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- ItemDefect-free Naphthalene Diimide Bithiophene Copolymers with Controlled Molar Mass and High Performance via Direct Arylation Polycondensation(Washington, DC : ACS Publications, 2015) Matsidik, Rukiya; Komber, Hartmut; Luzio, Alessandro; Caironi, Mario; Sommer, MichaelA highly efficient, simple, and environmentally friendly protocol for the synthesis of an alternating naphthalene diimide bithiophene copolymer (PNDIT2) via direct arylation polycondensation (DAP) is presented. High molecular weight (MW) PNDIT2 can be obtained in quantitative yield using aromatic solvents. Most critical is the suppression of two major termination reactions of NDIBr end groups: nucleophilic substitution and solvent end-capping by aromatic solvents via C–H activation. In situ solvent end-capping can be used to control MW by varying monomer concentration, whereby end-capping is efficient and MW is low for low concentration and vice versa. Reducing C–H reactivity of the solvent at optimized conditions further increases MW. Chain perfection of PNDIT2 is demonstrated in detail by NMR spectroscopy, which reveals PNDIT2 chains to be fully linear and alternating. This is further confirmed by investigating the optical and thermal properties as a function of MW, which saturate at Mn ≈ 20 kDa, in agreement with controls made by Stille coupling. Field-effect transistor (FET) electron mobilities μsat up to 3 cm2/(V·s) are measured using off-center spin-coating, with FET devices made from DAP PNDIT2 exhibiting better reproducibility compared to Stille controls.
- ItemTemplated Self-Assembly of Ultrathin Gold Nanowires by Nanoimprinting for Transparent Flexible Electronics(Washington, DC : ACS Publications, 2016) Maurer, Johannes H. M.; González-García, Lola; Reiser, Beate; Kanelidis, Ioannis; Kraus, TobiasWe fabricated flexible, transparent, and conductive metal grids as transparent conductive materials (TCM) with adjustable properties by direct nanoimprinting of self-assembling colloidal metal nanowires. Ultrathin gold nanowires (diameter below 2 nm) with high mechanical flexibility were confined in a stamp and readily adapted to its features. During drying, the wires self-assembled into dense bundles that percolated throughout the stamp. The high aspect ratio and the bundling yielded continuous, hierarchical superstructures that connected the entire mesh even at low gold contents. A soft sintering step removed the ligand barriers but retained the imprinted structure. The material exhibited high conductivities (sheet resistances down to 29 Ω/sq) and transparencies that could be tuned by changing wire concentration and stamp geometry. We obtained TCMs that are suitable for applications such as touch screens. Mechanical bending tests showed a much higher bending resistance than commercial ITO: conductivity dropped by only 5.6% after 450 bending cycles at a bending radius of 5 mm.
- ItemThe Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors(Washington, DC : ACS Publications, 2015) Smith, Dan A.; Beweries, Torsten; Blasius, Clemens; Jasim, Naseralla; Nazir, Ruqia; Nazir, Sadia; Robertson, Craig C.; Whitwood, Adrian C.; Hunter, Christopher A.; Brammer, Lee; Perutz, Robin N.The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability β (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (−23.5 ± 0.3 kJ mol–1) interlocks our study with Laurence’s scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of pπ–dπ bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.
- ItemPhotoswitching of DNA Hybridization Using a Molecular Motor(Washington, DC : ACS Publications, 2018) Lubbe, Anouk S.; Liu, Qing; Smith, Sanne J.; de Vries, Jan Willem; Kistemaker, Jos C. M.; de Vries, Alex H.; Faustino, Ignacio; Meng, Zhuojun; Szymanski, Wiktor; Herrmann, Andreas; Feringa, Ben L.Reversible control over the functionality of biological systems via external triggers may be used in future medicine to reduce the need for invasive procedures. Additionally, externally regulated biomacromolecules are now considered as particularly attractive tools in nanoscience and the design of smart materials, due to their highly programmable nature and complex functionality. Incorporation of photoswitches into biomolecules, such as peptides, antibiotics, and nucleic acids, has generated exciting results in the past few years. Molecular motors offer the potential for new and more precise methods of photoregulation, due to their multistate switching cycle, unidirectionality of rotation, and helicity inversion during the rotational steps. Aided by computational studies, we designed and synthesized a photoswitchable DNA hairpin, in which a molecular motor serves as the bridgehead unit. After it was determined that motor function was not affected by the rigid arms of the linker, solid-phase synthesis was employed to incorporate the motor into an 8-base-pair self-complementary DNA strand. With the photoswitchable bridgehead in place, hairpin formation was unimpaired, while the motor part of this advanced biohybrid system retains excellent photochemical properties. Rotation of the motor generates large changes in structure, and as a consequence the duplex stability of the oligonucleotide could be regulated by UV light irradiation. Additionally, Molecular Dynamics computations were employed to rationalize the observed behavior of the motor–DNA hybrid. The results presented herein establish molecular motors as powerful multistate switches for application in biological environments.
- ItemConjugated Polymers as a New Class of Dual-Mode Matrices for MALDI Mass Spectrometry and Imaging(Washington, DC : ACS Publications, 2018) Horatz, Kilian; Giampà, Marco; Karpov, Yevhen; Sahre, Karin; Bednarz, Hanna; Kiriy, Anton; Voit, Brigitte; Niehaus, Karsten; Hadjichristidis, Nikos; Michels, Dominik L.; Lissel, FranziskaMatrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) and MALDI MS imaging are ubiquitous analytical methods in medical, pharmaceutical, biological, and environmental research. Currently, there is a strong interest in the investigation of low molecular weight compounds (LMWCs), especially to trace and understand metabolic pathways, requiring the development of new matrix systems that have favorable optical properties and a high ionization efficiency and that are MALDI silent in the LMWC area. In this paper, five conjugated polymers, poly{[N,N'-bis(2-octyldodecyl)-naphtalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'(2,2'-bithiophene)} (PNDI(T2)), poly(3-dodecylthiophene-2,5-diyl) (P3DDT), poly{[2,3-bis(3-octyloxyphenyl)quinoxaline-5,8-diyl]-alt-(thiophene-2,5-diyl)} (PTQ1), poly{[N,N'-bis(2-octyldodecyl)-isoindigo-5,5'-diyl]-alt-5,5'(2,2'-bithiophene)} (PII(T2)), and poly(9,9-di-n-octylfluorenyl-2,7-diyl) (P9OFl) are investigated as matrices. The polymers have a strong optical absorption, are solution processable, and can be coated into thin films, allowing a vast reduction in the amount of matrix used. All investigated polymers function as matrices in both positive and negative mode MALDI, classifying them as rare dual-mode matrices, and show a very good analyte ionization ability in both modes. PNDI(T2), P3DDT, PTQ1, and PII(T2) are MALDI silent in the full measurement range (>m/z = 150k), except at high laser intensities. In MALDI MS experiments of single analytes and a complex biological sample, the performance of the polymers was found to be as good as two commonly used matrices (2,5-DHB for positive and 9AA for negative mode measurements). The detection limit of two standard analytes was determined as being below 164 pmol for reserpine and below 245 pmol for cholic acid. Additionally P3DDT was used successfully in first MALDI MS imaging experiments allowing the visualization of the tissue morphology of rat brain sections.
- ItemRing-Closure Mechanisms Mediated by Laccase to Synthesize Phenothiazines, Phenoxazines, and Phenazines(Washington, DC : ACS Publications, 2020) Hahn, Veronika; Mikolasch, Annett; Weitemeyer, Josephine; Petters, Sebastian; Davids, Timo; Lalk, Michael; Lackmann, Jan-Wilm; Schauer, FriederThe green and environmentally friendly synthesis of highly valuable organic substances is one possibility for the utilization of laccases (EC 1.10.3.2). As reactants for the herein described syntheses, different o-substituted arylamines or arylthiols and 2,5-dihydroxybenzoic acid and its derivatives were used. In this way, the formation of phenothiazines, phenoxazines, and phenazines was achieved in aqueous solution mediated by the laccase of Pycnoporus cinnabarinus in the presence of oxygen. Two types of phenothiazines (3-hydroxy- and 3-oxo-phenothiazines) formed in one reaction assay were described for the first time. The cyclization reactions yielded C–N, C–S, or C–O bonds. The syntheses were investigated with regard to the substitution pattern of the reaction partners. Differences in C–S and C–N bond formations without cyclization are discussed.
- ItemSynthesis and Characterization of Oxide Chloride Sr2VO3Cl, a Layered S = 1 Compound(Washington, DC : ACS Publications, 2023) Sannes, Johnny A.; Kizhake Malayil, Ranjith K.; Corredor, Laura T.; Wolter, Anja U. B.; Grafe, Hans-Joachim; Valldor, MartinThe mixed-anion compound with composition Sr2VO3Cl has been synthesized for the first time, using the conventional high-temperature solid-state synthesis technique in a closed silica ampule under inert conditions. This compound belongs to the known Sr2TmO3Cl (Tm = Sc, Mn, Fe, Co, Ni) family, but with Tm = V. All homologues within this family can be described with the tetragonal space group P4/nmm (No. 129); from a Rietveld refinement of powder X-ray diffraction data on the Tm = V homologue, the unit cell parameters were determined to a = 3.95974(8) and c = 14.0660(4) Å, and the atomic parameters in the crystal structure could be estimated. The synthesized powder is black, implying that the compound is a semiconductor. The magnetic investigations suggest that Sr2VO3Cl is a paramagnet at high temperatures, exhibiting a μeff = 2.0 μB V-1 and antiferromagnetic (AFM) interactions between the magnetic vanadium spins (θCW = −50 K), in line with the V-O-V advantageous super-exchange paths in the V-O layers. Specific heat capacity studies indicate two small anomalies around 5 and 35 K, which however are not associated with long-range magnetic ordering. 35Cl ss-NMR investigations suggest a slow spin freezing below 4.2 K resulting in a glassy-like spin ground state.
- ItemSegregated Network Polymer Composites with High Electrical Conductivity and Well Mechanical Properties based on PVC, P(VDFTFE), UHMWPE, and rGO(Washington, DC : ACS Publications, 2020) Shiyanova, Kseniya A.; Gudkov, Maksim V.; Gorenberg, Arkady Ya; Rabchinskii, Maxim K.; Smirnov, Dmitry A.; Shapetina, Maria A.; Gurinovich, Tatiana D.; Goncharuk, Galina P.; Kirilenko, Demid A.; Bazhenov, Sergey L.; Melnikov, Valery P.The formation of a segregated network structure (wittingly uneven distribution of a filler) is one of the most promising strategies for the fabrication of electrically conductive polymer composites at present. However, the simultaneous achievement of high values of electrical conductivity with the retention of well mechanical properties within this approach remains a great challenge. Here, by means of X-ray photoelectron spectra (XPS), near-edge X-ray absorption fine structure (NEXAFS) spectra, scanning electron microscopy (SEM), dielectric spectroscopy, and compression engineering stress-strain curve analysis, we have studied the effect of a segregated network structure on the electrical conductivity and mechanical properties of a set of polymer composites. The composites were prepared by applying graphene oxide (GO) with ultralarge basal plane size (up to 150 μm) onto the surface of polymer powder particles, namely, poly(vinyl chloride) (PVC), poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)), and ultrahigh-molecular-weight poly(ethylene) (UHMWPE) with the subsequent GO reduction and composite hot pressing. A strong dependence of the segregated network polymer composites' physical properties on the polymer matrix was demonstrated. Particularly, 12 orders of magnitude rise of the polymers' electrical conductivity up to 0.7 S/m was found upon the incorporation of the reduced GO (rGO). A 17% increase in the P(VDF-TFE) elastic modulus filled by 1 wt % of rGO was observed. Fracture strength of PVC/rGO at 0.5 wt % content of the filler was demonstrated to decrease by fourfold. At the same time, the change in strength was not significant for P(VDF-TFE) and UHMWPE composites in comparison with pure polymers. Our results show a promise to accelerate the development of new composites for energy applications, such as metal-free supercapacitor plates and current collectors of lithium-ion batteries, bipolar plates of proton-exchange membrane fuel cells, antistatic elements of various electronic devices, etc. © 2020 American Chemical Society.
- ItemBlind Super-Resolution Approach for Exploiting Illumination Variety in Optical-Lattice Illumination Microscopy(Washington, DC : ACS Publications, 2021) Samanta, Krishnendu; Sarkar, Swagato; Acuña, Sebastian; Joseph, Joby; Ahluwalia, Balpreet Singh; Agarwal, KrishnaOptical-lattice illumination patterns help in pushing high spatial frequency components of the sample into the optical transfer function of a collection microscope. However, exploiting these high-frequency components require precise knowledge of illumination if reconstruction approaches similar to structured illumination microscopy are employed. Here, we present an alternate blind reconstruction approach that can provide super-resolution without the requirement of extra frames. For this, the property of exploiting temporal fluctuations in the sample emissions using “multiple signal classification algorithm” is extended aptly toward using spatial fluctuation of phase-modulated lattice illuminations for super-resolution. The super-resolution ability is shown for sinusoidal and multiperiodic lattice with approximately 3- and 6-fold resolution enhancements, respectively, over the diffraction limit. © 2021 The Authors. Published by American Chemical Society
- ItemDehydroabietylamine-Based Cellulose Nanofibril Films: A New Class of Sustainable Biomaterials for Highly Efficient, Broad-Spectrum Antimicrobial Effects(Washington, DC : ACS Publications, 2019) Hassan, Ghada; Forsman, Nina; Wan, Xing; Keurulainen, Leena; Bimbo, Luis M.; Johansson, Leena-Sisko; Sipari, Nina; Yli-Kauhaluoma, Jari; Zimmermann, Ralf; Stehl, Susanne; Werner, Carsten; Saris, Per E.J.; Österberg, Monika; Moreira, Vânia M.The design of antimicrobial surfaces as integral parts of advanced biomaterials is nowadays a high research priority, as the accumulation of microorganisms on surfaces inflicts substantial costs on the health and industry sectors. At present, there is a growing interest in designing functional materials from polymers abundant in nature, such as cellulose, that combine sustainability with outstanding mechanical properties and economic production. There is also the need to find suitable replacements for antimicrobial silver-based agents due to environmental toxicity and spread of resistance to metal antimicrobials. Herein we report the unprecedented decoration of cellulose nanofibril (CNF) films with dehydroabietylamine 1 (CNF-CMC-1), to give an innovative contact-active surface active against Gram-positive and Gram-negative bacteria including the methicillin-resistant S. aureus MRSA14TK301, with low potential to spread resistance and good biocompatibility, all achieved with low surface coverage. CNF-CMC-1 was particularly effective against S. aureus ATCC12528, causing virtually complete reduction of the total cells from 10 5 colony forming units (CFU)/mL bacterial suspensions, after 24 h of contact. This gentle chemical modification of the surface of CNF fully retained the beneficial properties of the original film, including moisture buffering and strength, relevant in many potential applications. Our originally designed surface represents a new class of ecofriendly biomaterials that optimizes the performance of CNF by adding antimicrobial properties without the need for environmentally toxic silver. © Copyright 2019 American Chemical Society.