cepted Jan u ary 19th, 2009) The crys tal struc ture of 2-amino-5-nitropyridine at low tem per a ture was pre vi ously de - ter mined by other au thors [1]. In this pa per, the com ple men tary X-ray study at am bi ent tem per a ture is re ported. The small dif fer ences in lat tice pa ram e ters mea sure ment in both ex per i ments were found. The dif fer en tial scan ning ca lo ri met ric (DSC) mea sure ments were per formed. No phase tran si tion was found in the tem per a ture range K. Ad di tion ally, the de tailed vi bra tional spec tro scopic anal y sis of 2-amino- 5-nitropyridine are re ported. Pow der in fra red and Raman spec tra of the ti tle com pound were mea sured at room tem per a ture. The mo lec u lar struc ture of 2-amino-5-nitro pyridine has been cal cu lated with the aid of den sity func tional (B3LYP) method with the ex tended G(d,p) ba sis set. The cal cu lated geo met ri cal pa ram e ters of in ves ti gated mol e - cule in gas phase were com pared with ex per i men tal X-ray data. The har monic fre quen - cies, po ten tial en ergy dis tri bu tion (PED) and IR in ten si ties of 2-amino-5-nitro pyridine were cal cu lated with B3LYP method. The as sign ment of the ex per i men tal spec tra has been made as sum ing the cal cu lated PED. Key words: 2-amino-5-nitropyridine, vi bra tional spec tra, DFT, hy dro gen bonds, PED

15 Pol ish J. Chem., 83, (2009) Ad e nine and Some of Its An a logues in DMSO-d 6 So lu tion: an NMR and GIAO-DFT Study by K. Dybiec, S. Molchanov and A. Gryff-Keller ** Fac ulty of Chem is try, War saw Uni ver sity of Tech nol ogy, Noakowskiego 3, War saw, Po land ** agryff@ch.pw.edu.pl (Re ceived De cem ber 19th, 2008; ac cepted Jan u ary 11th, 2009) The re sults of GIAO-DFT cal cu la tions [at B3LYP/ G(2d,p) PCM and PBE1PBE/6-311+G(2fd,p) PCM lev els] of 13 C NMR and 15 N NMR pa ram e ters have been em ployed to re in ves ti gate tau tom er ism of ad e nine in DMSO so lu tion. The sep a rate 13 C NMR sig nals of N7-H and N9-H ad e nine tautomers have been ob served for the first time. The ex per i men tal 13 C chem i cal shifts, 3 J(C,H) cou pling con stants and 15 N chem i cal shifts of ad e nine and three of its methyl de riv a tives (9MeA, 7MeA and 3MeA) have been quan ti ta tively an a lyzed us ing the cal cu lated pa ram e ter val ues. This pro ce dure has pro - vided the so lu tion pop u la tions of the pre dom i nant ad e nine tautomers be ing in agree ment with the avail able lit er a ture data. The ap par ent de pend ence be tween the amino group ge - om e try and the chem i cal shift of the ad ja cent car bon in 2-aminopyridine sys tem has also been dis cussed. Key words: ad e nine, methyladenines, tau tom er ism, GIAO-DFT study, NMR

16 Pol ish J. Chem., 83, (2009) Ef fects of Strong Inter-hy dro gen Bond Dy nam i cal Cou plings in the Po lar ized IR Spec tra of trans- -Hydromuconic Acid Crys tals by H.T. Flakus 1**, M. Jab³oñska 1,2 and A. Tyl 1 1 In sti tute of Chem is try, Uni ver sity of Silesia, 9 Szkolna Street, Katowice, Po land ** flakus@ich.us.edu.pl 2 In sti tute of En vi ron men tal En gi neer ing of the Pol ish Acad emy of Sci ences, 34 Maria Cu rie-sk³odowska Street, Zabrze, Poland (Re ceived De cem ber 19th, 2008; ac cepted Jan u ary 29th, 2009) This pa per pres ents the re sults of in ves ti ga tions of po lar ized IR spec tra of trans- hydromuconic acid (HMA) crys tals. The spec tra were mea sured by a trans mis sion method us ing po lar ized light at room tem per a ture and at 77 K for three dif fer ent crys tal - line faces. The o ret i cal anal y sis of the re sults con cerned lin ear dichroic ef fects, H/D iso to - pic and tem per a ture ef fects ob served in the spec tra of the hy dro gen and deu te rium bonds in HMA crys tals at the fre quency ranges of the O H and the O D bands. The ba sic crys tal spec tral prop er ties could be sat is fac to rily in ter preted in a quan ti ta tive way for a centrosymmetric cy clic hy dro gen bond dimer model. Model cal cu la tions, per formed within the lim its of the strong-cou pling model, al lowed for quan ti ta tive in ter pre ta tion and for the un der stand ing of the ba sic prop er ties of the hy dro gen bond IR spec tra of HMA crys tals in clud ing H/D iso to pic, tem per a ture and dichroic ef fects. Such a model ex plains not only the two-branch struc ture of the O H and O D bands in crys tal line spec tra, but also some es sen tial lin ear dichroic ef fects in the band fre quency ranges mea sured for iso - to pi cally di luted HMA crys tals. In the scope of our stud ies the mech a nism of H/D iso to - pic self-or ga ni za tion pro cesses, tak ing place in the crys tal hy dro gen bond lat tices, was also stud ied. It was proved that for iso to pi cally di luted crys tal line sam ples of HMA, a non-ran dom dis tri bu tion of pro tons and deu ter ons oc curs ex clu sively in the hy dro gen bond dimers. Nev er the less, these dy nam i cal co-op er a tive in ter ac tions be tween the hy dro gen bonds do not in volve of the ad ja cent hy dro gen bond dimers in each unit cell. The two-branch fine struc ture pat tern of the O H and O D bands was as cribed to the vibronic mech a nism of vi bra tional di pole se lec tion rule break ing for IR tran si tions in centrosymmetric hy dro gen bond dimers. The lin ear dichroic ef fect, dif fer en ti at ing prop - er ties of the two op po site spec tral branches of the O H and O D bands, was also dis - cussed. Key words: hy dro gen bond, mo lec u lar crys tals, po lar ized IR spec tra, H/D iso to pic ef fects, lin ear dichroic ef fects, tem per a ture ef fects, iso to pic di lu tion, H/D iso to pic self-or ga ni za tion effects

17 Pol ish J. Chem., 83, (2009) Stud ies on the Deamination of the Ethyl Es ter of 5-Amino-3-methylisoxazole-4-carboxylic Acid by S. Ryng ** and M. Szostak Department of Organic Chemistry, Faculty of Pharmacy, University of Medicine, Grodzka 9, Wroclaw, Poland ** (Re ceived De cem ber 30th, 2008; ac cepted Jan u ary 16th, 2009) The un usual be hav ior of the ethyl es ter of 5-amino-3-methylisoxazole-4-carboxylic acid (1) dur ing deamination is de scribed. Pos si ble ex pla na tions for the anom a lies of the diazotization re ac tion are pro posed. Deamination meth ods lead ing to ethyl es ter of 3-methylisoxazole-4-carboxylic acid (5) are pre sented. 5 will serve as a lead com pound for a new se ries of immunomodulatory agents. Key words: isoxazoles, diazotization, deamination, hy dro gen bond ing, im mu no log i cal ac tiv ity

18 Pol ish J. Chem., 83, (2009) The o ret i cal and Spec tro scopic Study of In fra red Spec tra of Hy dro gen-bonded 2,4-Dithiouracil Crys tal and Its Deuterated Derivative by J. Kwiendacz, M. Boczar,. Boda and M.J. Wójcik** Fac ulty of Chem is try, Jagiellonian Uni ver sity, Kraków, Ingardena 3, Po land ** wojcik@chemia.uj.edu.pl; Fax (Re ceived Jan u ary 9th, 2009; ac cepted Jan u ary 24th, 2009) The o ret i cal sim u la tion of the bandshape and fine struc ture of the N H(D) stretch ing bands is pre sented for 2,4-dithiouracil and its deuterated de riv a tive tak ing into ac count an har mon ic cou pling be tween the high-fre quency N H(D) stretch ing and the low-fre - quency N S stretch ing vi bra tions, res o nance in ter ac tion be tween two equiv a lent hy dro - gen bonds in the dimer, anharmonicity of the po ten tials for the low-fre quency vi bra tions in the ground and ex cited state of the N H(D) stretch ing mode, Fermi res o nance be tween the N H(D) stretch ing and the first over tone of the N H(D) bend ing vi bra tions, and elec - tri cal anharmonicity. The ef fect of deuteration has been suc cess fully re pro duced by our model cal cu la tions. In fra red, far-in fra red, Raman and low-fre quency Raman spec tra of the polycrystalline 2,4-dithiouracil have been re corded. The ge om e try and ex per i men tal fre quen cies are com pared with the re sults of har monic and an har mon ic DFT cal cu la tions. Key words: 2,4-dithiouracil, hy dro gen bond, vi bra tional spec tra, quan tum-me chan i cal cal cu la tions

19 Pol ish J. Chem., 83, (2009) Nonconventional Hy dro gen Bond ing and Ver ti cal Elec tron De tach ment in An ionic Com plexes of Gold with DNA Bases: Few Es say ist ic Frag ments by E. S. Kryachko 1,2 1 Bogolyubov In sti tute for The o ret i cal Phys ics, Kiev-143, Ukraine 2 On leave from: De part ment of Chem is try, Uni ver sity of Liege, B-4000 Liege, Bel gium eu gene.kryachko@ulg.ac.be; e_kryachko@ya hoo.com (Re ceived Jan u ary 13th, 2009; ac cepted Feb ru ary 18th, 2009) The pres ent work per forms the com pu ta tional Gedanken ex per i ments on an ion pho to - elec tron spec tros copy for the com plexes [Au-DNA base] es tab lished be tween the auride an ion Au and the DNA bases thanks to the nonconventional hy dro gen bond where Au casts as the nonconventional pro ton ac cep tor. The fas ci nat ing phe nom e non of the pro ton ac cep tor char ac ter of Au to form a va ri ety of nonconventional hy dro gen bonds with the DNA bases is computationally un veiled in the pres ent work which also shed a light on the mech a nism of the ver ti cal elec tron de tach ments of [Au-DNA base] and their fur ther ac - cess of the ground elec tronic states of the neu tral par ent hood com plexes [Au-DNA base]. Key words: hy dro gen bond, gold, DNA bases, nonconventional hy dro gen bond, ver ti cal elec tron de tach ment

20 Pol ish J. Chem., 83, (2009) Diazene, a Po ten tial New Hy dro gen Bond Do nor and Ac cep tor with Blue-Shifted N H Stretch ing Modes: A The o ret i cal Study by A. Karpfen **, E. Liedl and P. Wolschann ** Uni ver sity of Vi enna, In sti tute for The o ret i cal Chem is try, Währinger Straße 17, A-1090 Vi enna, Austria **Cor re spond ing au thors: A. K. FAX: ; al fred.karpfen@univie.ac.at; P. W. FAX: ; pe ter.wolschann@univie.ac.at (Re ceived Jan u ary 21st, 2009; ac cepted Feb ru ary 3rd, 2009) The struc ture and vi bra tional spec tra of hy dro gen-bonded com plexes formed be tween trans-hnnh (diazene or diimide) and the fluoromethanes CH 3 F, CH 2 F 2, and CHF 3 are stud ied at the MP2/ G(2d,2p) level. For each fluoromethane, com plex struc tures were de tected in which diazene plays ei ther the role of a hy dro gen bond do nor or a hy dro - gen bond ac cep tor. In ad di tion to the well-known blue shifts of the fluoromethane C H stretch ing fre quen cies, blue-shifted N H stretch ing fre quen cies are pre dicted for the diazene mol e cule, ir re spec tive of whether HNNH acts as do nor or ac cep tor. It is shown that this find ing can be in ter preted as a con se quence of the neg a tive intramolecular cou - pling (NIC) be tween N N and N H stretch ing de grees of free dom in the iso lated HNNH mol e cule which, upon com plex for ma tion, leads to a neg a tive intramolecular re sponse (NIR). Key words: blue-shift, hy dro gen bond, diazene, MP2, N H stretch

21 Pol ish J. Chem., 83, (2009) In fra red Ma trix Iso la tion and The o ret i cal Study of Methylglyoxal by M. Mucha, M. Sa³dyka and Z. Mielke ** Fac ulty of Chem is try, Uni ver sity of Wroc³aw, F. Joliot-Cu rie 14, Wroc³aw, Po land ** zm@wchuwr.pl (Re ceived Jan u ary 24th, 2009; ac cepted Feb ru ary 14th, 2009) Methylglyoxal (MG) was stud ied by ma trix-iso la tion IR spec tros copy sup ported by MP2/ G(2d,2p) cal cu la tions. The ex per i men tal re sults show that the mol e cule ex ists in the trans con for ma tion (C s sym me try). The trans-mg iso mer is es ti mated to lie 4.96 kcal/mol be low the cis-mg iso mer and the ro ta tional bar rier is 5.48 kcal/mol on the ground-state path way from trans- to cis-mg. The spec tra ev i dence for ma tion of weak mo lec u lar MG N 2 com plexes when the ar gon ma trix is doped both with MG and N 2. Key words: methylglyoxal, in fra red spec tra, ma trix iso la tion, ab in itio cal cu la tions

22 Pol ish J. Chem., 83, (2009) As sem bly of Protonated Tetramethylpyrazine (TMP) in Triiodide. Vi bra tional Spec tra and DFT Sim u la tions by L. Sobczyk 1, G. Bator 1**, W. Sawka-Dobrowolska 1, J. Nowicka-Scheibe 2, E. Grech 2 and A. Pawlukojæ 3 1 Fac ulty of Chem is try, Uni ver sity of Wroc³aw, Joliot-Cu rie 14, Wroc³aw, Po land ** gb@wchuwr.pl 2 Department of Inor ganic and Analytical Chem is try, West Pomeranian Uni ver sity of Tech nol ogy, Piastów Al. 12, PL Szczecin, Po land 3 In sti tute of Nu clear Chem is try and Tech nol ogy, Dorodna 16, War saw, Po land (Re ceived Jan u ary 26th, 2009; ac cepted March 2nd, 2009) In the com plex of tetramethylpyrazine (TMP) with HI 3 two protonated mol e cules of TMP form the as sem bly of com po si tion (TMP H + ) 2 TMP(I 3 ) 2. The X-ray struc ture, de ter mined at 100 K, shows the + N-H N hy dro gen bonds mark edly shorter than those found pre vi - ously [13] at room tem per a ture (2.828 vs Å). The DFT cal cu la tions for iso lated cat ion yield the value of Å that re flects the soft ness of the hy dro gen bond po ten tial. The cal cu la tions of vi bra tional fre quen cies for crys tal line state re flect very well the IR spec tra. This re lates par tic u larly to the (NH + ) mode. A re mark able dis crep ancy is ob - served when cal cu la tions are per formed for iso lated as sem blies. Key words: protonated tetramethylpyrazine, complexation, vi bra tional spec tra, DFT cal cu la tions

23 Pol ish J. Chem., 83, (2009) Blue and Red Fre quency Shift Ef fects Re lated with XA H B Y Com plex For ma tion by K.S. Rutkowski 1**, A. Karpfen 2, S.M. Melikova 1 and P. Rodziewicz 3 1 Department of Physics, St. Petersburg University, Uljanovskaja 1, St. Pe ters burg, Rus sian Fed er a tion **e- mail: rutkowsk@molsp.phys.spbu.ru 2 University of Vienna, Institute of Theoretical Chemistry, Währinger Strasse 17, A-1090 Vienna, Austria 3 Interdisziplinaeres Zentrum fuer Molekulare Materialien (ICMM) und Com puter-chemie-centrum (CCC), Department Chemie und Pharmazie, Friedrich-Alexander-Universitaet, Erlangen-Nuernberg, Naegelbachstr. 25, D Erlangen, Ger many (Re ceived Feb ru ary 4th, 2009; ac cepted Feb ru ary 23rd, 2009) Re sults of FTIR spec tro scopic mea sure ments in cryosolutions and ab in itio cal cu la tions per formed for a set of com plexes sta bi lized by con ven tional and im proper H-bonds have been pre sented and an a lyzed. The main at ten tion is paid to the blue and red fre - quency shift ef fects on the stretch ing vi bra tions which were ob served/or pre dicted for com plexes of a weak to me dium strength, formed be tween so called CH ac ids and var i ous elec tron do nor coun ter parts. It has been shown that the fea tures of the di pole mo ment func tion and the type of intramolecular cou pling be tween the vic i nal bonds of the in - ter act ing coun ter parts pre de fine in the most ex tent the sign of the fre quency shift of re spec tive stretch ing vi bra tions. Key words: hy dro gen bond, CH B in ter ac tions, blue and red shifts, liq uid phase

24 Pol ish J. Chem., 83, (2009) Syn the sis, Pharmacological Properties, and Com pu ta tional Study of 1-[3-(4-Aryl-1-piperazinyl)]propyl De riv a tives of Amides of 7-Methyl-3-phenyl-2,4-dioxo-1,2,3,4- tetrahydropyrido[2,3-d]py rim i dine-5-carboxylic Acid by A. Sabiniarz 1**, H. Œladowska 1, J. Sapa 2, B. Filipek 2, M. Dudek 2, G. Godyñ 2 and J. yta 3 1 De part ment of Chem is try of Drugs, Wroc³aw Uni ver sity of Med i cine, Tamka 1, Wroc³aw, Po land ** fastola@poczta.onet..pl; aska_sklo@o2.pl 2 Laboratory of Pharmacological Screening, Faculty of Pharmacy, Jagiellonian University, Collegium Medicum, Medyczna 9, Kraków, Po land 3 Fac ulty of Chem is try, Uni ver sity of Wroc³aw, Joliot-Cu rie 14, Wroc³aw, Po land (Re ceived Feb ru ary 13th, 2009; ac cepted March 8th, 2009) Two se ries of novel 1-[3-(4-aryl-1-piperazinyl)]- and 1-[2-hydroxy-3-(4-aryl-1- pipera - zinyl)]propyl de riv a tives of amides of 7-methyl-3-phenyl-2,4-dioxo- 1,2,3,4- tetra hydro - pyrido[2,3-d]py rim i dine-5-carboxylic acid (32 46) were syn the sized. In the writh ing syn drome test all the amides stud ied dis played an al ge sic ac tion. The most po tent ef fect was pro duced by com pounds 32, 34, and 46. In the hot plate test only two amides, 34 and 37, showed strong an al ge sic ac tiv ity. Fur ther more, most of the in ves ti gated sub - stances sig nif i cantly sup pressed spon ta ne ous lo co mo tor ac tiv ity in mice and pro longed bar bi tu rate sleep of these an i mals. QSAR anal y sis of the 14 new and 14 ear lier de scribed com pounds was made. Key words: pyrido[2,3-d]py rimi dines, arylpiperazines, amides, an al ge sic ac tiv ity, SAR, 2D-QSAR anal y sis, sed a tive

25 Pol ish J. Chem., 83, (2009) Prin ci pal Com po nents Anal y sis of In fra red Spec tra of Liq uid Acetylacetone by B. Czarnik-Matusewicz, M. Matusiak-Kucharska and J.P. Hawranek ** Fac ulty of Chem is try, Uni ver sity of Wroc³aw, F. Joliot-Cu rie 14, Wroc³aw, Po land ** hjp@wchuwr.pl (Re ceived Feb ru ary 23rd, 2009; ac cepted March 22nd, 2009) The spec trum of the ab sorp tion in dex in the Mid-In fra red (MIR) re gion was de ter mined for intramolecularly hy dro gen-bonded liq uid acetylacetone from trans mis sion stud ies. In the MIR re gion very thin lay ers with thick nesses of a few mi crom e ters had to be used to ob tain re li able data. The keto-enol tau to meric equi lib rium in the pure liq uid was stud ied by Prin ci pal Com po nents Anal y sis (PCA) of a set of tem per a ture de pend ent MIR spec tra in the range from 25 to 75 C. Iden ti fi ca tions for nu mer ous bands ob served in the liq uid phase were pro posed bas ing on the re sults ob tained by means of the sep a ra tion ob tained in the load ings plot. Key words: thin film in fra red spec tra, acetylacetone, hy dro gen bond ing, Prin ci pal Com po nents Analysis

26 Pol ish J. Chem., 83, (2009) Non-Em pir i cal Quan tum Chem i cal Stud ies on Hydration of trans- and cis-[pt(nh 3 ) 2 Cl 2 ]. Possible Role of Relativistic Effects by H. Chojnacki 1,**, J. Kuduk-Jaworska 2, I. Jaroszewicz 2 and J.J. Jañski 2 1 Institute of Physical and Theoretical Chemistry, Wroc³aw University of Technology, Wyb. Wyspiañskiego 27, Wroc³aw, Po land 2 Fac ulty of Chem is try, Wroc³aw Uni ver sity, F. Joliot-Cu rie 14, Wroc³aw, Po land ** Henryk.Chojnacki@pwr.wroc.pl (Re ceived Feb ru ary 25th, 2009; ac cepted March 22nd, 2009) The mo ti va tion to this work re sults from the rec og ni tion of cis-dia mminedi - chloroplatinum(ii) (cisplatin) hydration pro cesses as es sen tial for the fate of this drug in host or gan ism. Ap ply ing quan tum chem i cal cal cu la tions, there were eval u ated the first stages of wa ter mol e cule im pact on plat i num com plexes: cisplatin and its trans iso mer. Non-em pir i cal quan tum chem i cal cal cu la tions have been per formed for re ac tions of cisand trans-diamminedichloroplatinum(ii) (transplatin) with the wa ter mol e cule, as sum - ing the as so cia tive mode of re ac tions run ning with the ad di tion of a fifth ligand to a square pla nar d 8 com plex and for ma tion of a trigonal-bipyramidal struc ture of the tran si tion state. For the ob tained struc tures of re ac tants, tran si tion states, and prod ucts, the ther mo - dy namic char ac ter is tics (en er gies and Gibbs free en er gies) were es ti mated. Energetics for the ligand ex change re ac tions were es ti mated both in gas phase and wa ter so lu tion by us ing the PCM model. The hydration re ac tions un der con sid er ation are prin ci pally en do - ther mic ex cept of the solvated transplatin. Bas ing on our ab in itio ZORA cal cu la tions, the pos si ble role of rel a tiv is tic ef fects in the re ac tion mech a nism is pointed out as well. Ob - tained re sults may throw some light on pro cesses which de ter mine the in ter change of pro-drug (cisplatin) into ac ti vated drug (aqua-form) and im pli cate their sig nif i cance in de sign ing of anticancer, Pt-con tain ing chemotherapeutics. Key words: cisplatin, transplatin, in ter ac tions with wa ter mol e cule, quan tum chem i cal cal cu la tions, rel a tiv is tic ZORA calculations

27 Pol ish J. Chem., 83, (2009) REVIEW ARTICLE Hy dro gen Bond ing of An i lines: Ex per i men tal and The o ret i cal Stud ies of Com plexes of Various Compositions by V.E. Borisenko De part ment of Phys ics, Tyumen State Uni ver sity, Tyumen , Rus sian Fed er a tion v.e.borisenko@mail.ru (Re ceived Feb ru ary 27th, 2009; ac cepted March 15th, 2009) Re view of works on stud ies of the in flu ence of the po si tion, num ber and a kind of sub - stitu ents in phenyl ring of an i line on pro ton do nor abil ity in hy dro gen bond, spec tral, geo - met ric, electrooptic and force char ac ter is tics of amino group in com plexes with dif fer ent pro ton ac cep tors of 1:1 and 1:2 com po si tion in intra- and intermolecular hy - dro gen bonds is pre sented. The in flu ence of pro ton do nors and pro ton ac cep tors on the kind of cor re la tion be tween spec tral, geo met ric, force and electrooptic char ac ter is tics of the amino group is an a lyzed. Ob tained re sults dem on strate the pos si bil ity of quan ti - ta tive de scrip tion of the changes of dy namic, geo met ric, force and electrooptic prop er ties of amino group in sub sti tuted an i lines on pass ing from free mol e cules to bonded ones and ex tend the un der stand ing of the role of var i ous fac tors in the pro cess of mo lec u lar ag gre - ga tion. Key words: an i line de riv a tives, hy dro gen bonds, va lence an gles, force con stants, electrooptic pa ram e ters, equi lib rium con stants, enthalpy of com plexes, correlations