Publications

@article{PoloFonseca2025,

title = {Enhancing the Self‐Assembly of Step‐Growth Polymers by Narrowing Their Molar Mass Distribution: A Dynamic Bond‐Mediated Approach},

author = {Lucas Polo Fonseca and Shaghayegh Hamzehlou and Olaia Garagarza and Daniele Mantione and Aritz Lamas and Xabier Lopez de Pariza and Fermin Elizalde and Marta Ximenis Campins and Amaia Agirre and Gabriel Perli and Haritz Sardon},

doi = {10.1002/ange.202509710},

issn = {1521-3757},

year  = {2025},

date = {2025-09-22},

journal = {Angewandte Chemie},

volume = {137},

number = {39},

publisher = {Wiley},

abstract = {AbstractStep‐growth polymerization (SGP) typically produces polymers with exceptional versatility in terms of applications, but its inherently uncontrolled nature leads to broad molecular weight distributions (Đ) and consequently polymers with poor nanostructure control in comparison to chain growth polymers. In this study, we provide a solution to this long‐lasting problem by introducing a new concept, asymmetric dynamic bond mediated polymerization (ADBP). In this case, the polymerization between asymmetric and reversibly deactivated AA’‐type dielectrophiles and B2‐type dinucleophiles has a preferential reaction pathway between the functionality A’ of the asymmetric AA’ monomer with B2. We observe that this polymerization allows us to achieve better control of the step‐growth process where in the first stage only well‐defined trimers and dimers are primarily formed up to conversion (p) ≤ 0.6, followed by their polymerization stage (p ≥ 0.6). This leads to polymers with reduced Đ (<1.5), in comparison to traditional SGP, and improved molar mass control. Such technique is further exploited to prepare polyurethanes with Đ = 1.2, which exhibit the ability to form microphase‐separated domains with higher ordering, giving rise to polyurethane thermosets with superior mechanical properties compared to a traditional SGP analog.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Prasad2025,

title = {Lab safety alert: a real case of isocyanate exposure},

author = {Akshaya Maria Prasad and Gabriel Perli and Marta Ximenis and Ainara Tejero and Agurtzane Mugica and Lucas Polo Fonseca and Ainara Sangroniz and Fernando Vidal and Haritz Sardon},

doi = {10.1039/d5py90051d},

issn = {1759-9962},

year  = {2025},

date = {2025-06-24},

journal = {Polym. Chem.},

volume = {16},

number = {25},

pages = {2905--2909},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {A real-world laboratory accident highlights underestimated dermal risks posed by reactive isocyanates. First-aid actions and essential safety insights are shared to reinforce best laboratory safety practices.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Lamas2024,

title = {Exploiting the Base‐Triggered Thiol/Vinyl Ether Addition to Prepare Well‐Defined Microphase Separated Thermo‐Switchable Adhesives},

author = {Aritz Lamas and Lucas Polo Fonseca and Cécile Moussard and Daniela de Morais Zanata and Gabriel Perli and Marta Ximenis and Xabier Lopez de Pariza and Guillem Seychal and Marco Caliari and Miren Itxaso and Robert Aguirresarobe and Iñigo Calvo and Haritz Sardon},

doi = {10.1002/adfm.202412584},

issn = {1616-3028},

year  = {2025},

date = {2025-01-00},

journal = {Adv Funct Materials},

volume = {35},

number = {2},

publisher = {Wiley},

abstract = {AbstractSwitchable adhesives are materials of utmost importance due to their capability of having their adhesion/cohesion properties reversibly triggered upon stimuli, allowing on‐demand surface attaching/detaching. Still, several challenges mainly associated with complex uncontrolled chemical processes hinders their production. In this study, it is found that unexpectedly vinyl ethers are able to react with thiols in the presence of a catalytic concentration of base, which allows the preparation of well‐defined phase‐separated switchable adhesives. Indeed, these findings show that base‐catalyzed thiol‐acrylate and thiol‐vinyl ether are highly orthogonal, making the acrylate reaction faster. This is explored to react in the first stage thiols with acrylates in the presence of vinyl ethers to end‐cap all the oligomers with stable vinyl ethers and suppress undesirable disulfide formation. In a second stage the UV‐triggered thiol‐ene “click reaction” is carried out, forming the network. It is shown that the network prepared by this approach presents superior adhesion due to greater backbone length, a controlled crosslinking motif, and better‐defined microphase separation. Additionally, the adhesives made by this strategy are thermo‐switchable due to the temperature‐triggered base‐catalyzed thioether dynamic covalent character at 200 °C. Despite providing superior adhesive properties, the proposed technology endows scalable, thermo‐switchable, and O2‐resistant adhesives with huge industrialization potential.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Matxinandiarena2024,

title = {Crystallization-Induced Self-Assembly of Poly(ethylene glycol) Side Chains in Dithiol–yne-Based Comb Polymers: Side Chain Spacing and Molecular Weight Effects},

author = {Eider Matxinandiarena and Mario Iván Peñas and Brennan J. Curole and Monika Król and Lucas Polo Fonseca and Janne Ruokolainen and Scott M. Grayson and Leire Sangroniz and Alejandro J. Müller},

doi = {10.1021/acs.macromol.4c00527},

issn = {1520-5835},

year  = {2024},

date = {2024-05-28},

journal = {Macromolecules},

volume = {57},

number = {10},

pages = {4906--4917},

publisher = {American Chemical Society (ACS)},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Clarke2024,

title = {Cyclic and Linear Tetrablock Copolymers Synthesized at Speed and Scale by Lewis Pair Polymerization of a One-Pot (Meth)acrylic Mixture and Characterized at Multiple Levels},

author = {Ryan W. Clarke and Maria Rosaria Caputo and Lucas Polo Fonseca and Michael L. McGraw and Liam T. Reilly and Kevin A. Franklin and Alejandro J. Müller and Eugene Y.-X. Chen},

doi = {10.1021/jacs.3c14136},

issn = {1520-5126},

year  = {2024},

date = {2024-02-21},

journal = {J. Am. Chem. Soc.},

volume = {146},

number = {7},

pages = {4930--4941},

publisher = {American Chemical Society (ACS)},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{LopezdePariza2023,

title = {Polythiourethanes: Synthesis, applications, and opportunities},

author = {Xabier Lopez de Pariza and Paula Fanlo and Lucas Polo Fonseca and Alaitz Ruiz de Luzuriaga and Haritz Sardon},

doi = {10.1016/j.progpolymsci.2023.101735},

issn = {0079-6700},

year  = {2023},

date = {2023-10-00},

journal = {Progress in Polymer Science},

volume = {145},

publisher = {Elsevier BV},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Fanjul-Mosteirín2023,

title = {Bio-based non-isocyanate poly(hydroxy urethane)s (PHU) derived from vanillin and CO_{2}},

author = {Noé Fanjul-Mosteirín and Lucas Polo Fonseca and Andrew P. Dove and Haritz Sardon},

doi = {10.1039/d3ma00111c},

issn = {2633-5409},

year  = {2023},

date = {2023-06-06},

journal = {Mater. Adv.},

volume = {4},

number = {11},

pages = {2437--2448},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {In this study, we demonstrate that vanillin is a valuable source of aromaticity that can be explored for poly(hydroxy urethane) production with competitive properties, avoiding the use of oil-based or hazardous precursors.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2023,

title = {Reducing the carbon footprint of polyurethanes by chemical and biological depolymerization: Fact or fiction?},

author = {L. Polo Fonseca and A. Duval and E. Luna and M. Ximenis and S. De Meester and L. Avérous and H. Sardon},

doi = {10.1016/j.cogsc.2023.100802},

issn = {2452-2236},

year  = {2023},

date = {2023-06-00},

journal = {Current Opinion in Green and Sustainable Chemistry},

volume = {41},

publisher = {Elsevier BV},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2023b,

title = {From nano to the macro: tuning hierarchical aggregation of thermoresponsive PEG/PCL-based polyurethanes via molar mass/composition control},

author = {Lucas Polo Fonseca},

doi = {10.1007/s13233-023-00137-6},

issn = {2092-7673},

year  = {2023},

date = {2023-03-00},

journal = {Macromol. Res.},

volume = {31},

number = {3},

pages = {285--297},

publisher = {Springer Science and Business Media LLC},

abstract = {AbstractAmphiphilic hyperbranched polyurethanes (HPUs) based on PEG and PCL are promising for several biomedical applications. However, the lack of control over the molar mass and composition hinders a deep understanding of the aqueous self-assembly of HPUs. In this paper, the control over the HPU molar mass and composition was provided by dynamic urea bond-mediated polymerization (DUBMP), enabling a careful evaluation of their aqueous self-assembly by 1H NMR, DLS, and Cryo-TEM. HPUs containing a single PCL block per chain self-assemble into nanoaggregates (Rh ≈ 10 nm) in water up to its cloud-point temperature (Tcp) of 34 °C. On the other hand, HPUs with more than one PCL block per chain self-assemble into nanoaggregates and their clusters below Tcp. In this case, the solution behavior can be tuned by the HPU molar mass. Increasing $$overline{{mathrm{M} }_{mathrm{w}}}$$

                  

                    

                      M

                      w

                    

                    ¯

                  

                 from 4 to 19 kDa, HPUs of similar composition can form colloidally stable cluster suspensions ($$overline{{mathrm{M} }_{mathrm{w}}}$$

                  

                    

                      M

                      w

                    

                    ¯

                  

                 = 4 kDa) and phase separate into a denser liquid aggregate–cluster phase ($$overline{{mathrm{M} }_{mathrm{w}}}$$

                  

                    

                      M

                      w

                    

                    ¯

                  

                 = 7 kDa) or into a highly viscous aggregate-network phase ($$overline{{mathrm{M} }_{mathrm{w}}}$$

                  

                    

                      M

                      w

                    

                    ¯

                  

                 = 19 kDa). This type of control over the hierarchical aggregation of HPUs was reported for the first time and is interesting for biomedical applications.

                Graphical abstract},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2022,

title = {Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐\textit{Ð} Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control},

author = {Lucas Polo Fonseca},

doi = {10.1002/macp.202200129},

issn = {1521-3935},

year  = {2022},

date = {2022-10-00},

journal = {Macro Chemistry & Physics},

volume = {223},

number = {19},

publisher = {Wiley},

abstract = {AbstractDynamic urea bond‐mediated polymerization (DUBMP) has been employed for the synthesis of linear, branched, telechelic, and random‐block polyurethanes (PUs) with low molar‐mass dispersity relative to conventionally synthesized PUs (Đ < 1.5). However, the reason for the improved control of the molar mass and reduction in dispersity, promoted by DUBMP, has not been explained. In this paper, the DUBMP synthesis of linear PU based on low‐molar‐mass poly(ethylene glycol) (PEG) and isophorone diisocyanate is studied comprehensively. The lower viscosity of the PEG‐based PU allows DUBMP to reach high conversions (≈0.97) for the first time, while molar mass and Đ vary substantially with reaction conditions, despite yielding similar/equal conversion values. Both molar mass and Đ increase with an increase in reaction temperature, or with a reduction of the amine/isocyanate molar ratio. Therefore, evidence suggests that DUBMP provides diffusion control due to the lower mobility of the longer chains associated with an isocyanate‐deactivator‐rich environment. An increase in the reaction temperature, and/or a decrease in the amine/isocyanate molar ratio, reduces the diffusion control, leading to higher Đ values and molar mass. Tuning of the reaction conditions allows obtaining PU of controlled molar mass (11 kDa ≤ Mw ≤ 42 kDa) and 1.3 < Đ < 1.75.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2022b,

title = {Dynamic Urea Bond‐Mediated Polymerization for Solvent‐Free Low‐\textit{Ð} Linear Polyurethanes of Controlled Molar Mass: Hypothesis of Diffusion Control},

author = {Lucas Polo Fonseca},

doi = {10.1002/macp.202200129},

issn = {1521-3935},

year  = {2022},

date = {2022-10-00},

journal = {Macro Chemistry & Physics},

volume = {223},

number = {19},

publisher = {Wiley},

abstract = {AbstractDynamic urea bond‐mediated polymerization (DUBMP) has been employed for the synthesis of linear, branched, telechelic, and random‐block polyurethanes (PUs) with low molar‐mass dispersity relative to conventionally synthesized PUs (Đ < 1.5). However, the reason for the improved control of the molar mass and reduction in dispersity, promoted by DUBMP, has not been explained. In this paper, the DUBMP synthesis of linear PU based on low‐molar‐mass poly(ethylene glycol) (PEG) and isophorone diisocyanate is studied comprehensively. The lower viscosity of the PEG‐based PU allows DUBMP to reach high conversions (≈0.97) for the first time, while molar mass and Đ vary substantially with reaction conditions, despite yielding similar/equal conversion values. Both molar mass and Đ increase with an increase in reaction temperature, or with a reduction of the amine/isocyanate molar ratio. Therefore, evidence suggests that DUBMP provides diffusion control due to the lower mobility of the longer chains associated with an isocyanate‐deactivator‐rich environment. An increase in the reaction temperature, and/or a decrease in the amine/isocyanate molar ratio, reduces the diffusion control, leading to higher Đ values and molar mass. Tuning of the reaction conditions allows obtaining PU of controlled molar mass (11 kDa ≤ Mw ≤ 42 kDa) and 1.3 < Đ < 1.75.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2021,

title = {Thermo- and UV-responsive amphiphilic nanogels via reversible [4+4] photocycloaddition of PEG/PCL-based polyurethane dispersions},

author = {Lucas Polo Fonseca and Maria Isabel Felisberti},

doi = {10.1016/j.eurpolymj.2021.110800},

issn = {0014-3057},

year  = {2021},

date = {2021-11-00},

journal = {European Polymer Journal},

volume = {160},

publisher = {Elsevier BV},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Fonseca2021,

title = {ABS composites with cellulose fibers: Towards fiber-matrix adhesion without surface modification},

author = {Lucas Polo Fonseca and Walter R. Waldman and Marco Aurelio De Paoli},

doi = {10.1016/j.jcomc.2021.100142},

issn = {2666-6820},

year  = {2021},

date = {2021-07-00},

journal = {Composites Part C: Open Access},

volume = {5},

publisher = {Elsevier BV},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2020,

title = {A one-pot, solvent-free, and controlled synthetic route for thermoresponsive hyperbranched polyurethanes},

author = {Lucas Polo Fonseca and Daniela de Morais Zanata and Cony Gauche and Maria Isabel Felisberti},

doi = {10.1039/d0py01026j},

issn = {1759-9962},

year  = {2020},

date = {2020-10-13},

journal = {Polym. Chem.},

volume = {11},

number = {39},

pages = {6295--6307},

publisher = {Royal Society of Chemistry (RSC)},

abstract = {
Hyperbranched polyurethanes (HPUs) are known for their multifunctionality and versatile properties.
},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{PoloFonseca2019,

title = {Dynamic urea bond mediated polymerization as a synthetic route for telechelic low molar mass dispersity polyurethanes and its block copolymers},

author = {Lucas Polo Fonseca and Maria I. Felisberti},

doi = {10.1016/j.eurpolymj.2019.05.052},

issn = {0014-3057},

year  = {2019},

date = {2019-09-00},

journal = {European Polymer Journal},

volume = {118},

pages = {213--221},

publisher = {Elsevier BV},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Perin2019,

title = {Macroporous hydrogels based on carbohydrates monomethacrylates and dimethacrylates: singular properties from carbohydrate‐based crosslinkers},

author = {Giovanni Bortoloni Perin and Lucas Polo Fonseca and Maria Isabel Felisberti},

doi = {10.1002/jctb.5973},

issn = {1097-4660},

year  = {2019},

date = {2019-06-00},

journal = {J of Chemical Tech & Biotech},

volume = {94},

number = {6},

pages = {1913--1924},

publisher = {Wiley},

abstract = {AbstractBACKGROUNDReadily available feedstock and biocompatibility make carbohydrate‐based hydrogels promising materials for biomedical applications. However, carbohydrate‐based crosslinkers are rather underexplored when compared with crosslinkers derived from fossil resources. In this study, novel fully bio‐based hydrogels derived from enzymatically produced d‐fructose and d‐glucose methacrylate monomers were synthesized with different amounts of d‐fructose dimethacrylate crosslinker.RESULTSThe use of a carbohydrate‐based crosslinker endows hydrogels with high swelling coefficients, up to 2400%, and superior mechanical resistance (compressive modulus up to 9.5 kPa with a maximum stress up to 50 kPa) compared with conventional crosslinkers based on fossil resources. Hydrogels shape and crosslinking density influences hydrogel morphology, swelling behavior and mechanical resistance. Moreover, hydrogels presented cell viability, biodegradability and hydrolysis‐resistance over a wide range of pH.CONCLUSIONThe use of a highly hydrophilic crosslinker based on carbohydrate for hydrogels synthesis enables the use of high crosslinker concentration, which improves mechanical properties, however with minor loss of the water swelling capacity, compared with conventional fossil‐based crosslinkers. This is an important advantage over conventional crosslinkers based on fossil resources. Moreover, slab hydrogels hold higher stress under compression–decompression cycles, and present higher resistance to hydrolysis in basic medium due to the thicker pore walls than cylindrical ones. © 2019 Society of Chemical Industry},

keywords = {},

pubstate = {published},

tppubtype = {article}

}