[reaction: see text] Stereo-controlled syntheses of two possible C1-C25 diastereomers of spirastrellolide A containing the cis-disubstituted tetrahydropyran and [6,6]-spiroacetal are reported, exploiting boron-mediated asymmetric aldol and allylation methodology. 相似文献
A detailed evaluation of the structural and dynamical properties of isolated water dimers and tetramers using the Lemberg, Stillinger and Rahman potential energy surface and microcanonical molecular dynamics simulations are reported. The lowest-energy configurations of these clusters were obtained by simulated thermal quenching. Relative root-mean-square bond length fluctuations were used to characterize phase transitions. Solid-like, pre-melting, liquid-like, and dissociated states were identified. Global-local minimum transitions and the minimum energy path to dissociation of the dimer were also characterized. 相似文献
A renormalization group method is used to construct approximants for the magnetization,m, and the static structure factor,
(q), for the simple cubic Ising model. Using the best values for the thermal critical index, the transition temperature, and the nearest-neighbor correlation function as input, we obtain recursion relations form and
(q) which lead to reasonable results over a wide range of temperatures and wave numbers. 相似文献
A group of dissolved-bioavailable organochlorine (OC) pesticides and inorganic anions in water and total OC pesticides in sediments were measured in the Malheur Watershed, a semi-arid region in the western United States, over a 2-year period. OC pesticide levels were compared with those from a 1990 study of the lower section of the river, the most recent data available. After calculating the dissolved fraction from the 1990, study it seems that DDD and dieldrin levels have decreased in the water by 50-70%, while DDE and DDT have changed little. Although banned nearly 30 years ago, DDT is still persistent throughout the Malheur River basin/watershed because it was found in all water samples tested. All of the OC pesticides tested during the 2-year study are well below the criterion continuous concentration for aquatic community exposure as defined by the U.S. Environmental Protection Agency (EPA). OC pesticides appear to be decreasing, however, at lower Ontario there remains a human health risk (EPA Human Health Risk Water Quality Criteria) for DDT, because this criteria includes daily consumption of water and fish from the river. Overall, although the upper forest watershed sites have lower OC pesticide concentrations, they represent an important contribution to the total DDT load to this watershed, a source not previously acknowledged. The large increase in DDT and sigmaDDT between the Ontario sites may indicate a possible historical point source of contamination or historical preferential deposition of contamination. Normalized sediment (sigmaDDT/organic carbon) strongly correlates with dissolved water sigmaDDT. 相似文献
The method of calculating radiation damping effects by means of energy balance is applied to a simple model problem. The balance equation is derived from the conservation law for energy that is a consequence of the equations of motion for the system by integrating over a four-dimensional space-time region bounded in the wave zone by two future-directed null cones and in the near zone by twot=const surfaces. It is assumed that the sources are in slow motion and the fields are calculated by the method of matched asymptotic expansions. Our principle conclusion is that even though the damping isO(3) where is an expansion parameter the fields need only be determined toO(1) to calculate the effects of damping by this method.Work supported in part by NSF Grant No. 79-11664-01. 相似文献
We have created surfaces which switch from cationic at pH < 3 to anionic at pH > 5, by attaching aminodicarboxylic acid units to silica and gold substrates. Charge reversal was demonstrated by monitoring the adsorption of cationic dyes (methylene blue and a tetracationic porphyrin) and an anionic sulfonated porphyrin, at a range of pH using UV-vis absorption and reflection spectroscopy. The cationic dyes bind under neutral conditions (pH 5-7) and are released at pH 1-4, whereas the anionic dye binds under acidic conditions (pH 1-4) and is released at pH 5-7. Gold surfaces were functionalized with two different amphoteric disulfides with short (CH(2))(2) and long (CH(2))(10)CONH(CH(2))(6) linkers; the longer disulfide gave surfaces exhibiting charge reversal in a narrower pH range. Adsorption is much faster on the functionalized gold (t(1/2) = 62 s) than on functionalized silica (t(1/2) = 6900 s), but the final extents of coverage on both surface are similar, for a given dye at a given pH, with maximal coverages of around 2 molecules nm(-)(2). These charge-reversal processes are reversible and can be repeatedly cycled by changing the pH. We have also created surfaces which undergo irreversible proton-triggered charge switching, using a carbamate-linked thiol carboxylic acid which cleaves in acid. These surfaces are versatile new tools for controlling electrostatic self-assembly at surfaces. 相似文献
The crystal and molecular structure of carbodiimides 2 (5,6,18,19-tetradehydro-5,12,13,18,25,26-hexahydrotetrabenzo[d,h,m,q][1,3,10,12]tetraazacyclooctadecine) and 3 (8,10,22,24-tetraazapentacyclo[23.3.1.1(3,7).1(11,15).1(17,21)]dotriaconta-1(29),3,5,7(32),8,9,11,13,15(31),17,19,21(30),22,23,25,27-hexadecaene) have been determined. The activation barriers for the racemization of carbodiimides 1 (6,7-dihydrodibenzo[d,h][1,3]diazonine), 2, and 3 have been determined. While 1 presents a relatively high barrier (17.4 kcal mol(-)(1)), 2 and 3 have very low activation barriers (between 5 and 7 kcal mol(-)(1)). We tentatively conclude that open-chain and large-ring carbodiimides racemize by nitrogen inversion or trans-rotation while medium-size cyclic carbodiimides racemize by cis-rotation. 相似文献
The rate constant of the reaction OH (v = 0) + O3 HO2 + O2 was measured over the temperature range from 220 to 450°K at total pressures between 2 and 5 torr using ultraviolet fluorescent scattering for the detection of OH radicals. An Arrhenius expression, k1 = 1.3 × 10?12 exp(?1900/RT) cm3/sec was obtained and the rate constant for the reaction HO2 + O3OH + 2O2 was inferred to be less than 0.1 k1 over the entire temperature interval. 相似文献
High-molecular-weight, film-forming, amorphous polyamides have been prepared from 2,6(7)-diamino-9,10-dihydro-9,10-ethanoantracene with adipic, sebacic, dodecanoic, isophthalic, 4,4′-oxybibenzoic, 2,6-naphthoic, 4,4′-bibenzoic, and terephthalic acid. Thermal elimination of ethylene from these polymers has yielded the corresponding polyamides from 2,6(7)-diaminoanthracene which were of high molecular weight, film forming, and crystalline. 相似文献
The mass spectral fragmentation patterns for 1-substituted derivatives of anhydro (3-chloroacetyl-2-hydroxyimidazo[1,2-a]pyridinium hydroxide) (Ia to Ie) and 2-acyl substituted derivatives of anhydro(1-benzyl-3-hydroxyimidazo[1,2-a]pyridinium hydroxide) (IIa and IIb) are reported. In all cases the mass spectra may be interpreted on the basis of initial cleavage of the ‘carbonyl-heteroatom’ bond of the mesoionic system, followed by fragmentation. 相似文献