Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity

We report the synthesis, structural characterization, and functionality of an open-framework hybrid that combines Ca2+ ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl) isophthalic acid (PiPhtA). Ca-PiPhtA-I is obtained by slow crystallization at ambient conditions from acidic (pH≈3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data.All connectivity modes of the “parent” Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca PiPhtA-I is 5.7 ×10−4 S·cm−1. It increases to 1.3 × 10−3 S·cm−1 upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10−3 S·cm−1, measured at 98% RH and T = 24 °C. Ea for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction.Proyecto nacional MAT2010-1517

Cost of Diapause on Life-History Traits Under Restricted Resources in Multivoltine Bruchid Acanthoscelides pallidipennis (Coleoptera: Bruchidae)

ABSTRACT The diapause generation of multivoltine insects requires additional energy reserves for diapause maintenance compared with the nondiapause generation. This requirement suggests that the cost of diapause has an effect on life-history traits. We investigated diapause costs in a multivoltine bruchid, Acanthoscelides pallidipennis Motschulsky (Coleoptera: Bruchidae). In the laboratory, lifehistory traits of A. pallidipennis were compared between nondiapause and diapause treatments. Fecundity and body size of adults were reduced in the diapause treatment compared with the nondiapause treatment. Larger females laid more eggs than smaller females in both treatments. The reduced fecundity of diapause females likely was caused by their reduced body size as a limiting factor. Our Þndings support the hypothesis that the cost of diapause results in a difference in life-history traits between nondiapause and diapause generations