A macrocyclic ligand able to bind gallium(III) by preorganized pendant arms; coordination and kinetic studies

The equilibria and kinetics of the binding of gallium(III) to 4-(N),10-(N)-bis[2-(3-hydroxo-2-oxo-2-H-pyridine-1-y1)acetamido]-1,7-dimethyl-1,4,7,10-tetraazacyclododecane (L) were investigated in acidic medium at ionic strength 1 M (NaClO4). Spectrophotometric titrations in the UV region revealed that L is able to bind Ga3+ also at high H+ concentration. The kinetic (stopped-flow) experiments are interpreted on the basis of three parallel reaction paths (i) M3+ + H2L2+ = M(H2L)5+ where M(H2L)5+ is in a steady state, (ii) M(OH)2+ + H2L2+ = M(HL)4+ + H2O and (iii) M(OH)2+ + HL+ = ML3+ + H2O. The first-order rate constants for conversion of the outer-sphere into the inner-sphere complexes are similar to those of the Ga(III)/tropolone system which is known to react according to the dissociative Id mechanism and to the relevant rate constants for water exchange at the metal ion. The effects of pH on the UV-Vis absorption, fluorescence emission properties and NMR spectral features on the Ga(III)/L system were also investigated. Spectrophotometric titrations in the UV region reveal that, in acid medium the prevailing species is M(HL)4+ whereas the chelate ML3+ prevails for [H+] < 0.01 M. The results indicate metal coordination at the oxygen atoms of the 3-hydroxo-2-oxopyridine residues.     

Critical thermodynamics of the two-dimensional +/-J Ising spin glass

We compute the exact partition function of 2d Ising spin glasses with binary couplings. In these systems, the ground state is highly degenerate and is separated from the first excited state by a gap of size 4J. Nevertheless, we find that the low temperature specific heat density scales as exp(-2J/T), corresponding to an "effective" gap of size 2J; in addition, an associated crossover length scale grows as exp(J/T). We justify these scalings via the degeneracy of the low lying excitations and by the way low energy domain walls proliferate in this model.     

Glycosidic monoterpenes from Linaria capraria

During our systematic study on the species of genus Linaria (Scrophulariaceae) present in Italy, we examined the glycosidic fraction of Linaria capraria Moris et De Not., a species endemic of Tuscany archipelago. This fraction is particularly complex and we considered in this article only the medium polarity components. In accordance with previous studies, L. capraria shows acyl derivatives of antirrhinoside 1 as specific chemotaxonomic iridoidic markers. L. capraria exhibits a complex composition, with regard to iridoidic constituents, with several chromatographic problems to be resolved. We then isolated, besides the known antirrhinoside 1, two acyl derivatives of antirrhinoside, the 6'-O-senecioyl derivative, 2, and the 6'-O-angeloyl derivative, 3. In addition a glucoside of an acyclic monoterpene, 4, was also isolated, which may be correlated to the other monoterpenic glycosides isolated from other species of Scrophulariaceae.     

Stereoselective iodocyclization of 3-acylamino-2-methylene alkanoates: synthesis of analogues of N-benzoyl-syn-phenylisoserine

[reaction: see text] A convenient approach to racemic analogues of N-benzoyl-syn-phenylisoserine was realized via the stereoselective iodocyclization of amides obtained from Baylis-Hillman adducts.     

Variable-frequency EPR study of Mn(2+)-doped NH(4)Cl(0.9)I(0.1) single crystal at 9.6, 36, and 249.9 GHz: structural phase transition

Multifrequency electron paramagnetic resonance studies on the Mn(2+) impurity ion in a mixed single crystal NH(4)Cl(0.9)I(0.1) were carried out at 9.62 (X-band) in the range 120-295 K, at 35.87 (Q-band) at 77 and 295 K, and at 249.9 GHz (far-infrared band) at 253 K. The high-field EPR spectra at 249.9 GHz are well into the high-field limit leading to a considerable simplification of the spectra and their interpretation. Three magnetically inequivalent, but physically equivalent, Mn(2+) ions with their respective magnetic Z-axes oriented along the crystallographic [100], [010], [001] axes were observed. Simultaneous fitting of EPR line positions observed at X-, Q-, and far infra-red bands was performed using a least-squares procedure and matrix diagonalization to estimate accurately the Mn(2+) spin-Hamiltonian parameters. The temperature variation of the linewidth and peak-to-peak intensities of the EPR lines indicate the presence of lambda-transitions in the mixed NH(4)Cl(0.9)I(0.1) crystal at 242 and 228 K consistent with those observed in the pure NH(4)Cl and NH(4)I crystals, respectively. A superposition-model analysis of the spin-Hamiltonian parameters reveals that the local environment of the Mn(2+) ion is considerably reorganized to produce axially symmetric crystal fields about the respective Z-axes of the three magnetically inequivalent ions as a consequence of the vacancy created due to charge-compensation when the divalent Mn(2+) ion substitutes for a monovalent NH(4)(+) ion in the NH(4)Cl(0.9)I(0.1) crystal. This reorganization is almost the same as that observed in NH(4)Cl and NH(4)I single crystals, although the latter two are characterized by different, simple cubic and face-centered cubic, structures.     

Primal separation for 0/1 polytopes

 The 0/1 primal separation problem is: Given an extreme point xˉ of a 0/1 polytope P and some point x ^*, find an inequality which is tight at xˉ, violated by x ^* and valid for P or assert that no such inequality exists. It is known that this separation variant can be reduced to the standard separation problem for P. We show that 0/1 optimization and 0/1 primal separation are polynomial time equivalent. This implies that the problems 0/1 optimization, 0/1 standard separation, 0/1 augmentation, and 0/1 primal separation are polynomial time equivalent. Then we provide polynomial time primal separation procedures for matching, stable set, maximum cut, and maximum bipartite graph problems, giving evidence that these algorithms are conceptually simpler and easier to implement than their corresponding counterparts for standard separation. In particular, for perfect matching we present an algorithm for primal separation that rests only on simple max-flow computations. In contrast, the known standard separation method relies on an explicit minimum odd cut algorithm. Consequently, we obtain a very simple proof that a maximum weight perfect matching of a graph can be computed in polynomial time. Received: August 20, 2001 / Accepted: April 2002 Published online: December 9, 2002 RID="⋆" ID="⋆" This research was developed while the author was on leave at the Istituto di Analisi dei Sistemi ed Informatica, Viale Manzoni 30, 00185 Roma, supported by the project TMR-DONET nr. ERB FMRX-CT98-0202 of the European Union. Mathematics Subject Classification (2000): 90C10, 90C60, 90C57     

Strain-driven morphology of Si1-xGex islands grown on Si(100)

A study has been carried out on the morphology and structure of three-dimensional (3D) SiGe islands grown by molecular beam epitaxy (MBE) on Si(100) substrates. Samples of Si1-xGex alloys have been prepared to investigate the effects either of the alloy composition or of the growth temperature. Atomic force microscopy (AFM) evidenced the growth of 3D islands and transmission electron microscopy (TEM) demonstrated wetting layer growth on Si(100), independently on the deposition conditions. Energy dispersive spectroscopy (EDS) micro-analyses carried out on cross-sections of large Si1-xGex islands with defects allowed a measurement of the Ge distribution in the islands. To the best of our knowledge, these have been the first experimental evidences of a composition change inside SiGe islands. The interpretation of the experimental results has been done in terms of strain-enhanced diffusion mechanisms both of the growing species (Si and Ge) and of small islands.     

High-performance AlGaAs-based VCSELs emitting in the 760 nm wavelength range

Vertical-cavity surface-emitting lasers (VCSELs) showing continuous-wave operation with emission wavelengths ranging between 717 and 790 nm have been fabricated. The samples are grown by solid source molecular beam epitaxy on GaAs substrates and are entirely based on the AlGaAs material system. A maximum single-mode output power of 2.0 mW is obtained at 754 nm wavelength by using the inverted surface relief technique.     

Dielectric dispersion and magnetic properties of Ba-modified Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>

The polycrystalline samples of Ba-modified Pb(Fe_1/2Nb_1/2)O₃ (i.e., (Pb_1-xBa_x)(Fe_1/2Nb_1/2)O₃ PBFN, with x=0,0.05,0.07) were synthesized by a mechanosynthesis (i.e., high-energy ball milling) route followed by a mixed oxide method. Structural analysis provides the information on formation of single-phase orthorhombic structure on substitution of a small amount (x=0.07) of Ba at the Pb-site of Pb(Fe_0.50Nb_0.50)O₃ (PFN). The ferroelectric–paraelectric phase transition in PFN was observed at 383 K, which decreases on increasing Ba-concentration in PBFN. Detailed studies of dielectric properties of PBFW show the following: (i) diffuse phase transition, (ii) low loss tangent, (iii) low activation energy, and (iv) low frequency dielectric dispersion. An anomaly in the ac conductivity was found very close to phase transition temperature. The activation energy is found to decrease from 0.19 to 0.01 eV on increasing Ba-concentration to 7% (x=0.07). Temperature field-dependent magnetization measurements of all the samples showed antiferromagnetic transition at ∼15 K (for x=0.07). PBFN sample showed a slight increase in the coercivity (i.e., from 400 Oe (PFN) to 500 Oe (PBFN, for x=0.07) at 2 K. PACS 61.10.Nz; 68.37.Hk; 75.50.Ss; 75.60.Ej; 77.22.Ch; 77.22.Gm     

Characterization of a Pd-Fe bimetallic model catalyst

Small bimetallic Pd-Fe particles supported on a well ordered alumina film grown on NiAl (1 1 0) were studied focusing on the geometric, electronic, adsorption, as well as magnetic properties. The morphology, growth mode and surface composition were investigated by combining scanning tunneling microscopy (STM), temperature-programmed desorption (TPD) and infrared spectroscopy (IRAS) using CO as a probe molecule. Information on the electronic properties of the bimetallic systems was obtained by means of X-ray photoelectron spectroscopy (XPS). These measurements were amended by in situ ferromagnetic resonance spectroscopy to address the magnetic properties of the bimetallic particles. The subsequent deposition of the metals at 300 K varying the order of metal deposition resulted in two distinct bimetallic systems. Pd deposited on existing Fe particles forms a shell, however, FMR and XPS suggest that intermixing of Pd and Fe occurs to some extent. For the reverse order, a larger amount of Fe is required to coat Pd particles, due to the strong tendency of Pd to segregate to the surface of the particles.