Anja S. Goldmann

Color Tunability and Electrochemiluminescence of Silver Nanoclusters

Colorful clusters: Silver nanoclusters consisting of only a few atoms exhibit large chemical-environment-responsive shifts of their optical absorption and emission bands, that is, large solvatochromism (see picture). The photophysical characteristics and electrochemiluminescence of the Ag clusters give them remarkable advantages over larger nanoparticles in applications such as molecular sensing.

Post-Functionalization of Polymers via Orthogonal Ligation Chemistry†

The establishment of advanced living/controlled polymerization protocols allows for engineering synthetic polymers in a precise fashion. Combining advanced living/controlled polymerization techniques with highly efficient coupling chemistries facilitates quantitative, modular, and orthogonal functionalization of synthetic polymer strands at their chain termini as well as side-chain functionalization. The review highlights the current status of selected post-functionalization techniques of polymers via orthogonal ligation chemistries, major characteristics of the specific transformation chemistry, as well as the characterization of the products.

Controlled Cell Adhesion on Poly(dopamine) Interfaces Photopatterned with Non‐Fouling Brushes

Bioinspired poly(dopamine) (PDA) films are merged with antifouling poly(MeOEGMA) brushes utilizing a nitrile imine-mediated tetrazole-ene cycloaddition (NITEC)-based phototriggered surface encoding protocol. The antifouling brushes were photopatterned on PDA surfaces, leading cells to form confluent layers in the non-irradiated sections, while no adhesion occurred on the brushes resulting in a remarkably precise cell pattern. The presented strategy paves the way for the design of tailor-made patterned cell interfaces.

Grafting efficiency of synthetic polymers onto biomaterials: A comparative study of grafting- from versus grafting- to

In the present study, the two grafting techniques grafting-from - by activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) - and grafting-to - by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) - were systematically compared, employing cellulose as a substrate. In order to obtain a meaningful comparison, it is crucial that the graft lengths of the polymers that are grafted from and to the substrates are essentially identical. Herein, this was achieved by utilizing the free polymer formed in parallel to the grafting-from reaction as the polymer for the grafting-to reaction. Four graft lengths were investigated, and the molar masses of the four free polymers (21 ≤ M(n) ≤ 100 kDa; 1.07 ≤ Đ(M) ≤ 1.26), i.e. the polymers subsequently employed in the grafting-to reaction, were shown to be in the same range as the molar masses of the polymers grafted from the surface (23 ≤ M(n) ≤ 87 kDa; 1.08 ≤ Đ(M) ≤ 1.31). The molecular weights of the chains grafted from the surface were established after cleavage from the cellulose substrates via size exclusion chromatography (SEC). High-resolution Fourier transform infrared microscopy (FT-IRM) was employed as an efficient tool to study the spatial distribution of the polymer content on the grafted substrates. In addition, the functionalized substrates were analyzed by X-ray photoelectron spectroscopy (XPS), contact angle (CA) measurements, and field-emission scanning electron microscopy (FE-SEM). For cellulose substrates modified via the grafting-from approach, the content of polymer on the surfaces increased with increasing graft length, confirming the possibility to tailor not only the length of the polymer grafts but also the polymeric content on the surface. In comparison, for the grafting-to reaction, the grafted content could not be controlled by varying the length of the preformed polymer: the polymer content was essentially the same for the four graft lengths. Consequently, the obtained results, when employing cellulose as a substrate and under these conditions, suggest that the grafting-from approach is superior to the grafting-to technique with respect to controlling the distribution of the polymeric content on the surface.

Photo‐Patterning of Non‐Fouling Polymers and Biomolecules on Paper

Functional cellulose substrates with tetrazole moieties are generated to serve as universal platforms for the spatio-temporal immobilization of synthetic ultra-low fouling polymer brushes and protein species via a nitrile imine-mediated tetrazole-ene cycloaddition (NITEC)-based protocol. Poly(carboxybetaine acrylamide) brushes are grafted from initiators photo-patterned by NITEC utilizing single electron transfer living radical polymerization. Streptavidin is photo-immobilized with remarkable efficiency, opening the possibility to generate new materials for biomedical and biosensing applications.

Mild and modular surface modification of cellulose via hetero Diels-Alder (HDA) cycloaddition.

A combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and hetero Diels-Alder (HDA) cycloaddition was used to effect, under mild (T ≈ 20 °C), fast, and modular conditions, the grafting of poly(isobornyl acrylate) (M(n) = 9800 g mol(-1), PDI = 1.19) onto a solid cellulose substrate. The active hydroxyl groups expressed on the cellulose fibers were converted to tosylate leaving groups, which were subsequently substituted by a highly reactive cyclopentadienyl functionality (Cp). By employing the reactive Cp-functionality as a diene, thiocarbonyl thio-capped poly(isobornyl acrylate) synthesized via RAFT polymerization (mediated by benzyl pyridine-2-yldithioformiate (BPDF)) was attached to the surface under ambient conditions by an HDA cycloaddition (reaction time: 15 h). The surface-modified cellulose samples were analyzed in-depth by X-ray photoelectron spectroscopy, scanning electron microscopy, elemental analysis, Fourier transform infrared (FT-IR) spectroscopy as well as Fourier transform infrared microscopy employing a focal plane array detector for imaging purposes. The analytical results provide strong evidence that the reaction of suitable dienophiles with Cp-functional cellulose proceeds under mild reaction conditions (T ≈ 20 °C) in an efficient fashion. In particular, the visualization of individual modified cellulose fibers via high-resolution FT-IR microscopy corroborates the homogeneous distribution of the polymer film on the cellulose fibers.

Hierarchical Nacre Mimetics with Synergistic Mechanical Properties by Control of Molecular Interactions in Self‐Healing Polymers

Designing the reversible interactions of biopolymers remains a grand challenge for an integral mimicry of mechanically superior biological composites. Yet, they are the key to synergistic combinations of stiffness and toughness by providing sacrificial bonds with hidden length scales. To address this challenge, dynamic polymers were designed with low glass-transition temperature T(g) and bonded by quadruple hydrogen-bonding motifs, and subsequently assembled with high-aspect-ratio synthetic nanoclays to generate nacre-mimetic films. The high dynamics and self-healing of the polymers render transparent films with a near-perfectly aligned structure. Varying the polymer composition allows molecular control over the mechanical properties up to very stiff and very strong films (E≈45 GPa, σ(UTS)≈270 MPa). Stable crack propagation and multiple toughening mechanisms occur in situations of balanced dynamics, enabling synergistic combinations of stiffness and toughness. Excellent gas barrier properties complement the multifunctional property profile.

Efficient Photochemical Approaches for Spatially Resolved Surface Functionalization

Materials interfaces--with a gas, a liquid, or another solid--are highly important for advanced applications. Besides their topological design, controlling interactions at these interfaces is typically realized by tuning the chemical composition of the materials surface. In areas such as nanoscience or biology, it is, however, highly desirable to impart heterogeneously distributed properties. Photopatterning, more than micro- and nanoprinting methods, is often the method of choice for precise functionalization, especially in terms of versatility. Recently, a range of new or rediscovered photochemistry approaches have been applied to precision surface functionalization, with the common aim of increasing efficiency and resolution while concomitantly lowering the amount of required energy. A survey of such methods is presented in this Review, with a focus on those we have explored.

Spatially controlled photochemical peptide and polymer conjugation on biosurfaces

An efficient phototriggered Diels-Alder conjugation is utilized to graft in an effective and straightforward approach poly(trifluoro ethyl methacrylate) (Mn = 3700 Da, Đ = 1.27) and a model peptide (GIGKFLHS) onto thin hyaluronan films and cellulose surfaces. The surfaces were functionalized with an o-quinodimethane moiety - capable of releasing a caged diene - via carbodiimide mediated coupling. The o-quinodimethane group is employed as a photoactive linker to tether predefined peptide/polymer strands in a spatially controlled manner onto the biosurface by photoenol ligation. An in-depth characterization employing XPS, ToF-SIMS, SPR, ellipsometry, and AFM was conducted to evidence the effectiveness of the presented approach.

Biomimetic Dopamine‐Diels–Alder Switches

Mussel adhesives function as tools for surface modifications of a wide variety of materials due to their remarkable adhesion properties. Herein, a combination of bioinspired mussel adhesives based on a dopamine derivative, polymer chemistry, and well-established Diels-Alder (DA) chemistry leads to a bioinspired switchable surface system that possesses the capability of attaching and detaching specific polymers on demand. A dopaminemaleimide compound, which has been attached to a gold surface under maritime conditions undergoes DA- and retro-DA-click-conjugations with cyclopentadiene-carrying PEG chains. The surface attachment and the subsequent DA/rDA cycles are evidenced via XPS analysis.