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Little Live Pets 28847 Cozy DOZYS, Multi-Colour

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N. Eshuis, N. Hermkens, B. J. van Weerdenburg, M. C. Feiters, F. P. Rutjes, S. S. Wijmenga and M. Tessari, J. Am. Chem. Soc., 2014, 136, 2695 CrossRef CAS PubMed .

R. Pievo, C. Casati, P. Franchi, E. Mezzina, M. Bennati and M. Lucarini, ChemPhysChem, 2012, 13, 2659–2661 CrossRef CAS PubMed. Z. D. Pardo, G. L. Olsen, M. E. Fernandez-Valle, L. Frydman, R. Martinez-Alvarez and A. Herrera, J. Am. Chem. Soc., 2012, 134, 2706 CrossRef CAS PubMed . Taking this data in combination, the absence of an encapsulation process would have been unlikely. Nevertheless, conclusive proof was found with 2D DOSY spectroscopy which recorded the diffusion coefficients of glutaric acid and of the hexameric cage, isolated and also when combined in solution. As expected, the free glutaric acid diffuses faster ( D = 1.05 × 10 −5 cm 2 s −1) than the hexameric cage ( D = 0.24 × 10 −5 cm 2 s −1) due to its smaller size. By contrast, when measuring the encapsulated guest, the diffusion coefficient is significantly reduced ( D = 0.24 × 10 −5 cm 2 s −1), showing approximately the same value as the cage. Therefore, it was proven that the complex diffuses through solution as one supramolecular entity. Study example B This example considers non-covalently bound oligomers, another relevant molecular class in the field of supramolecular chemistry. 31 In particular, a calix[5]arene, consisting of four methylene-bridged phenyl-ether units and a single 12-aminododecyl substituent (structure 3 in Fig. 2C), was synthesised and studied with 1H-NMR and DOSY NMR in the absence and the presence of acids. The aim of this study was to investigate possible oligomerisation of the calix[5]arene induced by the protonation of the amino-group and its subsequent inclusion in another calix[5]arene molecule ( Fig. 2C top). This was suggested by the 1H-NMR spectrum of 3 with HCl, showing different peak sets of either the unthreaded groups at the ends of the oligomer or the threaded core units. D. Li, I. Keresztes, R. Hopson and P. G. Williard, Acc. Chem. Res., 2009, 42, 270 CrossRef CAS PubMed . R. Novoa-Carballal, E. Fernandez-Megia, C. Jimenez and R. Riguera, Nat. Prod. Rep., 2011, 28, 78 RSC .E. L. Gavey and J. M. Rawson, Comprehensive Supramolecular Chemistry II, Elsevier, 2nd edn, 2017, vol. 2, pp. 151–180 Search PubMed. A. Comotti, S. Bracco and P. Sozzani, Comprehensive Supramolecular Chemistry II, Elsevier, 2nd edn, 2017, vol. 2, pp. 75–99 Search PubMed. J. Marchand, E. Martineau, Y. Guitton, B. Le Bizec, G. Dervilly-Pinel and P. Giraudeau, Metabolomics, 2018, 14, 60 CrossRef PubMed .

E. Martineau, S. Akoka, R. Boisseau, B. Delanoue and P. Giraudeau, Anal. Chem., 2013, 85, 4777 CrossRef CAS PubMed . E. G. Bagryanskaya and S. R. A. Marque, Electron Paramagn. Reson., 2017, 25, 180–235 Search PubMed. When comparing the 1H-NMR spectra of resorcin[4]arene 1 with and without glutaric acid 2, different guest signals of 2 are found upfield-shifted. Additionally, integration yielded a host–guest stoichiometry of around 1 : 1, indicating six enclosed guest molecules. The extend of the encapsulation process was shown to increase with higher concentrations of glutaric acid and longer reaction times, which was readily observable due to the high sensitivity of the host aryl peak at 6.1 ppm. This supported the proposed encapsulation mechanism and additionally indicated a slowly occurring exchange mechanism at the expense of solvent molecules, in this case chloroform. Fig. 2 500 MHz (a) 1D 1H spectrum, (b) 1H pure shift spectrum recorded using the unmodified Zangger–Sterk pulse sequence, (c) vertical expansion of the spectrum (b and d) 1H pure shift spectrum acquired with the pulse sequence modified to remove sidebands, for a mixture containing rosuvastatin (1) and 2.8% of its precursor BEM (2). (e) 1D 1H spectrum of BEM. Spectra c and d were acquired in approximately 9 h with an sw1 of 39.0625 Hz and 16 chunks using an RSNOB spatially selective spin inversion element with a peak RF amplitude of 47 Hz. Reproduced from ref. 25 with permission from the Royal Society of Chemistry.

M. Urbanczyk, A. Shchukina, D. Golowicz and K. Kazimierczuk, Magn. Reson. Chem., 2019, 57, 4 CrossRef CAS PubMed . P. A. Faull, K. E. Korkeila, J. M. Kalapothakis, A. Gray, B. J. McCullough and P. E. Barran, Int. J. Mass Spectrom., 2009, 283, 140–148 CrossRef CAS. G. Liu, M. Levien, N. Karschin, G. Parigi, C. Luchinat and M. Bennati, Nat. Chem., 2017, 9, 676 CrossRef CAS PubMed . newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}}}\) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash{#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

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