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61.
Venkatraman S Anand VG PrabhuRaja V Rath H Sankar J Chandrashekar TK Teng W Senge KR 《Chemical communications (Cambridge, England)》2002,(16):1660-1661
First successful syntheses and structural characterization of new core modified meso aryl azuliporphyrins by a simple [3 + 1] methodology are reported. 相似文献
62.
Zhenpin Lu Henrik Quanz Julia Ruhl Georg Albrecht Christian Logemann Derck Schlettwein Peter R. Schreiner Hermann A. Wegner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4303-4307
We present a new concept to control the conformations of molecules in the excited state through harvesting negative hyperconjugation. The strategy was realized with the 2,3,1,4‐benzodiazadiborinane scaffold, which was prepared by a new synthetic procedure. Photochemical studies identified dual light emission, which was assigned to well‐defined conformers. The emission at longer wavelength can be switched off by restricting the rotational degrees of freedom in the solid state as well as by controlling the energy levels of the excited states through adjusting the solvent polarity. 相似文献
63.
64.
Kristina O. Kvashnina Anna Yu. Romanchuk Ivan Pidchenko Lucia Amidani Evgeny Gerber Alexander Trigub Andre Rossberg Stephan Weiss Karin Popa Olaf Walter Roberto Caciuffo Andreas C. Scheinost Sergei M. Butorin Stepan N. Kalmykov 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):18044-18044
65.
A method for the extraction, transfer and desorption of anions and cations under controlled potential conditions employing a new integrated three-electrode device is described. The device, containing working, reference and counter electrodes, was prepared from tubes that could be moved vertically with respect to each other. In this way, a small amount of solvent, held by capillary force, remained between the electrodes when the device was lifted out of a solution after an extraction. This design allowed the potential control to be maintained at all times. With the new integrated device, it was possible to perform potential controlled desorption into vials containing as little as 200 microl of solution. The required ion exchange capacity was obtained by electrodeposition of a polypyrrole coating on the surface of the glassy carbon working electrode. Solid-phase microextractions of several cations or anions were performed simultaneously under potentiostatic control by doping the polypyrrole coating with different anions such as perchlorate and p-toluenesulfonate. The efficiency of the extractions, which could be altered by varying the potential of the working electrode, could be increased by 150 to 200% compared to extractions using normal solid-phase microextraction conditions under open circuit conditions. A constant potential of +1.0 V and -0.5 V with respect to the silver pseudo reference electrode, was found to be well-suited for the extraction of samples containing ppm concentrations of anions (chloride, nitrite, bromide, nitrate, sulfate and phosphate) and cations (cadmium, cobalt and zinc), respectively. 相似文献
66.
Dr. David Scheerer Prof. Dr. Heng Chi Dr. Dan McElheny Prof. Dr. Timothy A. Keiderling Prof. Dr. Karin Hauser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(16):3524-3534
Site-specific isotopic labeling of molecules is a widely used approach in IR spectroscopy to resolve local contributions to vibrational modes. The induced frequency shift of the corresponding IR band depends on the substituted masses, as well as on hydrogen bonding and vibrational coupling. The impact of these different factors was analyzed with a designed three-stranded β-sheet peptide and by use of selected 13C isotope substitutions at multiple positions in the peptide backbone. Single-strand labels give rise to isotopically shifted bands at different frequencies, depending on the specific sites; this demonstrates sensitivity to the local environment. Cross-strand double- and triple-labeled peptides exhibited two resolved bands that could be uniquely assigned to specific residues, the equilibrium IR spectra of which indicated only weak local-mode coupling. Temperature-jump IR laser spectroscopy was applied to monitor structural dynamics and revealed an impressive enhancement of the isotope sensitivity to both local positions and coupling between them, relative to that of equilibrium FTIR spectroscopy. Site-specific relaxation rates were altered upon the introduction of additional cross-strand isotopes. Likewise, the rates for the global β-sheet dynamics were affected in a manner dependent on the distinct relaxation behavior of the labeled oscillator. This study reveals that isotope labels provide not only local structural probes, but rather sense the dynamic complexity of the molecular environment. 相似文献
67.
Nilsson SL Bylund D Jörntén-Karlsson M Petersson P Markides KE 《Electrophoresis》2004,25(13):2100-2107
A chemometrics approach has been used for evaluating the effect of four experimental parameters when coupling capillary electrophoresis (CE) to electrospray ionization-mass spectrometry (ESI-MS). Electrospray voltage, sheath-liquid flow rate, nebulizing gas flow rate, and spray needle position in respect to the MS orifice were varied according to a full factorial design. In addition to main effects, two interaction effects could be identified as significant when measuring the peak intensity of the analytes, from a sample mixture containing peptides and pharmaceuticals. The first interaction effects, between the nebulizing gas flow rate and the sheath-liquid flow rate, and the second interaction effect, between the nebulizing gas flow rate and the spray position, could further explain the impact that these variables have on the spray performance. The number of theoretical plates and the baseline noise were also measured. The sheath-liquid flow was found to significantly affect the separation efficiency, while the noise level mainly was controlled by the nebulizing gas flow. The same factorial design was also used for a CE capillary with lower internal diameter (ID) and the effects of the same variables were compared on those capillaries using equal injection volume for both capillaries. Similar trends were obtained in both capillaries but capillary ID was shown to be a significant variable when evaluating both capillaries in a single model. It was found that a capillary with 25 microm ID provided improved CE-MS performance over than corresponding 50 microm ID capillary. Enhanced sensitivity was obtained using the narrow-bore capillary, and at lower sheath-liquid flow rate the 25 microm ID capillary also gave rise to more efficient peaks. 相似文献
68.
Arafat A Schroën K de Smet LC Sudhölter EJ Zuilhof H 《Journal of the American Chemical Society》2004,126(28):8600-8601
This communication presents the first functionalization of a hydrogen-terminated silicon-rich silicon nitride (Si3Nx) surface with a well-defined, covalently attached organic monolayer. Properties of the resulting monolayers are monitored by measurement of the static water contact angle, X-ray photoelectron spectroscopy (XPS), and infrared reflection absorption spectroscopy (IRRAS). Further functionalization was performed by reaction of Si3Nx with a trifluoroethanol ester alkene (CH2=CH-(CH2)8CO2CH2CF3) followed by basic hydrolysis to afford the corresponding carboxylic acid-terminated monolayer with hydrophilic properties. These results show that Si3Nx can be functionalized with a tailor-made organic monolayer, has highly tunable wetting properties, and displays significant potential for further functionalization. 相似文献
69.
70.
Jakubczyk D Barth C Kubas A Anastassacos F Koelsch P Fink K Schepers U Brenner-Weiß G Bräse S 《Analytical and bioanalytical chemistry》2012,403(2):473-482
N-Acyl-l-homoserine lactones (AHLs) are synthesized by Gram-negative bacteria. These quorum-sensing molecules play an important role
in the context of bacterial infection and biofilm formation. They also allow communication between microorganisms and eukaryotic
cells (inter-kingdom signalling). However, very little is known about the entire mechanism of those interactions. Precise
structural studies are required to analyse the different AHL isomers as only one form is biologically most active. Theoretical
studies combined with experimental infrared and Raman spectroscopic data are therefore undertaken to characterise the obtained
compounds. To mimic interactions between AHL and cell membranes, we studied the insertion of AHL in supported lipid bilayers,
using vibrational sum-frequency-generation spectroscopy. Deuterium-labelled AHLs were thus synthesized. Starting from readily
available deuterated fatty acids, a two-step procedure towards deuterated N-acyl-l-homoserine lactones with varying chain lengths is described. This included the acylation of Meldrum’s acid followed by amidation.
Additionally, the detailed analytical evaluation of the products is presented herein. 相似文献