EPR spectroscopic characterization of persistent germyl-substituted Pb(III)- and Sn(III)-radicals.
In this report we present the synthesis and the detailed electron paramagnetic resonance (EPR) spectroscopic characterization of novel trivalent lead- and tin-based radicals comprising sterically demanding germyl substituents. The investigated radicals are derived from the recently reported trihypersilyl-substituted tetryl radicals *PbHyp3 and *SnHyp3. The tetryl radicals *Pb(Ge(SiMe3)3)3 (8), *Pb(Ge(SiMe3)3)2Si(SiMe3)3 (9), *PbGe(SiMe3)3(Si(SiMe3)3)2 (10), and *Sn(Ge(SiMe3)3)3 (11) show substitution patterns derived from stepwise (9, 10) or complete (8, 11) substitution of hypersilyl groups (Hyp = Si(SiMe3)3) in *PbHyp3 and *SnHyp3 by homologous hypergermyl groups (Hge = Ge(SiMe3)3). They …
Highly Defined, Colloid‐Like Ionic Clusters in Solution
Many societal challenges at the beginning of the 21st century lead to an apparent and growing need for functional materials and novel ways of materials synthesis and assembly. Rising to the challenge, the utilization of small, self-assembling building blocks for the bottom-up construction of new types of polymers and nanostructures has enjoyed increasing popularity among materials researchers in the recent past. Supramolecular materials like foldamers, surface films, nanoparticles, etc. are created by exploiting noncovalent forces [1] leading to an ordered arrangement of nanoscale building blocks. [2] In the search for new polymers based on noncovalent molecular forces, we are motivated by …
Aggregation behavior of amphiphilic p(HPMA)-co-p(LMA) copolymers studied by FCS and EPR spectroscopy.
A combined study of fluorescence correlation spectroscopy and electron paramagnetic resonance spectroscopy gave a unique picture of p(HPMA)-co-p(LMA) copolymers in aqueous solutions, ranging from the size of micelles and aggregates to the composition of the interior of these self-assembled systems. P(HPMA)-co-p(LMA) copolymers have shown high potential as brain drug delivery systems, and a detailed study of their physicochemical properties can help to elucidate their mechanism of action. Applying two complementary techniques, we found that the self-assembly behavior as well as the strength of hydrophobic attraction of the amphiphilic copolymers can be tuned by the hydrophobic LMA content or…
A Polyphenylene Dendrimer Drug Transporter with Precisely Positioned Amphiphilic Surface Patches
The design and synthesis of a polyphenylene dendrimer (PPD 3) with discrete binding sites for lipophilic guest molecules and characteristic surface patterns is presented. Its semi-rigidity in combination with a precise positioning of hydrophilic and hydrophobic groups at the periphery yields a refined architecture with lipophilic binding pockets that accommodate defined numbers of biologically relevant guest molecules such as fatty acids or the drug doxorubicin. The size, architecture, and surface textures allow to even penetrate brain endothelial cells that are a major component of the extremely tight blood-brain barrier. In addition, low to no toxicity is observed in in vivo studies using…
How Structure-Related Collapse Mechanisms Determine Nanoscale Inhomogeneities in Thermoresponsive Polymers
Continuous wave electron paramagnetic resonance (CW EPR) spectroscopy on the amphiphilic spin probe TEMPO in solutions of selectively chosen functional, thermoresponsive poly(propylene oxide) (PPO)- and poly(ethylene oxide) (PEO)-based copolymers of both linear and branched structure is used to elucidate their host–guest interactions and inverse phase transitions. Three different fundamental types of host–guest interactions between probes and polymers could be correlated to the phase transition mechanisms (supported by MD simulations), evidencing that these proceed via nanoscale inhomogeneities of the polymers. Because of their ability to host small amphiphilic guest molecules, thermorespon…
Load-collapse-release cascades of amphiphilic guest molecules in charged dendronized polymers through spatial separation of noncovalent forces.
The ability to pack guest molecules into charged dendronized polymers (denpols) and the possibility to release these guest molecules from subsequently densely aggregated denpols in a load-collapse-release cascade is described. Charged denpols, which constitute molecular objects with a persistent, well-defined envelope and interior, are capable of incorporating large amounts of amphiphilic guest molecules. Simultaneously, multivalent ions can coordinate to the surfaces of charged denpols, leading to counterion-induced aggregation of the already guest-loaded host structures. Thus, although the local guest concentration in denpol-based molecular transport might already be initially high due to…
Stimuli-Responsive Tertiary Amine Functional PEGs Based on N,N-Dialkylglycidylamines
Amine-functional poly(ethylene glycol) (PEG) copolymers have been prepared that exhibit thermo- and pH- responsive behavior in aqueous solution. Three novel tertiary di(n-alkyl)glycidylamine monomers have been introduced for anionic ring-opening copolymerization (AROcP) with ethylene oxide (EO): N,N-di(n-butyl)glycidylamine (DButGA), N,N-di(n-hexyl)glycidylamine (DHexGA), and N,N-di(n-octyl)glycidylamine (DOctGA). Via controlled AROcP we synthesized well-defined (Mw/Mn = 1.05–1.14), water-soluble block- and gradient-type PEG copolymers, containing up to 25 mol % of the respective dialkylglycidylamine comonomer. Molecular weights ranged from 4900 to 12 000 g mol–1. Detailed in-situ 1H NMR ki…
Impact of Amino-Functionalization on the Response of Poly(ethylene glycol) (PEG) to External Stimuli
It is shown that amino-functionalization of poly(ethylene glycol) (PEG) with the comonomer N,N-diethyl glycidyl amine (DEGA) triggers the emergence of extraordinary stimuli responsiveness and phase behavior of PEG. In dependence of the solution pH, tapered PEG-co-PDEGA exhibits a highly cooperative two-step inverse phase transition with respect to temperature. The polymer forms dispersed metastable nanoglobules in the medically relevant temperature range around human body temperature. Independently, cloud points can be adjusted between 40 and 90 °C via the pH of the solution. Changing the polymer architecture to a block structure, in pronounced contrast, the polymer exhibits a gradual growt…
Dinitrogen complexation with main group radicals
In this report we present data from hyperfine sublevel correlation spectroscopy (HYSCORE), an electron paramagnetic resonance (EPR) spectroscopic technique, that reveals weak but distinct interactions between several main group element radicals and physically dissolved dinitrogen in solution. These interactions are the basis for a well-defined coordination of N2 to the paramagnetic centers. The complexes formed are primarily of the van der Waals-type but also feature a non-negligible orbital overlap between dinitrogen and the radicals' SOMO. Our spectroscopic findings are strongly supported by experiments with isotope-labeled 15N2, spectral simulations and quantum chemical and density funct…
DNA condensation with spermine dendrimers: interactions in solution, charge inversion, and morphology control
In this report, we characterize the formation of structured condensates of 884 base pair, double stranded DNA and spin-labeled, second generation dendrons (SL-G2) that are spermine-based and cationic using continuous wave electron paramagnetic resonance spectroscopy (CW EPR) and transmission electron microscopy (TEM). The electrostatic interaction between DNA and SL-G2 in solution leads to condensation of DNA into densely packed structures. At a particular charge ratio of 2.3 (cationic charges/anionic charges), the structures appear as thick rod-like condensates of parallelly ordered, stretched DNA and SL-G2. Depending on the concentration of DNA, the charge ratio and the ionic strength, wh…