Studies aimed at the synthesis of morphine V an economic approach to (±)-reticuline from 3,4-dihydropapaverine

Regioselective demethylation of 3,4-dihydropapaveraldine ($\text{2}$a) at 7 and 3' positions affords a properly substituted diphenolic key intermidiate ($\text{2}$d) for the synthesis of reticuline and N-norreticuline.     

Why and how to avoid standard kinetic equations I. Principles and band conduction problem

A review of ideas leading to full rejection of any finite or partially-infinite order kinetic equation linearized in external field is given on grounds of the time-convolution Generalized Master Equations (GME). By two examples (two-level and band conduction problem), it is shown how standard kinetic equations result from GME in the lowest order approximations which obscure, however, a direct correspondence with the Kubo linear response theory. Without approximations, on the other hand, the rigorous approach is shown to be fully equivalent with the Kubo results. It is argued and illustrated that usual technical simplicity and seeming physical lucidity of standard theories (connected with the presence of field-independent transfer or scattering rates in the fielddependent linearized theory) are just owing to structural features which are solely due to the lowest order approximations involved. These features (i.e. also the possibility of standard physical interpretation of kinetic phenomena) are proved to disappear completely as far as the theory goes properly to higher orders.     

On the critical exponents of random k‐SAT

There has been much recent interest in the satisfiability of random Boolean formulas. A random k‐SAT formula is the conjunction of m random clauses, each of which is the disjunction of k literals (a variable or its negation). It is known that when the number of variables n is large, there is a sharp transition from satisfiability to unsatisfiability; in the case of 2‐SAT this happens when m/n → 1, for 3‐SAT the critical ratio is thought to be m/n ≈ 4.2. The sharpness of this transition is characterized by a critical exponent, sometimes called ν = ν_k (the smaller the value of ν the sharper the transition). Experiments have suggested that ν₃ = 1.5 ± 0.1. ν₄ = 1.25 ± 0.05, ν₅ = 1.1 ± 0.05, ν₆ = 1.05 ± 0.05, and heuristics have suggested that ν_k → 1 as k → ∞. We give here a simple proof that each of these exponents is at least 2 (provided the exponent is well defined). This result holds for each of the three standard ensembles of random k‐SAT formulas: m clauses selected uniformly at random without replacement, m clauses selected uniformly at random with replacement, and each clause selected with probability p independent of the other clauses. We also obtain similar results for q‐colorability and the appearance of a q‐core in a random graph. © 2002 Wiley Periodicals, Inc. Random Struct. Alg., 21: 182–195, 2002     

Unavoidable Traces Of Set Systems

Sauer, Shelah, Vapnik and Chervonenkis proved that if a set system on n vertices contains many sets, then the set system has full trace on a large set. Although the restriction on the size of the groundset cannot be lifted, Frankl and Pach found a trace structure that is guaranteed to occur in uniform set systems even if we do not bound the size of the groundset. In this note we shall give three sequences of structures such that every set system consisting of sufficiently many sets contains at least one of these structures with many sets.     

The auction algorithm for the transportation problem

The auction algorithm is a parallel relaxation method for solving the classical assignment problem. It resembles a competitive bidding process whereby unassigned persons bid simultaneously for objects, thereby raising their prices. Once all bids are in, objects are awarded to the highest bidder. This paper generalizes the auction algorithm to solve linear transportation problems. The idea is to convert the transportation problem into an assignment problem, and then to modify the auction algorithm to exploit the special structure of this problem. Computational results show that this modified version of the auction algorithm is very efficient for certain types of transportation problems.     

Partially isometric dilations of noncommuting -tuples of operators

Given a row contraction of operators on a Hilbert space and a family of projections on the space that stabilizes the operators, we show there is a unique minimal joint dilation to a row contraction of partial isometries that satisfy natural relations. For a fixed row contraction the set of all dilations forms a partially ordered set with a largest and smallest element. A key technical device in our analysis is a connection with directed graphs. We use a Wold decomposition for partial isometries to describe the models for these dilations, and we discuss how the basic properties of a dilation depend on the row contraction.

     

Activity of microemulsion-based nanoparticles at the human bio-nano interface: concentration-dependent effects on thrombosis and hemolysis in whole blood

Background: Although microemulsion-based nanoparticles (MEs) may be useful for drug delivery or scavenging, these benefits must be balanced against potential nanotoxicological effects in biological tissue (bio-nano interface). We investigated the actions of assembled MEs and their individual components at the bio-nano interface of thrombosis and hemolysis in human blood. Methods: Oil-in-water MEs were synthesized using ethylbutyrate, sodium caprylate, and pluronic F-68 (ME4) or F-127 (ME6) in 0.9% NaCl_w/v. The effects of MEs or components on thrombosis were determined using thrombo-elastography, platelet contractile force, clot elastic modulus, and platelet counting. For hemolysis, ME or components were incubated with erythrocytes, centrifuged, and washed for measurement of free hemoglobin by spectroscopy. Results and conclusions: The mean particle diameters (polydispersity index) for ME6 and ME4 were 23.6 ± 2.5 nm (0.362) and 14.0 ± 1.0 nm (0.008), respectively. MEs (0, 0.03, 0.3, 3 mM) markedly reduced the thromboelastograph maximal amplitude in a concentration-dependent manner (49.0 ± 4.2, 39.0 ± 5.6, 15.0 ± 8.7, 3.8 ± 1.3 mm, respectively), an effect highly correlated (r2 = 0.94) with similar changes caused by pluronic surfactants (48.7 ± 10.9, 30.7 ± 15.8, 20.0 ± 11.3, 2.0 ± 0.5) alone. Neither oil nor sodium caprylate alone affected the thromboelastograph. The clot contractile force was reduced by ME (27.3 ± 11.1–6.7 ± 3.4 kdynes/cm², P = 0.02, n = 5) whereas the platelet population not affected (175 ± 28–182 ± 23 10⁶/ml, P = 0.12, n = 6). This data suggests that MEs reduced platelet activity due to associated pluronic surfactants, but caused minimal changes in protein function necessary for coagulation. Although pharmacological concentrations of sodium caprylate caused hemolysis (EC₅₀ = 213 mM), MEs and pluronic surfactants did not disrupt erythrocytes. Knowledge of nanoparticle activity and potential associated nanotoxicity at this bio-nano interface enables rational ME design for in vivo applications.