skip to main content

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 11:00 PM ET on Thursday, January 16 until 2:00 AM ET on Friday, January 17 due to maintenance. We apologize for the inconvenience.


Title: Covalently‐Attached, Surface‐Eroding Polymer Coatings on Magnesium Alloys for Corrosion Control and Temporally Varying Support of Cell Adhesion
Abstract

For degradable magnesium (Mg) alloy‐based stents it would be desirable to delay early corrosion to maintain mechanical strength. Similarly, early after stent placement reduced thrombogenicity is an important feature, while chronically, endothelial cell adhesion and vessel integration are desirable. In this study, surface eroding polymers of amino‐grafted poly(1,3‐trimethylene carbonate) (PTMC‐NH2) and PTMC‐NH2combined with sulfobetaine bearing polymer PSB (PTMC‐NHCO‐PSB) are developed, and these polymers are covalently attached onto 6‐phosphonohexanoic acid (PHA)‐coated AZ31 Mg alloy surfaces in sequence. In vitro degradation testing in ovine plasma shows PTMC, PTMC‐NH2, and PTMC‐NHCO‐PSB cast films experience a gradual thickness and mass loss with maintenance of smooth surfaces, confirming surface erosion behavior. The PTMC‐NH2polymer is firmly bound to the PHA‐modified AZ31 surface and demonstrates a resistance to peeling. PTMC, PTMC‐NH2, and PTMC‐NHCO‐PSB coated AZ31 have a lower corrosion rate versus polylactide‐co‐glycolide coated and untreated AZ31. PTMC‐NHCO‐PSB coated AZ31 inhibits platelet deposition and smooth muscle cell adhesion and growth, but after 2‐week immersion in plasma, this surface supports endothelial cell adhesion and growth. These results suggest PTMC‐NHCO‐PSB surface eroding coating offers a means of controlling corrosion while providing a temporally varying bio‐functionality for biodegradable vascular stent applications.

 
more » « less
PAR ID:
10456879
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Advanced Materials Interfaces
Volume:
7
Issue:
15
ISSN:
2196-7350
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Polymeric coatings can provide temporary stability to bioresorbable metallic stents at the initial stage of deployment by alleviating rapid degradation and providing better interaction with surrounding vasculature. To understand this interfacing biocompatibility, this study explored the endothelial-cytocompatibility of polymer-coated magnesium (Mg) alloys under static and dynamic conditions compared to that of non-coated Mg alloy surfaces. Poly (carbonate urethane) urea (PCUU) and poly (lactic-co-glycolic acid) (PLGA) were coated on Mg alloys (WE43, AZ31, ZWEKL, ZWEKC) and 316L stainless steel (316L SS, control sample), which were embedded into a microfluidic device to simulate a vascular environment with dynamic flow. The results from attachment and viability tests showed that more cells were attached on the polymer-coated Mg alloys than on non-coated Mg alloys in both static and dynamic conditions. In particular, the attachment and viability on PCUU-coated surfaces were significantly higher than that of PLGA-coated surfaces of WE43 and ZWEKC in both static and dynamic conditions, and of AZ31 in dynamic conditions (P<0.05). The elementary distribution map showed that there were relatively higher Carbon weight percentages and lower Mg weight percentages on PCUU-coated alloys than PLGA-coated alloys. Various levels of pittings were observed underneath the polymer coatings, and the pittings were more severe on the surface of Mg alloys that corroded rapidly. Polymer coatings are recommended to be applied on Mg alloys with relatively low corrosion rates, or after pre-stabilizing the substrate. PCUU-coating has more selective potential to enhance the biocompatibility and mitigate the endothelium damage of Mg alloy stenting. 
    more » « less
  2. Airway obstruction conditions are relatively rarely observed in clinical settings but nevertheless, extremely challenging to handle, especially when observed in pediatric patients. Several surgical procedures, including tracheal resection, end-to-end tracheal anastomosis, and tracheoplasty, have been developed and practised of late, to treat airway obstruction. However, the clinical outcome is typically not satisfactory due to airway restenosis conditions that develop following surgery. Various types of stents are currently available for airway stenting ranging from non-degradable silicone tubes and bio-inert metallic stents (bare or coated with polymer matrix) to hybrid silicone tubes strengthened by metallic cores, but none of the stents provides the satisfactory long-term effectiveness. Therefore, there is a significant clinical need for a biodegradable airway stent that would maintain airway patency and totally degrade over time after meeting the desired objectives. The present study aims to investigate biodegradable magnesium-aluminum-zinc-calcium-manganese (AZXM) alloy as a potential tracheal stent. The new AZXM alloy was fabricated by partially replacing aliminum in commercial AZ31 alloy with calcium. The present study demonstrates that calcium preferentially segregates along the grain boundaries as intermetallic phases (Mg2Ca) and is homogeneously distributed in the magnesium matrix. The extruded AZXM alloy showed less pitting, higher corrosion resistance in Hank's Balanced Salt Solution (HBSS) compared to the as-cast and solution-treated AZXM alloys and exhibited optimized mechanical properties. In vitro cytotoxicity evaluation using human trachea epithelial cells demonstrated excellent cyto-compatibility of AZXM alloys compared to pure Mg and commercial AZ31 validated by a very preliminary rabbit in vivo tracheal model study. Preliminary results show that the approach to use biodegradable AZXM alloys as a tracheal stent is indeed promising, although further alloy processing is required to improve the ductility needed followed by a more exhaustive in vivo study to demonstrate full viability for stent applications.

     
    more » « less
  3. Abstract

    Tracheal stenting currently using non‐degradable stents is commonplace for treatment of trauma, prolonged intubation related adult airway obstructions, and pediatric patients‐associated tracheal stenosis conditions. Degradable tracheal stent placement will avoid complications of stent removal and restenosis. Widespread reports exist on degradable magnesium alloys success for orthopedic and cardiovascular applications but none to date for intra tracheal use. This research explores the use of pure Mg, AZ31, and Mg‐3Y alloys for degradable tracheal stent assessment.In vitroevaluation of magnesium, prototype stents in a bioreactor simulate the airway environment and corrosion. Micro‐CT imaging and biocompatibility evaluation helped assess the 24‐week degradation of intraluminal alloy stents following implantation in a rat trachealin vivobypass model. Histological analysis indicate tissue response of the harvested stented trachea segments after each time point. Corrosion studies for each alloy indicate significant differences between the simulated and controlin vitroconditions. AZ31 exhibited the lowest volume loss of 6.8% in saline, while pure Mg displayed the lowest volume loss of 4.6% in simulated airway fluid (SAF), both at 1‐week time points. Significant differences in percentage of total volume lost after 6 months were determined between the alloys over time. MgY alloy displayed the slowest corrosion losing only 15.1% volume after 24 weeks of immersion. Additionally,in vitromagnesium alloy corrosion was not significantly different from the percentage of total volume lostin vivoat 1‐week time point. The study demonstrates promise of magnesium alloys for intraluminal tracheal stent application albeit viability of a clinically translatable model warrants further studies. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 107B: 1844–1853, 2019.

     
    more » « less
  4. Abstract

    Petroleum‐based plastics levy significant environmental and economic costs that can be alleviated with sustainably sourced, biodegradable, and bio‐based polymers such as polyhydroxyalkanoates (PHAs). However, industrial‐scale production of PHAs faces barriers stemming from insufficient product yields and high costs. To address these challenges, we must look beyond the current suite of microbes for PHA production and investigate non‐model organisms with versatile metabolisms. In that vein, we assessed PHA production by the photosynthetic purple non‐sulfur bacteria (PNSB)Rhodomicrobium vannieliiandRhodomicrobium udaipurense.We show that both species accumulate PHA across photo‐heterotrophic, photo‐hydrogenotrophic, photo‐ferrotrophic, and photo‐electrotrophic growth conditions, with either ammonium chloride (NH4Cl) or dinitrogen gas (N2) as nitrogen sources. Our data indicate that nitrogen source plays a significant role in dictating PHA synthesis, with N2fixation promoting PHA production during photoheterotrophy and photoelectrotrophy but inhibiting production during photohydrogenotrophy and photoferrotrophy. We observed the highest PHA titres (up to 44.08 mg/L, or 43.61% cell dry weight) when cells were grown photoheterotrophically on sodium butyrate with N2, while production was at its lowest during photoelectrotrophy (as low as 0.04 mg/L, or 0.16% cell dry weight). We also find that photohydrogenotrophically grown cells supplemented with NH4Cl exhibit the highest electron yields – up to 58.89% – while photoheterotrophy demonstrated the lowest (0.27%–1.39%). Finally, we highlight superior electron conversion and PHA production compared to a related PNSB,Rhodopseudomonas palustrisTIE‐1. This study illustrates the value of studying non‐model organisms likeRhodomicrobiumfor sustainable PHA production and indicates future directions for exploring PNSB metabolisms.

     
    more » « less
  5. null (Ed.)
    In this study, a compact cold sprayed (CS) Ti coating was deposited on Mg alloy using a high pressure cold spray (HPCS) system. The wear and corrosion behavior of the CS Ti coating was compared with that of CS Al coating and bare Mg alloy. The Ti coating yielded lower wear rate compared to Al coating and Mg alloy. Electrochemical impedance spectroscopy (EIS) and cyclic potentiodynamic polarization (CPP) tests revealed that CS Ti coating can substantially reduce corrosion rate of AZ31B in chloride containing solutions compared to CS Al coating. Interestingly, Ti-coated Mg alloy demonstrated negative hysteresis loop, depicting repassivation of pits, in contrast to AZ31B and Al-coated AZ31B with positive hysteresis loops where corrosion potential (Ecorr) > repassivation potential (Erp); indicating irreversible growth of pits. AZ31B and Al-coated AZ31B were most susceptible to pitting corrosion, while Ti-coated Mg alloy indicated noticeable resistance to pitting in 3.5 wt % NaCl solution. In comparison to Al coating, Ti coating considerably separated the AZ31BMg alloy surface from the corrosive electrolyte during long term immersion test for 11 days. 
    more » « less