Pub Date : 2018-12-05DOI: 10.1002/9781119508557.ch19
Geon Dae Moon
: I will describe some examples in genomics and in neuroscience where one needs to find different fully data-driven adaptive statistical methods for testing or for estimation. In all those examples, the key is to find concentration inequalities which either allow to very precisely calibrate the tuning parameter or to deeply understand how quantiles of test statistics are behaving. The main concentration tools are either "Talagrand" type inequalities for counting processes, Bernstein or Rosenthal type inequalities, or U-statistics - chaos inequalities. Abstract : In this lecture we present some new concentration inequalities for Feynman-Kac particle processes. We analyze different types of stochastic particle models, including particle profile occupation measures, genealogical tree based evolution models, particle free energies, as well as backward Markov chain particle models. We illustrate these results with a series of topics related to computational physics and biology, stochastic optimization, signal processing and Bayesian statistics, and many other probabilistic machine learning algorithms. Special emphasis is given to the stochastic modeling, and to the quantitative performance analysis of a series of advanced Monte Carlo methods, including particle filters, genetic type island models, Markov bridge models, and interacting particle Markov chain Monte Carlo methodologies. Abstract : The mathematical foundations of statistical learning theory heavily relies on concentration inequalities and empirical processes techniques. Learning an order relation over a Banach space involves performance measures which have higher order statistics, such as rank statistics, as empirical counterparts. The classical questions of consistency, universal and fast rates of convergence require dedicated tools which involve projection arguments and concentration inequalities for U- and R-processes. In the talk, we will present some results and open problems motivated by statistical problems of major interest. : in high Abstract : I will describe some results about concentration of volume of high dimensional convex bodies obtained in the last decade. Central limit theorem for convex bodies is one of the main achievement of these series of work. I will also present some open problems, like the thin shell conjecture and the problem of spectral gap, a conjecture due to Kannan Lovasz and Simonovits. Extension of these results to new classes of probability measures, like Cauchy measure or more generally κ -concave measures will be discussed. Abstract : Compressed sensing is an area of information theory where one seeks to recover an unknown signal from few measurements. A signal is often modeled as a vector in R n , and linear measurements are given as y = Ax where A is an m by n matrix. Best known results of compressed sensing are for random linear measurements, thus A is a random matrix. We will learn about some probabilistic successes and challenges in this area, with many c
{"title":"Applications","authors":"Geon Dae Moon","doi":"10.1002/9781119508557.ch19","DOIUrl":"https://doi.org/10.1002/9781119508557.ch19","url":null,"abstract":": I will describe some examples in genomics and in neuroscience where one needs to find different fully data-driven adaptive statistical methods for testing or for estimation. In all those examples, the key is to find concentration inequalities which either allow to very precisely calibrate the tuning parameter or to deeply understand how quantiles of test statistics are behaving. The main concentration tools are either \"Talagrand\" type inequalities for counting processes, Bernstein or Rosenthal type inequalities, or U-statistics - chaos inequalities. Abstract : In this lecture we present some new concentration inequalities for Feynman-Kac particle processes. We analyze different types of stochastic particle models, including particle profile occupation measures, genealogical tree based evolution models, particle free energies, as well as backward Markov chain particle models. We illustrate these results with a series of topics related to computational physics and biology, stochastic optimization, signal processing and Bayesian statistics, and many other probabilistic machine learning algorithms. Special emphasis is given to the stochastic modeling, and to the quantitative performance analysis of a series of advanced Monte Carlo methods, including particle filters, genetic type island models, Markov bridge models, and interacting particle Markov chain Monte Carlo methodologies. Abstract : The mathematical foundations of statistical learning theory heavily relies on concentration inequalities and empirical processes techniques. Learning an order relation over a Banach space involves performance measures which have higher order statistics, such as rank statistics, as empirical counterparts. The classical questions of consistency, universal and fast rates of convergence require dedicated tools which involve projection arguments and concentration inequalities for U- and R-processes. In the talk, we will present some results and open problems motivated by statistical problems of major interest. : in high Abstract : I will describe some results about concentration of volume of high dimensional convex bodies obtained in the last decade. Central limit theorem for convex bodies is one of the main achievement of these series of work. I will also present some open problems, like the thin shell conjecture and the problem of spectral gap, a conjecture due to Kannan Lovasz and Simonovits. Extension of these results to new classes of probability measures, like Cauchy measure or more generally κ -concave measures will be discussed. Abstract : Compressed sensing is an area of information theory where one seeks to recover an unknown signal from few measurements. A signal is often modeled as a vector in R n , and linear measurements are given as y = Ax where A is an m by n matrix. Best known results of compressed sensing are for random linear measurements, thus A is a random matrix. We will learn about some probabilistic successes and challenges in this area, with many c","PeriodicalId":186753,"journal":{"name":"Diarylethene Molecular Photoswitches","volume":"168 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"2018-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"115538475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Steps in the hydroxylation pathway of the flavoprotein phenol hydroxylase with resorcinol as substrate have been studied by a combination of fluorescence and absorbance stopped flow techniques. In the presence of azide, a series of highly fluorescent oxygenated flavin intermediates has been observed, corresponding to those previously detected by absorbance measurements (Detmer, K., and Massey, V. (1985) J. Biol. Chem. 260, 5998-6005). In addition, yet another intermediate has been found as the immediate product of the reaction of the reduced enzyme with 02. This new species is nonfluorescent in the presence of azide, but fluorescent in the absence of monovalent anions and had escaped detection in previous absorbance studies because of the similarity in its rates of formation and conversion to the next intermediate and similarity in their spectra. These two early intermediates are tentatively identified as the anionic and protonated species of the flavin C4a-hydroperoxide or, alternatively, as two conformationally different forms of the enzyme hydroperoxide. The next intermediate, previously referred to as intermediate 11, is also highly fluorescent and so is considered unlikely to be due to a complex of a flavin alkoxy1 radical and a substituted cyclohexadienyl radical, as proposed by Anderson et al. (Anderson, R. F., Patel, K. B., and Stratford, M. R. L. (1990) J. Biol. Chem. 265, 1952-1957). The conversion of intermediate I1 to the next intermediate, intermediate I11 (the C4a-hydroxyflavin), is characterized by a large substrate deuterium isotope effect in the 320-390 nm range, but not by fluorescence or by absorbance at wavelengths >400 nm. This is ascribed to dissociation from the enzyme of a cyclohexadienone product, leaving the enzyme in its C4a-hydroxyflavin form. The latter eliminates H 2 0 to re-form oxidized flavin, but in a competing reaction, in the presence of excess substrate, forms a very stable complex, which decays orders of magnitude more slowly than the uncomplexed enzyme.
以间苯二酚为底物的黄蛋白酚羟化酶的羟化途径的步骤已经通过荧光和吸光度停止流动技术的组合研究。在叠氮化物的存在下，观察到一系列高荧光氧合黄素中间体，与以前通过吸光度测量检测到的产物相对应(Detmer, K.， and Massey, V. (1985) J. Biol.)。化学，260,5998-6005)。此外，还发现了另一种中间体，作为还原酶与02反应的直接产物。这个新物种在叠氮化物存在时是不荧光的，但在没有单价阴离子的情况下是荧光的，并且在以前的吸光度研究中逃脱了检测，因为它的形成和转化到下一个中间体的速度相似，并且它们的光谱相似。这两种早期中间体暂定为黄素c4a -氢过氧化物的阴离子和质子化种，或者，作为氢过氧化物酶的两种构象不同形式。下一个中间体，以前称为中间体11，也是高荧光的，因此被认为不太可能是由于黄素烷氧基1自由基和取代的环己二烯基自由基的复合物，如Anderson等人提出的(Anderson, R. F.， Patel, K. B.， and Stratford, M. R. L. (1990) J. Biol.)。化学，265,1952-1957)。中间体I1向下一个中间体I11 (C4a-hydroxyflavin)的转化，在320-390 nm范围内表现出较大的底物氘同位素效应，但在波长>400 nm处不受荧光或吸光度的影响。这归因于环己二酮产物的酶解离，使酶以c4a -羟黄素形式存在。后者消除h20以重新形成氧化的黄素，但在竞争性反应中，在过量底物的存在下，形成非常稳定的复合物，其衰变速度比未络合的酶慢几个数量级。
{"title":"Reaction Mechanism","authors":"Kazuko Maeda-Yoritag, Vincent Masseyg","doi":"10.1351/goldbook.r05173","DOIUrl":"https://doi.org/10.1351/goldbook.r05173","url":null,"abstract":"Steps in the hydroxylation pathway of the flavoprotein phenol hydroxylase with resorcinol as substrate have been studied by a combination of fluorescence and absorbance stopped flow techniques. In the presence of azide, a series of highly fluorescent oxygenated flavin intermediates has been observed, corresponding to those previously detected by absorbance measurements (Detmer, K., and Massey, V. (1985) J. Biol. Chem. 260, 5998-6005). In addition, yet another intermediate has been found as the immediate product of the reaction of the reduced enzyme with 02. This new species is nonfluorescent in the presence of azide, but fluorescent in the absence of monovalent anions and had escaped detection in previous absorbance studies because of the similarity in its rates of formation and conversion to the next intermediate and similarity in their spectra. These two early intermediates are tentatively identified as the anionic and protonated species of the flavin C4a-hydroperoxide or, alternatively, as two conformationally different forms of the enzyme hydroperoxide. The next intermediate, previously referred to as intermediate 11, is also highly fluorescent and so is considered unlikely to be due to a complex of a flavin alkoxy1 radical and a substituted cyclohexadienyl radical, as proposed by Anderson et al. (Anderson, R. F., Patel, K. B., and Stratford, M. R. L. (1990) J. Biol. Chem. 265, 1952-1957). The conversion of intermediate I1 to the next intermediate, intermediate I11 (the C4a-hydroxyflavin), is characterized by a large substrate deuterium isotope effect in the 320-390 nm range, but not by fluorescence or by absorbance at wavelengths >400 nm. This is ascribed to dissociation from the enzyme of a cyclohexadienone product, leaving the enzyme in its C4a-hydroxyflavin form. The latter eliminates H 2 0 to re-form oxidized flavin, but in a competing reaction, in the presence of excess substrate, forms a very stable complex, which decays orders of magnitude more slowly than the uncomplexed enzyme.","PeriodicalId":186753,"journal":{"name":"Diarylethene Molecular Photoswitches","volume":"152 1","pages":"0"},"PeriodicalIF":0.0,"publicationDate":"1900-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"115792980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：