Efficient preparation of carbohydrate- and related polyol-amphiphiles by hydrazone ligation

The hydrazone ligation can be used to couple clustered-glycosides or glycomimetics functionalized with a hydrazino group with lipophilic glyoxylyl acid derivatives to give the corresponding amphiphiles in high yield and purity.     

Single electron tunneling rates in multijunction circuits

The rate of electron tunneling through normal metal tunnel junctions is calculated for the case of ultrasmall junction capacitances. The so-called Coulomb blockade of electron tunneling at low temperatures is shown to be strongly affected by the external electrical circuit. Under the common experimental condition of a low impedance environment the Coulomb blockade is suppressed for single tunnel junctions. However, a Coulomb gap structure emerges for junctions embedded in a high impedance environment. For a double junction setup a Coulomb blockade of tunneling arises even for low impedance environments due to the charge quantization on the metallic island between the junctions. An approach using circuit analysis is presented which allows to reduce the calculation of tunneling rates in multijunction circuits to those of a single junction in series with an effective capacitance. The range of validity of the socalled local rule and global rule rates is clarified. It is found that the tunneling rate tends towards the global rule rate as the number of junctions is increased. Some specific results are given for a one-dimensional array of tunnel junctions.     

Discussion of “Second order topological sensitivity analysis” by J. Rocha de Faria et al.

The aim of this discussion is to expose incorrect results in a previous IJSS article.     

Study of thermal aging effect on space charge in poly(methyl methacrylate)

Charges evolution in poly(methyl methacrylate) (PMMA) samples under thermal aging effect has been studied by means of two complementary techniques, thermal step method (TSM) and thermally stimulated depolarization current (TSDC). For the first method, measurements reveal that injected charges, whose quantity is found depending on the number of applied temperature cycles, remain close to the surface sample. TSDC measurements have been carried out for different temperatures ranging from 25 °C to 140 °C. Three distinguishable dipolar relaxations (β₁, β₂ and α) have been highlighted. In the same way, the presence of polarization and injected charges has been confirmed. In support of electric characterization, X-ray reflectometry has been used. The obtained results equally emphasized the thermal aging effect on the material.     

Photochemical expulsion of the neutral monodentate ligand L in Ru(terpy*)(diimine)(L)2+: a dramatic effect of the steric properties of the spectator diimine ligand

A series of photoreactive complexes of the type Ru(terpy*)(N-N)(L)(2+), where terpy* is 4'-(3,5-ditertiobutylphenyl)-2,2':6',2' '-terpyridine, N-N is the bidentate chelate phen or dmp (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline), and L is the monodentate ligand dms, MeBN, or MeOBN (dms = dimethyl sulfide, MeBN = 2,6-dimethyl benzonitrile, MeOBN = 2,6-dimethoxybenzonitrile), has been synthesized and fully characterized by proton NMR spectroscopy, electrospray mass spectrometry, and UV-vis spectroscopy. The X-ray structures of four complexes were also obtained. In neat pyridine, the quantum yields for the photosubsitution of L by pyridine were measured and showed dramatic variations depending on the steric interactions between the spectator bidentate ligand and the leaving monodentate ligand L. The use of dmp instead of phen multiplied the photosubstitution efficiency by a factor of 20-50, depending on L. This effect could be qualitatively correlated to the distortions observed in the X-ray structures of the corresponding complexes. The highly distorted structure of Ru(terpy)(dmp)(dms)(PF(6))(2) showed a very high photosubsitution quantum yield phi = 0.36 in neat pyridine. The high photoreactivity of some of the compounds makes them particularly promising as components of future light-driven molecular machines.     

Comparison of Boolean algebras

In this work, some results related to superatomic Boolean interval algebras are presented, and proved in a topological way. Let x be an uncountable cardinal. To each I x, we can associate a superatomic interval Boolean algebra B _I of cardinality x in such a way that the following properties are equivalent: (i) I I x, (ii) B _I is a quotient algebra of B _J, and (iii) there is an homomorphism f from B _J into B _I such that for every atom b of B _I, there is an atom a of B _J satisfying f(a)=b. As a corollary, there are 2 ^x isomorphism types of superatomic interval Boolean algebras of cardinality x. This case is quite different from the countable one.     

Structure-based optimization of a non-beta-lactam lead results in inhibitors that do not up-regulate beta-lactamase expression in cell culture

Bacterial expression of beta-lactamases is the most widespread resistance mechanism to beta-lactam antibiotics, such as penicillins and cephalosporins. There is a pressing need for novel, non-beta-lactam inhibitors of these enzymes. One previously discovered novel inhibitor of the beta-lactamase AmpC, compound 1, has several favorable properties: it is chemically dissimilar to beta-lactams and is a noncovalent, competitive inhibitor of the enzyme. However, at 26 microM its activity is modest. Using the X-ray structure of the AmpC/1 complex as a template, 14 analogues were designed and synthesized. The most active of these, compound 10, had a K(i) of 1 microM, 26-fold better than the lead. To understand the origins of this improved activity, the structures of AmpC in complex with compound 10 and an analogue, compound 11, were determined by X-ray crystallography to 1.97 and 1.96 A, respectively. Compound 10 was active in cell culture, reversing resistance to the third generation cephalosporin ceftazidime in bacterial pathogens expressing AmpC. In contrast to beta-lactam-based inhibitors clavulanate and cefoxitin, compound 10 did not up-regulate beta-lactamase expression in cell culture but simply inhibited the enzyme expressed by the resistant bacteria. Its escape from this resistance mechanism derives from its dissimilarity to beta-lactam antibiotics.     

New divalent samarocenes for butadiene polymerisation: influence of the steric effect and the electron density on the catalytic activity

Two new divalent samarocenes, Cp^*′₂Sm(THF) (1) and (Cp^Ph3)₂Sm(THF) (2) (Cp^*′=C₅Me₄ⁿPr, Cp^Ph3=H₂C₅Ph₃-1,2,4), were synthesized and characterized by ¹H NMR and elemental analysis. The activity of 1 and 2 as butadiene polymerisation catalysts was studied, in the presence of MAO and MMAO, and compared to this of Cp^*₂Sm(THF)₂ (3) and (Cp⁴ⁱ)₂Sm (4) (Cp^*=C₅Me₅, Cp⁴ⁱ=C₅HⁱPr₄), in the same conditions. The 1/MAO system presents the highest activity. The less active 2/MAO system leads to a high cis-1,4 regular structure up to 97%. The MMAO cocatalyst is found very sensitive to the steric hindrance of the samarocenes: the activity decreases from 1/MAO to 1/MMAO, and no activity is observed in the case of complexes 2 and 4, associated to MMAO. Complexes 1 and 2 can be both oxidized with AlMe₃ to give the corresponding Sm/Al bimetallics and , respectively.