Organic coatings deposited by plasma processes

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Plasma polymerization is a unique dry process to deposit polymers without the use of a catalyst. The plasma polymers deposited by PECVD are often very crosslinked and can lead a wide range of polymers with different physicochemical properties from the same precursor in different plasma conditions (power, pressure, continuous or pulsed mode, precursor flowrate, frequency etc.). Plasma polymers are characterized by low mean molecular weights (m/z < 1500, obtenu par MALDI-ToF)), and not comparable with traditional polymers. Since the last decade the researchers have shown a growing interest to deposit polymer coatings with the maximum of retention of the chemical moieties present in the organic precursor by means of a pulsed wave mode . The latter allows to significantly decrease the mean power in order to lead to a lower fragmentation of the precursor and therefore retain the desired chemical groups of the precursor in the deposited coatings. Plasma polymers with primary amines or carboxylic groups are in particularly interesting for immobilization of biomolecules via a covalent peptide bond. The latter are very interesting in the field of biomedical applications, biosensors, etc.

Coatings presenting bioadhesive and bio-nonadhesive

Coatings presenting bioadhesive and bio-nonadhesive

Plasma polymers obtained from ethylene glycol (PPEG) are known to present anti-adhesive(antifouling) properties with respect to proteins and cells[7].This is the reason why pulsed plasmas have been optimized to deposit PPEG thin layers. PEG and PCL(PolyCaproLactone) are both FDA (Food and Drug Administration) approved polymers. Contrary to PEG layers, PCL polymers give rise to cell adhesive surfaces. 

In the figure below, we have developed, with the help of a microlithographic mask, micropatterns presenting adhesive and non-adhesive properties with respect to ovary cancer cells. PPEG were deposited in the pitches of 100 µm width and PPCL (from  eCL precursor)between the pitches(20 µm lines).

It is also possible to optimize adhesive and nonadhesive surfaces by means of pulsed plasma polymerization by copolymerizing the two precursors (EG and eCL).

.p2          p1  

It is also possible to optimize adhesive and nonadhesive surfaces by means of pulsed plasma polymerization by copolymerizing the two precursors (EG and eCL).

p3

Synthesis of  PCL-co-PEG polymers by a pulsed RF discharge 

Furthermore amphiphilic PEG- perfluorodecamethacrylate (PFDA) copolymers have been optimized in a pulsed RF low pressure plasma for their antifouling properties with respect to two proteins with different size and isoelectric points. The PEG-PFDA copolymers optimized in terms of their surface energy present antifouling properties.  

Recently we have developed  in the framework of Plan Cancer – INSERM, Project ID PC201404) CORAPLAS (Controlled Release of Antineoplastic Drug from Low and Atmospheric Pressure Plasma Polymerized Biodegradable Coatings for Oncological Applications), a drug delivery device in the form of patches  from the plasma copolymerization of polycaprolactone-polyethylene-glycol (PCL-PEG) with the incorporation of carboplatin in a sandwich structure of copolymers. The leaching out of carboplatin up to 1000h has been measured in vitro, and the cytotoxicity of the drug delivery device has been measured in-vivo on 24 BALB mice which have developed inguinal lymphatic tumors.

p4

 

Multilayer copolymers deposited on the biocompatible collagen substrate 

 

 

 1) V. Kumar, J. Pulpytel, G. Guido, H. Rauscher,  F. Rossi and F. Arefi-Khonsari

Amphiphilic copolymer coatings via Plasma polymerization process: Switching and anti-biofouling characteristics. Plasma Process. Polym., Plasma Process. Polym.2011, 8 , 373-385

 2) S. Bhatt, J. Pulpytel, G. Ceccone, P. Lisboa, F. Rossi, V. Kumar,,  F. Arefi-Khonsari

Nanostructured Protein Repellant Amphiphilic Copolymer Coatings with Optimized Surface Energy by Inductively Excited Low-Pressure Plasma, Langmuir, 2011, 27 (23), pp 14570–14580

3) S. Bhatt, J. Pulpytel, M. Mirshahi, F. Arefi-Khonsari

 Catalyst Free Plasma Assisted Copolymerization of Poly (ε-caprolactone)-Poly (ethylene glycol) for Biomedical Applications, ACS Macro Lett. 1 (2012) 764−767

4) S. Bhatt, J. Pulpytel, M. Mirshahi,F. Arefi-Khonsari, Nano sized poly (e-caprolactone)-poly (ethylene glycol) coatings developed by catalyst free plasma assisted copolymerization process for biomedical applications , RSC Adv., 2012, 2, 9114-9123

 5) S. Bhatt, J. Pulpytel, S. Mori, M. Mirshahi, F. Arefi-Khonsari

Cell Repellent Coatings Developed by an OpenAir Atmospheric Pressure Non-Equilibrium Argon Plasma Jet for Biomedical Applications. Plasma Process. Polym. 2013, DOI: 10.1002/ppap.201300076

6) S. Bhatt, J. Pulpytel, M. Mirshahi, F. Arefi-Khonsari, Plasma Co-polymerized Nano Coatings - As a Biodegradable Solid Carrier for Tunable Drug Delivery Applications

Polymer, Volume 54, Issue 18, 16 August 2013, Pages 4820–4829

7) S. Bhatt, J. Pulpytel, F. Arefi-Khonsari, Low and atmospheric plasma polymerisation of nanocoatings for bio-applications.

Surface Innovations, ISSN 2050-6252 | E-ISSN 2050-6260, Volume 3, 2015, pp. 63-83, Themed issue on anti-fouling and related engineering surfaces

8)A. Baitukha, I. Al-Dybiat, A. Valinataj-Omran, J. Pulpytel, M. Pocard, M. Mirshahi and F. Arefi-Khonsari, Low Pressure Plasma Processing of Collagen Membranes for Anti-Cancer Drug Delivery, J Material Sci Eng.2018, 7:6 DOI: 10.4172/2169-0022.100

9)A. Baitukha, I. Al-Dybiat, A. Valinataj-Omran, J. Pulpytel, M.  Pocard, M. Mirshahi, F.  Arefi-Khonsari, Optimization of a low-pressure plasma process for fabrication of a Drug T Delivery System (DDS) for cancer treatment, Materials Science & Engineering C 105(2019)

 

 

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