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排序方式: 共有278条查询结果,搜索用时 15 毫秒
1.
Böcking T Kilian KA Hanley T Ilyas S Gaus K Gal M Gooding JJ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(23):10522-10529
Surface modification with oligo(ethylene oxide) functionalized monolayers terminated with reactive headgroups constitutes a powerful strategy to provide specific coupling of biomolecules with simultaneous protection from nonspecific adsorption on surfaces for the preparation of biorecognition interfaces. To date, oligo(ethylene oxide) functionalized monolayer-forming molecules which can be activated for attachment of biomolecules but which can selectively form monolayers onto hydrogen terminated silicon have yet to be developed. Here, self-assembled monolayers (SAMs) containing tetra(ethylene oxide) moieties protected with tert-butyl dimethylsilyl groups were formed by thermal hydrosilylation of alkenes with single-crystal Si(111)-H. The protection group was used to avoid side reactions with the hydride terminated silicon surface. Monolayer formation was carried out using solutions of the alkene in the high-boiling-point solvent 1,3,5-triethylbenzene. The protecting group was removed under very mild acidic conditions to yield a free hydroxyl functionality, a convenient surface moiety for coupling of biological entities via carbamate bond formation. The chemical composition and structure of the monolayers before and after deprotection were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. To demonstrate the utility of this surface for covalent modification, two reagents were compared and contrasted for their ability to activate the surface hydroxyl groups for coupling of free amines, carbonyl diimidazole (CDI), and disuccinimidyl carbonate (DSC). Analysis of XP spectra before and after activation by CDI or DSC, and after subsequent reaction with glycine, provided quantitative information on the extent of activation and overall coupling efficiencies. CDI activated surfaces gave poor coupling yields under various conditions, whereas DSC mediated activation followed by aminolysis at neutral pH was found to be an efficient method for the immobilization of amines on tetra(ethylene oxide) modified surfaces. 相似文献
2.
S. T. Howard J. P. Huke I. W. Parsons S. J. Till 《International journal of quantum chemistry》1991,39(1):71-91
The usefulness of the MS -Xα method for calculating molecular transition properties is investigated in a study of NO2. Two-dimensional potential surfaces are obtained in C2v symmetry for the X?2A1/Ã2B2 system. Potential curves that approximately follow the asymmetric stretch coordinate are also presented: On investigation, no symmetry-broken solutions were found. At all nuclear geometries investigated, the muffin-tin sphere radii were chosen by an energy-minimization technique. The inclusion of corrections to the muffin-tin form of the Xα total energy is shown to be essential, if the computed surfaces are to be qualitatively correct. The transition dipole moment connecting the two states is evaluated as a function of nuclear coordinates, using the transition-state approximation. Finally, the radiative decay of a single vibronic level in NO2 is modeled and the relevance to experiment is discussed. 相似文献
3.
Till Opatz 《Tetrahedron》2004,60(39):8613-8626
Carbohydrates are useful polyfunctional scaffold molecules which allow the selective attachment of a number of different side chains. The combinatorial solid phase synthesis of diverse amino acid or peptide conjugates of a polyfunctional glucose scaffold based on a set of selectively removable and orthogonally stable protecting groups is described. The resulting carbohydrate-peptide hybrids constitute potential turn mimetics. 相似文献
4.
Daniel Sebena Kevin Rudolph Bibhisan Roy Christoph Wlper Till Nitschke Sarah Lampe Michael Giese Jens Voskuhl 《Molecules (Basel, Switzerland)》2022,27(9)
In this article, we present fluorescent guanidiniocarbonyl-indoles as versatile oxo-anion binders. Herein, the guanidiniocarbonyl-indole (GCI) and methoxy-guanidiniocarbonyl-indole (MGCI) were investigated as ethylamides and compared with the well-known guanidiniocarbonyl-pyrrole (GCP) concerning their photophysical properties as well as their binding behavior towards oxo-anions. Hence, a variety of anionic species, such as carboxylates, phosphonates and sulfonates, have been studied regarding their binding properties with GCP, GCI and MGCI using UV-Vis titrations, in combination with the determination of the complex stoichiometry using the Job method. The emission properties were studied in relation to the pH value using fluorescence spectroscopy as well as the determination of the photoluminescence quantum yields (PLQY). Density functional theory (DFT) calculations were undertaken to obtain a better understanding of the ground-lying electronic properties of the investigated oxo-anion binders. Additionally, X-ray diffraction of GCP and GCI was conducted. We found that GCI and MGCI efficiently bind carboxylates, phosphonates and sulfonates in buffered aqueous solution and in a similar range as GCP (Kass ≈ 1000–18,000 M−1, in bis-tris buffer, pH = 6); thus, they could be regarded as promising emissive oxo-anion binders. They also exhibit a visible fluorescence with a sufficient PLQY. Additionally, the excitation and emission wavelength of MGCI was successfully shifted closer to the visible region of the electromagnetic spectrum by introducing a methoxy-group into the core structure, which makes them interesting for biological applications. 相似文献
5.
Matthias Krumb Dr. Maximilian Jäger Alice Voss Loreen Immig Dr. Karin Peters Danuta Kowalczyk Prof. Dr. Albrecht Bufe Prof. Dr. Till Opatz Prof. Dr. Otto Holst Prof. Dr. Christian Vogel Dr. Marcus Peters 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(3):928-933
Arabinogalactan, a microheterogeneous polysaccharide occurring in plants, is known for its allergy-protective activity, which could potentially be used for preventive allergy treatment. New treatment options are highly desirable, especially in a preventive manner, due to the constant rise of atopic diseases worldwide. The structural origin of the allergy-protective activity of arabinogalactan is, however, still unclear and isolation of the polysaccharide is not feasible for pharmaceutical applications due to a variation of the activity of the natural product and contaminations with endotoxins. Therefore, a pentasaccharide partial structure was selected for total synthesis and subsequently coupled to a carrier protein to form a neoglycoconjugate. The allergy-protective activity of arabinogalactan could be reproduced with the partial structure in subsequent in vivo experiments. This is the first example of a successful simplification of arabinogalactan with a single partial structure while retaining its allergy-preventive potential. 相似文献
6.
Nicola Otto Prof. Dr. Till Opatz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13064-13077
Owing to their various modes of reactivity, α‐aminonitriles represent versatile building blocks for the construction of a wide range of nitrogen heterocycles. The present Concept article focuses on synthetic methodologies using their bifunctional nature which is the basis of their reactivity as α‐amino carbanions and as iminium ions. Reactions exclusively taking place on either the amine or on the nitrile moiety will not be considered. 相似文献
7.
Cem B. Yildiz Kinga I. Leszczyska Sandra Gonzlez‐Gallardo Michael Zimmer Akin Azizoglu Till Biskup Christopher W. M. Kay Volker Huch Henry S. Rzepa David Scheschkewitz 《Angewandte Chemie (International ed. in English)》2020,59(35):15087-15092
Main group analogues of cyclobutane‐1,3‐diyls are fascinating due to their unique reactivity and electronic properties. So far only heteronuclear examples have been isolated. Here we report the isolation and characterization of all‐silicon 1,3‐cyclobutanediyls as stable closed‐shell singlet species from the reversible reactions of cyclotrisilene c‐Si3Tip4 (Tip=2,4,6‐triisopropylphenyl) with the N‐heterocyclic silylenes c‐[(CR2CH2)(NtBu)2]Si: (R=H or methyl) with saturated backbones. At elevated temperatures, tetrasilacyclobutenes are obtained from these equilibrium mixtures. The corresponding reaction with the unsaturated N‐heterocyclic silylene c‐(CH)2(NtBu)2Si: proceeds directly to the corresponding tetrasilacyclobutene without detection of the assumed 1,3‐cyclobutanediyl intermediate. 相似文献
8.
Johannes C. B. Dietschreit Annika Wagner T. Anh Le Philipp Klein Prof. Dr. Hermann Schindelin Prof. Dr. Till Opatz Prof. Dr. Bernd Engels Prof. Dr. Ute A. Hellmich Prof. Dr. Christian Ochsenfeld 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):12769-12773
The absence of fluorine from most biomolecules renders it an excellent probe for NMR spectroscopy to monitor inhibitor–protein interactions. However, predicting the binding mode of a fluorinated ligand from a chemical shift (or vice versa) has been challenging due to the high electron density of the fluorine atom. Nonetheless, reliable 19F chemical-shift predictions to deduce ligand-binding modes hold great potential for in silico drug design. Herein, we present a systematic QM/MM study to predict the 19F NMR chemical shifts of a covalently bound fluorinated inhibitor to the essential oxidoreductase tryparedoxin (Tpx) from African trypanosomes, the causative agent of African sleeping sickness. We include many protein–inhibitor conformations as well as monomeric and dimeric inhibitor–protein complexes, thus rendering it the largest computational study on chemical shifts of 19F nuclei in a biological context to date. Our predicted shifts agree well with those obtained experimentally and pave the way for future work in this area. 相似文献
9.
Sisourat N Sann H Kryzhevoi NV Kolorenč P Havermeier T Sturm F Jahnke T Kim HK Dörner R Cederbaum LS 《Physical review letters》2010,105(17):173401
The interatomic electronic decay after inner-valence ionization of a neon atom by a single photon in a neon-helium dimer is investigated. The excited neon atom relaxes via interatomic Coulombic decay and the excess energy is transferred to the helium atom and ionizes it. We show that the decay process is only possible if the dimer's bond stretches up to 6.2 ?, i.e., to more than twice the equilibrium interatomic distance of the neutral dimer. Thus, it is demonstrated that the electronic decay, taking place at such long distances, is driven by the nuclear motion. 相似文献
10.
Cover Picture: Absolute Configuration from Different Multifragmentation Pathways in Light‐Induced Coulomb Explosion Imaging (ChemPhysChem 16/2016) 下载免费PDF全文
Dr. Martin Pitzer Gregor Kastirke Dr. Maksim Kunitski Dr. Till Jahnke Dr. Tobias Bauer Christoph Goihl Florian Trinter Carl Schober Kevin Henrichs Jasper Becht Stefan Zeller Helena Gassert Markus Waitz Andreas Kuhlins Hendrik Sann Felix Sturm Florian Wiegandt Dr. Robert Wallauer Dr. Lothar Ph. H. Schmidt Allan S. Johnson Manuel Mazenauer Benjamin Spenger Sabrina Marquardt Sebastian Marquardt Prof. Dr. Horst Schmidt‐Böcking Prof. Dr. Jürgen Stohner Prof. Dr. Reinhard Dörner Dr. Markus Schöffler Prof. Dr. Robert Berger 《Chemphyschem》2016,17(16):2448-2448