An anisotropic high-spin qubit with long coherence time could scale the quantum system up. It has been proposed that Grover's algorithm can be implemented in such systems. Dimetallic aza[80]fullerenes M@CN (M = Y or Gd) possess an unpaired electron located between two metal ions, offering an opportunity to manipulate spin(s) protected in the cage for quantum information processing. Herein, we report the crystallographic determination of Gd@CN for the first time. This molecular magnet with a collective high-spin ground state (S = 15/2) generated by strong magnetic coupling (J = 350 ± 20 cm) has been unambiguously validated by magnetic susceptibility experiments. Gd@CN has quantum coherence and diverse Rabi cycles, allowing arbitrary superposition state manipulation between each adjacent level. The phase memory time reaches 5 μs at 5 K by dynamic decoupling. This molecule fulfills the requirements of Grover's searching algorithm proposed by Leuenberger and Loss.
Neural tube defects (NTDs) are among the most common and severe congenital malformations and result from incomplete closure of the neural tube during early development. Maternal exposure to polycyclic aromatic hydrocarbons (PAHs) has been suggested to be a risk factor for NTDs and previous studies imply that the mechanism underlying the association between PAH exposure and NTDs may involve oxidative stress and apoptosis. The objectives of this study were to investigate whether there is a direct effect of maternal benzo[α] pyrene (BaP) exposure on the closure of the neural tube in mice, and to examine the underlying mechanisms by combining animal experiments and human subject studies. We found that intraperitoneal injection of BaP from embryonic day 7 at a dose of 250 mg kg-1 induced NTDs (13.3% frequency) in ICR mice. BaP exposure significantly increased expression of genes associated with oxidative stress, Cyp1a1, Sod1 and Sod2, while repressing Gpx1. Elevated apoptosis and higher protein expression of cleaved caspase-3 in the neuroepithelium of treated embryos were observed. Pre-treatment with vitamin E, added to food, significantly protected against BaP-induced NTDs (1.4% frequency) (P < 0.05). Vitamin E also partly normalized oxidative stress related gene expression and excess apoptosis in BaP-treated embryos. Examination of human neural tissues revealed that increased levels of protein carbonyl and apoptosis were related with maternal exposure to PAHs and the risk of NTDs. Collectively, these results suggest that BaP exposure could induce NTDs and that this may involve increased oxidative stress and apoptosis, while vitamin E may have a protective effect.
Eight-membered carbocycles are found in a wide variety of natural products that exhibit a broad range of biological and medicinal activities (cf. the most potent anticancer drug, taxol). However, the synthesis of eight-membered carbocycles is quite challenging as traditional approaches are met with entropic and enthalpic penalties in the ring-forming transition states. These negative effects can be totally or partially avoided with the implementation of transition-metal-catalyzed/mediated cycloadditions. In this Focus Review, examples of elegant and efficient metal-catalyzed and some metal-mediated cycloadditions (including Ni- catalyzed [4+4] and Rh-catalyzed [4+2+2] and [5+2+1] reactions) are presented to illustrate this. Application of these cycloaddition reactions in total synthesis is also presented to show the significance of these reactions in addressing challenges in natural product synthesis.
Background: Medical students are affected by high levels of general anxiety disorder. However, few studies have specifically focused on the applicability of universal anxiety screening tools in this sample. This study was aimed to evaluate the psychometric property of the 7-item Generalized Anxiety Disorder Scale (GAD-7) among Chinese medical university students.Methods: A questionnaire survey was conducted among 1,021 medical postgraduates from six polyclinic hospitals. Internal consistency and convergent validity of the GAD-7 were evaluated. Factor analyses were used to test the construct validity of the scale. An item response theory (IRT) framework was used to estimate the parameters of each item. Multi-group confirmatory analyses and differential item function analyses were used to evaluate the measurement equivalence of the GAD-7 across age, gender, educational status, and residence.Results: Cronbach's α coefficient was 0.93 and the intraclass correlation coefficients ranged from 0.71 to 0.87. The GAD-7 summed score was significantly correlated with measures of depression symptoms, perceived stress, sleep disorders, and life satisfaction. Parallel analysis and confirmatory factor analysis supported the one-factor structure of the GAD-7. Seven items showed appropriate discrimination and difficulty parameters. The GAD-7 showed good measurement equivalence across demographic characteristics. The total test information of the scale was 22.85, but the test information within the range of mild symptoms was relatively low.Conclusions: The GAD-7 has good reliability, validity, and measurement invariance among Chinese medical postgraduate students, but its measurement precision for mild anxiety symptoms is insufficient.
The total synthesis of (+)-asteriscanolide is reported. The synthetic route features two key reactions: 1) the rhodium(I)-catalyzed [(5+2)+1] cycloaddition of a chiral ene-vinylcyclopropane (ene-VCP) substrate to construct the [6.3.0] carbocyclic core with excellent asymmetric induction, and 2) an alkoxycarbonyl-radical cyclization that builds the bridging butyrolactone ring with high efficiency. Other features of this synthetic route include the catalytic asymmetric alkynylation of an aldehyde to synthesize the chiral ene-VCP substrate, a highly regioselective conversion of the [(5+2)+1] cycloadduct into its enol triflate, and the inversion of the inside-outside tricycle to the outside-outside structure by an ester-reduction/elimination to enol-ether/hydrogenation procedure. In addition, density functional theory (DFT) rationalization of the chiral induction of the [(5+2)+1] reaction and the diastereoselectivity of the radical annulation has been presented. Equally important is that we have also developed other routes to synthesize asteriscanolide using the rhodium(I)-catalyzed [(5+2)+1] cycloaddition as the key step. Even though these routes failed to achieve the total synthesis, these experiments gave further useful information about the scope of the [(5+2)+1] reaction and paved the way for its future application in synthesis.
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