Water-induced formation of an alkali-ion dimer in cryptomelane nanorods

Tunneled metal oxides such as α-Mn₈O₁₆ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K⁺ ions (which act as structure-stabilizing dopants) and H₂O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K⁺-doped α-Mn₈O₁₆ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H₂O displaces K⁺ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K²⁺ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li⁺/Na⁺ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.

Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K²⁺) in the tunnels of hollandite.     

Optimal pricing for a heterogeneous portfolio for a given risk factor and convex distance measure

Consider a portfolio containing heterogeneous risks. The premiums of the policyholders might not cover the amount of the payments which an insurance company pays the policyholders. When setting the premium, this risk has to be taken into consideration. On the other hand the premium that the insured pays has to be fair. This fairness is measured by a function of the difference between the risk and the premium paid—we call this function a distance function. For a given small probability of insolvency, we find the premium for each class, such that the distance function is minimized. Next we formulate and solve the dual problem, which is minimizing the insolvency probability under the constraint that the distance function does not exceed a given level. This paper generalizes a previous paper [Zaks, Y., Frostig, E., Levikson, B., 2006. Optimal pricing of a heterogeneous portfolio for a given risk level. Astin Bull. 36 (1), 161–185] where only a square distance function was considered.     

Application of tris-allyl-DOTA in the preparation of DOTA-peptide conjugates

The synthesis of tris-allyl-DOTA starting from cyclen and its application in the preparation of DOTA-peptide conjugates is reported. Clinically important conjugates such as DOTA-Tyr³-octreotide (DOTA-TOC), DOTA-Tyr³-octreotate (DOTA-TATE) as well as a DOTA-RGD peptide were synthesized in high yields with Fmoc solid phase peptide synthesis. The final, extremely reliable de-allylation was achieved on solid phase by different methods identifying morpholine/Pd(0) as the most suitable one obtaining all DOTA peptide conjugates in high yields. All DOTA-peptides were purified by reversed phase HPLC and structural identity was proved using MALDI-TOF mass spectrometry.     

Cellulose-polyamide 66 blends. Part II: Mechanical behavior

Blends of the natural polymer cellulose with a synthetic polymer, polyamide 66, are studied in order to determine if the expected strong interaction between them, due to hydrogen bonds, could improve their mechanical properties such as strength and elongation at break. In a previous work {Part I, J. Polym. Sci. Polym. Phys., 32 , 1437 (1994)}, the preparation technique and the characterization of cellulose-polyamide 66 (PA66) blends were described in detail. Several samples in the composition range between 0 to 70 wt % of PA66 were carefully dried and examined using dynamic mechanical and tensile tests. Based on previous work a new percolation model has been developed. It takes both linear and nonlinear mechanical behaviors into account and allows for the effect of adhesion between material domains. From comparison between experimental and predicted data, it is concluded that a partial miscibility between the amorphous phases of cellulose and PA66 exists and is responsible for a strong adhesion at their interface. Solid-state ¹³C nuclear magnetic resonance has also been used to study these samples and supports the existence of strong interactions between both homopolymers. © 1995 John Wiley & Sons, Inc.     

Correct structures of Diels-Alder adducts from the natural cyclolignan thuriferic acid and its 8-epimer

A detailed analysis of one- and two-dimensional ¹H and ¹³C NMR data for the endo and the exo adducts, obtained by Diels-Alder reaction of thuriferic and epithuriferic acids with cyclopentadiene is described. The unequivocal spectral data assignment of the endo and exo structures was complemented with molecular modelling studies and confirmed through X-ray diffraction studies.