Synthesis of the apoptosis inducing agent apoptolidin. Assembly of the C(16)-C(28) fragment

[reaction--see text] A stereoselective synthesis of the C(16)-C(28) fragment of the apoptosis inducing agent apoptolidin is described. Key steps include two propionate aldol reactions and a stereoselective Mukaiyama aldol addition of enolsilane 19 to beta-methoxy aldehyde 4.     

Growth of uncapped, subnanometer size gold clusters prepared via electroporation of vesicles

Electric-field-induced transient pore formation (electroporation) in synthetic unilamellar vesicles is utilized for the preparation of subnanometer size uncapped gold quantum dots. With the precursor AuCl4(-) placed in the aqueous bulk solution and the reducing agent BH4(-) originally entrapped in the vesicles' compartments, the redox reaction--that occurs in the bulk--is initiated by the opening of transient pores in the vesicles' bilayers. The absence of caps permits (i) continued growth of the Au clusters formed, (ii) the assessment of their true absorption spectra unaltered by stabilizing ligands, and (iii) the previously inaccessible live observation of the growth of the clusters in the molecular size regime. The normally rapid self-aggregation of Au atoms is slowed to the time scales of hour and week by their adsorption at the exterior surface of the vesicles. The UV spectra exhibit novel, time-dependent, oscillating red and blue shifts of the characteristic absorption band, which can be attributed to the evolution of cluster size transiently halting at magic aggregation numbers corresponding to Au2, Au8, Au20, and Au34. Subsequent growth is associated with a monotonic red shift of the absorption band up to the characteristic surface plasmon absorption at 520 nm.     

Sorption and desorption of radiostrontium on powdered bentonite: Effect of pH and fulvic acid

The effect of pH and fulvic acid on the sorption of Sr on bentonite was investigated by using batch experiments. The sorption and desorption isotherms of Sr on bentonite were determined at room temperature, at pH 6.0±0.2 and in presence of 0.1M NaCl. It was found that the sorption of Sr is independent at pH<8, and then increases slightly with increasing pH. Fulvic acid increases the sorption of Sr significantly on bentonite at low pH, but decreases the sorption of Sr at pH>8. The sorption of Sr on bentonite can be described by a reversible sorption process and the sorption mechanism consists mainly of ion exchange. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic Study of the Bromine-Catalyzed Isomerization of Methyl- and Chloro-Maleic Acids in Aqueous Ce(IV)-Br -H2SO4 Medium

Methylmaleic (citraconic, CTA) acid and methylfumaric (measaconic, MSA) acid in aqueous sulfuric acid solution undergo bromine-catalyzed reversible cis-trans isomerization in the presence of ceric and bromide ions. The positional isomerization of CTA or MSA to itaconic acid (ITA) is not observed. The method of high performance liquid chromatography (HPLC) was applied to study the kinetics of this catalyzed isomerization. The major catalytic species is best expressed as the Br^?₂ · radical anion. Under suitable catalytic conditions, there is a tendency for the [MSA]/[CTA] ratio to reach an equilibrium value of 4.10 at 25° for the CTA+Br^?₂ · ? MSA+Br^?₂ · reaction. Chloromaleic (CMA) and chlorofumaric (CFA) acids undergo similar isomerization with an equilibrium [CFA]/[CMA] ratio of 10.3 at 25°. The isomerization of maleic acid (MA) to fumaric acid (FA) is essentially irreversible with 50 as the lower limit of the equilibrium [FA]/[MA] ratio. The substituent has an important effect on the reversibility of this catalyzed isomerization of butenedicarboxylic acids. The thermodynamic parameters ΔH° and ΔS° at 25° for the CTA+Br^?₂ · ? MSA+Br^?₂ · reaction were found to be ?5.1±0.7 kj/mol and ?6.0±3.3 J/mol K, respectively. The present method gives a plausible way to measure the differences in enthalpy and entropy between the trans- and cis-isomers of butenedicarboxylic acids (CRCO₂H=CR'CO₂H) in aqueous solution.     

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.     

On the surjectivity of the almost linear operator and its applications

LetL be a self-adjoint linear operator andN be the gradient of a functional ϕ, which is almost quadratic. We first give a theorem on the surjectivity of the operatorL+N, then apply the result to semilinear elliptic systems: