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301.
A second-generation strategy for construction of (+)-nodulisporic acids A and B based on the development of a new, effective modular indole synthesis exploiting a sequential Stille cross-coupling/Buchwald-Hartwig union/cyclization tactic is disclosed. This strategy evolved due to the considerable acid instability of the C(24) hydroxyl group observed in several advanced intermediates during our first-generation approach. 相似文献
302.
Smith AB Davulcu AH Cho YS Ohmoto K Kürti L Ishiyama H 《The Journal of organic chemistry》2007,72(13):4596-4610
A first-generation strategy for construction of (+)-nodulisporic acids A (1) and B (2) is described. The strategy entails union of the eastern and western hemisphere subtargets via the indole synthesis protocol developed in our laboratory. Subsequent elaboration of rings E and F, however, revealed the considerable acid instability of the C(24) hydroxyl, thereby preventing further advancement. Nonetheless, preparation of the heptacyclic core of (+)-nodulisporic acids A and B, the total synthesis of (+)-nodulisporic acid F, the simplest member of the nodulisporic acid family, and elaboration of the heptacyclic core of (-)-nodulisporic acid D were achieved. 相似文献
303.
Amos FF Morin SA Streifer JA Hamers RJ Jin S 《Journal of the American Chemical Society》2007,129(46):14296-14302
We report a simple and inexpensive approach to directly assemble arrays of cadmium sulfide (CdS) semiconductors onto transparent flexible poly(ethylene terephthalate) (PET) sheets via a polymer-mediated selective nucleation and growth process from an aqueous solution. This strategy of assembling functional materials onto plastics utilizes the surface functional molecules of the UV photooxidation patterned polymer to direct the nucleation and growth of CdS. We demonstrated that such assembled structures are viable for flexible macroelectronics, as manifested by the fabrication of CdS photodetector arrays on PET that can withstand bending. The best devices exhibited a specific detectivity of 3 x 10(11) cm Hz(1/2) W(-1) at 514-nm excitation wavelength at a modulation frequency of 90 Hz at room temperature. This direct assembly strategy eliminates additional lithography and etching steps during the deposition of the active inorganic semiconductor layer, is general to other inorganic materials and plastic substrates, and can enable low-cost, wearable, and/or disposable flexible electronics. 相似文献
304.
Analogues of discodermolide in which the complete C-1 to C-7 fragment is replaced with a coumarin moiety display equivalent potency to that of the natural product. 相似文献
305.
Efficient algorithm for "on-the-fly" error analysis of local or distributed serially correlated data
Kent DR Muller RP Anderson AG Goddard WA Feldmann MT 《Journal of computational chemistry》2007,28(14):2309-2316
We describe the Dynamic Distributable Decorrelation Algorithm (DDDA) which efficiently calculates the true statistical error of an expectation value obtained from serially correlated data "on-the-fly," as the calculation progresses. DDDA is an improvement on the Flyvbjerg-Petersen renormalization group blocking method (Flyvberg and Peterson, J Chem Phys 1989, 91, 461). This "on-the-fly" determination of statistical quantities allows dynamic termination of Monte Carlo calculations once a specified level of convergence is attained. This is highly desirable when the required precision might take days or months to compute, but cannot be accurately estimated prior to the calculation. Furthermore, DDDA allows for a parallel implementation which requires very low communication, O(log(2)N), and can also evaluate the variance of a calculation efficiently "on-the-fly." Quantum Monte Carlo calculations are presented to illustrate "on-the-fly" variance calculations for serial and massively parallel Monte Carlo calculations. 相似文献
306.
Amos FF Sharbaugh DM Talham DR Gower LB Fricke M Volkmer D 《Langmuir : the ACS journal of surfaces and colloids》2007,23(4):1988-1994
Thin tablets and films of calcium carbonate have been grown at the air-water interface via an amorphous precursor route using soluble process-directing agents and a Langmuir monolayer based on resorcarene. By using appropriate concentrations of poly(acrylic acid-sodium salt) in combination with Mg2+ ion, an initially amorphous film is deposited on the monolayer template, which subsequently crystallizes into a mosaic film composed of a mixture of single-crystalline and spherulitic patches of calcite and aragonite. Of particular importance is the synthesis of single-crystalline "tablets" of aragonite (approximately 600 nm thick), because this phase generally forms needle-like polycrystalline aggregates when grown in vitro. To our knowledge, a tabular single-crystalline morphology of aragonite has only been observed in the nacreous layer of mollusk shells. Therefore, this in vitro system may serve as a useful model for examining mechanistic issues pertinent to biomineralization, such as the influence of organic templates on nucleation from an amorphous phase. 相似文献
307.
Refinable functions underlie the theory and constructions of wavelet systems on the one hand and the theory and convergence analysis of uniform subdivision algorithms on the other. The regularity of such functions dictates, in the context of wavelets, the smoothness of the derived wavelet system and, in the subdivision context, the smoothness of the limiting surface of the iterative process. Since the refinable function is, in many circumstances, not known analytically, the analysis of its regularity must be based on the explicitly known mask. We establish in this paper a formula that computes, for isotropic dilation and in any number of variables, the sharp L2-regularity of the refinable function φ in terms of the spectral radius of the restriction of the associated transfer operator to a specific invariant subspace. For a compactly supported refinable function φ, the relevant invariant space is proved to be finite dimensional and is completely characterized in terms of the dependence relations among the shifts of φ together with the polynomials that these shifts reproduce. The previously known formula for this compact support case requires the further assumptions that the mask is finitely supported and that the shifts of φ are stable. Adopting a stability assumption (but without assuming the finiteness of the mask), we derive that known formula from our general one. Moreover, we show that in the absence of stability, the lower bound provided by that previously known formula may be abysmal. Our characterization is further extended to the FSI (i.e., vector) case, to the unisotropic dilation matrix case, and to even snore general setups. We also establish corresponding results for refinable distributions. 相似文献
308.
Ali Nazemi Ryan C. Amos Colin V. Bonduelle Elizabeth R. Gillies 《Journal of polymer science. Part A, Polymer chemistry》2011,49(12):2546-2559
The functionalization of nanomaterials with dendritic surface moieties was recently demonstrated to be an effective means of displaying biological ligands and potentially modulating the biological properties of these materials. With the aim of extending this surface functionalization approach to biodegradable polymer assemblies, poly(ethylene oxide)‐polycaprolactone (PEO‐PCL) block copolymers with terminal azide or methoxy groups were prepared and were assembled to form micelles or vesicles with varying loadings of surface azides. Dendrons bearing peripheral amines, guanidines, or hydroxyls were prepared and conjugated to the assemblies, and the conjugation yields were measured and compared as a function of azide loading and assembly type (micelle versus vesicle). A small molecule rhodamine derivative was also conjugated, allowing the effect of sterics to be studied. The effects of the surface functionalization on the aggregation state of the assemblies were studied by light scattering and transmission electron microscopy. Overall, the results revealed interesting differences between the two systems with respect to both the reaction yields and the stabilities. Furthermore, micelles functionalized with dendrons bearing peripheral guanidines were found to exhibit enhanced cell uptake relative to control micelles, demonstrating that this approach can be used to modulate the biological properties of the materials. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
309.
We describe a method for measuring the lateral focal spot size of a multiphoton laser scanning microscope (LSM) with unprecedented accuracy. A specimen consisting of an aluminum film deposited on a glass coverslip was brought into focus in a LSM and the laser intensity was then increased enough to perform nanoablation of the metal film. This process leaves a permanent trace of the raster path usually taken by the beam during the acquisition of an optical image. A scanning electron microscope (SEM) was then used to determine the nanoablated line width to high accuracy, from which the lateral spot size and hence resolution of the LSM can be determined. To demonstrate our method, we performed analysis of a multiphoton LSM at various infrared wavelengths, and we report measurements of optical lateral spot size with an accuracy of 20 nm, limited only by the resolution of the SEM. 相似文献
310.
N-Toluenesulfonyl aziridines comprise effective second electrophiles in the solvent controlled three-component linchpin union of silyl dithianes for the stereocontrolled convergent elaboration of protected 1,5-amino alcohols. This tactic, in conjunction with a one-flask sequential cyclization, constitutes an effective general strategy for the construction of indolizidine and related alkaloids, illustrated here with the total syntheses of (-)-indolizidine 223AB (1) and alkaloid (-)-205B (2). 相似文献