The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical het...The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical heterogeneity that falls outside assumptions of homogeneity and indistinguishability made by Boltzmann, Gibbs, Tolman and Von Neumann in their H-Theorems. Epicatalysis operates outside these assumptions. Hence, H-Theorems do not apply to it and the second law is bypassed, not broken. There is no contradiction with correctly understood established physics. Other phenomena also based on heterogeneous statistics include non-maxwellian adsorption, the field-induced thermoelectric effect and the reciprocal Hall effect. Elementary particles have well known distributions such as Fermi-Dirac and Bose Einstein, but composite particles such as those involved in chemical reactions, have complex intractable statistics not necessarily maxwellian and best determined by quantum modeling methods. A step by step solution for finding the quantum thermodynamic properties of a quantum composite gas, that avoids the computational requirement of modeling a large number of composite particles includes 1) quantum molecular modeling of a few particles, 2) determining their available microstates, 3) producing their partition function, 4) generating their statistics, and 5) producing the epicatalytic parameter for the generalized law of mass action.展开更多
目的:探究款冬花经烟草甲虫蛀蚀后化学成分的变化。方法:测定未虫蛀款冬花、烟草甲虫蛀蚀后的款冬花及烟草甲虫排泄物的氢核磁共振(^(1)H nuclear magnetic resonance,^(1)H NMR)图谱并进行化合物指认归属。采用主成分分析(principal co...目的:探究款冬花经烟草甲虫蛀蚀后化学成分的变化。方法:测定未虫蛀款冬花、烟草甲虫蛀蚀后的款冬花及烟草甲虫排泄物的氢核磁共振(^(1)H nuclear magnetic resonance,^(1)H NMR)图谱并进行化合物指认归属。采用主成分分析(principal component analysis,PCA)、偏最小二乘法-判别分析(partial least squares discriminate analysis,PLS-DA)和正交偏最小二乘法-判别分析(orthogonal partial least squares discriminate analysis,OPLS-DA)对虫蛀款冬花进行鉴别。根据变量重要性投影(variable importance in the projection,VIP)明确变化的化学成分,并采用t检验加以验证。结果:根据^(1)H NMR图谱共指认33个化合物。多元统计分析结果表明,未虫蛀款冬花、烟草甲虫蛀蚀后的款冬花和排泄物部分可分别聚为一类。从化学成分含量的差异结果看,款冬花被虫蛀后款冬酮的含量下降,在排泄物中异亮氨酸、缬氨酸等氨基酸的含量升高,绿原酸、异绿原酸等款冬花的次生代谢产物含量下降。结论:首次将^(1)H NMR结合多元统计分析用于中药材虫蛀后化学成分的变化研究,为中药材变质现象的研究提供了新的思路和方法。展开更多
文摘The law of mass action, based on maxwellian statistics, cannot explain recent epicatalysis experiments but does when generalized to non-maxwellian statistics. Challenges to the second law are traced to statistical heterogeneity that falls outside assumptions of homogeneity and indistinguishability made by Boltzmann, Gibbs, Tolman and Von Neumann in their H-Theorems. Epicatalysis operates outside these assumptions. Hence, H-Theorems do not apply to it and the second law is bypassed, not broken. There is no contradiction with correctly understood established physics. Other phenomena also based on heterogeneous statistics include non-maxwellian adsorption, the field-induced thermoelectric effect and the reciprocal Hall effect. Elementary particles have well known distributions such as Fermi-Dirac and Bose Einstein, but composite particles such as those involved in chemical reactions, have complex intractable statistics not necessarily maxwellian and best determined by quantum modeling methods. A step by step solution for finding the quantum thermodynamic properties of a quantum composite gas, that avoids the computational requirement of modeling a large number of composite particles includes 1) quantum molecular modeling of a few particles, 2) determining their available microstates, 3) producing their partition function, 4) generating their statistics, and 5) producing the epicatalytic parameter for the generalized law of mass action.
文摘目的:探究款冬花经烟草甲虫蛀蚀后化学成分的变化。方法:测定未虫蛀款冬花、烟草甲虫蛀蚀后的款冬花及烟草甲虫排泄物的氢核磁共振(^(1)H nuclear magnetic resonance,^(1)H NMR)图谱并进行化合物指认归属。采用主成分分析(principal component analysis,PCA)、偏最小二乘法-判别分析(partial least squares discriminate analysis,PLS-DA)和正交偏最小二乘法-判别分析(orthogonal partial least squares discriminate analysis,OPLS-DA)对虫蛀款冬花进行鉴别。根据变量重要性投影(variable importance in the projection,VIP)明确变化的化学成分,并采用t检验加以验证。结果:根据^(1)H NMR图谱共指认33个化合物。多元统计分析结果表明,未虫蛀款冬花、烟草甲虫蛀蚀后的款冬花和排泄物部分可分别聚为一类。从化学成分含量的差异结果看,款冬花被虫蛀后款冬酮的含量下降,在排泄物中异亮氨酸、缬氨酸等氨基酸的含量升高,绿原酸、异绿原酸等款冬花的次生代谢产物含量下降。结论:首次将^(1)H NMR结合多元统计分析用于中药材虫蛀后化学成分的变化研究,为中药材变质现象的研究提供了新的思路和方法。
