Self-assembly of metallosupramolecules directed by (N-H)(2)center dot center dot center dot SCN-M (M = Co, Ni), C-H center dot center dot center dot pi and pi-pi synthons

This work deals with the synthesis, spectroscopic and structural investigation of pyrazolyl complexes of the type trans-[M(NCS)(2)(HPz)(4)] {M=Co (1), Ni (2); HPz=pyrazole}. Single crystal X-ray studies on 1 and 2 reveal the formation of similar supramolecular arrangements derived from self-assembly of monomers linked together through intermolecular N-H center dot center dot center dot SCN hydrogen bonds, C-H center dot center dot center dot pi interactions and pi-pi stacking. (c) 2005 Elsevier B.V. All rights reserved.

Ab initio study of high tridymite by the formalism generator coordinate Hartree-Fock

The Generator Coordinate Hartree-Fock (GCHF) Method is applied to generate extended 14s 8p and 17s 11p Gaussian basis sets for the atoms O and Si, respectively. The role of the weight functions in the assessment of the numerical integration range of the GCHF is shown. The Gaussian basis sets are contracted to [6s4p] O atom and [8s5p] Si atom by the Dunning's segmented contraction scheme. To evaluate the quality of our contracted [6s4p] and [8s5p] bases in molecular calculations we accomplish calculations of total and orbital energies in the Hartree-Fock-Roothaan method for O-2 and SiO molecules. We compare the results obtained with the our (14s 8p) and (17s 11p) bases sets with the of 6-311G basis and with values from the literature. The addition of one d polarization function in the silicon basis and its utilization with the basis for oxygen leads to the calculation of electronic properties and IR Spectrum of high tridymite in space group D-3d. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Self-assembly of organometallic Pd(II) complexes via CH3 center dot center dot center dot pi interactions: the first example of a cyclopalladated compound with herringbone stacking pattern

Two binuclear cyclometallated compounds [Pd(C-2,N-dmba)(mu-N-3)](2) (1) and [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] (2) (dmba = N,N-dimethylbenzylarnine) have been synthesized and characterized by elemental 3 analysis, IR and NMR spectroscopies and single crystal X-ray diffraction crystallography. The ability of CH3 groups to form C(sp(3))-H...pi hydrogen bonds with phenyl rings is responsible for the molecular self-assembly within the crystals of 1 and 2. Compound 1 crystallizes as one-dimensional supramolecular chains whereas the crystal packing of 2 consists of a herringbone of sandwiches composed by two inversely related [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] molecules. (c) 2007 Elsevier B.V. All rights reserved.

On the coupling of the self-dual field to dynamical U(1) matter and its dual theory

We consider arbitrary U (1) charged matter non-minimally coupled to the self-dual field in d = 2 + 1. The coupling includes a linear and a rather general quadratic term in the self-dual field. By using both Lagragian gauge embedding and master action approaches we derive the dual Maxwell Chern-Simons-type model and show the classical equivalence between the two theories. At the quantum level the master action approach in general requires the addition of an awkward extra term to the Maxwell Chern-Simons-type theory. Only in the case of a linear coupling in the self-dual field can the extra term be dropped and we are able to establish the quantum equivalence of gauge invariant correlation functions in both theories.

Fabrication and analysis of self-assembled photonic crystals structures

This paper presents the fabrication and analysis of a three-dimensional FCC photonic crystal (PhC) based on a self-assembly synthesis of monodispersive latex spheres. Experimental optical characterization, achieved by measurements of the specular reflectance under variable angles, indicated the clear presence of a Bragg diffraction pattern. Results are further explored by theoretical calculations based on the Finite Difference Time Domain (FDTD) method to determine the full PhC band structure.

Photo luminescence: A probe for short, medium and long-range self-organization order in ZrTiO4 oxide

Photoluminescent disordered ZrTiO4 powders were obtained by the polymeric precursor soft-chemical method. This oxide system (ordered and disordered) was characterized by photoluminescence, Raman spectroscopy, X-ray diffraction, differential scanning calorimetry and UV vis absorption experiments. The UV absorption tail formation in the disordered oxides was related to the diminution of optical band gap. In the disordered phase, this oxide displayed broad band photoluminescence caused by change in coordination number of titanium and zirconium with oxygen atoms. The gap decreased from 3.09 eV in crystalline oxide to 2.16 eV in disordered oxide. The crystalline oxide presented an orthorhombic alpha-PbO2-type structure in which Zr4+ and Ti4+ were randomly distributed in octahedral coordination polyhedra with oxygen atoms. The amorphous-crystalline transition occurred at almost 700 degrees C, at which point the photoluminescence vanished. The Raman peak at close to 80-200 cm(-1) indicated the presence of locally ordered Ti-O-n and Zr-O-n polyhedra in disordered photoluminescent oxides. (c) 2006 Elsevier B.V. All rights reserved.

Clinical performance of a self-etching adhesive at 18 months

Purpose: To test the null hypothesis that beveling and/or etching enamel would not affect the 18-month clinical performance of the self-etching adhesive Clearfil SE Bond (CSEB) in noncarious cervical lesions (NCCL). Methods: With Institutional Review Board approval, 34 patients were enrolled in this study. A total of 120 NCCL was selected and assigned to four groups: (1) CSEB was applied without any cavity preparation; (2) CSEB was applied after beveling enamel; (3) CSEB was applied after etching enamel for 15 seconds with 35% phosphoric acid; (4) CSEB was applied after beveling and etching enamel. A microfilled composite resin was used for all restorations. Resuts: At 6 months after initial placement, 120 restorations (a 100% recall rate) were evaluated. At 18 months, 87 restorations (a 72.5% recall rate) were available for evaluation. A survival rate of 100% was measured for all groups at both 6 and 18 months. Sensitivity to air decreased significantly only for Group 3 (no bevel+acid etch) from baseline to 18 months without statistical changes from 6 months to 18 months. None of the other parameters resulted in significant differences for any of the four groups. However, when data were pooled, both the overall marginal discoloration and the overall marginal adaptation were significantly worse at 18 months than at baseline, while sensitivity to air decreased significantly from baseline to 18 months. The 18-month survival rate of the self-etching adhesive Clearfil SE Bond was not improved by enamel bevel or by enamel etching. Both overall marginal adaptation and overall marginal discoloration were worse at 18 months than at baseline.

Reproducibility and validity of self-perceived oral health conditions

The reproducibility and validity of self-perceived periodontal, dental, and temporomandibular joint (TMJ) conditions were investigated. A questionnaire was applied in interview to 200 adults aged from 35 to 44, who were attending as casual patients at Araraquara School of Dentistry, Sauo Paulo State University, Sauo Paulo, Brazil. Clinical examination was based on the guidelines of the World Health Organization manual. The interview and the clinical examination were performed in two occasions, by a calibrated examiner. Reproducibility and validity were, respectively, verified by kappa statistics (kappa) and sensitivity (Sen) and specificity (Spec) values, having clinical examination as the validation criterion. The results showed an almost perfect agreement for self-perceived TMJ (kappa=0.85) and periodontal conditions (kappa=0.81), and it was substantial for dental condition (kappa=0.69). Reproducibility according to clinical examination showed good results (kappa=0.73 for CPI index, kappa=0.96 for dental caries, and kappa=0.74 for TMJ conditions). Sensitivity and specificity values were higher for self-perceived dental (Sen=0.84, Spec=1.0) and TMJ conditions (Sen=1.0, Spec=0.8). With regard to periodontal condition, specificity was low (0.43), although sensitivity was very high (1.0). Self-perceived oral health was reliable for the examined conditions. Validity was good to detect dental conditions and TMJ disorders, and it was more sensitive than specific to detect the presence of periodontal disease.

One-year clinical performance of self-etch adhesives in posterior restorations

Purpose: To evaluate the 1-year clinical performance of three self-etching adhesives (Adper Prompt L-Pop, Clearfil S-3 Bond, iBond) in posterior composite restorations using one etch&rinse adhesive (One-Step Plus) as control. Methods: Upon approval by the Institutional Review Board, 121 restorations were inserted in 38 subjects. The adhesives were applied as per manufacturers' instructions. Preparations were restored with a nanofilled resin composite (Filtek Supreme) and evaluated at baseline, 6 months, and 1 year. Statistical analyses included the Chi-square distribution with the McNemar non-parametric test (P< 0.05). Results: At 1 year, 111 restorations in 35 subjects were evaluated using the USPHS modified criteria. No significant changes were observed for the etch&rinse adhesive One-Step Plus. At 1 year the number of Alfa ratings decreased significantly for Clearfil S-3 Bond and for iBond in the categories color match, marginal staining, and marginal adaptation. For Adper Prompt L-Pop, marginal adaptation at 1 year was significantly worse than at baseline. Postoperative sensitivity to air improved significantly for Adper Prompt L-Pop, Clearfil S-3 Bond, and iBond. When the evaluation criteria were paired at 1 year, iBond resulted in a significantly lower number of Alfa ratings than any of the other adhesives for color match, marginal staining, and marginal adaptation. One-Step Plus resulted in a greater number of Alfa ratings for marginal adaptation than either Adper Prompt L-Pop or Clearfil S-3 Bond. Marginal adaptation was significantly better for Clearfil S-3 Bond than for Adper Prompt L-Pop. The post-operative sensitivity measured at 1 year for Adper Prompt L-Pop was statistically better than that for One-Step Plus.

Localized mechanics of dentin self-etching adhesive system

The bond strength of composite resins (CRs) to dentin is influenced by the interfacial microstructure of the hybrid layer (HL) and the resin tags (TAG). The contemporary self-etching primer adhesive systems overcame the inconvenient of the etch-and-rinse protocol. Studies, however, have demonstrated that HL thickness and TAG length vary according to the wetting time and additional use of acid-etching prior to self-etching primers. This study investigated the localized stress distribution in the HL and the dentin/adhesive interface. Two HL thicknesses (3 or 6 mu m), two TAG lengths (13 or 17 mu m) and two loading conditions (perpendicular and oblique-25 degrees) were investigated by the finite element (FE) analysis. Five two-dimensional FE models (M) of a dentin specimen restored with CR (38 x 64 mu m) were constructed: M1 - no HL and no TAG; M2 - 3 mu m of HL and 13 mu m of TAG; M3 - 3 mu m of HL and 17 mu m of TAG; M4 - 6 mu m of HL and 13 mu m of TAG; and M5 - 6 mu m of HL and 17 mu m of TAG. Two distributed loadings (L) (20N) were applied on CR surface: L1 - perpendicular, and L2 - oblique (25 degrees). Fixed interfacial conditions were assigned on the border of the dentin specimen. Ansys 10.0 (Ansys (R), Houston, PA, USA) software was used to calculate the stress fields. The peak of von Mises (sigma(vM)) and maximum principal stress (sigma(max)) was higher in L2 than in L1. Microstructures (HL and TAG) had no effect on local stresses for L1. Decreasing HL decreased sigma(vM) and sigma(max) in all structures for L2, but the TAG length had influence only on the peributular dentin. The thickness of HL had more influence on the sigma(vM) and sigma(max) than TAG length. The peritubular dentin and its adjacent structures showed the highest sigma(vM) and sigma(max), mainly in the oblique loading.

The generator coordinate Hartree-Fock method as strategy for building Gaussian basis sets to ab initio study of the process of adsorption of sulfur on platinum (200) surface

The scheme named generator coordinate Hartree-Fock method (GCHF) is used to build (22s14p) and (33s22p16d9f) gaussian basis sets to S ((3)P) and Pt ((3)D) atoms, respectively. Theses basis sets are contracted to [13s10p] and [19s13p9d5f] through of Dunning's segmented contraction scheme and are enriched with d and g polarization functions, [13s10p1d] and [19s13p9d5flg]. Finally, the [19s13p9d5f1g] basis Set to Pt ((3)D) was supplemented with s and d diffuse functions, [20s13p10d5flg], and used in combination with [13s10p1d] to study the effects of adsorption of S ((3)D) atom on a pt ((3)D) atom belonged to infinite Pt (200) surface. Atom-atom overlap population, bond order, and infrared spectrum of [pt(_)S](2 -) were calculated properties and were carried out at Hartree-Fock-Roothaan level. The results indicate that the process of adsorption of S ((3)P) on pt ((3)D) in the infinite Pt (200) surface is mainly caused by a strong contribution of sigma between the 3p(z) orbital of S ((3)P) and the 6s orbital of pt ((3)D). (c) 2004 Elsevier B.V. All rights reserved.

SELF-CONSISTENT SOLUTION OF THE SCHWINGER-DYSON EQUATIONS FOR THE NUCLEON AND MESON PROPAGATORS

The Schwinger-Dyson equations for the nucleon and meson propagators are solved self-consistently in an approximation that goes beyond the Hartree-Fock approximation. The traditional approach consists in solving the nucleon Schwinger-Dyson equation with bare meson propagators and bare meson-nucleon vertices; the corrections to the meson propagators are calculated using the bare nucleon propagator and bare nucleon-meson vertices. It is known that such an approximation scheme produces the appearance of ghost poles in the propagators. In this paper the coupled system of Schwinger-Dyson equations for the nucleon and the meson propagators are solved self-consistently including vertex corrections. The interplay of self-consistency and vertex corrections on the ghosts problem is investigated. It is found that the self-consistency does not affect significantly the spectral properties of the propagators. In particular, it does not affect the appearance of the ghost poles in the propagators.