An expeditious and convenient synthesis of acylsulfonamides utilizing polymer-supported reagents

Acylsulfonamides can be rapidly and conveniently synthesized from a variety of carboxylic acids and sulfonamides utilizing the commercially available reagents, PS-DCC and DMAP under mild reaction conditions. DMAP can be efficiently scavenged by utilization of a silica-supported tosic acid cartridge (Si-SCX). In most of the cases studied, products with high purities and yields were obtained without the need for further purification.     

Assessment of Tissue Distribution and Metabolism of MP1, a Novel Pyrrolomycin,in Mice Using a Validated LC-MS/MS Method

MP1 is a novel marinopyrrole analogue with activity in MYCN amplified neuroblastoma cell lines. A rapid, selective, and sensitive liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) method was developed and validated for quantitation of MP1 in mouse plasma. Analyte separation was achieved using a Waters Acquity UPLC^®BEH C18 column (1.7 µm, 100 × 2.1 mm). Mobile phase consisted of 0.1% acetic acid in water (10%) and methanol (90%) at a total flow rate of 0.25 mL/min. The mass spectrometer was operated at unit resolution in the multiple reaction monitoring (MRM) mode, using precursor ion > product ion transitions of 324.10 > 168.30 m/z for MP1 and 411.95 > 224.15 m/z for PL-3. The MS/MS response was linear over the concentration range from 0.2–500 ng/mL for MP1, correlation coefficient (r²) of 0.988. Precision (% RSD) and accuracy (% bias) were within the acceptable limits as per FDA guidelines. MP1 was stable under storage and laboratory handling conditions. The validated method was successfully applied to assess the solubility, in-vitro metabolism, plasma protein binding, and bio-distribution studies of MP1.     

Doubly stochastic matrices whose squares are idempotent

Formulas for the doubly stochastic square roots of the idempotents are presented. Such square roots must necessarily satisfy per A²≤perA.     

X-ray absorption fine structure study of amorphous metal oxide thin films prepared by photochemical metalorganic deposition

The oxidation state and local geometry of the metal centers in amorphous thin films of Fe₂O₃ (Fe³⁺ oxidation state), CoFe₂O₄ (Co²⁺/Fe³⁺ oxidation states), and Cr₂O₃ (Cr³⁺ oxidation state) are determined using K edge X-ray absorption near-edge structure (XANES) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy. The metal oxide thin films were prepared by the solid-state photochemical decomposition of the relevant metal 2-ethylhexanoates, spin cast as thin films. No peaks are observed in the X-ray diffraction patterns, indicating the metal oxides are X-ray amorphous. The oxidation state of the metals is determined from the edge position of the K absorption edges, and in the case of iron-containing samples, an analysis of the pre-edge peaks. In all cases, the EXAFS analysis indicates the first coordination shell consists of oxygen atoms in an octahedral geometry, with a second shell consisting of metals. No higher shells are observed beyond 3.5 Å for all samples, indicating the metal oxides are truly amorphous, consistent with X-ray diffraction results.     

Sharp Trace Hardy–Sobolev-Maz’ya Inequalities and the Fractional Laplacian

In this work we establish trace Hardy and trace Hardy–Sobolev–Maz’ya inequalities with best Hardy constants for domains satisfying suitable geometric assumptions such as mean convexity or convexity. We then use them to produce fractional Hardy–Sobolev–Maz’ya inequalities with best Hardy constants for various fractional Laplacians. In the case where the domain is the half space, our results cover the full range of the exponent ${s \in}$ (0, 1) of the fractional Laplacians. In particular, we give a complete answer in the L ² setting to an open problem raised by Frank and Seiringer (“Sharp fractional Hardy inequalities in half-spaces,” in Around the research of Vladimir Maz’ya. International Mathematical Series, 2010).     

On the Origins of Some Spectroscopic Properties of “Purple Iron” (the Tetraoxoferrate(VI) Ion) and Its Pourbaix Safe-Space

In this work, the authors attempt to interpret the visible, infrared and Raman spectra of ferrate(VI) by means of theoretical physical-inorganic chemistry and historical highlights in this field of interest. In addition, the sacrificial decomposition of ferrate(VI) during water treatment will also be discussed together with a brief mention of how Rayleigh scattering caused by the decomposition of Fe^VIO₄²⁻ may render absorbance readings erroneous. This work is not a compendium of all the instrumental methods of analysis which have been deployed to identify ferrate(VI) or to study its plethora of reactions, but mention will be made of the relevant techniques (e.g., Mössbauer Spectroscopy amongst others) which support and advance this overall discourse at appropriate junctures, without undue elaboration on the foundational physics of these techniques.     

Direct, loss-tolerant characterization of nonclassical photon statistics

We experimentally investigate a method of directly characterizing the photon-number distribution of nonclassical light beams that is tolerant to losses and makes use of only standard binary detectors. This is achieved in a single measurement by calibrating the detector using some small amount of prior information about the source. We demonstrate the technique on a freely propagating heralded two-photon-number state created by conditional detection of a two-mode squeezed state generated by parametric down-conversion.     

Autoconfocal microscopy with a cw laser and thermionic detection

We introduce an application of thermionic emission in a PMT photocathode. Because of the nonlinear dependence of thermionic emission on absorbed laser power, a conventional PMT is found to produce a virtual pinhole effect that rejects unfocused light at least as strongly as a physical pinhole. This virtual pinhole effect is exploited in a scanning transmission confocal microscope equipped with a cw laser source. Because the area of the PMT photocathode is large, signal descanning is not required and thermionic detection acts as a self-aligned pinhole. Our technique of thermionic-detection autoconfocal microscopy is further implemented with graded-field contrast to obtain enhanced phase-gradient sensitivity in unlabeled samples, such as rat hippocampal brain slices.     

Derivatives of molecular Vibrational force constants with a singular Jacobian

Counter examples are presented that negate the generality of Gans' claim that a singular jacobian demands the existence of one off-diagonal force constant F_st possessing the extremal property ?F_rr/?F_st = ∞ for all of the n diagonal force constants F_rr (r = 1, > 62; n) in a symmetry species containing n vibrations.