Professor Andrzej Duda In Memoriam

Przedstawiono najważniejsze osiągnięcia naukowe Profesora Andrzeja Dudy, wieloletniego Kierownika Zakładu Chemii Polimerów Centrum Badań Molekularnych i Makromolekularnych Polskiej Akademii Nauk. Profesor Duda opublikował ponad 100 prac naukowych, wygłosił kilkadziesiąt wykładów na zaproszenie, w tym także wykłady plenarne na prestiżowych konferencjach międzynarodowych. W niniejszym, krótkim omówieniu prac Profesora skupiliśmy się przede wszystkim na dwóch zagadnieniach, spośród których szczególnie pierwsze było według naszego przekonania głównym osiągnięciem, rozwiązującym ważny problem dotyczący kopolimeryzacji monomerów chiralnych. Profesor Duda, po raz pierwszy w chemii polimerów, ustalił że polimeryzacja chiralnych monomerów przebiega niezmiennie wobec katalizatorów achiralnych oraz chiralnych o takim samym znaku jak znak monomeru, natomiast zastosowanie katalizatora o odwrotnej chiralności pozwala na znaczne zmniejszenie szybkości polimeryzacji. Jest to zjawisko o zasadniczym znaczeniu w kopolimeryzacji, szczególnie kiedy chiralny monomer jest znacznie bardziej reaktywny niż drugi komonomer. Mniej szczegółowo omówiono inne osiągnięcia Profesora Andrzeja Dudy, dodano też pełną bibliografię Jego prac.This paper is describing major scientific achievements of the recently late Professor Andrzej Duda, Chairman of the Department of Polymer Chemistry of The Centre of Molecular and Macromolecular Studies of Polish Academy of Sciences. Professor Duda published over 100 scientific papers and has given several dozens of plenary and invited lectures at the scientific symposia. However, in the present paper, we are mostly describing accomplishment that all of us, and also Professor, have considered as his seminal work, that solved a long time controversial subject. Namely, how to influence reactivities of chiral monomers, using chiral catalysts. Professor Duda had shown, and this subject is mostly described, that reactivity of a chiral monomer can be unchanged (when compared with an achiral catalyst) when polymerized with catalyst of the same chirality and may be many times depressed (the feature highly valuable in several instances) when polymerized with a catalyst with an opposite chirality. This feature is very important in the copolymerization processes, when chiral monomer is much more reactive than the other comonomer. Besides, some other contributions of Professor Duda to Polymer Sciences are also, although briefly mentioned. Full list of papers is given in the second part of the paper

Pamięci Profesora Andrzeja Dudy

Przedstawiono najważniejsze osiągnięcia naukowe Profesora Andrzeja Dudy, wieloletniego Kierownika Zakładu Chemii Polimerów Centrum Badań Molekularnych i Makromolekularnych Polskiej Akademii Nauk. Profesor Duda opublikował ponad 100 prac naukowych, wygłosił kilkadziesiąt wykładów na zaproszenie, w tym także wykłady plenarne na prestiżowych konferencjach międzynarodowych. W niniejszym, krótkim omówieniu prac Profesora skupiliśmy się przede wszystkim na dwóch zagadnieniach, spośród których szczególnie pierwsze było według naszego przekonania głównym osiągnięciem, rozwiązującym ważny problem dotyczący kopolimeryzacji monomerów chiralnych. Profesor Duda, po raz pierwszy w chemii polimerów, ustalił że polimeryzacja chiralnych monomerów przebiega niezmiennie wobec katalizatorów achiralnych oraz chiralnych o takim samym znaku jak znak monomeru, natomiast zastosowanie katalizatora o odwrotnej chiralności pozwala na znaczne zmniejszenie szybkości polimeryzacji. Jest to zjawisko o zasadniczym znaczeniu w kopolimeryzacji, szczególnie kiedy chiralny monomer jest znacznie bardziej reaktywny niż drugi komonomer. Mniej szczegółowo omówiono inne osiągnięcia Profesora Andrzeja Dudy, dodano też pełną bibliografię Jego prac.This paper is describing major scientific achievements of the recently late Professor Andrzej Duda, Chairman of the Department of Polymer Chemistry of The Centre of Molecular and Macromolecular Studies of Polish Academy of Sciences. Professor Duda published over 100 scientific papers and has given several dozens of plenary and invited lectures at the scientific symposia. However, in the present paper, we are mostly describing accomplishment that all of us, and also Professor, have considered as his seminal work, that solved a long time controversial subject. Namely, how to influence reactivities of chiral monomers, using chiral catalysts. Professor Duda had shown, and this subject is mostly described, that reactivity of a chiral monomer can be unchanged (when compared with an achiral catalyst) when polymerized with catalyst of the same chirality and may be many times depressed (the feature highly valuable in several instances) when polymerized with a catalyst with an opposite chirality. This feature is very important in the copolymerization processes, when chiral monomer is much more reactive than the other comonomer. Besides, some other contributions of Professor Duda to Polymer Sciences are also, although briefly mentioned. Full list of papers is given in the second part of the paper

Stereocomplexed PLA microspheres: Control over morphology, drug encapsulation and anticancer activity

Lung cancer is the leading cause of cancer death because of smoking and air pollution. Therefore, new ideas should be provided for lung cancer treatment in which the delivery of anticancer drugs to the local tumor site can be achieved. For this purpose, we propose the use of stereocomplexed spherical microspheres with sizes between 0.5 and 10 mu m loaded with doxorubicin (DOX) to be administered through the nasal route. In order to gain control over the microsphere morphology, size, and drug loading capacity, we systematically studied the influence of the solvent used for preparation and the functionalization of their building blocks, namely poly-L-lactide (PLLA) and poly-D-lactide (PDLA) with blocked or unblocked L-proline moieties. We could demonstrate that DOX release is generally determined by the size of the microspheres. The antiproliferative activity of DOX released from the different microspheres was shown in vitro using the A549 lung cancer cell line as a model. Moreover, when in direct contact to the cancer cells, smaller microspheres were uptaken and could serve as a reservoir for local drug release. Our findings not only provide a novel strategy to prepare PLA microspheres with controllable morphology and release of anti-cancer drugs but also offer additional possibilities for the application of stereocomplexed particles in anticancer therapy, with suitable sizes for nasal administration.M. Brzezinski and M. Socka acknowledges for support from the National Science Centre Poland Grant DEC-2016/23/D/ST5/02458. S. Wedepohl and M. Calderon gratefully acknowledge financial support from Bundesministerium fur Bildung and Forschung (BMBF) through the NanoMatFutur award (13N12561) and IKERBASQUE-Basque Foundation for Science

Self-Assembly of Triblock Copolymers from Cyclic Esters as a Tool for Tuning Their Particle Morphology

This paper presents the effect of end groups, chain structure, and stereocomplexation on the microparticle and nanoparticle morphology and thermal properties of the supramolecular triblock copolyesters. Therefore, the series of the triblock copolymers composed of l,l- and d,d-lactide, trimethylene carbonate (TMC), and ε-caprolactone (CL) with isopropyl (<i>i</i>Pr) or 2-ureido-4-[1<i>H</i>]-pyrimidinone (UPy) end groups at both chain ends were synthesized. In addition, these copolymers were intermoleculary stereocomplexed by polylactide (PLA) blocks with an opposite configuration of repeating units to promote their self-assembly in various organic solvents. The combination of two noncovalent interactions of the end groups and PLA enantiomeric chains leads to stronger interactions between macromolecules and allows for alteration of their segmental mobility. The simple tuning of the copolymer microstructure and functionality induced the self-assembly of macromolecules at liquid/liquid interfaces, which consequently leads to their phase separation in the form of particles with diameters ranging from 0.1 μm to 10 μm. This control is essential for their potential applications in the biomedical field, where biocompatible and well-defined microparticles and nanoparticles are highly desirable

On the Mechanisms of the Effects of Ionizing Radiation on Diblock and Random Copolymers of Poly(Lactic Acid) and Poly(Trimethylene Carbonate)

This article demonstrates that ionizing radiation induces simultaneous crosslinking and scission in poly(trimethylene carbonate-co-d-lactide) diblock and random copolymers. Copolymer films were electron-beam (EB) irradiated up to 300 kGy under anaerobic conditions and subsequently examined by evaluation of their structure (FT-IR, NMR), molecular weight, intrinsic viscosities, and thermal properties. Radiation chemistry of the copolymers is strongly influenced by the content of ester linkages of the lactide component. At low lactide content, crosslinking reaction is the dominant one; however, as the lactide ratio increases, the ester linkages scission becomes more competent and exceeds the crosslinking. Electron paramagnetic resonance (EPR) measurements indicate that higher content of amorphous carbonate units in copolymers leads to a reduction in free radical yield and faster radical decay as compared to lactide-rich compositions. The domination of scission of ester bonds was confirmed by identifying the radiolytically produced alkoxyl and acetyl radicals, the latter being more stable due to its conjugated structure

Mechanistic investigation of N-isopropylacrylamide atom transfer radical polymerization in aqueous medium. 1 Experimental investigation

peer reviewe