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261.
262.
Insect vector-borne diseases pose serious health problems, so there is a high demand for efficient molecules that could reduce transmission. Using molecular docking and molecular dynamics (MD) simulation, we studied a series of compounds acting on human and insect muscarinic acetylcholine receptors (mAChRs), a novel target of synergistic agents in pest control. We characterized early conformational changes of human M1 and fruit fly type-A mAChR G protein-coupled receptors (GPCRs) in response to DEET, IR3535, and muscarine binding based on the MD analysis of the activation microswitches known to form the signal transduction pathway in class A GPCRs. We indicated groups of microswitches that are the most affected by the presence of a ligand. Moreover, to increase selectivity towards insects, we proposed a new, bitopic, photoswitchable mAChR ligand—BQCA-azo-IR353 and studied its interactions with both receptors. Modeling data showed that using a bitopic ligand may be a promising strategy in the search for better insect control. 相似文献
263.
The plasma-activated removal of oil from contaminated silicon substrates and galvanized steel sheets has been performed using dielectric barrier discharges (DBD) at atmospheric pressure. Removal rates were determined by ellipsometric measurement of the oil film thickness, using polished silicon as substrates. With galvanized steel sheets, qualitative and quantitative investigations were done using fluorescence microscopic characterization of theplasma-treated surfaces. Both the ellipsometric and the fluorescence microscopic measurements yield the dependence of the removal rate on treatment parameterssuch as plasma–gas composition and gas flow. The film thickness measurements were calibrated using quantitative IR spectroscopic measurements. It could be shown that the removal rate increases with increasing oxygen content in the process gas, static removal rates of 0.6 nm/s and 7 nm/s being obtainedin pure nitrogen and in pure oxygen, respectively. Fluorescence microscopic investigations showed that oil can be removed even from grooves in the galvanized steel sheets. 相似文献
264.
265.
Tommi Palomki Miguel A. Caro Niklas Wester Sami Sainio Jarkko Etula Leena‐Sisko Johansson Jeon G. Han Jari Koskinen Tomi Laurila 《Electroanalysis》2019,31(4):746-755
Undoped a‐C thin films were deposited with varying power density from 10 to 25 W/cm2 using unbalanced closed‐field magnetron sputtering (CFUBMS). The effect of power density on the physical and electrochemical properties was investigated by experimental characterization methods and atomistic simulations. XPS indicated that the films were composed mostly of sp2‐bonded carbon (55–58 at.%) with a small amount of oxygen (8–9 at.%) in the surface region. The films appeared completely amorphous in XRD. The ID/IG ratio obtained by Raman spectroscopy indicated an increase from 1.76 to 2.34 with power density. The experimental and simulated data suggested a possible ordering and/or clustering of the sp2 phase with power density as the cause of the improved electrical properties of the a‐C films. The electrochemical properties of a‐C were between those of glassy carbon and tetrahedral amorphous carbon with potential windows ranging from 2.77 to 2.93 V and double‐layer capacitance values around 0.90 μF cm?2. Electron transfer for Ru(NH3)63+/2+ and FcMeOH+1/0 was reversible whereas that for IrCl62?/3? was quasi‐reversible. Peak potential separation of dopamine and oxidation potential of ascorbic acid decreased with power density, correlating with the structural and electrical changes of the films. The a‐C thin films deposited by CFUBMS are inherently conductive and their physical properties can be adjusted by varying the deposition parameters to a wide range of electrochemical applications. 相似文献
266.
Patricia J. Nance Niklas B. Thompson Paul H. Oyala Jonas C. Peters 《Angewandte Chemie (International ed. in English)》2019,58(19):6220-6224
Species with 2‐center, 3‐electron (2c/3e?) σ bonds are of interest owing to their fascinating electronic structures and potential for interesting reactivity patterns. Report here is the synthesis and characterization of a pair of zerovalent (d9) trigonal pyramidal Rh and Ir complexes that feature 2c/3e? σ bonds to the Si atom of a tripodal tris(phosphine)silatrane ligand. X‐ray diffraction, continuous wave and pulse electron paramagnetic resonance, density‐functional theory calculations, and reactivity studies have been used to characterize these electronically distinctive compounds. The data available highlight a 2c/3e? bonding framework with a σ*‐SOMO of metal 4‐ or 5dz2 parentage that is partially stabilized by significant mixing with Si (3pz) and metal (5‐ or 6pz) orbitals. Metal‐ligand covalency thus buffers the expected destabilization of transition‐metal (TM)‐silyl σ*‐orbitals by d–p mixing, affording well‐characterized examples of TM–main group, and hence polar, 2c/3e? σ “half‐bonds”. 相似文献
267.
Nadine Leber Leonard Kaps Aiting Yang Misbah Aslam Mariacristina Giardino Adrian Klefenz Niklas Choteschovsky Sebastian Rosigkeit Asmaa Mostafa Lutz Nuhn Detlef Schuppan Rudolf Zentel 《Macromolecular bioscience》2019,19(7)
Immunosuppressive M2 macrophages govern the immunophathogenic micromilieu in many severe diseases including cancer or fibrosis, thus, their re‐polarization through RNA interference is a promising concept to support combinatorial therapies. For targeted siRNA delivery, however, safe and stable carriers are required that manage cell specific transport to M2 macrophages. Here, siRNA‐loaded cationic nanogels are reported with α‐mannosyl decorated surfaces that target and modify M2 macrophages selectively. Via amphiphilic precursor block copolymers bearing one single α‐mannosyl moiety at their chain end mannosylated cationic nanohydrogel particles (ManNP) were obtained of 20 nm diameter determined by dynamic light scattering and cryogenic electron transmission microscopy. α‐Mannosyl surface modification is confirmed by agglutination with concanavalin A. SiRNA‐loaded ManNP preferentially targets the overexpressed mannose receptor CD206 on M2 macrophages, as shown by in vitro cell uptake studies in M2 polarized primary macrophages. This specificity is confirmed, since ManNP uptake could be reduced by blocking of CD206 with mannan. Effective ManNP‐guided siRNA delivery is confirmed by sequence‐specific gene knockdown of CSF‐1R in M2‐type macrophages exclusively, while the expression levels in M1‐polarized macrophages is not affected. In conclusion, α‐mannosyl‐functionalized ManNPs are promising universal siRNA carriers for targeted immunomodulatory treatment of immunosuppressive macrophages. 相似文献
268.
Niklas Noll Prof. Dr. Frank Würthner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):444-450
A cyclic dinuclear ruthenium(bda) (bda: 2,2’-bipyridine-6,6’-dicarboxylate) complex equipped with oligo(ethylene glycol)-functionalized axial calix[4]arene ligands has been synthesized for homogenous catalytic water oxidation. This novel Ru(bda) macrocycle showed significantly increased catalytic activity in chemical and photocatalytic water oxidation compared to the archetype mononuclear reference [Ru(bda)(pic)2]. Kinetic investigations, including kinetic isotope effect studies, disclosed a unimolecular water nucleophilic attack mechanism of this novel dinuclear water oxidation catalyst (WOC) under the involvement of the second coordination sphere. Photocatalytic water oxidation with this cyclic dinuclear Ru complex using [Ru(bpy)3]Cl2 as a standard photosensitizer revealed a turnover frequency of 15.5 s−1 and a turnover number of 460. This so far highest photocatalytic performance reported for a Ru(bda) complex underlines the potential of this water-soluble WOC for artificial photosynthesis. 相似文献
269.
Niklas H. Fischer Dr. Erik Fumi Dr. Maria Teresa Oliveira Prof. Peter W. Thulstrup Prof. Frederik Diness 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202103788
Cyclic peptides are promising next-generation therapeutics with improved biological stability and activity. A catalyst-free stapling method for cysteine-containing peptides has been developed that enables fine-tuning of the macrocycle by using the appropriate regioisomers of fluorobenzene linkers. Stapling was performed on the unprotected linear peptide or, more conveniently, directly on-resin after peptide synthesis. NMR spectroscopy and circular dichroism studies demonstrate that the type of stapling can tune the secondary structures of the peptides. The method was applied to a set of potential agonists for melanocortin receptors, generating a library of macrocyclic potent ligands with ortho, meta or para relationships between the thioethers. Their small but significant differences in potency and efficacy demonstrate how the method allows facile fine-tuning of macrocyclic peptides towards biological targets from the same linear precursor. 相似文献
270.
Niklas Gangloff Daniel Nahm Lisa Döring Dirk Kuckling Robert Luxenhofer 《Journal of polymer science. Part A, Polymer chemistry》2015,53(14):1680-1686
The highly modular Ugi four‐component reaction (Ugi‐4CR) was used to directly obtain polymers of high molar mass bearing aromatic residues in the backbone. By using at least two bifunctional monomers, the Ugi‐4CR can be employed to synthesize polymers through a polycondensation under mild conditions in the absence of catalysts. This highly versatile approach allows the creation of vast libraries of molecules by a comparably small pool of compounds. We investigated the six different possible types of the Ugi four‐component polymerization (Ugi‐4CP) to generate polyamides using commercially available monomers without further purification. After substantial adjustments of reaction parameters, we were able to obtain a polymer of high molar mass, albeit only for one out of the six types of the Ugi‐4CP. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1680–1686 相似文献