Stereoelectronic interactions control reactivity of peroxycarbenium cations, the key intermediates in (per)oxidation chemistry. Computational analysis suggests that alcohol involvement as a third component in the carbonyl/peroxide reactions remained invisible due to the absence of sufficiently deep kinetic traps needed to prevent the escape of mixed alcohol/peroxide products to the more stable bisperoxides. Synthesis of β-alkoxy-β-peroxylactones, a new type of organic peroxides, was accomplished by interrupting a thermodynamically driven peroxidation cascade. The higher energy β-alkoxy-β-peroxylactones do not transform into the more stable bisperoxides due to the stereoelectronically imposed instability of a cyclic peroxycarbenium intermediate as a consequence of amplified inverse alpha-effect. The practical consequence of this fundamental finding is the first three-component cyclization/condensation of β-ketoesters, H2O2, and alcohols that provides β-alkoxy-β-peroxylactones in 15–80 % yields. 相似文献
Two new natural compounds, astolides A,B, were isolated from Streptomyces hygroscopicus collected from the alkaline soil obtained from Saratov region, Russia. The structures were elucidated by interpretation of UV spectroscopic, MS, 1D and 2D NMR data. The relative configurations were determined by analysis of NOESY/ROESY spectra and coupling constants. The isolated compounds were evaluated for their inhibitory activity against bacteria, fungi and yeasts and showed pronounced antifungal activity. Both compounds are noticeably cytotoxic, being active against doxorubicin-resistant human leukemia cell line. 相似文献
A conic linear system is a system of the form?P(d): find x that solves b - Ax∈CY, x∈CX,? where CX and CY are closed convex cones, and the data for the system is d=(A,b). This system is“well-posed” to the extent that (small) changes in the data (A,b) do not alter the status of the system (the system remains solvable or not). Renegar defined the “distance to ill-posedness”,
ρ(d), to be the smallest change in the data Δd=(ΔA,Δb) for which the system P(d+Δd) is “ill-posed”, i.e., d+Δd is in the intersection of the closure of feasible and infeasible instances d’=(A’,b’) of P(·). Renegar also defined the “condition measure” of the data instance d as C(d):=∥d∥/ρ(d), and showed that this measure is a natural extension of the familiar condition measure associated with systems of linear
equations. This study presents two categories of results related to ρ(d), the distance to ill-posedness, and C(d), the condition measure of d. The first category of results involves the approximation of ρ(d) as the optimal value of certain mathematical programs. We present ten different mathematical programs each of whose optimal
values provides an approximation of ρ(d) to within certain constants, depending on whether P(d) is feasible or not, and where the constants depend on properties of the cones and the norms used. The second category of
results involves the existence of certain inscribed and intersecting balls involving the feasible region of P(d) or the feasible region of its alternative system, in the spirit of the ellipsoid algorithm. These results roughly state that
the feasible region of P(d) (or its alternative system when P(d) is not feasible) will contain a ball of radius r that is itself no more than a distance R from the origin, where the ratio R/r satisfies R/r≤c1C(d), and such that r≥ and R≤c3C(d), where c1,c2,c3 are constants that depend only on properties of the cones and the norms used. Therefore the condition measure C(d) is a relevant tool in proving the existence of an inscribed ball in the feasible region of P(d) that is not too far from the origin and whose radius is not too small.
Received November 2, 1995 / Revised version received June 26, 1998?Published online May 12, 1999 相似文献
In the present paper we study the well-posedness using the Galerkin method and the stabilization considering multiplier techniques for a fourth-order nonlinear Schrödinger equation in domains with moving boundaries. We consider two situations for the stabilization: the conservative case and the dissipative case. 相似文献
In recent years, capillary electrophoresis coupled to mass spectrometry (CE-MS) has been increasingly applied in clinical research especially in the context of chronic and age-associated diseases, such as chronic kidney disease, heart failure and cancer. Biomarkers identified using this technique are already used for diagnosis, prognosis and monitoring of these complex diseases, as well as patient stratification in clinical trials. CE-MS allows for a comprehensive assessment of small molecular weight proteins and peptides (<20 kDa) through the combination of the high resolution and reproducibility of CE and the distinct sensitivity of MS, in a high-throughput system. In this study we assessed CE-MS analytical performance with regards to its inter- and intra-day reproducibility, variability and efficiency in peptide detection, along with a characterization of the urinary peptidome content. To this end, CE-MS performance was evaluated based on 72 measurements of a standard urine sample (60 for inter- and 12 for intra-day assessment) analyzed during the second quarter of 2021. Analysis was performed per run, per peptide, as well as at the level of biomarker panels. The obtained datasets showed high correlation between the different runs, low variation of the ten highest average individual log2 signal intensities (coefficient of variation, CV < 10%) and very low variation of biomarker panels applied (CV close to 1%). The findings of the study support the analytical performance of CE-MS, underlining its value for clinical application. 相似文献
A new biomimetic approach for performing CaCO3 synthesis exclusively inside micron‐sized polyelectrolyte capsules, based on the fermentative formation of a precipitative agent (CO32− anion) by urease‐catalyzed urea hydrolysis, was developed. Precipitated CaCO3 completely fills the interior capsule volume and has a metastable vaterite phase.