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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 3506-3510 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fluorescence excitation and emission spectra have been measured for solid solutions of 2,2':5',2‘-terthiophene in n-decane at 77, 10, and 4.2 K. At 4.2 K the spectra exhibit full vibrational resolution (origin inhomogeneous FWHM approximately 5 cm−1). At 4.2 K narrow band excitation and detection establish that there are four independent but nearly identical excitation/emission pairs with origins at 24 806, 24 827, 24 835, and 24 879 cm−1. Whether this multiplicity is caused by the presence of different isomers or comes from a single isomer that can occupy in the n-decane lattice in four different ways is not known with certainty. However, the similarity of the vibronic development and energetic considerations suggest that the spectra arise from a single isomer present in four rather similar n-decane sites or from four slightly different conformations of a single isomer. The overlap of excitation and emission origins and the vibrational development of the spectra establish that the S0 to S1 transition is symmetry allowed (probably reasonably described as the 1 1A1 to 1 1B2 transition where the excited state is derived from the ground state by the promotion of one electron from the HOMO to LUMO).
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 4783-4789 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Vibrationally resolved fluorescence and fluorescence excitation spectra have been measured for solid solutions of 2,2'-bithiophene, 2,2'-thienylpyrrole, and 2,2'-bipyrrole in n-hexane at 4.2 K. The vibronic development of the spectra of all three molecules is very similar to what has been reported previously for longer polythiophene oligomers. Bithiophene and thienylpyrrole have similar S0 to S1 excitation energies: 29 603 and 30 006 cm−1, respectively. The S0 to S1 excitation energy of bipyrrole is significantly higher, 32 720 cm−1, indicating nonplanarity of the pyrrole rings. The vibrational development of the spectra and coincident origin energies in excitation and emission establish that the S0 to S1 transition is symmetry allowed for all three molecules, reasonably described in simple molecular orbital theory as the promotion of one electron from the highest energy occupied molecular orbital (HOMO) to the lowest energy unoccupied molecular orbital (LUMO).
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 1684-1691 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fluorescence and fluorescence excitation spectra for low temperature n-alkane solutions of α,ω-dithenylpolyenes with two, three, and four polyene double bonds have been measured. The fundamental frequencies in the vibronic development of the fully resolved spectra are either nearly identical to modes seen for unsubstituted polyenes or nearly identical to modes seen for polythiophene oligomers. The degree to which thiophene ring modes contribute to the spectra decreases with increasing polyene chain length. In the tetraene, the 2 1Ag state is 2760 cm−1 lower in energy than the 1 1Bu state, in the triene it is 1570 cm−1 lower, and in the diene these two states are nearly degenerate. The 2 1Ag and 1 1Bu excitation energies are well fit by a simple theoretical model which also gives a description of the π-electron distributions in the 1 1Ag, 2 1Ag, and 1 1Bu states.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 2492-2495 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The 0–0 excitation energy of a 1Ag state of 2,2'-bithiophene has been determined by measuring the two-photon fluorescence excitation spectrum of a dilute solution of this molecule in crystalline n-hexane at 77 K. Because the 0–0 energy is what would have been predicted by extrapolating previously measured α,ω-dithienylpolyene 2 1Ag 0–0 energies to zero polyene chain length, it is assigned to the 2 1Ag state. The 0–0 band is centered at 36 173 cm−1, approximately 6570 cm−1 above the 0–0 of the 1 1Ag to 1 1Bu transition. This order of bithiophene excited singlet states is opposite to that of the linear polyene with the same number of double bond but may reverse for chains longer than six repeat units.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 165-169 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Fluorescence and fluorescence excitation spectra have been measured for solid solutions of tetrathiophene in tetradecane at 12 and 4.2 K. At 4.2 K, the spectra exhibit full vibrational resolution {inhomogeneous origin [full width at half-maximum, (FWHM)] approximately 5 cm−1 }. Narrow band excitation and detection establish that there are four independent, but nearly identical excitation/emission pairs with dipole allowed origins at 22 248, 22 241, 22 214, and 22 187 cm−1. The data are consistent with the idea that these multiple spectra come from a single tetrathiophene confomer which can occupy four different sites in the tetradecane lattice. The vibrational frequencies of the modes in the ground (excited) state that couple strongly to the electronic excitation are 162, 327, 703, 1478, and 1531 cm−1 (161, 333, 688, 1235, and 1551 cm−1 ). The overlap of the excitation and emission origins and vibrational development of the spectra establish that the S0 to S1 transition is symmetry allowed (1 1Ag to 1 1Bu for C2h all-trans tetrathiophene) with the excited 1 1Bu state described reasonably as being derived from the ground state by the promotion of one electron from the highest energy occupied molecular orbital to the lowest energy unoccupied molecular orbital (HOMO to LUMO).
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 97 (1993), S. 3091-3094 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0368-492X
    Source: Emerald Fulltext Archive Database 1994-2005
    Topics: Computer Science
    Notes: We present a detailed explanation of a mathematical method and numerical technique applied to solve an irregular non-linear fitting problem that results from attempts to model the calorimetric profiles generated by the binding of phenolic ligands to the insulin hexamer. The method employed uses a non-traditional approach to modeling data. Rather than start with a simplified model, we use a hierarchical tree of physical models with different degrees of sophistication. Starting with the model of highest dimension, we work our way to an optimum model which is of a lower dimension and is less complex. The algorithm uses two complementary techniques. First, a sensitivity analysis in the vicinity of the optimal point for each model is used to estimate errors in the parameters; that, in turn, provides the user with insight for model simplification. Second, we utilize the optimized model in the prediction of new experimental curves. The core of the method combines a strategy based on the proper split of the initial global numerical task into three locally independent subtasks, and induces a specific split in the search space. The application of three different optimization techniques (two parametric and one variational) with an alternating objective function defined in corresponding subspaces, in combination with the search along the hierarchical tree of mathematical models, enables us to overcome difficult computational problems, including over-parametrization. We have obtained very accurate fits to a number of calorimetric curves, resulting in a quantitative description of intrinsic functional (free ligand concentration) and vector (equilibrium coefficients and enthalpies of binding) parameters. These quantitative results can now be used to improve the stability of insulin formulations. We believe that, with small modifications to the model, the method and algorithms presented in this article can be applied to other protein-ligand systems.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of nanoparticle research 2 (2000), S. 173-181 
    ISSN: 1572-896X
    Keywords: biodegradable ; poly(lactic acid-co-glycolic acid) ; drug delivery ; particle size ; aggregation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics , Technology
    Notes: Abstract Microparticles and nanoparticles of poly(lactic acid-co-glycolic acid) (PLAGA) are excellent candidates for the controlled release of many pharmaceutical compounds because of their biodegradable nature. The preparation of submicron PLAGA particles poses serious challenges that are not necessarily present when preparing microparticles. We have evaluated several combinations of organic solvents and surfactants used in the formulation of PLAGA nanoparticles. Critical factors such as the ability to separate the nanoparticles from the surfactant, the ability to re-suspend the nanoparticles after freeze-drying, formulation yield and nanoparticle size were studied. The smallest particles were obtained using the surfactant/solvent combination of sodium dodecyl sulfate and ethyl acetate (65 nm) and the largest particles were obtained using poly(vinyl alcohol) and dichloromethane (466 nm). However, the optimal nanoparticles were produced using either acetone or ethyl acetate as the organic solvent and poly(vinyl alcohol) or human serum albumin as the surfactant. This is because the most critical measure of performance of these nanoparticles proved to be their ability to re-suspend after freeze-drying.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 1573-904X
    Keywords: LysB28ProB29-human insulin ; insulin ; cobalt insulin hexamers ; hexameric association ; hexameric dissociation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Investigations into the kinetic assembly and dissociation of hexameric LysB28ProB29-human insulin (LysPro), a rapid-acting insulin analog produced by the sequence inversion of amino acids at positions B28 and B29, were designed to explain the impact that the sequence inversion has on the formulation and pharmacokinetics of the insulin analog. Methods. The kinetics of phenolic ligand binding to human insulin and LysPro were studied by stopped-flow spectroscopy. The kinetics of R6 hexamer disruption were studied by extraction of Co(II) with EDTA. Results. Phenolic ligand binding to human insulin yielded rate constants for a fast and slow phase that increased with increasing ligand concentration and are attributed to the T6 → T3R3 and T3R3 → R6 transitions, respectively. However, the kinetics of phenolic ligand binding with LysPro was dominated by rates of hexamer assembly. The kinetic differences between the insulin species are attributed to alterations at the monomer-monomer interface in the dimer subunit of the LysPro analog. The extraction of Co(II) from both hexameric complexes by EDTA chelation is slow at pH 8.0 and highly dependent on ligand concentration. Cobalt extraction from LysPro was pH dependent. Of the various phenolic ligands tested, the relative affinities for binding to the human and LysPro hexamer are resorcinol 〉 phenol 〉 m-cresol. Conclusions. The extraction data support the formation of an R6-type LysPro hexamer under formulation conditions, i.e., in the presence of divalent metal and phenolic ligand, that is similar in nature to that observed in insulin. However, the formation kinetics of LysPro identify a radically different monomeric assembly process that may help explain the more rapid pharmacokinetics observed with the hexameric formulation of LysPro insulin relative to human insulin.
    Type of Medium: Electronic Resource
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  • 10
    Publication Date: 1992-01-01
    Print ISSN: 0021-9606
    Electronic ISSN: 1089-7690
    Topics: Chemistry and Pharmacology , Physics
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