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Cryogels are polymeric materials with a sponge-like microstructure and have attracted significant attention in recent decades. Research has focused on their composition, fabrication techniques, characterization methods as well as potential or existing fields of applications. The use of functional precursors or functionalizing ligands enables the preparation of cryogels with desired properties such as biocompatibility or responsivity. They can also exhibit adsorptive properties or can be used for catalytical purposes. Although a very brief overview about several functional (macro-)monomers and functionalizing ligands has been provided by previous reviewers for certain cryogel applications, so far there has been no particular focus on the evaluation of the functionalization success and the characterization methods used. This review will provide a comprehensive overview of different characterization methods most recently used for the evaluation of cryogel functionalization. Furthermore, new functional (macro-)monomers and subsequent cryogel functionalization strategies are discussed, based on synthetic polymers, biopolymers and a combination of both. This review highlights the importance of the functionalization aspect in cryogel research in order to produce materials with tailored properties for certain applications.
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The urgent need for sustainable alternatives to fossil fuels in the transportation sector is driving research into novel energy carriers that can meet the high energy density requirements of heavy-duty vehicles without exacerbating the climate change. This concept article examines the synthesis, mechanisms, and challenges associated with oxymethylene ethers (OMEs), a promising class of synthetic fuels potentially derived from carbon dioxide and hydrogen. We highlight the importance of OMEs in the transition towards non-fossil energy sources due to their compatibility with the existing Diesel infrastructure and their cleaner combustion profile. The synthesis mechanisms, including the Schulz-Flory distribution and its implications for OME chain length specificity, and the role of various catalysts and starting materials are discussed in depth. Despite advancements in the field, significant challenges remain, such as overcoming the Schulz-Flory distribution, efficiently managing water as an undesirable byproduct, and improving the overall energy efficiency of the OME synthesis. Addressing these challenges is crucial for OMEs to become a viable alternative fuel, contributing to the reduction of greenhouse gas emissions and the transition to a sustainable energy future in the transportation sector.
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Polyanions can internalize into cells via endocytosis without any cell disruption and are therefore interesting materials for biomedical applications. In this study, amino-acid-derived polyanions with different alkyl side-chains are synthesized via postpolymerization modification of poly(pentafluorophenyl acrylate), which is synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization, to obtain polyanions with tailored hydrophobicity and alkyl branching. The success of the reaction is verified by size-exclusion chromatography, NMR spectroscopy, and infrared spectroscopy. The hydrophobicity, surface charge, and pH dependence are investigated in detail by titrations, high-performance liquid chromatography, and partition coefficient measurements. Remarkably, the determined pK a-values for all synthesized polyanions are very similar to those of poly(acrylic acid) (pK a = 4.5), despite detectable differences in hydrophobicity. Interactions between amino-acid-derived polyanions with L929 fibroblasts reveal very slow cell association as well as accumulation of polymers in the cell membrane. Notably, the more hydrophobic amino-acid-derived polyanions show higher cell association. Our results emphasize the importance of macromolecular engineering toward ideal charge and hydrophobicity for polymer association with cell membranes and internalization. This study further highlights the potential of amino-acid-derived polymers and the diversity they provide for tailoring properties toward drug delivery applications.
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To supply chemical structures of polymers for machine learning applications, decoding is necessary. Here, we present a protocol for generating polymer fingerprints (PFPs), which are representations of molecular structures, using a polymer-specific decoder. We outline steps for downloading, installing, and basic application of the software. Moreover, we present procedures for processing and analyzing polymer structure data and the preparation for integration into machine learning methods. On this basis, we explain how artificial neural networks can be utilized to predict polymer properties. For complete details on the use and execution of this protocol, please refer to Köster et al.1.
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Aprendizaje Automático , Redes Neurales de la Computación , Polímeros , Programas Informáticos , Polímeros/química , Estructura MolecularRESUMEN
Dual-ion batteries (DIBs) represent a promising alternative for lithium ion batteries (LIBs) for various niche applications. DIBs with polymer-based active materials, here poly(2,2,6,6-tetramethylpiperidinyl-N-oxyl methacrylate) (PTMA), are of particular interest for high power applications, though they require appropriate electrolyte formulations. As the anion mobility plays a crucial role in transport kinetics, Li salts are varied using the well-dissociating solvent γ-butyrolactone (GBL). Lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalate)borate (LiBOB) improve cycle life in PTMA||Li metal cells compared to other Li salts and a LiPF6- and carbonate-based reference electrolyte, even at specific currents of 1.0â A g-1 (≈10C), whereas LiDFOB reveals a superior rate performance, i. e., ≈90 % capacity even at 5.0â A g-1 (≈50C). This is attributed to faster charge-transfer/mass transport, enhanced pseudo-capacitive contributions during the de-/insertion of the anions into the PTMA electrode and to lower overpotentials at the Li metal electrode.
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Via inline-nuclear magnetic resonance measurements, the homogeneously catalyzed poly(oxymethylene dimethyl ether) fuel synthesis using trioxane and dimethoxy methane is investigated. Besides the Brønsted acid (BA) catalyst triflic acid (TfOH) different metal halides are studied as Lewis-acidic (LA) catalysts. Among the used LAs, MgCl2, the weakest based on electronegativity, reveals the highest catalytical activity. Additionally, the influence of the concentration of BA and LA is investigated. An increase in BA concentration leads to an exponential increase of the reaction rate, while increasing the concentration of the LA leads to a volcano plot with its optimum at a LA : BA ratio of 1 : 3. The influence of the LA on the electron density of the intermediate formaldehyde is concluded as the main factor for this behavior.
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Liposome-based technologies derived from lipids and polymers (e.g., PEGylated liposomes) have been recognized because of their applications in nanomedicine. However, since such systems represent myriad challenges and may promote immune responses, investigation of new biomaterials is mandatory. Here, we report on a biophysical investigation of liposomes decorated with bioconjugated copolymers in the presence (or absence) of amantadine (an antiviral medication). First, copolymers of poly(N,N-dimethylacrylamide-co-fluoresceinacrylate-co-acrylic acid-N-succinimide ester)-block-poly(N-isopropylacrylamide) (PDMA-b-PNIPAM) containing a fluorescence label were biofunctionalized with short peptides that resemble the sequence of the loops 220 and 130 of the binding receptor of the hemagglutinin (HA) protein of the influenza A virus. Then, the bioconjugated copolymers were self-assembled along with liposomes composed of 1,2 dimyristoyl-sn-glycero-3-phosphocholine, sphingomyelin, and cholesterol (MSC). These biohybrid systems, with and without amantadine, were systematically characterized using differential scanning calorimetry (DSC), dynamic light scattering (DLS), and cryogenic transmission electron microscopy (cryoTEM). Finally, the systems were tested in an in vitro study to evaluate cytotoxicity and direct immunofluorescence in Madin Darbin Canine Kidney (MDCK) cells. The biohybrid systems displayed long-term stability, thermo-responsiveness, hydrophilic-hydrophobic features, and fluorescence properties and were presumable endowed with cell targeting properties intrinsically integrated into the amino acid sequences of the utilized peptides, which indeed turn them into promising nanodevices for biomedical applications.
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Amantadina , Liposomas , Liposomas/química , Amantadina/química , Polímeros/química , Animales , Antivirales/química , Antivirales/farmacología , Células de Riñón Canino Madin Darby , PerrosRESUMEN
We present a luminescent Ir(III) complex featuring a bidentate halogen bond donor site capable of strong anion binding. The tailor-made Ir(III)(L)2 moiety offers a significantly higher emission quantum yield (8.4 %) compared to previous Ir(III)-based chemo-sensors (2.5 %). The successful binding of chloride, bromide and acetate is demonstrated using emission titrations. These experiments reveal association constants of up to 1.6×105â M-1. Furthermore, a new approach to evaluate the association constant by utilizing the shift of the emission was used for the first time. The experimentally observed characteristics are supported by quantum chemical simulations.
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Homometallic titanium oxo clusters (TOC) are one of the most important groups of metal oxo clusters. In a previous article, TOC structures with carboxylato and phosphonato ligands were reviewed and categorized. This work is now extended to clusters with other ligands. Comparison of the different cluster types shows how the interplay between condensation of the titanium polyhedra by means of bridging oxygen atoms and the coordination characteristics of the ligands influences the cluster structures and allows working out basic construction principles of the cluster core.
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1,4-Bis(iodomethyl)benzene and 1,3,5-tris(iodomethyl)benzene were used as initiators for the cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx) and its copolymerization with tert-butyl (3-(4,5-dihydrooxazol-2-yl)propyl)carbamate (BocOx) or methyl 3-(4,5-dihydrooxazol-2-yl)propanoate (MestOx). Kinetic studies confirmed the applicability of these initiators. Termination with suitable nucleophiles resulted in two- and three-armed cross-linkers featuring acrylate, methacrylate, piperazine-acrylamide, and piperazine-methacrylamide as polymerizable ω-end groups. Matrix-assisted laser desorption/ionization mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy confirmed the successful attachment of the respective ω-end groups at all initiation sites for every prepared cross-linkers. Except for acrylate, each ω-end group remained stable during deprotection of BocOx containing cross-linkers. The cryogels were prepared using EtOx-based cross-linkers, as confirmed by solid-state NMR spectroscopy, scanning electron microscopy, and thermogravimetric analysis. Stability tests revealed a complete dissolution of the acrylate-containing gels at pH = 14, whereas the piperazine-acrylamide-based cryogels featured excellent hydrolytic stability.
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Polymeric nanoparticles (PNPs) are frequently researched and used in drug delivery. The degradation of PNPs is highly dependent on various properties, such as polymer chemical structure, size, crystallinity, and melting temperature. Hence, a precise understanding of PNP degradation behavior is essential for optimizing the system. This study focused on enzymatic hydrolysis as a degradation mechanism by investigation of the degradation of PNP with various crystallinities. The aliphatic polyester polylactide ([C3H4O2]n, PLA) was used as two chiral forms, poly l-lactide (PlLA) and poly d-lactide (PdLA), and formed a unique crystalline stereocomplex (SC). PNPs were prepared via a nanoprecipitation method. In order to further control the crystallinity and melting temperatures of the SC, the polymer poly(3-ethylglycolide) [C6H8O4]n (PEtGly) was synthesized. Our investigation shows that the PNP degradation can be controlled by various chemical structures, crystallinity and stereocomplexation. The influence of proteinase K on PNP degradation was also discussed in this research. AFM did not reveal any changes within the first 24 h but indicated accelerated degradation after 7 days when higher EtGly content was present, implying that lower crystallinity renders the particles more susceptible to hydrolysis. QCM-D exhibited reduced enzyme adsorption and a slower degradation rate in SC-PNPs with lower EtGly contents and higher crystallinities. A more in-depth analysis of the degradation process unveiled that QCM-D detected rapid degradation from the outset, whereas AFM exhibited delayed changes of degradation. The knowledge gained in this work is useful for the design and creation of advanced PNPs with enhanced structures and properties.
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Inorganic photoacids and photobases comprising of photoactive transition metal complexes (TMCs) offer the ability to modulate proton transfer reactions through light irradiation, while utilizing the excellent optical properties of the latter. This provides a powerful tool for precise control over chemical reactions and processes, with implications for both fundamental science and practical applications. In this contribution, we present a novel molecular architecture amending an Fe-NHC complex with a pendant quinoline, as a prototypical photobase, as a representative earth-abundant TMC based inorganic photobase. We characterize the excited-state properties and proton-transfer dynamics using steady-state absorption and emission spectroscopy as well as pump wavelength dependent transient absorption spectroscopy in various protic solvents. The kinetics and thermodynamics of proton transfer in the quinoline moiety are influenced by both the presence of the metal center and the choice of the solvent. Furthermore, we see indications of intramolecular energy transfer from the quinoline to the MLCT state as a limiting factor for panchromatic photobasicity of the complex.
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Hybrid nanoparticles (HNPs) were designed by combining a PLGA core with a lipid shell that incorporated PEG-Lipid conjugates with various functionalities (-RGD, -cRGD, -NH2, and -COOH) to create targeted drug delivery systems. Loaded with a neutral lipid orange dye, the HNPs were extensively characterized using various techniques and investigated for their uptake in human monocyte-derived macrophages (MDMs) using FC and CLSM. Moreover, the best-performing HNPs (i.e., HNP-COOH and HNP-RGD as well as HNP-RGD/COOH mixed) were loaded with the anti-inflammatory drug BRP-201 and prepared in two size ranges (dH ~140 nm and dH ~250 nm). The HNPs were examined further for their stability, degradation, MDM uptake, and drug delivery efficiency by studying the inhibition of 5-lipoxygenase (5-LOX) product formation, whereby HNP-COOH and HNP-RGD both exhibited superior uptake, and the HNP-COOH/RGD (2:1) displayed the highest inhibition.
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The in-depth analytical characterization of polymers, in particular regarding intended biomedical applications, is becoming increasingly important to elucidate their structure-property relationships. Specifically, end group analysis of e.g. polymers featuring a 'stealth effect' towards the immune system is of particular importance because of their use in coupling reactions to bioactive compounds. Herein, we established a liquid chromatography (LC) protocol to analyse bicyclo[6.1.0]nonyne-functionalized poly(2-alkyl-2-oxazoline)s (POx)s as promising functional polymers that can be applied in strain-promoted click reactions. This work involved the synthesis of poly(2-methyl-2-oxazoline) (PMeOx) and poly(2-ethyl-2-oxazoline) (PEtOx) by living cationic ring-opening polymerization (CROP) with different molar masses ranging from 2 up to 17.5 kDa and, to our knowledge, the first liquid chromatographic analysis of PMeOx. The developed analytical protocol enables the quantitative determination of post-polymerization reaction sequences with respect to the conversion of the ω-end groups. All synthesized polymers were straightforwardly analysed on a C18-derivatized silica monolithic column under reversed-phase chromatographic conditions with a binary mobile phase gradient comprising a mixture of acetonitrile and water. Subsequent mass spectrometry of collected elution fractions enabled the confirmation of the desired ω-end group functionalities and the identification of synthetic by-products.
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In this work, we present a concise modular assembly strategy using one universal heteroleptic 2,6-di(quinolin-8-yl)pyridine-based ruthenium(II) complex as a starting building block. Extending the concept from established ligand modifications and subsequent complexation (classical route), the later appearing chemistry-on-the-complex methodology was used for late-stage syntheses, i.e., assembling discrete building blocks to molecular architectures (here: dyad and triads). We focused on Suzuki-Miyaura and Sonogashira cross-couplings as two of the best-known C-C bond forming reactions. Both were performed on one building block complex bearing a bromine and TIPS-protected alkyne for functional group interconversion (bromine to TMS-protected alkyne, a benzyl azide, or a boronic acid pinacol ester moiety with ≥95% isolated yield and simple purification) as well as building block assemblies using both a triarylamine-based donor and a naphthalene diimide-based acceptor in up to 86% isolated yield. Additionally, the developed purification via automated flash chromatography is simple compared to tedious manual chromatography for ruthenium(II)-based substrates in the classical route. Based on the preliminary characterization by steady-state spectroscopy, the observed emission quenching in the triad (55%) serves as an entry to rationally optimize the modular units via chemistry-on-the-complex to elucidate energy and electron transfer.
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HYPOTHESIS: There is a lack of understanding of the interplay between the copolymer composition profile and thermal transition observed in aqueous solutions of N-isopropyl acrylamide (NIPAM) copolymers, as well as the correlation between this transition and the formation and structure of copolymer self-assemblies. EXPERIMENTS: For this purpose, we investigated the response of five copolymers with the same molar mass and chemical composition, but with different composition profile in aqueous solution against temperature. Using complementary analytical techniques, we probed structural properties at different length scales, from the molecular scale with Nuclear Magnetic Resonance (NMR) to the colloidal scale with Dynamic Light Scattering (DLS) and Small Angle Neutron Scattering (SANS). FINDINGS: NMR and SANS investigations strengthen each other and allow a clear picture of the change of copolymer solubility and related copolymer self-assembly as a function of temperature. At the molecular scale, dehydrating NIPAM units drag N,N-dimethyl acrylamide (DMA) moieties with them in a gradual collapse of the copolymer chain; this induces a morphological transition of the self-assemblies from star-like nanostructures to crew-cut micelles. Interestingly, the transition spans a temperature range which depends on the monomer distribution profile in the copolymer chain, with the asymmetric triblock copolymer specimen revealing the broadest one. We show that the broad morphological transitions associated with gradient copolymers can be mimicked and even surpassed by the use of stepwise gradient (asymmetric) copolymers, which can be more easily and reproducibly synthesized than linear gradient copolymers.
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Benzo[d]-X-zolyl-pyridinyl (XO, S, NH) radicals represent a promising class of redox-active molecules for organic batteries. We present a multistep screening procedure to identify the most promising radical candidates. Experimental investigations and highly correlated wave function-based calculations are performed to determine benchmark redox potentials. Based on these, the accuracies of different methods (semi-empirical, density functional theory, wave function-based), solvent models, dispersion corrections, and basis sets are evaluated. The developed screening procedure consists of three steps: First, a conformer search is performed with CREST. The molecules are selected based on the redox potentials calculated using GFN2-xTB. Second, HOMO energies calculated with reparametrized B3LYP-D3(BJ) and the def2-SVP basis set are used as selection criteria. The final molecules are selected based on the redox potentials calculated from Gibbs energies using BP86-D3(BJ)/def2-TZVP. With this multistep screening approach, promising molecules can be suggested for synthesis, and structure-property relationships can be derived.
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Sustainable battery concepts are of great importance for the energy storage demands of the future. Organic batteries based on redox-active polymers are one class of promising storage systems to meet these demands, in particular when combined with environmentally friendly and safe electrolytes. Deep Eutectic Solvents (DESs) represent a class of electrolytes that can be produced from sustainable sources and exhibit in most cases no or only a small environmental impact. Because of their non-flammability, DESs are safe, while providing an electrochemical stability window almost comparable to established battery electrolytes and much broader than typical aqueous electrolytes. Here, we report the first all-organic battery cell based on a DES electrolyte, which in this case is composed of sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and N-methylacetamide (NMA) alongside the electrode active materials poly(2,2,6,6-tetramethylpiperidin-1-yl-oxyl methacrylate) (PTMA) and crosslinked poly(vinylbenzylviologen) (X-PVBV2+ ). The resulting cell shows two voltage plateaus at 1.07â V and 1.58â V and achieves Coulombic efficiencies of 98 %. Surprisingly, the X-PVBV/X-PVBV+ redox couple turned out to be much more stable in NaTFSI : NMA 1 : 6 than the X-PVBV+ /X-PVBV2+ couple, leading to asymmetric capacity fading during cycling tests.
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The COVID-19 mRNA vaccines represent a milestone in developing non-viral gene carriers, and their success highlights the crucial need for continued research in this field to address further challenges. Polymer-based delivery systems are particularly promising due to their versatile chemical structure and convenient adaptability, but struggle with the toxicity-efficiency dilemma. Introducing anionic, hydrophilic, or "stealth" functionalities represents a promising approach to overcome this dilemma in gene delivery. Here, two sets of diblock terpolymers are created comprising hydrophobic poly(n-butyl acrylate) (PnBA), a copolymer segment made of hydrophilic 4-acryloylmorpholine (NAM), and either the cationic 3-guanidinopropyl acrylamide (GPAm) or the 2-carboxyethyl acrylamide (CEAm), which is negatively charged at neutral conditions. These oppositely charged sets of diblocks are co-assembled in different ratios to form mixed micelles. Since this experimental design enables countless mixing possibilities, a machine learning approach is applied to identify an optimal GPAm/CEAm ratio for achieving high transfection efficiency and cell viability with little resource expenses. After two runs, an optimal ratio to overcome the toxicity-efficiency dilemma is identified. The results highlight the remarkable potential of integrating machine learning into polymer chemistry to effectively tackle the enormous number of conceivable combinations for identifying novel and powerful gene transporters.