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Laboratory 6. Inorganic Polymers
Head of laboratory: Dr. Maria CAZACU
Topics Team Main Results Research Groups
Group 6.1: Compounds, polymers and organic-inorganic materials with adaptive properties

Project manager: Dr. Maria CAZACU,

I. Amphiphilic organo-siloxane compounds. By chemical modification of the small-molecular or polymeric siloxanes with different hydrophilic functional groups, new materials are obtained, capable of self-assembly, a phenomenon that directs the final properties and applications. In particular, siloxane surfactants with synthetically adjustable surface properties are studied, capable of acting as nanoparticle stabilizers, micellar solubilizing agents, phase transfer agents, ligands for self-assembled metal complexes, etc.

II. Dielectric elastomers for application as active elements in electromechanical devices: sensors, actuators, electricity generators (33 articles published in the last 8 years occupying an important position among the research groups in this field worldwide).

Electromechanical actuators and enery generators
C. Tugui, G.T. Stiubianu, M.S. Serbulea, M. Cazacu, Silicone dielectric elastomers optimized by crosslinking pattern-a simple approach to high-performance actuators,
Polymer Chemistry 11 (19), 3271-3284, (2020), DOI: 10.1039/D0PY00223B

C. Ţugui, M.S. Serbulea, M. Cazacu, Preparation and characterisation of stacked planar actuators, Chem. Eng. J. 364, 217–225 (2019),
M. Asandulesa, V. E. Musteata, A. Bele, M. Dascălu, S. Bronnikov, C. Racleş, Molecular dynamics of polysiloxane polar-nonpolar co-networks and blends studied by dielectric relaxation spectroscopy, Polymer, 149, 73–84, (2018),
A. Bele, C. Ţugui, M. Asandulesa, D. Ionita, L. Vasiliu, G. Stiubianu, M. Iacob, C. Racles, M. Cazacu, Conductive stretchable composites properly engineered to develop highly compliant electrodes for dielectric elastomer actuators. Smart Materials and Structures, 27(10), 105005, (2018).
C. Racleş, M. Dascălu, A. Bele, V. Tiron, M. Asandulesa, C. Ţugui, A.L. Vasiliu, M. Cazacu, All-silicone elastic composites with counter-intuitive piezoelectric response, designed for electromechanical applications, J. Mater. Chem. C, 5(28), 6997–7010 (2017),
C. Ţugui; C. Ursu; L. Săcărescu; M. Asăndulesa; G. Stoian; G. Ababei, M. Cazacu, Stretchable energy harvesting devices: attempts to produce high-performance electrodes, ACS Sustain. Chem. Eng., 5, 7851-7858 (2017),
C. Ţugui, S. Vlad, M. Iacob, C.D. Vărgănici, L. Pricop, M. Cazacu, Interpenetrating poly(urethane-urea)–polydimethylsiloxane networks designed as active elements in electromechanical transducers; Polym. Chem., 7, 15, 2709-2719 (2016),
C. Ţugui, G. Stiubianu, M. Iacob, C. Ursu, A. Bele, S. Vlad, M. Cazacu, Bimodal silicone interpenetrating networks sequentially built as electroactive dielectric elastomers, J. Mater. Chem. C, 3, 8963 – 8969, (2015),

M. Iacob, A. Bele, X. Patras, S. Pasca, M. Butnaru, M. Alexandru, M. Cazacu, Preparation of new electroactive silicone composites and their testing as artificial muscles, Mater. Sci. Eng., C 43, 392-402, (2014),

B1. Instalaţie modulară şi procedeu pentru obţinerea generatoarelor polimerice stratificate; A. Bele, M. Cazacu, M. Neagu, M. Popescu, C. Racleş, G. E. Ioanid, nr. 132642 A0, 26.02.2018.
B2. Procedeu de obţinere a siliconilor coloraţi transparenţi, C. Racleş, M. Cazacu, Cererea de brevet de invenţie nr. A/01085/2017.
B3. D.M. Opriş [CH]; S. Dünki [CH]; C. Racleş [RO]; A. Bele [RO]; M. Cazacu [RO],  High permittivity polymers based on functionalized silicones, Zusammenfassung von WO2015/135086 (A1), 2015.
B4. Cazacu, M., Ştiubianu, G., Procedure to prepare room temperature vulcanization silicone rubber filled with lignin, Brevet de   Inventie cu numărul 00126477, 2013.

B5. Ignat, M., Zarnescu, G., Hamciuc, E., Hamciuc, C., Cazacu, M., Sava, I., Microactuator based on polymer Brevet RO 127096 A2, 2012.

III. Ligands and metal coordination structures by the use of siloxane and silane segments as highly flexible and hydrophobic substrates, spacers or terminations with strong impact especially on the conformation, surface, catalytic and biological properties of the resulting compounds. The number of such structures registered in the CCDC database is a modest one, being enriched with the over 100 structures registered by the team since 2011 (over 65 articles published by the team). For the advanced study of these compounds (magnetic, biological, catalytic properties) collaborations are established with groups from abroad (Austria, France, Slovakia, Serbia, Norway, USA, Spain, Portugal).

Metal complexes and coordination polymers with ligands having siloxane spacers

S. Shova, A. Vlad, M. Cazacu, J. Krzystek, A. Ozarowski, M. Malcek, L. Bucinsky, P. Rapta, J. Cano, J. Telser, V. Arion, Dinuclear manganese(III) complexes with bioinspired coordination and variable linkers showing weak exchange effects: a synthetic, structural, spectroscopic and computation study, Dalton Trans. (2019),
Crystal smectic E revisited for(E)-N-(biphenyl-4-ylmethylene)-4-butylaniline– mesomorphism, crystal structure and FTIR study; V. Cozan, M. Avadanei, S. Shova, M.-F. Zaltariov, Lyq. Cryst. 46, 492-501, (2019),

M.F. Zaltariov, M. Hammerstad, H. J. Arabshahi, K. Jovanovic, K. W. Richter, M. Cazacu, S. Shova, M. Balan, N. H. Andersen, S. Radulovic, J. Reynisson, K. K. Andersson,  V. B. Arion, New iminodiacetate−thiosemicarbazone hybrids and their copper(II) complexes are potential Ribonucleotide Reductase R2 inhibitors with high antiproliferative activity, Inorg. Chem. 56(6), 3532-3549 (2017),
C. Racleş, M.F. Zaltariov, M. Iacob, M. Silion, M. Avădănei, A. Bargan, Siloxane-based metal–organic frameworks with remarkable catalytic activity in mild environmental photodegradation of azo dyes. Appl. Catal. B: Environ., 205, 78–92 (2017), DOI: 10.1016/j.apcatb.2016.12.034
 M.F. Zaltariov, V. Vieru, M. Zalibera, M. Cazacu, N.M. R. Martins, L. M. D. R. S. Martins, P. Rapta, G. Novitchi, S. Shova, A. J. L. Pombeiro, V. B. Arion, A bis(μ-chlorido)-bridged Cobalt(II) complex with silyl-containing Schiff base as a catalyst precursor in the solvent-free oxidation of cyclohexane, Eur. J. Inorg. Chem. 4324-4334, (2017), DOI:10.1002/ejic.201700875
M.F. Zaltariov, M. Cazacu, L. Săcărescu, A. Vlad, G. Novitchi, C. Train, S. Shova, V.B. Arion, Oxime-bridged Mn6 clusters inserted in one-dimensional coordination polymer, Macromolecules, 49(17), 6163-6172 (2016),
M. Cazacu, S. Shova, A. Soroceanu, P. Machata, L. Bucinsky, M. Breza, P. Rapta, J. Telser, J. Krzystek, V. B. Arion, Charge and spin states in Schiff base metal complexes with a disiloxane unit exhibiting a strong noninnocent ligand character: synthesis, structure, spectroelectrochemistry, and theoretical calculations, Inorg. Chem. 54 (12), 5691–5706, (2015),
M.F. Zaltariov, M. Cazacu, S. Shova, A. Vlad, I. Stoica, E. Hamciuc, Hydrogen-bonded supramolecular polymers containing dimethylsilane groups: Synthesis, crystal structure and characterization, J. Polym.  Sci.  Part A: Polym. Chem.  50 (18), 3775-3787, (2012),

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