A novel method for metal‐free oxothiolation of ynamides to construct oxazolidine‐2,4‐diones bearing sulfur‐substituted quaternary carbon atoms has been developed. It represents a rare C?O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C?O, C?S, and C?Cl bonds. This redox‐neutral protocol can be applied to the synthesis of multisubstituted oxazolidine‐2,4‐diones with good chemoselectivity and good yields of isolated products under mild conditions. 相似文献
Timosaponin BIII, as one of the steroid saponins isolated from Anemarrhena asphodeloides Bge., was proved to have many pharmacological activities in recent years and became a natural active compound with good development prospect. In the present study, a simple and rapid method using high-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry was developed for the determination of the structures of timosaponin BIII and its metabolites in rats after administrating intragastrically at 300 mg kg−1. By comparing their changes in molecular masses (ΔM), retention times and spectral patterns with those of the parent compound, nine metabolites were detected and identified in urine, and eight in plasma as well as four in brain. It is also indicated that the deglycosylation and oxidation reactions were the main metabolic pathways in the biotransformation of timosaponin BIII in vivo and the structures of the nine metabolites were identified and proposed to be timosaponin BII(M1), the hydroxylated metabolite of TBII(M2), the hydroxylated metabolites of TBIII(M3 and M4), deglycosylation and monooxygenation product of TBIII(M5), the deglycosylation product of TBII(M6), timosaponin AIII(M8), the isomers of timosaponin AIII(M7 and M9).
Compared with the dominant aromatic conjugated materials, photovoltaic applications of their quinoidal counterparts featuring rigid and planar molecular structures have long been unexplored despite their narrow optical bandgaps, large absorption coefficients, and excellent charge‐transport properties. The design and synthesis of dithienoindophenine derivatives (DTIPs) by stabilizing the quinoidal resonance of the parent indophenine framework is reported here. Compared with the ambipolar indophenine derivatives, DTIPs with the fixed molecular configuration are found to be p‐type semiconductors exhibiting excellent unipolar hole mobilities up to 0.22 cm2 V?1 s?1, which is one order of magnitude higher than that of the parent IP‐O and is even comparable to that of QQT(CN)4‐based single‐crystal field‐effect transistors (FET). DTIPs exhibit better photovoltaic performance than their aromatic bithieno[3,4‐b]thiophene (BTT) counterparts with an optimal power‐conversion efficiency (PCE) of 4.07 %. 相似文献
A new and atom‐economic palladium‐catalyzed aminomethylamination of allenes with aminals by C N bond activation is described. This direct and operationally simple method provides a fundamentally novel approach for the synthesis of 1,3‐diamines. Mechanistic studies suggest that a unique cationic π‐allylpalladium complex containing an aminomethyl moiety is generated as a key intermediate through the carbopalladation of the allene with a cyclometalated palladium–alkyl species. 相似文献
Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL‐responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL‐induced enantioselective synthesis. By irradiation with either left‐handed or right‐handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left‐handed CPL resulted in crystals with a left‐handed helical structure, and right‐handed CPL led to crystals with a right‐handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers. 相似文献
To further explore an efficient modified route for the shift from an antibacterial fluoroquinolone to an antitumor one,mono-Schiff bases 6a-6h related to ciprofloxacin C3 carbonylhydrazone and bis-Schiff bases 4a-4h corresponding to C3/C7 carbonylhydrazone/hydrazone attached on a skeleton of ciprofloquinolone were designed and synthesized,and their in vitro antitumor activity against CHO,HL60,L1210 cells and antibacterial activity against Staphylococcus aureus and Escherichia coli were also reported. 相似文献
We have developed a new numerical ray-tracing approach for LIDAR signal power function computation, in which the light round-trip propagation is analyzed by geometrical optics and a simple experiment is employed to acquire the laser intensity distribution. It is relatively more accurate and flexible than previous methods. We emphatically discuss the relationship between the inclined angle and the dynamic range of detector output signal in biaxial LIDAR system. Results indicate that an appropriate negative angle can compress the signal dynamic range. This technique has been successfully proved by comparison with real measurements. 相似文献
T-lymphocyte (T-cell) is a very important component in human immune system. T-cell epitopes can be used for the accurately monitoring the immune responses which activation by major histocompatibility complex (MHC), and rationally designing vaccines. Therefore, accurate prediction of T-cell epitopes is crucial for vaccine development and clinical immunology. In current study, two types peptide features, i.e., amino acid properties and chemical molecular features were used for the T-cell epitopes peptide representation. Based on these features, random forest (RF) algorithm, a powerful machine learning algorithm, was used to classify T-cell epitopes and non-T-cell epitopes. The classification accuracy, sensitivity, specificity, Matthews correlation coefficient (MCC), and area under the curve (AUC) values for proposed method are 97.54%, 97.22%, 97.60%, 0.9193, and 0.9868, respectively. These results indicate that current method based on the combined features and RF is effective for T-cell epitopes prediction. 相似文献