113 - Polskie Stowarzyszenie Biomateriałów

I N Ż Y N I E R I A B I O M A T E R I A Ł Ó WNumber 113Numer 113Volume XVRok XVAPRIL 2012KWIECIEŃ 2012ISSN 1429-7248PUBLISHER:WYDAWCA:Polish Societyfor Biomaterialsin KrakowPolskieStowarzyszenieBiomateriałóww KrakowieEditorialcommittee:KOMITETREDAKCYJNY:Editor-in-ChiefRedaktor naczelnyJan ChłopekEditorRedaktorElżbieta PamułaSecretary of editorialSekretarz redakcjiDesignProjektKatarzyna TrałaAugustyn PowroźnikADDRESS OFEDITORIAL OFFICE:ADRES REDAKCJI:AGH-UST30/A3, Mickiewicz Av.30-059 Krakow, PolandAkademiaGórniczo-Hutniczaal. Mickiewicza 30/A-330-059 KrakówIssue: 200 copiesNakład: 200 egz.Journal of Polish Society for Biomaterials and Faculty of Materials Science and Ceramics AGH-USTCzasopismo Polskiego Stowarzyszenia Biomateriałów i Wydziału Inżynierii Materiałowej i Ceramiki AGHScientific PublishingHouse AKAPITWydawnictwo NaukoweAKAPITe-mail: wn@akapit.krakow.pl

SPIS TREŚCICONTENTSEXPRESSION PATTERN OF HISTONE H3SUBTYPES IN ARTICULAR CHONDROCYTESA. Kulczycka, J. Orchel, A. Orchel,Z. Dzierżewicz, I. Bednarek 2Self-assembling Micelles Obtainedfrom PLLA/PEG and PDLA/PEG BlockCopolymers in Aqueous SolutionsX. WU, S. LI 6Synthesis and properties of bioresorbableand highly flexible 1,3-trimethylenecarbonate/ε-caprolactone copolymersM. Pastusiak, P. Dobrzyński, A. Smola, M. Sobota 9Development of innovative biopolymers designedfor bone regeneration applicationsand in vitro study of their biocompatibilityand osteogenic capacity on human bonemarrow mesenchymal stem cellsM. A. Basile, G. Gomez d’Ayala, P. Laurienzo,M. Malinconico, A. Oliva 13DEGRADATION ANALYSIS OF RADIOSENSITIZERCONTROL RELEASE SYSTEM BASED ON THENMR SPECTROSCOPYA. Buszman, J. Kasperczyk, J. Jaworska 16BIOCOMPATIBILITY OF L-LACTIDE-CO-GLYCOLIDE-CO-TRIMETHYLENE-CARBONATE SHAPE MEMORYTERPOLYMER WITH HUMAN CHONDROCYTESR. Kłosek, J. Komacki, A. Orchel, K. Jelonek,P. Dobrzyński, J. Kasperczyk, Z. Dzierżewicz 23Degradation process of TMC-basedpolymers by mass spectrometryJ. Jaworska, J. Kasperczyk, M. Maksymiak,G. Adamus, P. Dobrzyński 26Biomimetic Ca-P coatings obtained bychemical/electrochemical methodsfrom Hanks’ solution on a Ti surfaceM. Pisarek, A. Roguska, L. Marcon, M. Andrzejczuk 29A revised surgical concept of AnteriorCruciate Ligament replacementin a rabbit model.Preliminary investigationsK. Ficek, J. Wieczorek, E. Stodolak-Zych,Y. Kosenyuk 33Composite electrospun membranesstimulate mineralization in bonecell cultureI. Rajzer, E. Menaszek 35HARNESSING BIOPOLYESTERS IN THE DESIGNOF FUNCTIONAL MATERIALS FORBIOMEDICAL APPLICATIONSE. Renard, J. Babinot, P. Lemechko, J. Ramier,G. Vergnol, D. L. Versace, D. Grande, V. Langlois 19Wersja papierowa czasopisma „Engineering of Biomaterials / Inżynieria Biomateriałów” jest jego wersją pierwotnąPrinted version of „Engineering of Biomaterials / Inżynieria Biomateriałów” is a primary version of the journalWydanie dofinansowane przez Ministra Nauki i Szkolnictwa WyższegoStreszczane w Applied Mechanics ReviewsEdition financed by the Minister of Science and Higher EducationAbstracted in Applied Mechanics Reviews

EXPRESSION PATTERN OFHISTONE H3 SUBTYPES INARTICULAR CHONDROCYTESAnna Kulczycka 1 *, Joanna Orchel 2 , Arkadiusz Orchel 3 ,Zofia Dzierżewicz 3 , Ilona Bednarek 11Department of Biotechnology and Genetic Engineering,Medical University of Silesia,Narcyzów 1, 41-206 Sosnowiec, Poland2Department of Molecular Biology,Medical University of Silesia,Narcyzów 1, 41-206 Sosnowiec, Poland3Department of Biopharmacy,Medical University of Silesia,Narcyzów 1, 41-206 Sosnowiec, Poland* e-mail: a_kulczycka@wp.plAbstractThree-dimensional cell culture used for tissueengineering has its own rules and directions. Thereis a deficiency of proliferative markers suitable fortissue engineering research when cells are crosslinkedin network of fibers or suspended in hydrogel.It limits cell harvesting or impairs the flow to cell areaconventional chemicals used as proliferative markers.According to current published data, the expressionof replication-dependent histone H3 genes couldbe novel proliferative marker of cells. The intensivesynthesis of H3 histones is tightly correlated with DNAsynthesis and H3 mRNA is rapidly degraded when theS phase is completed or inhibited by cell cycle inhibitors.Based on this relation, non-dividing cells containno H3 mRNA. The aim of the study was to determineexpression pattern of replication-dependent H3 subtypesand tissue-specific H3/t subtype in normal humanconnective tissue cells. Analyzed cellular model waschondrocytes cell line due to the phenomenon thatarticular cartilage doesn’t have natural ability to healits injuries, consequently development of cartilageengineering is necessary. Evaluation of expressionpattern was performed using Reverse TranscriptionPCR and reaction products were visualized on the gelelectrophoresis. This study demonstrated that RT-PCRtechnique can be successfully used to study the expressionof different histone H3 subtypes. Presentedelectrophoregram showed differential expression ofthe analyzed subtypes (no expression of H3/g andH3/t subtypes). Incubation with sodium butyrate andquantitative Real Time PCR enabled quantificationof mRNA level of selected H3/d subtype. This partof study showed a significant reduction in the mRNAlevel of H3/d when the sodium butyrate was added.Obtained results indicated the possibility of using theexpression of individual histone H3 subtype as a newproliferative marker.Keywords: histone H3 subtypes, proliferative marker,chondrocytes, RT-PCR, sodium butyrate.[Engineering of Biomaterials 113 (2012) 2-5]Self-assembling MicellesObtained from PLLA/PEG andPDLA/PEG Block Copolymersin Aqueous SolutionsXiaohan WU, Suming LI*Max Mousseron Institute on Biomolecules, UMR CNRS5247, University Montpellier I, 34060 Montpellier, France* e-mail: lisuming@univ-montp1.frAbstractA series of polylactide-poly(ethylene glycol) (PLA-PEG) block copolymers were synthesized by ring-openingpolymerization of L- or D-lactide in the presenceof mono- or dihydroxyl PEG, using nontoxic zinc lactateas catalyst. Micelles were then prepared by directdissolution of the obtained copolymers in aqueousmedium without heating or using any organic solvents.Aqueous gel permeation chromatography and dynamiclight scattering measurements were carried out tocharacterize the resulting micelles. Generally, mixedmicelles containing both PLLA/PEG and PDLA/PEGcopolymers appear lager and more compact comparedto single ones. However, the size of mixed micellesis smaller than that of single ones which exhibit an anisotropicstructure since stereocomplexation disfavorsthe formation of anisotropic micelles. The copolymerparameters such as structures, molar mass and PEGfraction strongly influence the formation of anisotropicmicelles, and thus lead to various micellar sizes.Keywords: polylactide, poly(ethylene glycol), stereocomplexation,self-assembly, anisotropy[Engineering of Biomaterials 113 (2012) 6-8]

Synthesis and properties ofbioresorbable and highlyflexible 1,3-trimethylenecarbonate/ε-caprolactonecopolymersMałgorzata Pastusiak, Piotr Dobrzyński*, Anna Smola,Michał SobotaPolish Academy of Sciences,Centre of Polymer and Carbon Materials,34 Sklodowska-Curie Street, 41-819 Zabrze, Poland* e-mail: pdobrzynski@cmpw-pan.edu.plAbstractEthyl etoxy zinc (II) has been prepared and emergedas very effective initiators for ring-opening polymerizationof 1,3-trimethylene carbonate (TMC) and itscopolymerization with ε-caprolactone (CL) to producehigh molar mass polymers. The copolymerization ofTMC and CL was performed in bulk at 120°C. Theobtained copolymers were characterized by multiblockmicrostructure. The highest reactivity rate was demonstratedby trimethylene carbonate in comparison withε-caprolactone monomer. The thermal and mechanicalproperties of the copolymers were strongly dependenton the monomer composition. Preliminary tests ofmonomers copolymerization using reactive extrusionyielded positive result.Keywords: copolymerization, caprolactone, trimethylenecarbonate, bioresorbable polymers[Engineering of Biomaterials 113 (2012) 9-12]Development of innovativebiopolymers designedfor bone regenerationapplications and invitro study of theirbiocompatibility andosteogenic capacityon human bone marrowmesenchymal stem cellsMaria Assunta Basile 1 *, Giovanna Gomez d’Ayala 2 ,Paola Laurienzo 2 , Mario Malinconico 2 , Adriana Oliva 11Department of Biochemistry and Biophysics,Second University of Naples,Via De Crecchio 7, 80138 Naples, Italy2Institute of Chemistry and Technology of Polymers,Via Campi Flegrei 34, 80078 Pozzuoli, Italy* e-mail: mariaassunta.basile@unina2.itAbstractIn the frame of a project aiming to the improvementof the properties of biodegradable polyester-baseddevices, designed for bone regeneration, we haveprepared and characterized novel composites basedon poly(ε-caprolactone) (PCL). In particular, we reportin this paper the functional changes made throughradical grafting on PCL to obtain the less hydrophobicderivatives, PCL-MA-GMA [maleic anhydride (MA)-glycidylmethacrylate (GMA)] and PCL-DMAEA [N-(dimethyl-amino)ethylacrylate].In addition, we studied invitro the biocompatibility and the osteogenic capacityof these novel polyesters on human bone marrow (BM)mesenchymal stem cells (MSC).Keywords: functionalization of poly(ε-caprolactone),bone marrow mesenchymal stem cells.[Engineering of Biomaterials 113 (2012) 13-15]

DEGRADATION ANALYSIS OFRADIOSENSITIZER CONTROLRELEASE SYSTEM BASED ONTHE NMR SPECTROSCOPYAndrzej Buszman 1 *, Janusz Kasperczyk 1,2 ,Joanna Jaworska 11Centre of Polymer and Carbon Materials PAS,M. Curie-Skłodowskiej 34 St., 41-819 Zabrze, Poland2Department of Biopharmacy,School of Pharmacy and Division of Laboratory Medicine,Medical University of Silesia,Narcyzów 1 St., 41-200 Sosnowiec, Poland* e-mail: abuszman@cmpw-pan.edu.plAbstractThe degradation process of multilayer radiosensitizerreleasing systems was conducted and examinedvia the nuclear magnetic resonance spectroscopy.Copolymers of glycolide and lactide with differentchain microstructure were used as biocompatible drugcarriers. Metronidazole was used as radiosensitizer.The changes of copolymers chain microstructure weremonitored during 16 weeks of hydrolytic degradationof material in artificial Cerebro-spinal Fluid Solution.This study shows distinct differences in the rate ofcopolymer degradation and changes of the degreeof randomness, directly connected with the type ofcomonomers and the comonomeric molar ratio. During16 weeks of hydrolytic degradation, copolymers withL-lactidyl units remain resistant to hydrolysis whilematerials with D,L-lactidyl units are completely degraded.Examined materials can be used as carriers ofagents for different types of short-, mid- and long-termtherapies based on control release systems.Keywords: biodegradable polyesters, NMR spectroscopy,hydrolytic degradation, polymeric chainmicrostructure[Engineering of Biomaterials 113 (2012) 16-18]HARNESSING BIOPOLYESTERSIN THE DESIGN OF FUNCTIONALMATERIALS FOR BIOMEDICALAPPLICATIONSEstelle Renard, Julien Babinot, Pierre Lemechko,Julien Ramier, Gwenaelle Vergnol, Davy Louis Versace,Daniel Grande, Valerie Langlois*1Institut de Chimie et des Matériaux Paris Est,UMR 7182 CNRS- Université Paris Est Créteil,94320 Thiais, France* e-mail: langlois@icmpe.cnrs.frAbstractThe present contribution illustrates the versatilityof poly(3-hydroxyalkanoate)s (PHAs) in the design ofa wide variety of biodegradable and/or biocompatiblemacromolecular architectures with controlled degradability.Firstly, functionalized PHAs were preparedfrom unsaturated PHAs. Pendant double bonds havebeen turned into carboxyl, hydroxyl, alkyne or epoxygroups. These reactive functions were used for furthergrafting hydrolyzable polylactide (PLA) or poly(ε-caprolactone)(PCL) as well as hydrophilic poly(ethyleneglycol) (PEG). Additionally, block copolymers with aPLA, PCL or PEG segment have been prepared byring-opening polymerization or “click” chemistry froma PHA oligomeric macroinitiator. Functional PHAs representbiodegradable aliphatic polyesters with manypossibilities to tune physico-chemical characteristics,such as hydrophilicity and degradation rate, thus makingthe resulting materials suitable as devices for drugdelivery or as scaffolds for tissue engineering. Herein,we address the recent trends in the synthesis of thesepolymeric materials and their applications in controlleddrug delivery and tissue engineering.Keywords: poly(3-hydroxyalkanoate)s, block andgraft copolymers, drug delivery, tissue engineering[Engineering of Biomaterials 113 (2012) 19-22]

BIOCOMPATIBILITY OFL-LACTIDE-CO-GLYCOLIDE-CO-TRIMETHYLENE-CARBONATESHAPE MEMORY TERPOLYMERWITH HUMAN CHONDROCYTESRafał Kłosek 1 *, Jakub Komacki 1 , Arkadiusz Orchel 1 ,Katarzyna Jelonek 2 , Piotr Dobrzyński 2 ,Janusz Kasperczyk 1,2 , Zofia Dzierżewicz 11Department of Biopharmacy,School of Pharmacy and Division of Laboratory Medicine,Medical University of Silesia, Katowice2Centre of Polymer and Carbon Materials PAS, Zabrze* e-mail: rafalklosek@gmail.comAbstractBiomedical application of biodegradable shape memoryterpolymers obtained from L-lactide, glycolide,trimethylene carbonate (TMC) have been intensivelyinvestigated in recent years. All applicable biomedicalmaterials must be biocompatible, which meansthat they cannot cause toxic, cytotoxic, allergic, orcarcinogenic reactions. The first study evaluating thebiocompatibility of the material is determination of itscytotoxicity.The purpose of this study was to assess the biocompatibilityof poly(L-lactide-co-glycolide-co-trimethylene-carbonate)75:13:12, synthesized using Zr(Acac) 4as an initiator of polymerization. The terpolymer wasdegraded for 30, 60 and 90 days at 37şC in water.The effect of degradation products on the growth ofhuman articular chondrocytes was determined usingthe sulforhodamine B assay. The examined terpolymerwas characterized by means of NMR spectroscopy,GPC and DSC. The results showed that the studiedterpolymer was biocompatible with tested cells.Keywords: Shape-memory polymers (SMP), biodegradablepolymers, cytotoxicity, degradation products,in vitro, biocompatibility of terpolymer[Engineering of Biomaterials 113 (2012) 23-25]Degradation process ofTMC-based polymers bymass spectrometryJoanna Jaworska*, Janusz Kasperczyk, MagdalenaMaksymiak, Grażyna Adamus, Piotr DobrzyńskiCentre of Polymer and Carbon Materials,Skłodowskiej- Curie 34 st., 41-819 Zabrze, Poland* e-mail: maciejowska@wp.plAbstractThis paper presents results of degradation processinvestigations of resorbable poly(lactide-trimethylenecarbonate). Materials used in this work were synthesizedby the ring opening polymerization. Polymerizationwas carried out in bulk using Zr(acac) 4 as initiator. Theresulting copolymers were characterized by high resolutionNMR spectroscopy. Then the copolymers wereallowed to degrade in H 2 O for 53 weeks. These conditionsallowed to analyze the degradation products ofpoly(lactide-trimethylene carbonate) and to determinethe structure of oligomers using multi-stage massspectrometry technique (ESI-MS n ). ESI-MS analysisrevealed the presence of two kinds of oligomers.[Engineering of Biomaterials 113 (2012) 26-28]

Biomimetic Ca-P coatingsobtained by chemical/electrochemical methodsfrom Hanks’ solutionon a Ti surfaceM. Pisarek 1 *, A. Roguska 1,2 , L. Marcon 3 , M. Andrzejczuk 21Institute of Physical Chemistry, Polish Academy of Sciences,Kasprzaka 44/52, 01-224 Warsaw, Poland2Faculty of Materials Science and Engineering,Warsaw University of Technology,Woloska 141, 02-507 Warsaw, Poland3Interdisciplinary Research Institute,USR CNRS 3078 Parc de la Haute Borne,50 av. de Halley 59658 Villeneuve d’Ascq, France* e-mail: mpisarek@ichf.edu.plAbstractThe purpose of this study was to investigate thebioactivity of porous calcium phosphate coatings ontitanium prepared using a two-step procedure (chemicaletching or anodic oxidation of Ti followed by soakingin simulated body fluid or direct electrodepositionfrom Hanks’ solution). In order to evaluate the potentialuse of the coatings for biomedical applications, theadsorption of serum albumin, the most abundantprotein in the blood, and the attachment of living cells(osteoblasts, U2OS) were studied.Keywords: biomaterials, biomimetic, surface analysis,protein adsorption, U2OS cells[Engineering of Biomaterials 113 (2012) 29-32]A revised surgical conceptof Anterior CruciateLigament replacementin a rabbit model.Preliminary investigationsKrzysztof Ficek 1 *, Jarosław Wieczorek 2 ,Ewa Stodolak-Zych 3 , Yuriy Kosenyuk 21Galen - Orthopaedics,6 Jerzego St., 43-150 Bierun, Poland2National Research Institute of Animal Production,Department of Biotechnology Reproduction Animals,1 Krakowska St., 32-083 Balice, Poland3AGH University of Science and Technology,Faculty of Materials Science and Ceramics,Department of Biomaterials,30 Mickiewicz Av, 30-059 Krakow, Poland* e-mail: galen@galen.plAbstractIn this project the anterior cruciate ligament (ACL)replacement in a rabbit model was performed forthe preclinical phase of investigations of a new formof biomaterial i.e. polymer beads (granules). Thismaterial, based on resorbable aliphatic polyester(polylactide - PLA) was used as a filler of the bonetunnels to enhance tendon-to-bone healing. The highspecific surface area and well known biocompatibilityof this material designated it as an osteoconductiveagent in reconstructive ligament surgery. Additionally,a new surgical concept was proposed which retainsthe natural elasticity of the harvested tendon. Thismethod ensures fixation of the grafted tendon withinthe bone tunnels in their entire length.Keywords: ACL reconstruction, tendon implant,resorbable material[Engineering of Biomaterials 113 (2012) 33-34]

Elektroprzędzone membranykompozytowe stymulująmineralizację w hodowlachkomórek kostnychIzabella Rajzer 1 *, Elżbieta Menaszek 2Composite electrospunmembranes stimulatemineralization in bonecell cultureIzabella Rajzer 1 *, Elżbieta Menaszek 21ATH Akademia Techniczno-Humanistyczna w Bielsku-Białej,Wydział Nauk o Materiałach i Środowisku,Instytut Inżynierii Tekstyliów i Materiałów Polimerowych,ul. Willowa 2, 43-309 Bielsko-Biała2UJ Uniwersytet Jagielloński, Collegium Medicum,Zakład Cytobiologii,ul. Medyczna 9, 30-068 Kraków* e-mail: irajzer@ath.bielsko.plStreszczenieBiodegradowalne nanowłókniste membrany poddanobadaniom in vitro, pozwalającym na ocenę stopniaróżnicowania się i mineralizacji komórek kostnych wobecności potencjalnych podłoży tkankowych. Przedstawionebadania oceniają wpływ mikrostruktury i składuchemicznego wytworzonych podłoży na przyczepność,proliferację i morfologię osteoblastów (NHOst).Badania procesu mineralizacji i aktywności ALP pozwoliłyna ocenę procesu różnicowania się komórek.Słowa kluczowe: podłoża dla inżynierii tkankowej,elektroprzędzone membrany, mineralizacja, różnicowaniekomórek[Inżynieria Biomateriałów 113 (2012) 35-39]1ATH University of Bielsko-Biala,Faculty of Materials and Environmental Sciences,Institute of Textile Engineering and Polymer Science,2 Willowa St., 43-309 Bielsko-Biala, Poland2UJ Jagiellonian University, Collegium Medicum,Department of Cytobiology,9 Medyczna St., 30-068 Krakow, Poland* e-mail: irajzer@ath.bielsko.plAbstractA biodegradable nanofibrous nonwoven membraneswere analyzed in vitro as potential scaffoldsfor differentiation and mineralization of bone cells.In this study we investigate the effects of electrospunmembranes microstructure and chemical compositionon attachment, proliferation, and morphology ofhuman NHOst osteoblasts. Mineralization processand ALP activity were studied to estimate the cellsdifferentiation.Keywords: scaffolds for tissue engineering, electrospunmembranes, mineralization, cell differentiation[Engineering of Biomaterials 113 (2012) 35-39]