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Off-stoichiometry thiol-ene polymer

March 13, 2024

An off-stoichiometry thiol-ene polymer is a polymer platform comprising off-stoichiometry thiol-enes (OSTE) and off-stoichiometry thiol-ene-epoxies (OSTE+).

Example of the curing process of the OSTE+ polymers. The respective properties of the polymer after 1st and 2nd cure.

The OSTE polymers comprise off-stoichiometry blends of thiols and allyls. After complete polymerization, typically by UV micromolding, the polymer articles contain a well-defined number of unreacted thiol or allyls groups both on the surface and in the bulk. These surface anchors can be used for subsequent direct surface modification or bonding.[1]

In later versions epoxy monomers were added to form ternary thiol-ene-epoxy monomer systems (OSTE+), where the epoxy in a second step reacts with the excess of thiols creating a final polymer article that is completely inert.[2] Some of the critical features of OSTE+ polymers include uncomplicated and rapid fabrication of complex structures in a standard chemistry labs, hydrophilic native surface properties and covalent bonding via latent epoxy chemistry.[3]

Development edit

The OSTE polymer resins were originally developed by Tommy Haraldsson and Fredrik Carlborg at the group of Micro and Nanosystems[4] at the Royal Institute of Technology (KTH) to bridge the gap between research prototyping and commercial production of microfluidics devices.[1] The resins were later adapted and improved for commercial applications by the Swedish start-up Mercene Labs AB under the name OSTEMER.

Reaction mechanism edit

The OSTE resins are cured via a rapid thiol-ene "Click" reaction between thiols and allyls. The thiols and allyls react in a perfectly alternating fashion and has a very high conversion rate (up to 99%),[5] the initial off-stoichiometry of the monomers will exactly define the number off unreacted groups left after the polymerization. With the right choice of monomers very high off-stoichiometry ratios can be attained while maintaining good mechanical properties.[1]

The off-stoichiometry thiol-ene-epoxies, or OSTE+ polymers, are created in a two-step curing process where a first rapid thiol-ene reaction defines the geometric shape of the polymer while leaving an excess of thiols and all the epoxy unreacted. In a second step all the remaining thiol groups and the epoxy groups are reacted to form an inert polymer.[6]

Properties edit

OSTE polymers edit

The main advantages put forward of the UV-cured OSTE polymers in microsystems have been their i) dry bonding capacity by reacting a polymer with thiol excess to a second polymer with allyl excess at room-temperature using only UV-light, ii) their well-defined and tunable number of surface anchors (thiols or allyls) present on the surface that can be used for direct surface modification[7] and iii) their wide tuning range of mechanical properties from rubbery to thermoplastic-like depending only on the choice of off-stoichiometry.[8][1] The glass transition temperature typically varies from below room-temperature for high off-stoichiometric ratios to 75 °C for a stoichiometric blend of tetrathiol and triallyl.[9] They are typically transparent in the visible range. A disadvantage put forward with the OSTE-polymers is the leaching out of unreacted monomers at very high off-stoichiometric ratios which may affect cells and proteins in lab-on-chips,[1] although cell viability has been observed for cell cultures on low off-stoichiometric OSTE.[10]

OSTE+ polymers edit

The dual-cure thiol-ene-epoxies, or OSTE+ polymers, differ from the OSTE-polymers in that they have two separated curing steps. After the first UV-initiated step, the polymer is rubbery and can easily be deformed[11] and it has surface anchors available for surface modification.[12] During the second step, when all the thiols and epoxies are reacted the polymer stiffens and can bond to a wide number of substrates, including itself, via the epoxy chemistry. The advantages put forward for the OSTE+ are i) their unique ability for integration and bonding via the latent epoxy chemistry and the low built-in stresses in the thiol-enes polymers[13] ii) their complete inertness after final cure iii) their good barrier properties[14] and the possibility to scale up manufacturing using industrial reaction injection molding.[15] Both stiff and rubbery versions of the OSTE+ polymers have been demonstrated, showing their potential in microsystems for valving and pumping similar to PDMS components, but with the benefit of withstanding higher pressures.[11] The commercial version of the OSTE+ polymer, OSTEMER 322, has been shown to be compatible with many cell lines.[16]

Fabrication edit

OSTE polymers edit

The OSTE resins can be cast and cured in a structured silicone molds[1] or coated permanent photoresist.[17] OSTE polymers have also shown excellent photostructuring capability[18] using photomasks, enabling for example powerful and flexible capillary pumps.[19]

OSTE+ polymers edit

The OSTE+ resins are first UV-cured in the same way as the OSTE-polymers but are later thermally cured to stiffen and bond to a substrate.

Applications edit

Lab-on-a-chip edit

OSTE+ allows for soft lithography microstructuring, strong biocompatible dry bonding to almost any substrate during Lab-on-a-chip (LoC) manufacturing, while simultaneously mimicking the mechanical properties found in thermoplastic polymers, hence allowing for true prototyping of commercial LoC.[20] The commonly used materials for microfluidics suffer from unwieldy steps and often ineffective bonding processes, especially when packaging biofunctionalized surfaces, which makes LoC assembly difficult and costly [21][22] OSTE+ polymer which effectively bonds to nine dissimilar types of substrates, requires no surface treatment prior to the bonding at room temperature, features high Tg, and achieves good bonding strength to at least 100 °C.[20] Moreover, it has been demonstrated that excellent results can be obtained using photolithography on OSTE polymer, opening wider potential applications.[23]

Bio packaging edit

Biosensors are used for a range of biological measurements.[24][25]

OSTE packaging for biosensing has been demonstrated for QCM,[26] and photonic ring resonator sensors.[27]

Wafer bonding edit

Adhesive wafer bonding has become an established technology in microelectromechanical systems (MEMS) integration and packaging applications.[28] OSTE is suitable for heterogeneous silicon wafer level integration depending on its application in low temperature processes due to its ability to cure even in room temperatures.[29]

Microarray imprinting and surface energy patterning edit

Imprinting of arrays with hydrophilic-in-hydrophobic microwells is made possible using an innovative surface energy replication approach by means of a hydrophobic thiol-ene polymer formulation. In this polymer, hydrophobic-moiety-containing monomers self-assemble at the hydrophobic surface of the imprinting stamp, which results in a hydrophobic replica surface after polymerization. After removing the stamp, microwells with hydrophobic walls and a hydrophilic bottom are obtained. Such fast and inexpensive procedure can be utilised in digital microwell array technology toward diagnostic applications.[30][31]

OSTE e-beam resist edit

OSTE resin can also be used as e-beam resist, resulting in nanostructures that allow direct protein functionalization.[32]

References edit

  1. ^ a b c d e f Carlborg, Carl Fredrik; Haraldsson, Tommy; Öberg, Kim; Malkoch, Michael; van der Wijngaart, Wouter (2011). "Beyond PDMS: off-stoichiometry thiol–ene (OSTE) based soft lithography for rapid prototyping of microfluidic devices". Lab on a Chip. 11 (18): 3136–47. doi:10.1039/c1lc20388f. ISSN 1473-0197. PMID 21804987.
  2. ^ Saharil, Farizah; Carlborg, Carl Fredrik; Haraldsson, Tommy; van der Wijngaart, Wouter (2012). "Biocompatible "click" wafer bonding for microfluidic devices". Lab on a Chip. 12 (17): 3032–5. doi:10.1039/c2lc21098c. ISSN 1473-0197. PMID 22760578.
  3. ^ [1] Vastesson, Proc. IEEE Transducers 2013 Barcelona, 408-411 (2013)
  4. ^ [2] MICROFLUIDICS & LAB-ON-CHIP
  5. ^ Hoyle, Charles E. (2010). "Thiol-Ene Click Chemistry". Angewandte Chemie International Edition. 49 (9): 1540–1573. doi:10.1002/anie.200903924. PMID 20166107.
  6. ^ [3] Saharil, Journal of Micromechanics and Microengineering 23, 025021 (2013)
  7. ^ [4] BIOMICROFLUIDICS 6, 016505 (2012)
  8. ^ [5] Lafleur , Analyst 138, 845-849 (2013)
  9. ^ [6] 2014-03-01 at the Wayback Machine OSTE+ Official datasheet
  10. ^ [7] Errando-Herranz, Proc. MicroTAS 2013 Freiburg, (2013)
  11. ^ a b [8] Hansson, Proc. IEEE MEMS 2014 San Francisco, (2014)
  12. ^ [9] Zhou, Proc. MicroTAS 2013 Freiburg, (2013)
  13. ^ Hoyle, Charles E. (2004). "Thiol-enes: Chemistry of the past with promise for the future". Journal of Polymer Science Part A: Polymer Chemistry. 42 (21): 5301–5338. Bibcode:2004JPoSA..42.5301H. doi:10.1002/pola.20366.
  14. ^ [10] Saharil, Journal of Micromechanics and Microengineering 23, 025021 (2013)
  15. ^ Sandström, N; Shafagh, R Z; Vastesson, A; Carlborg, C F; Wijngaart, W van der; Haraldsson, T (2015). "Reaction injection molding and direct covalent bonding of OSTE+ polymer microfluidic devices". Journal of Micromechanics and Microengineering. 25 (7): 075002. Bibcode:2015JMiMi..25g5002S. doi:10.1088/0960-1317/25/7/075002. S2CID 53682690.
  16. ^ Sticker, Drago; Rothbauer, Mario; Lechner, Sarah; Hehenberger, Marie-Therese; Ertl, Peter (2015-11-24). "Multi-layered, membrane-integrated microfluidics based on replica molding of a thiol–ene epoxy thermoset for organ-on-a-chip applications". Lab Chip. 15 (24): 4542–4554. doi:10.1039/c5lc01028d. ISSN 1473-0189. PMID 26524977.
  17. ^ Fredrik, Carlborg, Carl; M., Cretich; Tommy, Haraldsson; L., Sola; M., Bagnati; M., Chiari; Wouter, van der Wijngaart (2011-01-01). "Biosticker : patterned microfluidic stickers for rapid integration with microarrays": 311–313. {{cite journal}}: Cite journal requires |journal= (help)CS1 maint: multiple names: authors list (link)
  18. ^ Hillmering, Mikael; Pardon, Gaspard; Vastesson, Alexander; Supekar, Omkar; Carlborg, Carl Fredrik; Brandner, Birgit D.; Wijngaart, Wouter van der; Haraldsson, Tommy (2016-02-15). "Off-stoichiometry improves the photostructuring of thiol–enes through diffusion-induced monomer depletion". Microsystems & Nanoengineering. 2: 15043. doi:10.1038/micronano.2015.43. ISSN 2055-7434. PMC 6444721. PMID 31057810.
  19. ^ Hansson, Jonas; Yasuga, Hiroki; Haraldsson, Tommy; Wijngaart, Wouter van der (2016-01-05). "Synthetic microfluidic paper: high surface area and high porosity polymer micropillar arrays". Lab Chip. 16 (2): 298–304. doi:10.1039/c5lc01318f. ISSN 1473-0189. PMID 26646057.
  20. ^ a b [11] Saharil , Lab Chip 12, 3032-3035 (2012)
  21. ^ [12] J. Micromech. Microeng. 18 (2008) 067001 (4pp)
  22. ^ [13] J. Micromech. Microeng. 21 (2011) 025008 (8pp)
  23. ^ [14] 1. Pardon G, et al., Microfluidics and Nanofluidics. 2014 Feb 14.
  24. ^ [15] Homola, Chemical Reviews, 108 (2), 462–493, 2008
  25. ^ [16] Carlborg, Proc. MicroTAS 2011 Seatle, 311-313 (2011)
  26. ^ [17] Sandström, Proc. IEEE Transducers 2011 Beijing, 2778-2781 (2011)
  27. ^ [18] Errando-Herranz, Opt. Express 21, 21293 (2013)
  28. ^ [19] Niklaus F, Stemme G, Lu J-Q and Gutmann R J 2006 Adhesive wafer bonding J. Appl. Phys. 99 03110
  29. ^ [20][permanent dead link] Forsberg, Journal of Micromechanics and Microengineering 23, 085019 (2013)
  30. ^ Decrop, Deborah; Pardon, Gaspard; Shafagh, Reza; Spacic, Dragana; van der Wijngaart, Wouter; Lammertyn, Jeroen; Haraldsson, Tommy (2017). "Single-Step Imprinting of Femtoliter Microwell Arrays Allows Digital Bioassays with Attomolar Limit of Detection". ACS Applied Materials & Interfaces. 9 (12): 10418–10426. doi:10.1021/acsami.6b15415. PMID 28266828.
  31. ^ Shafagh, Reza; Decrop, Deborah; Ven, Karen; Vanderbeke, Arno; Hanusa, Robert; Pardon, Gaspard; Haraldsson, Tommy; Lammertyn, Jeroen; van der Wijngaart, Wouter (2019). "Reaction injection molding of hydrophilic-in-hydrophobic femtolitre-well arrays". Microsystems & Nanoengineering. 5 (25): 25. Bibcode:2019MicNa...5...25Z. doi:10.1038/s41378-019-0065-2. PMC 6545322. PMID 31231538.
  32. ^ Shafagh, Reza; Vastesson, Alexander; Guo, Weijin; van der Wijngaart, Wouter; Haraldsson, Tommy (2018). "E-Beam Nanostructuring and Direct Click Biofunctionalization of Thiol–Ene Resist". ACS Nano. 12 (10): 9940–9946. doi:10.1021/acsnano.8b03709. PMID 30212184. S2CID 52271550.

March 13, 2024
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An off stoichiometry thiol ene polymer is a polymer platform comprising off stoichiometry thiol enes OSTE and off stoichiometry thiol ene epoxies OSTE Example of the curing process of the OSTE polymers The respective properties of the polymer after 1st and 2nd cure The OSTE polymers comprise off stoichiometry blends of thiols and allyls After complete polymerization typically by UV micromolding the polymer articles contain a well defined number of unreacted thiol or allyls groups both on the surface and in the bulk These surface anchors can be used for subsequent direct surface modification or bonding 1 In later versions epoxy monomers were added to form ternary thiol ene epoxy monomer systems OSTE where the epoxy in a second step reacts with the excess of thiols creating a final polymer article that is completely inert 2 Some of the critical features of OSTE polymers include uncomplicated and rapid fabrication of complex structures in a standard chemistry labs hydrophilic native surface properties and covalent bonding via latent epoxy chemistry 3 Contents 1 Development 2 Reaction mechanism 3 Properties 3 1 OSTE polymers 3 2 OSTE polymers 4 Fabrication 4 1 OSTE polymers 4 2 OSTE polymers 5 Applications 5 1 Lab on a chip 5 2 Bio packaging 5 3 Wafer bonding 5 4 Microarray imprinting and surface energy patterning 5 5 OSTE e beam resist 6 ReferencesDevelopment editThe OSTE polymer resins were originally developed by Tommy Haraldsson and Fredrik Carlborg at the group of Micro and Nanosystems 4 at the Royal Institute of Technology KTH to bridge the gap between research prototyping and commercial production of microfluidics devices 1 The resins were later adapted and improved for commercial applications by the Swedish start up Mercene Labs AB under the name OSTEMER Reaction mechanism editThe OSTE resins are cured via a rapid thiol ene Click reaction between thiols and allyls The thiols and allyls react in a perfectly alternating fashion and has a very high conversion rate up to 99 5 the initial off stoichiometry of the monomers will exactly define the number off unreacted groups left after the polymerization With the right choice of monomers very high off stoichiometry ratios can be attained while maintaining good mechanical properties 1 The off stoichiometry thiol ene epoxies or OSTE polymers are created in a two step curing process where a first rapid thiol ene reaction defines the geometric shape of the polymer while leaving an excess of thiols and all the epoxy unreacted In a second step all the remaining thiol groups and the epoxy groups are reacted to form an inert polymer 6 Properties editOSTE polymers edit The main advantages put forward of the UV cured OSTE polymers in microsystems have been their i dry bonding capacity by reacting a polymer with thiol excess to a second polymer with allyl excess at room temperature using only UV light ii their well defined and tunable number of surface anchors thiols or allyls present on the surface that can be used for direct surface modification 7 and iii their wide tuning range of mechanical properties from rubbery to thermoplastic like depending only on the choice of off stoichiometry 8 1 The glass transition temperature typically varies from below room temperature for high off stoichiometric ratios to 75 C for a stoichiometric blend of tetrathiol and triallyl 9 They are typically transparent in the visible range A disadvantage put forward with the OSTE polymers is the leaching out of unreacted monomers at very high off stoichiometric ratios which may affect cells and proteins in lab on chips 1 although cell viability has been observed for cell cultures on low off stoichiometric OSTE 10 OSTE polymers edit The dual cure thiol ene epoxies or OSTE polymers differ from the OSTE polymers in that they have two separated curing steps After the first UV initiated step the polymer is rubbery and can easily be deformed 11 and it has surface anchors available for surface modification 12 During the second step when all the thiols and epoxies are reacted the polymer stiffens and can bond to a wide number of substrates including itself via the epoxy chemistry The advantages put forward for the OSTE are i their unique ability for integration and bonding via the latent epoxy chemistry and the low built in stresses in the thiol enes polymers 13 ii their complete inertness after final cure iii their good barrier properties 14 and the possibility to scale up manufacturing using industrial reaction injection molding 15 Both stiff and rubbery versions of the OSTE polymers have been demonstrated showing their potential in microsystems for valving and pumping similar to PDMS components but with the benefit of withstanding higher pressures 11 The commercial version of the OSTE polymer OSTEMER 322 has been shown to be compatible with many cell lines 16 Fabrication editOSTE polymers edit The OSTE resins can be cast and cured in a structured silicone molds 1 or coated permanent photoresist 17 OSTE polymers have also shown excellent photostructuring capability 18 using photomasks enabling for example powerful and flexible capillary pumps 19 OSTE polymers edit The OSTE resins are first UV cured in the same way as the OSTE polymers but are later thermally cured to stiffen and bond to a substrate Applications editLab on a chip edit OSTE allows for soft lithography microstructuring strong biocompatible dry bonding to almost any substrate during Lab on a chip LoC manufacturing while simultaneously mimicking the mechanical properties found in thermoplastic polymers hence allowing for true prototyping of commercial LoC 20 The commonly used materials for microfluidics suffer from unwieldy steps and often ineffective bonding processes especially when packaging biofunctionalized surfaces which makes LoC assembly difficult and costly 21 22 OSTE polymer which effectively bonds to nine dissimilar types of substrates requires no surface treatment prior to the bonding at room temperature features high Tg and achieves good bonding strength to at least 100 C 20 Moreover it has been demonstrated that excellent results can be obtained using photolithography on OSTE polymer opening wider potential applications 23 Bio packaging edit Biosensors are used for a range of biological measurements 24 25 OSTE packaging for biosensing has been demonstrated for QCM 26 and photonic ring resonator sensors 27 Wafer bonding edit Adhesive wafer bonding has become an established technology in microelectromechanical systems MEMS integration and packaging applications 28 OSTE is suitable for heterogeneous silicon wafer level integration depending on its application in low temperature processes due to its ability to cure even in room temperatures 29 Microarray imprinting and surface energy patterning edit Imprinting of arrays with hydrophilic in hydrophobic microwells is made possible using an innovative surface energy replication approach by means of a hydrophobic thiol ene polymer formulation In this polymer hydrophobic moiety containing monomers self assemble at the hydrophobic surface of the imprinting stamp which results in a hydrophobic replica surface after polymerization After removing the stamp microwells with hydrophobic walls and a hydrophilic bottom are obtained Such fast and inexpensive procedure can be utilised in digital microwell array technology toward diagnostic applications 30 31 OSTE e beam resist edit OSTE resin can also be used as e beam resist resulting in nanostructures that allow direct protein functionalization 32 References edit a b c d e f Carlborg Carl Fredrik Haraldsson Tommy Oberg Kim Malkoch Michael van der Wijngaart Wouter 2011 Beyond PDMS off stoichiometry thiol ene OSTE based soft lithography for rapid prototyping of microfluidic devices Lab on a Chip 11 18 3136 47 doi 10 1039 c1lc20388f ISSN 1473 0197 PMID 21804987 Saharil Farizah Carlborg Carl Fredrik Haraldsson Tommy van der Wijngaart Wouter 2012 Biocompatible click wafer bonding for microfluidic devices Lab on a Chip 12 17 3032 5 doi 10 1039 c2lc21098c ISSN 1473 0197 PMID 22760578 1 Vastesson Proc IEEE Transducers 2013 Barcelona 408 411 2013 2 MICROFLUIDICS amp LAB ON CHIP Hoyle Charles E 2010 Thiol Ene Click Chemistry Angewandte Chemie International Edition 49 9 1540 1573 doi 10 1002 anie 200903924 PMID 20166107 3 Saharil Journal of Micromechanics and Microengineering 23 025021 2013 4 BIOMICROFLUIDICS 6 016505 2012 5 Lafleur Analyst 138 845 849 2013 6 Archived 2014 03 01 at the Wayback Machine OSTE Official datasheet 7 Errando Herranz Proc MicroTAS 2013 Freiburg 2013 a b 8 Hansson Proc IEEE MEMS 2014 San Francisco 2014 9 Zhou Proc MicroTAS 2013 Freiburg 2013 Hoyle Charles E 2004 Thiol enes Chemistry of the past with promise for the future Journal of Polymer Science Part A Polymer Chemistry 42 21 5301 5338 Bibcode 2004JPoSA 42 5301H doi 10 1002 pola 20366 10 Saharil Journal of Micromechanics and Microengineering 23 025021 2013 Sandstrom N Shafagh R Z Vastesson A Carlborg C F Wijngaart W van der Haraldsson T 2015 Reaction injection molding and direct covalent bonding of OSTE polymer microfluidic devices Journal of Micromechanics and Microengineering 25 7 075002 Bibcode 2015JMiMi 25g5002S doi 10 1088 0960 1317 25 7 075002 S2CID 53682690 Sticker Drago Rothbauer Mario Lechner Sarah Hehenberger Marie Therese Ertl Peter 2015 11 24 Multi layered membrane integrated microfluidics based on replica molding of a thiol ene epoxy thermoset for organ on a chip applications Lab Chip 15 24 4542 4554 doi 10 1039 c5lc01028d ISSN 1473 0189 PMID 26524977 Fredrik Carlborg Carl M Cretich Tommy Haraldsson L Sola M Bagnati M Chiari Wouter van der Wijngaart 2011 01 01 Biosticker patterned microfluidic stickers for rapid integration with microarrays 311 313 a href Template Cite journal html title Template Cite journal cite journal a Cite journal requires journal help CS1 maint multiple names authors list link Hillmering Mikael Pardon Gaspard Vastesson Alexander Supekar Omkar Carlborg Carl Fredrik Brandner Birgit D Wijngaart Wouter van der Haraldsson Tommy 2016 02 15 Off stoichiometry improves the photostructuring of thiol enes through diffusion induced monomer depletion Microsystems amp Nanoengineering 2 15043 doi 10 1038 micronano 2015 43 ISSN 2055 7434 PMC 6444721 PMID 31057810 Hansson Jonas Yasuga Hiroki Haraldsson Tommy Wijngaart Wouter van der 2016 01 05 Synthetic microfluidic paper high surface area and high porosity polymer micropillar arrays Lab Chip 16 2 298 304 doi 10 1039 c5lc01318f ISSN 1473 0189 PMID 26646057 a b 11 Saharil Lab Chip 12 3032 3035 2012 12 J Micromech Microeng 18 2008 067001 4pp 13 J Micromech Microeng 21 2011 025008 8pp 14 1 Pardon G et al Microfluidics and Nanofluidics 2014 Feb 14 15 Homola Chemical Reviews 108 2 462 493 2008 16 Carlborg Proc MicroTAS 2011 Seatle 311 313 2011 17 Sandstrom Proc IEEE Transducers 2011 Beijing 2778 2781 2011 18 Errando Herranz Opt Express 21 21293 2013 19 Niklaus F Stemme G Lu J Q and Gutmann R J 2006 Adhesive wafer bonding J Appl Phys 99 03110 20 permanent dead link Forsberg Journal of Micromechanics and Microengineering 23 085019 2013 Decrop Deborah Pardon Gaspard Shafagh Reza Spacic Dragana van der Wijngaart Wouter Lammertyn Jeroen Haraldsson Tommy 2017 Single Step Imprinting of Femtoliter Microwell Arrays Allows Digital Bioassays with Attomolar Limit of Detection ACS Applied Materials amp Interfaces 9 12 10418 10426 doi 10 1021 acsami 6b15415 PMID 28266828 Shafagh Reza Decrop Deborah Ven Karen Vanderbeke Arno Hanusa Robert Pardon Gaspard Haraldsson Tommy Lammertyn Jeroen van der Wijngaart Wouter 2019 Reaction injection molding of hydrophilic in hydrophobic femtolitre well arrays Microsystems amp Nanoengineering 5 25 25 Bibcode 2019MicNa 5 25Z doi 10 1038 s41378 019 0065 2 PMC 6545322 PMID 31231538 Shafagh Reza Vastesson Alexander Guo Weijin van der Wijngaart Wouter Haraldsson Tommy 2018 E Beam Nanostructuring and Direct Click Biofunctionalization of Thiol Ene Resist ACS Nano 12 10 9940 9946 doi 10 1021 acsnano 8b03709 PMID 30212184 S2CID 52271550 Retrieved from https en wikipedia org w index php title Off stoichiometry thiol ene polymer amp oldid 1190909682, wikipedia, wiki, book, books, library,

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