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991.
Pascal L. W. Welzen Sydney W. Martinez Ciriano Shoupeng Cao Alexander F. Mason Imke A. B. Welzen-Pijpers Jan C. M. van Hest 《Journal of polymer science. Part A, Polymer chemistry》2021,59(12):1241-1252
Polymersomes have gained much interest within the biomedical field as drug delivery systems due to their ability to transport and protect cargo from the harsh environment inside the body. For an improved drug efficacy, control over cargo release is however also an important factor to take into account. An often employed method is to incorporate pH sensitive groups in the vesicle membrane, which induce disassembly and content release when the particles have reached a target site in the body with the appropriate pH, such as the acidic microenvironment of tumor tissue or the endosome. In this paper, biodegradable poly(ethylene glycol)-poly(caprolactone-gradient-trimethylene carbonate)-based polymeric vesicles have been developed with disassembly features at mild acidic conditions. Modifying the polymer backbone with imidazole moieties results in vesicle disassembly upon protonation due to the lowered pH. Furthermore, upon increasing the pH efficient re-assembly into vesicles is observed due to the switchable amphiphilic nature of the polymer. When this re-assembly process is conducted in presence of cargo, enhanced encapsulation is achieved. Furthermore, the potency of the polymeric system for future biomedical applications such as adjuvant delivery is demonstrated. 相似文献
992.
Xianwen Lou Sandra M. C. Schoenmakers Joost L. J. van Dongen Miguel Garcia-Iglesias Nicolás M. Casellas Marcos Fernández-Castaño Romera Rint P. Sijbesma E. W. Meijer Anja R. A. Palmans 《Journal of polymer science. Part A, Polymer chemistry》2021,59(12):1151-1161
A comprehensive understanding of the structure, self-assembly mechanism, and dynamics of one-dimensional supramolecular polymers in water is essential for their application as biomaterials. Although a plethora of techniques are available to study the first two properties, there is a paucity in possibilities to study dynamic exchange of monomers between supramolecular polymers in solution. We recently introduced hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize the dynamic nature of synthetic supramolecular polymers with only a minimal perturbation of the chemical structure. To further expand the application of this powerful technique some essential experimental aspects have been reaffirmed and the technique has been applied to a diverse library of assemblies. HDX-MS is widely applicable if there are exchangeable hydrogen atoms protected from direct contact with the solvent and if the monomer concentration is sufficiently high to ensure the presence of supramolecular polymers during dilution. In addition, we demonstrate that the kinetic behavior as probed by HDX-MS is influenced by the internal order within the supramolecular polymers and by the self-assembly mechanism. 相似文献
993.
Dr. Selina Beatrice van der Meer Theresa Seiler Christin Buchmann Georgia Partalidou Dr. Sophia Boden Dr. Kateryna Loza Dr. Marc Heggen Dr. Jürgen Linders Dr. Oleg Prymak Prof. Dr. Cristiano L. P. Oliveira Prof. Dr. Laura Hartmann Prof. Dr. Matthias Epple 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1451-1464
Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by 1H NMR spectroscopy, 1H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative 1H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm2 per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles. 相似文献
994.
Tuba Iftikhar Dr. Natalya V. Izarova Dr. Jan van Leusen Prof. Dr. Paul Kögerler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(33):8500-8508
The propensity of the new, phenylphosphonate-stabilized polyoxotungstate [(C6H5PVO)2P4W24O92]16− to act as a precursor for new 3d metal-functionalized polyanions has been investigated. Reactions with MnII and CuII induce the formation of the previously unknown polyoxotungstate archetype {P4W27}, isolated as salts of the polyanions [Na⊂{MnII(H2O)}{WO(H2O)}P4W26O98]13− ( 1 ) and [K⊂{CuII(H2O)}{W(OH)(H2O)}P4W27O99]14− ( 2 ), which were characterized in the solid state (single-crystal X-ray diffraction, elemental and TG analyses, IR spectroscopy, SQUID magnetometry) and in aqueous solution (UV/Vis spectroscopy, cyclic voltammetry). 相似文献
995.
Simone Pilon Steen Ingemann Jørgensen Prof. Dr. Jan H. van Maarseveen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2310-2314
After earlier unsuccessful attempts, this work reports the application of covalent templating for the synthesis of mechanically interlocked molecules (MiMs) bearing no supramolecular recognition sites. Two linear strands were covalently connected in a perpendicular fashion by a central ketal linkage. After subsequent attachment of the first strand to a template via temporary benzylic linkages, the second was linked to the template in a backfolding macrocyclization. The resulting pseudo[1]rotaxane structure was successfully converted to a [2]catenane via a second macrocyclization and cleavage of the ketal and temporary linkages. 相似文献
996.
Dr. Ali Abdulkarim Marvin Nathusius Rainer Bäuerle Dr. Karl-Philipp Strunk Dr. Sebastian Beck Dr. Hans Joachim Räder Prof. Annemarie Pucci Dr. Christian Melzer Daniel Jänsch Dr. Jan Freudenberg Prof. Uwe H. F. Bunz Prof. Klaus Müllen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):281-288
The synthesis of unsubstituted oligo-para-phenylenes ( OPP ) exceeding para-hexaphenylene—in the literature often referred to as p-sexiphenyl—has long remained elusive due to their insolubility. We report the first preparation of unsubstituted para-nonaphenylenes ( 9PP s) by extending our precursor route to poly-para-phenylenes ( PPP ) to a discrete oligomer. Two geometric isomers of methoxylated syn- and anti-cyclohexadienylenes were synthesized, from which 9PP was obtained via thermal aromatization in thin films. 9PP was characterized via optical, infrared and solid-state 13C NMR spectroscopy as well as atomic force microscopy and mass spectrometry, and compared to polymeric analogues. Due to the lack of substitution, para-nonaphenylene, irrespective of the precursor isomer employed, displays pronounced aggregation in the solid state. Intermolecular excitonic coupling leads to formation of H-type aggregates, red-shifting emission of the films to greenish. 9PP allows to study the structure–property relationship of para-phenylene oligomers and polymers, especially since the optical properties of PPP depend on the molecular shape of the precursor. 相似文献
997.
Roos C. W. van Lier Dr. A. Dowine de Bruijn Prof. Dr. Gerard Roelfes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1430-1437
Dehydroalanine (Dha) residues are attractive noncanonical amino acids that occur naturally in ribosomally synthesised and post-translationally modified peptides (RiPPs). Dha residues are attractive targets for selective late-stage modification of these complex biomolecules. In this work, we show the selective photocatalytic modification of dehydroalanine residues in the antimicrobial peptide nisin and in the proteins small ubiquitin-like modifier (SUMO) and superfolder green fluorescent protein (sfGFP). For this purpose, a new water-soluble iridium(III) photoredox catalyst was used. The design and synthesis of this new photocatalyst, [Ir(dF(CF3)ppy)2(dNMe3bpy)]Cl3, is presented. In contrast to commonly used iridium photocatalysts, this complex is highly water soluble and allows peptides and proteins to be modified in water and aqueous solvents under physiologically relevant conditions, with short reaction times and with low reagent and catalyst loadings. This work suggests that photoredox catalysis using this newly designed catalyst is a promising strategy to modify dehydroalanine-containing natural products and thus could have great potential for novel bioconjugation strategies. 相似文献
998.
Dr. Gabriele Hierlmeier Dr. Peter Coburger Dr. Daniel J. Scott Dr. Thomas M. Maier Dr. Stefan Pelties Prof. Dr. Robert Wolf Daniel M. Pividori Prof. Dr. Karsten Meyer Dr. Nicolaas P. van Leest Prof. Dr. Bas de Bruin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(60):14936-14946
Reactions of di-tert-butyldiphosphatetrahedrane ( 1 ) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations. 相似文献
999.
Islam Md. Shahidul Alam Md Nur van de Ven Theo. G. M. 《Cellulose (London, England)》2021,28(14):9475-9488
Cellulose - Textile filaments were fabricated from a solution obtained from carboxymethylated cellulose dissolved in aqueous NaOH solution, by wet spinning in an acid coagulation bath. Spinning is... 相似文献
1000.
Jakob Heller Tobias F. Pascher Dr. Christian van der Linde Dr. Milan Ončák Prof. Dr. Martin K. Beyer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16367-16376
Hydrated aluminium cations have been investigated as a photochemical model system with up to ten water molecules by UV action spectroscopy in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Intense photodissociation was observed starting at 4.5 eV for two to eight water molecules with loss of atomic hydrogen, molecular hydrogen and water molecules. Quantum chemical calculations for n=2 reveal that solvation shifts the intense 3s–3p excitations of Al+ into the investigated photon energy range below 5.5 eV. During the photochemical relaxation, internal conversion from S1 to T2 takes place, and photochemical hydrogen formation starts on the T2 surface, which passes through a conical intersection, changing to T1. On this triplet surface, the electron that was excited to the Al 3p orbital is transferred to a coordinated water molecule, which dissociates into a hydroxide ion and a hydrogen atom. If the system remains in the triplet state, this hydrogen radical is lost directly. If the system returns to singlet multiplicity, the reaction may be reversed, with recombination with the hydroxide moiety and electron transfer back to aluminium, resulting in water evaporation. Alternatively, the hydrogen radical can attack the intact water molecule, forming molecular hydrogen and aluminium dihydroxide. Photodissociation is observed for up to n=8. Clusters with n=9 or 10 occur exclusively as HAlOH+(H2O)n-1 and are transparent in the investigated energy range. For n=4–8, a mixture of Al+(H2O)n and HAlOH+(H2O)n-1 is present in the experiment. 相似文献