Interaction of Hydrogen with MOF-5

Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals.     

More corrections to the sixth-order anomalous magnetic moment of the muon

The contribution to the sixth-order muon anomaly from second-order electron vacuum polarization is determined analytically to orderm _e/m _μ. The result, including the contributions from graphs containing proper and improper fourth-order electron vacuum polarization subgraphs, is $$\begin{gathered} \left( {\frac{\alpha }{\pi }} \right)^3 \left\{ {\frac{2}{9}\log ^2 } \right.\frac{{m_\mu }}{{m_e }} + \left[ {\frac{{31}}{{27}}} \right. + \frac{{\pi ^2 }}{9} - \frac{2}{3}\pi ^2 \log 2 \hfill \\ \left. { + \zeta \left( 3 \right)} \right]\log \frac{{m_\mu }}{{m_e }} + \left[ {\frac{{1075}}{{216}}} \right. - \frac{{25}}{{18}}\pi ^2 + \frac{{5\pi ^2 }}{3}\log 2 \hfill \\ \left. { - 3\zeta \left( 3 \right) + \frac{{11}}{{216}}\pi ^4 - \frac{2}{9}\pi ^2 \log ^2 2 - \frac{1}{9}log^4 2 - \frac{8}{3}a_4 } \right] \hfill \\ + \left[ {\frac{{3199}}{{1080}}\pi ^2 - \frac{{16}}{9}\pi ^2 \log 2 - \frac{{13}}{8}\pi ^3 } \right]\left. {\frac{{m_e }}{{m_\mu }}} \right\} \hfill \\ \end{gathered} $$ . To obtain the total sixth-order contribution toa _μ?a _e, one must add the light-by-light contribution to the above expression.     

The biotin-streptavidin interaction can be reversibly broken using water at elevated temperatures

The biotin-streptavidin system is the strongest noncovalent biological interaction known, having a dissociation constant, K(d), in the order of 4x10(-14) M. The strength and specificity of the interaction has led it to be one of the most widely used affinity pairs in molecular, immunological, and cellular assays. However, it has previously been impossible to re-use any streptavidin solid support, since the conditions needed to break the interaction with biotin has led to the denaturation of the streptavidin. Here, we show that a short incubation in nonionic aqueous solutions at temperatures above 70 degrees C can efficiently break the interaction without denaturing the streptavidin tetramer. Both biotin and the streptavidin remain active after dissociation and both molecules can therefore be re-used. The efficiency of the regeneration allowed solid supports with streptavidin to be used many times, here exemplified with the multiple re-use of streptavidin beads used for sample preparation prior to automated DNA sequencing. The results suggest that streptavidin regeneration can be introduced as an improvement in existing methods and assays based on the streptavidin system as well as emerging solid phase applications in fields, such as microfluidics and nanotechnology.     

A Geometric Integration Approach to Nonsmooth,Nonconvex Optimisation

The optimisation of nonsmooth, nonconvex functions without access to gradients is a particularly challenging problem that is frequently encountered, for example in model parameter optimisation problems. Bilevel optimisation of parameters is a standard setting in areas such as variational regularisation problems and supervised machine learning. We present efficient and robust derivative-free methods called randomised Itoh–Abe methods. These are generalisations of the Itoh–Abe discrete gradient method, a well-known scheme from geometric integration, which has previously only been considered in the smooth setting. We demonstrate that the method and its favourable energy dissipation properties are well defined in the nonsmooth setting. Furthermore, we prove that whenever the objective function is locally Lipschitz continuous, the iterates almost surely converge to a connected set of Clarke stationary points. We present an implementation of the methods, and apply it to various test problems. The numerical results indicate that the randomised Itoh–Abe methods can be superior to state-of-the-art derivative-free optimisation methods in solving nonsmooth problems while still remaining competitive in terms of efficiency.

     

Synthesis of click‐reactive HPMA copolymers using RAFT polymerization for drug delivery applications

This study describes a versatile strategy combining reversible addition fragmentation transfer (RAFT) polymerization and click chemistry to synthesize well‐defined, reactive copolymers of N‐(2‐hydroxypropyl)methacrylamide (HPMA) for drug delivery applications. A novel azide containing monomer N‐(3‐azidopropyl)methacrylamide (AzMA) was synthesized and copolymerized with HPMA using RAFT polymerization to provide p(HPMA‐co‐AzMA) copolymers with high control of molecular weight (～10–54 kDa) and polydispersity (≤1.06). The utility of the side‐chain azide functionality by Cu(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) was demonstrated by efficient conjugation (up to 92%) of phosphocholine, a near infrared dye, and poly(ethylene glycol) (PEG) with different substitution degrees, either alone or in combination. This study introduces a novel and versatile method to synthesize well‐defined click‐reactive HPMA copolymers for preparing a panel of bioconjugates with different functionalities needed to systemically evaluate and tune the biological performance of polymer‐based drug delivery. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5091–5099     

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Efficient and regioselective N-1 alkylation of 4-chloropyrazolo[3,4-d]pyrimidine

Efficient and N-1 selective alkylation of 4-chloropyrazolo[3,4-d]pyrimidine can be achieved when the heterocycle is reacted with alcohols under Mitsunobu conditions. The 1-alkyl-pyrazolo[3,4-d]pyrimidines formed can be functionalized further according to known methods, to give a variety of 1,4-disubstituted pyrazolo[3,4-d]pyrimidines. The first example of a palladium-catalyzed coupling reaction on a 4-halopyrazolo[3,4-d]pyrimidine is described.