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81.
The syntheses, structures, and spectroscopy of a series of oligomeric tertiary oligophenylureas possessing one to five phenyl rings are reported. A convergent synthetic method employing tertiary monoamine and diamine building blocks is employed. NMR and molecular modeling are indicative of folded structures for all of the oligophenylureas in which adjacent phenyl rings have a splayed face-to-face geometry. NMR chemical shifts, absorption and emission maxima, and electrochemical oxidation potentials are all dependent upon the number of phenyl rings. The addition of a first inner phenyl has a pronounced effect on the chemical shifts, while a second and third inner phenyl have diminished effects. The oxidation potentials of the oligophenylureas display an abrupt decrease upon the addition of the second inner phenyl. The absorption and emission spectra are relatively insensitive to the addition of one to three inner phenyl rings. The electronic structures of the oligophenylureas possessing one to eight rings have been analyzed using ZINDO calculations. The frontier orbitals of the ureas with one to three phenyl rings are localized on a single phenyl ring (the inner ring for the three-ring urea), whereas the frontier orbitals of the higher oligomers are delocalized over two phenyl rings. In all cases, urea-localized n,pi* transitions are lower in energy than the phenyl-localized pi,pi* transitions. The changes in properties with added phenyl rings parallel those previously observed for multilayered cyclophanes; however, they are less pronounced because of weaker coupling between the phenyl rings of the oligophenylureas. 相似文献
82.
Optical absorbance changes are commonly used to characterize intermediates which appear in the bleaching sequence of rhodopsin and in the photocycle of bacteriorhodopsin. Absorbance changes can be caused by an intermediate's rotational diffusion, and when this occurs it can distort absorbance changes due to the structural evolution of intermediates. Linear polarization of an optical probe source at 54.7 degrees (the magic angle) relative to the polarization direction of a linearly polarized actinic source has often been used to eliminate signals due to rotational diffusion. We used Jones calculus to investigate the validity of the magic-angle strategy. Taylor expansion of the result in powers of the absorbances of the bleached ground state and of the intermediates leads to a relatively simple expression which can be used to determine whether rotational contributions are likely under various experimental conditions. This expression shows that in first order no dichroism-dependent term appears in the absorbance measured at magic angle. In second order, however, linear dichroism contributes to signals. For the sequence of rhodopsin intermediates: rhodopsin hv----bathorhodopsin in equilibrium BSI----lumirhodopsin, where BSI is a recently discovered blue-shifted intermediate, we determined the magnitude of the dichroism signals to be, on average, less than 2% of the true absorbance change due to the intermediates themselves (and hence undetectable). Freedom from dichroism artifacts in this case results from the fact that the transition dipoles of these intermediates are similar to that of rhodopsin. Larger and certainly detectable dichroism signals are predicted to occur, even at the magic angle, for later intermediates which have transition dipole moments which differ significantly from that of rhodopsin.(ABSTRACT TRUNCATED AT 250 WORDS) 相似文献
83.
84.
Rashid MA Gustafson KR Crouch RC Groweiss A Pannell LK Van QN Boyd MR 《Organic letters》2002,4(19):3293-3296
Poecillastrin A (1), a new polyketide-derived macrolide lactam, was isolated from a deep-water collection of the marine sponge Poecillastra species. The structure of poecillastrin A (1) was assigned using NMR data acquired at 500 MHz with an inverse-detection cryogenic probe and at 800 MHz with a room-temperature probe. 相似文献
85.
C. R. Lewis 《Journal of polymer science. Part A, Polymer chemistry》1983,21(5):1543-1550
Metals may be chemically incorporated into organic lithographic resists that contain or can be functionalized with ? OH groups. A wide range of metal incorporation (0.04–12% of total solids by weight) has been demonstrated for AZ-1370 (Shipley), a diazo-type photo- and electron resist. The novolac component of the resist is reacted with an organometallic halide, RyMX (R = alkyl, aryl; M = transition or main group metal; X = CI, Br; 1 ≤ y ≤ 4, depending on M) to introduce the corresponding organometallic function into the resist. 相似文献
86.
Three-dimensional (3-D) structures with micron-sized features have been fabricated via the direct-write assembly of polyelectrolyte inks. By mixing oppositely charged species under solution conditions that promote polyelectrolyte exchange reactions, we have created concentrated fluids capable of flowing through microscale deposition nozzles. Ink deposition into an alcohol/water coagulation reservoir yielded polyelectrolyte filaments that rapidly solidify to enable three-dimensional patterning of microperiodic structures with self-supporting features. The influence of ink and reservoir chemistry on the phase behavior, rheological properties, and assembly of concentrated polyelectrolyte complexes is reported with an emphasis on the optimal conditions for 3-D writing. 相似文献
87.
Kevin F. Morris Eugene J. Billiot Fereshteh H. Billiot Jordan A. Ingle Kevin B. Krause Corbin R. Lewis 《Journal of Dispersion Science and Technology》2019,40(5):716-727
Molecular dynamics (MD) simulations were used to investigate the binding of six chiral compounds to the amino acid-based molecular micelle (MM) poly-(sodium undecyl-(L)-leucine-leucine) or poly(SULL). The MM investigated is used as a chiral selector in capillary electrophoresis. The project goal was to characterize the chiral recognition mechanism in these separations and to move toward predictive models to identify the best amino acid-based MM for a given separation. Poly(SULL) was found to contain six binding sites into which chiral compounds could insert. Four sites had similar sizes, shapes, and electrostatic properties. Enantiomers of alprenolol, propranolol, 1,1′-bi-2-naphthyl-2,2′-diyl hydrogen phosphate, 1,1′-bi-2-naphthol, chlorthalidone, or lorazepam were separately docked into each binding pocket and MD simulations with the resulting intermolecular complexes were performed. Solvent-accessible surface area calculations showed the compounds preferentially associated with binding sites where they penetrated into the MM core and shielded their non-polar atoms from solvent. Furthermore, with five of the six compounds the enantiomer with the most favorable free energy of MM association also experienced the most favorable intermolecular hydrogen bonding interactions with the MM. This result suggests that stereoselective intermolecular hydrogen bonds play an important role in chiral discrimination in separations using amino acid-based MMs.GRAPHICAL ABSTRACT 相似文献
88.
Mass spectra of five benzotriazinone derivatives are reported and the fragmentation mechanisms are discussed. That the first loss of 28 mass units is a nitrogen molecule appears to be characteristic of the molecules. 相似文献
89.
Nicole Brasseur Karina Lewis Jacques Rousseau Johan E. van Ller 《Photochemistry and photobiology》1996,64(4):702-706
Abstract— The clinical perfusion agent 99m Tc-MIBI was used to monitor changes in tumor vascular perfusion (TVP) induced by Photofrin® (Pll)-mediated photodynamic therapy (PDT). BALB/c mice bearing an EMT-6 tumor on each hind thigh were given an intravenous injection of 1, 2 or 5 mg kg−1 PII. Twenty-four hours later, one tumor was illuminated (600–650 run, 200 mW cm−2 400 J cm−2 ) while the other served as a control. At various time intervals after PDT (0, 2 and 24 h) mice received an intravenous injection of 99m Tc-hexakismethoxy(sobutyusonitri-le (MIBI) (0.18 MBq g−1 ) and were sacrificed 2 min later. The light-treated and the untreated tumors were then dissected, the radioactivity was counted and the percentage of the injected dose per gram of tumor (%ID g−1 ) was calculated as a measure of TVP. We observed that TVP is drug dose dependent, develops progressively with time post-PDT and is inversely related to PDT efficacy. Our data show that early tumor retention of 99m MIBI is a simple method to assess TVP and vascular damage induced by PDT. 相似文献
90.
In an effort to identify promising non-hydroxamate inhibitors of matrix metalloproteinases (MMPs), several new zinc-binding groups (ZBGs) based on pyrone, pyrothione, hydroxypyridinone, and hydroxypyridinethione chelators have been examined. Structural studies with tris(pyrazolyl)borate model complexes show that these ligands bind to the MMP active site zinc(II) ion in a bidentate fashion, similar to that found with hydroxamate-based inhibitors. Fluorescence- and colorimetric-based enzyme assays have been used to determine the IC50 values for these ZBGs against MMP-3; mixed O,S-donor ligands were found to be remarkably potent, with IC50 values as much as 700-fold lower than that found for acetohydroxamic acid. Inhibitory activity was found to parallel metal binding affinity as determined in titrations with model complexes. These results demonstrate that MPIs based on new ZBGs are feasible and may indeed improve the overall performance of inhibitors designed against these important medicinal targets. 相似文献