Limitations and Extensions of the Lock-and-Key Principle: Differences between Gas State, Solution and Solid State Structures

The lock-and-key concept is discussed with respect to necessary extensions. Formation of supramolecular complexes depends not only, and often not even primarily on an optimal geometric fit between host and guest. Induced fit and allosteric interactions have long been known as important modifications. Different binding mechanisms, the medium used and pH effects can exert a major influence on the affinity. Stereoelectronic effects due to lone pair orientation can lead to variation of binding constants by orders of magnitude. Hydrophobic interactions due to high-energy water inside cavities modify the mechanical lock-and-key picture. That optimal affinities are observed if the cavity is only partially filled by the ligand can be in conflict with the lock-and-key principle. In crystals other forces than those between host and guest often dominate, leading to differences between solid state and solution structures. This is exemplified in particular with calixarene complexes, which by X-ray analysis more often than other hosts show guest molecules outside their cavity. In view of this the particular problems with the identification of weak interactions in crystals is discussed

Noncovalent interactions: A brief account of a long history

The history of noncovalent interactions is outlined, starting with early interpretations of the symmetry of crystals, then with the fast development of coordination chemistry, and of fundamental analyses in the last century. An attempt is made to provide for the practicing scientists who use noncovalent interactions a historical background of the field, paying credit to often forgotten predecessors. A separate section shows that only in the 20th century instrumentation provided a firm basis for the exploration of noncovalent interactions. Selected examples illustrate the early and rather accurate calculations of some noncovalent energies. With the advent of supramolecular chemistry, noncovalent interactions became a mainstream field of science; this allowed further insight into the nature and strength of these seemingly weak forces. Intermolecular interactions in biological systems have also received early attention. As far as possible, exact references are given for the original publications

"Tolerization" of human T-helper cell clones by chronic exposure to alloantigen

Induction of clonal anergy in T-helper (Th) cells may have a role in regulating immune responses. A model system for studying Th cell tolerization at the clonal level in vitro could be useful for investigating the mechanisms involved. Accordingly, alloreactive helper cells were maintained in culture with interleukin 2 (IL 2) by intermittent stimulation with specific antigen. Regardless of the frequency of antigen stimulation, clones of age less than ca. 35 population doublings (PD) were found to undergo antigen-specific autocrine clonal expansion in the absence of exogenous IL 2. Such young clones (designated as phase I) could therefore not be "tolerized" by frequent exposure to antigen. In contrast, most clones of age greater than ca. 35 PD could be tolerized by frequent exposure to antigen (designated as phase II clones). Their autocrine proliferation was then blocked, although they still recognized antigen specifically as shown by their retained ability to secrete interferon-gamma (IFN-gamma) and granulocyte-macrophage colony stimulating factor (GM-CSF). The mechanism of response failure involved both an inability to upregulate IL 2 receptors in the absence of exogenous IL 2, as well as an inability to secrete IL 2. These defects were not overcome by stimulation with mitogens or calcium ionophore and phorbol esther in place of alloantigen. T-cell receptor, alpha, beta, and gamma-chain gene rearrangements remained identical in phase I and phase II clones. Tolerization of phase II clones could be avoided by increasing the period between antigen exposures. Despite this, whether or not phase II cells were capable of autocrine proliferation, they were found to have acquired the novel function of inducing suppressive activity in fresh lymphocytes. Suppressor-induction was blocked by the broadly reactive MHC class II-specific monoclonal antibody (moAb) TU39, but not by moAb preferentially reacting only with HLA-DR, DQ, or DP. Sequential immunoprecipitation on T-cell clones showed the presence of a putative non-DR, DQ, DP, TU39+ molecule on phase II clones. However, this molecule was also found on phase I clones. The nature of the TU39-blockable suppressor-inducing determinant present on phase II but not on (most) phase I clones thus remains to be clarified. In addition to suppressor-induction activity, phase II clones also acquired lytic potential as measured in a lectin approximation system. Cytotoxic (CTX) potential was also not influenced by the frequency of antigenic stimulation and could be viewed as a constitutive modulation of clonal functio

Nanoporous-gold-based composites : toward tensile ductility

We report on mechanical tests on interpenetrating-phase nanocomposite materials made by vacuum impregnation of nanoscale metal networks with a polymer. The metal component is nanoporous gold made by dealloying, whereas two epoxy resins and polyurethane are explored as the polymer component. The composites are strong and deformable in compression. Although previous observations invariably indicate tensile brittleness for nanoporous gold, composite samples made from cm-sized nanoporous samples enable macroscopic tensile and four-point bending tests that show ductility. This implies that the high strength of individual metal objects such as nanowires can now be incorporated into a strong and ductile material from which macroscopic things can be formed. In fact, a rule-of-mixture-type analysis of the stresses carried by the metal phase suggests quantitative agreement with data reported from separate experiments on small-scale gold nanostructures

Modification of spintronic terahertz emitter performance through defect engineering

Spintronic ferromagnetic/non-magnetic heterostructures are novel sources for the generation of THz radiation based on spin-to-charge conversion in the layers. The key technological and scientific challenge of THz spintronic emitters is to increase their intensity and frequency bandwidth. Our work reveals the factors to engineer spintronic Terahertz generation by introducing the scattering lifetime and the interface transmission for spin polarized, non-equilibrium electrons. We clarify the influence of the electron-defect scattering lifetime on the spectral shape and the interface transmission on the THz amplitude, and how this is linked to structural defects of bilayer emitters. The results of our study define a roadmap of the properties of emitted as well as detected THz-pulse shapes and spectra that is essential for future applications of metallic spintronic THz emitters.Comment: 33 pages, 13 figure

Fuzzy Q-Learning for Mobility Robustness Optimization in Wireless Networks

Abstract-The high popularity of smartphones and mobile PCs is expected to increase wireless data traffic in the order of 1000 times by 202

SchussenAktivplus: reduction of micropollutants and of potentially pathogenic bacteria for further water quality improvement of the river Schussen, a tributary of Lake Constance, Germany

The project focuses on the efficiency of combined technologies to reduce the release of micropollutants and bacteria into surface waters via sewage treatment plants of different size and via stormwater overflow basins of different types. As a model river in a highly populated catchment area, the river Schussen and, as a control, the river Argen, two tributaries of Lake Constance, Southern Germany, are under investigation in this project. The efficiency of the different cleaning technologies is monitored by a wide range of exposure and effect analyses including chemical and microbiological techniques as well as effect studies ranging from molecules to communities

Zur Nutzung der durch die Massenmedien verbreiteten politischen Informationen und Argumentationen durch Jugendliche

Ziel der Untersuchung ist es, objektive und subjektive Bedingungen, die die Nutzung politischer Informationen von Presse, Rundfunk und Fernsehen fördern oder hemmen, empirisch nachzuweisen und in ihren Wechselbeziehungen aufzuzeigen. Hierzu wurden 2548 Jugendliche und junge Erwachsene befragt. Nach einem Überblick über die Mediennutzung Jugendlicher wird nach dem Zusammenhang zwischen der Nutzung politischer Medienbeiträge und politischen Einstellungen und Aktivitäten Jugendlicher gefragt. Vor diesem Hintergrund werden inhaltliche Erwartungen Jugendlicher an die Massenmedien, Erwartungshaltungen gegenüber Dokumentarfilmen sowie das Interesse an populärwissenschaftlichen Büchern behandelt. Ein weiterer Schwerpunkt betrifft die Nutzung der Jugendmedien. Abschließend werden die Häufigkeit des Empfangs von Westsendern sowie Einflüsse des Empfangs von Westsendern auf Einstellungen und Verhaltensweisen von Jugendlichen untersucht. (ICE2