Relationship between conformational flexibility and chelate cooperativity

A family of four biscarbamates (AA) and four bisphenols (DD) were synthesized, and H-bonding interactions between all AA?DD combinations were characterized using (1)H NMR titrations in carbon tetrachloride. A chemical double mutant cycle analysis shows that there are no secondary electrostatic interactions or allosteric cooperativity in these systems, and the system therefore provides an ideal platform for investigating the relationship between chemical structure and chelate cooperativity. Effective molarities (EMs) were measured for 12 different systems, where the number of rotors in the chains connecting the two H-bond sites was varied from 5 to 20. The association constants vary by less than an order of magnitude for all 12 complexes, and the variation in EM is remarkably small (0.1-0.9 M). The results provide a relationship between EM and the number of rotors in the connecting chains (r): EM ≈ 10r(-3/2). The value of 10 M is the upper limit for the value of EM for a noncovalent intramolecular interaction. Introduction of rotors reduces the value of EM from this maximum in accord with a random walk analysis of the encounter probability of the chain ends (r(-3/2)). Noncovalent EMs never reach the very high values observed for covalent processes, which places limitations on the magnitudes of the effects that one is likely to achieve through the use of chelate cooperativity in supramolecular assembly and catalysis. On the other hand, the decrease in EM due to the introduction of conformational flexibility is less dramatic than one might expect based on the behavior of covalent systems, which limits the losses in binding affinity caused by poor preorganization of the interaction sites.     

A Symplectic Slice Theorem

We provide a model for an open invariant neighborhood of any orbit in a symplectic manifold endowed with a canonical proper symmetry. Our results generalize the constructions of Marle and Guillemin and Sternberg for canonical symmetries that have an associated momentum map. In these papers the momentum map played a crucial role in the construction of the tubular model. The present work shows that in the construction of the tubular model, the so-called Chu map, can be used instead, which exists for any canonical action, unlike the momentum map. Hamilton's equations for any invariant Hamiltonian function take on a particularly simple form in these tubular variables. As an application we will find situations, that we will call tubewise Hamiltonian, in which the existence of a standard momentum map in invariant neighborhoods is guaranteed.     

Biophysical changes induced by cholesterol on phosphatidylcholine artificial biomembranes containing alamethicin oligomers

Cholesterol is an important constituent of eukaryotic cell membranes, whose interaction with phospholipids leads to a broad range of biological roles, such as: maintenance of proper fluidity, formation of raft domains, reduction of passive permeability of various chemical species through the bilayer (e.g., glucose, glycerol, K⁺, Na⁺ and Cl⁻ ions), and increased mechanical strength of the membrane. In this work we studied an interesting paradigm, as to whether cholesterol-containing phosphatidylcholine biomembranes influence the kinetics and transport features of alamethicin oligomers embedded into it. We demonstrate that moderate relative amounts of cholesterol increase the electrical conductance of various sub-conductance states of the alamethicin oligomer, caused probably by a non-monotonic change in the lumped dipole moment of the biomembrane. Our data suggest that biomembrane stiffness caused by cholesterol, visibly modifies the association-dissociation rates of alamethicin oligomerization in the biomembrane. Moreover, increasing concentrations of cholesterol seem to lead to more stable intermediate alamethicin oligomers. We show that in the presence of cholesterol, as the diameter of the alamethicin oligomer increases, so does the time of another monomer to get picked up. These results brings into focus the interesting issue of how oligomerization of proteins affects their interaction affinities for membrane-based lipids.     

Singular Reduction of Poisson Manifolds

The conditions under which it is possible to reduce a Poisson manifold via a regular foliation have been completely characterized by Marsden and Ratiu. In this Letter we show that this characterization can be generalized in a natural way to the singular case and, as a corollary, we obtain that when the singular distribution is given by the tangent spaces to the orbits created by a Hamiltonian Lie group action, one reproduces the Universal Reduction Procedure of Arms, Cushman, and Gotay.     

Operatorial form of the theory of polarization optical devices: I. Spectral theory of the basic devices

While the theory of operators in quantum mechanics is expressed nowadays in a pure operatorial form (wrapped mostly in Dirac's symbolic language), in optics the polarization device operators and their action are analyzed yet in the old matrix (Jones or Muller) formalism. The theory of polarization device operators has not taken systematically advantage of the very general, fundamental and deep results of the spectral theory of operators, on the basis of which it can be structured in an elegant deductive and physically expressive form. In this paper we apply the spectral theorem to the polarization device operators, we calculate their expansions in a pure operatorial Dirac-dyadic form and give some examples which illustrate the advantages from the physical insight viewpoint of such an approach. We are concerning here only with the basic polarization devices, to which correspond normal operators.     

烟草(Nicotiana tabacum)原生质体再生成植株及影响植株分化的某些因素

从烟草(品种革新一号)单倍体花粉植株的叶和茎产生的愈伤组织,结合悬浮培养,获得的细胞分离出原生质体。在液体培养基中静置培养,12小时后原生质体开始变为卵圆形,细胞壁明显可见,24小时后完成第一次细胞分裂。以后继续分裂形成浅黄色的愈伤组织,在培养四星期后可达1毫米大小,再放到转床上进行旋转培养18天左右,愈伤组织可达3—4毫米大小。当转移到分化培养基后,分别分化出苗及根,长成完整的植株。 原生质体再生细胞的分裂与分化,不仅受不同器官来源的愈伤组织及其年龄的影响;还受分化培养基的基本成份及所用细胞分裂素的类型等的影响。