Calorimetric Studies on the pH Dependence in Hairpin Formation within the Human Enkephalin Enhancer Region

Two complementary 23 base-pair oligomers with sequences analogous to the 3, 5-cyclic adenosine monophosphate (cAMP) inducible enhancer region of the human enkaphalin gene were shown previously⁽⁶⁾ to undergo reversible conformational transformation from duplex to two individual hairpin structures, with two GT and two AC base mismatches, respectively. The present study uses differential scanning calorimetry (DSC) to determine H values for both the dissociation of the duplex formed by the complementary stands and the melting of each hairpin structure. Melting of the hairpins was studied at several different pH values and both the H and cooperative unit (CU) parameters for the hairpin with the AC base mismatches was found to be pH dependent. Increased values for H of melting and cooperative unit size at lower pH values supports the possibility of protonation of adenosine bases and formation of stable AC base pairs in this latter hairpin.     

Brown–Peterson Cohomology from Morava K ‐Theory, II

We improve on some results with Ravenel and Yagita in a paper by the same name. In particular, we generalize when injectivity, surjectivity, and exactness of Morava Ktheory implies the same for Brown–Peterson cohomology. A type of flatness is no longer assumed, but instead it is a consequence of weaker assumptions. The main application is an easier proof that QS2k+1 has this flatness property. In addition, we show that if elements in the Brown–Peterson cohomology generate all of the Morava Ktheories, then they also generate the Brown–Peterson cohomology and it is Landweber flat.     

Frequency-domain interferometric second-harmonic spectroscopy

We report a new spectroscopic technique to measure simultaneously the intensity and the phase of second-harmonic (SH) radiation over a broad spectral range without laser tuning. Temporally separated SH pulses from two sources, excited by the same broad-bandwidth 15-fs Ti:sapphire fundamental pulse, interfere in a spectrometer to yield frequency-domain interference fringes. We demonstrate the technique by measuring the strongly bias-dependent phase of SH radiation from a Si/SiO(2)/Cr metal-oxide-semiconductor capacitor in the spectral range of the SiE(1) critical point.     

Measurement and prediction of ultralow frequency ocean ambient noise off the eastern U.S. coast

Ultralow frequency (0.02-2 Hz) acoustic ambient noise was monitored from January to April 1991 at six ocean bottom stations off the eastern U.S. coast. The depths of the stations ranged from about 100 m to 2500 m. The measured spectra are in good agreement with predictions made using Cato's theory [J. Acoust. Soc. Am. 89, 1076-1095 (1991)] for noise generation by surface-wave orbital motion after extending the calculations to incorporate horizontally stratified environments. Contributions from both the linear, single-frequency (virtual monopole) and the nonlinear, double-frequency (dipole) mechanisms are clearly recognizable in the data. The predictions make use of directional wave data obtained from surface buoys deployed during the SWADE experiment and an ocean bottom model derived from compressional wave speed data measured during the EDGE deep seismic reflection survey. The results demonstrate conclusively that nonlinear surface-wave interactions are the dominant mechanism for generating deep-ocean ULF noise in the band 0.2-0.7 Hz.     

Analysis of a ginger extract by high-performance liquid chromatography coupled to nuclear magnetic resonance spectroscopy using superheated deuterium oxide as the mobile phase

A methanolic extract of powdered ginger was separated on a Xterra RP 18 column using deuterium oxide as the eluent and a temperature gradient from 50 to 130 degrees C at 4 degrees C/min. On-line and off-line HPLC-NMR analysis yielded spectra for vanillin, dihydroferulic acid, zingerone and ferulic acid. The identification of dihydroferulic acid and zingerone were confirmed by mass spectroscopy.     

Cruciform pi-systems: hybrid phenylene-ethynylene/phenylene-vinylene oligomers

The cruciform pentamers 3a-g were synthesized by a combined Horner-Sonogashira approach; their band gaps vary significantly with emission varying from blue to red depending upon their substituent pattern.     

A biosensing model system: selective interaction of biotinylated PPEs with streptavidin-coated polystyrene microspheres

Formation of a highly fluorescent composite formed from the biotinylated PPE 3 and streptavidin covered polystyrene microspheres is reported.     

Comparison of "polynaphthalenes" prepared by two mechanistically distinct routes

The Bergman cyclization has long been known to produce polymers as side products. More recently, this attribute has been harnessed for the production of conjugated materials. However, the structures of these polymers have not been established. To resolve this question, the metal-catalyzed polymerization of 1,4-dibromonaphthalene and thermal polymerization of o-diethynylbenzene were conducted. Two distinct polymers were obtained. Comparison of IR spectroscopy, MALDI-TOF MS, solid-state NMR spectroscopy, UV-vis reflectance spectroscopy, and pyrolysis GC-MS data indicates that only one of the polymers is consistent with poly(1,4-naphthalene).     

Enzymatic synthesis of an indole diterpene by an oxidosqualene cyclase: mechanistic, biosynthetic, and phylogenetic implications

Petromindole (1) is an unusual indole diterpene that bears a triterpene-like carbon skeleton, suggesting biogenesis from 3-(omega-oxido-geranylgeranyl)indole (4). We found that lupeol synthase (LUP1) from Arabidopsis thaliana cyclizes 4 to 1. Chiral HPLC comparisons of racemic 1 (from biomimetic cyclization of N-pivaloyl-4) with the LUP1 product and authentic 1 established the absolute stereochemistry of petromindole (3S) as that of cyclic triterpenes. Quantum mechanical calculations and conformational analysis of intermediates in the cyclization of 4 to 1 indicated that petromindole biosynthesis differs fundamentally from that of other indole diterpenes. This analysis revealed that radarins also originate from cyclization of 4 but undergo a backbone rearrangement rather than annulation to indole. The combined results support our hypothesis that native fungal petromindole synthase evolved from a pentacyclic triterpene synthase distant from most other indole diterpene synthases.