Donald Trump, Silvio Berlusconi, Marine Le Pen, Hugo Chávez—populists are on the rise across the globe. But what exactly is populism? Should everyone who criticizes Wall Street or Washington be ...called a populist? What precisely is the difference between right-wing and left-wing populism? Does populism bring government closer to the people or is it a threat to democracy? Who are "the people" anyway and who can speak in their name? These questions have never been more pressing.In this groundbreaking volume, Jan-Werner Müller argues that at populism's core is a rejection of pluralism. Populists will always claim that they and they alone represent the people and their true interests. Müller also shows that, contrary to conventional wisdom, populists can govern on the basis of their claim to exclusive moral representation of the people: if populists have enough power, they will end up creating an authoritarian state that excludes all those not considered part of the proper "people." The book proposes a number of concrete strategies for how liberal democrats should best deal with populists and, in particular, how to counter their claims to speak exclusively for "the silent majority" or "the real people."Analytical, accessible, and provocative, What Is Populism? is grounded in history and draws on examples from Latin America, Europe, and the United States to define the characteristics of populism and the deeper causes of its electoral successes in our time.
Involution Seiler, Werner M
2009, 2010, 20090918, 2014-07-30, Volume:
24
eBook
The book provides a self-contained account of the formal theory of general, i.e. also under- and overdetermined, systems of differential equations which in its central notion of involution combines ...geometric, algebraic, homological and combinatorial ideas. It presents for the first time in book form the theory of Pommaret bases, a special kind of Gröbner bases closely related to Koszul homology, and contains an extensive discussion of the existence and uniqueness of solutions of formally well-posed initial value problems and a novel presentation of Vessiot's dual version of the Cartan-Kähler theory. Special emphasis is put on a constructive approach leading to effective algorithms.
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In the wide area of supramolecular chemistry, cucurbit
n
urils (CB
n
) present themselves as a young family of molecular containers, able to form stable complexes with various guests, including drug ...molecules, amino acids and peptides, saccharides, dyes, hydrocarbons, perfluorinated hydrocarbons, and even high molecular weight guests such as proteins (
e.g.
, human insulin). Since the discovery of the first CB
n
, CB6, the field has seen tremendous growth with respect to the synthesis of new homologues and derivatives, the discovery of record binding affinities of guest molecules in their hydrophobic cavity, and associated applications ranging from sensing to drug delivery. In this review, we discuss in detail the fundamental properties of CB
n
homologues and their cyclic derivatives with a focus on their synthesis and their applications in catalysis.
Major developments in the synthesis of cucurbiturils and applications related to their high-affinity binding and catalysis have recently taken place.
Following up on scattered reports on interactions of conventional chaotropic ions (for example, I−, SCN−, ClO4−) with macrocyclic host molecules, biomolecules, and hydrophobic neutral surfaces in ...aqueous solution, the chaotropic effect has recently emerged as a generic driving force for supramolecular assembly, orthogonal to the hydrophobic effect. The chaotropic effect becomes most effective for very large ions that extend beyond the classical Hofmeister scale and that can be referred to as superchaotropic ions (for example, borate clusters and polyoxometalates). In this Minireview, we present a continuous scale of water–solute interactions that includes the solvation of kosmotropic, chaotropic, and hydrophobic solutes, as well as the creation of void space (cavitation). Recent examples for the association of chaotropic anions to hydrophobic synthetic and biological binding sites, lipid bilayers, and surfaces are discussed.
Chaos reigns: The unexpectedly high affinity of large anions to macrocyclic hosts, proteins, membranes, colloids, and interfaces results from a generic driving force for association in aqueous solution, namely the chaotropic effect. It is most effective for superchaotropic anions, positioned between chaotropic and hydrophobic ions on an expanded Hofmeister scale.
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Host–guest chemistry commenced to a large degree with the work of Pedersen, who in 1967 first reported the synthesis of crown ethers. The past 45 years have witnessed a substantial progress in the ...field, from the design of highly selective host molecules as receptors to their application in drug delivery and, particularly, analyte sensing. Much effort has been expended on designing receptors and signaling mechanism for detecting compounds of biological and environmental relevance. Traditionally, the design of a chemosensor comprises one component for molecular recognition, frequently macrocycles of the cyclodextrin, cucurbituril, cyclophane, or calixarene type. The second component, used for signaling, is typically an indicator dye which changes its photophysical properties, preferably its fluorescence, upon analyte binding. A variety of signal transduction mechanisms are available, of which displacement of the dye from the macrocyclic binding site is one of the simplest and most popular ones. This constitutes the working principle of indicator displacement assays. However, indicator displacement assays have been predominantly exploited in a static fashion, namely, to determine absolute analyte concentrations, or, by using combinations of several reporter pairs, to achieve a differential sensing and, thus, identification of specific food products or brands. In contrast, their use in biological systems, for example, with membranes, cells, or with enzymes has been comparably less explored, which led us to the design of the so-called tandem assays, that is, dynamically analyte-responsive host–dye systems, in which the change in analyte concentrations is induced by a biological reaction or process. This methodological variation has practical application potential, because the ability to monitor these biochemical pathways or to follow specific molecules in real time is of paramount interest for both biochemical laboratories and the pharmaceutical industry. We will begin by describing the underlying principles that govern the use of macrocycle-fluorescent dye complexes to monitor time-dependent changes in analyte concentrations. Suitable chemosensing ensembles are introduced, along with their fluorescence responses (switch-on or switch-off). This includes supramolecular tandem assays in their product- and substrate-selective variants, and in their domino and enzyme-coupled modifications, with assays for amino acid decarboxylases, diamine, and choline oxidase, proteases, methyl transferases, acetylcholineesterase (including an unpublished direct tandem assay), choline oxidase, and potato apyrase as examples. It also includes the very recently introduced tandem membrane assays in their published influx and unpublished efflux variants, with the outer membrane protein F as channel protein and protamine as bidirectionally translocated analyte. As proof-of-principle for environmental monitoring applications, we describe sensing ensembles for volatile hydrocarbons.
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Ternary complexes between the macrocyclic host cucurbit8uril, dicationic dyes, and chiral aromatic analytes afford strong induced circular dichroism (ICD) signals in the near‐UV and visible regions. ...This allows for chirality sensing and peptide‐sequence recognition in water at low micromolar analyte concentrations. The reversible and noncovalent mode of binding ensures an immediate response to concentration changes, which allows the real‐time monitoring of chemical reactions. The introduced supramolecular method is likely to find applications in bioanalytical chemistry, especially enzyme assays, for drug‐related analytical applications, and for continuous monitoring of enantioselective reactions, particularly asymmetric catalysis.
Strong and diagnostic induced circular dichroism signals in the near‐UV or visible region are obtained when chiral, optically transparent analytes bind to an achiral chemosensing ensemble composed of a macrocyclic host and dye. This affords a novel, supramolecular detection method for chiral aromatic analytes in water.
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Macrocyclic hosts of the cyclodextrin, sulfonatocalixarene, and cucurbituril type can be employed as discrete supramolecular drug delivery systems, thereby complementing existing supramolecular drug ...formulation strategies based on polymers, hydrogels, liposomes, and related microheterogeneous systems. Cucurbiturils, in particular, stand out in that they do not only provide a hydrophobic cavity to encapsulate the drug in the form of a host–guest complex, but in that they possess cation-receptor properties, which favor the encapsulation of protonated drugs over their unprotonated forms, resulting in pronounced pKa shifts up to 5 units. These pKa shifts can be rationally exploited to activate prodrug molecules, to stabilize the active form of drug molecules, to enhance their solubility, and to increase their degree of ionization, factors which can jointly serve to enhance the bioavailability of drugs, particularly weakly basic ones. Additionally, macrocycles can serve to increase the chemical stability of drugs by protecting them against reactions with nucleophiles (e.g., thiols) and electrophiles, by increasing their photostability, and by causing a higher thermal stability in the solid state. Detailed examples of the different effects of macrocyclic encapsulation of drugs and the associated pKa shifts are provided and discussed. Other important considerations, namely a potential lowering of the bioactivity of drugs by macrocyclic complexation, interferences of the macrocycles with biocatalytic processes, the toxicity of the macrocyclic host molecules, and problems and opportunities related to a targeted release and the rate of release of the drug from the host–guest complexes are critically evaluated.
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Macrocyclic hosts of the cyclodextrin, sulfonatocalixarene, and cucurbituril type can be employed as discrete supramolecular drug delivery systems, thereby complementing existing supramolecular drug ...formulation strategies based on polymers, hydrogels, liposomes, and related microheterogeneous systems. Cucurbiturils, in particular, stand out in that they do not only provide a hydrophobic cavity to encapsulate the drug in the form of a host-guest complex, but in that they possess cation-receptor properties, which favor the encapsulation of protonated drugs over their unprotonated forms, resulting in pronounced pK(a) shifts up to 5 units. These pK(a) shifts can be rationally exploited to activate prodrug molecules, to stabilize the active form of drug molecules, to enhance their solubility, and to increase their degree of ionization, factors which can jointly serve to enhance the bioavailability of drugs, particularly weakly basic ones. Additionally, macrocycles can serve to increase the chemical stability of drugs by protecting them against reactions with nucleophiles (e.g., thiols) and electrophiles, by increasing their photostability, and by causing a higher thermal stability in the solid state. Detailed examples of the different effects of macrocyclic encapsulation of drugs and the associated pK(a) shifts are provided and discussed. Other important considerations, namely a potential lowering of the bioactivity of drugs by macrocyclic complexation, interferences of the macrocycles with biocatalytic processes, the toxicity of the macrocyclic host molecules, and problems and opportunities related to a targeted release and the rate of release of the drug from the host-guest complexes are critically evaluated.
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