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11.
Sphinganines can be synthesized in just three steps from easily prepared serine-derived Weinreb amide 4. Pre-deprotonation of the acidic (N-H and O-H) protons of 4 allows for its efficient conversion to amino ketones 5. Such ketones can be selectively reduced to either erythro- or threo-sphinganines. Partially protected sphinganines 11 are also readily accessible in five steps from 4. Thus, Weinreb amide 4 represents one of the most versatile templates described to date for sphinganine synthesis.  相似文献   
12.
A reinvestigation of Auletta sp. yielded the novel compound milnamide C (3) plus the known compounds milnamide A (1), milnamide B (hemiasterlin) (2), jasplakinolide (5), and geodiamolides A (6), D (7), E (8), and G (9). The isolation work was guided by cytoskeletal bioactivity data. Compounds 2 and 3 were shown to cause microtubule depolymerization, and 6-9 were shown to cause microfilament disruption. This biological activity and the structural elucidation of 3, including X-ray analysis, are reported here. [structure: see text]  相似文献   
13.
The synthesis, metal, ammonium and alkyl ammonium cation coordination chemistry and electrochemical recognition studies of new diester-and diamide-calix[4]arenediquinone receptors are described. In addition the synthesis and coordination properties of a novel diamide benzo-15-crown-5-calix[4]arene molecule is reported.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.  相似文献   
14.
We present the first recording of the high-resolution spectrum of an induced chiral dimer. Three conformers of the induced chiral dimers of ethanol have been observed using a pulsed molecular-beam Fourier transform microwave spectrometer. The rotational constants of the normal isotopomers of the three species have been determined to be (a) A=5113.826(5), B=1329.7214(4), and C=1257.5151(3) MHz, (b) A=5086.459(5), B=1316.6508(4), and C=1243.6329(4) MHz, and (c) A=4851.608(5), B=1369.7558(6), and C=1243.4184(4) MHz. The observed species have been assigned to calculated structures via Kraitchman double substitution analyses and ab initio calculations. The Kraitchman analyses and the fitted centrifugal distortion parameters suggest that the deuterium bond is significantly stronger than the hydrogen bond in the dimers of ethanol.  相似文献   
15.
The equilibrium distribution of species formed between Cu(II) and N-acetylneuraminic (sialic) acid (I, LH) at 298 K has been determined using a two-dimensional (2D) simulation analysis of electron paramagnetic resonance (EPR) spectra. In acidic solutions (pH values < 4), the major species present are Cu(2+), [CuL]+ [logbeta = 1.64(4)], and [CuL2] [logbeta = 2.77(5)]. At intermediate pH values (4.0 < pH < 7.5), [CuL2H-1]- [logbeta = -2.72(7)] and two isomers of [CuLH-1] [logbeta (overall) = -3.37(2)] are present. At alkaline pH values (7.5 < pH < 11), the major species present is [CuL2H-2]2-, modeled as three isomers with unique giso and Aiso values [logbeta (overall) = -8.68(3)]. Two further species ([CuLH-3]2- and [CuL2H-3]3-) appear at pH values > 11. It is proposed that [CuL]+ most likely features I coordinated via the deprotonated carboxylic acid group (O1) and the endocyclic oxygen atom (OR) forming a five-membered chelate ring. Select Cu(II)-I species of the form [CuLH-1] may feature I acting as a dianionic tridentate chelate, via oxygen atoms derived from O1, OR, and one deprotonated hydroxy group (O7 or O8) from the glycerol tail. Alternatively, I may coordinate Cu(II) in a bidentate fashion as the tert-2-hydroxycarboxylato (O1,O2) dianion. Spectra predicted for Cu(II)-I complexes in which I is coordinated in either a O1,OR {I1-} or O1,O2 {I2-} bidentate fashion {e.g., [CuL]+ (O1,O R), [CuL2] (bis-O1,O R), [CuLH-1] (isomer: O1, O2), [CuL2H-1]- (O1, O R; O1, O2), and [CuL2H-2]2- (isomer: bis-O1, O2)} have "irregular" EPR spectra that are ascribed to the existence of Cu(II)-I(monomer) <==> Cu(II)-I(polymer) equilibria. The formation of polymeric Cu(II)-I species will be favored in these complexes because the glycerol-derived hydroxyl groups at the complex periphery (O, 7O, 8O9) are available for further Cu(II) binding. The presence of polymeric Cu(II)-I species is supported by EPR spectral data from solutions of Cu(II) and the homopolymer of I, colominic acid (Ipoly). Conversely, spectra predicted for Cu(II)-I complexes where I is coordinated in a {I2-} tridentate {e.g., [CuLH-1] (isomer: O1, O R, O7, or O8) and [CuL2H-2]2- (isomer: bis-O1,O R,O7, or O8)} or tetradentate fashion {I3-} {e.g., [CuLH-3]2- (O1, O R, O, 8O9)} are typical for mononuclear tetragonally elongated Cu(II) octahedra. In this latter series of complexes, the tendency toward the formation of polymeric Cu(II)-I analogues is small because the polydentate I effectively wraps up the mononuclear Cu(II) center. This work shows that Cu(II) could potentially mediate the chemistry of sialoglycoconjugate-containing proteins in human biology, such as the sialylated amyloid precursor protein of relevance to Alzheimer's disease.  相似文献   
16.
Reactions between N,N′-dimethylethylene diamine and a range of 2,3,5,6-tetrafluoropyridine derivatives provided ready access to the corresponding tetrahydropyrido[2,3-b]pyrazine systems if the substituent located at the 4-position of the pyridine ring was either hydrogen or an electron withdrawing substituent. In contrast, the presence of electron donating substituents at the 4-position made the formation of ring-fused products much more difficult. The two-step sequential nucleophilic substitution procedures from pentafluoropyridine gave convenient and adaptable methodology for the synthesis of polyfunctional tetrahydropyrido[2,3-b]pyrazine scaffolds of interest to the life science discovery arenas.  相似文献   
17.
Thiophene-3-carboxamides bearing allyl or benzyl substituents at nitrogen undergo dearomatising cyclisation on treatment with LDA. Rearrangements transform the dearomatised products into pyrrolinones, azepinones or partially saturated azepinothiophenes.  相似文献   
18.
Experimental and numerical results for binding Aedes aegypti densonucleosis virus (AeDNV) using anion and cation exchange membranes are presented. AeDNV particles are adsorbed by anion and cation exchange membranes providing the virus particles and membranes are oppositely charged. Q membranes which are strongly basic anion exchangers were the most effective. Dynamic and static capacities for Q membranes were found to be similar. A numerical model is proposed which assumes a log normal pore size distribution. By estimating the required parameters from static binding experiments, the model may be used to calculate the breakthrough curve for virus adsorption.  相似文献   
19.
At the end of the final spin cycle of the laundry process, the residual moisture content (RMC) of fabric is directly related to the dynamic surface tension of the residual water in the fabric. The LaPlace equation for capillary rise predicts that the capillary rise of solutions in a capillary is proportional to the surface tension at the air-liquid interface. If fabric can be considered to be a large ensemble of capillaries due to interfiber spacing, then the RMC of fabrics will be directly related to the surface tension of residual solution in the fabric. The use of a tailored rinse additive has the potential to decrease the surface tension of solution significantly, thus leading to a decrease in the residual water content of the fabric. It is expected that as the surfactant concentration increases the surface tension decreases. Hence, the RMC of fabrics must decrease with increasing surfactant concentration. However, a peak is observed in the RMC of fabrics before the critical micelle concentration (CMC) is reached. Prior to the CMC, it is proposed that a sudden adsorption of surfactant is occurring on the fabric surface leading to a decrease in bulk monomer concentration. The decrease in free monomer concentration should result in an increase in the equilibrium surface tension of the residual solution leading to a concomitant increase in RMC. Because the dynamic surface tension is measured on a short time scale (on the order of milliseconds), there will be less adsorption of monomer onto the newly created air-liquid interface of the bubbles during the measurement process. This decrease in adsorption should lead to a pronounced increase in the dynamic surface tension. This indeed was observed. The RMC correlates very well with the dynamic surface tension of the residual solution.  相似文献   
20.
Conversion of substituted 2-oxindoles into 2-thionoindoles followed by Raney nickel desulfurization provides a mild method for synthesizing the core EFGH rings of diazonamide A.  相似文献   
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