Role of vitreous matrix on the optical activity of Ge-doped silica

We report an experimental study on the relationship between the optical activity of Ge-oxygen deficient centers and dynamic properties and conformational heterogeneity of vitreous matrix in silica. We focus our attention on the absorption band at ∼5.2 eV (B_2β) and on the two related emissions at ∼4.2 eV (α_E) and at ∼3.1 eV (β). From the temperature dependence of B_2β band we estimate a mean energy value of 26 meV for local vibrational modes coupled to the electronic transition, suggesting that the chromophore and its surrounding have access to low frequency dynamics. From the thermal behavior of the two emissions we distinguish the two competitive relaxation processes from the first singlet excited state S₁: the radiative one, giving rise the α_E band, and the thermally activated intersystem-crossing process between S₁ and the triplet state T₁, originating the β band. The intersystem-crossing rate increases on increasing the temperature, determining an opposite thermal behavior of the intensity of the two emissions. However, this temperature dependence cannot be rationalized by a simple Arrhenius law and the α_E decay kinetics at high temperatures do not follow a single exponential law, suggesting a complex landscape of configurational energies of the process.     

Targeting apoptosis via chemical design: inhibition of bid-induced cell death by small organic molecules

Bid is a key member of the Bcl-2 family proteins involved in the control of the apoptotic cascade in cells, leading to cell death. Uncontrolled cell death is associated with several human pathologies, such as neurodegenerative diseases and ischemic injuries. Therefore, Bid represents a potential yet unexplored and challenging target for strategies aimed at the development of therapeutic agents. Here we show that a multidisciplinary NMR-based approach that we named SAR by ILOEs (structure activity relationships by interligand nuclear Overhauser effect) allowed us to rationally design a series of 4-phenylsulfanyl-phenylamine derivatives that are capable of occupying a deep hydrophobic crevice on the surface of Bid. These compounds represent the first antiapoptotic small molecules targeting a Bcl-2 protein as shown by their ability to inhibit tBid-induced SMAC release, caspase-3 activation, and cell death.     

Synthesis, structure, and kinetics and stereochemistry of base-catalyzed hydrolysis of meso- and rac-[Co2(tmpdtne)Cl2]4+, bis(pentaamine) complexes devoid of deprotonatable NH centers

The bis(pentadentate) ligand tmpdtne binds two Co(II) centers, and the entity is readily oxidized to the dicobalt(III) derivative [Co(2)(tmpdtne)Cl(2)](4+) which has been separated into two isomeric forms. NMR studies establish these as meso and rac isomers arising from the different or same absolute configurations for the asym configuration about each Co(III) center. Each dinuclear ion base hydrolyses to the dihydroxo derivative [Co(2)(tmpdtne)(OH)(2)](4+) with retained asym configurations about each metal ion and also retained rac or meso configurations. The kinetics for the stepwise loss of the two Cl(-) ligands is uniphasic, and data are presented to show that the loss of the first chloride is rate determining and is followed by very rapid intramolecular and loss of the second Cl(-) via a hydroxo-bridged species to yield the observed dihydroxo derivative. Meso and rac forms of the latter have been crystallized. The X-ray crystal structure of the rac-dihydroxo complex is reported, and it establishes the configurations of all the complexes reported. The (1)H NMR spectra for the hydroxo ions show very high field Co-OH resonances (ca. delta-0.5 ppm) not observed previously for such ions, and this result is discussed in the context of published (1)H NMR data for bridged Co-OH-Co species. The base hydrolysis kinetics for the dichloro ions are first order in [OH(-)], and deprotonation at an alpha-CH(2) center (alpha to a pyridyl) is identified as the source of the catalysis, since there is no NH center available for deprotonation on the ligand. These data further support the new pseudoaminate base hydrolysis mechanism first reported in 2003. The values of k(OH) for the second-order base-catalyzed reaction are ca. 4.0 M(-1) s(-1) for both the rac and meso isomers, and these results are discussed in terms of the increased acidities of these 4+ cations compared to their 2+ ion counterparts.     

Incorporation conditions guiding the aggregation of a glycosylphosphatidyl inositol (GPI)-anchored protein in Langmuir monolayers

This work investigates the process of incorporation of a glycosylphosphatidyl inositol (GPI)-anchored alkaline phosphatase into Langmuir monolayers of dimyristoyl phosphatidic acid (DMPA). Three different methods of protein incorporation were assayed. When the protein solution was injected below the air–water interface after formation of the lipid monolayer a micro-heterogeneous distribution of alkaline phosphatase throughout the interface was observed. Adsorption kinetics studied by fluorescence microscopy, associated with surface pressure measurements, led to the proposition of a model in which the protein penetration is modulated by the surface packing of the monolayer and intermolecular interactions occurring between the phospholipid and the protein. At initial surface pressures higher than 20 mN m⁻¹, the protein is quickly adsorbed on the interface and the lateral diffusion drives the alkyl chains to turn towards the air phase while the polypeptide moiety faces the aqueous subphase.     

Partially and totally asynchronous algorithms for linear complementarity problems

A unified treatment is given for partially and totally asynchronous parallel successive overrelaxation (SOR) algorithms for the linear complementarity problem. Convergence conditions are established and compared to previous results. Convergence of the partially asynchronous method for the symmetric linear complementarity problem can be guaranteed if the relaxation factor is sufficiently small. Unlike previous results, this relaxation factor interval does not depend explicitly on problem size.This material is based on research supported by the Air Force Office of Scientific Research Grant No. AFOSR-89-0410.The author wishes to thank the referee for pointing out how to improve the bound (12). The same technique can be used to reduce the factorn in Ref. 5, p. 553, to .     

Jahn-Teller distortion and dissociation of CCl4+ by transient X-ray spectroscopy simultaneously at the carbon K- and chlorine L-edge

X-ray Transient Absorption Spectroscopy (XTAS) and theoretical calculations are used to study CCl₄⁺ prepared by 800 nm strong-field ionization. XTAS simultaneously probes atoms at the carbon K-edge (280–300 eV) and chlorine L-edge (195–220 eV). Comparison of experiment to X-ray spectra computed by orbital-optimized density functional theory (OO-DFT) indicates that after ionization, CCl₄⁺ undergoes symmetry breaking driven by Jahn–Teller distortion away from the initial tetrahedral structure (T_d) in 6 ± 2 fs. The resultant symmetry-broken covalently bonded form subsequently separates to a noncovalently bound complex between CCl₃⁺ and Cl over 90 ± 10 fs, which is again predicted by theory. Finally, after more than 800 fs, L-edge signals for atomic Cl are observed, indicating dissociation to free CCl₃⁺ and Cl. The results for Jahn–Teller distortion to the symmetry-broken form of CCl₄⁺ and formation of the Cl–CCl⁺₃ complex characterize previously unobserved new species along the route to dissociation.

Dynamics of CCl₄⁺ prepared by 800 nm strong-field ionization, as studied with X-ray transient absorption spectroscopy (XTAS) and quantum chemical calculations.     

In Vivo Biological Behavior of Polymer Scaffolds of Natural Origin in the Bone Repair Process

Autologous bone grafts, used mainly in extensive bone loss, are considered the gold standard treatment in regenerative medicine, but still have limitations mainly in relation to the amount of bone available, donor area, morbidity and creation of additional surgical area. This fact encourages tissue engineering in relation to the need to develop new biomaterials, from sources other than the individual himself. Therefore, the present study aimed to investigate the effects of an elastin and collagen matrix on the bone repair process in critical size defects in rat calvaria. The animals (Wistar rats, n = 30) were submitted to a surgical procedure to create the bone defect and were divided into three groups: Control Group (CG, n = 10), defects filled with blood clot; E24/37 Group (E24/37, n = 10), defects filled with bovine elastin matrix hydrolyzed for 24 h at 37 °C and C24/25 Group (C24/25, n = 10), defects filled with porcine collagen matrix hydrolyzed for 24 h at 25 °C. Macroscopic and radiographic analyses demonstrated the absence of inflammatory signs and infection. Microtomographical 2D and 3D images showed centripetal bone growth and restricted margins of the bone defect. Histologically, the images confirmed the pattern of bone deposition at the margins of the remaining bone and without complete closure by bone tissue. In the morphometric analysis, the groups E24/37 and C24/25 (13.68 ± 1.44; 53.20 ± 4.47, respectively) showed statistically significant differences in relation to the CG (5.86 ± 2.87). It was concluded that the matrices used as scaffolds are biocompatible and increase the formation of new bone in a critical size defect, with greater formation in the polymer derived from the intestinal serous layer of porcine origin (C24/25).     

Synthesis of heteroleptic bis(diimine)carbonylchlororuthenium(II) complexes from photodecarbonylated precursors

The reactions of bidentate diimine ligands (L2) with binuclear [Ru(L1)(CO)Cl2]2 complexes [L1 not equal to L2 = 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (4,4'-Me2bpy), 5,5'-dimethyl-2,2'-bipyridine (5,5'-Me2bpy), 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), 5,6-dimethyl-1,10-phenanthroline (5,6-Me2phen), di(2-pyridyl)ketone (dpk), di(2-pyridyl)amine (dpa)] result in cleavage of the dichloride bridge and the formation of cationic [Ru(L1)(L2)(CO)Cl]+ complexes. In addition to spectroscopic characterization, the structures of the [Ru(bpy)(phen)(CO)Cl]+, [Ru(4,4'-Me2bpy)(5,6-Me2phen)(CO)Cl]+ (as two polymorphs), [Ru(4,4'-Me2bpy)(4,7-Me2phen)(CO)Cl]+, [Ru(bpy)(dpa)(CO)Cl]+, [Ru(5,5'-Me2bpy)(dpa)(CO)Cl]+, [Ru(bpy)(dpk)(CO)Cl]+, and [Ru(4,4'-Me2bpy)(dpk)(CO)Cl]+ cations were confirmed by single crystal X-ray diffraction studies. In each case, the structurally characterized complex had the carbonyl ligand trans to a nitrogen from the incoming diimine ligand, these complexes corresponding to the main isomers isolated from the reaction mixtures. The synthesis of [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)(NO3)]+ from [Ru(4,4'-Me2bpy)(5,6-Me2bpy)(CO)Cl]+ and AgNO3 demonstrates that exchange of the chloro ligand can be achieved.