Ruthenium-catalyzed selective hydrogenation of bis-arylidene tetramic acids. Application to the synthesis of novel structurally diverse pyrrolidine-2,4-diones

Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data.     

Novel pyrrolidine-thiohydantoins/thioxotetrahydropyrimidinones as highly effective catalysts for the asymmetric Michael addition

The synthesis of novel organocatalysts consisting of a pyrrolidine moiety and a thiohydantoin or a thioxotetrahydropyrimidinone ring is described. The compound combining the pyrrolidine with the thioxotetrahydropyrimidinone was found to be a highly effective catalyst for the Michael reaction. Low catalyst loadings (1-2.5%) can be employed leading to quantitative yields and excellent stereoselectivities in the reaction between cyclic ketones and nitroolefins.     

Propagation of a plane wave to a materially uniform but inhomogeneous body

We produce the equations of small deformations superimposed upon large for materially uniform but inhomogeneous bodies and specialize to an isotropic material and to a homogeneous finite elastic deformation. By assuming the small deformation to be a plane wave, a set of equations for the amplitude of the wave is produced which is accompanied by an additional set of conditions. By requiring a non-trivial solution for the amplitude, we obtain the secular equation and from it a set of necessary and sufficient conditions for having a real wave speed. The second set of conditions that have to be satisfied is due to the materials inhomogeneity. Essentially, the present analysis enhances the approach of Hayes and Rivlin for materially uniform but inhomogeneous bodies. The outcome is that for such bodies the restrictions on the constitutive law for having real wave speeds for an isotropic material subjected to a pure homogeneous deformation involves the field of the inhomogeneity as well.     

The achievable region method in the optimal control of queueing systems; formulations,bounds and policies

We survey a new approach that the author and his co-workers have developed to formulate stochastic control problems (predominantly queueing systems) asmathematical programming problems. The central idea is to characterize the region of achievable performance in a stochastic control problem, i.e., find linear or nonlinear constraints on the performance vectors that all policies satisfy. We present linear and nonlinear relaxations of the performance space for the following problems: Indexable systems (multiclass single station queues and multiarmed bandit problems), restless bandit problems, polling systems, multiclass queueing and loss networks. These relaxations lead to bounds on the performance of an optimal policy. Using information from the relaxations we construct heuristic nearly optimal policies. The theme in the paper is the thesis that better formulations lead to deeper understanding and better solution methods. Overall the proposed approach for stochastic control problems parallels efforts of the mathematical programming community in the last twenty years to develop sharper formulations (polyhedral combinatorics and more recently nonlinear relaxations) and leads to new insights ranging from a complete characterization and new algorithms for indexable systems to tight lower bounds and nearly optimal algorithms for restless bandit problems, polling systems, multiclass queueing and loss networks.     

Survivable networks,linear programming relaxations and the parsimonious property

We consider the survivable network design problem — the problem of designing, at minimum cost, a network with edge-connectivity requirements. As special cases, this problem encompasses the Steiner tree problem, the traveling salesman problem and thek-edge-connected network design problem. We establish a property, referred to as the parsimonious property, of the linear programming (LP) relaxation of a classical formulation for the problem. The parsimonious property has numerous consequences. For example, we derive various structural properties of these LP relaxations, we present some algorithmic improvements and we perform tight worst-case analyses of two heuristics for the survivable network design problem.The research of both authors was partially supported by the National Science Foundation under grant ECS-8717970 and the Leaders for manufacturing program at MIT.     

On the worst case complexity of potential reduction algorithms for linear programming

There are several classes of interior point algorithms that solve linear programming problems in O(√nL) iterations. Among them, several potential reduction algorithms combine both theoretical (O(√nL) iterations) and practical efficiency as they allow the flexibility of line searches in the potential function, and thus can lead to practical implementations. It is a significant open question whether interior point algorithms can lead to better complexity bounds. In the present paper we give some negative answers to this question for the class of potential reduction algorithms. We show that, even if we allow line searches in the potential function, and even for problems that have network structure, the bound O(√nL) is tight for several potential reduction algorithms, i.e., there is a class of examples with network structure, in which the algorithms need at least Θ(√nL) iterations to find an optimal solution. The research of the author was partially supported by a Presidential Young Investigator Award DDM-9158118 with matching funds from Draper Laboratory.     

COPPER BENZOCHLORIN, A NOVEL PHOTOSENSITIZER FOR PHOTODYNAMIC THERAPY: EFFECTS ON A TRANSPLANTABLE UROTHELIAL TUMOR

Abstract— An iminum salt of octaethylbenzochlorin with copper in the aromatic ring, CDSI, was tested for its tumoricidal effects on theA–27 N-[4-(5-notro-2-furyl)-2-thiazoly] formamide tumor line. CDSI was found to be an effective photosensitiz4r in vivo when used in combination with either a xenon arc lamp or a pulsed alexandrite laser. Hemodynamically, CDSI and light caused a rapid decrease in tumor blood flow. skin photosensitization was found to be minimal when drug-injected mice werwe illuminated in a solar simulator.     

Influence of aggregates and solvent aromaticity on the emission of conjugated polymers

The influence of aggregates and solvent aromaticity on the photophysics and fluorescence dynamics of two conjugated polymers is studied. The two polymers are derivatives of poly(p-phenylene vinylene) (PPV) containing different kinked moieties along the main chain. The polymers contain 2,6-diphenylpyridine and m-terphenyl kinked moieties and they are abbreviated as PN and PC, respectively. The insertion of kinked segments along the main chain shifts the emission spectrum from the yellow-orange spectral region, common to PPV derivatives, to the blue-green spectral region. The results show that in dilute solutions the polymers decay monoexponentially, while in concentrated ones the fluorescence decays biexponentially, indicating fluorescence quenching. This is attributed to an energy transfer process from polymer chains to aggregates that occurs within a few tens of picoseconds. By comparing the photophysics and fluorescence dynamics of polymer PN in a nonaromatic and an aromatic solvent, we conclude that the polymer conformation adopted in the aromatic solvent leads to a higher fluorescence quantum yield and a longer fluorescence lifetime. Furthermore, the fluorescence quenching of PN because of aggregates is faster and more efficient in the aromatic than in the nonaromatic solvent. These results can be explained through a more extended chain conformation of PN in the aromatic solvent.     

Femtosecond time resolved fluorescence dynamics of a cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene)

A recently synthesized cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene) was studied by means of steady state and femtosecond time resolved upconversion spectroscopy in aqueous and EtOH solutions. Steady state spectroscopic measurements showed that the polymer emits at the blue-green spectral region and that aggregates are formed in concentrated polymer solutions. The fluorescence dynamics of the polymer in concentrated solutions, studied at a range of emission wavelengths, exhibited a wavelength dependent and multiexponential decay, indicating the existence of various decay mechanisms. Specifically, a rapid decay at short emission wavelengths and a slow rise at long wavelengths were observed. Both features reveal an energy transfer process from isolated to aggregated chains. The contribution of the energy transfer process as well as of the isolated chains and the aggregates on the overall fluorescence decay of the polymer was determined. The dependence of the energy transfer rate and efficiency on polymer concentration was also examined.