Synthesis of dinucleoside (N3'-->MeP5') methanephosphonamidates

[structure: see text] Three different approaches were used for the synthesis of dinucleoside methanephosphonamidates [3'-NH-P(O)(CH3)O-5'], starting from dichloromethylphosphine or dichloromethanephosphonate as the phosphorus-containing moiety. 5'-DMT-3'-amino-3'-deoxythymidine and N(4)-benzoyl-5'-DMT-3'-amino-2',3'-dideoxycytidine were used as the aminonucleoside precursors and the respective 3'-protected nucleosides (thymidine or N(4)-benzoyl-2'-deoxycytidine) as the 5'-hydroxyl reagents.     

Polysiloxanes with chlorobenzyl groups as precursors of new organic‐silicone materials

Various polysiloxanes bearing chlorobenzyl side groups were synthesized by the hydrolytic polycondensation of the 73:27 mol/mol mixture of [2‐(4‐chloromethylphenyl)ethyl] methyldichlorosilane and [1‐(4‐chloromethylphenyl)ethyl] methyldichlorosilane followed by the cationic equilibration or coequilibration with octamethylcyclotetrasiloxane, D₄. 1,3‐Divinyltetramethyl‐disiloxane was used as the chain end blocker to obtain a vinyl–Si ended chlorobenzyl‐substituted polysiloxane. In some cases, the polymer was additionally treated with dimethylvinylchlorosilane to achieve full substitution of chain ends by the vinyl group. Cohydrolysis of the chlorobenzylic monomer mixture with dimethyldichlorosilane was also practiced. Multiblock copolymers were obtained by polyhydrosilylation of the α,ω‐divinylsilyl chlorobenzyl‐substituted polysiloxanes with α,ω‐dihydrosilyl polydimethylsiloxanes. All these polymers and copolymers containing reactive chlorobenzylic groups were demonstrated to be convenient precursors of functional polysiloxanes of potential practical use. Some specific functional groups, such as quaternary ammonium salt groups of biocidal activity or azobenzene groups making the polymer sensitive to external stimuli by light, may be readily generated on polysiloxane under mild conditions. The chlorobenzylic substituted polysiloxanes may be also used as macroinitiators of the atom transfer radical polymerization, to obtain polysiloxanes with grafted organic polymers, such as styrene, 4‐chloromethylstyrene, and n‐butylacrylate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1682–1692, 2004     

Geometrization of linear perturbation theory for diffeomorphism-invariant covariant field equations. II. Basic gauge-invariant variables with applications to de sitter space-time

In a companion paper, a systematic treatment of linearized perturbations and a new geometric definition of gauge-invariant variables, based on the theory of vector bundles and applicable to the case of an arbitrary system of covariant field equations, were carefully presented. One of the purposes of the present paper is to specify a necessary and sufficient condition that a given, finite set of gaugeinvariant variables, denoted collectively by ω and referred to as the complete set of basic variables, can be used to extract the equivalence classes of perturbations from ω in a unique way. The above set is complete because it has the following property: a knowledge of ω is all one needs in the sense that ifx represents an arbitrary point of the “space-time” manifoldX andG denotes any gauge-invariant tensor field onX, then the value ofG atx∈X is uniquely specified by giving the germs of basic gauge-invariant variables atx∈X. Arguments are proposed that ω also has a stronger property which is more immediately useful: anyG is obtainable directly from the basic variables through purely algebraic and differential operations. These results are of practical interest, and one concrete setting where one is led to the explicit definition of ω occurs when considering the infinitesimal perturbation of the metric tensor itself (pure gravity) defined on a fixed background de Sitter space-time and obeying the linearized empty-space Einstein equations with nonnegative cosmological constant Λ; the case Λ=0 corresponds to linear perturbation theory in Minkowski space-time.     

Two ideals

We find two ideals on neither of which is whose quotient Boolean algebras are homogeneous but nonisomorphic. This solves a problem of Just and Krawczyk (1984).

     

Quantum Riemann surfaces III. the exceptional cases

We discuss quantum deformations of Riemann surfaces whose fundamental groups are Abelian (the exceptional Riemann surfaces). We prove uniformization theorems, state deformation estimates, and study the dependence of quantum Riemann surfaces on the deformation parameter.Supported in part by NSF grant DMS-9206936.Supported in part by DOE grant DE-FG02-88ER25065.     

Modeling the induction of lipid membrane electropermeabilization

Experiments show significant effects of an electric field on lipid membrane, leading to a pore formation when a high intensity field is applied. The phenomenon of electroporation is preceded by the induction and expansion of defects, responsible for the pre-pore excitation. We examine the mechanism of the induction of the field-driven defects by Monte Carlo simulations. The study is based on the improved Pink's model, which includes explicit interactions between the polar heads and energy of interactions between the heads and the field. No anomalous deformation of the molecules is considered. The study, provided for bilayer dipalmitoyl-phosphatidylcholine (DPPC) membrane in the gel (300 K) and fluid (330 K) phases, shows dependence of the membrane conformational and energetical state on the value of the electric field. We observe that the electric field affects the number of molecules in the gel and in the fluid states. In the layer at the negative potential, when the transmembrane voltage is above U(c) approximately 280 mV, lipid heads abruptly reorient and the number of local spots with fluid conformation increases. The other layer slightly tends to tighten its structure, producing additional mechanical stress between layers. Lipids showed complete insensitivity to the electric field within physiological limits, U<70 mV.     

Ionic liquids with perfluorinated alkoxyaluminates

Ionic liquids with the weakly coordinating perfluoroalkoxyaluminate anions, Al(ORF)4-, are obtained by a metathesis reaction of LiAl(ORF)4 and [bmim]Cl or [bmpyr]Cl in high yields. The compounds [bmim][Al(hfip)4] and [bmpyr][Al(hfip)4] have surprisingly low viscosities at elevated temperatures (60 degrees C) and an exceptionally high electrochemical window, which might render them useful for certain applications.     

Temperature dependence of ligand-protein complex formation as reflected by saturation transfer difference NMR experiments

We show that temperature is an important parameter for the sensitivity of saturation transfer difference (STD) spectroscopy. A decreased intensity of STD signals is observed for lactose binding to growth-regulatory galectin7 (p53-induced gene 1), as well as for nucleotide binding to annexin A6, when the temperature is increased from 281 to 298-310 K. Opposite temperature effects on STD intensity are observed for S-peptide binding to S-protein to reconstitute RNase S. However, the STD signals for tryptophan binding to downstream regulatory element antagonist modulator of the human prodynorphin gene (DREAM)are relatively unaffected between 281 and 298 K. The known kinetics of the binding of ATP by the uncoupling protein from brown adipose tissue mitochondria (UCP1) predicted an observable STD at 310 K, but rapid sample degradation limits the experiments to much lower temperatures. Temperature strongly influences the kinetics and affinity constant of various types of complex formation and in so doing influences the observed STD effects. Therefore, temperature can be exploited to facilitate the optimization of STD-based applications, and at the same time minimize the number of test samples. STD-based screening protocols to detect new target-specific compounds may yield a larger number of potential ligands if screened at various temperatures.