The high resolution mass spectrum of 2-acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-α-D-glucopyranose

2-Acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-α-D-glucopyranose (I), and its analogs specifically mono (trideuterioacetylated) at O-1 (III), at N-2 (II), at O-4 (IV) and at O-6 (V), have been examined by high-resolution mass spectrometry. From the elemental compositions of the fragment ions, the mass-number shifts resulting from deuterium incorporation and analysis of metastable transitions, it has been possible to specify in detail the fragmentation pathways undergone by this molecule. The principal degradations of I proceed by initial rapid decomposition of the molecular ion (whose intensity is insignificant) by three routes: (i) by loss of the C-1 acetoxyl group as a radical to give the glycosyl cation (a), (ii) by loss of the 1-acetyl group as a radical to give an acyclic ion m/e 346 (b) and (iii) by loss of a C-6 fragment and acetic acid derived from the 3-acetate group to give m/e 241 (c).     

Tuning Aqueous Supramolecular Polymerization by an Acid-Responsive Conformational Switch

Besides their widespread use in coordination chemistry, 2,2’-bipyridines are known for their ability to undergo cis–trans conformational changes in response to metal ions and acids, which has been primarily investigated at the molecular level. However, the exploitation of such conformational switching in self-assembly has remained unexplored. In this work, the use of 2,2’-bipyridines as acid-responsive conformational switches to tune supramolecular polymerization processes has been demonstrated. To achieve this goal, we have designed a bipyridine-based linear bolaamphiphile, 1 , that forms ordered supramolecular polymers in aqueous media through cooperative aromatic and hydrophobic interactions. Interestingly, addition of acid (TFA) induces the monoprotonation of the 2,2’-bipyridine moiety, leading to a switch in the molecular conformation from a linear (trans) to a V-shaped (cis) state. This increase in molecular distortion along with electrostatic repulsions of the positively charged bipyridine-H⁺ units attenuate the aggregation tendency and induce a transformation from long fibers to shorter thinner fibers. Our findings may contribute to opening up new directions in molecular switches and stimuli-responsive supramolecular materials.     

Characterisation of sol-gel prepared (HfO2)x(SiO2)1-x (x=0.1, 0.2 and 0.4) by 1H, 13C, 17 O and 29Si MAS NMR, FTIR and TGA

The HfO2-SiO2 system is attracting interest as a possible new dielectric material in semiconductor devices. Knowledge of the location of hafnium within the silica network and the effect hafnium has on the structure will be central to the successful use of this material system in this application. Here, sol-gel techniques have been used to manufacture (HfO2)x(SiO2)1-x samples (x=0.1, 0.2 and 0.4, each heat treated at 250, 500 and 750 degrees C) and these have been characterised by magic angle spinning (MAS) NMR (1H, 13C, 17 O, 29Si), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis. 29Si MAS NMR showed that increasing the hafnia content decreases the connectivity of the silicate network, i.e. increases the range of differently connected SiO4 (Qn) units with more having increased numbers of non-bridging oxygens (i.e. lower n). FTIR and 17 O MAS NMR showed unequivocally that the x=0.4 sample phase-separated at higher temperatures, while in the x=0.1 sample the hafnium was homogeneously mixed into the SiO2 phase without any phase separation.     

A 3D Shape Measurement Technique that Makes Use of a Printed Line Pattern

The in-house validation of finite element models for bird strike events is currently carried out by means of experimental tests on flat plates. High displacement speeds in these experiments require a low exposure time of the high-speed camera (up to 1/50,000 s). In order to acquire images of sufficient quality, a special, high-intensity light source has to be used, which does not always turn out to be possible. Therefore, the regions with high displacement speeds often result in blurry images. In such cases, a printed line pattern to estimate the shape of the plate during the test, offers major advantages over a speckle pattern in terms of the reconstruction and optimization of the blurry regions. In this article, a stereo vision technique is presented that was developed to reconstructs 3D shape maps using images of impacted plates with printed line patterns. It is shown that two cameras are necessary to calculate accurate shape maps in case of large deflections. The resulting shapes can be used for the validation of numerical simulations.