On strongly stable normal operators in Krein spaces

For bounded normal operators in Krein spaces we give a necessary and sufficient condition for strong stability. The same result for unitary operators was obtained by M.G.Krein [1] (see also [2]). For selfadjoint operators we refer to the papers of P.Jonas, H.Langer [3] and H.Langer [4].     

Iminophosphines: synthesis, formation of 2,3-dihydro-1H-benzo[1,3]azaphosphol-3-ium salts and N-(pyridin-2-yl)-2-diphenylphosphinoylaniline, coordination chemistry and applications in platinum group catalyzed Suzuki coupling reactions and hydrosilylations

The aprotic and protic bi- and multidentate iminophosphines 2-Ph₂PC₆H₄N=CR¹R² (R¹=H, R²=Ph=2a; R¹=Me R²=Ph=2b; R¹=H, R²=2-thienyl=2c; R¹=H, R²=C₆H₄-2-PPh₂=2d; R¹=H, R²=C₆H₄-2-OH=2e, R¹=H, R²=C₆H₄-2-OH-3-Bu^t=2f; R¹=H, R²=CH₂C(O)Me=2g) have been prepared by the acid catalyzed condensation of 2-(diphenylphosphino)aniline with the corresponding aldehyde–ketone. Iminophosphine 2d can be reduced with sodium cyanoborohydride to give the corresponding amino-diphosphine 2-Ph₂PC₆H₄N(H)CH₂C₆H₄-2-PPh₂ (2h). In the presence of a stoichiometric quantity of acid, 2-(diphenylphosphino)aniline reacts in an unexpected manner with benzaldehyde, salicylaldehyde, or acetophenone to give the corresponding 2,3-dihydro-1H-benzo[1,3]azaphosphol-3-ium salts and with pyridine-2-carboxaldehyde to give N-(pyridin-2-ylmethyl)-2-diphenylphosphinoylaniline, the latter of which has been characterized by single-crystal X-ray crystallography, as its palladium dichloride derivative. The attempted condensation of 2-(diphenylphosphino)aniline with pyridine-2-carboxaldehyde to give the corresponding pyridine-functionalized iminophosphine resulted in an unusual transformation involving the diastereoselective addition of two equivalents of aldehyde to give 1,2-dipyridin-2-yl-2-(o-diphenylphosphinoyl)phenylamino-ethanol, which has been characterized by a single-crystal X-ray structure determination. The bidentate iminophosphine 2-Ph₂PC₆H₄N=C(H)Ph reacts with [(cycloocta-1,5-diene)PdClX] X=Cl, Me) to give [Pd{2-Ph₂PC₆H₄N=C(H)Ph}ClX] and the imino-diphosphine 2-Ph₂PC₆H₄N=C(H)C₆H₄-PPh₂ reacts with [(cycloocta-1,5-diene)PdClMe] to give [Pd{2-Ph₂PC₆H₄N=C(H)C₆H₄---PPh₂}ClMe] and each has been characterized by single-crystal X-ray crystallography. The monobasic iminophosphine 2-Ph₂PC₆H₄N=C(Me)CH₂C(O)Me reacts with [Ni(PPh₃)₂Cl₂] in the presence of NaH to give the phosphino–ketoiminate complex [Ni{2-Ph₂PC₆H₄N=C(Me)CHC(O)Me}Cl], which has been structurally characterized. Mixtures of iminophosphines 2a–h and a palladium source catalyze the Suzuki cross coupling of 4-bromoacetophenone with phenyl boronic acid. The efficiency of these catalysts show a marked dependence on the palladium source, catalysts formed from [Pd₂(OAc)₆] giving consistently higher conversions than those formed from [Pd₂(dba)₃] and [PdCl₂(MeCN)₂]. Catalysts formed from neutral bi- and terdentate iminophosphines 2a–d gave significantly higher conversions than those formed from their monobasic counterparts 2e–f. Notably, under our conditions the conversions obtained with 2a–c compare favorably with those of the standards; catalysts formed from tris(2-tolyl)phosphine and tris(2,4-di-tert-butylphenyl)phosphite and a source of palladium. In addition, mixtures of [Ir(COD)Cl]₂ and 2a–h are active for the hydrosilylation of acetophenone; in this case catalysts formed from monobasic iminophosphines 2e–f giving the highest conversions.     

A NON-EMPIRICAL LCAO MO SCF INVESTIGATION OF SOME ASPECTS OF STRUCTURE AND BONDING IN THE THIATHIOPHTHEN RING SYSTEM

Abstract

Non-empirical LCAO MO SCF calculations have been performed on prototype symmetrical and unsymmetrical thiathiophthen ring systems to investigate structure and bonding as a function of change in geometry. Substituent effects have been investigated and it is shown that within the theoretical limitations the energy differences between symmetrical and unsymmetrical structures are quite small. Comparison has been made with UPS and ESCA data pertaining to valence and core levels respectively and some consideration given to the thiathiophthen radical anion and dianion ring systems.     

Classification of the Ricci tensor

This paper contains a classification of the Ricci tensorR . The method of derivation is analogous to the spinor version of the Petrov classification of the Weyl tensor. It is shown how the various classes are related to the number and type of eigenvectors and eigenvalues ofR . The classification is useful in the geometrization of various fields. The case of a real scalar field is treated in detail.Supported in part by the National Research Council of Canada.     

Development of a validated liquid chromatography/tandem mass spectrometry method for the distinction of thyronine and thyronamine constitutional isomers and for the identification of new deiodinase substrates

Thyronines (THs) and thyronamines (TAMs) are two groups of endogenous iodine-containing signaling molecules whose representatives differ from each other only regarding the number and/or the position of the iodine atoms. Both groups of compounds are substrates of three deiodinase isozymes, which catalyze the sequential reductive removal of iodine from the respective precursor molecule. In this study, a novel analytical method applying liquid chromatography/tandem mass spectrometry (LC-MS/MS) was developed. This method permitted the unequivocal, simultaneous identification and quantification of all THs and TAMs in the same biological sample. Furthermore, a liquid-liquid extraction procedure permitting the concurrent isolation of all THs and TAMs from biological matrices, namely deiodinase (Dio) reaction mixtures, was established. Method validation experiments with extracted TH and TAM analytes demonstrated that the method was selective, devoid of matrix effects, sensitive, linear over a wide range of analyte concentrations and robust in terms of reproducible recoveries, process efficiencies as well as intra-assay and inter-assay stability parameters. The method was applied to study the deiodination reactions of iodinated THs catalyzed by the three deiodinase isozymes. With the HPLC protocol developed herein, sufficient chromatographic separation of all constitutional TH and TAM isomers was achieved. Accordingly, the position of each iodine atom removed from a TH substrate in a Dio-catalyzed reaction was backtracked unequivocally. While several established deiodination reactions were verified, two as yet unknown reactions, namely the phenolic ring deiodination of 3',5'-diiodothyronine (3',5'-T2) by Dio2 and the tyrosyl ring deiodination of 3-monoiodothyronine (3-T1) by Dio3, were newly identified.     

Application of negative ion MS/MS to the identification of N-glycans released from carcinoembryonic antigen cell adhesion molecule 1 (CEACAM1)

Structures of N-glycans released from rat CEACAM1 expressed in human embryonic kidney cells were determined by MALDI and negative ion nanospray MS/MS techniques. The major carbohydrates were bi-, tri- and tetra-antennary complex glycans with and without sialic acid, fucose and bisecting GlcNAc residues. High-mannose glycans, predominantly Man(5)GlcNAc(2), were also found. The negative ion fragmentation technique easily identified the branching pattern of the triantennary glycans (mainly branched on the 6-antenna) and the presence of 'bisecting' GlcNAc residues (attached to the 4-position of the core mannose), features that are difficult to determine by traditional techniques. Sialic acids were in both alpha2-3 and alpha2-6 linkage as determined by MALDI-TOF MS following linkage-specific derivatization.     

Ultraheavy Yukawa-bound states of fourth-generation at Large Hadron Collider

A study of bound states of the fourth-generation quarks in the range of 500?C700 GeV is presented, where the binding energies are expected to be mainly of Yukawa origin, with QCD subdominant. Near degeneracy of their masses exhibits a new ??isospin??. The production of a colour-octet, isosinglet vector meson via $q\bar q \to \omega_8$ is the most interesting. Its leading decay modes are $\pi_8^\pm W^\mp$ , $\pi_8^0Z^0$ , and constituent quark decay, with $q\bar q$ and $t\bar t'$ and $b\bar b'$ subdominant. The colour octet, isovector pseudoscalar ?? ₈ meson decays via constituent quark decay, or to Wg. This work calls for more detailed study of fourth-generation phenomena at LHC.     

MALDI-MS/MS with Traveling Wave Ion Mobility for the Structural Analysis of N-Linked Glycans

The preference for singly charged ion formation by MALDI makes it a better choice than electrospray ionization for profiling mixtures of N-glycans. For structural analysis, fragmentation of negative ions often yields more informative spectra than fragmentation of positive ones but such ions are more difficult to produce from neutral glycans under MALDI conditions. This work investigates conditions for the formation of both positive and negative ions by MALDI from N-linked glycans released from glycoproteins and their subsequent MS/MS and ion mobility behaviour. 2,4,6-Trihydroxyacetophenone (THAP) doped with ammonium nitrate was found to give optimal ion yields in negative ion mode. Ammonium chloride or phosphate also yielded prominent adducts but anionic carbohydrates such as sulfated N-glycans tended to ionize preferentially. Carbohydrates adducted with all three adducts (phosphate, chloride, and nitrate) produced good negative ion CID spectra but those adducted with iodide and sulfate did not yield fragment ions although they gave stronger signals. Fragmentation paralleled that seen following electrospray ionization providing superior spectra than could be obtained by PSD on MALDI-TOF instruments or with ion traps. In addition, ion mobility drift times of the adducted glycans and the ability of this technique to separate isomers also mirrored those obtained following ESI sample introduction. Ion mobility also allowed profiles to be obtained from samples whose MALDI spectra showed no evidence of such ions allowing the technique to be used in conditions where sample amounts were limiting. The method was applied to N-glycans released from the recombinant human immunodeficiency virus glycoprotein, gp120.     

Atmospheric Oxygen Mediated Radical Hydrothiolation of Alkenes

A mild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. A variety of sulfur containing motifs including alkanethiols, thiophenols and thioacids undergo an atmospheric oxygen-mediated radical hydrothiolation reaction with a plethora of alkenes in good yield with excellent functional group compatibility, typically with short reaction times to furnish a range of functionalized products. Biomolecules proved tolerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds through radical intermediates in a thiol-ene reaction manifold. The methodology offers an efficient “green” approach for thiol-ene mediated “click” ligation and a milder alternative to thermally initiated hydrothiolation processes.     

The evolution of viscoelasticity near the gel point of end-linking poly(dimethylsiloxane)s

The linear viscoelasticity of polymers near the gel point can be described by two scaling laws. The material at the gel point has a power-law linear viscoelastic relaxation modulus, and the relaxation exponent has been found to vary with the composition of the precursor materials, i.e., it is not universal for gelation. A second scaling law describes the evolution of the linear viscoelastic properties through the gel point. The rate of change of the dynamic mechanical modulus/viscosity is observed to scale as a power-law function of frequency. This power-law function defines a dynamic critical exponent, and this has been found to be independent of precursor composition for end-linking poly(dimethylsiloxane) polymers and equal to κ = 0.21 ± 0.02. This exponent may be a universal measure of gelation. The technique of Time Resolved Mechanical Spectroscopy is used to observe the evolution of linear viscoelastic properties of crosslinking polymers in situ in the rheometer. A stretched exponential relaxation modulus describes the evolution of mechanical properties in the vicinity of the gel point very well. The exponents which characterize the divergence of the zero-shear viscosity and the equilibrium modulus are not universal, since they are related to the relaxation exponent and the dynamic critical exponent.