Evaluating and clustering retrosynthesis pathways with learned strategy

With recent advances in the computer-aided synthesis planning (CASP) powered by data science and machine learning, modern CASP programs can rapidly identify thousands of potential pathways for a given target molecule. However, the lack of a holistic pathway evaluation mechanism makes it challenging to systematically prioritize strategic pathways except for using some simple heuristics. Herein, we introduce a data-driven approach to evaluate the relative strategic levels of retrosynthesis pathways using a dynamic tree-structured long short-term memory (tree-LSTM) model. We first curated a retrosynthesis pathway database, containing 238k patent-extracted pathways along with ∼55 M artificial pathways generated from an open-source CASP program, ASKCOS. The tree-LSTM model was trained to differentiate patent-extracted and artificial pathways with the same target molecule in order to learn the strategic relationship among single-step reactions within the patent-extracted pathways. The model achieved a top-1 ranking accuracy of 79.1% to recognize patent-extracted pathways. In addition, the trained tree-LSTM model learned to encode pathway-level information into a representative latent vector, which can facilitate clustering similar pathways to help illustrate strategically diverse pathways generated from CASP programs.

Tree-structured long short-term memory neural model learns to understand the retrosynthesis design strategies from patent-extracted retrosynthetic pathway data.     

Two new compounds derived from bufalin

The biotransformation of bufalin by cell suspension cultures of Platycodon grandiflorus was investigated and two new biotransformed products were obtained,which was 3-epi-telocinobufagin and 3-epi-bufalin-3-O-β-D-glucoside.     

Fluorinated nitroxides as ESR probes of solvation

Some newly synthesized fluorinated nitroxides, such as t-butyl perfluoroalkyl nitroxides Bu^tN(O) R_f (R_f=CF₃, 5; C₂F₅, 6; n-C₃F₇, 7) and s-butyl perfluoroacyl nitroxides Bu^sN(O) COR_f (R_f=CF₃, 9; n-C₃F₇, 10) have been employed as ESR probes of solvation in different common organic solvents. In aprotic solvents, the measured a_N values for each of the nitroxyl probes show a linear correlation with the cybotactic polar solvent parameters E_T (Dimroth) and Z (Kosowar), i.e. a_N=bE_T+c, and a_N=b′Z+c′. The physical significance for the slope (b or b′), the slope×E_T or slope×Z, the extrapolated intercept on a_N axis, c or c′, are linked, respectively, to the sensitivity of a specific nitroxide toward solvation, the magnitude of the overall solvation effect on the a_N value, and the intrinsic a_N value of each nitroxide in the ideal gaseous state. The intercept on the a_N axis may also serve as a new measure of electronegativity for perfluoroalkyl groups, CF₃, C₂F₅, n-C₃F₇, and perfluoroacyl groups, CF₃CO, n-C₃F₇CO. In protic solvents, i.e. alcohols and carboxylic acids, however, a_N values of all the probes, kept almost no change with the increase in E_T and Z. Furthermore, the plots of a_N versus non-cybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ε), all show random variations.     

Mechanism transition of self-pumped phase conjugation in KTa1 −xNbxO3:Fe crystals

Mechanism transitions of Self-Pumped Phase Conjugation (SPPC) with wavelength and doping concentration are observed in KTN:Fe (KTa_{1 –x} Nb _x O₃:Fe with _x = 0.48) crystals. The SPPC mechanism in KTN: Fe (0.4 wt. %) crystal transforms from Stimulated Photorefractive Backscattering and Four-Wave Mixing (SPB-FWM) to cat (or total internal reflection) as the wavelength increases from 514.5 nm to 620 nm. SPPC at 514.5 nm is formed with the cat mechanism in a 0.2 wt. % doped KTN:Fe crystal, while with the SPB-FWM mechanism in a 0.4 wt. % doped one. These mechanism transitions are discussed with respect to the dependence of the backscattering gain coefficient of the crystals on wavelength and doping concentration.     

Proteomic analysis of mouse liver for the evaluation of effects of Scutellariae radix by liquid chromatography with tandem mass spectrometry

Scutellariae radix or Scutellaria baicalensis is a medicinal plant that contains major flavonoids such as baicalein, baicalin, wogonin and wogonosides. The present work describes the development of an approach using proteomic analysis of mouse liver to study the effects of prolonged exposure to substances present in chemically standardized Scutellariae radix extracts. Histopathological examination of the mouse liver was compared with the proteome data. The botanical extracts were prepared using pressurized liquid extraction (PLE). A method without isotope labeling was developed, using proteolytic digestion with one- and two-dimensional liquid chromatography with tandem mass spectrometry, and was used to characterize the extent of differential protein expression in mouse liver in response to external factors such as extracts from Scutellariae radix. From the histopathological examination and proteome data, significant changes in the mouse livers were not observed for the low-dose group. The Scutellariae radix extracts at high dose were observed to cause damage at the bile duct and expression change of a number of proteins including some involved in catabolism of triglyceride-rich particles, carbohydrate metabolism, regulators of cell signaling processes, and enzymes involved in biotransformation. Thus, proteomic analysis of liver samples from mice treated with botanical extracts is a promising approach to provide information on any potential toxicity effects of the extracts. The present method also provides another means for comparing proteomes in biological samples such as liver lysates from mice subjected to different treatments.     

大学无机化学实验中碱式碳酸铜制备方法探讨

探讨大学无机化学实验中有关碱式碳酸铜制备的实验方法,并以Cu(NO3)2为原料、NaOH和Na2CO3的混合液为沉淀剂制备碱式碳酸铜。讨论反应物最佳配比、pH、温度等因素对产品的影响,并对所制产品进行XRD分析,提出一种制备碱式碳酸铜的大学无机化学实验方法。     

稀土掺杂PbO2电极的制备及催化性能研究

以SnCl4.5H2O,Sb2O3,La（NO3）3（或Nd（NO3））为前驱体（摩尔比分别为Sn∶Sb∶La（Nd）=100∶6∶（0.5,1,2）,制备稀土（La,Nd）掺杂Sn,Sb溶胶,以钛电极为基体,用溶胶-凝胶法制备稀土（La,Nd）掺杂SnO2中间层,热处理温度为450和500℃,热处理时间共5 h;采用电沉积法制备PbO2表面层,得到改性PbO2阳极,优化了制备改性PbO2电极的稀土掺杂量。以含油污水为目标有机物,借助于CODCr去除情况分析电极的电催化氧化能力;分析了电极结构与电催化特性之间的关系。采用SEM和XRD分析了制备电极的表面形貌、晶体结构并通过电化学工作站对其析氧电位进行了表征分析。结果表明,中间层掺杂La元素的电极,掺杂比为Sn∶Sb∶La=100∶6∶1时电极性能最好;而中间层掺杂Nd元素,掺杂比为Sn∶Sb∶Nd=100∶6∶2时电极的性能最好,此比例时电极对目标有机物CODCr去除率分别为91.90%和90.93%。     

将A-L理论推广到无限维李代数

为使由Alhassid与Levine所提出的动力学李代数方法（简称A－L理论）能适用于更多的散射体系，在h(∞)中引入了有效集合C（有限维）的概念．按照微扰理论的意义，C中的代数元所对应的群参量是较低次微扰的结果，而不属于C的代数元所对应的群参量则相当于较高次做扰所产生的修正结果．因此可以近似地利用C来代替h(∞)．这样，不仅简化了计算程序并且对于很多具有现实意义的散射过程的计算成为可能．     

共线散射体系A+BC的平-振能量传递──无限维李代数处理方法

利用无限维李代数方法处理了在BC分子能谱中含有二级与三级非简谐项的散射体系A＋BC的平-振能量传递问题，获得了散射过程的含有主要动力学参量的跃迁矩阵元和跃迁几率的解析表达式