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Hyaluronan and Phospholipid Association in Biolubrication
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface and Corrosion Science.ORCID iD: 0000-0002-2288-819X
2013 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 14, no 12, 4198-4206 p.Article in journal (Refereed) Published
Abstract [en]

It is becoming increasingly clear that the outstanding lubrication of synovial joints is achieved by a sophisticated hierarchical structure of cartilage combined with synergistic actions of surface-active components present in the synovial fluid. In this work we focus on the association of two components of the synovial fluid, hyaluronan and dipalmitoyl phosphatidyl choline (DPPC), in bulk solution and at interfaces. We demonstrate that hyaluronan associates with DPPC vesicles and adsorbs to supported DPPC bilayers. The association structures formed at the interface are sufficiently stable to allow sequential adsorption of DPPC and hyaluronan, whereby promoting the formation of thick composite layers of these two components. The lubricating ability of such composite layers was probed by the AFM colloidal probe technique and found to be very favorable with low friction coefficients and high load bearing capacity. With DPPC as the last adsorbed component, a friction coefficient of 0.01 was found up to pressures significantly above what is encountered in healthy synovial joints. Hyaluronan as the last added component increases the friction coefficient to 0.03 and decreases the load bearing capacity somewhat (but still above what is needed in the synovial joint). Our data demonstrate that self-assembly structures formed by hyaluronan and phospholipids at interfaces are efficient aqueous lubricants, and it seems plausible that such self-assembly structures contribute to the exceptional lubrication of synovial joints.

Place, publisher, year, edition, pages
2013. Vol. 14, no 12, 4198-4206 p.
Keyword [en]
Supported Lipid-Bilayers, Quartz-Crystal Microbalance, Surface-Active Phospholipids, Articular-Cartilage, Boundary Lubrication, Synovial-Fluid, Aqueous-Solutions, Forces Apparatus, Amorphous Layer, Acid
National Category
Biochemistry and Molecular Biology Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-139285DOI: 10.1021/bm400947vISI: 000328240400006Scopus ID: 2-s2.0-84890402874OAI: oai:DiVA.org:kth-139285DiVA: diva2:684604
Funder
Swedish Foundation for Strategic Research Vinnova
Note

QC 20140108

Available from: 2014-01-08 Created: 2014-01-08 Last updated: 2017-12-06Bibliographically approved
In thesis
1. Multilayer Based Nanogels and Bio-lubricants
Open this publication in new window or tab >>Multilayer Based Nanogels and Bio-lubricants
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Surface chemistry plays an important role in numerous technological innovations, and gives the ability to modify and control surface and interface properties. Layer-by-Layer (LbL) self-assembly is a simple concept that can provide a route to versatile combination of materials as well as fine control of film thickness, hydrophobicity, thermal, optical and electrical properties. This methodology has thus received attention from both academic and industrial experts. A large variety of polymers, proteins and nanoparticles can be utilized in the LbL process. In my PhD-thesis work I made use of the LbL technique to build surface grafted nanogels and bio-lubricant films.

Various surface sensitive techniques have been applied in this PhD thesis work. The three main methods were quartz crystal microbalance with dissipation (QCM-D), total internal reflection Raman (TIR-Raman) spectroscopy, and atomic force microscopy (AFM). In lieu of conventional methods such as reflectometry or ellipsometry, we have combined data obtained from QCM-D and TIR-Raman to gain information on wet and dry LbL films as well as their water content. The relatively new AFM imaging mode known as PeakForce QNM was used to investigate topographical and nano-mechanical properties of LbL films. The colloidal probe technique was implemented with AFM for normal and lateral force measurements.

It is becoming increasingly clear that biopolymers are important for a sustainable society since they are renewable, have useful properties and often are environmentally benign. One main part in this thesis work was to fabricate thin chitosan (CHI) nanogels covalently attached to solid surfaces. This was achieved by first assembling a chitosan/poly(acrylic acid) multilayer using silane chemistry and the LbL method. Next, the chitosan molecules were selectively cross-linked in the film, and finally poly(acrylic acid) was (partly) rinsed out of the nanogel. The final composition and the responsiveness of the nanogel to pH and ionic strength changes were found to depend on the cross-linking density. Statistical analysis, known as target factor analysis, was used to analyze TIR Raman spectra and draw conclusions about e.g. the composition of multilayers during the build-up process, and the kinetics of cross-linking of chitosan.

The other main part in this thesis work also utilized the LbL methodology, but here the main goal was to gain understanding on the unprecedented lubrication of synovial joints. It is in general terms due to a sophisticated hierarchical structure of cartilage combined with synergistic actions of surface-active components present in the synovial fluid, but many aspects of this fascinating biotribological system remain poorly understood. I focused on the lubricating ability of synovial fluid components, and in particular on the association of two components of the synovial fluid, hyaluronan and dipalmitoyl phosphatidyl choline (DPPC), in bulk solution and at interfaces. We found that hyaluronan associated with DPPC vesicles in bulk and adsorbed to supported DPPC bilayers, and that the LbL method could be utilized for forming composite layers of these two components. These composite layers had very favorable lubrication properties, with a low friction coefficient as low as 0.01, and they were also sufficiently stable to shear and load up to the pressure that broke healthy cartilage.

 

 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. xi, 52 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:3
National Category
Natural Sciences
Identifiers
urn:nbn:se:kth:diva-140688 (URN)978-91-7501-993-2 (ISBN)
Public defence
2014-02-14, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council
Note

QC 20140130

Available from: 2014-01-30 Created: 2014-01-30 Last updated: 2014-01-30Bibliographically approved
2. Biolubricants and Biolubrication
Open this publication in new window or tab >>Biolubricants and Biolubrication
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The main objective of this thesis work was to gain understanding of the principles of biolubrication, focusing on synergistic effects between biolubricants. To this end surface force and friction measurements were carried out by means of Atomic Force Microscopy, using hydrophilic and hydrophobic model surfaces in salt solutions of high ionic strength (≈ 150 mM) in presence of different biolubricants. There was also a need to gain information on the adsorbed layers formed by the biolubricants. This was achieved by using a range of methods such as Atomic Force Microscopy PeakForce imaging, Quartz Crystal Microbalance with Dissipation, Dynamic Light Scattering and X-Ray Reflectometry. By combining data from these techniques, detailed information about the adsorbed layers could be obtained.The biolubricants that were chosen for investigation were a phospholipid, hyaluronan, lubricin, and cartilage oligomeric matrix protein (COMP) that all exist in the synovial joint area. First the lubrication ability of these components alone was investigated, and then focus was turned to two pairs that are known or assumed to associate in the synovial area. Of the biolubricants that were investigated, it was only the phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) that was found to be an efficient lubricant on its own. Deposited DPPC bilayers on silica surfaces were found to be able to provide very low friction coefficients (≈ 0.01) up to high pressures, ≈ 50 MPa. A higher load bearing capacity was found for DPPC in the liquid crystalline state compared to in the gel state.The first synergy pair that was explored was DPPC and hyaluronan, that is known to associate on the cartilage surface, and we also noticed association between hyaluronan and DPPC vesicles as well as with adsorbed DPPC bilayers. By combining these two components a lubrication performance similar to that of DPPC alone could be achieved, even though the friction coefficient in presence of hyaluronan was found to be slightly higher. The synergy here is thus not in form of an increased performance, but rather that the presence of hyaluronan allows a large amount of the phospholipid lubricant to accumulate where it is needed, i.e. on the sliding surfaces.The other synergy pair was lubricin and COMP that recently has been shown to be co-localized on the cartilage surface, and thus suggested to associate with each other. Lubricin, as a single component, provided poor lubrication of PMMA surfaces, which we utilized as model hydrophobic surfaces. However, if COMP first was allowed to coat the surface, and then lubricin was added a low friction coefficient (≈ 0.03) was found. In this case the synergy arises from COMP facilitating strong anchoring of lubricin to the surface in conformations that provide good lubrication performance.

Abstract [sv]

Huvudsyftet med det här avhandlingsarbetet var att öka förståelsen för den låga friktion som finns i vissa biologiska system, med fokus på synergistiska effekter mellan de smörjande molekylerna. För detta ändamål studerades ytkrafter och friktion med hjälp av atomkraftsmikroskopi. Mätningarna utfördes med hydrofila och hydrofoba modellytor i lösningar med hög salthalt (≈ 150 mM) i närvaro av smörjande biomolekyler. Det var också nödvändigt att få information om de adsorberade skikten av biomolekyler. Det åstadkoms med hjälp av en rad tekniker så som AFM PeakForce avbildning, kvartskristallmikrovåg, dynamisk ljusspridning och röntgen reflektometri. Genom att kombinera data från dessa tekniker erhölls detaljerad information om de smörjande skikten.De smörjande biomolekyler som valdes ut för studierna var en fosfolipid, hyaluronan, lubricin, and cartilage oligomeric matrix protein (COMP) vilka alla finns i synovialledsområdet. Först undersöktes den smörjande förmågan hos dessa komponenter var för sig, och sedan fokuserade vi på två par av biomolekyler som man vet eller antar bildar associationsstrukturer i synovialleder. Av de enskilda biomolekyler som undersöktes var det endast fosfolipiden 1,2-dipalmitoyl-sn-glycero-3-fosfokoline (DPPC) som visade sig vara en effektivt smörjande molekyl. Deponerade biskikt av DPPC på silikaytor gav upphov till mycket låga friktionskoefficienter (≈ 0.01) upp till höga pålagda tryck, ≈ 50 MPa. DPPC bilager i flytande kristallin fas visade sig ha högre lastbärande förmåga än DPPC bilager i geltillstånd.Det första synergistiska par som undersöktes var DPPC och hyaluronan vilka man vet associerar på broskytan, och vi visade att hyaluronan associerar med såväl DPPC vesiklar som med DPPC bilager. Genom att kombinera dessa två komponenter uppmättes en smörjande förmåga som var jämförbar med den som DPPC ensam uppvisar. Även om friktionskoefficienten var något högre i närvaro av hyaluronan. Synergieffekten här består inte av en bättre smörjande förmåga, utan istället gör närvaron av hyaluronan att de smörjande fosfolipiderna kan ansamlas i stora mängder där de behövs, dvs. på de glidande ytorna.Det andra synergiparet var lubricin och COMP vilka nyligen har visats vara lokaliserade på samma platser på broskytan, vilket tyder på att de associerar med varandra. På egen hand var lubricins smörjande förmåga av PMMA, våra hydrofoba modellytor, dålig. Emellertid, om COMP först adsorberades på PMMA och sedan lubricin tillsattes uppmättes en låg friktionskoefficient (≈ 0.03). I det här fallet består synergin av att COMP möjliggör en stark inbindning till ytan av lubricin i konformationer som ger god smörjande förmåga.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. vi, 62 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:56
Keyword
Hyaluronan, Phospholipid, Lubricin, Cartilage Oligomeric Matrix Protein, COMP, Adsorption, Surface Force, Friction, Biolubrication, Boundary Lubrication, Load Bearing Capacity, Synergistic Effects, DLS, QCM-D, AFM., Hyaluronan, Fosfolipid, Lubricin, Cartilage Oligomeric Matrix Protein, COMP, Adsorption, Ytkraft, Friktion, Biologisk smörjning, Gränsskiktssmörjning, Lastbärande förmåga, Synergieffekter, DLS, QCM-D, AFM.
National Category
Physical Chemistry Polymer Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-156632 (URN)978-91-7595-348-9 (ISBN)
Public defence
2014-12-16, E3, Osquarsbacke 14, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Projects
Stiftelsen för strategisk forskning - SSF
Note

QC 20141202

Available from: 2014-12-02 Created: 2014-12-01 Last updated: 2014-12-02Bibliographically approved

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