Conformation of receptor-associated PGI2: An investigation by molecular modeling

Summary To elucidate the conformation of receptor-associated prostacyclin (PGI₂), we first performed structure-activity correlation analysis of over 200 PGI₂ analogues and derived from this analysis several crucial features pertaining to structural requirements for PGI₂ activity [Ah-lim Tsai and Kenneth K. Wu, Eicosanoids, 2 (1989) 131–143]. These structural features proved to be useful guidelines for selecting model molecules for further investigations by molecular mechanics. By properly selecting four analogues with either rigid or uniquely oriented -side chain structure for geometric fitting, we succeeded in maximally minimizing the degree of freedom of the carboxylate terminus of PGI₂. We were able to define the spatial relationship among the four critical functional groups, i.e., C1-COOH, C6a-O, C11-OH and C15-OH. More information is needed, however, to define the geometry of the -side chain, particularly for the moiety beyond C15. Nevertheless, results from structure-activity correlation analysis and molecular modeling provide useful information regarding the conformation of receptor-associated PGI₂, which assumes an elongated conformation instead of the traditional hairpin structure.     

Non-quadratic-intensity dependence of two-photon absorption induced fluorescence of organic chromophores in solution

We have provided a model to interpret the non-quadratic-intensity dependence behavior commonly observed in the two-photon fluorescence (TPF) experiment excited with high laser intensity. The model also provides one with a different technique to measure the two-photon absorption cross section of an organic chromophore in solution. In contrast to the commonly used low intensity technique that depends on the quadratic-intensity law, the present technique is based on the non-quadratic-intensity dependence of two-photon fluorescence. Auxiliary data such as two-photon quantum efficiency and fluorescence collection efficiency, essential in the low intensity method, are not required in the present technique. TPF measurements of Rhodamine B in methanol are carried out to demonstrate the validity of the present method. The method is used to determine the two-photon absorption cross section of a new chromophore attached with tricyano-derivatized furan as the electron acceptor. The two-photon absorption cross section measured using this method is also compared with that using a conventional transmission technique.     

Is there stereoselectivity in spin trapping superoxide by 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide?

[reaction: see text] Ester-containing nitrones, including 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide 5, have been reported to be robust spin traps for superoxide (O2*-). Using a chiral column, we have been able to isolate the two enantiomers of nitrone 5. With enantiomerically pure nitrone 5a and 5b we explored whether one of these isomers was solely responsible for the EPR spectrum of aminoxyl 6. Data obtained demonstrate that the spin trapping of O2*- by nitrone 5a and nitrone 5b affords the identical EPR spectra and lifetimes in homogeneous aqueous solution and exhibits the same ratio of cis and trans isomers. Quantum chemical modeling in vacuo also finds no difference, aside from the expected optical activity, arising from the difference in stereochemistry.     

Optimizing separation conditions for polycyclic aromatic hydrocarbons in micellar electrokinetic chromatography

We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS.     

Photochemistry of bicyclo[2.2.2]oct-7-ene-2,5-diones and the corresponding 5-hydroxyimino and 5-methylene derivatives

Synthesis and photochemistry of several title compounds 1-3 containing multiple chromophoric systems are described. The Diels-Alder reactions of 2,6,6-trimethylcyclohexa-2,4-dienone (5) with acetylenes 6a-d provided the adducts 7a-d, which upon hydrolysis furnished the desired bicyclo[2.2.2]octenediones 1a-d. Oximes 2a-d were prepared from diones 1a-d by treatment with hydroxylamine hydrochloride in pyridine. 5-Methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d were obtained via chemoselective Wittig reaction of the corresponding diones 1a-d. Bicyclo[2.2.2]octenediones 1a-c underwent chemoselective oxa-di-pi-methane rearrangement under sensitized conditions and suffered formal ketene extrusion upon direct irradiation. Direct irradiation of 1d afforded 11d via formal ketene extrusion but under sensitization it remained unchanged. Oximes 2a-d suffered ketene extrusion upon direct irradiation and E/Z isomerization under sensitized conditions. On the other hand, 5-methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d generally underwent 1,3-acyl shift. The plausible courses of all these photochemical processes are discussed.     

A miniature Q-band low noise amplifier using 0.13-/spl mu/m CMOS technology

A miniature Q-band low noise amplifier (LNA) using 0.13-/spl mu/m standard mixed signal/radio frequency complementary metal-oxide-semiconductor (CMOS) technology is presented in this letter. This three-stage common source thin-film microstrip LNA achieves a peak gain of 20dB at 43GHz with a compact chip size of 0.525mm/sup 2/. The 3-dB frequency bandwidth ranges from 34 to 44GHz and the minimum noise figure is 6.3dB at 41GHz. The LNA outperforms all the reported commercial standard CMOS Q-band LNAs, with the highest gain, highest output IP3, and smallest chip size.     

Comprehensive Study of Emitter-Ledge Thickness of InGaP/GaAs HBTs

A comprehensive study of emitter-ledge thickness of InGaP/GaAs heterojunction bipolar transistors (HBTs) has been undertaken. It is shown that the recombination rate and electron densities are drastically increased near the exposed base surface between the base contact and the emitter ledge. In contrast, the corresponding hole densities are decreased. If the emitter ledge is too thick, current will flow through the undepleted ledge, which increases the emitter-size effect. In contrast, if the emitter ledge is too thin, it may not effectively passivate the surface. Therefore, the thickness of the emitter ledge is a crucial issue and should be carefully considered. It is shown that, from simulated and experimental results, the optimum emitter-ledge thickness of InGaP/GaAs HBT is 100-200 Aring     

A Novel Pt/In0.52Al0.48As Schottky Diode-Type Hydrogen Sensor

On the basis of a Pt/In_0.52Al_0.48As metal-semiconductor structure, a novel hydrogen sensor is fabricated and demonstrated. The studied Pt/In_0.52Al_0.48As Schottky diode-type hydrogen sensor exhibits significant sensing performance including high relative sensitivity ratio of about 2600% (under the 1% H₂/air gas and V_R=-0.5 V at 30 degC), large current variation of 310 muA (under the 1% H₂/air gas and V_R=-5 V at 200 degC), widespread reverse-voltage regime (0~-5 V), stable hydrogen-sensing current-voltage (I-V) curves, and fast transient response time of 1.5 s. The calculated Schottky barrier-height change and series-resistance variation, from the thermionic-emission model and Norde method, are 87.0 meV and 288 Omega, respectively (under the 1% H₂/air gas at 30 degC). The hydrogen concentrations and operating temperatures tested in this letter are in the range of 15 ppm-1% H₂/air and 30 degC-250 degC, respectively. Based on the excellent integration compatibility with InP-based electronic devices, the studied device provides the potentiality in high-performance sensor-array applications