Characterization of the solvation environment provided by dilute aqueous solutions of novel siloxane polysoaps using the fluorescence probe pyrene

Solubilization environment afforded by several of the novel allyl glycidyl ether-modified methylhydrosiloxane polymers are investigated using a common polycyclic aromatic hydrocarbon fluorescence probe, pyrene. The backbone of the polymer has been modified by the addition of an alkyl chain of varying length (either C8, C12, or C18) and to differing degrees of substitution. The nomenclature adopted for the purposes of these studies is as follows: "AGENT" represents the backbone polymer with no alkyl substitution, and "OAGENT", "DAGENT", and "SAGENT" are substituted with n-octyl, n-dodecyl, and n-octadecyl, respectively. The percentage of alkyl substitution is designated as 10, 15, and 20%. The pyrene polarity scale (defined as the ratio of the intensity of peak I to peak III) was used to determine the relative dipolarity of the cybotactic region provided by approximately 1 w/w% aqueous polymer solutions compared to 10 mM sodium dodecylsulfate (SDS) micellar solution. Results indicate that 10-15% DAGENT afforded the most hydrophobic solubilization site, followed by 15% OAGENT and 15% SAGENT. In addition, as the degree of alkyl substitution of DAGENT increased from 10 to 20%, the cybotactic region appeared to become more hydrophobic. Furthermore, a deeper investigation into the relative size of the solubilization site revealed that all alkyl-substituted polymers promoted excimer formation at relatively low pyrene concentrations, indicating the possibility of localized concentration enhancement within the solvation pockets and/or compartmentalization of the solute molecules. The pyrene fluorescence excitation data strongly indicates ground-state heterogeneity that is most prominent in AGENT and decreases as the alkyl chain length is increased. This provides a relative sense of the size and shape of the solvation pockets afforded by each polymer solution. An overall analysis of the collected data indicated that these alkyl-substituted polymers may provide a more selective and efficient pseudostationary phase in electrokinetic chromatography with better solvation capacity for hydrophobic compounds compared to SDS.     

The active-site structure of umecyanin, the stellacyanin from horseradish roots

The type 1 copper sites of cupredoxins typically have a His(2)Cys equatorial ligand set with a weakly interacting axial Met, giving a distorted tetrahedral geometry. Natural variations to this coordination environment are known, and we have utilized paramagnetic (1)H NMR spectroscopy to study the active-site structure of umecyanin (UMC), a stellacyanin with an axial Gln ligand. The assigned spectra of the Cu(II) UMC and its Ni(II) derivative [Ni(II) UMC] demonstrate that this protein has the typical His(2)Cys equatorial coordination observed in other structurally characterized cupredoxins. The NMR spectrum of the Cu(II) protein does not exhibit any paramagnetically shifted resonances from the axial ligand, showing that this residue does not contribute to the singly occupied molecular orbital (SOMO) in Cu(II) UMC. The assigned paramagnetic (1)H NMR spectrum of Ni(II) UMC demonstrates that the axial Gln ligand coordinates in a monodentate fashion via its side-chain amide oxygen atom. The alkaline transition, a feature common to stellacyanins, influences all of the ligating residues but does not alter the coordination mode of the axial Gln ligand in UMC. The structural features which result in Cu(II) UMC possessing a classic type 1 site as compared to the perturbed type 1 center observed for other stellacyanins do not have a significant influence on the paramagnetic (1)H NMR spectra of the Cu(II) or Ni(II) proteins.     

Synthesis of 1,1-diarylethylenes from an α-stannyl β-silylstyrene

The synthesis of a family of 1,1-diarylethylenes from an α-stannyl β-silylstyrene through a combination of a Stille coupling and a protodesilylation reaction is described. This approach avoids the problematic cine-substitution, which is a well documented side reaction during the palladium-assisted elaboration of α-substituted vinylstannanes to 1,1-disubstituted ethylenes.     

AN ULTRAVIOLET RADIATION ACTION SPECTRUM FOR IMMEDIATE PIGMENT DARKENING

The wavelength dependence for immediate pigment darkening (IPD) was investigated by exposing the midback skin of volunteers to a series of incremental fluences of narrow waveband radiation isolated by band-pass filters in the310–400 nm region. The threshold IPD fluence for each waveband was determined by visual assessment of the skin responses immediately after each exposure. The action spectrum, constructed from the mean threshold fluences, was broad and extended from 320 nm to 400 nm with a peak at around 340 nm. No IPD could be evoked at 310 nm, even after erythemogenic fluences. The spectrum was similar in each of the three skin types investigated (III, IV, V). The broad nature of the action spectrum within the UVA region suggests that IPD may serve as an alternative endpoint for measuring photoprotection against these wavelengths.     

Comparative resin kinetics using in situ fluorescence measurements

The aminolysis of a novel activated ester resin was utilized for kinetic study via continuous in situ fluorescence measurements. A variety of resin compositions (polystyrene, JandaJel, ArgoPore, TentaGel, NovaGel, and PEGA) and solvents (dimethylformamide, acetonitrile, tetrahydrofuran, 1,2-dichlorethane, and toluene) were tested to compare their effects on the reaction rate. A linear relationship between the reaction rate and (solvent polarity x swelling of resin) was elucidated for the aminolysis reaction.     

A novel technique to specifically analyze the secretome of cells and tissues

The secretome of cells and tissues may reflect a broad variety of pathological conditions and thus represents a rich source of biomarkers. The identity of secreted proteins, usually isolated from cell supernatants or body fluids, is hardly accessible by direct proteome analysis, because these proteins are often masked by high amounts of proteins actually not secreted by the investigated cells. Here, we present a novel method for the specific detection of proteins secreted by human tissue specimen as well as cultured cells and chose liver as a model. The method is based on the metabolic labelling of proteins synthesized during a limited incubation period. Then, the cell supernatant is filtered, precipitated, and subjected to two-dimensional gel electrophoresis. Whereas fluorography detected a large number of proteins derived from residual plasma and dead cells, the autoradiographs selectively displayed genuinely secreted proteins. We demonstrate the feasibility of this approach by means of the secretomes of the hepatocellular carcinoma-derived cell line HepG2 and human liver slices. The selective identification of cell- and tissue-specific protein secretion profiles may help to identify novel sets of biomarkers for wide clinical applications.     

Generation of 3-pyridyl biaryl systems via palladium-catalyzed Suzuki cross-couplings of aryl halides with 3-pyridylboroxin

The synthesis of 3-pyridyl biaryl systems can be readily achieved by means of palladium-catalyzed Suzuki cross-coupling reactions between aryl halides and 3-pyridylboroxin. A series of cross-couplings were conducted in order to investigate the scope and limitations of this protocol.     

Different forms of perturbation theory for the calculation of the correlation energy

Different forms of perturbation theory for the calculation of correlation energy in both closed-and open-shell systems are discussed. For closed-shell systems, Epstein–Nesbet perturbation theory is compared with Møller–Plesset (MP ) perturbation theory based on canonical Hartree–Fock orbitals and with MP theory based on internally consistent SCF orbitals. The traditional MP theory gives superior results despite its use of an inferior zeroth-order Hamiltonian. This behavior is rationalized in terms of the larger denominators present in the traditional MP theory. These conclusions are used to support the restricted open-shell perturbation methods proposed recently by Murray and Davidson, and these new methods are compared with spin-restricted Epstein–Nesbet theory and the unrestricted MP (UMP ) approach. © 1992 John Wiley & Sons, Inc.     

Tuning the singlet oxygen quantum yield of near-IR-absorbing porphyrazines

We report the quantum yields for singlet oxygen production by a series of porphyrazines (pz) of the form M[pz(An;B4-n)] (Scheme 1), where the peripheral substituent A is [S-R]2 with R = (CH2CH2O)3H, B is a fused alpha,alpha'-dialkoxybenzo group and M = 2H, Mg or Zn. These compounds show intense near-IR absorbance/emission (longest wavelength emission, approximately 830 nm). Their solubilities vary with R, whereas their optical properties do not. We show that singlet oxygen sensitization by these luminescent compounds can be "tuned" from essentially off to on by varying n and selection among M = 2H, Mg or Zn. The quantum yields vary ca 60-fold within the set of compounds studied, from phidelta = 0.007 for compound 3 to phidelta = approximately 0.4 for compound 11.     

Microwave-assisted "libraries from libraries" approach toward the synthesis of allyl- and C-cyclopropylalkylamides

Cascade reactions of internal and terminal alkynes, zirconocene hydrochloride, dimethylzinc, and phosphinoyl imines (prepared in one step from aldehydes and diphenylphosphinoyl amide) lead to allylic phosphinoyl amides after aqueous workup. Microwave acceleration allows the completion of this one-pot reaction sequence in 10 min. These allylic amides can be converted into a variety of derivatives, including carbamates and sulfonamides, or reacted prior to workup with diiodomethane to give novel C-cyclopropylalkylamides. A solution-phase "libraries from libraries" approach was used to generate an intermediate 20-member library which was subsequently expanded to a 100-member library by a series of N-functionalizations. The biological activity was evaluated in an assay for competitive binding to the estrogen receptor (ERalpha), revealing three potent lead compounds of a new structural type.