Reaction of starch 1 dissolved in dimethyl sulfoxide (DMSO) with bulky thexyldimethylchlorosilane (TDSCl) in the presence of pyridine leads to regioselectively functionalized silyl ethers with a degree of substitution (DS) up to 1.8. The control of the DSSi, of the regioselectivity, and of the reaction pathway is described in detail. The reaction proceeds homogeneously up to DSSi of 0.6. With ongoing silylation the polymers form a separate phase incorporating the silylating agent to form TDS‐starches with DSSi values higher than 1.0. After peracetylation of the silyl starches, the substitution pattern has been characterized not only in the anhydroglucose repeating units (AGU) but also in the non‐reducing terminal end groups (TEG) by means of two‐dimensional 1H NMR techniques. Up to DSSi 1.0, a very high regioselective functionalization of the primary 6‐OH groups in the AGU as well as in the TEG is detectable. With increasing silylation (DSSi > 1.0), the subsequent silylation takes place at the 2‐OH groups of the AGU and at the 3‐OH groups of the TEG. These results are compared with our own investigations on the silylation of starch in the reaction system N‐methylpyrrolidone (NMP)/ammonia and on the silylation of cellulose in N,N‐dimethylacetamide (DMA)/LiCl/pyridine solution. 相似文献
The tip-sample distance (z) dependence of tip-enhanced Raman scattering (TERS) has been investigated. The intensities of both, the Raman lines and the broad TERS background, exhibit strong decays with increasing z, which are nearly complete within 10 nm withdrawal of the STM tip in z direction. Interestingly, the maximum of the broad Lorentzian-shaped TER background is substantially blue shifted in energy with z. This effect is ascribed to a corresponding blue shift of the energies of localized plasmon modes upon tip retraction. Both experimental results fit very well data of a simple theoretical near-field model. 相似文献
Amino acid-derived thioamides are prepared and evaluated as ligands in the rhodium-catalyzed asymmetric transfer hydrogenation of ketones in 2-propanol. It is found that increasing the steric bulk at the C-terminus of the ligand had a positive impact on both activity and selectivity in the reduction reaction. In order to find the optimum catalyst, a study is performed on a series of thioamide ligands having substituents of varying size. 相似文献
This instrument combines the capabilities of ion/ion reactions with ion mobility (IM) and time-of-flight (TOF) measurements for conformation studies and top-down analysis of large biomolecules. Ubiquitin ions from either of two electrospray ionization (ESI) sources are stored in a three dimensional (3D) ion trap (IT) and reacted with negative ions from atmospheric sampling glow discharge ionization (ASGDI). The proton transfer reaction products are then separated by IM and analyzed via a TOF mass analyzer. In this way, ubiquitin +7 ions are converted to lower charge states down to +1; the ions in lower charge states tend to be in compact conformations with cross sections down to ~880 Å2. The duration and magnitude of the ion ejection pulse on the IT exit and the entrance voltage on the IM drift tube can affect the measured distribution of conformers for ubiquitin +7 and +6. Alternatively, protein ions are fragmented by collision-induced dissociation (CID) in the IT, followed by ion/ion reactions to reduce the charge states of the CID product ions, thus simplifying assignment of charge states and fragments using the mobility-resolved tandem mass spectrum. Instrument characteristics and the use of a new ion trap controller and software modifications to control the entire instrument are described. 相似文献
What's the matter? The laboratory Raman spectra for carbonic acid (H2CO3), both for the β‐polymorph and its amorphous state, are required to detect carbonic acid on the surface of the pole caps of Mars in 2009, when the Mars Microbeam Raman Spectrometer lands on the planet. The picture shows a martian crater with ice of unknown composition, possibly containing carbonic acid (image adapted from DLR, with permission from ESA, DLR, and FU Berlin –‐G. Neukum).