On the asymmetric autocatalysis of aldol reactions: The case of 4‐nitrobenzaldehyde and acetone. A critical appraisal with a focus on theory

Under neutral conditions, spontaneous mirror symmetry breaking has been occasionally reported for aldol reactions starting from achiral reagents and conditions. Chiral induction might be interpreted in terms of autocatalysis exerted by chiral mono‐aldol or bis‐aldol products as source of initial enantiomeric excesses, which may account for such experimental observations. We describe here a thorough Density Functional Theory (DFT) study on this complex and otherwise difficult problem, which provides some insights into this phenomenon. The picture adds further rationale to an in‐depth analysis by Moyano et al, who showed the isolation and characterization of bis‐aldol adducts and their participation in a complex network of reversible steps. However, the lack of enantiodiscrimination (ees vanish rapidly in solution) suggests, according to the present results, a weak association in complexes formed by the catalysts and substrates. The latter would also be consistent with almost flat transition states having similar heights for competitive catalyst‐bound transition structures (actually, we were unable to locate them at the level explored). Overall, neither autocatalysis as once conjectured nor mutual inhibition of enantiomers appears to be operating mechanisms. Asymmetric amplification in early stages harnessing unavoidable enantiomeric imbalances in reaction mixtures of chiral products represents a plausible interpretation.     

Testing the Equality of the Intra‐Subject Treatment Covariance Matrices in a Crossover Study

In a 2 × 2 crossover bioavailability study, the sets of estimates of the pharmacokinetic parameters quite often have a symmetric covariance structure between the two treatments. For testing the equality of the intra‐subject covariance matrices for the two treatments in such studies, we suggest in this paper some statistical tests. When the response vectors are bivariate, we propose an exact test. Since the statistical procedures depend on the assumption of a symmetric covariance structure between the two treatments, we put forth some statistical tests for this assumption. We then apply the discussed tests to real data from a crossover bioavailability trial.     

Symmetry control of chemical reactions: Applications to the Berry pseudorotation of five-coordinate transition metal complexes

A symmetry analysis of the Berry pseudorotation of trigonal bipyramidal transition metal complexes is presented. Predictions are made regarding which electronic configurations are allowed to undergo pseudorotation and which configurations are symmetry forbidden. A comparison to reported fluxional five-coordinate complexes shows that the predictions are consistent with experimental observations.     

Emergence of network structure due to spike-timing-dependent plasticity in recurrent neuronal networks. II. Input selectivity—symmetry breaking

Spike-timing-dependent plasticity (STDP) is believed to structure neuronal networks by slowly changing the strengths (or weights) of the synaptic connections between neurons depending upon their spiking activity, which in turn modifies the neuronal firing dynamics. In this paper, we investigate the change in synaptic weights induced by STDP in a recurrently connected network in which the input weights are plastic but the recurrent weights are fixed. The inputs are divided into two pools with identical constant firing rates and equal within-pool spike-time correlations, but with no between-pool correlations. Our analysis uses the Poisson neuron model in order to predict the evolution of the input synaptic weights and focuses on the asymptotic weight distribution that emerges due to STDP. The learning dynamics induces a symmetry breaking for the individual neurons, namely for sufficiently strong within-pool spike-time correlation each neuron specializes to one of the input pools. We show that the presence of fixed excitatory recurrent connections between neurons induces a group symmetry-breaking effect, in which neurons tend to specialize to the same input pool. Consequently STDP generates a functional structure on the input connections of the network.     

不同处理对银沙槐种子休眠破除和幼苗生长的影响

对银沙槐种子破除休眠的适宜方法及其幼苗生长进行研究。结果表明:破口和沙磨处理休眠破除效果最好,但容易引起种子腐烂死亡;分别用65、80和95℃热水处理种子,以95℃1 min破除种子休眠效果最好,且幼苗长势好,65℃效果最差,80℃可破除部分种子休眠,除80℃外延长热水处理时间可导致死种子数增加,95℃则引致大部分种子死亡;液氮浸种处理效果均显著,其中以液氮处理10 min效果最好,但幼苗多为不正常苗而致死;硫酸处理以浸种120 min效果最好,但处理时间过长可导致死种子数增多,且造成少数幼苗根部腐蚀死亡。综上所述,打破银沙槐种子休眠的较优处理方法是硫酸120 min浸种处理和95℃1 min热水处理。     

GA3和变温层积对天女木兰种子萌发及内源激素的影响

用不同质量浓度GA3浸泡天女木兰种子并结合变温层积处理,应用高效液相色谱法对不同时期种子中4种激素GA3、IAA、ABA、ZR含量进行测定,并测量种胚长和萌发率,以探讨天女木兰种胚发育,内源激素含量变化与种子休眠萌发之间的调控关系,为进一步研究种子休眠机理提供理论基础。结果表明:(1)天女木兰成熟种子胚发育不完全,胚乳内高浓度ABA和低浓度GA3是其休眠的主要原因。(2)GA3处理能促使天女木兰种子提前30d完成形态后熟,并以1 500mg·L-1 GA3处理效果最佳。(3)在变温层积过程,天女木兰种胚发育可分三个阶段:阶段Ⅰ(0~70d)完成种胚进一步分化;阶段Ⅱ(70~120d)种胚快速生长时期;阶段Ⅲ(120~150d)休眠完全解除,种子具备发芽能力。种子能否打破休眠主要取决于阶段Ⅰ和Ⅱ的状况。(4)GA3/ABA、IAA/ABA和ZR/ABA在种子后熟期间的变化同胚生长发育存在一致性,认为内源激素的相对水平对种子休眠具有重要的调控作用。     

盐生植物种子的休眠、休眠解除及萌发的特点

本文讨论了盐生植物种子的休眠、休眠解除及萌发的特点 ,主要内容有 :( 1 )盐生植物种子的休眠类型 ;( 2 )打破盐生植物种子休眠的必要条件 ;( 3)盐生种子萌发与土壤盐度的关系。并讨论了盐度抑制盐生植物种子的机理。最后 ,作者提出了将来研究盐生植物种子萌发需要解决的几个重点问题以及研究盐生植物种子休眠和萌发问题的意义