Diverse motifs of mannoside clustering on a beta-cyclodextrin core

[reaction: see text] A new method for the synthesis of beta-cyclodextrin-based cluster mannosides by application of the Sonogashira cross-coupling reaction is described. The method allows for the persubstitution of the beta-cyclodextrin at either 2- and 3-positions to give two types of heptavalent clusters, at both 2- and 6-positions to give clusters with 14 mannopyranoside units and at 2-, 3-, and 6-positions to obtain clusters with 21 mannopyranoside ligands.     

A quantal Tolman temperature

The conventional Tolman temperature based on the assumption of the traceless condition of energy-momentum tensor for matter fields is infinite at the horizon if Hawking radiation is involved. However, we note that the temperature associated with Hawking radiation is of relevance to the trace anomaly, which means that the traceless condition should be released. So, a trace anomaly-induced Stefan-Boltzmann law is newly derived by employing the first law of thermodynamics and the property of the temperature independence of the trace anomaly. Then, the Tolman temperature is quantum-mechanically generalized according to the anomaly-induced Stefan-Boltzmann law. In an exactly soluble model, we show that the Tolman factor does not appear in the generalized Tolman temperature which is eventually finite everywhere, in particular, vanishing at the horizon. It turns out that the equivalence principle survives at the horizon with the help of the quantum principle, and some puzzles related to the Tolman temperature are also resolved.     

Enzymatic Desymmetrising Redox Reactions for the Asymmetric Synthesis of Biaryl Atropisomers

Atropisomeric biaryls carrying ortho‐hydroxymethyl and formyl groups were made enantioselectively by desymmetrisation of dialdehyde or diol substrates. The oxidation of the symmetrical diol substrates was achieved using a variant of galactose oxidase (GOase), and the reduction of the dialdehydes using a panel of ketoreductases. Either M or P enantiomers of the products could be formed, with absolute configurations assigned by time‐dependent DFT calculations of circular dichroism spectra. The differing selectivities observed with different biaryl structures offer an insight into the detailed structure of the active site of the GOase enzyme.     

On the Structure and Chiral Aggregation of Liquid Crystalline Star-Shaped Triazines H-Bonded to Benzoic Acids

The ability of a star-shaped tris(triazolyl)triazine derivative to hierarchically build supramolecular chiral columnar organizations through the formation of H-bonded complexes with benzoic acids was studied from a theoretical and experimental point of view. The combined study has been done at three different levels including the study of the structure of the triazine core, the association with benzoic acids in stoichiometry 1:3, and the assembly of 1:3 complexes in helical aggregates. Although the star-shaped triazine core crystallizes in a non-C₃ conformation, the C₃-symmetric conformation is theoretically predicted to be more stable and gives rise to a favorable C₃ supramolecular 1:3 complex upon the interaction with three benzoic acids in their voids. In addition, calculations at different levels (DFT, PM7, and MM3) for the 1:3 host-guest complex predict the formation of large stable columnar helical aggregates stabilized by the compact packing of the interstitial acids by π–π and CH⋅⋅⋅π interactions. The acids restrict the movement of the the star-shaped triazine cores along the stacking axis causing a template effect in the self-assembly of the complex. Theoretical predictions correlate with experimental results, since the interaction with achiral or chiral 3,4,5-(4-alkoxybenzyloxy)benzoic acids gives rise to supramolecular complexes that organize in bulk hexagonal columnar mesophases stable at room temperature with intracolumnar order. The existence of supramolecular chirality in the mesophase was determined for complexes formed by acids derived from (S)-2-octanol. Chiral aggregation was also evidenced for complexes formed in dodecane.     

Disjoint Hamilton cycles in the random geometric graph

We consider the standard random geometric graph process in which n vertices are placed at random on the unit square and edges are sequentially added in increasing order of edge‐length. For fixed k?1, weprove that the first edge in the process that creates a k‐connected graph coincides a.a.s. with the first edge that causes the graph to contain k/2 pairwise edge‐disjoint Hamilton cycles (for even k), or (k?1)/2 Hamilton cycles plus one perfect matching, all of them pairwise edge‐disjoint (for odd k). This proves and extends a conjecture of Krivelevich and M ler. In the special case when k = 2, our result says that the first edge that makes the random geometric graph Hamiltonian is a.a.s. exactly the same one that gives 2‐connectivity, which answers a question of Penrose. (This result appeared in three independent preprints, one of which was a precursor to this article.) We prove our results with lengths measured using the ?_p norm for any p>1, and we also extend our result to higher dimensions. © 2011 Wiley Periodicals, Inc. J Graph Theory 68:299‐322, 2011     

Phase transition of quantum-corrected Schwarzschild black hole

We study the thermodynamic phase transition of a quantum-corrected Schwarzschild black hole. The modified metric affects the critical temperature which is slightly less than the conventional one. The space without black holes is not the hot flat space but the hot curved space due to vacuum fluctuations so that there appears a type of Gross–Perry–Yaffe phase transition even for the very small size of black hole, which is impossible for the thermodynamics of the conventional Schwarzschild black hole. We discuss physical consequences of the new phase transition in this framework.     

Magnetic Hyperthermia Enhancement in Iron-based Materials Driven by Carbon Support Interactions

Magnetic hyperthermia (MH) shows great potential in clinical applications because of its very localized action and minimal side effects. Because of their high saturation magnetization values, reduced forms of iron are promising candidates for MH. However, they must be protected in order to overcome their toxicity and instability (i. e., oxidation) under biological conditions. In this work, a novel methodology for the protection of iron nanoparticles through confinement within graphitic carbon layers after thermal treatment of preformed nanoparticles supported on carbon is reported. We demonstrate that the size and composition of the nascent confined iron nanoparticles, as well as the thickness of their protective carbon layer can be controlled by selecting the nature of the carbon support. Our findings reveal that a higher nanoparticle–carbon interaction, mediated by the presence of oxygen-containing groups, induces the formation of small and well-protected α-Fe-based nanoparticles that exhibit promising results towards MH based on their enhanced specific absorption rate values.     

Effect of polyethyleneimine ion on the sorption of a reactive dye onto Leacril fabric: electrokinetic properties and surface free energy of the system

Data are presented on the kinetics, electrokinetics, and surface free energy in the process of adsorption of polyethyleneimine (PEI) as a pretreatment of Leacril, later dyed with the reactive dye Remazol Brilliant Blue R (RBBR). The electrokinetic potential of Leacril is negative, due probably to the presence of sulfonate and sulfate end-group onto Leacril fibers. The zeta potential of Leacril decreases in absolute value as a function of NaCl concentration in solution, probably because of compression of the electrical double layer. The zeta potential of Leacril as a function of the concentration of PEI in solution increases because of the adsorption of PEI ions through chemical reaction between the sulfonate end-groups of Leacril and the amine groups of PEI. The adsorption kinetics shows that an increase in the concentration of PEI, brings about an increase in the amount of RBBR adsorbed onto the fiber. This may be an indication of the chemical reaction between the reactive groups of the polyelectrolyte and dye molecules. The behavior of the surface free energy of the systems involved confirms these conclusions.     

Towards a reliable molecular mass determination of intact glycoproteins by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Different matrices and sample-matrix preparation procedures have been tested in order to study their influence on the matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra of intact glycoproteins, which present different degrees of glycosylation (human transferrin; bovine fetuin; bovine alpha(1)-acid-glycoprotein; recombinant human erythropoietin; and the novel erythropoiesis stimulating protein). Using sinapinic acid (SA) and the fast evaporation method, the studied glycoproteins became susceptible to fragmentation at any laser intensity, suggesting that this 'hot' matrix is unsuitable for a reliable molecular mass determination of glycosylated compounds. In contrast, 2,5-dihydroxybenzoic acid (DHB) and 6-aza-2-thiothymine (ATT), with an adequate sample-matrix preparation, provided improved results. Samples containing DHB after crystallization by vacuum drying demonstrated the best performance because the labile functional groups from the glycoforms were apparently fragmented to a lower extent. The average molecular masses obtained using this methodology were in all cases a better estimation than those values reported in the literature. The results were reproducible, and sensitivity was similar to that obtained with SA and the fast evaporation method. These excellent results suggest that this MALDI-TOF-MS methodology could be useful for an improved determination of the average molecular mass values of microheterogeneous compounds such as glycoproteins, glycosylated compounds or, in general, molecular mass values of molecules with similar labile functional groups.