New insights on surface-enhanced Raman scattering based on controlled aggregation and spectroscopic studies, DFT calculations and symmetry analysis for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine adsorbed onto citrate-stabilized gold nanoparticles

Asystematic study on the surface-enhanced Raman scattering (SERS) for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) adsorbed onto citrate-modified gold nanoparticles (cit-AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit-AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge-transfer (CT) effects. The most strongly enhanced vibrations belong to a(1) and b(2) representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright (C) 2010 John Wiley & Sons, Ltd.

Development of a spectrophotometric Sequential Injection Analysis (SIA) procedure for determination of ammonium: A Response Surface Methodology (RSM) approach

This paper describes the optimization and use of a Sequential Injection Analysis (SIA) procedure for ammonium determination in waters. Response Surface Methodology (RSM) was used as a tool for optimization of a procedure based on the modified Berthelot reaction. The SIA system was designed to (i) prepare the reaction media by injecting an air-segmented zone containing the reagents in a mixing chamber, (ii) to aspirate the mixture back to the holding coil after homogenization, (iii) drive it to a thermostated reaction coil, where the flow is stopped for a previously established time, and (iv) to pump the mixture toward the detector flow cell for the spectrophotometric measurements. Using a 100 mu mol L(-1) ammonium solution, the following factors were considered for optimization: reaction temperature (25 - 45 degrees C), reaction time (30 - 90 s), hypochlorite concentration (20 - 40 mmol L(-1)) nitroprusside concentration (10 - 40 mmol L(-1)) and salicylate concentration (0.1 - 0.3 mol L(-1)). The proposed system fed the statistical program with absorbance data for fast construction of response surface plots. After optimization of the method, figures of merit were evaluated, as well as the ammonium concentration in some water samples. No evidence of statistical difference was observed in the results obtained by the proposed method in comparison to those obtained by a reference method based on the phenol reaction. (C) 2010 Elsevier B.V. All rights reserved.

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

In order to evaluate the interactions between Au/Cu atoms and clean Si(l 11) surface, we used synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations. Optimized geometries and energies on different adsorption sites indicate that the binding energies at different adsorption sites are high, suggesting a strong interaction between metal atom and silicon surface. The Au atom showed higher interaction than Cu atom. The theoretical and experimental data showed good agreement. Crown Copyright (C) 2009 Published by Elsevier B.V. All rights reserved.

Response surface models to predict broiler performance and applications for economic analysis

A study was carried out to elaborate response surface models using broiler performance data recovered from literature in order to predict performance and elaborate economic analyses. Nineteen studies published between 1995 and 2005 were retrieved using the systematic literature review method. Weight gain and feed conversion data were collected from eight studies that fulfilled the pre-established inclusion criteria, and a response surface model was adjusted using crude protein, environmental temperature, and age as independent variables. The models produced for weight gain (r² = 0.93) and feed conversion (r² = 0.85) were accurate, precise, and not biased. Protein levels, environmental temperature and age showed linear and quadratic effects on weight gain and feed conversion. There was no interaction between protein level and environmental temperature. Age and crude protein showed interaction for weight gain and feed conversion, whereas interaction between age and temperature was detected only for weight gain. It was possible to perform economic analyses to determine maximum profit as a function of the variables that were included in the model. It was concluded that the response surface models are effective to predict the performance of broiler chickens and allow the elaboration of economic analyses to optimize profit.

Analysis of the serological variability of Lettuce mosaic virus using monoclonal antibodies and surface plasmon resonance technology

A panel of 19 monoclonal antibodies (mAbs) was used to study the immunological variability of Lettuce mosaic virus (LMV), a member of the genus Potyvirus, and to perform a first epitope characterization of this virus. Based on their specificity of recognition against a panel of 15 LMV isolates, the mAbs could be clustered in seven reactivity groups. Surface plasmon resonance analysis indicated the presence, on the LMV particles, of at least five independent recognition/ binding regions, correlating with the seven mAbs reactivity groups. The results demonstrate that LMV shows significant serological variability and shed light on the LMV epitope structure. The various mAbs should prove a new and efficient tool for LIVIV diagnostic and field epidemiology studies.

Theoretical analysis of the energy levels induced by oxygen vacancies and the doping process (Co, Cu and Zn) on SnO2 (110) surface models

Density functional calculation at B3LYP level was employed to study the surface oxygen vacancies and the doping process of Co, Cu and Zn on SnO2 (110) surface models. Large clusters, based on (SnO2)(15) models, were selected to simulate the oxidized (Sn15O30), half-reduced (Sn15O29) and the reduced (Sn15O28) surfaces. The doping process was considered on the reduced surfaces: Sn13Co2O28, Sn13Cu2O28 and Sn13Zn2O28. The results are analyzed and discussed based on a calculation of the energy levels along the bulk band gap region, determined by a projection of the monoelectron level structure on to the atomic basis set and by the density of states. This procedure enables one to distinguish the states coming from the bulk, the oxygen vacancies and the doping process, on passing from an oxidized to a reduced surface, missing bridge oxygen atoms generate electronic levels along the band gap region, associated with 5s/5p of four-/five-fold Sn and 2p of in-plane O centers located on the exposed surface, which is in agreement with previous theoretical and experimental investigations. The formation energy of one and two oxygen vacancies is 3.0 and 3.9 eV, respectively. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Analysis of surface integrity for minimum quantity lubricant - MQL in grinding

The quality of machined components is currently of high interest, for the market demands mechanical components of increasingly high performance, not only from the standpoint of functionality but also from that of safety. Components produced through operations involving the removal of material display surface irregularities resulting not only from the action of the tool itself, but also from other factors that contribute to their superficial texture. This texture can exert a decisive influence on the application and performance of the machined component. This article analyzes the behavior of the minimum quantity lubricant (MQL) technique and compares it with the conventional cooling method. To this end, an optimized fluid application method was devised using a specially designed nozzle, by the authors, through which a minimum amount of oil is sprayed in a compressed air flow, thus meeting environmental requirements. This paper, therefore, explores and discusses the concept of the MQL in the grinding process. The performance of the MQL technique in the grinding process was evaluated based on an analysis of the surface integrity (roughness, residual stress, microstructure and microhardness). The results presented here are expected to lead to technological and ecological gains in the grinding process using MQL. (c) 2006 Elsevier Ltd. All rights reserved.

Comparison of fracture surface and plane section analysis for ceramic grain size characterisation

A method has been developed to obtain quantitative information about grain size and shape from fractured surfaces of ceramic materials. One elaborated a routine to split intergranular and transgranular grains facets of ceramic fracture surfaces by digital image processing. A commercial ceramic (ALCOA A-16, Al2O3-1.5% of CrO) was used to test the proposed method. Microstructural measurements of grain shape and size taken from fracture surfaces have been compared through descriptive statistics of distributions, with the corresponding measurements from polished and etched surfaces. The agreement between results, with the expected bias on grain size values from fractures, obtained for both types of surfaces allowed to infer that this new technique can be used to extract the relevant microstructural information from fractured surfaces, thus minimising the time consuming steps of sample preparation. (C) 2003 Elsevier Ltd. All rights reserved.

Comparative analysis of root surface smear layer removal by different etching modalities or erbium:yttrium-aluminum-garnet laser irradiation. A scanning electron microscopy study

The purpose of this study was to evaluate the effect of erbium:yttrium-aluminum-garnet (Er:YAG) laser (2.94 mu m) irradiation on the removal of root surface smear layer of extracted human teeth and to compare its efficacy with that of citric acid, ethylenediamine tetra-acetic acid (EDTA), or a gel containing a mixture of tetracycline hydrochloride (HCl) and citric acid, using scanning electron microscopy (SEM). Thirty human dentin specimens were randomly divided into six groups: G1 (control group), irrigated with 10 ml of physiologic saline solution; G2, conditioned with 24% citric acid gel; G3, conditioned with 24% EDTA gel; G4, conditioned with a 50% citric acid and tetracycline gel; G5, irradiated with Er:YAG laser (47 mJ/10 Hz/5.8 J/cm(2)/pulse); G6, irradiated with Er:YAG laser (83 mJ/10 Hz/10.3 J/cm(2)/pulse). Electron micrographs were obtained and analyzed according to a rating system. Statistical analysis was conducted with Kruskal-Wallis and Mann-Whitney tests (P < 0.05). G1 was statistically different from all the other groups; no statistically significant differences were observed between the Er:YAG laser groups and those undergoing the other treatment modalities. When the two Er:YAG laser groups were compared, the fluency of G6 was statistically more effective in smear layer removal than the one used in G5 (Mann-Whitney test, P < 0.01). Root surfaces irradiated by Er:YAG laser had more irregular contours than those treated by chemical agents. It can be concluded that all treatment modalities were effective in smear layer removal. The results of our study suggest that the Er:YAG laser can be safely used to condition diseased root surfaces effectively. Furthermore, the effect of Er:YAG laser irradiation on root surfaces should be evaluated in vivo so that its potential to enhance the healing of periodontal tissues can be assessed.

Effect of Er : YAG and diode laser irradiation on the root surface: Morphological and thermal analysis

Background: the aim of the present study was to compare the effects of Er:YAG and diode laser treatments of the root surface on intrapulpal temperature after scaling and root planing with hand instruments.Methods: Fifteen extracted single-rooted teeth were scaled and root planed with hand instruments. The teeth were divided into 3 groups of 5 each and irradiated on their buccal and lingual surfaces: group A: Er:YAG laser, 2.94 mum/100 mJ/10 Hz/ 30 seconds; group B: diode laser, 810 nm/1.0 W/0.05 ms/30 seconds; group C: diode laser, 810 nm/1.4 W/0.05 ms/30 seconds. The temperature was monitored by means of a type T thermocouple (copper-constantan) positioned in the pulp chamber to assess pulpal temperature during and before irradiation. Afterwards, the specimens were longitudinally sectioned, and the buccal and lingual surfaces of each root were analyzed by scanning electron microscopy.Results: In the Er:YAG laser group, the thermal analysis revealed an average temperature of -2.2 +/- 1.5degreesC, while in the diode laser groups, temperatures were 1.6 +/- 0.8degreesC at 1.0 W and 3.3 +/- 1.0degreesC at 1.4 W. Electronic micrographs revealed that there were no significant morphological changes, such as charring, melting, or fusion, in any group, although the specimens were found to be more irregular in the Er:YAG laser group.Conclusions: the application of Er:YAG and diode lasers at the utilized parameters did not induce high pulpal temperatures. Root surface irregularities were more pronounced after irradiation with an Er:YAG laser than with a diode laser.

Some practical advice on polynomial regression analysis from blocked response surface designs

It is often necessary to run response surface designs in blocks. In this paper the analysis of data from such experiments, using polynomial regression models, is discussed. The definition and estimation of pure error in blocked designs are considered. It is recommended that pure error is estimated by assuming additive block and treatment effects, as this is more consistent with designs without blocking. The recovery of inter-block information using REML analysis is discussed, although it is shown that it has very little impact if thc design is nearly orthogonally blocked. Finally prediction from blocked designs is considered and it is shown that prediction of many quantities of interest is much simpler than prediction of the response itself.

Laurdan Spectrum Decomposition as a Tool for the Analysis of Surface Bilayer Structure and Polarity: a Study with DMPG, Peptides and Cholesterol

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The interaction between atoms of Au and Cu with clean Si(111) surface: A study combining synchrotron radiation grazing incidence X-ray fluorescence analysis and theoretical calculations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A theoretical analysis on electronic structure of the (110) surface of TiO2-SnO2 mixed oxide

Mixed oxide compounds, such as TiO2-SnO2 system are widely used as gas sensors and should also provide varistor properties modifying the TiO2 surface. Therefore, a theoretical investigation has been carried out characterizing the effect of SnO2 on TiO2 addition on the electronic structure by means of ab initio SCF-LCAO calculations using all electrons. In order to take into account the finite size of the cluster, we have used the point charge model for the (TiO2)(15) cluster to study the effect on electronic structure of doping the TiO2 (110) Surface. The contracted basis set for titanium (4322/42/3), oxygen (33/3) and tin (43333/4333/43) atoms were used. The charge distributions, dipole moments, and density of states of doping TiO2 and vacancy formation are reported and analysed. (C) 2003 Elsevier B.V. All rights reserved.

A theoretical analysis of the TiO2/Sn doped (110) surface properties

We have used the periodic quantum-mechanical method with density functional theory at the B3LYP level in order to study TiO2/Sn doped (1 1 0) surfaces and have investigated the structural, electronic and energy band properties of these oxides. Our calculated relaxation directions for TiO2 is the experimental one and is also in agreement with other theoretical results. We also observe for the doped systems relaxation of lattice positions of the atoms. Modification of Sri, O and Ti charges depend on the planes and positions of the substituted atoms. Doping can modify the Fermi levels, energy gaps as well as the localization and composition of both valence and conduction band main components. Doping can also modify the chemical, electronic and optical properties of these oxides surfaces increasing their suitability for use as gas sensors and optoelectronic devices. (c) 2005 Elsevier B.V. All rights reserved.