Mass spectra of 1,19-epoxycardenolides
The mass spectra of six 18,19-epoxycardenolides (ECs) with various substituents in the 3β position — OH, OAc, rhamnosyloxy have been studied. In all the spectra the contribution of the fragments characteristic for cardenolides formed by the cleavage of the bonds of rings C and D were lowered. The strongest peaks were those of ions with m/z 259, 272, and 285 arising on the splitting out of the elements of rings A and B. It was established by the metastable defocusing (MD) method that in the case of the 3β-ols these fragments are formed from M+ and in the case of acetyl derivatives, in addition, they may arise from the (M — AcOH)+ ions. The spectra of the epoxycardenolides were compared with the structure of 3β,5β,14β,19-tetrahydroxycardenolide (strophanthidol) and its 3β-monoacetate and 3β,19-diacetate. The MD spectra and elementary compositions of the ions showed that other mass-spectrometric conditions strophanthidol monoacetate decomposes partially in the form of the 8,19-epoxycardenolide.
A biocatalytic hydroxylation-enabled unified approach to C19-hydroxylated steroids
Steroidal C19-hydroxylation is pivotal to the synthesis of naturally occurring bioactive C19-OH steroids and 19-norsteroidal pharmaceuticals. However, realizing this transformation is proved to be challenging through either chemical or biological synthesis. Herein, we report a highly efficient method to synthesize 19-OH-cortexolone in 80% efficiency at the multi-gram scale. The obtained C19-OH-cortexolone can be readily transformed to various synthetically useful intermediates including the industrially valuable 19-OH-androstenedione, which can serve as a basis for synthesis of C19-functionalized steroids as well as 19-nor steroidal drugs. Using this biocatalytic C19-hydroxylation method, the unified synthesis of six C19-hydroxylated pregnanes is achieved in just 4 to 9 steps. In addition, the structure of sclerosteroid B is revised on the basis of our synthesis. C19 hydroxylation is a unique feature of some bioactive steroids. Here, the authors developed a direct C19 hydroxylation approach to scalably access 19-OH-cortexolone in the host T. cucumeris and then converted the product into various pharmaceutically useful products via chemical synthesis.
Mining Words in the Minds of Second Language Learners: Learner-Specific Word Difficulty
While there have been many studies on measuring the size of learners’ vocabulary or the vocabulary they should learn, there have been few studies on what kind of words learners actually know. Therefore, we investigated theoretically and practically important models for predicting second language learners’ vocabulary and propose another model for this vocabulary prediction task. With the current models, the same word difficulty measure is shared by all learners. This is unrealistic because some learners have special interests. A learner interested in music may know special music-related terms regardless of their difficulty. To solve this problem, our model can define a learner-specific word difficulty measure. Our model is also an extension of these current models in the sense that these models are special cases of our model. In a qualitative evaluation, we defined a measure for how learner-specific a word is. Interestingly, the word with the highest learner-specificity was “twitter”. Although “twitter” is a difficult English word, some low-ability learners presumably knew this word through the famous micro-blogging service. Our qualitative evaluation successfully extracted such interesting and suggestive examples. Our model achieved an accuracy competitive with the current models.