Gel permeation chromatography methods in the analysis of lactide-based polymers

Tutkielman kirjallisuusosiossa tutustutaan polymeerikemian perusteisiin sekä erityisesti laktidipohjaisiin polymeereihin, niiden valmistamiseen, käyttökohteisiin ja analyysimenetelmiin. Kyseisiä polymeereja hyödynnetään esimerkiksi erilaisissa lääketieteellisissä sovelluksissa, mikä asettaa polymeer...

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Päätekijä: Nuuttila, Minna
Muut tekijät: Matemaattis-luonnontieteellinen tiedekunta, Faculty of Sciences, Kemian laitos, Department of Chemistry, Jyväskylän yliopisto, University of Jyväskylä
Aineistotyyppi: Pro gradu
Kieli:eng
Julkaistu: 2018
Aiheet:
Linkit: https://jyx.jyu.fi/handle/123456789/60101
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author Nuuttila, Minna
author2 Matemaattis-luonnontieteellinen tiedekunta Faculty of Sciences Kemian laitos Department of Chemistry Jyväskylän yliopisto University of Jyväskylä
author_facet Nuuttila, Minna Matemaattis-luonnontieteellinen tiedekunta Faculty of Sciences Kemian laitos Department of Chemistry Jyväskylän yliopisto University of Jyväskylä Nuuttila, Minna Matemaattis-luonnontieteellinen tiedekunta Faculty of Sciences Kemian laitos Department of Chemistry Jyväskylän yliopisto University of Jyväskylä
author_sort Nuuttila, Minna
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description Tutkielman kirjallisuusosiossa tutustutaan polymeerikemian perusteisiin sekä erityisesti laktidipohjaisiin polymeereihin, niiden valmistamiseen, käyttökohteisiin ja analyysimenetelmiin. Kyseisiä polymeereja hyödynnetään esimerkiksi erilaisissa lääketieteellisissä sovelluksissa, mikä asettaa polymeereille monia vaatimuksia esimerkiksi niiden hajoamisen suhteen. Polymeeriketjujen pilkkoutumista voidaan seurata esimerkiksi geelipermeaatiokromatografilaitteistolla (GPC), jonka toimintaperiaate esitetään. GPC:llä on mahdollista käyttää erilaisia tulosten analyysimenetelmiä, joita myös tarkastellaan (konventionaalinen kalibrointi, universaali kalibrointi ja triple detection –menetelmä). Lisäksi kirjallisuusosiossa tutustutaan viskometrian perusteisiin. Tutkielman kokeellisessa osassa (erikoistyö) tutkittiin GPC-laitteistolla laktidipohjaisia polymeerinäytteitä (PLLA, PLGA ja PLCL), jotka erosivat sisäisten viskositeettiensa ja näin myös moolimassojensa suhteen. Tarkoituksena oli tutkia, vaikuttiko analyysimenetelmä saatuihin tuloksiin. GPC:llä määritettiin näytteiden keskimääräiset molekyylimassat (Mn, Mp ja Mw) sekä polydispersiteetti (PD) ja tulokset analysoitiin kolmella eri menetelmällä (konventionaalinen kalibrointi, universaali kalibrointi I ja triple detection –menetelmä). Universaalissa kalibroinnissa käytettiin kirjallisuuden Mark-Houwinkin vakioita. Samalla selvitettiin triple detection -menetelmällä materiaalille ominaisia Mark-Houwinkin vakioita ja dn/dc-arvoja. Saadut tulokset olivat yleisesti verrattavissa kirjallisuusarvoihin ja niitä hyödynnettiin myös materiaalien keskinäisessä vertailussa. Lisäksi näytteiden sisäiset viskositeetit mitattiin mikroviskometrilla ja saadut tulokset olivat valmistajien ilmoittamien arvojen rajoissa. Samalla muodostettiin korrelaatio moolimassan ja sisäisen viskositeetin välille. Vertailtaessa eri menetelmillä analysoituja keskimääräisiä moolimassoja ja polydispersiteettejä havaittiin, että tuloksissa oli huomattavia eroja. Tästä syystä eri menetelmällä analysoidut GPC-tulokset eivät välttämättä olleet vertailukelpoisia. Lisäksi havaittiin, että universaalissa kalibroinnissa käytetyillä Mark-Houwinkin vakioilla oli suuri vaikutus saatuihin tuloksiin. Tuloksista huomattiin myös, että osa mitatuista parametreistä (muun muassa α-parametri) muuttui näytteiden sisäisen viskositeetin muuttuessa, joten tapa ilmoittaa vain yksi parametrin arvo riippumatta näytteen sisäisestä viskositeetista on kyseenalainen. Tämä on merkittävä huomio etenkin silloin, kun halutaan seurata polymeerin hajoamista. In the literary part of this Master’s thesis, the basics of polymer chemistry are discussed. Especially, the lactide-based polymers and their manufacturing routes are emphasized together with the applications and analyzing methods. These polymers are commonly used in the medical field and, for example, the degradation properties of the polymer are important to know to have an approval to use the material in medical devices. The follow-up of the degradation of those polymers can be performed by using gel permeation chromatography (GPC) device. The principles of the GPC are covered and also different ways to analyze the GPC data (the conventional calibration, triple detection, and universal calibration I method) are discussed. Additionally, the basics of viscometry are outlined. In the experimental part of this thesis, lactide-based polymer samples (PLLA, PLGA, and PLCL) with different inherent viscosities and thus with different molar masses were studied with the help of GPC. The target was to find out how the analyzing method affects the results. The measured average molar masses (Mn, Mp, and Mw) and polydispersity (PD) of the samples were determined with the universal calibration I, conventional calibration, and triple detection methods. In the universal calibration I method, the Mark-Houwink (M-H) parameters from the literature were utilized. Also, the material-specific M-H parameters together with the dn/dc values were calculated using the triple detection method. These parameters were generally comparable to the literature values and, with them, the comparison between the materials was performed. In addition, the inherent viscosities of the samples were measured with microviscometer and the results were in the ranges informed by the manufacturers. The correlation between molar mass and inherent viscosity was formed. When comparing the molar mass average and PD results, it could be seen that there was a notable difference in the results analyzed with different methods. For this reason, the results obtained from different methods were not necessarily comparable. There was also a notable difference observed when the results were analyzed twice with the universal calibration I method but with different M-H parameters. Therefore, the M-H parameters greatly affected the results. Also, a correlation between the inherent viscosity and some measured values (such the M-H α parameters) was observed. Thus, convention to inform only one value for the material ignoring the inherent viscosity is questionable. This is noteworthy, especially when the degradation of the polymers is on focus.
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Kyseisi\u00e4 polymeereja hy\u00f6dynnet\u00e4\u00e4n esimerkiksi erilaisissa\nl\u00e4\u00e4ketieteellisiss\u00e4 sovelluksissa, mik\u00e4 asettaa polymeereille monia vaatimuksia esimerkiksi niiden hajoamisen suhteen. Polymeeriketjujen pilkkoutumista voidaan seurata esimerkiksi geelipermeaatiokromatografilaitteistolla (GPC), jonka toimintaperiaate esitet\u00e4\u00e4n. GPC:ll\u00e4 on mahdollista k\u00e4ytt\u00e4\u00e4 erilaisia tulosten analyysimenetelmi\u00e4, joita my\u00f6s tarkastellaan (konventionaalinen kalibrointi, universaali kalibrointi ja triple detection \u2013menetelm\u00e4). Lis\u00e4ksi kirjallisuusosiossa tutustutaan viskometrian perusteisiin.\n\nTutkielman kokeellisessa osassa (erikoisty\u00f6) tutkittiin GPC-laitteistolla laktidipohjaisia polymeerin\u00e4ytteit\u00e4 (PLLA, PLGA ja PLCL), jotka erosivat sis\u00e4isten viskositeettiensa ja n\u00e4in my\u00f6s moolimassojensa suhteen. Tarkoituksena oli tutkia, vaikuttiko analyysimenetelm\u00e4 saatuihin tuloksiin. 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spellingShingle Nuuttila, Minna Gel permeation chromatography methods in the analysis of lactide-based polymers gel permeation chromatography lactide-based polymers molar mass averages polydispersity Soveltava kemia Applied Chemistry 4036 polymeerit viskositeetti polymers viscosity
title Gel permeation chromatography methods in the analysis of lactide-based polymers
title_full Gel permeation chromatography methods in the analysis of lactide-based polymers
title_fullStr Gel permeation chromatography methods in the analysis of lactide-based polymers Gel permeation chromatography methods in the analysis of lactide-based polymers
title_full_unstemmed Gel permeation chromatography methods in the analysis of lactide-based polymers Gel permeation chromatography methods in the analysis of lactide-based polymers
title_short Gel permeation chromatography methods in the analysis of lactide-based polymers
title_sort gel permeation chromatography methods in the analysis of lactide based polymers
title_txtP Gel permeation chromatography methods in the analysis of lactide-based polymers
topic gel permeation chromatography lactide-based polymers molar mass averages polydispersity Soveltava kemia Applied Chemistry 4036 polymeerit viskositeetti polymers viscosity
topic_facet 4036 Applied Chemistry Soveltava kemia gel permeation chromatography lactide-based polymers molar mass averages polydispersity polymeerit polymers viscosity viskositeetti
url https://jyx.jyu.fi/handle/123456789/60101 http://www.urn.fi/URN:NBN:fi:jyu-201811054624
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