Frequency Domain Fluorescence Lifetime Study of Crude Petroleum Oils

Frequency domain (FD) fluorescence lifetime data was collected for a series of 20 crude petroleum oils using a 405 nm excitation source and over a spectral range of ~426 to ~650 nm. Average fluorescence lifetimes were calculated using three different models: discrete multi-exponential, Gaussian distribution, and Lorentzian distribution. Fitting the data to extract accurate average lifetimes using the various models proved easier and less time consuming for the FD data than with Time Correlated Single Photon Counting (TCSPC) methods however the analysis of confidence intervals to the computed average lifetimes proved cumbersome for both methods. The uncertainty in the average lifetime was generally larger for the discrete lifetime multi-exponential model when compared to the distribution-based models. For the lifetime distributions, the data from the light crude oils with long lifetimes generally fit to a single decay term. Heavier oils with shorter lifetimes required multiple decay terms. The actual value for the average lifetime is more dependant on the specific fitting model employed than the data acquisition method used. Correlations between average fluorescence lifetimes and physical and chemical parameters of the crude oils were made with a view to developing a quantitative model for predicting the gross chemical composition of crude oils. It was found that there was no significant benefit gained by using FD over TCSPC other than more rapid data analysis in the FD case. For the FD data the Gaussian distribution model for fluorescence lifetime gave the best correlations with chemical composition allowing a qualitative correlation to some bulk oil parameters.

Vapoluminescent Behavior and the Single-Crystal-to-Single-Crystal Transformations of Chloroform Solvates of [Au2(μ-1,2-bis(diphenylarsino)ethane)2](AsF6)2

The mono- and di-chloroform solvates of [Au₂(μ-1,2-bis(diphenylarsino)ethane)₂](AsF₆)₂ undergo single-crystal-to-single-crystal transformations that result in gain (over 12 hours) or slow loss (over five years) of only one chloroform molecule. The change in solvation results in changes in the structure and luminescence of the digold cation. The cation consists of a pair of slightly bent As-Au-As units that are connected through the two bridging dpae ligands and by aurophilic interactions with Au⋅⋅⋅Au contacts of 3.05152(15) Å in the disolvate or 2.9570(5) Å in the monosolvate.     

A note on dual modules and the transpose

Archiv der Mathematik - It is a classical result in matrix algebra that any square matrix over a field can be conjugated to its transpose by a symmetric matrix. For F a non-Archimedean local field,...     

Synthesis,Structure, and DFT Analysis of the THF Solvate of 2-Picolyllithium: A 2-Picolyllithium Solvate with Significant Carbanionic Character

Previous studies of different solvates of 2-methylpyridyllithium (2-picolyllithium) have uncovered electronic structures corresponding to aza-allyl and enamido resonance forms of the metallated pyridine-based compounds. Here, we report the synthesis and characterization of [2-CH₂Li(THF)₂C₅H₄N], a new THF solvate. X-ray crystallographic studies reveal a dimeric arrangement featuring a non-planar eight-membered [NCCLi]₂ ring, in which the primary cation-anion interaction is between the central Li atom and the C atom of the deprotonated methyl group [length, 2.285(2) Å], suggesting a new carbanionic resonance structure for this 2-picolyllithium series. The significant carbanionic character of [2-CH₂Li(THF)₂C₅H₄N] was confirmed by gas-phase DFT calculations [B3LYP/6-311+G(d)] with the calculated electron density interrogated by means of quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses. For comparison these computational analyses were also performed on the literature structures of [2-CH₂Li(2-Picoline)C₅H₄N] and [2-CH₂Li(PMDETA)C₅H₄N]. In a reactivity study, [2-CH₂Li(THF)₂C₅H₄N] was found to undergo nucleophilic addition to pyridine to generate dipyridylmethane in a good yield.     

The development and validation of a novel LC–MS/MS method for the quantification of cenicriviroc in human plasma and cerebrospinal fluid

A high-performance liquid chromatography tandem mass spectrometric method was developed and validated for cenicriviroc (CVC) quantification in human plasma and cerebrospinal fluid (CSF). The method involved precipitation with acetonitrile and injecting supernatants onto the column. Separation was achieved on an XBridge C₁₈ column with a gradient elution of 0.1% formic acid in water and acetonitrile. Analyte detection was conducted in positive ion mode using selected reaction monitoring. The m/z transitions were: CVC (697.3 → 574.3) and CVC-d7 (704.4 → 574.3). Calibration curve ranged from 5 to 1000 ng/mL for plasma and from 0.241 to 15.0 ng/mL for CSF. The intra- and inter-day precision and accuracy were <15% for both plasma and CSF across four different concentrations. CVC recovery from plasma and artificial CSF was >90%. The method was utilized for the measurement of patients’ plasma and CSF samples taking a dose of 50, 150 and 300 mg q.d.     

On the nonexistence of certain Hughes generalized quadrangles

In this paper, we prove that the Hermitian quadrangle is the unique generalized quadrangle Γ of order (q ², q ³) containing some subquadrangle of order (q ², q) isomorphic to such that every central elation of the subquadrangle is induced by a collineation of Γ. Dedicated to Dan Hughes on the occasion of his 80th birthday.     

On closures of cycle spaces of flag domains

Open orbits D of noncompact real forms G ₀ acting on flag manifolds Z = G/Q of their semisimple complexifications G are considered. Given D and a maximal compact subgroup K ₀ of G ₀, there is a unique complex K ₀–orbit in D which is regarded as a point in the space of q-dimensional cycles in D. The group theoretical cycle space is defined to be the connected component containing C ₀ of the intersection of the G–orbit G(C ₀) with . The main result of the present article is that is closed in . This follows from an analysis of the closure of the universal domain in any G-equivariant compactification of the affine symmetric space G/K, where K is the complexification of K ₀ in G.     

On strongly-non-reflexive groups

A strong negative answer is given to the old question of whether every dual group is reflexive. Using ◊_ω1 a groupA is constructed so thatA, A*, A**, andA*** are weakly ω₁-separable groups of cardinalityω ₁ andA* is not isomorphic toA***. Research partially supported by NSF Grant No. DMS-8400451. Research partially supported by NSERC Grant No. A8948.     

Reaping Numbers of Boolean Algebras

A subset A of a Boolean algebra B is said to be (n,m)-reapedif there is a partition of unity p B of size n such that |{b p:b a 0}| m for all a A. The reaping number r_n,m (B) ofa Boolean algebra B is the minimum cardinality of a set A B\{0}which cannot be (n,m)-reaped. It is shown that for each n, thereis a Boolean algebra B such that r_n+1,2(B) r_n,2(B). Also, {r_n,m(B):mn } consists of at most two consecutive cardinals. The existenceof a Boolean algebra B such that r_n,m (B) r_n',m' (B) is equivalentto a statement in finite combinatorics which is also discussed.     

Positive Operator Majorization and <Emphasis Type="Italic">p</Emphasis>-hyponormality

In this note we examine the relationships between p-hyponormal operators and the operator inequality . This leads to a method for generating examples of p-hyponormal operators which are not q-hyponormal for any . Our methods are also shown to have implications for the class of Furuta type inequalities.