Additive Hermitian idempotent preservers between operator algebras

Let L be an additive map between (real or complex) matrix algebras sending $n\times n$ Hermitian idempotent matrices to $m\times m$ Hermitian idempotent matrices. We show that there are nonnegative integers $p,q$ with $n(p+q)=r\le m$ and an $m\times m$ unitary matrix U such that$L(A)=U[(I_p?A)\oplus (I_q?A^t)\oplus 0_{m?r}]U^{?},\text{for any}n\times n\text{Hermitian}A\text{with rational trace}.$ We also extend this result to the (complex) von Neumann algebra setting, and provide a supplement to the Dye-Bunce-Wright Theorem asserting that every additive map of Hermitian idempotents extends to a Jordan ?-homomorphism.     

Low-cost automated capillary electrophoresis instrument assembled from commercially available parts

A CE instrument that can be assembled from commercially available components with minimal construction effort is described. Except for the electronic control circuitry no specially made parts are required. It is based on a flexible design of microfluidic, electropneumatic, and electronic sections and different configurations can easily be implemented. Automated injection into the capillary is performed hydrodynamically by the application of a pressure for a controlled length of time. The performance of the device was tested with a contactless conductivity detector by separating different metal ions. In addition, nine metal cations related to the quality of honey were separated in 2.3 min and four honey samples were analysed quantitatively to demonstrate the applicability of the method.     

Supramolecular Tuning Enables Selective Oxygen Reduction Catalyzed by Cobalt Porphyrins for Direct Electrosynthesis of Hydrogen Peroxide

We report a supramolecular strategy for promoting the selective reduction of O₂ for direct electrosynthesis of H₂O₂. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H₂O₂ from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H₂O₂ and H₂O. Bimolecular pathways have been implicated in facilitating H₂O formation, therefore, we attribute this high H₂O₂ selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications.     

Validating additive correction schemes against gradient-based extrapolations

The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs () routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes.     

Graphs are (1,Δ+1)-choosable

A graph $G$ is $(k,k^{\prime })$-choosable if the following holds: For any list assignment $L$ which assigns to each vertex $v$ a set $L\left(v\right)$ of $k$ real numbers, and assigns to each edge $e$ a set $L\left(e\right)$ of $k^{\prime }$ real numbers, there is a total weighting $?:V\left(G\right)\cup E\left(G\right)\to R$ such that $?\left(z\right)\in L\left(z\right)$ for $z\in V\cup E$, and ${\sum }_{e\in E\left(u\right)}?\left(e\right)+?\left(u\right)\ne {\sum }_{e\in E\left(v\right)}?\left(e\right)+?\left(v\right)$ for every edge $uv$. This paper proves that if $G$ is a connected graph of maximum degree $\Delta \ge 2$, then $G$ is $(1,\Delta +1)$-choosable.     

Local force titration of wood surfaces by chemical force microscopy

Cellulose - Chemical force microcopy, a variation of atomic force microscopy, opened the door to visualize chemical nano-properties of various materials in their natural state. The key function of...     

Solid-State NMR Spectroscopy: A Powerful Technique to Directly Study Small Gas Molecules Adsorbed in Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have shown great potential in gas separation and storage, and the design of MOFs for these purposes is an on-going field of research. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a valuable technique for characterizing these functional materials. It can provide a wide range of structural and motional insights that are complementary to and/or difficult to access with alternative methods. In this Concept article, the recent advances made in SSNMR investigations of small gas molecules (i.e., carbon dioxide, carbon monoxide, hydrogen gas and light hydrocarbons) adsorbed in MOFs are discussed. These studies demonstrate the breadth of information that can be obtained by SSNMR spectroscopy, such as the number and location of guest adsorption sites, host–guest binding strengths and guest mobility. The knowledge acquired from these experiments yields a powerful tool for progress in MOF development.