@article{AlNajiSchlaadAntonietti2020,
  author    = {Al-Naji, Majd and Schlaad, Helmut and Antonietti, Markus},
  title     = {New (and old) monomers from biorefineries to make polymer chemistry more sustainable},
  series = {Macromolecular rapid communications},
  volume    = {42},
  journal   = {Macromolecular rapid communications},
  number    = {3},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1336},
  doi       = {10.1002/marc.202000485},
  pages     = {11},
  year      = {2020},
  abstract  = {This opinion article describes recent approaches to use the "biorefinery" concept to lower the carbon footprint of typical mass polymers, by replacing parts of the fossil monomers with similar or even the same monomer made from regrowing dendritic biomass. Herein, the new and green catalytic synthetic routes are for lactic acid (LA), isosorbide (IS), 2,5-furandicarboxylic acid (FDCA), and p-xylene (pXL). Furthermore, the synthesis of two unconventional lignocellulosic biomass derivable monomers, i.e., alpha-methylene-gamma-valerolactone (MeGVL) and levoglucosenol (LG), are presented. All those have the potential to enter in a cost-effective way, also the mass market and thereby recover lost areas for polymer materials. The differences of catalytic unit operations of the biorefinery are also discussed and the challenges that must be addressed along the synthesis path of each monomers.},
  language  = {en}
}
@misc{AlNajiSchlaadAntonietti2020,
  author    = {Al-Naji, Majd and Schlaad, Helmut and Antonietti, Markus},
  title     = {New (and old) monomers from biorefineries to make polymer chemistry more sustainable},
  series = {Zweitver{\"o}ffentlichungen der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Zweitver{\"o}ffentlichungen der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {3},
  issn      = {1866-8372},
  doi       = {10.25932/publishup-57061},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-570614},
  pages     = {13},
  year      = {2020},
  abstract  = {This opinion article describes recent approaches to use the "biorefinery" concept to lower the carbon footprint of typical mass polymers, by replacing parts of the fossil monomers with similar or even the same monomer made from regrowing dendritic biomass. Herein, the new and green catalytic synthetic routes are for lactic acid (LA), isosorbide (IS), 2,5-furandicarboxylic acid (FDCA), and p-xylene (pXL). Furthermore, the synthesis of two unconventional lignocellulosic biomass derivable monomers, i.e., alpha-methylene-gamma-valerolactone (MeGVL) and levoglucosenol (LG), are presented. All those have the potential to enter in a cost-effective way, also the mass market and thereby recover lost areas for polymer materials. The differences of catalytic unit operations of the biorefinery are also discussed and the challenges that must be addressed along the synthesis path of each monomers.},
  language  = {en}
}
@article{BehrendtHessLehmannetal.2019,
  author    = {Behrendt, Felix Nicolas and Hess, Andreas and Lehmann, Max and Schmidt, Bernd and Schlaad, Helmut},
  title     = {Polymerization of cystine-derived monomers},
  series = {Polymer Chemistry},
  volume    = {10},
  journal   = {Polymer Chemistry},
  number    = {13},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/c9py00118b},
  pages     = {1636 -- 1641},
  year      = {2019},
  abstract  = {Cystine was used as a platform chemical to prepare cyclic and acyclic monomers for entropy-driven ringopening polymerization (ED-ROMP) via olefin or disulfide metathesis and for step-growth polymerization. The olefin ED-ROMP of an olefin/disulfide containing 16-atom macrocycle using the 3rd generation Grubbs catalyst was examined in greater detail. Kinetic studies revealed that the catalyst turned inactive during the polymerization, which limited the achievable (apparent) polymer molar mass to similar to 70 kg mol(-1). Such limitation could be overcome with the disulfide ED-ROMP of the same macrocycle to yield polymers with molar masses of up to 180 kg mol(-1). The step-growth polymerizations of acyclic diene and dithiol monomers via olefin metathesis or oxidation were far less effective and yielded just low molar mass polymers or oligomers; photopolymerization of a thiol-ene monomer produced a polyester with a molar mass of 35 kg mol(-1).},
  language  = {en}
}
@misc{BehrendtSchlaad2016,
  author    = {Behrendt, Felix Nicolas and Schlaad, Helmut},
  title     = {Metathesis polymerization of cystine-based macrocycles},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-395080},
  pages     = {4},
  year      = {2016},
  abstract  = {Macrocycles based on L-cystine were synthesized by ring-closing metathesis (RCM) and subsequently polymerized by entropy-driven ring-opening metathesis polymerization (ED-ROMP). Monomer conversion reached ∼80\% in equilibrium and the produced poly(ester-amine-disulfide-alkene)s exhibited apparent molar masses (Mappw) of up to 80 kDa and dispersities (Đ) of ∼2. The polymers can be further functionalized with acid anhydrides and degraded by reductive cleavage of the main-chain disulfide.},
  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{BehrendtSchlaad2017,
  author    = {Behrendt, Felix Nicolas and Schlaad, Helmut},
  title     = {Metathesis polymerization of cystine-based macrocycles},
  series = {Polymer Chemistry},
  volume    = {8},
  journal   = {Polymer Chemistry},
  number    = {2},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/c6py01864e},
  pages     = {366 -- 369},
  year      = {2017},
  abstract  = {Macrocycles based on L-cystine were synthesized by ring-closing metathesis (RCM) and subsequently polymerized by entropy-driven ring-opening metathesis polymerization (ED-ROMP). Monomer conversion reached similar to 80\% in equilibrium and the produced poly (ester-amine-disulfide-alkene)s exhibited apparent molar masses (M-w(app)) of up to 80 kDa and dispersities (D) of similar to 2. The polymers can be further functionalized with acid anhydrides and degraded by reductive cleavage of the main-chain disulfide.},
  language  = {en}
}
@article{BogomolovaSeckerKoetzetal.2017,
  author    = {Bogomolova, Anna and Secker, Christian and Koetz, Joachim and Schlaad, Helmut},
  title     = {Thermo-induced multistep assembly of double-hydrophilic block copolypeptoids in water},
  series = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft},
  volume    = {295},
  journal   = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft},
  publisher = {Springer},
  address   = {New York},
  issn      = {0303-402X},
  doi       = {10.1007/s00396-017-4044-6},
  pages     = {1305 -- 1312},
  year      = {2017},
  abstract  = {The aqueous solution behavior of thermoresponsive-hydrophilic block copolypeptoids, i.e., poly(N-(n-propyl)glycine) (x) -block-poly(N-methylglycine) (y) (x = 70; y = 23, 42, 76), in the temperature range of 20-45 A degrees C is studied. Turbidimetric analyses of the 0.1 wt\% aqueous solutions reveal two cloud points at T (cp)similar to 30 and 45 A degrees C and a clearing point in between at T (cl)similar to 42 A degrees C. Temperature-dependent dynamic light scattering (DLS) suggest that right above the first collapse temperature, single polymer molecules assemble into large structures which upon further heating, i.e., at the clearing point temperature, disassemble into micelle-like structures. Upon further heating, the aggregates start to grow again in size, as recognized by the second cloud point, through a crystallization process.},
  language  = {en}
}
@article{BrosnanSchlaad2014,
  author    = {Brosnan, Sarah M. and Schlaad, Helmut},
  title     = {Modification of polypeptide materials by Thiol-X chemistry},
  series = {Polymer : the international journal for the science and technology of polymers},
  volume    = {55},
  journal   = {Polymer : the international journal for the science and technology of polymers},
  number    = {22},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0032-3861},
  doi       = {10.1016/j.polymer.2014.08.067},
  pages     = {5511 -- 5516},
  year      = {2014},
  abstract  = {Thiol-X chemistry has proven to be a valuable toolbox for modification of peptides, proteins, monomers, and polymers. Recently, this has become especially true for the modification of polypeptides (monomers or polymers), which has resulted in a plethora of novel polymers and materials. With this in mind, this highlight focuses on the recent literature concerning the modification of polypeptides by the use of thiol-X chemistry, in particular to synthetic polypeptides either at the monomer or polymer stage modified by thiol-ene, -Michael addition, and -yne chemistries. (C) 2014 Published by Elsevier Ltd.},
  language  = {en}
}
@article{BrosnanSchlaadAntonietti2015,
  author    = {Brosnan, Sarah M. and Schlaad, Helmut and Antonietti, Markus},
  title     = {Aqueous Self-Assembly of Purely Hydrophilic Block Copolymers into Giant Vesicles},
  series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition},
  volume    = {54},
  journal   = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition},
  number    = {33},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1433-7851},
  doi       = {10.1002/anie.201502100},
  pages     = {9715 -- 9718},
  year      = {2015},
  abstract  = {Self-assembly of macromolecules is fundamental to life itself, and historically, these systems have been primitively mimicked by the development of amphiphilic systems, driven by the hydrophobic effect. Herein, we demonstrate that self-assembly of purely hydrophilic systems can be readily achieved with similar ease and success. We have synthesized double hydrophilic block copolymers from polysaccharides and poly(ethylene oxide) or poly(sarcosine) to yield high molar mass diblock copolymers through oxime chemistry. These hydrophilic materials can easily assemble into nanosized (<500nm) and microsized (>5m) polymeric vesicles depending on concentration and diblock composition. Because of the solely hydrophilic nature of these materials, we expect them to be extraordinarily water permeable systems that would be well suited for use as cellular mimics.},
  language  = {en}
}
@article{CasseShkilnyyLindersetal.2012,
  author    = {Casse, Olivier and Shkilnyy, Andriy and Linders, J{\"u}rgen and Mayer, Christian and H{\"a}ussinger, Daniel and V{\"o}lkel, Antje and Th{\"u}nemann, Andreas F. and Dimova, Rumiana and C{\"o}lfen, Helmut and Meier, Wolfgang P. and Schlaad, Helmut and Taubert, Andreas},
  title     = {Solution behavior of double-hydrophilic block copolymers in dilute aqueous solution},
  series = {Macromolecules : a publication of the American Chemical Society},
  volume    = {45},
  journal   = {Macromolecules : a publication of the American Chemical Society},
  number    = {11},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0024-9297},
  doi       = {10.1021/ma300621g},
  pages     = {4772 -- 4777},
  year      = {2012},
  abstract  = {The self-assembly of double-hydrophilic poly(ethylene oxide)-poly(2-methyl-2-oxazoline) diblock copolymers in water has been studied. Isothermal titration calorimetry, small-angle X-ray scattering, and analytical ultracentrifugation suggest that only single polymer chains are present in solution. In contrast, light scattering and transmission electron microscopy detect aggregates with radii of ca. 100 nm. Pulsed field gradient NMR spectroscopy confirms the presence of aggregates, although only 2\% of the polymer chains undergo aggregation. Water uptake experiments indicate differences in the hydrophilicity of the two blocks, which is believed to be the origin of the unexpected aggregation behavior (in accordance with an earlier study by Ke et al. [Macromolecules 2009, 42, 5339-5344]). The data therefore suggest that even in double-hydrophilic block copolymers, differences in hydrophilicity are sufficient to drive polymer aggregation, a phenomenon that has largely been overlooked or ignored so far.},
  language  = {en}
}
@article{ChandranDoldBuvignieretal.2015,
  author    = {Chandran, Sivasurender and Dold, Stefanie and Buvignier, Amaury and Krannig, Kai-Steffen and Schlaad, Helmut and Reiter, G{\"u}nter and Reiter, Renate},
  title     = {Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States},
  series = {Langmuir},
  volume    = {31},
  journal   = {Langmuir},
  number    = {23},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.5b01212},
  pages     = {6426 -- 6435},
  year      = {2015},
  abstract  = {Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films.},
  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}
}
@misc{DaniTaeuberZhangetal.2018,
  author    = {Dani, Alessandro and Taeuber, Karoline and Zhang, Weiyi and Schlaad, Helmut and Yuan, Jiayin},
  title     = {Stable covalently photo-cross-linked porous poly(ionic liquid) membrane with gradient pore size},
  series = {Abstracts of papers : joint conference / The Chemical Institute of Cananda, CIC, American Chemical Society, ACS},
  volume    = {256},
  journal   = {Abstracts of papers : joint conference / The Chemical Institute of Cananda, CIC, American Chemical Society, ACS},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0065-7727},
  pages     = {1},
  year      = {2018},
  abstract  = {Porous polyelectrolyte membranes stable in a highly ionic environment are obtained by covalent crosslinking of an imidazolium-based poly(ionic liquid). The crosslinking reaction involves the UV light-induced thiol-ene (click) chemistry, and the phase separation, occurring during the crosslinking step, generates a fully interconnected porous structure in the membrane. The porosity is on the order of the micrometer scale and the membrane shows a gradient of pore size across the membrane cross-section. The membrane can separate polystyrene latex particles of different size and undergoes actuation in contact with acetone due to the asymmetric porous structure.},
  language  = {en}
}
@article{DaniTauberZhangetal.2017,
  author    = {Dani, Alessandro and Tauber, Karoline and Zhang, Weiyi and Schlaad, Helmut and Yuan, Jiayin},
  title     = {Stable Covalently Photo-Crosslinked Poly(Ionic Liquid) Membrane with Gradient Pore Size},
  series = {Macromolecular rapid communications},
  volume    = {38},
  journal   = {Macromolecular rapid communications},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1336},
  doi       = {10.1002/marc.201700167},
  pages     = {4},
  year      = {2017},
  abstract  = {Porous polyelectrolyte membranes stable in a highly ionic environment are obtained by covalent crosslinking of an imidazolium-based poly(ionic liquid). The crosslinking reaction involves the UV light-induced thiol-ene (click) chemistry, and the phase separation, occurring during the crosslinking step, generates a fully interconnected porous structure in the membrane. The porosity is on the order of the micrometer scale and the membrane shows a gradient of pore size across the membrane cross-section. The membrane can separate polystyrene latex particles of different size and undergoes actuation in contact with acetone due to the asymmetric porous structure.},
  language  = {en}
}
@article{DasElTawargyKhechineetal.2019,
  author    = {Das, Abhijna and El-Tawargy, Ahmed S. and Khechine, Emna and Noack, Sebastian and Schlaad, Helmut and Reiter, G{\"u}nter and Reiter, Renate},
  title     = {Controlling Nucleation in Quasi-Two-Dimensional Langmuir Poly(L-lactide) Films through Variation of the Rate of Compression},
  series = {Langmuir},
  volume    = {35},
  journal   = {Langmuir},
  number    = {18},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.9b00619},
  pages     = {6129 -- 6136},
  year      = {2019},
  abstract  = {We studied morphological changes in a quasi-two-dimensional Langmuir film of low molar mass poly(L-lactide) upon increasing the surface density, starting from randomly distributed molecules to a homogeneous monolayer of closely packed molecules, followed by nucleation and growth of mesoscopic, three-dimensional clusters from an overcompressed monolayer. The corresponding nucleation density of mesoscopic clusters within the monolayer can be tailored through variation of the rate of compression. For a given surface density and temperature, the nucleation probability was found to increase linearly with the rate of compression, allowing to adjust the density of mesoscopic clusters over nearly 2 orders magnitude.},
  language  = {en}
}
@article{DasNoackSchlaadetal.2020,
  author    = {Das, Abhijna and Noack, Sebastian and Schlaad, Helmut and Reiter, G{\"u}nter and Reiter, Renate},
  title     = {Exploring pathways to equilibrate Langmuir polymer films},
  series = {Langmuir},
  volume    = {36},
  journal   = {Langmuir},
  number    = {28},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.0c01268},
  pages     = {8184 -- 8192},
  year      = {2020},
  abstract  = {Focusing on the phase-coexistence region in Langmuir films of poly(L-lactide), we investigated changes in nonequilibrated morphologies and the corresponding features of the isotherms induced by different experimental pathways of lateral compression and expansion. In this coexistence region, the surface pressure II was larger than the expected equilibrium value and was found to increase upon compression, i.e., exhibited a nonhorizontal plateau. As shown earlier by using microscopic techniques [Langmuir 2019, 35, 6129-6136], in this plateau region, well-ordered mesoscopic clusters coexisted with a surrounding matrix phase. We succeeded in reducing Pi either by slowing down the rate of compression or through increasing the waiting time after stopping the movement of the barriers, which allowed for relaxations in the coexistence region. Intriguingly, the most significant pressure reduction was observed when recompressing a film that had already been compressed and expanded, if the recompression was started from an area value smaller than the one anticipated for the onset of the coexistence region. This observation suggests a "self-seeding" behavior, i.e., pre-existing nuclei allowed to circumvent the nucleation step. The decrease in Pi was accompanied by a transformation of the initially formed metastable mesoscopic clusters into a thermodynamically favored filamentary morphology. Our results demonstrate that it is practically impossible to obtain fully equilibrated coexisting phases in a Langmuir polymer film, neither under conditions of extremely slow continuous compression nor for long waiting times at a constant area in the coexistence region which allow for reorganization.},
  language  = {en}
}
@article{DebsharmaBehrendtLaschewskyetal.2019,
  author    = {Debsharma, Tapas and Behrendt, Felix Nicolas and Laschewsky, Andre and Schlaad, Helmut},
  title     = {Ring-opening metathesis polymerization of biomass-derived levoglucosenol},
  series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker},
  volume    = {58},
  journal   = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker},
  number    = {20},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1433-7851},
  doi       = {10.1002/anie.201814501},
  pages     = {6718 -- 6721},
  year      = {2019},
  abstract  = {The readily available cellulose-derived bicyclic compound levoglucosenol was polymerized through ring-opening metathesis polymerization (ROMP) to yield polylevoglucosenol as a novel type of biomass-derived thermoplastic polyacetal, which, unlike polysaccharides, contains cyclic as well as linear segments in its main chain. High-molar-mass polyacetals with apparent weight-average molar masses of up to 100kgmol(-1) and dispersities of approximately 2 were produced despite the non-living/controlled character of the polymerization due to irreversible deactivation or termination of the catalyst/active chain ends. The resulting highly functionalized polyacetals are glassy in bulk with a glass transition temperature of around 100 degrees C. In analogy to polysaccharides, polylevoglucosenol degrades slowly in an acidic environment.},
  language  = {en}
}
@article{DebsharmaSchmidtLaschewskyetal.2021,
  author    = {Debsharma, Tapas and Schmidt, Bernd and Laschewsky, Andre and Schlaad, Helmut},
  title     = {Ring-opening metathesis polymerization of unsaturated carbohydrate derivatives},
  series = {Macromolecules : a publication of the American Chemical Society},
  volume    = {54},
  journal   = {Macromolecules : a publication of the American Chemical Society},
  number    = {6},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0024-9297},
  doi       = {10.1021/acs.macromol.0c02821},
  pages     = {2720 -- 2728},
  year      = {2021},
  abstract  = {A series of biomass-derived levoglucosenyl alkyl ethers (alkyl = methyl, ethyl, n-propyl, isopropyl, and n-butyl) were synthesized and polymerized by ring-opening olefin metathesis polymerization using the Grubbs catalyst C793 at room temperature. Polymerizations were successfully performed in conventional solvents such as 1,4-dioxane and dichloromethane as well as in polar aprotic "green" solvents such as 2-methyltetrahydrofuran, dihydrolevoglucosenone (Cyrene), and ethyl acetate. The prepared polyacetals with degrees of polymerization of similar to 100 exhibit Schulz-Flory-type molar mass distributions and are thermoplastic materials with rather low glass transition temperatures in the range of 43-0 degrees C depending on the length of the alkyl substituent. Kinetic studies revealed that the polymerization proceeded rapidly to a steady state with a certain minimum monomer concentration threshold. When the steady state was reached, just about half of the [Ru] catalyst had been effective to initiate the polymerization, indicating that the initiation step was a slow process. The remaining catalyst was still active and did no longer react with monomers but with in-chain double bonds, cutting the formed polymer chains into shorter fragments. In the long term, all catalyst was consumed and propagating [Ru] chain ends were deactivated by the elimination of [Ru] from the chain ends to form inactive chains with terminal aldehyde groups.},
  language  = {en}
}
@article{DemirelGunerVerbraekenetal.2016,
  author    = {Demirel, A. Levent and Guner, Pinar Tatar and Verbraeken, Bart and Schlaad, Helmut and Schubert, Ulrich S. and Hoogenboom, Richard},
  title     = {Revisiting the Crystallization of Poly(2-alkyl-2-oxazoline)s},
  series = {Journal of polymer science : B, Polymer physics},
  volume    = {54},
  journal   = {Journal of polymer science : B, Polymer physics},
  publisher = {Wiley-Blackwell},
  address   = {Hoboken},
  issn      = {0887-6266},
  doi       = {10.1002/polb.23967},
  pages     = {721 -- 729},
  year      = {2016},
  abstract  = {Poly(2-alkyl-2-oxazoline)s (PAOx) exhibit different crystallization behavior depending on the length of the alkyl side chain. PAOx having methyl, ethyl, or propyl side chains do not show any bulk crystallization. Crystallization in the heating cycle, that is, cold crystallization, is observed for PAOx with butyl and pentyl side chains. For PAOx with longer alkyl side chains crystallization occurs in the cooling cycle. The different crystallization behavior is attributed to the different polymer chain mobility in line with the glass transition temperature (T-g) dependency on alkyl side chain length. The decrease in chain mobility with decreasing alkyl side chain length hinders the relaxation of the polymer backbone to the thermodynamic equilibrium crystalline structure. Double melting behavior is observed for PButOx and PiPropOx which is explained by the melt-recrystallization mechanism. Isothermal crystallization experiments of PButOx between 60 and 90 degrees C and PiPropOx between 90 and 150 degrees C show that PAOx can crystallize in bulk when enough time is given. The decrease of Tg and the corresponding increase in chain mobility at T > T-g with increasing alkyl side chain length can be attributed to an increasing distance between the polymer backbones and thus decreasing average strength of amide dipole interactions. (C) 2015 Wiley Periodicals, Inc.},
  language  = {en}
}
@article{DevRoeslerSchlaad2021,
  author    = {Dev, Akhil and R{\"o}sler, Alexander and Schlaad, Helmut},
  title     = {Limonene as a renewable unsaturated hydrocarbon solvent for living anionic polymerization of β-myrcene},
  series = {Polymer chemistry},
  volume    = {12},
  journal   = {Polymer chemistry},
  number    = {21},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/d1py00570g},
  pages     = {3084 -- 3087},
  year      = {2021},
  abstract  = {The acyclic monoterpene beta-myrcene is polymerized by anionic polymerization at room temperature using sec-butyllithium as the initiator and the cyclic monoterpene DL-limonene as an unsaturated hydrocarbon solvent. The polymerization is a living process and allows production of polymyrcenes with narrow molar mass distribution ((sic) similar to 1.06) and high content of 1,4 units (similar to 90\%) as well as block copolymers.},
  language  = {en}
}
@article{DiehlCernochZenkeetal.2010,
  author    = {Diehl, Christina and Cernoch, Peter and Zenke, Ingrid and Runge, Heike and Pitschke, Rona and Hartmann, Juergen and Tiersch, Brigitte and Schlaad, Helmut},
  title     = {Mechanistic study of the phase separation/crystallization process of poly(2-isopropyl-2-oxazoline) in hot water},
  issn      = {1744-683X},
  doi       = {10.1039/C0sm00114g},
  year      = {2010},
  abstract  = {The kinetics of the crystallization of thermoresponsive poly(2-isopropyl-2-oxazoline) in water and the time- dependent evolution of the morphology were examined using wide-angle X-ray scattering and conventional and cryogenic scanning electron microscopy. Results indicate that a temperature-induced phase separation produces a bicontinuous polymer network-like structure, which with the onset of crystallization collapses into individual particles (1-2 mu m in diameter) composed of a porous fiber mesh. Nanofibers then preferentially form at the particle surface, thus wrapping the microspheres like a ball of wool. The particle morphology is severely affected by changes in temperature and less by the initial polymer concentration.},
  language  = {en}
}
@misc{DoritiBrosnanWeidneretal.2016,
  author    = {Doriti, Afroditi and Brosnan, Sarah M. and Weidner, Steffen M. and Schlaad, Helmut},
  title     = {Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-95852},
  pages     = {3067 -- 3070},
  year      = {2016},
  abstract  = {Polysarcosine (Mn = 3650-20 000 g mol-1, Đ ∼ 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.},
  language  = {en}
}
@article{DoritiBrosnanWeidneretal.2016,
  author    = {Doriti, Afroditi and Brosnan, Sarah M. and Weidner, Steffen M. and Schlaad, Helmut},
  title     = {Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base},
  series = {Polymer Chemistry},
  volume    = {7},
  journal   = {Polymer Chemistry},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/c6py00221h},
  pages     = {3067 -- 3070},
  year      = {2016},
  abstract  = {Polysarcosine (M-n = 3650-20 000 g mol(-1), D similar to 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.},
  language  = {en}
}
@article{DoritiBrosnanWeidneretal.2016,
  author    = {Doriti, Afroditi and Brosnan, Sarah M. and Weidner, Steffen M. and Schlaad, Helmut},
  title     = {Synthesis of polysarcosine from air and moisture stable N-phenoxycarbonyl-N-methylglycine assisted by tertiary amine base},
  series = {Polymer Chemistry},
  volume    = {7},
  journal   = {Polymer Chemistry},
  publisher = {RSC Publ.},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/C6PY00221H},
  pages     = {3067 -- 3070},
  year      = {2016},
  abstract  = {Polysarcosine (Mn = 3650-20 000 g mol-1, Đ ∼ 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.},
  language  = {en}
}
@article{FuehrerSchlaad2014,
  author    = {Fuehrer, Felix N. and Schlaad, Helmut},
  title     = {ADMET polymerization of amino-acid-based diene},
  series = {Macromolecular chemistry and physics},
  volume    = {215},
  journal   = {Macromolecular chemistry and physics},
  number    = {22},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1352},
  doi       = {10.1002/macp.201400166},
  pages     = {2268 -- 2273},
  year      = {2014},
  abstract  = {1,4-Di(homo)allyl-2,5-diketopiperazines are synthesized and polymerized via ADMET using the Hoveyda-Grubbs 2nd generation catalyst. The but-3-enylated diketopiperazine can be converted into unsaturated tertiary polyamide with molar mass of <3000 g mol(-1), whereas the allylated diketopiperazine cannot. Double-bond isomerization occurs regardless of whether or not benzoquinone is present. A polyesteramide with a higher molar mass of ca. 4800 g mol(-1) is obtained by the alternating copolymerization (ALTMET) of 1,4-di(but-3-enyl)-2,5-di ketopiperazine and ethylene glycol diacrylate. A post-polymerization modification of the poly(ester)amides via radical thiol-ene chemistry, however, fails.},
  language  = {en}
}
@misc{GangloffUlbrichtLorsonetal.2016,
  author    = {Gangloff, Niklas and Ulbricht, Juliane and Lorson, Thomas and Schlaad, Helmut and Luxenhofer, Robert},
  title     = {Peptoids and Polypeptoids at the Frontier of Supra- and Macromolecular Engineering},
  series = {Chemical reviews},
  volume    = {116},
  journal   = {Chemical reviews},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0009-2665},
  doi       = {10.1021/acs.chemrev.5b00201},
  pages     = {1753 -- 1802},
  year      = {2016},
  language  = {en}
}
@article{GlatzelNoackSchanzenbachetal.2020,
  author    = {Glatzel, Julia and Noack, Sebastian and Schanzenbach, Dirk and Schlaad, Helmut},
  title     = {Anionic polymerization of dienes in 'green' solvents},
  series = {Polymer international},
  volume    = {70},
  journal   = {Polymer international},
  number    = {2},
  publisher = {Wiley},
  address   = {Hoboken},
  issn      = {0959-8103},
  doi       = {10.1002/pi.6152},
  pages     = {181 -- 184},
  year      = {2020},
  abstract  = {Isoprene and beta-myrcene were polymerized by anionic polymerization in bulk and in the 'green' ether solvents cyclopentyl methyl ether and 2-methyltetrahydrofuran and, for comparison, in cyclohexane and tetrahydrofuran. The polydienes produced in bulk and in cyclohexane contained high amounts of 1,4 units (>90\%) whereas those produced in ether solvents were rich in 1,2 and 3,4 units (36\%-86\%). Comparison of the microstructures and glass transition temperatures of the polydienes obtained in the various solvents suggests that conventionally used solvents can be substituted by environmentally more friendly alternatives.},
  language  = {en}
}
@article{GoebelHesemannFriedrichetal.2014,
  author    = {Goebel, Ronald and Hesemann, Peter and Friedrich, Alwin and Rothe, Regina and Schlaad, Helmut and Taubert, Andreas},
  title     = {Modular thiol-ene chemistry approach towards mesoporous silica monoliths with organically modified pore walls},
  series = {Chemistry - a European journal},
  volume    = {20},
  journal   = {Chemistry - a European journal},
  number    = {52},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {0947-6539},
  doi       = {10.1002/chem.201403982},
  pages     = {17579 -- 17589},
  year      = {2014},
  abstract  = {The surface modification of mesoporous silica monoliths through thiol-ene chemistry is reported. First, mesoporous silica monoliths with vinyl, allyl, and thiol groups were synthesized through a sol-gel hydrolysis-poly-condensation reaction from tetramethyl orthosilicate (TMOS) and vinyltriethoxysilane, allyltriethoxysilane, and (3-mercaptopropyl) trimethoxysilane, respectively. By variation of the molar ratio of the comonomers TMOS and functional silane, mesoporous silica objects containing different amounts of vinyl, allyl, and thiol groups were obtained. These intermediates can subsequently be derivatized through radical photoaddition reactions either with a thiol or an olefin, depending on the initial pore wall functionality, to yield silica monoliths with different pore-wall chemistries. Nitrogen sorption, small-angle X-ray scattering, solid-state NMR spectroscopy, elemental analysis, thermogravimetric analysis, and redox titration demonstrate that the synthetic pathway influences the morphology and pore characteristics of the resulting monoliths and also plays a significant role in the efficiency of functionalization. Moreover, the different reactivity of the vinyl and allyl groups on the pore wall affects the addition reaction, and hence, the degree of the pore-wall functionalization. This report demonstrates that thiol-ene photoaddition reactions are a versatile platform for the generation of a large variety of organically modified silica monoliths with different pore surfaces.},
  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{GressHeiligSmarslyetal.2009,
  author    = {Gress, Anja and Heilig, Anne and Smarsly, Bernd M. and Heydenreich, Matthias and Schlaad, Helmut},
  title     = {Hydrogen-bonded polymer nanotubes in water},
  issn      = {0024-9297},
  doi       = {10.1021/Ma900227t},
  year      = {2009},
  abstract  = {Intermolecular hydrogen bonding, not hydrophobic interaction, is the driving force for the spontaneous self- assembly of glycosylated polyoxazoline chains into nanotubes in dilute aqueous solution. The structural information is encoded in the relatively simple molecular structure of chains consisting of a tertiary polyamide backbone (hydrogen- accepting) and glucose side chains (hydrogen-donating). The formation of the nanotubes should occur through bending and closing of a 2D hydrogen-bonded layer of interdigitated polymer chains.},
  language  = {en}
}
@article{GuietGoebelKlinganetal.2015,
  author    = {Guiet, Amandine and Goebel, Caren and Klingan, Katharina and Lublow, Michael and Reier, Tobias and Vainio, Ulla and Kraehnert, Ralph and Schlaad, Helmut and Strasser, Peter and Zaharieva, Ivelina and Dau, Holger and Driess, Matthias and Polte, Joerg and Fischer, Anna},
  title     = {Hydrophobic Nanoreactor Soft-Templating: A Supramolecular Approach to Yolk@Shell Materials},
  series = {Advanced functional materials},
  volume    = {25},
  journal   = {Advanced functional materials},
  number    = {39},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1616-301X},
  doi       = {10.1002/adfm.201502388},
  pages     = {6228 -- 6240},
  year      = {2015},
  abstract  = {Due to their unique morphology-related properties, yolk@shell materials are promising materials for catalysis, drug delivery, energy conversion, and storage. Despite their proven potential, large-scale applications are however limited due to demanding synthesis protocols. Overcoming these limitations, a simple soft-templated approach for the one-pot synthesis of yolk@shell nanocomposites and in particular of multicore metal nanoparticle@metal oxide nanostructures (M-NP@MOx) is introduced. The approach here, as demonstrated for Au-NP@ITOTR (ITOTR standing for tin-rich ITO), relies on polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) inverse micelles as two compartment nanoreactor templates. While the hydrophilic P4VP core incorporates the hydrophilic metal precursor, the hydrophobic PS corona takes up the hydrophobic metal oxide precursor. As a result, interfacial reactions between the precursors can take place, leading to the formation of yolk@shell structures in solution. Once calcined these micelles yield Au-NP@ITOTR nanostructures, composed of multiple 6 nm sized Au NPs strongly anchored onto the inner surface of porous 35 nm sized ITOTR hollow spheres. Although of multicore nature, only limited sintering of the metal nanoparticles is observed at high temperatures (700 degrees C). In addition, the as-synthesized yolk@shell structures exhibit high and stable activity toward CO electrooxidation, thus demonstrating the applicability of our approach for the design of functional yolk@shell nanocatalysts.},
  language  = {en}
}
@article{GuietUnmuessigGoebeletal.2016,
  author    = {Guiet, Amandine and Unm{\"u}ssig, Tobias and G{\"o}bel, Caren and Vainio, Ulla and Wollgarten, Markus and Driess, Matthias and Schlaad, Helmut and Polte, J{\"o}rg and Fischer, Anna},
  title     = {Yolk@Shell Nanoarchitectures with Bimetallic Nanocores - Synthesis and Electrocatalytic Applications},
  series = {Earth \& planetary science letters},
  volume    = {8},
  journal   = {Earth \& planetary science letters},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1944-8244},
  doi       = {10.1021/acsami.6b06595},
  pages     = {28019 -- 28029},
  year      = {2016},
  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{HardyTorresRendonLealEganaetal.2016,
  author    = {Hardy, John G. and Torres-Rendon, Jose Guillermo and Leal-Egana, Aldo and Walther, Andreas and Schlaad, Helmut and Coelfen, Helmut and Scheibel, Thomas R.},
  title     = {Biomineralization of Engineered Spider Silk Protein-Based Composite Materials for Bone Tissue Engineering},
  series = {Materials},
  volume    = {9},
  journal   = {Materials},
  publisher = {MDPI},
  address   = {Basel},
  issn      = {1996-1944},
  doi       = {10.3390/ma9070560},
  pages     = {93 -- 108},
  year      = {2016},
  abstract  = {Materials based on biodegradable polyesters, such as poly(butylene terephthalate) (PBT) or poly(butylene terephthalate-co-poly(alkylene glycol) terephthalate) (PBTAT), have potential application as pro-regenerative scaffolds for bone tissue engineering. Herein, the preparation of films composed of PBT or PBTAT and an engineered spider silk protein, (eADF4(C16)), that displays multiple carboxylic acid moieties capable of binding calcium ions and facilitating their biomineralization with calcium carbonate or calcium phosphate is reported. Human mesenchymal stem cells cultured on films mineralized with calcium phosphate show enhanced levels of alkaline phosphatase activity suggesting that such composites have potential use for bone tissue engineering.},
  language  = {en}
}
@misc{HardyTorresRendonLealEganaetal.2017,
  author    = {Hardy, John G. and Torres-Rendon, Jose Guillermo and Leal-Ega{\~n}a, Aldo and Walther, Andreas and Schlaad, Helmut and C{\"o}lfen, Helmut and Scheibel, Thomas R.},
  title     = {Biomineralization of engineered spider silk protein-based composite materials for bone tissue engineering},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400519},
  pages     = {13},
  year      = {2017},
  abstract  = {Materials based on biodegradable polyesters, such as poly(butylene terephthalate) (PBT) or poly(butylene terephthalate-co-poly(alkylene glycol) terephthalate) (PBTAT), have potential application as pro-regenerative scaffolds for bone tissue engineering. Herein, the preparation of films composed of PBT or PBTAT and an engineered spider silk protein, (eADF4(C16)), that displays multiple carboxylic acid moieties capable of binding calcium ions and facilitating their biomineralization with calcium carbonate or calcium phosphate is reported. Human mesenchymal stem cells cultured on films mineralized with calcium phosphate show enhanced levels of alkaline phosphatase activity suggesting that such composites have potential use for bone tissue engineering.},
  language  = {en}
}
@article{HessSchmidtSchlaad2020,
  author    = {Hess, Andreas and Schmidt, Bernhard Volkmar Konrad Jakob and Schlaad, Helmut},
  title     = {Aminolysis induced functionalization of (RAFT) polymer-dithioester with thiols and disulfides},
  series = {Polymer Chemistry},
  volume    = {11},
  journal   = {Polymer Chemistry},
  number    = {48},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/d0py01365j},
  pages     = {7677 -- 7684},
  year      = {2020},
  abstract  = {A series of polystyrene- and poly(methyl methacrylate)-dithioesters was subjected to aminolysis under ambient atmospheric conditions, i.e., in the presence of oxygen. Polymer disulfide coupling by oxidation occurred within tens of minutes and the yield of disulfide-coupled polymer increased with decreasing polymer molar mass. Oxidation of thiolates is usually an unwanted side reaction, here it is employed to obtain exclusively polymeric mixed disulfides through in situ aminolysis/functionalization in the presence of a thiol. The in situ aminolysis/functionalization in the presence of a disulfide, Ellman's reagent or polymer disulfide, resulted in the exclusive formation of polymer-dithionitrobenzoic acid, which can be further reacted with a thiol to exchange the terminal functionality, or block copolymer with dynamic disulfide linker, respectively.},
  language  = {en}
}
@misc{HoogenboomSchlaad2016,
  author    = {Hoogenboom, Richard and Schlaad, Helmut},
  title     = {Thermoresponsive poly(2-oxazoline)s, polypeptoids, and polypeptides},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-395022},
  pages     = {17},
  year      = {2016},
  abstract  = {This review covers the recent advances in the emerging field of thermoresponsive polyamides or polymeric amides, i.e., poly(2-oxazoline)s, polypeptoids, and polypeptides, with a specific focus on structure-thermoresponsive property relationships, self-assembly, and applications.},
  language  = {en}
}
@misc{HoogenboomSchlaad2017,
  author    = {Hoogenboom, Richard and Schlaad, Helmut},
  title     = {Thermoresponsive poly(2-oxazoline)s, polypeptoids, and polypeptides},
  series = {Polymer Chemistry},
  volume    = {8},
  journal   = {Polymer Chemistry},
  number    = {1},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/c6py01320a},
  pages     = {24 -- 40},
  year      = {2017},
  abstract  = {This review covers the recent advances in the emerging field of thermoresponsive polyamides or polymeric amides, i.e., poly(2-oxazoline)s, polypeptoids, and polypeptides, with a specific focus on structure-thermoresponsive property relationships, self-assembly, and applications.},
  language  = {en}
}
@misc{HuZhaoZhangetal.2017,
  author    = {Hu, Shuangyan and Zhao, Junpeng and Zhang, Guangzhao and Schlaad, Helmut},
  title     = {Macromolecular architectures through organocatalysis},
  series = {Progress in Polymer Science},
  volume    = {74},
  journal   = {Progress in Polymer Science},
  publisher = {Elsevier},
  address   = {Oxford},
  issn      = {0079-6700},
  doi       = {10.1016/j.progpolymsci.2017.07.002},
  pages     = {34 -- 77},
  year      = {2017},
  abstract  = {In virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashion different polymer chains are covalently attached to each other within the macromolecule) and functionality (position and amount of functional groups that endow the entire macromolecule with specific chemical, physico-chemical or biological properties). (C) 2017 Published by Elsevier B.V.},
  language  = {en}
}
@article{JainWheelerEssetal.2019,
  author    = {Jain, Varun and Wheeler, Joshua J. and Ess, Daniel H. and Noack, Sebastian and Vacogne, Charlotte D. and Schlaad, Helmut and Bahr, Stephan and Dietrich, Paul and Meyer, Michael and Thissen, Andreas and Linford, Matthew R.},
  title     = {Poly(gamma-benzyl l-glutamate), by near-ambient pressure XPS},
  series = {Surface science spectra : SSS : an international journal \& database devoted to archiving spectra from surfaces \& interfaces},
  volume    = {26},
  journal   = {Surface science spectra : SSS : an international journal \& database devoted to archiving spectra from surfaces \& interfaces},
  number    = {2},
  publisher = {American Institute of Physics},
  address   = {Melville},
  issn      = {1055-5269},
  doi       = {10.1116/1.5109121},
  pages     = {10},
  year      = {2019},
  abstract  = {Near-ambient pressure x-ray photoelectron spectroscopy (NAP-XPS) is a less traditional form of XPS that allows samples to be analyzed at relatively high pressures, i. e., at greater than 2500 Pa. In this study, poly(.- benzyl L- glutamate) (PBLG) with a molar mass of 11.3 kg/mol was analyzed by NAP-XPS; here, we show the survey, C 1s, N 1s, and O 1s narrow scans of PBLG. The C 1s peak envelope was fitted in three different ways, to five, six, or seven synthetic peaks. In each fit, there was also a shake-up signal. The O 1s narrow scan was well fit with three peaks: CZO and CvO in a 1:2 ratio from the polymer, and a higher energy signal from water vapor. Hartree-Fock orbital energies of a model monomer served as a guide to an additional fit of the C 1s envelope.},
  language  = {en}
}
@article{KayaDebsharmaSchlaadetal.2020,
  author    = {Kaya, Kerem and Debsharma, Tapas and Schlaad, Helmut and Yagci, Yusuf},
  title     = {Cellulose-based polyacetals by direct and sensitized photocationic ring-opening polymerization of levoglucosenyl methyl ether},
  series = {Polymer Chemistry},
  volume    = {11},
  journal   = {Polymer Chemistry},
  number    = {43},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9954},
  doi       = {10.1039/d0py01307b},
  pages     = {6884 -- 6889},
  year      = {2020},
  abstract  = {This study aims to explore the photoinitiated cationic ring-opening polymerization of levoglucosenyl methyl ether (LGME), a chemical obtained from the most abundant biomass - cellulose. Direct and sensitized photopolymerizations of LGME using photoinitiators acting at the near UV or visible range in conjunction with diphenyliodonium hexafluoroantimonate (DPI) yielded unsaturated polyacetals with varying molar masses and distributions.},
  language  = {en}
}
@article{KeckeisZellerJungetal.2021,
  author    = {Keckeis, Philipp and Zeller, Enriko and Jung, Carina and Besirske, Patricia and Kirner, Felizitas and Ruiz-Agudo, Cristina and Schlaad, Helmut and C{\"o}lfen, Helmut},
  title     = {Modular toolkit of multifunctional block copoly(2-oxazoline)s for the synthesis of nanoparticles},
  series = {Chemistry - a European journal},
  volume    = {27},
  journal   = {Chemistry - a European journal},
  number    = {32},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {0947-6539},
  doi       = {10.1002/chem.202101327},
  pages     = {8283 -- 8287},
  year      = {2021},
  abstract  = {Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties. This concept was adapted to well-defined block copolymers of the poly(2-oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water-soluble, alkyne- and alkene-containing segments were synthesized and orthogonally modified with various low-molecular weight functional molecules by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and thiol-ene (TE) click reactions, respectively. Representative toolkit polymers were used for the synthesis of gold, iron oxide and silica nanoparticles.},
  language  = {en}
}
@article{KedrackiChekiniMaronietal.2014,
  author    = {Kedracki, Dawid and Chekini, Mahshid and Maroni, Plinio and Schlaad, Helmut and Nardin, Corinne},
  title     = {Synthesis and Self-Assembly of a DNA Molecular Brush},
  series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences},
  volume    = {15},
  journal   = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences},
  number    = {9},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1525-7797},
  doi       = {10.1021/bm5008713},
  pages     = {3375 -- 3382},
  year      = {2014},
  abstract  = {We report herein on the polymer-crystallization-assisted thiol-ene photosynthesis of an amphiphilic comb/graft DNA copolymer, or molecular brush, composed of a hydrophobic poly(2-oxazoline) backbone and hydrophilic short single-stranded nucleic acid grafts. Coupling efficiencies are above 60\% and thus higher as compared with the straight solid-phase-supported synthesis of amphiphilic DNA block copolymers. The DNA molecular brushes self-assemble into sub-micron-sized spherical structures in water as evidenced by light scattering as well as atomic force and electron microscopy imaging. The nucleotide sequences remain functional, as assessed by UV and fluorescence spectroscopy subsequent to isoindol synthesis at the surface of the structures. The determination of a vesicular morphology is supported by encapsulation and subsequent spectroscopy monitoring of the release of a water-soluble dye and spectroscopic quantification of the hybridization efficiency (30\% in average) of the functional nucleic acid strands engaged in structure formation: about one-half of the nucleotide sequences are available for hybridization, whereas the other half are hindered within the self-assembled structure. Because speciation between complementary and non complementary sequences in the medium could be ascertained by confocal laser scanning microscopy, the stable self-assembled molecular brushes demonstrate the potential for sensing applications.},
  language  = {en}
}
@article{KedrackiFilippovGouretal.2015,
  author    = {Kedracki, Dawid and Filippov, Sergey K. and Gour, Nidhi and Schlaad, Helmut and Nardin, Corinne},
  title     = {Formation of DNA-Copolymer Fibrils Through an Amyloid-Like Nucleation Polymerization Mechanism},
  series = {Macromolecular rapid communications},
  volume    = {36},
  journal   = {Macromolecular rapid communications},
  number    = {8},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1336},
  doi       = {10.1002/marc.201400728},
  pages     = {768 -- 773},
  year      = {2015},
  abstract  = {Conjugation of a hydrophobic poly(2-oxazoline) bearing tertiary amide groups along its backbone with a short single stranded nucleotide sequence results in an amphiphilic comb/graft copolymer, which organizes in fibrils upon direct dissolution in water. Supported by circular dichroism, atomic force microscopy, transmission electron microscopy, and scattering data, fibrils are formed through inter- and intramolecular hydrogen bonding between hydrogen accepting amide groups along the polymer backbone and hydrogen donating nucleic acid grafts leading to the formation of hollow tubes.},
  language  = {en}
}
@article{KnechtReiterSchlaadetal.2017,
  author    = {Knecht, Volker and Reiter, Guenter and Schlaad, Helmut and Reiter, Renate},
  title     = {Structure Formation in Langmuir Peptide Films As Revealed from Coarse-Grained Molecular Dynamics Simulations},
  series = {Langmuir},
  volume    = {33},
  journal   = {Langmuir},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.7b01455},
  pages     = {6492 -- 6502},
  year      = {2017},
  abstract  = {Molecular dynamics simulations in conjunction with the Martini coarse-grained model have been used to investigate the (nonequilibrium) behavior of helical 22-residue poly(gamma-benzyl-L-glutamate) (PBLG) peptides at the water/vapor interface. Preformed PBLG mono- or bilayers homogeneously covering the water surface laterally collapse in tens of nanoseconds, exposing significant proportions of empty water surface. This behavior was also observed in recent AFM experiments at similar areas per monomer, where a complete coverage had been assumed in earlier work. In the simulations, depending on the area per monomer, either elongated clusters or fibrils form, whose heights (together with the portion of empty water surface) increase over time. Peptides tend to align with respect to the fiber axis or with the major principal axis of the cluster, respectively. The aspect ratio of the cluster observed is 1.7 and, hence, comparable to though somewhat smaller than the aspect ratio of the peptides in alpha-helical conformation, which is 2.2. The heights of the fibrils is 3 nm after 20 ns and increases to 4.5 nm if the relaxation time is increased by 2 orders of magnitude, in agreement with the experiment. Aggregates with heights of about 3 or 4.5 nm are found to correspond to local bi- or trilayer structures, respectively.},
  language  = {en}
}
@article{KoshkinaLangThiermannetal.2015,
  author    = {Koshkina, Olga and Lang, Thomas and Thiermann, Raphael and Docter, Dominic and Stauber, Roland H. and Secker, Christian and Schlaad, Helmut and Weidner, Steffen and Mohr, Benjamin and Maskos, Michael and Bertin, Annabelle},
  title     = {Temperature-Triggered Protein Adsorption on Polymer-Coated Nanoparticles in Serum},
  series = {Langmuir},
  volume    = {31},
  journal   = {Langmuir},
  number    = {32},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {0743-7463},
  doi       = {10.1021/acs.langmuir.5b00537},
  pages     = {8873 -- 8881},
  year      = {2015},
  abstract  = {The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region.},
  language  = {en}
}
@article{KoshkinaWestmeierLangetal.2016,
  author    = {Koshkina, Olga and Westmeier, Dana and Lang, Thomas and Bantz, Christoph and Hahlbrock, Angelina and W{\"u}rth, Christian and Resch-Genger, Ute and Braun, Ulrike and Thiermann, Raphael and Weise, Christoph and Eravci, Murat and Mohr, Benjamin and Schlaad, Helmut and Stauber, Roland H. and Docter, Dominic and Bertin, Annabelle and Maskos, Michael},
  title     = {Tuning the Surface of Nanoparticles: Impact of Poly(2-ethyl-2-oxazoline) on Protein Adsorption in Serum and Cellular Uptake},
  series = {Macromolecular bioscience},
  volume    = {16},
  journal   = {Macromolecular bioscience},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1616-5187},
  doi       = {10.1002/mabi.201600074},
  pages     = {1287 -- 1300},
  year      = {2016},
  abstract  = {Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach. With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles.},
  language  = {en}
}
@article{LoebbickeChananaSchlaadetal.2011,
  author    = {L{\"o}bbicke, Ruben and Chanana, Munish and Schlaad, Helmut and Pilz-Allen, Christine and G{\"u}nter, Christina and M{\"o}hwald, Helmuth and Taubert, Andreas},
  title     = {Polymer Brush Controlled Bioinspired Calcium Phosphate Mineralization and Bone Cell Growth},
  series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences},
  volume    = {12},
  journal   = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences},
  number    = {10},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {1525-7797},
  doi       = {10.1021/bm200991b},
  pages     = {3753 -- 3760},
  year      = {2011},
  abstract  = {Polymer brushes on thiol-modified gold surfaces were synthesized by using terminal thiol groups for the surface initiated free radical polymerization of methacrylic acid and dimethylaminotheyl methacrylate, respectively. Atomic force microscopy shows that the resulting poly(methacrylic acid (PMAA) and poly(dimethylaminothyl methacrylate) (PDM- AEMA) brushes are homogeneous. Contact angle measurements show that the brushes are pH responsive and can reversibly be protonated and deprotonated. Mineralization of the brushes with calcium phosphate at different pH yields homogeneously mineralized surfaces, and preosteoblastic cells proliferate-on be number of living cells on the mineralized hybrid surface is ca. 3 times (P corresponding nonmineralized brushes.},
  language  = {en}
}
@article{LuedeckeSchlaad2021,
  author    = {L{\"u}decke, Nils and Schlaad, Helmut},
  title     = {Inspired by mussel adhesive protein},
  series = {Polymer Chemistry},
  volume    = {12},
  journal   = {Polymer Chemistry},
  number    = {37},
  publisher = {Royal Society of Chemistry},
  address   = {Cambridge},
  issn      = {1759-9962},
  doi       = {10.1039/d1py00679g},
  pages     = {5310 -- 5319},
  year      = {2021},
  abstract  = {A set of new functionalized poly(2-oxazoline) homopolymers and copolymers carrying protected catecholic side chains were prepared by microwave-assisted cationic ring-opening (co)polymerization. The copolymerizations of 2-ethyl-2-oxazoline with either 2-(3,4-dimethoxyphenyl)-, 2-(3,4-dimethoxybenzyl)-, or 2-(3,4-dimethoxycinnamyl)-2-oxazoline (comonomer ratio 90 : 10) produced gradient or random copolymers with narrow molar mass distributions. During the copolymerization with the 2-(3,4-dimethoxycinnamyl)-2-oxazoline, however, chain coupling reactions occurred at monomer conversions of >50\%, supposedly via Michael-type addition of intermediately formed ketene N,O-acetal end groups to 3,4-dimethoxycinnamyl amide side chains. A poly[(2-ethyl-2-oxazoline)-grad-(2-(3,4-dimethoxyphenyl)-2-oxazoline)] was examplarily subjected to partial demethylation and acidic hydrolysis to give a hydrophilic copolymer carrying both catecholic and cationic units, which is designed as a bioinspired adhesive copolymer mimicking mussel adhesive protein.},
  language  = {en}
}
@article{LuedeckeWeidnerSchlaad2019,
  author    = {L{\"u}decke, Nils and Weidner, Steffen M. and Schlaad, Helmut},
  title     = {Poly(2-oxazoline)s Based on Phenolic Acids},
  series = {Macromolecular rapid communications},
  volume    = {41},
  journal   = {Macromolecular rapid communications},
  number    = {1},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1022-1336},
  doi       = {10.1002/marc.201900404},
  pages     = {5},
  year      = {2019},
  abstract  = {A series of phenolic-acid-based 2-oxazoline monomers with methoxy-substituted phenyl and cinnamyl side chains is synthesized and polymerized in a microwave reactor at 140 °C using methyl tosylate as the initiator. The obtained poly(2-oxazoline)s are characterized by NMR spectroscopy, MALDI-TOF mass spectrometry, and size-exclusion chromatography (SEC). Kinetic studies reveal that the microwave-assisted polymerization is fast and completed within less than ≈10 min for low monomer-to-initiator ratios of ≤25. Polymers with number-average molar masses of up to 6500 g mol-1 and low dispersity (1.2-1.3) are produced. The aryl methyl ethers are successfully cleaved with aluminum triiodide/N,N′-diisopropylcarbodiimide to give a poly(2-oxazoline) with pendent catechol groups.},
  language  = {en}
}