LABORATORY OF SUPRAMOLECULAR CHEMISTRY AND INTERPHASE PROCESSES

LABORATORY OF SUPRAMOLECULAR CHEMISTRY AND INTERPHASE PROCESSES

Research Team :

PhD Titus Constantinescu

PhD Petre Ionita

PhD Florica Spafiu

PhD Irina Cristina Covaci

PhD Alice Mihaela Mischie

Gabriela Manolescu, PhD Student

Ana-Cristina Radutiu, PhD Student

Elena-Nusa Hristea, PhD Student

Marioara Bem, PhD Student

Daniela Cristina Culita, PhD Student

Adrian Beteringhe, PhD Student

Madalina Tudose, PhD Student

Rodica Daniela Baratoiu, PhD Student

Anca Elena Barbu, PhD Student

Stefania Radulescu

Marin Marinescu

Rodica Tarboaca

Camelia Stancioiu

GENERAL PRESENTATION

The laboratory was created as GAS CHROMATOGRAPHY LABORATORY in 1972, then it became LABORATORY OF SEPARATION METHODS in 1980 and since 1990 the name has been SUPRAMOLECULAR CHEMISTRY AND INTERPHASES PROCESSES, all these changes being made according to the research topics.

During 1972-1990 period, we dealt with several practical, tehnological problems, such as: quality analysis, pollution agents, perfumes and aromas, fine synthesis and isolations of many natural products, biotechnology, etc. After 1990 the laboratory activity has turned to fundamental and advanced research: studies of interphasic processes mediated by crown ethers for some chemical species of practical and theoretical interest, obtaining of supramolecular complexes that include as partners crown ethers (already synthesised in our laboratory), alkali- metal cations or primary amines cations and pair anions synthesised from a molecular design already etablished. Another important accomplishment has been the synthesis through "interphasic-transfer" catalysis and creation of molecular design for some "intelligent compounds" with either unique or multiple specific properties. Other activities consist in the theoretical studies involving classic columns or glass capillary columns filled with already known stationary phases or synthesised in laboratory. The QSPR and QSAR studies are also an important part of present research activity.

The youngest members of the laboratory improve their knowledge and experimental skills through many post-graduate courses and PhD studies. The post-doc scholarships ensure specializations in different prestigious foreign universities.

Due to the nature of the researches and permanently improvement of the activity, the laboratory has collaboration relationships with Professor Alexandru T. Balaban from Texas A&M University USA, with the "Molecular Structure Laboratory" from this Institute, with the "RMN Department" from the "C.D. Nenitzescu" Institute of Organic Chemistry of Romanian Academy and with the Departments of Organic Chemistry, Analytical and Physical Chemistry from the Chemistry Faculty of University Bucharest and University "Politehnica" Bucharest. Collaboration with some Romanians companies ensure some supplementary funds for solving important research topics requested by those companies.

Doctoral activity:

Lucia Mutihac, "Aminoacids separation by liquid membranes", 1990.

Daniela Oana Popescu, "The active transport through liquid membranes miming biological membranes in the case of some biological active compounds", 1997

Petre Ionita, "Diphenylpicrylhydrazine derivatives type in the modelling of acid-basic and redox processes through interphasic transfer", 1997.

Adriana Zarna, "The complexes combinations of iodine with crown ethers involved in models of liquid membranes by biological interest. The iodination of tyrosine and simultaneous redox processes" 1998

Florica Spafiu, "New stationary phases of crown ethers type for gas chromatography with capillary columns", 1998.

Nicolae Zarna, "Structural and electronic implications about the physic-chemical properties of some compounds of N-Alcoxy-polynitroaniline derivatives type ", 1998.

Elena Puricel, "Thermodynamic measurements of some nonelectrolitical solutions obtained by gas chromatography", 1999.

Irina Cristina Covaci Cimpeanu, "New partners for achiral and chiral supramolecular complexes", 2000.

Ecaterina Tudor, "Structure-properties relations from kinetics, thermodynamic of solutions and retention data determinate through gas chromatography", 2000.

Alice Mihaela Mischie, "New nucleophylic processes involving macrociclyc ligands. Syntheses of organic derivatives with biological or biomedical interest", 2000.

Dana Gabriela Nourescu, "Supramolecular complexes of practically interest in the chemistry of some natural or synthetic compounds: steroid hormones and phenols", 2001.

Romanian Academy awards :

2000 – Romanian Academy "I. G. Murgulescu" award, Petre Ionita, "Hydrazyl free radicals, efficacy and perspective chemical compounds in the study and modelling of some physic – chemical compounds."

1991 – Romanian Academy "N. Teclu" award, Titus Constantinescu, Agneta Caragheorgheopol, Gabriela Stanciuc, Horia Caldararu, "Electronic structure of the aminyl radicals."

Publications:

2005

M. Tudose, P. Ionita, F. Dumitrascu, C. Draghici, M. T. Caproiu, I. C. Covaci, T. Constantinescu, M. D. Banciu and A. T. Balaban, "Synthesis and properties of dinitrobenzamido-TEMPO derivatives", Arkivoc, (iv), 2005, 225-237.

D. C. Culita, L. Patron, G. Marinescu and T. Constantinescu, Radostina Alexandrova and Gergana Raschova, "Coordination compounds with cholate anion as ligand. II. Coordination compounds of Cu(II), Co(II), Ni(II), Zn(II)", Rev. Roum. Chim., 50(9-10), 2005.

A. C. Radutiu, I. Baciu, M. T. Caproiu, P. Ionita, I. C. Covaci and T. Constantinescu, "Synthesis and properties of bis-dinitrophenyl derivatives of 1,7,10,16-tetraoxa-4,13-diazacyclooctadecane (Kriptofix 22)", Rev. Roum. Chim., 50(5), 2005, 341-347.

A. Beteringhe, "QSPR study on pK values of N-Methoxy-polynitroaniline derivatives", CEJC 3(4), 2005, 585-591.

A. Beteringhe, P. Filip and L. Tarko, "QSAR study for diaryiguanidines, noncompetitive NMDA receptor antagonists. A new topological index AAd derived from local invariants of the chemical graphs of diarylguanidines", Arkivoc, (x), 2005, 45-62, Issue in Honor of Professor Alexandru T. Balaban

R. Alexandrova, G. Rashkova, S. Slavov, M. Kirilova, G. Miloshev, E. Nikolova, D. Culita and L. Patron, "Cytotoxic and antiproliferative effects of Zn(II), Cu(II), Co(II) and La(III) complexes with cholic acid on human and animal tumor cell lines", XVII Congess of Anatomy with International Participation, Symposium of Imaging Anatomy, Hissar, Bulgaria, June, 10-12, 2005.

R. Alexandrova, T. Popova, G. Rashkova, S. Slavov, M. Alexandrov, M. Kirilova, G. Miloshev, Y. Martinova, E. Nikolova, D. Culita and L. Patron, "Study on antitumor and antimicrobial effects of Zn(II), Cu(II), Co(II) and La(III) complexes with cholic acid in vitro", 5th. International Symposium on Trace Elements in Human: New Perspectives, Athens, Greece, 13th – 15th October, 2005.

P. Ionita, B. C. Gilbert and V. Chechik, "Radical Mechanism of Place - Exchange Reaction of Au nanoparticles", Angew. Chemie Int. Ed., 44, 2005, 3720-3722.

P. Ionita, "Is DPPH Free Stable Radical a Good Scavenger for Oxigen Active Species?", Chemical Letters, 59, 2005, 11-16.

P. Ionita, A. Caragheorgheopol, B. C. Gilbert and V. Chechik, "Dipole-dipole interactions in spin-labeled Au nanoparticles as a measure of interspin distances", J.Phys.Chem. B, 109, 2005, 3734-3742.

2004

A. T. Balaban, S. C. Basak, A. Beteringhe, D. Mills and C. T. Supuran, "QSAR study using topological indices for inhibition of carbonic anhydrase II by sulfanilamides and Schiff bases", Molecular Diversity, 8, 2004, 401- 412.

A. Beteringhe and A. T. Balaban, „QSAR for toxicities of polychlorodibenzofurans, polychlorodibenzo-1,4-dioxins and polychlorodibenzobiphenyls", Arkivoc, (i), 2004, 163-182.

M. Bem, M. Vasilescu, M. T. Caproiu, C. Draghici, A. Beteringhe, T. Constantinescu, M. D. Banciu and A. T. Balaban, „Structural factors influencing the reaction rates of 4-aryloxy-7-nitro-benzofurazans with amino acids", CEJC, 2(4), 2004, 1-14.

V. Chechik, P. Ionita, B. C. Gilbert, A. Caragheorgheopol, H. Caldararu, H. Wellsted and A. Korte, "Spin-Labelled Au nanoparticles, Faraday Discussion", 125, 2004, 279-291.

F. Spafiu, V. Oprea and T. Constantinescu, „Application of glass capillary columns Chirasil-L-Val for gas chromatographic separation of the enantiomers of D,L-pantolactone and analysis of the calcium pantothenate", Rev. Roum. Chim., 49(2), 2004, 169-172.

2003

A. Beteringhe, I. Baciu, M. T. Caproiu, T. Constantinescu and A.T. Balaban, „O-Methyloximes of Testosterone and of 17 α-Methyltestosterone: TLC and QSPR of R_f Values, J. Planar Chromatography, 16, 2003, 268-270.

T. Constantinescu, P. Ionita, I. Chiorescu and G. Ionita, „Hydrazyl, Nitronyl, and Imino-Nitroxides: Synthesis, Properties and Reaction With Nitric Oxide and Nitrogen Dioxide", CEJC, 4, 2003, 465-476.

M. Bem, M. T. Caproiu, D. Stoicescu, T. Constantinescu and A.T. Balaban, „Synthesis of 4-aryloxy-7-nitrobenzofurazan Derivatives from 4-chloro-7-nitrobenzofurazan and Various Phenoxide Anions (Including Pharmaceuticals) in the Presence of Crown Ethers", CEJC, 3, 2003, 260-276.

M. Vasilescu, T. Constantinescu, M. Voicescu, H. Lemmetyinen and E. Vuorimaa, „Spectrophotometric Study of Luminol in Dimethyl Sulfoxide-Potassium Hydroxyde", J. Fluorescence, 13, 2003, 315-322.

I. C. Covaci, P. Ionita, M. T. Caproiu, R. Socoteanu, T. Constantinescu and A. T. Balaban, „1,3-bis(2,4,6-trinitrophenylaminooxy) propane and its 4-cyano-2,6-dinitrophenyl Congener: Synthesis and Properties", CEJC, 1, 2003, 57-68.

M. Bem, Daniela C. Culita, M. T. Caproiu, T. Constantinescu and M. D. Banciu, „Synthesis of 4-(4’-formylaryloxy)-7-nitrobenzofurazan derivatives from 4-chloro-7-nitrobenzofurazan and some formylphenols in the presence of crown ethers", Rev. Roum. Chim. 48(5), 2003, 387-392.

2002

E. N. Hristea, M. Hillebrand, M. T. Caproiu, H. Caldararu, T. Constantinescu and A. T. Balaban, "Scavenging the hydroxyl radical by 2,2-Diphehyl-1-picrylhydrazyl", Arkivoc, (ii,) 2002, 123-132, Issue in Honor of Professor Costin D. Nenitzescu

P. Ionita, A. Caragheorgheopol, B. C. Gilbert and V. Chechik, "EPR Study of a Place-Exchange Reaction on Au Nanoparticles: Two Branches of a Disulfide Molecule Do Not Adsorb Adjiacent to Each Other", J. Am. Chem. Soc., 124, 2002, 9048-9049.

M. Voicescu, M. Vasilescu, T. Constantinescu and A. Meghea, "On the luminiscence of luminol in DMSO in the presence of potassium superoxide-18-crown-6-ether and fluorescein", J. Luminiscence, 97, 2002, 60-67.

2001

I. C. Covaci, T. Constantinescu, M. T. Caproiu, H. Caldararu, P. Ionita and A. T. Balaban, "New Congeners of 1-Picryl-2-Phenyl-2-(para-picramidophenyl)-diazeniu betaine whose Picramido Groups Are Replaced by 4-Cyano-2,6-dinitrophenyl Analogs", Polish Journal Of Chemistry, 75 (10), 2001, 1427-1440.

P. Ionita, A. C. Whitwood and B. C. Gilbert, "Synthesis and characterisation of some novel hetero-diradicals containing linked hydrrazyl and aminoxyl (nitroxide moieties)", J. Chem. Soc. Perkin Trans 2, 9, 2001, 1453-1462.

G. Ionita, P. Ionita, V. E. Sahini and C. Luca, "Influence of cyclodextrins on the kinetics of oxidation of amino acids and BSA by hydrazyl radicals", J. Incl. Phenom. Macro. , 39(34), 2001, 269-271.

P. Ionita, M. T. Caproiu, H. Caldararu and G. Ionita, "Synthesis of new hydrazyl free radicals. Supramolecular complexes with crown ether and cyclodextrins", Rev. Roum. Chim. , 46, 2001, 363-369.

P. Ionita, M. T.Caproiu and C. Draghici, "Direct Amination Of 2,2-Diphenyl-1-Picrylhydrazine Through A Meisenheimer Complex", Rev. Roum. Chim., 46, 2001, 803-806.

P. Ionita, T. Constantinescu, H. Caldararu, G. Ionita and M. T. Caproiu, "Synthesis of new Hydrazyl Free Radicals. Supramolecular Complexes with Crown Ether and Cyclodextrins", Rev. Roum. Chim., 46, 2001, 363-370.

A. Mischie, F. Badea, M. T. Caproiu and T. Constantinescu, "The Synthesis of the New Chelating Compounds, 6-(Cholyloxymethyl)-3-Hydroxy-4H-Pyran-4-One and 6-[N-(1-Phenylethylsuccinamoyloxy) Methyl]-3-Hydroxy-4H-Pyran-4-One Through a Solid/Liquid Phase Transfer Procedure Mediated by 18Crown6 Ether", Rev. Roum. Chim., 46, 2001, 1067-1069.

A. Mischie, O. Maior, F. Badea, M. Vasilescu, A. Caragheorgheopol, H. Caldararu, R. Socoteanu, G. Pencu and T. Constantinescu, "Advanced Organic Materials. Esters of the Free Stable Radical 3-Carboxy-Proxyl Having Fluorescent or Complexing Properties", Rev. Roum. Chim., 46, 2001, 107-114.

D. Nourescu, E. N. Hristea, M. T. Caproiu, A. C. Radutiu, M. Vasilesc, M. Bem and T. Constantinescu, "Synthesis and properties of the new estrone and estradiol derivatives of C-3 phenoxy ether type involving a 4-nitrobenzofurazan moiety", Proc. Roum. Acad., Series B, 1, 2001, 7-11.

F. Spafiu, E. Tudor, V. Popa, T. Constantinescu, A. Stanciuc and C. Luca, "Gas chromatographic studies using glass capillary columns with naphtyl-azobenzo-crown ethers and related compounds as stationary phases", Rev. Roum. Chim., 46, 2001, 19-30.

F. Spafiu, G. Manolescu, S. Radulescu, C. Stancioiu, T. Constantinescu, "Gas chromatographic studies using glass capillary columns with naphtyl azocrown ethers and related compounds as stationary phases. Possible analytical applications", Rev. Roum. Chim., 46, 2001, 229-241.

2000

M. Olteanu, S. Geadau, A. Zarna and T. Constantinescu, "Supramolecular Structures at the Liquid/liquid interface. I Association of 18-Crown-6 and N-methoxy-picramide with bovine serum albumin in H₂O/CH₂Cl₂ diphazic system", Rev. Roum. Chim.,45, 2000, 369-374.

D. O. Popescu, P. Ionita, R. Socoteanu and M. T. Caproiu, "Syntesis of a new macrocyclic ligand containing two sulfonamide groups and a preliminary study of cation transport by this ligand", Rev. Roum. Chim. , 45, 2000, 357-360.

D. Nourescu, C. Luca, M. T. Caproiu, G. I. Pencu and T. Constantinescu, "Obtaintion of 17b -estradiol-17a -deuterium through stereoselective reduction of estrone, using NaBH₄ and LiBD₄ respectively in the presence of a crown ether", Rev. Roum. Chim., 45, 2000, 531-535.

M. Contineanu si E. N. Hristea, "Influenta modului de preparare a selenitului de magneziu asupra stabilitatii termice a speciilor paramagnetice formate radiolitic", Revista de Chimie, 51 (1), 2000, 45-50.

I. C. Covaci, T. Constantinescu, M. T. Caproiu, C. Luca and A. T. Balaban, "Solid Supramolecular Complexes of Potassium Salts of N-Methoxynitroaniline Derivatives and Methoxyamino-3,5-dinitropyridine with 18-Crown-6 Ether", Eur. J. Org. Chem., 2000, 3569-3573.

G. Ionita, V. E. Sahini, G. Semenescu and P. Ionita, "Kinetics of Oxidation of Amino Acids by some Free Stable Hydrazyl Radicals", Acta Chimica Slovenica, 47, 2000, 111-119.