Synthesis of 2H-1-benzopyrans via palladacycles with a metal-bonded stereogenic carbon

[reaction: see text] Stable oxapalladacycles have been prepared and converted into a series of highly functionalized 2H-1-benzopyrans via regioselective insertion of activated alkynes.     

Classification of Convex Ancient Solutions to Curve Shortening Flow on the Sphere

We prove that the only closed, embedded ancient solutions to the curve shortening flow on \(\mathbb {S}^2\) are equators or shrinking circles, starting at an equator at time \(t=-\infty \) and collapsing to the north pole at time \(t=0\). To obtain the result, we first prove a Harnack inequality for the curve shortening flow on the sphere. Then an application of the Gauss–Bonnet, easily allows us to obtain curvature bounds for ancient solutions leading to backwards smooth convergence to an equator. To complete the proof, we use an Aleksandrov reflection argument to show that maximal symmetry is preserved under the flow.     

Developing and applying quantitative skills maps for STEM curricula,with a focus on different modes of learning

Mapping quantitative skills across the science, technology, engineering and mathematics (STEM) curricula will help educators identify gaps and duplication in the teaching, practice and assessment of the necessary skills. This paper describes the development and implementation of quantitative skills mapping tools for courses in STEM at a regional university that offers both on-campus and distance modes of study. Key elements of the mapping project included the identification of key graduate quantitative skills, the development of curriculum mapping tools to record in which unit(s) and at what level of attainment each quantitative skill is taught, practised and assessed, and identification of differences in the way quantitative skills are developed for on-campus and distance students. Particular attention is given to the differences that are associated with intensive schools, which consist of concentrated periods of face-to-face learning over a three-four day period, and are available to distance education students enrolled in STEM units. The detailed quantitative skills mapping process has had an impact on the review of first-year mathematics units, resulted in crucial changes to the curriculum in a number of courses, and contributed to a more integrated approach, and a collective responsibility, to the development of students' quantitative skills for both face-to-face and online modes of learning.     

Targeted drug delivery utilizing protein-like molecular architecture

Nanotechnology-based drug delivery systems (nanoDDSs) have seen recent popularity due to their favorable physical, chemical, and biological properties, and great efforts have been made to target nanoDDSs to specific cellular receptors. CD44/chondroitin sulfate proteoglycan (CSPG) is among the receptors overexpressed in metastatic melanoma, and the sequence to which it binds within the type IV collagen triple-helix has been identified. A triple-helical "peptide-amphiphile" (alpha1(IV)1263-1277 PA), which binds CD44/CSPG, has been constructed and incorporated into liposomes of differing lipid compositions. Liposomes containing distearoyl phosphatidylcholine (DSPC) as the major bilayer component, in combination with distearoyl phosphatidylglycerol (DSPG) and cholesterol, were more stable than analogous liposomes containing dipalmitoyl phosphatidylcholine (DPPC) instead of DSPC. When dilauroyl phosphatidylcholine (DLPC):DSPG:cholesterol liposomes were prepared, monotectic behavior was observed. The presence of the alpha1(IV)1263-1277 PA conferred greater stability to the DPPC liposomal systems and did not affect the stability of the DSPC liposomes. A positive correlation was observed for cellular fluorophore delivery by the alpha1(IV)1263-1277 PA liposomes and CD44/CSPG receptor content in metastatic melanoma and fibroblast cell lines. Conversely, nontargeted liposomes delivered minimal fluorophore to these cells regardless of the CD44/CSPG receptor content. When metastatic melanoma cells and fibroblasts were treated with exogeneous alpha1(IV)1263-1277, prior to incubation with alpha1(IV)1263-1277 PA liposomes, to potentially disrupt receptor/liposome interactions, a dose-dependent decrease in the amount of fluorophore delivered was observed. Overall, our results suggest that PA-targeted liposomes can be constructed and rationally fine-tuned for drug delivery applications based on lipid composition. The selectivity of alpha1(IV)1263-1277 PA liposomes for CD44/CSPG-containing cells represents a targeted-nanoDDS with potential for further development and application.     

Electrochemical Measurement of Gold Oxide Reduction and Methods for Acid Neutralization and Minimization of Water in Wet Ionic Liquid

The formation and reduction of gold oxide in wet ionic liquid (IL), N‐trimethyl‐N‐butylammonium bis(trifluoromethanesulfonyl)imide, ([Me₃NⁿBu][TFSI]) is examined. The water concentration is determined using both the charge and peak current from the reduction of gold oxide and compared directly with Karl Fischer data. The quantitative determination of water in the IL is demonstrated for concentrations between 0.09 and 0.74 by weight (w%). The treatment of wet IL with dry nitrogen or molecular sieves reduces the water below background levels. Finally, methods for acid neutralization and the reduction of water with molecular sieves are conducted to minimize their impact on subsequent electrochemical measurements.     

A one-step homogeneous immunoassay for cancer biomarker detection using gold nanoparticle probes coupled with dynamic light scattering

A one-step homogeneous immunoassay for the detection of a prostate cancer biomarker, free-PSA (prostate specific antigen), was developed using gold nanoparticle probes coupled with dynamic light scattering (DLS) measurements. A spherical gold nanoparticle with a core diameter around 37 nm and a gold nanorod with a dimension of 40 by 10 nm were first conjugated with two different primary anti-PSA antibodies and then used as optical probes for the immunoassay. In the presence of antigen f-PSA in solution, the nanoparticles and nanorods aggregate together into pairs and oligomers through the formation of a sandwich type antibody-antigen-antibody linkage. The relative ratio of nanoparticle-nanorod pairs and oligomers versus individual nanoparticles was quantitatively monitored by DLS measurement. A correlation can be established between this relative ratio and the amount of antigen in solution. The light scattering intensity of nanoparticles and nanoparticle oligomers is several orders of magnitude higher than proteins and other typical molecules, making it possible to detect nanoparticle probes in the low picomolar concentration range. f-PSA in the concentration range from 0.1 to 10 ng/mL was detected by this one-step and washing-free homogeneous immunoassay.     

Control of molecular fragmentation using shaped femtosecond pulses

The possibility that chemical reactions may be controlled by tailored femtosecond laser pulses has inspired recent studies that take advantage of their short pulse duration, comparable to intramolecular dynamics, and high peak intensity to fragment and ionize molecules. In this article, we present an experimental quest to control the chemical reactions that take place when isolated molecules interact with shaped near-infrared laser pulses with peak intensities ranging from 1013 to 1016 W/cm2. Through the exhaustive evaluation of hundreds of thousands of experiments, we methodically evaluated the molecular response of 16 compounds, including isomers, to the tailored light fields, as monitored by time-of-flight mass spectrometry. Analysis of the experimental data, taking into account its statistical significance, leads us to uncover important trends regarding the interaction of isolated molecules with an intense laser field. Despite the energetics involved in fragmentation and ionization, the integrated second-harmonic generation of a given laser pulse (ISHG), which was recorded as an independent diagnostic parameter, was found to be linearly proportional to the total ion yield (IMS) generated by that pulse in all of our pulse shaping measurements. Order of magnitude laser control over the relative yields of different fragment ions was observed for most of the molecules studied; the fragmentation yields were found to vary monotonically with IMS and/or ISHG. When the extensive changes in fragmentation yields as a function of IMS were compared for different phase functions, we found essentially identical results. This observation implies that fragmentation depends on a parameter that is responsible for IMS and independent from the particular time-frequency structure of the shaped laser pulse. With additional experiments, we found that individual ion yields depend only on the average pulse duration, implying that coherence does not play a role in the observed changes in yield as a function of pulse shaping. These findings were consistently observed for all molecules studied (p-, m-, o-nitrotoluene, 2,4-dinitrotoluene, benzene, toluene, naphthalene, azulene, acetone, acetyl chloride, acetophenone, p-chrolobenzonitrile, N,N-dimethylformamide, dimethyl phosphate, 2-chloroethyl ethyl sulfide, and tricarbonyl-[eta5-1-methyl-2,4-cyclopentadien-1-yl]-manganese). The exception to our conclusion is that the yield of small singly-charged fragments resulting from a multiple ionization process in a subset of molecules, were found to be highly sensitive to the phase structure of the intense pulses. This coherent process plays a minimal role in photofragmentation; therefore, we consider it an exception rather than a rule. Changes in the fragmentation process are dependent on molecular structure, as evidenced in a number of isomers, therefore femtosecond laser fragmentation could provide a practical dimension to analytical chemistry techniques.     

Quantifying the fraction of glycine and alanine in beta-sheet and helical conformations in spider dragline silk using solid-state NMR

Solid-state two-dimensional refocused INADEQUATE MAS NMR experiments resolve distinct helical and beta-sheet conformational environments for both alanine and glycine in Nephila clavipes dragline silk fibers; the fraction of alanine and glycine in beta-sheet structures is determined to be 82% +/- 4% and 28% +/- 5%, respectively.     

Turnover of hydrogen isotopes in lake sturgeon blood: implications for tracking movements of wild populations

Naturally occurring deuterium (²H) in biota can be used to trace movement, migration and geographic origin of a range of organisms. However, to evaluate movements of animals using δ²H measurements of tissues, it is necessary to establish the turnover time of ²H in the tissues and the extent of isotopic discrimination from different environmental ²H sources to those tissues. We investigated the turnover of ²H in lake sturgeon (Acipenser fulvescens) blood by manipulating both environmental water δ²H and diet δ²H over a four-month period. The half-life of deuterium in lake sturgeon blood was 37.9 days after an increase in the environmental water δ²H of +714?‰. However, no clear turnover in blood ²H occurred over the same period in a separate trial following a change of ?63.8?‰ or +94.2?‰ in diet. These findings suggest that environmental water ²H exchanges much faster with blood than diets and that blood δ²H values can be used to trace movements of sturgeon and other fish moving among isotopically distinct waters.     

HDX Workbench: Software for the Analysis of H/D Exchange MS Data

Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is an established method for the interrogation of protein conformation and dynamics. While the data analysis challenge of HDX-MS has been addressed by a number of software packages, new computational tools are needed to keep pace with the improved methods and throughput of this technique. To address these needs, we report an integrated desktop program titled HDX Workbench, which facilitates automation, management, visualization, and statistical cross-comparison of large HDX data sets. Using the software, validated data analysis can be achieved at the rate of generation. The application is available at the project home page http://hdx.florida.scripps.edu .