Adsorption mechanism and valency of catechol-functionalized hyperbranched polyglycerols

Nature often serves as a model system for developing new adhesives. In aqueous environments, mussel-inspired adhesives are promising candidates. Understanding the mechanism of the extraordinarily strong adhesive bonds of the catechol group will likely aid in the development of adhesives. With this aim, we study the adhesion of catechol-based adhesives to metal oxides on the molecular level using atomic force microscopy (AFM). The comparison of single catechols (dopamine) with multiple catechols on hyperbranched polyglycerols (hPG) at various pH and dwell times allowed us to further increase our understanding. In particular, we were able to elucidate how to achieve strong bonds of different valency. It was concluded that hyperbranched polyglycerols with added catechol end groups are promising candidates for durable surface coatings

Multivalent non-covalent interactions lead to strongest polymer adhesion

Multivalent interactions play a leading role in biological processes such as the inhibition of inflammation or virus internalization. The multivalent interactions show enhanced strength and better selectivity compared to monovalent interactions, but they are much less understood due to their complexity. Here, we detect molecular interactions in the range of a few piconewtons to several nanonewtons and correlate them with the formation and subsequent breaking of one or several bonds and assign these bonds. This becomes possible by performing atomic force microcopy (AFM)-based single molecule force spectroscopy of a multifunctional polymer covalently attached to an AFM cantilever tip on a substrate bound polymer layer of the multifunctional polymer. Varying the pH value and the crosslinking state of the polymer layer, we find that bonds of intermediate strength (non-covalent), like coordination bonds, give the highest multivalent bond strength, even outperforming strong (covalent) bonds. At the same time, covalent bonds enhance the polymer layer density, increasing in particular the number of non-covalent bonds. In summary, we can show that the key for the design of stable and durable polymer coatings is to provide a variety of multivalent interactions and to keep the number of non-covalent interactions at a high leve

Detection of metastable electronic states by Penning trap mass spectrometry

State-of-the-art optical clocks achieve fractional precisions of $10^{-18}$ and below using ensembles of atoms in optical lattices or individual ions in radio-frequency traps. Promising candidates for novel clocks are highly charged ions (HCIs) and nuclear transitions, which are largely insensitive to external perturbations and reach wavelengths beyond the optical range, now becoming accessible to frequency combs. However, insufficiently accurate atomic structure calculations still hinder the identification of suitable transitions in HCIs. Here, we report on the discovery of a long-lived metastable electronic state in a HCI by measuring the mass difference of the ground and the excited state in Re, the first non-destructive, direct determination of an electronic excitation energy. This result agrees with our advanced calculations, and we confirmed them with an Os ion with the same electronic configuration. We used the high-precision Penning-trap mass spectrometer PENTATRAP, unique in its synchronous use of five individual traps for simultaneous mass measurements. The cyclotron frequency ratio $R$ of the ion in the ground state to the metastable state could be determined to a precision of $\delta R=1\cdot 10^{-11}$, unprecedented in the heavy atom regime. With a lifetime of about 130 days, the potential soft x-ray frequency reference at $\nu=4.86\cdot 10^{16}\,\text{Hz}$ has a linewidth of only $\Delta \nu\approx 5\cdot 10^{-8}\,\text{Hz}$, and one of the highest electronic quality factor ($Q=\frac{\nu}{\Delta \nu}\approx 10^{24}$) ever seen in an experiment. Our low uncertainty enables searching for more HCI soft x-ray clock transitions, needed for promising precision studies of fundamental physics in a thus far unexplored frontier

Penning-trap measurement of the QQ-value of the electron capture in 163Ho^{163}\mathrm{Ho} for the determination of the electron neutrino mass

The investigation of the absolute scale of the effective neutrino mass remains challenging due to the exclusively weak interaction of neutrinos with all known particles in the standard model of particle physics. Currently, the most precise and least model-dependent upper limit on the electron antineutrino mass is set by the KATRIN experiment from the analysis of the tritium \b{eta}-decay. Another promising approach is the electron capture in $^{163}\mathrm{Ho}$, which is under investigation using microcalorimetry within the ECHo and HOLMES collab orations. An independently measured Q-value of this process is vital for the assessment of systematic uncertainties in the neutrino mass determination. Here, we report a direct, independent determination of this $Q$-value by measuring the free-space cyclotron frequency ratio of highly charged ions of $^{163}\mathrm{Ho}$ and $^{163}\mathrm{Dy}$ in the Penning trap experiment \textsc{Pentatrap}. Combining this ratio with atomic physics calculations of the electronic binding energies yields a $Q$-value of $2863.2(0.6)\,\mathrm{eV}/c^{2}$ - a more than 50-fold improvement over the state-of-the-art. This will enable the determination of the electron neutrino mass on a sub-eV level from the analysis of the electron capture in $^{163}\mathrm{Ho}$

Functionalization of breast implants by cyclodextrin in-situ polymerization: a local drug delivery system for augmentation mammaplasty

Mammaplasty is a widely performed surgical procedure worldwide, utilized for breast reconstruction, in the context of breast cancer treatment, and aesthetic purposes. To enhance post-operative outcomes and reduce risks (hematoma with required evacuation, capsular contracture, implant-associated infection and others), the controlled release of medicaments can be achieved using drug delivery systems based on cyclodextrins (CDs). In this study, our objective was to functionalize commercially available silicone breast implants with smooth and textured surfaces through in-situ polymerization of two CDs: β-CD/citric acid and 2-hydroxypropyl-β-CD/citric acid. This functionalization serves as a local drug delivery system for the controlled release of therapeutic molecules that potentially can be a preventive treatment for post-operative complications in mammaplasty interventions. Initially, we evaluated the pre-treatment of sample surfaces with O2 plasma, followed by chitosan grafting. Subsequently, in-situ polymerization using both types of CDs was performed on implants. The results demonstrated that the proposed pre-treatment significantly increased the polymerization yield. The functionalized samples were characterized using microscopic and physicochemical techniques. To evaluate the efficacy of the proposed system for controlled drug delivery in augmentation mammaplasty, three different molecules were utilized: pirfenidone (PFD) for capsular contracture prevention, Rose Bengal (RB) as anticancer agent, and KR-12 peptide (KR-12) to prevent bacterial infection. The release kinetics of PFD, RB, and KR-12 were analyzed using the Korsmeyer-Peppas and monolithic solution mathematical models to identify the respective delivery mechanisms. The antibacterial effect of KR-12 was assessed against Staphylococcus epidermidis and Pseudomonas aeruginosa, revealing that the antibacterial rate of functionalized samples loaded with KR-12 was dependent on the diffusion coefficients. Finally, due to the immunomodulatory properties of KR-12 peptide on epithelial cells, this type of cells was employed to investigate the cytotoxicity of the functionalized samples. These assays confirmed the superior properties of functionalized samples compared to unprotected implants

RECENT DEVELOPMENT OF A BIOINSPIRED ANTIMICROBIAL SURFACE - A PREVENTIVE TECHNOLOGY FOR EXTENDED STAYS IN CONFINED SPACE ENVIRONMENTS

Challenges of space ight in LEO and exploration activities are manyfold. E.g., the more far away from the Earth, the more increased stays in closed systems (e.g. ISS, lunar and Martian habitats) are a common characteristic. This includes increased but very specific microbial loads caused by high humidity and temperature levels and especially based on the group of humans brought to the closed habitat. Furthermore, there is a higher dependency from biological systems (CELSS) being sensitive against unintended microbial contamination, as well as a need of not transferring microorganisms out of spaceships to outer, habitable bodies and vice versa (COSPAR Planetary Protection Policy). Proven technologies on Earth to counteract microbial contamination as biocides are not a suited alternative for space due to inherent problems of potential toxic effects on non-target organisms, unspecifity and resistancies to some microbial groups. Bioinspired technologies as using antimicrobial peptides from nature (e.g. from frog skin etc.), immobilised on surfaces, are a suited alternative. High exibility concerning the microbial target, low toxicity and an absence of resistancies are the main advantages. An overview about goals and first results of a corresponding activity, funded by ESA, will be given at the symposium

Enzyme ersetzen Plasmabehandlung

Durch die Verwendung eines Enzyms in wässriger Lösung können polymere hydrophobe Substrate in mit Wasser benetzbare Oberflächen umgewandelt werden. Dieser Prozess ist eine umweltfreundliche Alternative zur Plasmabehandlung von Oberflächen. Der Energiebedarf ist gering und es entstehen keine umweltgefährlichen Stoffe

Structural manipulation of colloidal silica

Structural properties of the nanosized silica Ludox TMA with novel functionalizations have been investigated. Silica is stabilized in aqueous solution at a pH value higher than the pK(a) of silicic acid. A surface modification consisting of poly(p-benzamide)s functionalized with derivatized nucleobases on the C-terminus and cationic pyridinium functions on the N-terminus of the polymer chain was carried out. Due to the negatively charged surface, strong physisorption of the cationic pyridinium functions occurs. It is possible to stabilize diluted solutions of silica without agglomeration in solvents with various polarities by using pyridinium cations. Defined structures could be created according to the hydrogen donor/acceptor potential of the introduced nucleobase. Surprisingly the interactions between the same nucleobases are already sufficient for strong particle-particle interactions. Dramatic effects on the structural behavior are characterized by PCS, (S)TEM and EFTEM

Trialkylammoniododecaborates: Anions for ionic liquids with potassium, lithium and protons as cations

Herein we report a new class of low-melting ionic liquids (IL) that consist of N,N,N-trialkylammonioundecahydrododecaborates(1-) as the anion and a range of cations. The cations include the common cations of conventional ILs such as tetraalkylammonium, N-alkylpyridinium, and N-methyl-N ''-alkylimidazolium. In addition, their salts with lithium, potassium, and proton cations also exist as ILs. Pulse radiolysis studies indicate that the anions do not react with solvated electrons. Entnommen aus <a href="http://www.fiz-technik.de/db/b_tema.htm" target="_blank">TEMA</a