Steady-State and Time-Resolved Fluorescence Polarization Behavior of Acenaphthene

Steady-state and time-resolved fluorescence polarization studies have been carried out on acenaphthene (ACE) in low-temperature glass solutions and at room temperature. In the low-temperature glass the fluorescence polarization values vary considerably with both emission and excitation wavelength. There is a time dependence (on the nanosecond time scale) of the fluorescence anisotropy, r(t), at 77 K, which has a strong dependence upon the excitation and emission wavelengths. Under these conditions, the time-dependent decay of the anisotropy is not attributable to chromophoric motion. The observations are consistent with emission from two closely lying and interconverting excited states. Rate constants for the photophysical processes involved have been determined by fitting the data using a model proposed by Fleming et. al. The results are discussed with particular reference to the care required in using dynamic fluorescence polarization measurements to determine energy transfer rates in systems containing this chromophore.     

Synthesis,Alkali Metal Picrate Extraction Properties,and X-Ray Crystal Structure of a Novel,Cage-Annulated Monoaza-18-Crown-6 Host

Compound 5, a cage-annulated monoaza-18-crown-6 macrocyclic polyether, has been synthesized, and its alkali metal picrate extraction capabilities have been assessed relative to those of the parent monoaza-18-crown-6 host system. It was observed that both 5 and monoaza-18-crown-6 are selective K⁺ picrate extractants; however, 5 appears generally to be a somewhat more efficient alkali metal picrate extractant than monoaza-18-crown-6. Interestingly, both the avidity and selectivity of 5 toward extraction of alkali metal picrates from aqueous solution into CHCl₃ appears to be pH dependent. In addition, the X-ray crystal structure of an unusual hydronium ion complex of 5 [i.e., 5(HCl)(H ₂ O)-(CHCl ₃ ) ₂] has been determined. The X-ray structure thus determined is compared with the corresponding structure of 5(HCl)(H ₂ O) that has been calculated via application of B3LYP Density Functional Theory.     

Solid-state aggregation of mercury bis-acetylides, Hg(CCR)2, R=Ph, SiMe3

The structures of Hg(CCR)₂ (R=Ph, SiMe₃) show unusual aggregation in the solid state. When R=Ph there are eight independent molecules in the asymmetric unit, while for R=SiMe₃ there are pentameric aggregates. The Hg…Hg distances are 3.7–4.0 Å, possibly indicating weak mercuriophilic interactions, but the main driving force for clustering appears to be interactions between Hg atoms and the CC bonds of adjacent molecules.     

Michael addition reactions between various nucleophilic glycine equivalents and (S,E)-1-enoyl-5-oxo-N-phenylpyrrolidine-2-carboxamide,an optimal type of chiral Michael acceptor in the asymmetric synthesis of β-phenyl pyroglutamic acid and related compounds

(S)-5-Oxo-N-phenyl-1-[(E)-3-phenylacryloyl]pyrrolidine-2-carboxamide, easily prepared from inexpensive and readily available, in both enantiomeric forms, glutamic/pyroglutamic acid was designed as an optimal type of chiral Michael acceptor for reactions with a series of nucleophilic glycine equivalents. A study of the corresponding Michael addition reactions revealed that the new generation of modular glycine derivatives, as a counterpart to the Michael acceptor, provides for operationally convenient preparation of β-phenyl pyroglutamic acids and related compounds with virtually complete chemical and stereochemical outcomes.     

The development and validation of a high performance liquid chromatography (HPLC)/tandem mass spectrometry assay for fenticonazole in human plasma and comparison with an HPLC-UV method

A method is described for the determination of fenticonazole in human female plasma. The method utilizes high performance liquid chromatography coupled to atmospheric pressure positive-ion chemical ionization triple quadrupole mass spectrometry. Multiple reaction monitoring is employed for selectivity and sensitivity which enables quantification over the range 0.5–20 ng mL⁻¹ with acceptable precision and accuracy. A comparison is made with an existing HPLC-UV assay and the utility of the technology of combined liquid chromatography and tandem mass spectrometry for subnanogram per mL assays is discussed.     

Correct charge state assignment of native electrospray spectra of protein complexes

Correct charge state assignment is crucial to assigning an accurate mass to supramolecular complexes analyzed by electrospray mass spectrometry. Conventional charge state assignment techniques fall short of reliably and unambiguously predicting the correct charge state for many supramolecular complexes. We provide an explanation of the shortcomings of the conventional techniques and have developed a robust charge state assignment method that is applicable to all spectra.     

Andrews–Gordon type identities from combinations of Virasoro characters

For p∈{3,4} and all p′>p, with p′ coprime to p, we obtain fermionic expressions for the combination χ _1,s ^p,p′+q ^Δ χ _p−1,s ^p,p′ of Virasoro (W ₂) characters for various values of s, and particular choices of Δ. Equating these expressions with known product expressions, we obtain q-series identities which are akin to the Andrews–Gordon identities. For p=3, these identities were conjectured by Bytsko. For p=4, we obtain identities whose form is a variation on that of the p=3 cases. These identities appear to be new. The case (p,p′)=(3,14) is particularly interesting because it relates not only to W ₂, but also to W ₃ characters, and offers W ₃ analogues of the original Andrews–Gordon identities. Our fermionic expressions for these characters differ from those of Andrews et al. which involve Gaussian polynomials. BF is partially supported by grant number RFBR 05-01-01007, and OF by the Australian Research Council (ARC).     

Dynamics of pulse propagation in phase-shifted fibre Bragg gratings: a numerical investigation

Fibre Bragg gratings (FBGs) are an integral component of optical fibre based communication systems for signal processing. Uniform FBGs and phase-shifted FBGs find major applications as add-drop filters in dense wavelength division multiplexing (DWDM) systems where these are used to filter out channels and to shape the signal spectrum. We investigate numerically the spatiotemporal deformation of pulses as they propagate through the gratings. In particular, the effect on the pulse dynamics of phase shift or defect present in the gratings, often introduced intentionally in a grating to generate a narrow transmission spike within the stopband, is studied in time domain. This study is of significance since the deformation in the pulse in time limits the maximum bit rate achievable, and hence the pulse duration and shape need to be analysed and controlled accurately. A time domain numerical tool based on the Transmission Line Modelling (TLM) method is developed to study the pulse dynamics. The results obtained give useful information about the signal dynamics in gratings with defects, including the signal oscillations trapped in the defect, to be considered in applications such as while designing spectral filters.