Isotope variations in white-tailed kites from various habitats in California: possible limitations in assessing prey utilization and population dynamics

White-tailed kite (Elanus leucurus) populations in the 1930s were close to extirpation in the United States. But by the 1940s, an upward trend towards recovery was apparent and continued to their current stable population levels. These dramatic fluctuations in kite numbers may have been related to changes in rodent prey populations due to the conversion of native habitats to agriculture. To address this question, we evaluated the use of stable isotope analysis in determining if a shift in diet could be isotopically differentiated in current and historic kite populations. We first compared delta13C, delta15N, and delta34S values from present-day kite flight feathers and prey fur samples from four locations in California. The total ranges of isotope values for kite and their rodent prey were similar within each site. Carbon isotope values ranged from -27.1 to -22.2 per thousand in Arcata, -26.1 to -16.9 per thousand in Davis, -27.0 to -15.0 per thousand in Cosumnes, and -28.2 to -11.6 per thousand in Santa Barbara. Nitrogen isotope values ranged from 3.2 to 15.7 per thousand in Arcata, 2.8 to 12.7 per thousand in Davis, 4.0 to 15.7 per thousand in Cosumnes, and 1.7 to 20.0 per thousand in Santa Barbara. Sulfur isotope values ranged from -7.8 to 12.4 per thousand in Arcata, -1.1 to 9.2 per thousand in Davis, 0.7 to 10.9 per thousand in Cosumnes, and -8.6 to 15.6 per thousand in Santa Barbara. Carbon, nitrogen, and sulfur isotope values at each site reflect typical trophic enrichments due to physiological processes. At each site, delta13C and delta15N values reflected the influence of a predominantly C3 or a mixed C3/C4 plant community. Sulfur isotope values reflect the influence of predominant marine or terrestrial sulfur sources at each site. However, variability in isotope values may limit the usefulness of such analyses for addressing prey utilization and population dynamics.     

The scheduling of deliveries in a production-distribution system with multiple buyers

In a real production and distribution business environment with one supplier and multiple heterogeneous buyers, the differences in buyers’ ordering cycles have influence on production arrangements. Consequently, the average inventory level (AIL) at the supplier’s end is affected by both the production policy and the ordering policy, typically by the scheduling of deliveries. Consequently, the average inventory holding cost is most deeply affected. In this paper, it is proposed that the scheduling of deliveries be formulated as a decision problem to determine the time point at which deliveries are made to buyers in order to minimize the supplier’s average inventory. A formulation of the average inventory level (AIL) in a production cycle at the supplier’s end using a lot-for-lot policy is developed. Under the lot-for-lot policy, the scheduling of deliveries (SP) is formulated as a nonlinear programming model used to determine the first delivery point for each buyer with an objective to minimize the sum of the product of the individual demand quantity and the first delivery time for each buyer. Thus, the SP model determines not only the sequence of the first deliveries to individual buyers, but also the time when the deliveries are made. An iterative heuristic procedure (IHP) is developed to solve the SP model assuming a given sequence of buyers. Six sequence rules are considered and evaluated via simulation.     

Nitrile functionalized methimazole-based ionic liquids

The alkylation reaction of 2-mercapto-1-methylimidazole 1b with 2-chloroacetonitrile and 2-chloropropionitrile produced S-alkyl methimazole chlorides 2a and 2b which were subjected to anion metathesis with lithium bis(trifluoromethanesulfonyl)amide, LiNTf(2), to afford nitrile functionalized methimazole-based room temperature ionic liquids 3a and 3b in 94% and 89% yields, respectively. Ionic liquids 3a and 3b have reasonably wide electrochemical windows. The efficient extraction of Ag(+) from aqueous media into 3a and 3b is also reported.     

Redox Properties and in Vivo Magnetic Resonance Imaging of Cyclodextrin-Polynitroxides Contrast Agents

This paper reports the synthesis, characterization and in vivo application of water-soluble supramolecular contrast agents (Mw: 5–5.6 kDa) for MRI obtained from β-cyclodextrin functionalized with different kinds of nitroxide radicals, both with piperidine structure ( CD2 and CD3 ) and with pyrrolidine structure ( CD4 and CD5 ). As to the stability of the radicals in presence of ascorbic acid, CD4 and CD5 have low second order kinetic constants (≤0.05 M⁻¹ s⁻¹) compared to CD2 (3.5 M⁻¹ s⁻¹) and CD3 (0.73 M⁻¹ s⁻¹). Relaxivity (r₁) measurements on compounds CD3 - CD5 were carried out at different magnetic field strength (0.7, 3, 7 and 9.4 T). At 0.7 T, r₁ values comprised between 1.5 mM⁻¹ s⁻¹ and 1.9 mM⁻¹ s⁻¹ were found while a significant reduction was observed at higher fields (r₁≈0.6-0.9 mM⁻¹ s⁻¹ at 9.4 T). Tests in vitro on HEK293 human embryonic kidney cells, L929 mouse fibroblasts and U87 glioblastoma cells indicated that all compounds were non-cytotoxic at concentrations below 1 μmol mL⁻¹. MRI in vivo was carried out at 9.4 T on glioma-bearing rats using the compounds CD3 - CD5 . The experiments showed a good lowering of T₁ relaxation in tumor with a retention of the contrast for at least 60 mins confirming improved stability also in vivo conditions.     

Thermally responsive supramolecular nanomeshes for on/off switching of the rotary motion of F1-ATPase at the single-molecule level

The artificial regulation of protein functions is essential for the realization of protein-based soft devices, because of their unique functions conducted within a nano-sized molecular space. We report that self-assembled nanomeshes comprising heat-responsive supramolecular hydrogel fibers can control the rotary motion of an enzyme-based biomotor (F(1)-ATPase) in an on/off manner at the single-molecule level. Direct observation of the interaction of the supramolecular fibers with a microbead unit tethered to the F(1)-ATPase and the clear threshold in the size of the bead required to stop ATPase rotation indicates that the bead was physically blocked so as to stop the rotary motion of ATPase. The temperature-induced formation and collapse of the supramolecular nanomesh can produce or destroy, respectively, the physical obstacle for ATPase so as to control the ATPase motion in an off/on manner. Furthermore, this switching of the F(1)-ATPase motion could be spatially restricted by using a microheating device. The integration of biomolecules and hard materials, interfaced with intelligent soft materials such as supramolecular hydrogels, is promising for the development of novel semi-synthetic nano-biodevices.     

Methimazole-based ionic liquids

The alkylation reaction of 2-mercapto-1-methylimidazole 1a with iodoethane and chlorobutane produced S-alkylmethimazole halides 2a and 2b which were subjected to anion metathesis with two different metal salts (MA) to afford methimazole-based room-temperature ionic liquids 3a, 3b, and 3c in 82%, 85%, and 87% yields, respectively. S-Alkylation giving 2a and 2b suggests that methimazole reacts through the thione tautomer.     

Up-Conversion Luminescence of the NaRF<Subscript>4</Subscript>-NaR′F<Subscript>4</Subscript> (R: Y,Yb, Er) Core-Shell Nanomaterials

Up-converting NaRF₄-NaR′F₄ (R: Y, Yb, Er) nanomaterials with different core-shell combinations were prepared with the co-precipitation method. The X-ray powder diffraction (XPD) measurements revealed the presence of both the cubic and hexagonal NaRF₄ phases. The crystallite sizes calculated with the Scherrer formula were 100 and 150 nm for the cubic and hexagonal phases, respectively. The FT-IR spectra showed water impurities. The up-conversion luminescence and luminescence decays were studied with NIR laser excitation at 970 nm. The up-conversion luminescence spectra showed strong red (640–685 nm) (⁴F_9/2 → ⁴I_15/2) and moderate green (515–560 nm) (²H_11/2, ⁴S_3/2 → ⁴I_15/2) Er³⁺ luminescence. The strongest up-conversion luminescence and longest red luminescence decay was obtained from the Na(Y,Yb)F₄-NaErF₄ core-shell combination.     

Numerical Simulation of the Formation of Granular Shock Wave Over Cylindrical Obstacle

A two dimensional (2‐D) stream of granular flow with zero initial granular temperature passing over a cylindrical obstacle is simulated by means of both molecular dynamics (MD) simulation and finite volume method (FVM). In experiments, a bow‐shaped shock wave with higher area fraction forms in front of the obstacle that was reproduced in our simulations. Due to the different circumstances to which particles are subjected, the granular flow is divided in two zones. One is undisturbed where quantities, such as space fraction (volume fraction for 3‐D and area fraction for 2‐D geometries), velocity and granular temperature are uniformly distributed and the other is called the shock wave zone. In this region, the values of the space fraction increases and the velocity of particles changes. From the MD simulation, it is found that the area fraction of the shock wave depends on surface roughness, coefficient of restitution (COR) of particles, the obstacle diameter as well as velocity of the granular stream, and a triangular region forms with almost zero velocity, and granular temperature forms in front of the cylindrical obstacle. The bigger is the size of the obstacle, the more stable this region is. In FVM simulations solid phase velocity and area fraction distributions similar to the MD simulation results are obtained for proper parameters.     

Extraction of silver(I) from aqueous solutions in the absence and presence of copper(II) with a methimazole-based ionic liquid

The ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], facilitates the efficient extraction of silver(I) from aqueous media via interaction with both the cation and anion components of the IL. Studies with a conventional aqueous-IL two phase system as well as microextraction of silver(I) by a thick IL film adhered to an electrode monitored in situ by cyclic voltammetry, established that [mimSBu][NTf(2)] can extract electroactive silver(I) ions from an aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of silver(I) further increase the acidity of the aqueous phase as a consequence of coordination with the IL cation component. Voltammetric and (1)H and (13)C NMR techniques have been used to establish the nature of the silver(I) complexes extracted, and show that the form of interaction with the IL differs from that outlined previously for the extraction of copper(II). Insights on the competition established when silver(I) is extracted in the presence of copper(II) are provided. Finally, it is noted that metallic silver can be directly electrodeposited at the electrode surface after extraction of silver(I) into [mimSBu][NTf(2)] and that back extraction of silver(I) into aqueous media is achieved by addition of an acidic aqueous solution.     

Isotope variations in white-tailed kites from various habitats in California: Possible limitations in assessing prey utilization and population dynamics

White-tailed kite (Elanus leucurus) populations in the 1930s were close to extirpation in the United States. But by the 1940s, an upward trend towards recovery was apparent and continued to their current stable population levels. These dramatic fluctuations in kite numbers may have been related to changes in rodent prey populations due to the conversion of native habitats to agriculture. To address this question, we evaluated the use of stable isotope analysis in determining if a shift in diet could be isotopically differentiated in current and historic kite populations. We first compared δ ¹³C, δ ¹⁵N, and δ ³⁴S values from present-day kite flight feathers and prey fur samples from four locations in California. The total ranges of isotope values for kite and their rodent prey were similar within each site. Carbon isotope values ranged from m 27.1 to m 22.2 in Arcata, m 26.1 to m 16.9 in Davis, m 27.0 to m 15.0 in Cosumnes, and m 28.2 to m 11.6 in Santa Barbara. Nitrogen isotope values ranged from 3.2 to 15.7 in Arcata, 2.8 to 12.7 in Davis, 4.0 to 15.7 in Cosumnes, and 1.7 to 20.0 in Santa Barbara. Sulfur isotope values ranged from m 7.8 to 12.4 in Arcata, m 1.1 to 9.2 in Davis, 0.7 to 10.9 in Cosumnes, and m 8.6 to 15.6 in Santa Barbara. Carbon, nitrogen, and sulfur isotope values at each site reflect typical trophic enrichments due to physiological processes. At each site, δ ¹³C and δ ¹⁵N values reflected the influence of a predominantly C₃ or a mixed C₃/C₄ plant community. Sulfur isotope values reflect the influence of predominant marine or terrestrial sulfur sources at each site. However, variability in isotope values may limit the usefulness of such analyses for addressing prey utilization and population dynamics.