TY - JOUR A1 - Deng, Zijun A1 - Wang, Weiwei A1 - Xua, Xun A1 - Gould, Oliver E. C. A1 - Kratz, Karl A1 - Ma, Nan A1 - Lendlein, Andreas T1 - Polymeric sheet actuators with programmable bioinstructivity JF - PNAS N2 - Stem cells are capable of sensing and processing environmental inputs, converting this information to output a specific cell lineage through signaling cascades. Despite the combinatorial nature of mechanical, thermal, and biochemical signals, these stimuli have typically been decoupled and applied independently, requiring continuous regulation by controlling units. We employ a programmable polymer actuator sheet to autonomously synchronize thermal and mechanical signals applied to mesenchymal stem cells (MSC5). Using a grid on its underside, the shape change of polymer sheet, as well as cell morphology, calcium (Ca2+) influx, and focal adhesion assembly, could be visualized and quantified. This paper gives compelling evidence that the temperature sensing and mechanosensing of MSC5 are interconnected via intracellular Ca2+. Up-regulated Ca2+ levels lead to a remarkable alteration of histone H3K9 acetylation and activation of osteogenic related genes. The interplay of physical, thermal, and biochemical signaling was utilized to accelerate the cell differentiation toward osteogenic lineage. The approach of programmable bioinstructivity provides a fundamental principle for functional biomaterials exhibiting multifaceted stimuli on differentiation programs. Technological impact is expected in the tissue engineering of periosteum for treating bone defects. KW - reversible shape-memory actuator KW - mesenchymal stem cells KW - calcium influx KW - HDAC1 KW - RUNX2 Y1 - 2020 U6 - https://doi.org/10.1073/pnas.1910668117 SN - 1091-6490 VL - 117 IS - 4 SP - 1895 EP - 1901 PB - National Academy of Sciences CY - Washington, DC ER - TY - JOUR A1 - Saretia, Shivam A1 - Machatschek, Rainhard Gabriel A1 - Lendlein, Andreas T1 - Degradation kinetics of oligo(ε-caprolactone) ultrathin films BT - Influence of crystallinity JF - MRS advances : a journal of the Materials Research Society (MRS) N2 - The potential of using crystallinity as morphological parameter to control polyester degradation in acidic environments is explored in ultrathin films by Langmuir technique. Films of hydroxy or methacrylate end-capped oligo(epsilon-caprolactone) (OCL) are prepared at the air-water interface as a function of mean molecular area (MMA). The obtained amorphous, partially crystalline or highly crystalline ultrathin films of OCL are hydrolytically degraded at pH similar to 1.2 on water surface or on silicon surface as-transferred films. A high crystallinity reduces the hydrolytic degradation rate of the films on both water and solid surfaces. Different acceleration rates of hydrolytic degradation of semi-crystalline films are achieved either by crystals complete melting, partially melting, or by heating them below their melting temperatures. Semi-crystalline OCL films transferred via water onto a solid surface retain their crystalline morphology, degrade in a controlled manner, and are of interest as thermoswitchable coatings for cell substrates and medical devices. Y1 - 2021 U6 - https://doi.org/10.1557/s43580-021-00067-4 SN - 2059-8521 VL - 6 IS - 33 SP - 790 EP - 795 PB - Springer Nature Switzerland AG CY - Cham ER - TY - JOUR A1 - Yue, Yanhua A1 - Melani, Giacomo A1 - Kirsch, Harald A1 - Paarmann, Alexander A1 - Saalfrank, Peter A1 - Campen, Richard Kramer A1 - Tong, Yujin T1 - Structure and Reactivity of a-Al2O3(0001) Surfaces: How Do Al-I and Gibbsite-like Terminations Interconvert? JF - The journal of physical chemistry / publ. weekly by the American Chemical Society. C, Energy, materials, and catalysis N2 - The alpha-Al2O3(0001) surface has been extensively studied because of its significance in both fundamental research and application. Prior work suggests that in ultra-high-vacuum (UHV), in the absence of water, the so-called Al-I termination is thermodynamically favored, while in ambient, in contact with liquid water, a Gibbsite-like layer is created. While the view of the alpha- Al2O3(0001)/H2O(l) interface appears relatively clear in theory, experimental characterization of this system has resulted in estimates of surface acidity, i.e., isoelectric points, that differ by 4 pH units and surface structure that in some reports has non-hydrogen-bonded surface aluminol (Al-OH) groups and in others does not. In this study, we employed vibrational sum frequency spectroscopy (VSFS) and density functional theory (DFT) simulation to study the surface phonon modes of the differently terminated alpha-Al2O3(0001) surfaces in both UHV and ambient. We find that, on either water dosing of the Al-I in UHV or heat-induced dehydroxylation of the Gibbsite-like in ambient, the surfaces do not interconvert. This observation offers a new explanation for disagreements in prior work on the alpha-Al2O3(0001)/liquid water interface -different preparation methods may create surfaces that do not interconvert-and shows that the surface phonon spectral response offers a novel probe of interfacial hydrogen bonding structure. Y1 - 2022 U6 - https://doi.org/10.1021/acs.jpcc.2c03743 SN - 1932-7447 SN - 1932-7455 VL - 126 IS - 31 SP - 13467 EP - 13476 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Tarazona Lizcano, Natalia Andrea A1 - Machatschek, Rainhard Gabriel A1 - Balcucho, Jennifer A1 - Castro-Mayorga, Jinneth Lorena A1 - Saldarriaga, Juan Francisco A1 - Lendlein, Andreas T1 - Opportunities and challenges for integrating the development of sustainable polymer materials within an international circular (bio)economy concept JF - MRS energy & sustainability : science & technology & socio-economics & policy N2 - The production and consumption of commodity polymers have been an indispensable part of the development of our modern society. Owing to their adjustable properties and variety of functions, polymer-based materials will continue playing important roles in achieving the Sustainable Development Goals (SDG)s, defined by the United Nations, in key areas such as healthcare, transport, food preservation, construction, electronics, and water management. Considering the serious environmental crisis, generated by increasing consumption of plastics, leading-edge polymers need to incorporate two types of functions: Those that directly arise from the demands of the application (e.g. selective gas and liquid permeation, actuation or charge transport) and those that enable minimization of environmental harm, e.g., through prolongation of the functional lifetime, minimization of material usage, or through predictable disintegration into non-toxic fragments. Here, we give examples of how the incorporation of a thoughtful combination of properties/functions can enhance the sustainability of plastics ranging from material design to waste management. We focus on tools to measure and reduce the negative impacts of plastics on the environment throughout their life cycle, the use of renewable sources for their synthesis, the design of biodegradable and/or recyclable materials, and the use of biotechnological strategies for enzymatic recycling of plastics that fits into a circular bioeconomy. Finally, we discuss future applications for sustainable plastics with the aim to achieve the SDGs through international cooperation.
Leading-edge polymer-based materials for consumer and advanced applications are necessary to achieve sustainable development at a global scale. It is essential to understand how sustainability can be incorporated in these materials via green chemistry, the integration of bio-based building blocks from biorefineries, circular bioeconomy strategies, and combined smart and functional capabilities. KW - biomaterial KW - degradable KW - functional KW - life cycle assessment KW - renewable KW - sustainability Y1 - 2022 U6 - https://doi.org/10.1557/s43581-021-00015-7 SN - 2329-2229 SN - 2329-2237 VL - 9 IS - 1 SP - 28 EP - 34 PB - Springer Nature CY - London ER - TY - JOUR A1 - Folikumah, Makafui Y. A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Reaction behaviour of peptide-based single thiol-thioesters exchange reaction substrate in the presence of externally added thiols JF - MRS communications / a publication of the Materials Research Society N2 - Identification of patterns in chemical reaction pathways aids in the effective design of molecules for specific applications. Here, we report on model reactions with a water-soluble single thiol-thioester exchange (TTE) reaction substrate, which was designed taking in view biological and medical applications. This substrate consists of the thio-depsipeptide, Ac-Pro-Leu-Gly-SLeu-Leu-Gly-NEtSH (TDP) and does not yield foul-smelling thiol exchange products when compared with aromatic thiol containing single TTE substrates. TDP generates an alpha,omega-dithiol crosslinker in situ in a 'pseudo intramolecular' TTE. Competitive intermolecular TTE of TDP with externally added "basic" thiols increased the crosslinker concentration whilst "acidic" thiols decreased its concentration. TDP could potentially enable in situ bioconjugation and crosslinking applications. KW - Biomaterials KW - Biomimetic KW - Mass spectrometry KW - Nuclear magnetic resonance KW - (NMR) Y1 - 2021 U6 - https://doi.org/10.1557/s43579-021-00041-z SN - 2159-6859 SN - 2159-6867 VL - 11 IS - 4 SP - 402 EP - 410 PB - Springer CY - Berlin ER - TY - JOUR A1 - Kleinpeter, Erich A1 - Heydenreich, Matthias A1 - Shainyan, Bagrat A. T1 - At the experimental limit of the NMR conformational analysis BT - Si-29 and C-13 NMR study of the conformational equilibrium of 1-phenyl-1-tert-butylsilacyclohexane JF - Organic letters N2 - The low temperature (95 K) NMR study of 1-Ph-1-t-Bu-silacyclohexane (1) showed the conformational equilibrium to be extremely one-sided toward thePh(ax),t-Bueq conformer. The barrier to interconversion has been measured (4.2-4.6 kcal/mol) and the conformational equilibrium [Delta nu = 1990.64 ppm (Si-29), 618.9 ppm (C-13), 1-Ph-ax:1-Pheq = (95.6-96.6%):(3.4-4.4%), K = 25 +/- 3, Delta G degrees = -RT ln K = 0.58-0.63 kcal/mol] analyzed. The assignment and quantification of the NMR signals is supported by MP2 and DFT calculations. Y1 - 2021 U6 - https://doi.org/10.1021/acs.orglett.0c03878 SN - 1523-7060 SN - 1523-7052 VL - 23 IS - 2 SP - 405 EP - 409 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Mullan, Thomas A1 - Maschio, Lorenzo A1 - Saalfrank, Peter A1 - Usvyat, Denis T1 - Reaction barriers on non-conducting surfaces beyond periodic local MP2 BT - Diffusion of hydrogen on alpha-Al2O3 (0001) as a test case JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - The quest for "chemical accuracy" is becoming more and more demanded in the field of structure and kinetics of molecules at solid surfaces. In this paper, as an example, we focus on the barrier for hydrogen diffusion on a alpha-Al2O3 (0001) surface, aiming for a couple cluster singles, doubles, and perturbative triples [CCSD(T)]-level benchmark. We employ the density functional theory (DFT) optimized minimum and transition state structures reported by Heiden, Usvyat, and Saalfrank [J. Phys. Chem. C 123, 6675 (2019)]. The barrier is first evaluated at the periodic Hartree-Fock and local Moller-Plesset second-order perturbation (MP2) level of theory. The possible sources of errors are then analyzed, which includes basis set incompleteness error, frozen core, density fitting, local approximation errors, as well as the MP2 method error. Using periodic and embedded fragment models, corrections to these errors are evaluated. In particular, two corrections are found to be non-negligible (both from the chemical accuracy perspective and at the scale of the barrier value of 0.72 eV): the correction to the frozen core-approximation of 0.06 eV and the CCSD(T) correction of 0.07 eV. Our correlated wave function results are compared to barriers obtained from DFT. Among the tested DFT functionals, the best performing for this barrier is B3LYP-D3. Y1 - 2022 U6 - https://doi.org/10.1063/5.0082805 SN - 0021-9606 SN - 1089-7690 VL - 156 IS - 7 PB - AIP Publishing CY - Melville ER - TY - JOUR A1 - Mawire, Phillip A1 - Mozirandi, Winnie A1 - Heydenreich, Matthias A1 - Chi, Godloves Fru A1 - Mukanganyama, Stanley T1 - Isolation and antimicrobial activities of phytochemicals from Parinari curatellifolia (Chrysobalanaceae) JF - Advances in pharmacological and pharmaceutical sciences N2 - The widespread use of antimicrobial agents to treat infectious diseases has led to the emergence of antibiotic resistant pathogens. Plants have played a central role in combating many ailments in humans, and Parinari curatellifolia has been used for medicinal purposes. Seven extracts from P. curatellifolia leaves were prepared using serial exhaustive extraction of nonpolar to polar solvents. The microbroth dilution method was used to evaluate antimicrobial bioactivities of extracts. Five of the extracts were significantly active against at least one test microbe. Mycobacterium smegmatis was the most susceptible to most extracts. The methanol and ethanol extracts were the most active against M. smegmatis with an MIC of 25 mu g/mL. The hexane extract was the most active against Candida krusei with an MIC of 25 mu g/mL. None of the extracts significantly inhibited growth of Klebsiella pneumoniae and Staphylococcus aureus. Active extracts were selected for fractionation and isolation of pure compounds using gradient elution column chromatography. TLC analyses was carried out for pooling fractions of similar profiles. A total of 43 pools were obtained from 428 fractions. Pools 7 and 10 were selected for further isolation of single compounds. Four compounds, Pc4963r, Pc4962w, Pc6978p, and Pc6978o, were isolated. Evaluation of antimicrobial activities of Pc4963r, Pc4962w, and Pc6978p showed that the compounds were most active against C. krusei with MFC values ranging from 50 to 100 mu g/mL. Only Pc6978p was shown to be pure. Using spectroscopic analyses, the structure of Pc6978p was determined to be beta-sitosterol. The antifungal effects of beta-sitosterol were evaluated against C. krusei in vitro and on fabrics. Results showed that beta-sitosterol reduced the growth of C. krusei attached to Mendy fabric by 83%. Therefore, P. curatellifolia can be a source of lead compounds for prospective development of novel antimicrobial agents. Further work needs to be done to improve the antifungal activity of the isolated compound using quantitative structure-activity relationships. Y1 - 2021 U6 - https://doi.org/10.1155/2021/8842629 SN - 2633-4682 SN - 2633-4690 PB - Hindawi CY - London ER - TY - JOUR A1 - Bekir, Marek A1 - Jelken, Joachim A1 - Jung, Se-Hyeong A1 - Pich, Andrij A1 - Pacholski, Claudia A1 - Kopyshev, Alexey A1 - Santer, Svetlana T1 - Dual responsiveness of microgels induced by single light stimulus JF - Applied physics letters N2 - We report on the multiple response of microgels triggered by a single optical stimulus. Under irradiation, the volume of the microgels is reversibly switched by more than 20 times. The irradiation initiates two different processes: photo-isomerization of the photo-sensitive surfactant, which forms a complex with the anionic microgel, rendering it photo-responsive; and local heating due to a thermo-plasmonic effect within the structured gold layer on which the microgel is deposited. The photo-responsivity is related to the reversible accommodation/release of the photo-sensitive surfactant depending on its photo-isomerization state, while the thermo-sensitivity is intrinsically built in. We show that under exposure to green light, the thermo-plasmonic effect generates a local hot spot in the gold layer, resulting in the shrinkage of the microgel. This process competes with the simultaneous photo-induced swelling. Depending on the position of the laser spot, the spatiotemporal control of reversible particle shrinking/swelling with a predefined extent on a per-second base can be implemented. Y1 - 2021 U6 - https://doi.org/10.1063/5.0036376 SN - 0003-6951 SN - 1077-3118 VL - 118 IS - 9 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Hoffmann, Falk A1 - Machatschek, Rainhard Gabriel A1 - Lendlein, Andreas T1 - Analytical model and Monte Carlo simulations of polymer degradation with improved chain cut statistics JF - Journal of materials research : JMR N2 - The degradation of polymers is described by mathematical models based on bond cleavage statistics including the decreasing probability of chain cuts with decreasing average chain length. We derive equations for the degradation of chains under a random chain cut and a chain end cut mechanism, which are compared to existing models. The results are used to predict the influence of internal molecular parameters. It is shown that both chain cut mechanisms lead to a similar shape of the mass or molecular mass loss curve. A characteristic time is derived, which can be used to extract the maximum length of soluble fragments l of the polymer. We show that the complete description is needed to extract the degradation rate constant k from the molecular mass loss curve and that l can be used to design polymers that lose less mechanical stability before entering the mass loss phase. KW - Modeling KW - Degradable KW - Polymer KW - Molecular weight KW - Simulation Y1 - 2022 U6 - https://doi.org/10.1557/s43578-022-00495-4 SN - 0884-2914 SN - 2044-5326 VL - 37 IS - 5 SP - 1093 EP - 1101 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Neffe, Axel T. A1 - Löwenberg, Candy A1 - Lendlein, Andreas T1 - Hydrogel networks by aliphatic dithiol Michael addition to glycidylmethacrylated gelatin JF - MRS advances : a journal of the Materials Research Society (MRS) N2 - Functionalization of gelatin with glycidylmethacrylate (GMA-gelatin) enables network formation employing the double bond, so that the reaction is orthogonal to the inherent functional groups in the biomacromolecule. Here, network formation by crosslinking of GMA-gelatin with hexane 1,6-dithiol or nonane 1,9-dithiol to tailor properties and enable a shape-memory effect is shown by H-1 NMR and FT-IR spectroscopy. Hydrogel swelling (460-1900 vol%) and mechanical properties (Young's modulus E = 59-512 kPa, elongation at break epsilon(b) = 44-127%) depended on the molecular composition of the networks and temperature. Increased crosslinker length, thiol:methacrylate molar ratio, and precursor concentrations led to denser networks. Change of properties with temperature suggested adoption of triple helices by gelatin chains, forming physical netpoints at lower temperatures (< 20 degrees C). However, the limited freedom of the gelatin chains to move allowed only a minimal extent of triple helices formation, as it became apparent from the related signal in wide-angle X-ray scattering and the thermal transition associated to triple helices in some networks by DSC. The presented strategy is likely transferable to other biomacromolecules, and the results suggest that too short crosslinkers may result in a significant amount of grafting rather than network formation. Y1 - 2021 U6 - https://doi.org/10.1557/s43580-021-00136-8 SN - 2059-8521 VL - 6 IS - 33 SP - 796 EP - 800 PB - Springer Nature Switzerland AG CY - Cham ER - TY - JOUR A1 - Lau, Skadi A1 - Maier, Anna A1 - Braune, Steffen A1 - Gossen, Manfred A1 - Lendlein, Andreas T1 - Effect of endothelial culture medium composition on platelet responses to polymeric biomaterials JF - International journal of molecular sciences N2 - Near-physiological in vitro thrombogenicity test systems for the evaluation of blood-contacting endothelialized biomaterials requires co-cultivation with platelets (PLT). However, the addition of PLT has led to unphysiological endothelial cell (EC) detachment in such in vitro systems. A possible cause for this phenomenon may be PLT activation triggered by the applied endothelial cell medium, which typically consists of basal medium (BM) and nine different supplements. To verify this hypothesis, the influence of BM and its supplements was systematically analyzed regarding PLT responses. For this, human platelet rich plasma (PRP) was mixed with BM, BM containing one of nine supplements, or with BM containing all supplements together. PLT adherence analysis was carried out in six-channel slides with plasma-treated cyclic olefin copolymer (COC) and poly(tetrafluoro ethylene) (PTFE, as a positive control) substrates as part of the six-channel slides in the absence of EC and under static conditions. PLT activation and aggregation were analyzed using light transmission aggregometry and flow cytometry (CD62P). Medium supplements had no effect on PLT activation and aggregation. In contrast, supplements differentially affected PLT adherence, however, in a polymer- and donor-dependent manner. Thus, the use of standard endothelial growth medium (BM + all supplements) maintains functionality of PLT under EC compatible conditions without masking the differences of PLT adherence on different polymeric substrates. These findings are important prerequisites for the establishment of a near-physiological in vitro thrombogenicity test system assessing polymer-based cardiovascular implant materials in contact with EC and PLT. KW - cyclic olefin copolymer KW - poly(tetrafluoroethylene) KW - endothelial cells KW - platelets KW - in vitro thrombogenicity testing Y1 - 2021 U6 - https://doi.org/10.3390/ijms22137006 SN - 1422-0067 SN - 1661-6596 VL - 22 IS - 13 PB - Molecular Diversity Preservation International CY - Basel ER - TY - JOUR A1 - Schönemann, Eric A1 - Koc, Julian A1 - Karthäuser, Jana A1 - Özcan, Onur A1 - Schanzenbach, Dirk A1 - Schardt, Lisa A1 - Rosenhahn, Axel A1 - Laschewsky, André T1 - Sulfobetaine methacrylate polymers of unconventional polyzwitterion architecture and their antifouling properties JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - Combining high hydrophilicity with charge neutrality, polyzwitterions are intensely explored for their high biocompatibility and low-fouling properties. Recent reports indicated that in addition to charge neutrality, the zwitterion's segmental dipole orientation is an important factor for interacting with the environment. Accordingly, a series of polysulfobetaines with a novel architecture was designed, in which the cationic and anionic groups of the zwitterionic moiety are placed at equal distances from the backbone. They were investigated by in vitro biofouling assays, covering proteins of different charges and model marine organisms. All polyzwitterion coatings reduced the fouling effectively compared to model polymer surfaces of poly(butyl methacrylate), with a nearly equally good performance as the reference polybetaine poly(3-(N-(2-(methacryloyloxy)ethyl)-N,N-dimethylammonio)propanesulfonate). The specific fouling resistance depended on the detailed chemical structure of the polyzwitterions. Still, while clearly affecting the performance, the precise dipole orientation of the sulfobetaine group in the polyzwitterions seems overall to be only of secondary importance for their antifouling behavior. Y1 - 2021 U6 - https://doi.org/10.1021/acs.biomac.0c01705 SN - 1525-7797 SN - 1526-4602 VL - 22 IS - 4 SP - 1494 EP - 1508 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Ihlenburg, Ramona A1 - Mai, Tobias A1 - Thünemann, Andreas F. A1 - Baerenwald, Ruth A1 - Saalwächter, Kay A1 - Koetz, Joachim A1 - Taubert, Andreas T1 - Sulfobetaine hydrogels with a complex multilength-scale hierarchical structure JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - Hydrogels with a hierarchical structure were prepared from a new highly water-soluble crosslinker N,N,N',N'-tetramethyl-N,N'-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and from the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The free radical polymerization of the two compounds is rapid and yields near-transparent hydrogels with sizes up to 5 cm in diameter. Rheology shows a clear correlation between the monomer-to-crosslinker ratio and the storage and loss moduli of the hydrogels. Cryo-scanning electron microscopy, low-field nuclear magnetic resonance (NMR) spectroscopy, and small-angle X-ray scattering show that the gels have a hierarchical structure with features spanning the nanometer to the sub-millimeter scale. The NMR study is challenged by the marked inhomogeneity of the gels and the complex chemical structure of the sulfobetaine monomer. NMR spectroscopy shows how these complications can be addressed via a novel fitting approach that considers the mobility gradient along the side chain of methacrylate-based monomers. KW - Defects KW - Hydrogels KW - Nuclear magnetic resonance spectroscopy KW - Scattering KW - X-ray scattering Y1 - 2021 U6 - https://doi.org/10.1021/acs.jpcb.0c10601 SN - 1520-6106 SN - 1520-5207 VL - 125 IS - 13 SP - 3398 EP - 3408 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lau, Skadi A1 - Gossen, Manfred A1 - Lendlein, Andreas A1 - Jung, Friedrich T1 - Differential sensitivity of assays for determining vein endothelial cell senescence JF - Clinical hemorheology and microcirculation : blood flow and vessels N2 - In vivo endothelialization of polymer-based cardiovascular implant materials is a promising strategy to reduce the risk of platelet adherence and the subsequent thrombus formation and implant failure. However, endothelial cells from elderly patients are likely to exhibit a senescent phenotype that may counteract endothelialization. The senescence status of cells should therefore be investigated prior to implantation of devices designed to be integrated in the blood vessel wall. Here, human umbilical vein endothelial cells (HUVEC) were cultivated up to passage (P) 4, 10 and 26/27 to determine the population doubling time and the senescence status by four different methods. Determination of the senescence-associated beta-galactosidase activity (SA-beta-Gal) was carried out by colorimetric staining and microscopy (i), as well as by photometric quantification (ii), and the expression of senescence-associated nuclear proteins p16 and p21 as well as the proliferation marker Ki67 was assessed by immunostaining (iii), and by flow cytometry (iv). The population doubling time of P27-cells was remarkably greater (103 +/- 65 h) compared to P4-cells (24 +/- 3 h) and P10-cell (37 +/- 15 h). Among the four different methods tested, the photometric SA-beta-Gal activity assay and the flow cytometric determination of p16 and Ki67 were most effective in discriminating P27-cells from P4- and P10-cells. These methods combined with functional endothelial cell analyses might aid predictions on the performance of implant endothelialization in vivo. KW - Ageing KW - population doubling time KW - senescence-associated KW - beta-galactosidase KW - cell cycle inhibitors KW - p16 KW - p21 KW - Ki67 Y1 - 2022 U6 - https://doi.org/10.3233/CH-211294 SN - 1386-0291 SN - 1875-8622 VL - 81 IS - 3 SP - 191 EP - 203 PB - IOS Press CY - Amsterdam ER - TY - JOUR A1 - Zhang, Pengfei A1 - Rešetič, Andraž A1 - Behl, Marc A1 - Lendlein, Andreas T1 - Multifunctionality in polymer networks by dynamic of coordination bonds JF - Macromolecular chemistry and physics N2 - The need for multifunctional materials is driven by emerging technologies and innovations, such as in the field of soft robotics and tactile or haptic systems, where minimizing the number of operational components is not only desirable, but can also be essential for realizing such devices. This study report on designing a multifunctional soft polymer material that can address a number of operating requirements such as solvent resistance, reshaping ability, self-healing capability, fluorescence stimuli-responsivity, and anisotropic structural functions. The numerous functional abilities are associated to rhodium(I)-phosphine coordination bonds, which in a polymer network act with their dynamic and non-covalently bonded nature as multifunctional crosslinks. Reversible aggregation of coordination bonds leads to changes in fluorescence emission intensity that responds to chemical or mechanical stimuli. The fast dynamics and diffusion of rhodium-phosphine ions across and through contacting areas of the material provide for reshaping and self-healing abilities that can be further exploited for assembly of multiple pieces into complex forms, all without any loss to material-sensing capabilities. KW - assembly capabilities KW - fluorescence stimuli‐ responsivity KW - multiple functions KW - reshaping abilities KW - rhodium(I)– phosphine KW - coordination bonds KW - solvent resistance Y1 - 2021 U6 - https://doi.org/10.1002/macp.202000394 SN - 1521-3935 VL - 222 IS - 3 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Göttlich, Richard A1 - Graulich, Nicole A1 - Huwer, Johannes A1 - Banerji, Amitabh T1 - Analog und digital BT - Chemieunterricht mit Potenzial JF - Chemie konkret : CHEMKON ; Forum für Unterricht und Didaktik Y1 - 2022 U6 - https://doi.org/10.1002/ckon.202200046 SN - 0944-5846 SN - 1521-3730 VL - 29 SP - 182 EP - 182 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Tartivel, Lucile A1 - Blocki, Anna M. A1 - Braune, Steffen A1 - Jung, Friedrich A1 - Behl, Marc A1 - Lendlein, Andreas T1 - An Inverse shape-memory hydrogel scaffold switching upon cooling in a tissue-tolerated temperature range JF - Advanced materials interfaces N2 - Tissue reconstruction has an unmet need for soft active scaffolds that enable gentle loading with regeneration-directing bioactive components by soaking up but also provide macroscopic dimensional stability. Here microporous hydrogels capable of an inverse shape-memory effect (iSME) are described, which in contrast to classical shape-memory polymers (SMPs) recover their permanent shape upon cooling. These hydrogels are designed as covalently photo cross-linked polymer networks with oligo(ethylene glycol)-oligo(propylene glycol)-oligo(ethylene glycol) (OEG-OPG-OEG) segments. When heated after deformation, the OEG-OPG-OEG segments form micelles fixing the temporary shape. Upon cooling, the micelles dissociate again, the deformation is reversed and the permanent shape is obtained. Applicability of this iSME is demonstrated by the gentle loading of platelet-rich plasma (PRP) without causing any platelet activation during this process. PRP is highly bioactive and is widely acknowledged for its regenerative effects. Hence, the microporous inverse shape-memory hydrogel (iSMH) with a cooling induced pore-size effect represents a promising candidate scaffold for tissue regeneration for potential usage in minimally invasive surgery applications. KW - active scaffold KW - critical micellation temperature KW - hydrogel KW - inverse KW - shape-memory effect KW - platelet-rich plasma Y1 - 2022 U6 - https://doi.org/10.1002/admi.202101588 SN - 2196-7350 VL - 9 IS - 6 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Machatschek, Rainhard Gabriel A1 - Heuchel, Matthias A1 - Lendlein, Andreas T1 - Hydrolytic stability of polyetherimide investigated in ultrathin films JF - Journal of materials research : JMR / Materials Research Society N2 - Increasing the surface hydrophilicity of polyetherimide (PEI) through partial hydrolysis of the imide groups while maintaining the length of the main-chain was explored for adjusting its function in biomedical and membrane applications. The outcome of the polymer analogous reaction, i.e., the degree of ring opening and chain cleavage, is difficult to address in bulk and microstructured systems, as these changes only occur at the interface. Here, the reaction was studied at the air-water interface using the Langmuir technique, assisted by atomic force microscopy and vibrational spectroscopy. Slow PEI hydrolysis sets in at pH > 12. At pH = 14, the ring opening is nearly instantaneous. Reduction of the layer viscosity with time at pH = 14 suggested moderate chain cleavage. No hydrolysis was observed at pH = 1. Hydrolyzed PEI films had a much more cohesive structure, suggesting that the nanoporous morphology of PEI can be tuned via hydrolysis. KW - 2D materials KW - Membrane KW - Polymer KW - Water KW - Nanostructure Y1 - 2021 U6 - https://doi.org/10.1557/s43578-021-00267-6 SN - 0884-2914 SN - 2044-5326 VL - 36 IS - 14 SP - 2987 EP - 2994 PB - Springer CY - Berlin ER - TY - JOUR A1 - Tang, Jo Sing Julia A1 - Smaczniak, Aline Debrassi A1 - Tepper, Lucas A1 - Rosencrantz, Sophia A1 - Aleksanyan, Mina A1 - Dähne, Lars A1 - Rosencrantz, Ruben R. T1 - Glycopolymer based LbL multilayer thin films with embedded liposomes JF - Macromolecular bioscience N2 - Layer-by-layer (LbL) self-assembly emerged as an efficient technique for fabricating coating systems for, e.g., drug delivery systems with great versatility and control. In this work, protecting group free and aqueous-based syntheses of bioinspired glycopolymer electrolytes aredescribed. Thin films of the glycopolymers are fabricated by LbL self-assembly and function as scaffolds for liposomes, which potentially can encapsulate active substances. The adsorbed mass, pH stability, and integrity of glycopolymer coatings as well as the embedded liposomes are investigated via whispering gallery mode (WGM) technology and quartz crystal microbalance with dissipation (QCM-D) monitoring , which enable label-free characterization. Glycopolymer thin films, with and without liposomes, are stable in the physiological pH range. QCM-D measurements verify the integrity of lipid vesicles. Thus, the fabrication of glycopolymer-based surface coatings with embedded and intact liposomes is presented. KW - glycopolymers KW - layer-by-layer self-assembly KW - liposomes KW - polyelectrolyte KW - multilayer film Y1 - 2022 U6 - https://doi.org/10.1002/mabi.202100461 SN - 1616-5187 SN - 1616-5195 VL - 22 IS - 4 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Breternitz, Joachim T1 - Structural systematic investigations of photovoltaic absorber materials N2 - The direct conversion of light from the sun into usable forms of energy marks one of the central cornerstones of the change of our living from the use of fossil, non-renewable energy resources towards a more sustainable economy. Besides the necessary societal changes necessary, it is the understanding of the solids employed that is of particular importance for the success of this target. In this work, the principles and approaches of systematic-crystallographic characterisation and systematisation of solids is used and employed to allow a directed tuning of the materials properties. The thorough understanding of the solid-state forms hereby the basis, on which more applied approaches are founded. Two material systems, which are considered as promising solar absorber materials, are at the core of this work: halide perovskites and II-IV-N2 nitride materials. While the first is renowned for its high efficiencies and rapid development in the last years, the latter is putting an emphasis on true sustainability in that toxic and scarce elements are avoided. N2 - Die direkte Umwandlung der Energie der Sonne bildet einen zentralen Baustein im Umbau unserer Gesellschaft von der Nutzung fossiler, nicht nachhaltiger Energieträger zum Erreichen einer nachhaltigen Wirtschaft. Neben den gesellschaftlichen Veränderungen ist es insbesondere das Verständnis der genutzten Festkörper, das den Motor dieser Entwicklung bildet. In dieser Arbeit werden Prinzipien der systematisch-kristallographischen Untersuchung und Kategorisierung von Festkörpern genutzt, um die Eigenschaften der Materialien gezielt steuern zu können. Dabei bildet das Verständnis des kristallinen Zustands und seine Untersuchung die Basis, auf der angewandtere Forschungsansätze aufbauen. In dieser Arbeit werden vor allem zwei Materialsysteme betrachtet, die als Absorbermaterialien in Solarzellen in Betracht gezogen werden: Halid-Perowskite und II-IV-N2-Nitrid Materialien. Die ersteren zeichnen sich insbesondere durch ihre erstaunlich hohen Effizienzen und rapide Entwicklung in den letzten Jahren aus, während das letztere System in besonderer Weise auf Nachhaltigkeit optimiert ist, und giftige oder seltene Elemente zu vermeiden sucht. KW - Materials Chemistry KW - Crystallography KW - Photovoltaics Y1 - 2023 ER - TY - JOUR A1 - Abdou, Nicole A1 - Alonso, Bruno A1 - Brun, Nicolas A1 - Landois, Perine A1 - Taubert, Andreas A1 - Hesemann, Peter A1 - Mehdi, Ahmad T1 - Ionic guest in ionic host BT - ionosilica ionogel composites via ionic liquid confinement in ionosilica supports JF - Materials chemistry frontiers N2 - Ionosilica ionogels, i.e. composites consisting of an ionic liquid (IL) guest confined in an ionosilica host matrix, were synthesized via a non-hydrolytic sol-gel procedure from a tris-trialcoxysilylated amine precursor using the IL [BMIM]NTf2 as solvent. Various ionosilica ionogels were prepared starting from variable volumes of IL in the presence of formic acid. The resulting brittle and nearly colourless monoliths are composed of different amounts of IL guests confined in an ionosilica host as evidenced via thermogravimetric analysis, FT-IR, and C-13 CP-MAS solid-state NMR spectroscopy. In the following, we focused on confinement effects between the ionic host and guest. Special host-guest interactions between the IL guest and the ionosilica host were evidenced by H-1 solid-state NMR, Raman spectroscopy, and broadband dielectric spectroscopy (BDS) measurements. The three techniques indicate a strongly reduced ion mobility in the ionosilica ionogel composites containing small volume fractions of confined IL, compared to conventional silica-based ionogels. We conclude that the ionic ionosilica host stabilizes an IL layer on the host surface; this then results in a strongly reduced ion mobility compared to conventional silica hosts. The ion mobility progressively increases for systems containing higher volume fractions of IL and finally reaches the values observed in conventional silica based ionogels. These results therefore point towards strong interactions and confinement effects between the ionic host and the ionic guest on the ionosilica surface. Furthermore, this approach allows confining high volume fractions of IL into self-standing monoliths while preserving high ionic conductivity. These effects may be of interest in domains where IL phases must be anchored on solid supports to avoid leaching or IL spilling, e.g., in catalysis, in gas separation/sequestration devices or for the elaboration of solid electrolytes for (lithium-ion) batteries and supercapacitors. Y1 - 2022 U6 - https://doi.org/10.1039/d2qm00021k SN - 2052-1537 VL - 6 IS - 7 SP - 939 EP - 947 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Bapolisi, Alain Murhimalika A1 - Kielb, Patrycja A1 - Bekir, Marek A1 - Lehnen, Anne-Catherine A1 - Radon, Christin A1 - Laroque, Sophie A1 - Wendler, Petra A1 - Müller-Werkmeister, Henrike A1 - Hartlieb, Matthias T1 - Antimicrobial polymers of linear and bottlebrush architecture BT - Probing the membrane interaction and physicochemical properties JF - Macromolecular rapid communications : publishing the newsletters of the European Polymer Federation N2 - Polymeric antimicrobial peptide mimics are a promising alternative for the future management of the daunting problems associated with antimicrobial resistance. However, the development of successful antimicrobial polymers (APs) requires careful control of factors such as amphiphilic balance, molecular weight, dispersity, sequence, and architecture. While most of the earlier developed APs focus on random linear copolymers, the development of APs with advanced architectures proves to be more potent. It is recently developed multivalent bottlebrush APs with improved antibacterial and hemocompatibility profiles, outperforming their linear counterparts. Understanding the rationale behind the outstanding biological activity of these newly developed antimicrobials is vital to further improving their performance. This work investigates the physicochemical properties governing the differences in activity between linear and bottlebrush architectures using various spectroscopic and microscopic techniques. Linear copolymers are more solvated, thermo-responsive, and possess facial amphiphilicity resulting in random aggregations when interacting with liposomes mimicking Escheria coli membranes. The bottlebrush copolymers adopt a more stable secondary conformation in aqueous solution in comparison to linear copolymers, conferring rapid and more specific binding mechanism to membranes. The advantageous physicochemical properties of the bottlebrush topology seem to be a determinant factor in the activity of these promising APs. KW - antimicrobial polymers KW - bottlebrush copolymers KW - liposomes KW - membrane KW - interactions KW - quartz crystal microbalance Y1 - 2022 U6 - https://doi.org/10.1002/marc.202200288 SN - 1521-3927 SN - 1022-1336 VL - 43 IS - 19 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kim, Jiyong A1 - Kim, Yohan A1 - Park, Kyoungwon A1 - Boeffel, Christine A1 - Choi, Hyung-Seok A1 - Taubert, Andreas A1 - Wedel, Armin T1 - Ligand Effect in 1-Octanethiol Passivation of InP/ZnSe/ZnS Quantum Dots-Evidence of Incomplete Surface Passivation during Synthesis JF - Small : nano micro N2 - The lack of anionic carboxylate ligands on the surface of InP/ZnSe/ZnS quantum dots (QDs), where zinc carboxylate ligands can be converted to carboxylic acid or carboxylate ligands via proton transfer by 1-octanethiol, is demonstrated. The as-synthesized QDs initially have an under-coordinated vacancy surface, which is passivated by solvent ligands such as ethanol and acetone. Upon exposure of 1-octanethiol to the QD surface, 1-octanethiol effectively induces the surface binding of anionic carboxylate ligands (derived from zinc carboxylate ligands) by proton transfer, which consequently exchanges ethanol and acetone ligands that bind on the incomplete QD surface. These systematic chemical analyses, such as thermogravimetric analysis-mass spectrometry and proton nuclear magnetic resonance spectroscopy, directly show the interplay of surface ligands, and it associates with QD light-emitting diodes (QD-LEDs). It is believed that this better understanding can lead to industrially feasible QD-LEDs. KW - colloidal quantum dots KW - incomplete surface passivation KW - indium KW - phosphide KW - surface chemistry KW - thiol passivation Y1 - 2022 U6 - https://doi.org/10.1002/smll.202203093 SN - 1613-6810 SN - 1613-6829 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Hartlieb, Matthias A1 - Mansfield, Edward D. H. A1 - Perrier, Sebastien T1 - A guide to supramolecular polymerizations JF - Polymer Chemistry N2 - Supramolecular polymers or fibers are non-covalent assemblies of unimeric building blocks connected by secondary interactions such as hydrogen bonds or pi-pi interactions. Such structures hold enormous potential in the development of future materials, as their non-covalent nature makes them highly modular and adaptive. Within this review we aim to provide a broad overview over the area of linear supramolecular polymers including the different mechanisms of their polymerization as well as methods essential for their characterization. The different non-covalent interactions able to form supramolecular polymers are discussed, and key examples for each species are shown. Particular emphasis is laid on the development of living supramolecular polymerization able to produce fibers with a controlled length and low length dispersity, and even enable the production of supramolecular block copolymers. Another important and very recent field is the development of out-of-equilibrium supramolecular polymers, where the polymerization process can be temporally controlled enabling access to highly adaptive materials. Y1 - 2020 U6 - https://doi.org/10.1039/c9py01342c SN - 1759-9954 SN - 1759-9962 VL - 11 IS - 6 SP - 1083 EP - 1110 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Doering, Ulrike A1 - Grigoriev, Dmitry A1 - Tapio, Kosti A1 - Bald, Ilko A1 - Böker, Alexander T1 - Synthesis of nanostructured protein-mineral-microcapsules by sonication JF - Soft matter N2 - We propose a simple and eco-friendly method for the formation of composite protein-mineral-microcapsules induced by ultrasound treatment. Protein- and nanoparticle-stabilized oil-in-water (O/W) emulsions loaded with different oils are prepared using high-intensity ultrasound. The formation of thin composite mineral proteinaceous shells is realized with various types of nanoparticles, which are pre-modified with Bovine Serum Albumin (BSA) and subsequently characterized by EDX, TGA, zeta potential measurements and Raman spectroscopy. Cryo-SEM and EDX mapping visualizations show the homogeneous distribution of the densely packed nanoparticles in the capsule shell. In contrast to the results reported in our previous paper,(1) the shell of those nanostructured composite microcapsules is not cross-linked by the intermolecular disulfide bonds between BSA molecules. Instead, a Pickering-Emulsion formation takes place because of the amphiphilicity-driven spontaneous attachment of the BSA-modified nanoparticles at the oil/water interface. Using colloidal particles for the formation of the shell of the microcapsules, in our case silica, hydroxyapatite and calcium carbonate nanoparticles, is promising for the creation of new functional materials. The nanoparticulate building blocks of the composite shell with different chemical, physical or morphological properties can contribute to additional, sometimes even multiple, features of the resulting capsules. Microcapsules with shells of densely packed nanoparticles could find interesting applications in pharmaceutical science, cosmetics or in food technology. Y1 - 2022 U6 - https://doi.org/10.1039/d1sm01638e SN - 1744-6848 VL - 18 IS - 13 SP - 2558 EP - 2568 PB - Royal Society of Chemistry CY - London ER - TY - JOUR A1 - Machatschek, Rainhard Gabriel A1 - Heuchel, Matthias A1 - Lendlein, Andreas T1 - Thin-layer studies on surface functionalization of polyetherimide BT - hydrolysis versus amidation JF - Journal of materials research : JMR / Materials Research Society N2 - Among the high-performance and engineering polymers, polyimides and the closely related polyetherimide (PEI) stand out by their capability to react with nucleophiles under relatively mild conditions. By targeting the phthalimide groups in the chain backbone, post-functionalization offers a pathway to adjust surface properties such as hydrophilicity, solvent resistance, and porosity. Here, we use ultrathin PEI films on a Langmuir trough as a model system to investigate the surface functionalization with ethylene diamine and tetrakis(4-aminophenyl)porphyrin as multivalent nucleophiles. By means of AFM, Raman spectroscopy, and interfacial rheology, we show that hydrolysis enhances the chemical and mechanical stability of ultrathin films and allows for the formation of EDC/NHS-activated esters. Direct amidation of PEI was achieved in the presence of a Lewis acid catalyst, resulting in free amine groups rather than cross-linking. When comparing amidation with hydrolysis, we find a greater influence of the latter on material properties. KW - Membrane KW - Nanostructure KW - Polymer KW - Raman spectroscopy KW - Scanning probe microscopy (SPM) KW - Surface reaction KW - Thin film Y1 - 2021 U6 - https://doi.org/10.1557/s43578-021-00339-7 SN - 0884-2914 SN - 2044-5326 VL - 37 IS - 1 SP - 67 EP - 76 PB - Springer CY - Berlin ER - TY - JOUR A1 - Buyinza, Daniel A1 - Derese, Solomon A1 - Ndakala, Albert A1 - Heydenreich, Matthias A1 - Yenesew, Abiy A1 - Koch, Andreas A1 - Oriko, Richard T1 - A coumestan and a coumaronochromone from Millettia lasiantha JF - Biochemical systematics and ecology N2 - The manuscript describes the phytochemical investigation of the roots, leaves and stem bark of Millettia lasiantha resulting in the isolation of twelve compounds including two new isomeric isoflavones lascoumestan and las-coumaronochromone. The structures of the new compounds were determined using different spectroscopic techniques. KW - Millettia lasiantha KW - Leguminosae KW - Coumestan KW - Coumaronochromone Y1 - 2021 U6 - https://doi.org/10.1016/j.bse.2021.104277 SN - 0305-1978 SN - 1873-2925 VL - 97 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Yang, Jin A1 - Ghosh, Samrat A1 - Roeser, Jérôme A1 - Acharjya, Amitava A1 - Penschke, Christopher A1 - Tsutsui, Yusuke A1 - Rabeah, Jabor A1 - Wang, Tianyi A1 - Tameu, Simon Yves Djoko A1 - Ye, Meng-Yang A1 - Grüneberg, Julia A1 - Li, Shuang A1 - Li, Changxia A1 - Schomaecker, Reinhard A1 - Van de Krol, Roel A1 - Seki, Shu A1 - Saalfrank, Peter A1 - Thomas, Arne T1 - Constitutional isomerism of the linkages in donor–acceptor covalent organic frameworks and its impact on photocatalysis JF - Nature Communications N2 - When new covalent organic frameworks (COFs) are designed, the main efforts are typically focused on selecting specific building blocks with certain geometries and properties to control the structure and function of the final COFs. The nature of the linkage (imine, boroxine, vinyl, etc.) between these building blocks naturally also defines their properties. However, besides the linkage type, the orientation, i.e., the constitutional isomerism of these linkages, has rarely been considered so far as an essential aspect. In this work, three pairs of constitutionally isomeric imine-linked donor-acceptor (D-A) COFs are synthesized, which are different in the orientation of the imine bonds (D-C=N-A (DCNA) and D-N=C-A (DNCA)). The constitutional isomers show substantial differences in their photophysical properties and consequently in their photocatalytic performance. Indeed, all DCNA COFs show enhanced photocatalytic H2 evolution performance than the corresponding DNCA COFs. Besides the imine COFs shown here, it can be concluded that the proposed concept of constitutional isomerism of linkages in COFs is quite universal and should be considered when designing and tuning the properties of COFs. Y1 - 2022 U6 - https://doi.org/10.1038/s41467-022-33875-9 SN - 2041-1723 VL - 13 IS - 1 PB - Nature Publishing Group UK CY - [London] ER - TY - GEN A1 - Moerschbacher, Bruno A1 - Jaworska, Małgorzata A1 - Peter, Martin G. T1 - Obituary of George A.F. Roberts (1939-2018) T2 - Reactive & functional polymers Y1 - 2020 U6 - https://doi.org/10.1016/j.reactfunctpolym.2020.104711 SN - 1381-5148 SN - 1873-166X VL - 156 PB - Elsevier CY - Amsterdam [u.a.] ER - TY - JOUR A1 - Franz, Alexandra A1 - Többens, Daniel M. A1 - Lehmann, Frederike A1 - Kärgell, Martin A1 - Schorr, Susan T1 - The influence of deuteration on the crystal structure of hybrid halide perovskites: a temperature-dependent neutron diffraction study of FAPbBr(3) JF - Acta crystallographica; Section B, Structural science, crystal engineering and materials N2 - This paper discusses the full structural solution of the hybrid perovskite formamidinium lead tribromide (FAPbBr(3)) and its temperature-dependent phase transitions in the range from 3 K to 300 K using neutron powder diffraction and synchrotron X-ray diffraction. Special emphasis is put on the influence of deuteration on formamidinium, its position in the unit cell and disordering in comparison to fully hydrogenated FAPbBr(3). The temperature-dependent measurements show that deuteration critically influences the crystal structures, i.e. results in partially-ordered temperature-dependent structural modifications in which two symmetry-independent molecule positions with additional dislocation of the molecular centre atom and molecular angle inclinations are present. KW - hybrid perovskite KW - FAPbBr(3) KW - deuteration KW - neutron powder diffraction KW - crystal structure Y1 - 2020 U6 - https://doi.org/10.1107/S2052520620002620 SN - 2052-5206 VL - 76 IS - 2 SP - 267 EP - 274 PB - Wiley-Blackwell CY - Oxford [u.a.] ER - TY - JOUR A1 - Gu, Sasa A1 - Risse, Sebastian A1 - Lu, Yan A1 - Ballauff, Matthias T1 - Mechanism of the oxidation of 3,3′,5,5′-tetramethylbenzidine catalyzed by peroxidase-like Pt nanoparticles immobilized in spherical polyelectrolyte brushes BT - a kinetic study JF - ChemPhysChem N2 - Experimental and kinetic modelling studies are presented to investigate the mechanism of 3,3 ',5,5 '-tetramethylbenzidine (TMB) oxidation by hydrogen peroxide (H2O2) catalyzed by peroxidase-like Pt nanoparticles immobilized in spherical polyelectrolyte brushes (SPB-Pt). Due to the high stability of SPB-Pt colloidal, this reaction can be monitored precisely in situ by UV/VIS spectroscopy. The time-dependent concentration of the blue-colored oxidation product of TMB expressed by different kinetic models was used to simulate the experimental data by a genetic fitting algorithm. After falsifying the models with abundant experimental data, it is found that both H2O2 and TMB adsorb on the surface of Pt nanoparticles to react, indicating that the reaction follows the Langmuir-Hinshelwood mechanism. A true rate constant k, characterizing the rate-determining step of the reaction and which is independent on the amount of catalysts used, is obtained for the first time. Furthermore, it is found that the product adsorbes strongly on the surface of nanoparticles, thus inhibiting the reaction. The entire analysis provides a new perspective to study the catalytic mechanism and evaluate the catalytic activity of the peroxidase-like nanoparticles. KW - kinetics KW - nanoparticles KW - reaction mechanisms KW - spherical polyelectrolyte KW - brushes KW - UV KW - vis spectroscopy Y1 - 2019 U6 - https://doi.org/10.1002/cphc.201901087 SN - 1439-4235 SN - 1439-7641 VL - 21 IS - 5 SP - 450 EP - 458 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Gharabekyan, Hrant H. A1 - Koetz, Joachim A1 - Poghosyan, Armen H. T1 - A protonated L-cysteine adsorption on gold surface BT - a molecular dynamics study JF - Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects N2 - The adsorption of protonated L-cysteine onto Au(111) surface was studied via molecular dynamics method. The detailed examination of trajectories reveals that a couple of picoseconds need to be strongly adsorbed at the gold surface via L-cysteine's sulfur and oxygen atoms. The average distances of L-cysteine's adsorbed sulfur and oxygen from gold plane are-2.7 angstrom and-3.2 angstrom, correspondingly. We found that the adsorption of L-cysteine takes place preferentially at bridge site with possibility of-82%. Discussing the conformation features of protonated L-cysteine, we consider that the most stable conformation of protonated L-cysteine is "reverse boat" position, where sulfur and oxygen pointed down to the gold surface, while the amino group is far from the gold surface. KW - MD simulations KW - gold surface KW - GOIP KW - l-cysteine KW - adsorption KW - protonation Y1 - 2021 U6 - https://doi.org/10.1016/j.colsurfa.2021.127452 SN - 0927-7757 SN - 1873-4359 VL - 629 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Bouakline, Foudhil A1 - Saalfrank, Peter T1 - Seemingly asymmetric atom-localized electronic densities following laser-dissociation of homonuclear diatomics JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry N2 - Recent experiments on laser-dissociation of aligned homonuclear diatomic molecules show an asymmetric forward-backward (spatial) electron-localization along the laser polarization axis. Most theoretical models attribute this asymmetry to interference effects between gerade and ungerade vibronic states. Presumably due to alignment, these models neglect molecular rotations and hence infer an asymmetric (post-dissociation) charge distribution over the two identical nuclei. In this paper, we question the equivalence that is made between spatial electron-localization, observed in experiments, and atomic electron-localization, alluded by these theoretical models. We show that (seeming) agreement between these models and experiments is due to an unfortunate omission of nuclear permutation symmetry, i.e., quantum statistics. Enforcement of the latter requires mandatory inclusion of the molecular rotational degree of freedom, even for perfectly aligned molecules. Unlike previous interpretations, we ascribe spatial electron-localization to the laser creation of a rovibronic wavepacket that involves field-free molecular eigenstates with opposite space-inversion symmetry i.e., even and odd parity. Space-inversion symmetry breaking would then lead to an asymmetric distribution of the (space-fixed) electronic density over the forward and backward hemisphere. However, owing to the simultaneous coexistence of two indistinguishable molecular orientational isomers, our analytical and computational results show that the post-dissociation electronic density along a specified space-fixed axis is equally shared between the two identical nuclei-a result that is in perfect accordance with the principle of the indistinguishability of identical particles. Published under an exclusive license by AIP Publishing. Y1 - 2021 U6 - https://doi.org/10.1063/5.0049710 SN - 0021-9606 SN - 1089-7690 VL - 154 IS - 23 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Qiu, Liang A1 - Zhang, Haoran A1 - Bick, Thomas A1 - Martin, Johannes A1 - Wendler, Petra A1 - Böker, Alexander A1 - Glebe, Ulrich A1 - Xing, Chengfen T1 - Construction of highly ordered glyco-inside nano-assemblies through RAFT dispersion polymerization of galactose-decorated monomer JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - Glyco-assemblies derived from amphiphilic sugar-decorated block copolymers (ASBCs) have emerged prominently due to their wide application, for example, in biomedicine and as drug carriers. However, to efficiently construct these glyco-assemblies is still a challenge. Herein, we report an efficient technology for the synthesis of glyco-inside nano-assemblies by utilizing RAFT polymerization of a galactose-decorated methacrylate for polymerization-induced self-assembly (PISA). Using this approach, a series of highly ordered glyco-inside nano-assemblies containing intermediate morphologies were fabricated by adjusting the length of the hydrophobic glycoblock and the polymerization solids content. A specific morphology of complex vesicles was captured during the PISA process and the formation mechanism is explained by the morphology of its precursor and intermediate. Thus, this method establishes a powerful route to fabricate glyco-assemblies with tunable morphologies and variable sizes, which is significant to enable the large-scale fabrication and wide application of glyco-assemblies. KW - galactose-decorated monomer KW - glyco-inside nano-assemblies KW - morphology KW - evolution KW - PISA KW - RAFT dispersion polymerization Y1 - 2021 U6 - https://doi.org/10.1002/anie.202015692 SN - 1433-7851 SN - 1521-3773 VL - 60 IS - 20 SP - 11098 EP - 11103 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Zhang, Shanshan A1 - Liu, Yue A1 - Machatschek, Rainhard Gabriel A1 - Lendlein, Andreas T1 - Ultrathin collagen type I films formed at the air-water interface JF - MRS advances : a journal of the Materials Research Society (MRS) N2 - Collagen-based biomaterials with oriented fibrils have shown great application potential in medicine. However, it is still challenging to control the type I collagen fibrillogenesis in ultrathin films. Here, we report an approach to produce cohesive and well-organized type I collagen ultrathin films of about 10 nm thickness using the Langmuir-Blodgett technique. Ellipsometry, rheology, and Brewster angle microscopy are applied to investigate in situ how the molecules behave at the air-water interface, both at room temperature and 37 degrees C. The interfacial storage modulus observed at room temperature vanishes upon heating, indicating the existence and disappearance of the network structure in the protein nanosheet. The films were spanning over holes as large as 1 mm diameter when transferred at room temperature, proving the strong cohesive interactions. A highly aligned and fibrillar structure was observed by atomic force microscopy (AFM) and optical microscopy. Y1 - 2022 U6 - https://doi.org/10.1557/s43580-021-00160-8 SN - 2059-8521 VL - 7 IS - 4 SP - 56 EP - 62 PB - Springer Nature Switzerland AG CY - Cham ER - TY - JOUR A1 - Sperlich, Eric A1 - Köckerling, Martin T1 - Cluster salts [Nb6Cl12(HIm)(6)]A(n) (with HIm=1H-imidazole and A=Mineral Acid Anion, n=1 or 2) made in and with Bronsted-basic ionic liquids and liquid mixtures JF - ChemistryOpen N2 - Four new hexanuclear niobium cluster compounds of the general formula [Nb6Cl12(HIm)(6)](A)(n) . x(solvent molecule) (HIm=1H-imidazole, A=mineral acid anion, Cl- (n=2) (1), (SO4)(2-) (n=1) (2), (CrO4)(2-) (n=1) (3), and (HAsO4)(2-) (n=1) (4)) were prepared. Their synthesis can be done in basic ionic liquids, which form on the addition of a mineral acid, which also delivers the counter anion for the final cluster compound, to an excess of the 1H-imidazole. Some addition of an auxiliary solvent, like methanol, improves the speed of crystallisation. The cluster unit comprises a hexanuclear Nb-6 unit of octahedral shape with the edges bridged by Cl atoms and the exo sites being occupied by N-bonded 1H-imidazole ligands. The cluster cation carries sixteen cluster-based electrons. Between the NH groups of the ligands of the cluster unit, the anions and the co-crystallised water (1), or 1H-imidazole and methanol molecules (2, 3, and 4) a network of hydrogen bonds exists. KW - cluster KW - ionic liquid KW - structure elucidation KW - heterocyclic ligand KW - Niobium Y1 - 2021 U6 - https://doi.org/10.1002/open.202000266 SN - 2191-1363 VL - 10 IS - 2 SP - 248 EP - 254 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Roy, Parna A1 - Mukherjee, Arpita A1 - Mondal, Pritha A1 - Bhattacharyya, Biswajit A1 - Narayan, Awadhesh A1 - Pandey, Anshu T1 - Electronic structure and spectroscopy of I-III-VI2 nanocrystals BT - a perspective JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - I-III-VI2 semiconductor nanocrystals have been applied to a host of energy conversion devices with great success. Large scale implementation of device concepts based on these materials has, however, been somewhat stymied by the strong role of defects in determining the optoelectronic characteristics of these materials. Here we present a perspective view of the role of electronic structure and defects on the physical properties, particularly the spectroscopy, of this family of materials. Applications of these materials are further discussed in this context. Y1 - 2022 U6 - https://doi.org/10.1021/acs.jpcc.1c10922 SN - 1932-7447 SN - 1932-7455 VL - 126 IS - 17 SP - 7364 EP - 7373 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Madani, Amiera A1 - Anghileri, Lucia A1 - Heydenreich, Matthias A1 - Möller, Heiko Michael A1 - Pieber, Bartholomäus T1 - Benzylic fluorination induced by a charge-transfer complex with a solvent-dependent selectivity switch JF - Organic letters / publ. by the American Chemical Society N2 - We present a divergent strategy for the fluorination of phenylacetic acid derivatives that is induced by a charge-transfer complex between Selectfluor and 4-(dimethylamino)pyridine. A comprehensive investigation of the conditions revealed a critical role of the solvent on the reaction outcome. In the presence of water, decarboxylative fluorination through a single-electron oxidation is dominant. Non-aqueous conditions result in the clean formation of alpha-fluoro-alpha-arylcarboxylic acids. KW - Charge transfer KW - Halogenation KW - Oxidation KW - Reaction products KW - Reagents Y1 - 2022 U6 - https://doi.org/10.1021/acs.orglett.2c02050 SN - 1523-7060 SN - 1523-7052 VL - 24 IS - 29 SP - 5376 EP - 5380 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wojcik, Michal A1 - Brinkmann, Pia A1 - Zdunek, Rafał A1 - Riebe, Daniel A1 - Beitz, Toralf A1 - Merk, Sven A1 - Cieslik, Katarzyna A1 - Mory, David A1 - Antonczak, Arkadiusz T1 - Classification of copper minerals by handheld laser-induced breakdown spectroscopy and nonnegative tensor factorisation JF - Sensors N2 - Laser-induced breakdown spectroscopy (LIBS) analysers are becoming increasingly common for material classification purposes. However, to achieve good classification accuracy, mostly noncompact units are used based on their stability and reproducibility. In addition, computational algorithms that require significant hardware resources are commonly applied. For performing measurement campaigns in hard-to-access environments, such as mining sites, there is a need for compact, portable, or even handheld devices capable of reaching high measurement accuracy. The optics and hardware of small (i.e., handheld) devices are limited by space and power consumption and require a compromise of the achievable spectral quality. As long as the size of such a device is a major constraint, the software is the primary field for improvement. In this study, we propose a novel combination of handheld LIBS with non-negative tensor factorisation to investigate its classification capabilities of copper minerals. The proposed approach is based on the extraction of source spectra for each mineral (with the use of tensor methods) and their labelling based on the percentage contribution within the dataset. These latent spectra are then used in a regression model for validation purposes. The application of such an approach leads to an increase in the classification score by approximately 5% compared to that obtained using commonly used classifiers such as support vector machines, linear discriminant analysis, and the k-nearest neighbours algorithm. KW - LIBS KW - NTF KW - HALS KW - classification KW - copper minerals Y1 - 2020 U6 - https://doi.org/10.3390/s20185152 SN - 1424-8220 VL - 20 IS - 18 PB - MDPI CY - Basel ER - TY - JOUR A1 - Kaya, Kerem A1 - Debsharma, Tapas A1 - Schlaad, Helmut A1 - Yagci, Yusuf T1 - Cellulose-based polyacetals by direct and sensitized photocationic ring-opening polymerization of levoglucosenyl methyl ether JF - Polymer Chemistry N2 - 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. Y1 - 2020 U6 - https://doi.org/10.1039/d0py01307b SN - 1759-9954 SN - 1759-9962 VL - 11 IS - 43 SP - 6884 EP - 6889 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Yan, Runyu A1 - Oschatz, Martin A1 - Wu, Feixiang T1 - Towards stable lithium-sulfur battery cathodes by combining physical and chemical confinement of polysulfides in core-shell structured nitrogen-doped carbons JF - Carbon N2 - Despite intensive research on porous carbon materials as hosts for sulfur in lithium-sulfur battery cathodes, it remains a problem to restrain the soluble lithium polysulfide intermediates for a long-term cycling stability without the use of metallic or metal-containing species. Here, we report the synthesis of nitrogen-doped carbon materials with hierarchical pore architecture and a core-shell-type particle design including an ordered mesoporous carbon core and a polar microporous carbon shell. The initial discharge capacity with a sulfur loading up to 72 wt% reaches over 900 mA h g(sulf)(ur)(-1) at a rate of C/2. Cycling performance measured at C/2 indicates similar to 90% capacity retention over 250 cycles. In comparison to other carbon hosts, this architecture not only provides sufficient space for a high sulfur loading induced by the high-pore-volume particle core, but also enables a dual effect of physical and chemical confinement of the polysulfides to stabilize the cycle life by adsorbing the soluble intermediates in the polar microporous shell. This work elucidates a design principle for carbonaceous hosts that is capable to provide simultaneous physical-chemical confinement. This is necessary to overcome the shuttle effect towards stable lithium-sulfur battery cathodes, in the absence of additional membranes or inactive metal-based anchoring materials. KW - lithium-sulfur battery KW - sulfur KW - porous carbon KW - cathode KW - polysulfides Y1 - 2020 U6 - https://doi.org/10.1016/j.carbon.2020.01.046 SN - 0008-6223 SN - 1873-3891 VL - 161 SP - 162 EP - 168 PB - Elsevier Science CY - Amsterdam [u.a.] ER - TY - JOUR A1 - Zhang, Pengfei A1 - Behl, Marc A1 - Balk, Maria A1 - Peng, Xingzhou A1 - Lendlein, Andreas T1 - Shape-programmable architectured hydrogels sensitive to ultrasound JF - Macromolecular rapid communications N2 - On-demand motion of highly swollen polymer systems can be triggered by changes in pH, ion concentrations, or by heat. Here, shape-programmable, architectured hydrogels are introduced, which respond to ultrasonic-cavitation-based mechanical forces (CMF) by directed macroscopic movements. The concept is the implementation and sequential coupling of multiple functions (swellability in water, sensitivity to ultrasound, shape programmability, and shape-memory) in a semi-interpenetrating polymer network (s-IPN). The semi-IPN-based hydrogels are designed to function through rhodium coordination (Rh-s-IPNH). These coordination bonds act as temporary crosslinks. The porous hydrogels with coordination bonds (degree of swelling from 300 +/- 10 to 680 +/- 60) exhibit tensile strength sigma(max) up to 250 +/- 60 kPa. Shape fixity ratios up to 90% and shape recovery ratios up to 94% are reached. Potential applications are switches or mechanosensors. KW - cavitation-based mechanical force KW - rhodium-phosphine coordination bonds KW - semi-IPN hydrogels KW - shape-memory effect Y1 - 2020 U6 - https://doi.org/10.1002/marc.201900658 SN - 1022-1336 SN - 1521-3927 VL - 41 IS - 7 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Akarsu, Pinar A1 - Grobe, Richard A1 - Nowaczyk, Julius A1 - Hartlieb, Matthias A1 - Reinicke, Stefan A1 - Böker, Alexander A1 - Sperling, Marcel A1 - Reifarth, Martin T1 - Solid-phase microcontact printing for precise patterning of rough surfaces BT - using polymer-tethered elastomeric stamps for the transfer of reactive silanes JF - ACS applied polymer materials N2 - We present a microcontact printing (mu CP) routine suitable to introduce defined (sub-) microscale patterns on surface substrates exhibiting a high capillary activity and receptive to a silane-based chemistry. This is achieved by transferring functional trivalent alkoxysilanes, such as (3-aminopropyl)-triethoxysilane (APTES) as a low-molecular weight ink via reversible covalent attachment to polymer brushes grafted from elastomeric polydimethylsiloxane (PDMS) stamps. The brushes consist of poly{N-[tris(hydroxymethyl)-methyl]acrylamide} (PTrisAAm) synthesized by reversible addition-fragmentation chain-transfer (RAFT)-polymerization and used for immobilization of the alkoxysilane-based ink by substituting the alkoxy moieties with polymer-bound hydroxyl groups. Upon physical contact of the silane-carrying polymers with surfaces, the conjugated silane transfers to the substrate, thus completely suppressing ink-flow and, in turn, maximizing printing accuracy even for otherwise not addressable substrate topographies. We provide a concisely conducted investigation on polymer brush formation using atomic force microscopy (AFM) and ellipsometry as well as ink immobilization utilizing two-dimensional proton nuclear Overhauser enhancement spectroscopy (H-1-H-1-NOESY-NMR). We analyze the mu CP process by printing onto Si-wafers and show how even distinctively rough surfaces can be addressed, which otherwise represent particularly challenging substrates. KW - microcontact printing KW - capillary-active substrates KW - silane chemistry KW - PDMS surface grafting KW - surface patterning KW - shuttled RAFT-polymerization Y1 - 2021 U6 - https://doi.org/10.1021/acsapm.1c00024 SN - 2637-6105 VL - 3 IS - 5 SP - 2420 EP - 2431 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Mazarei, Elham A1 - Barker, John R. T1 - CH2 + O-2 BT - reaction mechanism, biradical and zwitterionic character, and formation of CH2OO, the simplest Criegee intermediate JF - Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies N2 - The singlet and triplet potential surfaces for the title reaction were investigated using the CBS-QB3 level of theory. The wave functions for some species exhibited multireference character and required the CASPT2/6-31+G(d,p) and CASPT2/aug-cc-pVTZ levels of theory to obtain accurate relative energies. A Natural Bond Orbital Analysis showed that triplet (CH2OO)-C-3 (the simplest Criegee intermediate) and (CH2O2)-C-3 (dioxirane) have mostly polar biradical character, while singlet (CH2OO)-C-1 has some zwitterionic character and a planar structure. Canonical variational transition state theory (CVTST) and master equation simulations were used to analyze the reaction system. CVTST predicts that the rate constant for reaction of (CH2)-C-1 + O-3(2) is more than ten times as fast as the reaction of (CH2)-C-3 ((XB1)-B-3) + O-3(2) and the ratio remains almost independent of temperature from 900 K to 3000 K. The master equation simulations predict that at low pressures the (CH2O)-C-1 + O-3 product set is dominant at all temperatures and the primary yield of OH radicals is negligible below 600 K, due to competition with other primary reactions in this complex system. Y1 - 2021 U6 - https://doi.org/10.1039/d1cp04372b SN - 1463-9076 SN - 1463-9084 VL - 24 IS - 2 SP - 914 EP - 927 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Riemer, Nastja A1 - Riemer, Martin A1 - Krüger, Mandy A1 - Clarkson, Guy J. A1 - Shipman, Michael A1 - Schmidt, Bernd T1 - Synthesis of arylidene-beta-lactams via exo-selective Matsuda-Heck arylation of methylene-beta-lactams JF - The journal of organic chemistry : JOC N2 - exo-Methylene-beta-lactams were synthesized in two steps from commercially available 3-bromo-2-(bromomethyl)-propionic acid and reacted with arene diazonium salts in a Heck-type arylation in the presence of catalytic amounts of Pd(OAc)(2) under ligand-free conditions. The products, arylidene-beta-lactams, were obtained in high yields as single isomers. The beta-hydride elimination step of the Pd-catalyzed coupling reaction proceeds with high exo-regioselectivity and E-stereoselectivity. With aryl iodides, triflates, or bromides, the coupling products were isolated only in low yields, due to extensive decomposition of the starting material at elevated temperatures. This underlines that arene diazonium salts can be superior arylating reagents in Heck-type reactions and yield coupling products in synthetically useful yields and selectivities when conventional conditions fail. Y1 - 2021 U6 - https://doi.org/10.1021/acs.joc.1c00638 SN - 0022-3263 SN - 1520-6904 VL - 86 IS - 13 SP - 8786 EP - 8796 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Balischewski, Christian A1 - Choi, Hyung-Seok A1 - Behrens, Karsten A1 - Beqiraj, Alkit A1 - Körzdörfer, Thomas A1 - Gessner, Andre A1 - Wedel, Armin A1 - Taubert, Andreas T1 - Metal sulfide nanoparticle synthesis with ionic liquids state of the art and future perspectives JF - ChemistryOpen N2 - Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nano-particle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples. KW - Ionic liquids KW - ionic liquid crystals KW - ionic liquid precursors KW - metal KW - sulfides KW - catalysis KW - electrochemistry KW - energy materials KW - LED KW - solar KW - cells Y1 - 2021 U6 - https://doi.org/10.1002/open.202000357 SN - 2191-1363 VL - 10 IS - 2 SP - 272 EP - 295 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Quan, Ting A1 - Haerk, Eneli A1 - Xu, Yaolin A1 - Ahmet, Ibbi A1 - Höhn, Christian A1 - Mei, Shilin A1 - Lu, Yan T1 - Unveiling the formation of solid electrolyte interphase and its temperature dependence in "Water-in-Salt" supercapacitors JF - ACS applied materials & interfaces N2 - "Water-in-salt" (WIS) electrolytes have emerged as an excellent superconcentrated ionic medium for high-power energy storage systems such as supercapacitors due to their extended working potential compared to the conventional dilute aqueous electrolyte. In this work, we have investigated the performance of WIS supercapacitors using hollow carbon nanoplates as electrodes and compared it to that based on the conventional "salt-in-water" electrolytes. Moreover, the potentiostatic electrochemical impedance spectroscopy has been employed to provide an insightful look into the charge transport properties, which also, for the first time, reveals the formation of a solid-electrolyte interphase (SEI and their temperature-dependent impedance for charge transfer and adsorption. Furthermore, the effect of temperature on the electrochemical performance of the WIS supercapacitors in the temperature range from 15 to 60 degrees C has been studied, which presents a gravimetric capacitance of 128 F g(-1) and a volumetric capacitance of 197.12 F cm(-3) at 55 degrees C compared to 87.5 F g(-1) and 134.75 F cm(-3) at 15 degrees C. The in-depth understanding about the formation of SEI layer and the electrochemical performance at different temperatures for WIS supercapacitors will assist the efforts toward designing better aqueous electrolytes for supercapacitors. KW - "water-in-salt" KW - supercapacitor KW - solid electrolyte interphase KW - electrochemical impedance spectroscopy KW - temperature effect Y1 - 2021 U6 - https://doi.org/10.1021/acsami.0c19506 SN - 1944-8244 SN - 1944-8252 VL - 13 IS - 3 SP - 3979 EP - 3990 PB - American Chemical Society CY - Washington ER - TY - CHAP A1 - Ramadan, Shahenda A1 - Guerrero, Paula A1 - Nedielkov, Ruslan A1 - Klishin, Nikolai A1 - Dimova, Rumiana A1 - Silva, Daniel V. A1 - Möller, Heiko T1 - Building a mimetic system for unraveling protein-protein interactions on membranes T2 - European biophysics journal : with biophysics letters ; an international journal of biophysics Y1 - 2021 U6 - https://doi.org/10.1007/s00249-021-01558-w SN - 0175-7571 SN - 1432-1017 VL - 50 IS - SUPPL 1 SP - S153 EP - S153 PB - Springer CY - Berlin ; Heidelberg ; New York ER - TY - JOUR A1 - Behl, Marc A1 - Balk, Maria A1 - Lützow, Karola A1 - Lendlein, Andreas T1 - Impact of block sequence on the phase morphology of multiblock copolymers obtained by high-throughput robotic synthesis JF - European polymer journal : EPJ N2 - The chemical nature, the number length of integrated building blocks, as well as their sequence structure impact the phase morphology of multiblock copolymers (MBC) consisting of two non-miscible block types. We hypothesized that a strictly alternating sequence should favour phase segregation and in this way the elastic properties. A library of well-defined MBCs composed of two different hydrophobic, semi-crystalline blocks providing domains with well-separated melting temperatures (T(m)s) were synthesized from the same type of precursor building blocks as strictly alternating (MBCsalt) or random (MBCsran) MBCs and compared. Three different series of MBCsalt or MBCsran were synthesized by high-throughput synthesis by coupling oligo(e-caprolactone) (OCL) of different molecular weights (2, 4, and 8 kDa) with oligotetrahydrofuran (OTHF, 2.9 kDa) via Steglich esterification in which the molar ratio of the reaction partners was slightly adjusted. Maximum of weight average molecular weight (M-w) were 65,000 g center dot mol(-1), 165,000 g center dot mol(-1), and 168,000 g center dot mol(-1) for MBCsalt and 80,500 g center dot mol(-1), 100,000 g center dot mol(-1), and 147,600 g center dot mol(-1) for MBCsran. When Mw increased, a decrease of both Tms associated to the melting of the OCL and OTHF domains was observed for all MBCs. T-m (OTHF) of MBCsran was always higher than Tm (OTHF) of MBCsalt, which was attributed to a better phase segregation. In addition, the elongation at break of MBCsalt was almost half as high when compared to MBCsran. In this way this study elucidates role of the block length and sequence structure in MBCs and enables a quantitative discussion of the structure-function relationship when two semi-crystalline block segments are utilized for the design of block copolymers. KW - Multiblock copolymers KW - Sequence structure KW - Phase morphology KW - Polymer KW - library KW - Robotic synthesis KW - High-throughput Y1 - 2021 U6 - https://doi.org/10.1016/j.eurpolymj.2020.110207 SN - 0014-3057 SN - 1873-1945 VL - 143 PB - Elsevier CY - Oxford ER -