The Ghirlanda-Guerra Identities

If the variance of a Gaussian spin-glass Hamiltonian grows like the volume the model fulfills the Ghirlanda-Guerra identities in terms of the normalized Hamiltonian covariance.     

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.     

Phenylmercury(II) derivatives of tetraorganodichalcogenoimidodiphosphorus acids. Crystal and molecular structure of [PhHg{(OPR2)(SPPh2)N}]2 (R=Me, Ph)

The reactions between PhHgCl or PhHgAc and M[(XPR₂)(YPR′₂)N] (M=Na, K; X, Y=O, S; R, R′=Me, Ph, OEt), in 1:1 molar ratio, have been investigated. PhHg[(XPR₂)(YPR′₂)N] derivatives were isolated as microcrystalline powders and were characterised using IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and mass spectrometry. The molecular structure of PhHg[(OPR₂)(SPPh₂)N] [R=Me (1), Ph (2)] was investigated by X-ray diffraction. In the monomeric unit, PhHg[(OPR₂)(SPPh₂)N], the mercury atom forms the primary bonds with the carbon of the phenyl group and the sulfur atom of the phosphorus ligand [Hg(1)-S(1) 2.405(1) Å for 1, 2.398(2) Å for 2]. These primary bonds are significantly deviated from the expected linear arrangement [C(1)-Hg(1)-S(1) 166.4(2)° for 1, 165.0(2)° for 2]. Both compounds exhibit dimeric associations in the crystal through S,O-bridging organophosphorus ligands [Hg(1)-O(1) 2.556(4) Å for 1, 2.588(4) Å for 2], thus resulting in a distorted T-shaped arrangement of the CHgSO coordination core.. The formation of a 12-membered Hg₂O₂S₂P₄N₂ ring with different conformation in 1 and 2, respectively, results in different additional chalcogen atoms being in the proximity of the metal atom. Weak transannular Hg?O [2.753(4) Å] are also established in 1, leading to a tricyclic ladder structure with a planar central Hg₂O₂ ring.     

Accelerated iterative strategy for the divergent synthesis of dendritic macromolecules using a combination of living radical polymerization and an irreversible terminator multifunctional initiator

Our laboratory has reported the elaboration of an iterative strategy for the synthesis of dendritic macromolecules from conventional monomers. This synthetic method involves a combination of self‐regulated metal‐catalyzed living radical polymerization initiated from arenesulfonyl chlorides and an irreversible terminator multifunctional initiator (TERMINI). The previous TERMINI, (1,1‐dimethylethyl)[[1‐[3,5‐bis(S‐phenyl‐4‐N,N′ diethylthiocarbamate)phenyl]ethenyl]oxy]dimethylsilane, was prepared in nine reaction steps. The replacement of the previous TERMINI with one that requires only three steps for its synthesis, diethylthiocarbamic acid S‐{3‐[1‐(tert‐butyl‐dimethyl‐silanyloxy)‐vinyl]‐5‐diethylcarbamoylsulfanyl‐phenyl} ester, and the use of the more reactive Cu₂S/2,2′‐bipyridine rather than the Cu₂O/2,2′‐bipyridine self‐regulated catalyst have generated an accelerated method for the synthesis of dendritic macromolecules. This method provides rational design strategies for the synthesis of dendritic macromolecules with different compaction by the use of a single monomer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4894–4906, 2005     

Arenesulfonyl iodides: The third universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates and styrenes

The metal‐catalyzed living radical polymerization of methyl methacrylate and styrene initiated with freshly prepared p‐toluenesulfonyl iodide (TsI) and catalyzed with CuX/2,2′‐bipyridine (bpy), where X is Cl, Br, or I, and various self‐regulated copper‐based catalytic systems, such as copper/bpy, copper(I) oxide/bpy, copper(I) sulfide/bpy, copper(I) selenide/bpy, and copper(I) telluride/bpy, is reported. The exchange of C? I into C? Br and C? Cl takes place when the living radical polymerization of methyl methacrylate is catalyzed by copper(I) bromide/bpy and copper(I) chloride/bpy, respectively. Therefore, the use of the TsI initiator facilitates the synthesis, starting from a single initiator, of poly(methyl methacrylate) containing C? I, C? Br, and C? Cl chain ends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3920–3931, 2005     

Arenesulfonyl bromides: The second universal class of functional initiators for the metal‐catalyzed living radical polymerization of methacrylates,acrylates, and styrenes

The metal‐catalyzed living radical polymerization of methyl methacrylate, n‐butyl acrylate, and styrene, initiated with p‐toluenesulfonyl bromide and phenoxybenzene‐4,4′‐disulfonyl bromide and catalyzed with CuBr/2,2′‐bipyridine (bpy) and various self‐regulated Cu‐based catalytic systems such as Cu₂O/bpy, Cu₂S/bpy, Cu₂Se/bpy, and Cu₂Te/bpy, is reported. Similarities and differences between the arenesulfonyl chloride and arenesulfonyl bromide initiators are discussed. The arenesulfonyl bromide initiators require reduced reaction times to produce polymers in high conversions under milder reaction conditions than the corresponding arenesulfonyl chloride initiators. At the same time, they exhibit 100% initiator efficiency and generate polymers with narrow molecular weight distributions and functional chain ends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 319–330, 2005     

Energy dependence of the isovector imaginary nucleon optical-model potential

The differences between the imaginary depths of the optical-model potential s felt by neutrons and protons on ²⁰⁸Pb show evidence for an energy decrease of the isovector imaginary term of the nucleon-nucleus optical-model potential, analogous to that of the real part.     

Electrochemical behaviour of 1-benzyl-3-carbamoylpyridinium chloride,a NAD+ model compound

In aqueous media, 1-benzyl-3-carbamoylpyridinium ion undergoes an initially reversible one-electron reduction to produce a free radical, which irreversibly dimerises to a 4,4′-linked diastereoisomeric pair. At more negative potential, the free radical undergoes a further one-electron reduction to a mixture of 1,6- and 1,4-dihydropyridine derivatives. At sufficiently positive potential the dimers can be oxidised back to pyridinium cation. The dimeric products are strongly adsorbed on the electrode surface, also at potential values where 2e products are formed, and this is a preparative drawback for the dimers and the dihydropyridines. Such problems can be overcome by the addition of benzene and of surface-active substances respectively. A detailed mechanism of the electrochemical reduction of 1-benzyl-3-carbamoylpridinium ion is proposed.     

The complexity of proving chaoticity and the Church-Turing thesis

Proving the chaoticity of some dynamical systems is equivalent to solving the hardest problems in mathematics. Conversely, classical physical systems may "compute the hard or even the incomputable" by measuring observables which correspond to computationally hard or even incomputable problems.