PN-II-ID-PCE-2011-3-0164 (Program IDEI) - Nr.40/5.10.2011

- Increasing international visibility of the Photochemistry group by publishing of the derived results in international journals with high impact index

- Formation of young specialists in the field of organic and polymer synthesis with applications in producing of (nano)hybrid composites.

Main objectives:

•  Design and synthesis of new multifunctional monomers sensitive to UV irradiation, polymers and block copolymers – organic matrix for the incorporation of inorganic fillers

•  Preparation of metal nanoparticles, metal oxides and functionalized fillers, etc

•  Synthesis of new block copolymers by ATRP, microwaves

•  Establishing relationships between structure and properties, application perspectives.

Publications

Summary/ 2012

- A number of 16 organic-inorganic nanocomposites based on novel 10 photopolymerizable monomers, 4 hybrid nanocomposites of sol-gel type, and 3 hybrid composites with diblock copolymers, each containing Ag or Au nanoparticles (prior prepared or in situ via photochemical approach), and quartz or ZnO on the end-capped of diblock copolymer have been synthesized
- All monomers, polymers and nanocomposites were characterized by specific methods (NMR, FTIR, UV-vis, TEM, AFM, XPS, SEM/EDX, Zetasizer, raze X) to confirm the expected structure and their nanocharacteristics, in which the incorporated or in situ photogenerated nanoparticles presented different shapes (Au) and average sizes between 2 and 38 nm (Au, Ag)
- The results were reported in 5 papers (published) and 13 communications at national/international symposium
- Also, a PhD thesis that contains some of the above results was sustained (31.011.2012) in our institute (Dr. E.C. Buruiana –supervisor; Title: New acrylic polymers and block copolymers for photo(bio)applications) by Andreea L. Chibac (member of the project team).

Published papers /2012: 5 (FItotal: 15.94; SRItotal: 10.967)

1. T. Buruiana, V. Melinte, F. Jitaru, E.C. Buruiana, L. Balan, „Preparation of siloxane-based urethane dimethacrylates carrying carboxylic groups and the effect of silver nanoparticles on the proprties of composite polymer films”, J. Polym. Sci. Part A: Polym. Chem. 50, 874-883 (2012)

2. V. Melinte, T. Buruiana, L. Balan, E.C. Buruiana, „Photocrosslinkable acid urethane dimethacrylates from renewable natural oil and their use in the design of silver/gold polymeric nanocomposites”, React Funct. Polym. 72,252-259 (2012)

3.L. Balan, V. Melinte, T. Buruiana, R. Schneider, L. Vidal, „Controlling the morphology of gold nanoparticles synthesized photochemically in a polymer matrix through photonic parameters” Nanotechnology 23, 415705 (2012)

4. E.C. Buruiana, V. Podasca, T. Buruiana, „Synthesis of block copolymers derived from N-trityl-(S)-serine and pyrene end-labeled poly(methyl methacrylate) or poly(N-isopropylacrylamide) via ATRP”, J. Lumin. 132, 2704-2713 (2012)

5.A. Chibac, V. Melinte, T. Buruiana, L. Balan, E.C. Buruiana, „One-pot synthesis of photocrosslinked sol-gel hybrid composites containing silver nanoparticles in urethane-acrylic matrixes”, Chem. Eng. J. 200-202, 577-588 (2012)

Summary / December 2012 - June 2013

Our group taken in study the preparation of new cinnamate monomers/macromers to be used as co-monomers in photopolymerizable dental compositions, following mainly their photoreactivity by exposure to visible light (dental lamp) and some propertiesof the formed composites (water sorption, water solubility, mechanical parameters)
- Using a hybrid methacrylate (synthesized in lab.) in combination with cinnamate monomers, we investigated their copolymerization indused through UV irradiation (365 nm) or laser beam (775 nm, 200 femtoseconds) and characterized the resulting 2D hybrid structures in the presence or absence of ZnO nanoparticles (50-100 nm). For such hybrid scaffolds fluorescence properties were evidenced
- Also, nanoparticles and microfibers were obtained using electrospinning procedure of new block copolymers containing polycinnamate and polyadamantane/polymethacrylate blocks in solution.

Published papers december 2012 – june 2013: 3 (FI total: 5.473)

1. E.C. Buruiana, F. Jitaru, A. Matei, M. Dinescu, T. Buruiana, „Influence of UV irradiation and two photon processing on the cinnamate monomers polymerization and formation of hybrid composites with nanosized ZnO”, Eur. Polym. J. 48, 1976-1987 (2012)

2. E.C. Buruiana, F. Jitaru, V. Melinte, T. Buruiana, „Effect of Cinnamate Comonomers on the Dental Formulation Properties”, J. Appl. Polym. Sci. 127, 2442-2452 (2013)

3. E.C. Buruiana, F. Jitaru, N. Olaru, T. Buruiana ”Preparing and structuring of block copolymers with cinnamate and adamantane moieties” Des. Monom. Polym. 16, 1-13(2013)

Comunications (Oral/Poster) 2013: 1

1. Evaluation of new dimethacrylates used in formation of polymer composites with gold nanoparticles, A. L. Chibac, V. Melinte, T. Buruiana, E.C. Buruiana, 11-th Conference on Colloid and Surface Chemistry,Petru Poni Institute of Macromolecular Chemistry, Iasi, May 9-11, 2013.

Comunications (Oral/Poster) 2012: 13 (4/9)

1. Effect of photopolymerizable urethane dimethacrylates of quaternary type on the properties of dental composites; T. Buruiana, V. Melinte, E.C. Buruiana, POLYCHAR 20 - 20th World Forum on Advanced Materials, March 26-30, 2012, Dubrovnik, Croatia

2. Synthesis and properties of block copolymers with cinnamate units and end capped ZnO; F. Jitaru, E. C. Buruiana,T. Buruiana, A XXXII-a Conferinta Nationala de Chimie, 03-05 octombrie 2012, Calimanesti-Caciulata, Valcea

3. Synthesis of photosensitive amphiphilic block copolymers through modern methods of controlled radical polymerization; V. Melinte, T. Buruiana, A. Chibac, E.C. Buruiana, A XXXII-a Conferinta Nationala de Chimie, 03-05 octombrie 2012, Calimanesti-Caciulata

4. Synthesis of poly(vinyl acetate-co-4-acryloyloxybenzilidene-iminepyrene) and fluorescence study; V. E Podaşcă, E. C. Buruiană, Sesiunea de comunicări ştiinţifice organizată în cadrul Zilelor Universităţii "Alexandru Ioan Cuza”, 25-27 octombrie, 2012, Iasi

5. Synthesis of block copolymers with N-trityl(s)-serine and pyrene end-capped isopropylacrylamide and silver nanoparticles; E.C. Buruiana, Viorica Podasca, T. Buruiana, POLYCHAR 20 World Forum on Advanced Materials, March 26-30, 2012, Dubrovnik, Croatia

6. Photopolymerization of bis-cinnamates used as comonomers for dental resins and characterization of some composites; E.C. Buruiana, F. Jitaru, V. Melinte, T. Buruiana, XXIV IUPAC Symposion on Photochemistry, July 15-20, 2012, Coimbra, Portugal,

7. Preparation of hybrid acid dimethacrylates as photopolymerizable matrix for nanosilver particles; T. Buruiana, V. Melinte, F. Jitaru, L. Balan, E. C. Buruiana; XXIV IUPAC Symposion on Photochemistry, July 15-20, 2012, Coimbra, Portugal

8. Synthesis and characterization of photopolymerizable dental monomers containing phosphonated sequences; V. Melinte, T. Buruiana, E.C. Buruiana, POLYCHAR 20 - 20th World Forum on Advanced Materials, March 26-30, 2012, Dubrovnik, Croatia

9. Synthesis and Properties of Hybrid Composites based on Urethane Oligodimethacrylates and Noble Metal Nanoparticles; T. Buruiana, V. Melinte, A. Chibac, E.C. Buruiana, L. Balan, Vth International Conference on Molecular Materials (Molmat 2012), July 01 – 08, 2012, Barcelona, Spania

10. Fluorescent chemosensors based on pyrene-containing AB-type block copolymers; V. Melinte, T. Buruiana, A. Chibac, E.C. Buruiana, Vth International Conference on Molecular Materials (Molmat 2012), July 01-0.8, 2012, Barcelona, Spania

11. Effect of UV irradiation and two photon processing on the cinnamate monomers polymerization and formation of hybrid composites with micro/nanosized ZnO; E.C. Buruiana, F. Jitaru, A. Matei, M. Dinescu, T. Buruiana, Vth International Conference on Molecular Materials (Molmat 2012), July 01-08, 2012, Barcelona, Spania

12. Synthesis and properties control of hybrid composites derived from UV-curable urethane macromers and silver/gold nanoparticles; T. Buruiana, V. Melinte, F. Jitaru, L. Balan, E. C. Buruiana, 4th Bilateral Symposium on Functional Heterocylic and Heterochain Polymers for Advanced Materials, September 02-07, 2012, Iasi

13. Sinteza copolimerului poli(acetat de vinil-co-4-acriloiloxibenzaldehida) si modificarea acestuia cu unitati de piren; E.C. Buruiana, V. E. Podasca, A XXXII-a Conferinta Nationala de Chimie Calimanesti-Caciulata, 3-5 octombrie 2012, Valcea.