Pyrrole β-amides: Synthesis and characterization of a dipyrrinone carboxylic acid and an N-Confused fluorescent dipyrrinone

Pyrrole β-amides are useful building blocks for the preparation of novel molecular architectures that can be used in supramolecular chemistry and sensor development. Under basic conditions, pyrrole β-amides with an α-aldehyde produce different condensation products when reacted with pyrrolinones depending on the amide substitution. Secondary amides form the expected dipyrrinones, but unexpectedly undergo a subsequent trans-amidation with the pyrrolinone nitrogen to produce an unsymmetrical imide (an N-confused fluorescent dipyrrinone). Under the same conditions, tertiary amides produce the expected dipyrrinone carboxylic acids, which have been shown to have strong self-association properties as determined by vapor pressure osmometry measurements, NMR studies, and X-ray crystal structure determination. Furthermore, an N-confused fluorescent dipyrrinone was produced from the same trans-amidation reaction during attempts to decarboxylate a dipyrrinone amide with a 9-carboxylic moiety.     

Electron impact induced fragmentations and rearrangements of some phenyl substituted phosphine oxides

Electron impact induced fragmentations and rearrangements of 1-phenyl-2,2,3-trimethylphosphetane 1-oxide, 1-phenylphospholane 1-oxide and 1-phenylphosphorinane 1-oxide were investigated. A process common to all of these phosphine oxides was electron impact induced formation of new carbon-carbon bonds involving the phenyl rings. Evidence for such rearrangements included observation of hydrocarbon fragment ions containing seven or more carbons.     

Divergent reactivity of allene-containing α-diazoesters using Cu and Rh catalysis

A versatile intramolecular reaction of allene-containing diazomalonates that exhibits excellent chemoselectivity for either allenic C–H insertion or cyclopropanation is demonstrated. The identity of the product depends on the transition metal catalyst that is employed for the reaction. Rh catalysts promote exclusive C–H insertion with good diastereoselectivity for the trans product, while Cu catalysis enables intramolecular cyclopropanation to yield methylenecyclopropanes with moderate to good E:Z ratios.     

The hydrophobic-subtraction model of reversed-phase column selectivity

A recently developed treatment of reversed-phase column selectivity (the hydrophobic-subtraction model) is reviewed and extended, including its characterization of the selectivity of different column types (e.g., C1-C30, cyano, phenyl, etc.). The application of this model to retention data for various solutes and columns has provided new insights into the nature of different solute-column interactions and their relative importance in affecting sample retention and separation. Reversed-phase columns can be characterized by five selectivity parameters (H, S*, A, B and C), values of which are summarized here for more than 300 different columns. The selection of columns of either equivalent or different selectivity is readily achievable on the basis of their values of H, S*, etc. The development of the hydrophobic-subtraction model, its use in characterizing the selectivity of different reversed-phase liquid chromatography (RP-LC) columns, and its application to various practical problems as described here began in 1998. The original inspiration for this project owes much to Jack Kirkland, who also contributed actively to the initial studies that laid the foundation of this model; he has since provided other important support to this project. Jack and one of the authors (LRS) have enjoyed a strong professional relationship and personal friendship for the past 35 years, and it is the privilege of the authors to dedicate this paper and the work that it represents to Jack. His contributions to HPLC column technology have extended from the mid-1960s into the present century, and it is impossible to conceive of present day HPLC practice without Jack's contributions over the years. In this and other ways, his position as a pioneer and key implementer of HPLC is widely recognized. We wish Jack well in the years to come.     

Column selectivity in reversed-phase liquid chromatography. VI. Columns with embedded or end-capping polar groups

A previous model of column selectivity for reversed-phase liquid chromatography (RP-LC) has been applied to an additional 21 columns with embedded or end-capping polar groups (EPGs). Embedded-polar-group columns exhibit a significantly different selectivity vs. non-EPG, type-B columns, generally showing preferential retention of hydrogen-bond donors, as well as decreased retention for hydrogen-bond acceptors or ionized bases. EPG-columns are also generally less hydrophobic (more polar) than are non-EPG-columns. Interestingly, columns with polar end-capping tend to more closely resemble non-EPG columns, suggesting that the polar group has less effect on column selectivity when used to end-cap the column versus the case of an embedded polar group. Column selectivity data reported here for EPG-columns can be combined with previously reported values for non-EPG columns to provide a database of 154 different columns. This enables a comparison of any two of these columns in terms of selectivity. However, comparisons that involve EPG columns are more approximate.     

Likelihood analysis of the minimal AMSB model

We perform a likelihood analysis of the minimal anomaly-mediated supersymmetry-breaking (mAMSB) model using constraints from cosmology and accelerator experiments. We find that either a wino-like or a Higgsino-like neutralino LSP, \(\tilde{\chi }^0_{1}\), may provide the cold dark matter (DM), both with similar likelihoods. The upper limit on the DM density from Planck and other experiments enforces \(m_{\tilde{\chi }^0_{1}} \lesssim 3 \,\, \mathrm {TeV}\) after the inclusion of Sommerfeld enhancement in its annihilations. If most of the cold DM density is provided by the \(\tilde{\chi }^0_{1}\), the measured value of the Higgs mass favours a limited range of \(\tan \beta \sim 5\) (and also for \(\tan \beta \sim 45\) if \(\mu > 0\)) but the scalar mass \(m_0\) is poorly constrained. In the wino-LSP case, \(m_{3/2}\) is constrained to about \(900\,\, \mathrm {TeV}\) and \(m_{\tilde{\chi }^0_{1}}\) to \(2.9\pm 0.1\,\, \mathrm {TeV}\), whereas in the Higgsino-LSP case \(m_{3/2}\) has just a lower limit \(\gtrsim 650\,\, \mathrm {TeV}\) (\(\gtrsim 480\,\, \mathrm {TeV}\)) and \(m_{\tilde{\chi }^0_{1}}\) is constrained to \(1.12 ~(1.13) \pm 0.02\,\, \mathrm {TeV}\) in the \(\mu >0\) (\(\mu <0\)) scenario. In neither case can the anomalous magnetic moment of the muon, \((g-2)_\mu \), be improved significantly relative to its Standard Model (SM) value, nor do flavour measurements constrain the model significantly, and there are poor prospects for discovering supersymmetric particles at the LHC, though there are some prospects for direct DM detection. On the other hand, if the \(\tilde{\chi }^0_{1}\) contributes only a fraction of the cold DM density, future LHC Open image in new window -based searches for gluinos, squarks and heavier chargino and neutralino states as well as disappearing track searches in the wino-like LSP region will be relevant, and interference effects enable \(\mathrm{BR}(B_{s, d} \rightarrow \mu ^+\mu ^-)\) to agree with the data better than in the SM in the case of wino-like DM with \(\mu > 0\).     

Determining transport parameters for superconductor/normal metal point contacts at fixed temperature from conductance versus magnetic field data

Transport data for superconductor/normal metal point contacts often consists of normalized conductance versus applied voltage as a function of reduced temperature, from which the barrier parameter, Z, and the broadening parameter, Γ, for the contact can be determined, in addition to other features of interest. We present a new strategy for determining these parameters, namely from normalized conductance as a function of applied magnetic field at fixed temperature, even when conductance versus variable temperature data is absent. This analysis technique will be demonstrated for several point contacts, over a wide range of parameter values.     

On the solution of Polyakov's ansatz

I show that the functional differential equations for conserved currents in loop space are consistent with the integrability condition.