Abelian Subgroup Separability of Haken 3-Manifolds and Closed Hyperbolic n-Orbifolds

We prove that abelian subgroups of fundamental groups of Haken3-manifolds and closed hyperbolic n-orbifolds are separable.2000 Mathematical Subject Classification: 20E26, 51M10, 57M05.     

Looking for Difference Sets in Groups with Dihedral Images

We prove four theorems about groups with a dihedral (or cyclic) image containing a difference set. For the first two, suppose G, a group of order 2p with p an odd prime, contains a nontrivial (v, k, ) difference set D with order n = k – prime to p and self-conjugate modulo p. If G has an image of order p, then 0 2a + 2 for a unique choice of = ±1, and for a = (k – )/2p. If G has an image of order 2p, then and ( – 1)/( – 1). There are further constraints on n, a and . We give examples in which these theorems imply no difference set can exist in a group of a specified order, including filling in some entries in Smith's extension to nonabelian groups of Lander's tables. A similar theorem covers the case when p|n. Finally, we show that if G contains a nontrivial (v, k, ) difference set D and has a dihedral image D _2m with either (n, m) = 1 or m = p ^t for p an odd prime dividing n, then one of the C ₂ intersection numbers of D is divisible by m. Again, this gives some non-existence results.     

Cyclic 1,3-dipoles or acyclic phosphonium ylides? Electronic characterization of "Montréalones"

The structural features of a recently introduced class of 1,3-dipolar reagents have been computed by density functional theory and ab initio methods. The reagents are formally derived from Münchnones by replacement of the C O group with a PR3 unit. The parent species (PR3 = PH3) shows a long P...O interaction (2.55 A at the B3LYP/6-31+G(d) level), together with a nonplanar ring, and is best described as a weakly chelated acylamino-phosphonium ylide. The corresponding acyclic form, in which the P...O interaction is absent, is predicted to be 2-3 kcal mol-1 higher in enthalpy. Variation of the phosphorus substituents exerts a marked effect on the P...O distance, with electron-withdrawing groups favoring a covalent interaction [P...O 1.97 A for PR3 = PPh(catechyl)] and electron-donating groups favoring a weak interaction [P...O 3.92 A for PR3 = PPh3]. However, this variation has little effect on the relative energies of the cyclic and acyclic forms. The barriers for concerted cycloadditions with ethylene are 22.8 kcal mol-1 (PH3), 31.7 kcal mol-1 (PPh3), and 16.2 kcal mol-1 [PPh(catechyl) with axial O], which correspond with experimental observations and follow the same trend as the energies required to distort the dipole to the TS geometry.     

Elusive Double Perovskite Iodides: Structural,Optical, and Magnetic Properties

Halide double perovskites [A₂M^IM^IIIX₆] are an important class of materials that have garnered substantial interest as non-toxic alternatives to conventional lead iodide perovskites for optoelectronic applications. While numerous studies have examined chloride and bromide double perovskites, reports of iodide double perovskites are rare, and their definitive structural characterization has not been reported. Predictive models have aided us here in the synthesis and characterization of five iodide double perovskites of general formula Cs₂NaLnI₆ (Ln=Ce, Nd, Gd, Tb, Dy). The complete crystal structures, structural phase transitions, optical, photoluminescent, and magnetic properties of these compounds are reported.     

Formation of the serine octamer: Ion evaporation or charge residue

The mechanism of formation for clusters of serine generated by electrospray ionization is hypothesized to play a critical role in determining their ultimate properties. Under carefully manipulated electrospray source conditions, two distinct and well-separated distributions of clusters can be observed. The characteristics of the two cluster populations are consistent with different formation mechanisms, namely ion evaporation and charge residue. Upon further inspection, it is proposed that the magic number intensity, homochiral selectivity, and unique formation of the serine octamer are best explained within the context of the ion evaporation mechanism. As a consequence, solution phase properties of the octamer become important, particularly in relation to interface effects present on the surface of the charged droplet. In contrast, other clusters of serine, including the B form of the octamer, are probably generated by the charge residue mechanism and may have no connection to condensed phase phenomena.     

Interaction of first row transition metals with α1-3, α1-6 mannotriose and conserved trimannosyl core oligosaccharides: A comparative electrospray ionization study of doubly and singly charged complexes

Electrospray ionization and tandem mass spectrometry were used in the analysis of metalcoordinated oligosaccharides. Four transition metal ions, Cu²⁺, Mn²⁺, Co²⁺, and Zn²⁺, and the alkaline earth metal ion Ca²⁺, were each coordinated to the trimer α1–3, α1–6 mannotriose and the pentamer conserved trimannosyl core (mannotriosyl-chitobiose). Instrumental and concentration ratio optimization studies were carried out to determine the best conditions for producing the [M + Met]²⁺, [M + MetCl]⁺, and [M + Met ? H]⁺ ions (Met = metal dication). These precursors were then subjected to tandem mass spectrometry (MS/MS) analysis and compared. Both the ionic radii and efficacy of ligand coordination were observed as important criteria for producing the precursor ions. Tandem mass spectra for the Cu²⁺- and Zn²⁺-coordinated species did not produce significant structural information about either the trimer or the pentamer. Although tandem mass spectra for the Ca²⁺-, Co²⁺-, and Mn²⁺-coordinated trimer were very similar, those of the pentamer were not. MS/MS of the Co²⁺-coordinated pentamer was the most unique and exhibited very different dissociation pathways.     

Ionic liquids in vacuo; solution-phase X-ray photoelectron spectroscopy

The in situ monitoring of catalysis in Room Temperature Ionic Liquids (RTILs) is fundamental to the understanding of catalytic processes and the role of RTILs in catalytic turnover; we describe how XPS can be used to give information on both pure RTILs and catalytically-active RTIL-based solutions.     

Photon Equivalents as a Parameter for Scaling Photoredox Reactions in Flow: Translation of Photocatalytic C−N Cross‐Coupling from Lab Scale to Multikilogram Scale

With the development of new photocatalytic methods over recent decades, the translation of these chemical reactions to industrial‐production scales using continuous‐flow reactors has become a topic of increasing interest. In this context, we describe our studies toward elucidating an empirically derived parameter for scaling photocatalytic reactions in flow. By evaluating the performance of a photocatalytic C?N cross‐coupling reaction across multiple reactor sizes and geometries, it was demonstrated that expressing product yield as a function of the absorbed photon equivalents provides a predictive, empirical scaling parameter. Through the use of this scaling factor and characterization of the photonic flux within each reactor, the cross‐coupling was scaled successfully from the milligram scale in batch to a multi‐kilogram reaction in flow.     

Surface-amplified ligand disorder in CdSe quantum dots determined by electron and coherent vibrational spectroscopies

This Article reports measurements of the intra- and intermolecular ordering of tight-binding octylphosphonate ligands on the surface of colloidal CdSe quantum dots (QDs) within solid state films, and the dependence of this order on the size of the QDs. The order of the organic ligands, as probed by vibrational sum frequency generation (SFG) spectroscopy, decreases as the radius of the QDs decreases; this decrease is correlated with a decrease in the order of underlying Cd(2+), as detected by X-ray photoelectron spectroscopy (XPS) line width measurements, for radii of the QDs, R > 2.4 nm, and is independent of the disorder of the Cd(2+) for R < 2.4 nm. We believe that, for R < 2.4, the decreasing order of the ligands with decreasing size is due to an increase in the curvature of the QD surfaces. Disorder in the Cd(2+) results from the presence of a shell of Cd(2+)-surfactant complexes that form during synthesis, so this work demonstrates the possibility for chemical control over molecular order within films of colloidal QDs by changing the surfactant mixture.     

COMPARATIVE PHOTOCHEMICAL ANALYSIS OF HIGHLY PURIFIED 124 KILODALTON OAT and RYE PHYTOCHROMES in vitro

Abstract A direct comparison of the photochemical interconversions between red (P_r-) and far-red (P_fr-) absorbing forms of highly-purified 124 kDa oat and rye phytochromes under identical experimental conditions was performed. In two different buffer systems at 5°C, the quantum yields for the P_r to P_tr and P_fr to P_r phototransformations under constant red and far-red illumination, φ _r and φ_fr respectively, were determined to be 0.152-0.154 and 0.060-0.065 for oat preparations and 0.172-0.174 and 0.074-0.078 for rye preparations. These values as well as the wavelength dependence of the photoequilibrium produced under continuous illumination throughout the visible and near-ultraviolet spectrum were based on the absorption spectra of the two phytochrome preparations and revised molar absorption coefficients. The molar absorption coefficients were estimated by quantitative amino acid analysis and shown to be identical for the two monocot phytochromes (i.e. 132 mM ⁻¹ cm⁻¹ at the red absorption maximum for the P_r form). Because these measurements were performed under identical experimental conditions, including buffer, temperature, light fluence rate, and instrumentation, the differences observed must reflect structural features inherent to the two different monocotyledonous phytochromes.