Molecular dynamics simulation of continuous current flow through a model biological membrane channel

The conductance of sodium ions through a simplified channel-membrane system immersed in a reservoir of 1M NaCl in SPC/E water is examined by molecular dynamics simulation. An applied external potential of 1.1 V drives the ions and water through a channel of length 25 A producing a current of 19.6 pA, in reasonable agreement with experimental findings. The stream of ions and water molecules flows continuously because of the constant applied field and periodic boundary conditions. We also examine the potential profile across the simulation cell, the average density distributions of the various species in the reservoir and radially in the channel, and the ion velocity in the channel.     

Highly enantio- and diastereoselective one-pot synthesis of acyclic epoxy alcohols with three contiguous stereocenters

Two highly enantio- and diastereoselective one-pot procedures for the synthesis of epoxy alcohols with up to three contiguous stereocenters are reported. Route one involves asymmetric addition of an alkylzinc reagent to an enal followed by diastereoselective epoxidation. Route two entails asymmetric vinylation of an aldehyde with divinylzinc reagents and subsequent diastereoselective epoxidation. The oxidant for the epoxidation is generated by exposure of the allylic alkoxide intermediate and the remaining organozinc reagent to dioxygen. Upon addition of catalytic titanium tetraisopropoxide, the directed epoxidation yields the epoxy alcohols with good to excellent yields.     

Post-panning computer-aided analysis of phagotope collections selected with neurocysticercosis patient polyclonal antibodies: separation of disease-relevant and irrelevant peptide sequences

The homology of peptide sequences selected from a 7mer phage display library with antibodies elicited by the multicelled parasite Taenia solium in cerebrospinal fluid and serum of neurocysticercosis (NCC) patients and by antibodies of uninfected control patients with similar neurological complications of other ethiology (non-NCC) were analyzed using a PILEUP-Tudos sequence alignments program. The analysis generated dendrograms bearing two types of sequence clusters, those containing (1) only NCC patients-derived peptides and (2) both NCC- and control non-CC -- patient derivatives. By using ELISA, peptides that were selected by the antibodies were identified predominantly in the NCC-derived clusters. In repeated analysis in which sequences were added or removed, the first type of clusters maintained their structure, while the second type of clusters were split into many separate homology units dispersed throughout the guide tree. These results are interpreted as the ability of the analysis to segregate NCC-specific peptide sequences from other sequences. Altogether, this study demonstrates the high potential of the PILEUP-Tudos computer program to analyze phagotope collections recovered through biopanning with polyclonal antibodies elicited in patients by complex and as yet unknown multiple pathogenic antigens and to separate all phagotopes that are disease-relevant on the basis of the sequence homology.     

Fusion-fission of heavy and superheavy nuclei

The process of fusion-fission of heavy and superheavy nuclei (SHE) with Z=82–122 formed in the reactions with ⁴⁸Ca and ⁵⁸Fe ions at energies near and below the Coulomb barrier has been studied. The experiments were carried out at the U-400 accelerator of the Flerov Laboratory of Nuclear Reactions (JINR) and at the XTU Tandem accelerator of the National Laboratory of Legnaro (LNL) using the time-of-flight spectrometer of fission fragments CORSET and the neutron multidetector DEMON. As a result of the experiments, mass and energy distributions (MED) of fission fragments; fission, quasifission, and evaporation residue cross sections; and multiplicities of neutrons and γ-quanta and their dependences on the mechanism of formation and decay of compound systems have been studied.     

Matrix polynomials and the index problem for elliptic systems

The main new results of this paper concern the formulation of algebraic conditions for the Fredholm property of elliptic systems of P.D.E.'s with boundary values, which are equivalent to the Lopatinskii condition. The Lopatinskii condition is reformulated in a new algebraic form (based on matrix polynomials) which is then used to study the existence of homotopies of elliptic boundary value problems. The paper also contains an exposition of the relevant parts of the theory of matrix polynomials and the theory of elliptic systems of P.D.E.'s.

     

Tracking dissipation in capture reactions

Nuclear dissipation in capture reactions is investigated using backtracing, a new analysis protocol. Combining analysis procedure with dynamical models, the difficult and long-standing problem of competition and mixing between quasifission and fusion-fission is solved for the first time. The nature of the relevant dissipation is determined as one-body dissipation. At low excitation energy where shell effects are strongly effective, the shape of the mass distribution could be a powerful check of the nature and the magnitude of the dissipation.     

Novel syn intramolecular pathway in base-catalyzed 1,2-elimination reactions of beta-acetoxy esters

As part of a comprehensive investigation of electronic effects on the stereochemistry of base-catalyzed 1,2-elimination reactions, we observed a new syn intramolecular pathway in the elimination of acetic acid from beta-acetoxy esters and thioesters. 1H and 2H NMR investigation of reactions using stereospecifically labeled tert-butyl (2R*,3R*)-3-acetoxy-2,3-2H2-butanoate (1) and its (2R*,3S*) diastereomer (2) shows that 23 +/- 2% syn elimination occurs. The elimination reactions were catalyzed with KOH or (CH3)4NOH in ethanol/water under rigorously non-ion-pairing conditions. By contrast, the more sterically hindered beta-trimethylacetoxy ester produces only 6 +/- 1% syn elimination. These data strongly support an intramolecular (Ei) syn path for elimination of acetic acid, most likely through the oxyanion produced by nucleophilic attack at the carbonyl carbon of the beta-acetoxy group. The analogous thioesters, S-tert-butyl (2R*,3R*)-3-acetoxy-2,3-2H2-butanethioate (3) and its (2R*,3S*) diastereomer (4), showed 18 +/- 2% syn elimination, whereas the beta-trimethylacetoxy substrate gave 5 +/- 1% syn elimination. The more acidic thioester substrates do not produce an increased amount of syn stereoselectivity even though their elimination reactions are at the E1cb interface.