@article{MaticSchlaad2018,
  author    = {Matic, Aleksandar and Schlaad, Helmut},
  title     = {Thiol-ene photofunctionalization of 1,4-polymyrcene},
  series = {Polymer international},
  volume    = {67},
  journal   = {Polymer international},
  number    = {5},
  publisher = {Wiley},
  address   = {Hoboken},
  issn      = {0959-8103},
  doi       = {10.1002/pi.5534},
  pages     = {500 -- 505},
  year      = {2018},
  abstract  = {1,4-Polymyrcene was synthesized by anionic polymerization of -myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, ethyl 2-mercaptopropionate and 2-methyl-2-propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4-polymyrcene decreased in the order 1 degrees thiol (ca 95\%) > 2 degrees thiol (ca 80\%) > 3 degrees thiol (<5\%), due to the reversibility of the thiol-ene reaction. Remarkably, thiol addition to the side-chain double bonds was 8 - 10 times (1 degrees thiol) or 24 times (2 degrees thiol) faster than to the main-chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10-fold excess of thiol with respect to myrcene units, the thiol-ene addition was accompanied by chain coupling reactions, which in the extreme case of 3 degrees thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl-thioglycolate-functionalized 1,4-polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. (c) 2018 Society of Chemical Industry},
  language  = {en}
}
@article{GoldhahnSchubertSchlaadetal.2018,
  author    = {Goldhahn, Christian and Schubert, Jonas and Schlaad, Helmut and Ferri, James K. and Fery, Andreas and Chanana, Munish},
  title     = {Synthesis of Metal@Protein@Polymer Nanoparticles with Distinct Interfacial and Phase Transfer Behavior},
  series = {Chemistry of materials : a publication of the American Chemical Society},
  volume    = {30},
  journal   = {Chemistry of materials : a publication of the American Chemical Society},
  number    = {19},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0897-4756},
  doi       = {10.1021/acs.chemmater.8b02314},
  pages     = {6717 -- 6727},
  year      = {2018},
  abstract  = {In this study, we present a novel and facile method for the synthesis of multiresponsive plasmonic nanoparticles with an interesting interfacial behavior. We used thiol-initiated photopolymerization technique to graft poly(N-isopropylacrylamide) onto the surface of protein-coated gold nanoparticles. The combination of the protein bovine serum albumin with the thermoresponsive polymer leads to smart hybrid nanoparticles, which show a stimuli-responsive behavior of their aggregation and a precisely controllable phase transfer behavior. Three interconnected stimuli, namely, temperature, ionic strength, and pH, were identified as property tuning switches. The aggregation was completely reversible and was quantified by determining Smoluchowski's instability ratios with time-resolved dynamic light scattering. The tunable hydrophobicity via the three stimuli was used to study interfacial activity and phase transfer behavior of the nanoparticles at an octanol/water interface. Depending on the type of coating (i.e., protein or protein/polymer) as well as the three external stimuli, the nanoparticles either remained in the aqueous phase (aggregated or nonaggregated), accumulated at the oil/water interface, wet the glass wall between the glass vial and the octanol phase, or even crossed the oil/water interface. Such smart and interfacially active nanoparticles with external triggers that are capable of crossing oil/water interfaces under physiological conditions open up new avenues for a variety of applications ranging from the development of drug-delivery nanosystems across biological barriers to the preparation of new catalytic materials.},
  language  = {en}
}
@article{VacogneWeiTaueretal.2018,
  author    = {Vacogne, Charlotte Dominique and Wei, Chunxiang and Tauer, Klaus and Schlaad, Helmut},
  title     = {Self-assembly of alpha-helical polypeptides into microscopic and enantiomorphic spirals},
  series = {Journal of the american chemical society},
  volume    = {140},
  journal   = {Journal of the american chemical society},
  number    = {36},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0002-7863},
  doi       = {10.1021/jacs.8b06503},
  pages     = {11387 -- 11394},
  year      = {2018},
  abstract  = {Helical structures are ubiquitous in biological materials and often serve a structural purpose. Bioinspired helical materials can be challenging to synthesize and rarely reach the degree of hierarchy of their natural counterparts. Here we report the first example of particles synthesized by direct emulsification of polypeptides found to display spiral morphologies in the dry state. The polypeptides were alpha-helical homo- and copolypeptides of gamma-benzyl glutamate and allylglycine. The chirality of the spirals was controlled by the chirality of the alpha-helices. Notably, right-handed alpha-helical polypeptides (rich in 1, residues) produced clockwise spirals, whereas left-handed alpha-helical polypeptides (rich in D residues) produced the enantiomorphs, i.e., counterclockwise spirals. The disruption of the alpha-helical conformation by the introduction of chiral defects led to less regular spirals and in some cases their suppression. A hypothesis for the transmission of helicity and chirality from a molecular to a higher hierarchical level, involving fibril bundling of coiled alpha-helices, is proposed.},
  language  = {en}
}
@article{NoackSchanzenbachKoetzetal.2018,
  author    = {Noack, Sebastian and Schanzenbach, Dirk and Koetz, Joachim and Schlaad, Helmut},
  title     = {Polylactide-based amphiphilic block copolymers},
  series = {Macromolecular rapid communications},
  volume    = {40},
  journal   = {Macromolecular rapid communications},
  number    = {1},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1336},
  doi       = {10.1002/marc.201800639},
  pages     = {6},
  year      = {2018},
  abstract  = {The aqueous self-assembly behavior of a series of poly(ethylene glycol)-poly(l-/d-lactide) block copolymers and corresponding stereocomplexes is examined by differential scanning calorimetry, dynamic light scattering, and transmission electron microscopy. Block copolymers assemble into spherical micelles and worm-like aggregates at room temperature, whereby the fraction of the latter seemingly increases with decreasing lactide weight fraction or hydrophobicity. The formation of the worm-like aggregates arises from the crystallization of the polylactide by which the spherical micelles become colloidally unstable and fuse epitaxically with other micelles. The self-assembly behavior of the stereocomplex aggregates is found to be different from that of the block copolymers, resulting in rather irregular-shaped clusters of spherical micelles and pearl-necklace-like structures.},
  language  = {en}
}
@article{ZhengBaiTaoetal.2018,
  author    = {Zheng, Botuo and Bai, Tianwen and Tao, Xinfeng and Schlaad, Helmut and Ling, Jun},
  title     = {Identifying the Hydrolysis of Carbonyl Sulfide as a Side Reaction Impeding the Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride},
  series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences},
  volume    = {19},
  journal   = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences},
  number    = {11},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1525-7797},
  doi       = {10.1021/acs.biomac.8b01119},
  pages     = {4263 -- 4269},
  year      = {2018},
  abstract  = {Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization. Herein, we discover that during polymerization hydrogen sulfide evolves from the hydrolysis of carbonyl sulfide, which is the byproduct of ring-opening reaction, and reacts with NNTA to produce cyclic oligopeptoids. The capture of N-ethylethanethioic acid as an intermediate product confirms the reaction mechanism together with density functional theory quantum computational results. By bubbling the polymerization solution with argon, the side reaction can be suppressed to allow the synthesis of polysarcosine with high molar mass (M-n = 11,200 g/mol, D = 1.25) even in the presence of similar to 10,000 ppm of water.},
  language  = {en}
}
@article{HardyBertinTorresRendonetal.2018,
  author    = {Hardy, John G. and Bertin, Annabelle and Torres-Rendon, Jose Guillermo and Leal-Egana, Aldo and Humenik, Martin and Bauer, Felix and Walther, Andreas and C{\"o}lfen, Helmut and Schlaad, Helmut and Scheibel, Thomas R.},
  title     = {Facile photochemical modification of silk protein-based biomaterials},
  series = {Macromolecular bioscience},
  volume    = {18},
  journal   = {Macromolecular bioscience},
  number    = {11},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1616-5187},
  doi       = {10.1002/mabi.201800216},
  pages     = {6},
  year      = {2018},
  abstract  = {Silk protein-based materials show promise for application as biomaterials for tissue engineering. The simple and rapid photochemical modification of silk protein-based materials composed of either Bombyx mori silkworm silk or engineered spider silk proteins (eADF4(C16)) is reported. Radicals formed on the silk-based materials initiate the polymerization of monomers (acrylic acid, methacrylic acid, or allylamine) which functionalize the surface of the silk materials with poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(allylamine) (PAAm). To demonstrate potential applications of this type of modification, the polymer-modified silks are mineralized. The PAA- and PMAA-functionalized silks are mineralized with calcium carbonate, whereas the PAAm-functionalized silks are mineralized with silica, both of which provide a coating on the materials that may be useful for bone tissue engineering, which will be the subject of future investigations.},
  language  = {en}
}
@article{BehrendtSchlaad2018,
  author    = {Behrendt, Felix Nicolas and Schlaad, Helmut},
  title     = {Entropy-Driven Ring-Opening Disulfide Metathesis Polymerization for the Synthesis of Functional Poly(disulfide)s},
  series = {Macromolecular rapid communications},
  volume    = {39},
  journal   = {Macromolecular rapid communications},
  number    = {6},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1336},
  doi       = {10.1002/marc.201700735},
  pages     = {4},
  year      = {2018},
  abstract  = {Metal-free entropy-driven disulfide metathesis polymerization of unsaturated L-cystine based macrocycles produces high-molar-mass heterofunctional poly(disulfide)s, i.e., poly(ester-disulfide-alkene) and poly(amide-disulfide-alkene); M-w(app) = 44-60 kDa, (sic) > 1.7. The polymerization is fast and reaches equilibrium within 1-5 minutes (monomer conversion 70-90\%) in polar aprotic solvents such as N,N-dimethylacetamide, dimethylsulfoxide, or y-valerolactone. Thiol-terminated polymers are stable in bulk or when dissolved in weakly polar solvents, but rapidly depolymerize in dilute polar solution.},
  language  = {en}
}
@article{ChenSongZhaoetal.2018,
  author    = {Chen, Ye and Song, Qilei and Zhao, Junpeng and Gong, Xiangjun and Schlaad, Helmut and Zhang, Guangzhao},
  title     = {Betulin-Constituted multiblock amphiphiles for broad-spectrum protein resistance},
  series = {ACS applied materials \& interfaces},
  volume    = {10},
  journal   = {ACS applied materials \& interfaces},
  number    = {7},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1944-8244},
  doi       = {10.1021/acsami.7b16255},
  pages     = {6593 -- 6600},
  year      = {2018},
  abstract  = {Multiblock-like amphiphilic polyurethanes constituted by poly(ethylene oxide) and biosourced betulin are designed for antifouling and synthesized by a convenient organocatalytic route comprising tandem chain-growth and step-growth polymerizations. The doping density of betulin (D-B) in the polymer chain structure is readily varied by a mixed-initiator strategy. The spin-coated polymer films exhibit unique nanophase separation and protein resistance behaviors. Higher D-B leads to enhanced surface hydrophobicity and, unexpectedly, improved protein resistance. It is found that the surface holds molecular-level heterogeneity when D-B is substantially high due to restricted phase separation; therefore, broad-spectrum protein resistance is achieved despite considerable surface hydrophobicity. As D-B decreases, the distance between adjacent betulin units increases so that hydrophobic nanodomains are formed, which provide enough landing areas for relatively small-sized proteins to adsorb on the surface.},
  language  = {en}
}