Variation in chick-a-dee calls of tufted titmice, Baeolophus bicolor: note type and individual distinctiveness

The chick-a-dee call of chickadee species (genus Poecile) has been the focus of much research. A great deal is known about the structural complexity and the meaning of variation in notes making up calls in these species. However, little is known about the likely homologous "chick-a-dee" call of the closely related tufted titmouse, Baeolophus bicolor. Tufted titmice are a prime candidate for comparative analyses of the call, because their vocal and social systems share many characteristics with those of chickadees. To address the paucity of data on the structure of chick-a-dee calls of tufted titmice, we recorded birds in field and aviary settings. Four main note types were identified in the call: Z, A, D(h), and D notes. Several acoustic parameters of each note type were measured, and statistical analyses revealed that the note types are acoustically distinct from one another. Furthermore, note types vary in the extent of individual distinctiveness reflected in their acoustic parameters. This first step towards understanding the chick-a-dee call of tufted titmice indicates that the call is comparable in structure and complexity to the calls of chickadees.     

The h-SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze

We describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb_0.5W₃O₁₀, in the following denoted as h-Sb_xWO_3+2x with x=0.167, to demonstrate its analogy to classical A_xWO₃ tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C<T<620 °C. It was obtained as a dark-blue polycrystalline powder, and as thin, needle-shaped, blue single crystals. h-Sb_xWO_3+2x crystallizes in the hexagonal space group P6/mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner-sharing WO₆ octahedra. h-Sb_xWO_3+2x has a resistivity of ρ_{300 K}≈1.28 mΩ cm at room temperature, with little if any temperature-dependence on cooling. DFT calculations on a simplified model for this compound find a metallic-like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point.     

Quantitative evaluation of liposomal doxorubicin and its metabolites in spheroids

Analytical and Bioanalytical Chemistry - Accurate measurement and understanding of therapeutic uptake and metabolism is key in the drug development process. This work examines the amount of...     

Transition-Metal-Mediated Modification of Biomolecules

The site-selective modification of biomolecules has grown spectacularly in recent years. The presence of a large number of functional groups in a biomolecule makes its chemo- and regioselective modification a challenging goal. In this context, transition-metal-mediated reactions are emerging as a powerful tool owing to their unique reactivity and good functional group compatibility, allowing highly efficient and selective bioconjugation reactions that operate under mild conditions. This Minireview focuses on the current state of organometallic chemistry for bioconjugation, highlighting the potential of transition metals for the development of chemoselective and site-specific methods for functionalization of peptides, proteins and nucleic acids. The importance of the selection of ligands attached to the transition metal for conferring the desired chemoselectivity will be highlighted.     

N,N′-Ethylene-Bridged Bis-2-Aryl-Pyrrolinium Cations to E-Diaminoalkenes: Non-Identical Stepwise Reversible Double-Redox Coupled Bond Activation Reactions

This work presents a stepwise reversible two-electron transfer induced hydrogen shift leading to the conversion of a bis-pyrrolinium cation to an E-diaminoalkene and vice versa. Remarkably, the forward and the reverse reaction, which are both reversible, follow two completely different reaction pathways. Establishing such unprecedented property in this type of processes was possible by developing a novel synthetic route towards the starting dication. All intermediates involved in both the forward and the backward reactions were comprehensively characterized by a combination of spectroscopic, crystallographic, electrochemical, spectroelectrochemical, and theoretical methods. The presented synthetic route opens up new possibilities for the generation of multi-pyrrolinium cation scaffold-based organic redox systems, which constitute decidedly sought-after molecules in contemporary chemistry.     

Correction strategy for diffusion-weighted images corrupted with motion: application to the DTI evaluation of infants' white matter

Objective

Diffusion imaging techniques such as DTI and HARDI are difficult to implement in infants because of their sensitivity to subject motion. A short acquisition time is generally preferred, at the expense of spatial resolution and signal-to-noise ratio. Before estimating the local diffusion model, most pre-processing techniques only register diffusion-weighted volumes, without correcting for intra-slice artifacts due to motion or technical problems. Here, we propose a fully automated strategy, which takes advantage of a high orientation number and is based on spherical-harmonics decomposition of the diffusion signal.

Material and methods

The correction strategy is based on two successive steps: 1) automated detection and resampling of corrupted slices; 2) correction for eddy current distortions and realignment of misregistered volumes. It was tested on DTI data from adults and non-sedated healthy infants.

Results

The methodology was validated through simulated motions applied to an uncorrupted dataset and through comparisons with an unmoved reference. Second, we showed that the correction applied to an infant group enabled to improve DTI maps and to increase the reliability of DTI quantification in the immature cortico-spinal tract.

Conclusion

This automated strategy performed reliably on DTI datasets and can be applied to spherical single- and multiple-shell diffusion imaging.     

Elements of Design‐Based Science Activities That Affect Students' Motivation

The primary purpose of this study was to examine the ways in which a 12‐week afterschool science and engineering program affected middle school students' motivation to engage in science and engineering activities. We used current motivation research and theory as a conceptual framework to assess 14 students' motivation through questionnaires, structured interviews, and observations. Students reported that during the activities they perceived that they were empowered to make choices in how to complete things, the activities were useful to them, they could succeed in the activities, they enjoyed and were interested in the hands‐on activities and some presentations, they felt cared for by the facilitators and received help when they were stuck or confused, and they put forth effort. Based on our examination of data across our three data sources, we identified motivating opportunities that were provided to students during the activities. These motivating opportunities can serve as examples to help both formal and informal science educators better connect motivation theory to practice so that they can create motivating opportunities for students. Furthermore, this study provides a methodological example of how students' motivation can be examined during the context of authentic science and engineering instruction.     

Development and full validation of an HPLC methodology to quantify atorvastatin and curcumin after their intranasal co‐delivery to mice

There is increasing interest in atorvastatin and curcumin owing to their potential anticancer activity. A new, accurate and sensitive HPLC method was developed, for the first time, to simultaneously quantify atorvastatin and curcumin in mouse plasma and brain, liver, lung and spleen tissues following protein precipitation sample preparation. The chromatographic separation was achieved in 13 min on a C₁₈ column, at 35°C, using a mobile phase composed of acetonitrile–methanol–2% (v/v) acetic acid (37.5:2.5:60, v/v/v) at a flow rate of 1.0 mL/min. The detection of analytes and internal standard was carried out at 247, 425 and 250 nm, respectively. According to international guidelines, the method was shown to be selective, with lower limits of quantification ranging from 10 to 500 ng/mL for curcumin, and from 100 to 600 ng/mL for atorvastatin, linear over a wide concentration range (r² ≥ 0.9971) and with acceptable accuracy (bias ± 12.29%) and precision (coefficient of variation ≤13.15%). The analytes were reproducibly recovered at a percentage >81.10% and demonstrated to be stable under various experimental conditions in all biological matrices. This method can be easily applied to in vivo biodistribution studies related to the intranasal administration of atorvastatin and curcumin, separately or simultaneously.     

Stereodynamics of 9,11-Diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecanes. Highly Restricted Nitrogen Inversion and Isolated Phenyl Rotation. X-ray Crystallographic, Dynamic NMR, and Molecular Mechanics Studies

The (1)H NMR spectra of 10-benzyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (BnPh(2)()) and 10-methyl-9,11-diphenyl-10-azatetracyclo[6.3.0.0.(4,11)0.(5,9)]undecane (MePh(2)()) decoalesce due to slowing inversion at nitrogen and to slowing isolated bridgehead phenyl rotation. The high nitrogen inversion barriers in MePh(2)() (DeltaG() = 12.2 +/- 0.1 kcal/mol at 250 K) and BnPh(2)() (DeltaG() = 10.6 +/- 0.1 kcal/mol at 215 K) are typical of tertiary amines in which at least one C-N-C bond angle is constrained to a small value. Compared to the minuscule rotation barriers about sp(2)-sp(3) carbon-carbon bonds in simple molecular systems, the bridgehead phenyl rotation barriers in MePh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) and BnPh(2)() (DeltaG() = 9.8 +/- 0.1 kcal/mol at 210 K) are unusually high. Molecular mechanics calculations (MMX force field) suggest that the origin of the high phenyl rotation barriers lies in the close passage of an o-phenyl proton and a methyl (or benzylmethylene) proton in the transition state. BnPh(2)() crystallized from hexane as white needles in the monoclinic system Pn. Unit cell dimensions are as follows: a = 12.198(1) ?, b = 6.1399(6) ?, c = 14.938(2) ?, beta = 107.470(4) degrees, V = 1067.1(2) ?(3), Z = 2. In the crystal molecular structure, the imine bridge CNC bond angle in BnPh(2)() is constrained to a small value (96 degrees ). The benzylic phenyl group is oriented gauche to the nitrogen lone pair.     

Characterization of a highly stable zwitterionic hydrophilic interaction chromatography stationary phase based on hybrid organic–inorganic particles

We have characterized a sulfobetaine stationary phase based on 1.7 μm ethylene-bridged hybrid organic–inorganic particles, which is intended for use in hydrophilic interaction chromatography. The efficiency of a column packed with this material was determined as a function of flow rate, demonstrating a minimum reduced plate height of 2.4. The batch-to-batch reproducibility was assessed using the separation of a mixture of acids, bases, and neutrals. We compared the retention and selectivity of the hybrid sulfobetaine stationary phase to that of several benchmark materials. The hybrid sulfobetaine material gave strong retention for polar neutrals and high selectivity for methyl groups, hydroxy groups, and configurational isomers. Large differences in cation and anion retention were observed among the columns. We characterized the acid and base stability of the hybrid sulfobetaine stationary phase, using accelerated tests at pH 1.3 and 11.0, both at 70°C. The results support a recommended pH range of 2–10. We also investigated the performance of columns packed with this material for metal-sensitive analytes, comparing conventional stainless steel column hardware to hardware that incorporates hybrid surface technology to mitigate interactions with metal surfaces. Compared to the conventional columns, the hybrid surface technology columns showed a greatly improved peak shape.