@article{KuntzeViljakkaTitovetal.2022, author = {Kuntze, Kim and Viljakka, Jani and Titov, Evgenii and Ahmed, Zafar and Kalenius, Elina and Saalfrank, Peter and Priimagi, Arri}, title = {Towards low-energy-light-driven bistable photoswitches}, series = {Photochemical \& photobiological sciences / European Society for Photobiology}, volume = {21}, journal = {Photochemical \& photobiological sciences / European Society for Photobiology}, number = {2}, publisher = {Springer}, address = {Heidelberg}, issn = {1474-905X}, doi = {10.1007/s43630-021-00145-4}, pages = {159 -- 173}, year = {2022}, abstract = {Thermally stable photoswitches that are driven with low-energy light are rare, yet crucial for extending the applicability of photoresponsive molecules and materials towards, e.g., living systems. Combined ortho-fluorination and -amination couples high visible light absorptivity of o-aminoazobenzenes with the extraordinary bistability of o-fluoroazobenzenes. Herein, we report a library of easily accessible o-aminofluoroazobenzenes and establish structure-property relationships regarding spectral qualities, visible light isomerization efficiency and thermal stability of the cis-isomer with respect to the degree of o-substitution and choice of amino substituent. We rationalize the experimental results with quantum chemical calculations, revealing the nature of low-lying excited states and providing insight into thermal isomerization. The synthesized azobenzenes absorb at up to 600 nm and their thermal cis-lifetimes range from milliseconds to months. The most unique example can be driven from trans to cis with any wavelength from UV up to 595 nm, while still exhibiting a thermal cis-lifetime of 81 days.
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.}, language = {en} } @article{XieXuWangetal.2022, author = {Xie, Dongjiu and Xu, Yaolin and Wang, Yonglei and Pan, Xuefeng and H{\"a}rk, Eneli and Kochovski, Zdravko and Eljarrat, Alberto and M{\"u}ller, Johannes and Koch, Christoph T. and Yuan, Jiayin and Lu, Yan}, title = {Poly(ionic liquid) nanovesicle-templated carbon nanocapsules functionalized with uniform iron nitride nanoparticles as catalytic sulfur host for Li-S batteries}, series = {ACS nano}, volume = {16}, journal = {ACS nano}, number = {7}, publisher = {American Chemical Society}, address = {Washington}, issn = {1936-0851}, doi = {10.1021/acsnano.2c01992}, pages = {10554 -- 10565}, year = {2022}, abstract = {Poly(ionic liquid)s (PIL) are common precursors for heteroatom-doped carbon materials. Despite a relatively higher carbonization yield, the PIL-to-carbon conversion process faces challenges in preserving morphological and structural motifs on the nanoscale. Assisted by a thin polydopamine coating route and ion exchange, imidazoliumbased PIL nanovesicles were successfully applied in morphology-maintaining carbonization to prepare carbon composite nanocapsules. Extending this strategy further to their composites, we demonstrate the synthesis of carbon composite nanocapsules functionalized with iron nitride nanoparticles of an ultrafine, uniform size of 3-5 nm (termed "FexN@C "). Due to its unique nanostructure, the sulfur-loaded FexN@C electrode was tested to efficiently mitigate the notorious shuttle effect of lithium polysulfides (LiPSs) in Li-S batteries. The cavity of the carbon nanocapsules was spotted to better the loading content of sulfur. The well-dispersed iron nitride nanoparticles effectively catalyze the conversion of LiPSs to Li2S, owing to their high electronic conductivity and strong binding power to LiPSs. Benefiting from this well-crafted composite nanostructure, the constructed FexN@C/S cathode demonstrated a fairly high discharge capacity of 1085 mAh g(-1) at 0.5 C initially, and a remaining value of 930 mAh g(-1 )after 200 cycles. In addition, it exhibits an excellent rate capability with a high initial discharge capacity of 889.8 mAh g(-1) at 2 C. This facile PIL-to-nanocarbon synthetic approach is applicable for the exquisite design of complex hybrid carbon nanostructures with potential use in electrochemical energy storage and conversion.}, language = {en} } @article{NeffeLoewenbergJulichGruneretal.2021, author = {Neffe, Axel T. and L{\"o}wenberg, Candy and Julich-Gruner, Konstanze K. and Behl, Marc and Lendlein, Andreas}, title = {Thermally-induced shape-memory behavior of degradable gelatin-based networks}, series = {International journal of molecular sciences}, volume = {22}, journal = {International journal of molecular sciences}, number = {11}, publisher = {Molecular Diversity Preservation International}, address = {Basel}, issn = {1422-0067}, doi = {10.3390/ijms22115892}, pages = {15}, year = {2021}, abstract = {Shape-memory hydrogels (SMH) are multifunctional, actively-moving polymers of interest in biomedicine. In loosely crosslinked polymer networks, gelatin chains may form triple helices, which can act as temporary net points in SMH, depending on the presence of salts. Here, we show programming and initiation of the shape-memory effect of such networks based on a thermomechanical process compatible with the physiological environment. The SMH were synthesized by reaction of glycidylmethacrylated gelatin with oligo(ethylene glycol) (OEG) alpha,omega-dithiols of varying crosslinker length and amount. Triple helicalization of gelatin chains is shown directly by wide-angle X-ray scattering and indirectly via the mechanical behavior at different temperatures. The ability to form triple helices increased with the molar mass of the crosslinker. Hydrogels had storage moduli of 0.27-23 kPa and Young's moduli of 215-360 kPa at 4 degrees C. The hydrogels were hydrolytically degradable, with full degradation to water-soluble products within one week at 37 degrees C and pH = 7.4. A thermally-induced shape-memory effect is demonstrated in bending as well as in compression tests, in which shape recovery with excellent shape-recovery rates R-r close to 100\% were observed. In the future, the material presented here could be applied, e.g., as self-anchoring devices mechanically resembling the extracellular matrix.}, language = {en} } @article{BochoveGrijpmaLendleinetal.2021, author = {Bochove, Bas van and Grijpma, Dirk W. and Lendlein, Andreas and Sepp{\"a}l{\"a}, Jukka}, title = {Designing advanced functional polymers for medicine}, series = {European polymer journal : EPJ}, volume = {155}, journal = {European polymer journal : EPJ}, publisher = {Elsevier}, address = {Oxford}, issn = {0014-3057}, doi = {10.1016/j.eurpolymj.2021.110573}, pages = {2}, year = {2021}, language = {en} } @article{HwangZhangYouketal.2021, author = {Hwang, Jinyeon and Zhang, Wuyong and Youk, Sol and Schutjajew, Konstantin and Oschatz, Martin}, title = {Understanding structure-property relationships under experimental conditions for the optimization of lithium-ion capacitor anodes based on all-carbon-composite materials}, series = {Energy technology : generation, conversion, storage, distribution}, volume = {9}, journal = {Energy technology : generation, conversion, storage, distribution}, number = {3}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2194-4296}, doi = {10.1002/ente.202001054}, pages = {8}, year = {2021}, abstract = {The nanoscale combination of a conductive carbon and a carbon-based material with abundant heteroatoms for battery electrodes is a method to overcome the limitation that the latter has high affinity to alkali metal ions but low electronic conductivity. The synthetic protocol and the individual ratios and structures are important aspects influencing the properties of such multifunctional compounds. Their interplay is, herein, investigated by infiltration of a porous ZnO-templated carbon (ZTC) with nitrogen-rich carbon obtained by condensation of hexaazatriphenylene-hexacarbonitrile (HAT-CN) at 550-1000 degrees C. The density of lithiophilic sites can be controlled by HAT-CN content and condensation temperature. Lithium storage properties are significantly improved in comparison with those of the individual compounds and their physical mixtures. Depending on the uniformity of the formed composite, loading ratio and condensation temperature have different influence. Most stable operation at high capacity per used monomer is achieved with a slowly dried composite with an HAT-CN:ZTC mass ratio of 4:1, condensed at 550 degrees C, providing more than 400 mAh g(-1) discharge capacity at 0.1 A g(-1) and a capacity retention of 72\% after 100 cycles of operation at 0.5 A g(-1) due to the homogeneity of the composite and high content of lithiophilic sites.}, language = {en} } @article{PanSarhanKochovskietal.2022, author = {Pan, Xuefeng and Sarhan, Radwan Mohamed and Kochovski, Zdravko and Chen, Guosong and Taubert, Andreas and Mei, Shilin and Lu, Yan}, title = {Template synthesis of dual-functional porous MoS2 nanoparticles with photothermal conversion and catalytic properties}, series = {Nanoscale}, volume = {14}, journal = {Nanoscale}, number = {18}, publisher = {RSC Publ. (Royal Society of Chemistry)}, address = {Cambridge}, issn = {2040-3372}, doi = {10.1039/d2nr01040b}, pages = {6888 -- 6901}, year = {2022}, abstract = {Advanced catalysis triggered by photothermal conversion effects has aroused increasing interest due to its huge potential in environmental purification. In this work, we developed a novel approach to the fast degradation of 4-nitrophenol (4-Nip) using porous MoS2 nanoparticles as catalysts, which integrate the intrinsic catalytic property of MoS2 with its photothermal conversion capability. Using assembled polystyrene-b-poly(2-vinylpyridine) block copolymers as soft templates, various MoS 2 particles were prepared, which exhibited tailored morphologies (e.g., pomegranate-like, hollow, and open porous structures). The photothermal conversion performance of these featured particles was compared under near-infrared (NIR) light irradiation. Intriguingly, when these porous MoS2 particles were further employed as catalysts for the reduction of 4-Nip, the reaction rate constant was increased by a factor of 1.5 under NIR illumination. We attribute this catalytic enhancement to the open porous architecture and light-to-heat conversion performance of the MoS2 particles. This contribution offers new opportunities for efficient photothermal-assisted catalysis.}, language = {en} } @article{ZhaoSarhanEljarratetal.2022, author = {Zhao, Yuhang and Sarhan, Radwan Mohamed and Eljarrat, Alberto and Kochovski, Zdravko and Koch, Christoph and Schmidt, Bernd and Koopman, Wouter-Willem Adriaan and Lu, Yan}, title = {Surface-functionalized Au-Pd nanorods with enhanced photothermal conversion and catalytic performance}, series = {ACS applied materials \& interfaces}, volume = {14}, journal = {ACS applied materials \& interfaces}, number = {15}, publisher = {American Chemical Society}, address = {Washington, DC}, issn = {1944-8244}, doi = {10.1021/acsami.2c00221}, pages = {17259 -- 17272}, year = {2022}, abstract = {Bimetallic nanostructures comprising plasmonic and catalytic components have recently emerged as a promising approach to generate a new type of photo-enhanced nanoreactors. Most designs however concentrate on plasmon-induced charge separation, leaving photo-generated heat as a side product. This work presents a photoreactor based on Au-Pd nanorods with an optimized photothermal conversion, which aims to effectively utilize the photo-generated heat to increase the rate of Pd-catalyzed reactions. Dumbbell-shaped Au nanorods were fabricated via a seed-mediated growth method using binary surfactants. Pd clusters were selectively grown at the tips of the Au nanorods, using the zeta potential as a new synthetic parameter to indicate the surfactant remaining on the nanorod surface. The photothermal conversion of the Au-Pd nanorods was improved with a thin layer of polydopamine (PDA) or TiO2. As a result, a 60\% higher temperature increment of the dispersion compared to that for bare Au rods at the same light intensity and particle density could be achieved. The catalytic performance of the coated particles was then tested using the reduction of 4-nitrophenol as the model reaction. Under light, the PDA-coated Au-Pd nanorods exhibited an improved catalytic activity, increasing the reaction rate by a factor 3. An analysis of the activation energy confirmed the photoheating effect to be the dominant mechanism accelerating the reaction. Thus, the increased photothermal heating is responsible for the reaction acceleration. Interestingly, the same analysis shows a roughly 10\% higher reaction rate for particles under illumination compared to under dark heating, possibly implying a crucial role of localized heat gradients at the particle surface. Finally, the coating thickness was identified as an essential parameter determining the photothermal conversion efficiency and the reaction acceleration.}, language = {en} } @article{FloydSongHapeshietal.2022, author = {Floyd, Thomas G. and Song, Ji-Inn and Hapeshi, Alexia and Laroque, Sophie and Hartlieb, Matthias and Perrier, Sebastien}, title = {Bottlebrush copolymers for gene delivery: influence of architecture, charge density, and backbone length on transfection efficiency}, series = {Journal of materials chemistry : B, materials for biology and medicine}, volume = {10}, journal = {Journal of materials chemistry : B, materials for biology and medicine}, number = {19}, publisher = {Royal Society of Chemistry}, address = {London [u.a.]}, issn = {2050-750X}, doi = {10.1039/d2tb00490a}, pages = {3696 -- 3704}, year = {2022}, abstract = {The influence of polymer architecture of polycations on their ability to transfect mammalian cells is probed. Polymer bottle brushes with grafts made from partially hydrolysed poly(2-ethyl-2-oxazoline) are used while varying the length of the polymer backbone as well as the degree of hydrolysis (cationic charge content). Polyplex formation is investigated via gel electrophoresis, dye-displacement and dynamic light scattering. Bottle brushes show a superior ability to complex pDNA when compared to linear copolymers. Also, nucleic acid release was found to be improved by a graft architecture. Polyplexes based on bottle brush copolymers showed an elongated shape in transmission electron microscopy images. The cytotoxicity against mammalian cells is drastically reduced when a graft architecture is used instead of linear copolymers. Moreover, the best-performing bottle brush copolymer showed a transfection ability comparable with that of linear poly(ethylenimine), the gold standard of polymeric transfection agents, which is used as positive control. In combination with their markedly lowered cytotoxicity, cationic bottle brush copolymers are therefore shown to be a highly promising class of gene delivery vectors.}, language = {en} } @article{AbbasiXuKhezrietal.2022, author = {Abbasi, Ali and Xu, Yaolin and Khezri, Ramin and Etesami, Mohammad and Lin, C. and Kheawhom, Soorathep and Lu, Yan}, title = {Advances in characteristics improvement of polymeric membranes/separators for zinc-air batteries}, series = {Materials Today Sustainability}, volume = {18}, journal = {Materials Today Sustainability}, publisher = {Elsevier}, address = {Amsterdam}, issn = {2589-2347}, doi = {10.1016/j.mtsust.2022.100126}, pages = {17}, year = {2022}, abstract = {Zinc-air batteries (ZABs) are gaining popularity for a wide range of applications due to their high energy density, excellent safety, and environmental friendliness. A membrane/separator is a critical component of ZABs, with substantial implications for battery performance and stability, particularly in the case of a battery in solid state format, which has captured increased attention in recent years. In this review, recent advances as well as insight into the architecture of polymeric membrane/separators for ZABs including porous polymer separators (PPSs), gel polymer electrolytes (GPEs), solid polymer electrolytes (SPEs) and anion exchange membranes (AEMs) are discussed. The paper puts forward strategies to enhance stability, ionic conductivity, ionic selectivity, electrolyte storage capacity and mechanical properties for each type of polymeric membrane. In addition, the remaining major obstacles as well as the most potential avenues for future research are examined in detail.}, language = {en} } @article{MayerPicconiRobinsonetal.2022, author = {Mayer, Dennis and Picconi, David and Robinson, Matthew S. and G{\"u}hr, Markus}, title = {Experimental and theoretical gas-phase absorption spectra of thionated uracils}, series = {Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature}, volume = {558}, journal = {Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0301-0104}, doi = {10.1016/j.chemphys.2022.111500}, pages = {9}, year = {2022}, abstract = {We present a comparative study of the gas-phase UV spectra of uracil and its thionated counterparts (2-thiouracil, 4-thiouracil and 2,4-dithiouracil), closely supported by time-dependent density functional theory calculations to assign the transitions observed. We systematically discuss pure gas-phase spectra for the (thio)uracils in the range of 200-400 nm (similar to 3.2-6.4 eV), and examine the spectra of all four species with a single theoretical approach. We note that specific vibrational modelling is needed to accurately determine the spectra across the examined wavelength range, and systematically model the transitions that appear at wavelengths shorter than 250 nm. Additionally, we find in the cases of 2-thiouracil and 2,4-dithiouracil, that the gas-phase spectra deviate significantly from some previously published solution-phase spectra, especially those collected in basic environments.}, language = {en} }