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821.
822.
Variously substituted tolanes were employed to show that the push-pull effect is also active in CC triple bonds by the successful correlation of the occupation quotient pi/pi of the pi orbital in resonance with the substituted phenyl moieties of tolanes versus the bond length of the CC triple bond. In addition, the influences of the ortho phenyl ring substituents on the 13C chemical shifts of the triple bond carbon atoms, which were estimated by Rubin et al.(4) to be "inapplicable for describing triple bond polarization", were re-evaluated, leading to the conclusion that, while anisotropic effects of ortho substituents are negligible, the steric ortho-substituent effects do in fact dominate the deviations obtained. A detailed theoretical NBO/NCS study has been employed to illuminate the facts of this case. 相似文献
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Anna C. Crecelius Anja Baumgaertel Ulrich S. Schubert 《Journal of mass spectrometry : JMS》2009,44(9):1277-1286
The detailed characterization of macromolecules plays an important role for synthetic chemists to define and specify the structure and properties of the successfully synthesized polymers. The search for new characterization techniques for polymers is essential for the continuation of the development of improved synthesis methods. The application of tandem mass spectrometry for the detailed characterization of synthetic polymers using the soft ionization techniques matrix‐assisted laser desorption/ionization mass spectrometry (MALDI‐MS) and electrospray ionization mass spectrometry (ESI‐MS), which became the basic tools in proteomics, has greatly been increased in recent years and is summarized in this perspective. Examples of a variety of homopolymers, such as poly(methyl methacrylate), poly(ethylene glycol), as well as copolymers, e.g. copolyesters, are given. The advanced mass spectrometric techniques described in this review will presumably become one of the basic tools in polymer chemistry in the near future. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
825.
Dr. Qiuhua Liang Prof. Dr. Geert Brocks Dr. Anja Bieberle-Hütter 《Chemphyschem》2023,24(5):e202200429
Magnetic exchange force microscopy (MExFM) is an important experimental technique for mapping the magnetic structure of surfaces with atomic resolution relying on the spin-dependent short-range exchange interaction between a magnetic tip and a magnetic surface. RuO2 is a significant compound with applications in heterogeneous catalysis and electrocatalysis. It has been characterized recently as an antiferromagnetic (AFM) material, and its magnetism has been predicted somewhat surprisingly to play an important role in its catalytic properties. In the current study, we explore theoretically whether MExFM can visualize the magnetic surface structure of RuO2. We use density functional theory (DFT) calculations to extract the exchange interactions between a ferromagnetic Fe tip interacting with an AFM RuO2(110) surface, as a function of tip-surface distance and the position of the tip over the surface. Mimicking the MExFM experiment, these data are then used to calculate the normalized frequency shift of an oscillating cantilever tip versus the minimum tip-surface distance, and construct corrugation height line profiles. It is found that the exchange interaction between tip and surface is strongest for a parallel configuration of the spins of the tip and of the surface; it is weakest for an anti-parallel orientation. In a corrugation profile, this gives rise to a sizable height difference of 25 pm between the spin-up and spin-down Ru atoms in the RuO2(110) surface at a normalized frequency shift =−10.12 fNm1/2. The O atoms in the surface are not or hardly visible in the corrugation profile. 相似文献
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827.
The issue of self-cleaning significantly gained popularity due to the work of Barthlott and coworkers on the so called “Lotos-Effect®”. They found out, that the cleanliness of the Lotos leaves originates from a combined effect of surface topography and hydrophobicity. The symbol of the beautiful Lotos flower as well as the fascination of surfaces being cleaned without any manual activity, simply by a rain shower, has since then stimulated the fantasy of many researchers. Our vision is to copy this mechanism from mother nature and to implement it into coating systems in such a way, that conventional application techniques, e.g. spray-coating, can be applied without the necessity of further process steps like e.g. soft lithography. Three different approaches will be presented in this paper. Roughness and contact angle measurements have been used to quantify the self-cleaning properties. 相似文献
828.
Franziska Hausig-Punke Gregor Dekevic Fabian H. Sobotta Jana I. Solomun Friederike Richter Denise Salzig Anja Traeger Johannes C. Brendel 《Macromolecular bioscience》2023,23(5):2370016
Cationic pH-responsive polymers promise to overcome critical challenges in cellular delivery. Ideally, the polymers become selectively charged along the endosomal pathway disturbing only the local membrane and avoiding unintended interactions or cytotoxic side effects at physiological conditions. Polypiperazines represent a novel, hydrophilic class of pH-responsive polymers whose response can be tuned within the relevant pH range (5–7.4). The authors discovered that the polypiperazines are effectively binding plasmid DNA (pDNA) and demonstrate high efficiency in transfection. By design of experiments (DoE), a wide parameter space (pDNA and polymer concentration) is screened to identify the range of effective concentrations for transfection. An isopropyl modified polypiperazine is highly efficient over a wide range of concentrations outperforming linear polyethylenimine (l-PEI, 25 kDa) in regions of low N*/P ratios. A quantitative polymerase chain reaction (qPCR) surprisingly revealed that the pDNA within the piperazine-based polyplexes can be amplified in contrast to polyplexes based on l-PEI. The pDNA must therefore be more accessible and bound differently than for other known transfection polymers. Considering the various opportunities to further optimize their structure, polypiperazines represent a promising platform for designing effective soluble polymeric vectors, which are charge-neutral at physiological conditions. 相似文献
829.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献