Optical changes and writing on hydrotalcite supported gold nanoparticles

Gold nanoparticles (AuNP) incorporated into hydrotalcite (HT), provide an interesting type of pigment in which temperature can modulate the plasmon resonance and the aggregation phenomenon. As inferred from microscopy techniques, the preferential binding sites are located at the border of the HT external basal surface, leading to aggregates of gold nanoparticles displaying characteristic plasmon resonance and interference bands around 520 and 700 nm, respectively. The thermally induced color changes in the HT-supported gold material arise from the competition between of nanoparticles aggregation and fusion processes, as characterized by TEM and STM. A laser beam can also induce such changes, allowing the writing of optical information on this type of material.

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.

Supramolecular Approach to Gold Nanoparticle/Triruthenium Cluster Hybrid Materials and Interfaces

A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.

Ex Situ Scanning Electrochemical Microscopy (SECM) Investigation of Bismuth- and Bismuth/Lead Alloy Film-Modified Gold Electrodes in Alkaline Medium

Scanning electrochemical microscopy (SECM) in feedback mode was employed to characterise the reactivity and microscopic peculiarities of bismuth and bismuth/lead alloys plated onto gold disk substrates in 0.1 molL(-1) NaOH solutions. Methyl viologen was used as redox mediator, while a platinum microelectrode was employed as the SECM tip. The metal films were electrodeposited ex situ from NaOH solutions containing either bismuth ions only or both bismuth and lead ions. Approach curves and SECM images indicated that the metal films were conductive and locally reactive with oxygen to provide Bi(3+) and Pb(2+) ions. The occurrence of the latter chemical reactions was verified by local anodic stripping voltammetry (ASV) at the substrate solution interface by using a mercury-coated platinum SECM tip. The latter types of measurements allowed also verifying that lead was not uniformly distributed onto the bismuth film electrode substrate. These findings were confirmed by scanning electron microscopy images. The surface heterogeneity produced during the metal deposition process, however, did not affect the analytical performance of the bismuth coated gold electrode in anodic stripping voltammetry for the determination of lead in alkaline media, even in aerated aqueous solutions. Under the latter conditions, stripping peak currents proportional to lead concentration with a satisfactory reproducibility (within 5% RSD) were obtained.

Use of copper and gold electrodes as sensitive elements for fabrication of an electronic tongue: Discrimination of wines and whiskies

A low-cost method is proposed to classify wine and whisky samples using a disposable voltammetric electronic tongue that was fabricated using gold and copper substrates and a pattern recognition technique (Principal Component Analysis). The proposed device was successfully used to discriminate between expensive and cheap whisky samples and to detect adulteration processes using only a copper electrode. For wines, the electronic tongue was composed of copper and gold working electrodes and was able to classify three different brands of wine and to make distinctions regarding the wine type, i.e., dry red, soft red, dry white and soft white brands. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.

Surface-Enhanced Resonance Raman Scattering of Polyaniline on Silver and Gold Colloids

The interaction of emeraldine base (PANI-EB) with silver and gold colloids was probed by using Surface-Enhanced Resonance Raman Scattering (SERRS) at 3 different exciting radiations. Due to the great sensitivity of SERRS technique the detection limit of PANI-EB concentration was ca. 2 x 10(-7) mol L(-1) in Ag and Au colloidal suspensions. The UV-vis-NIR spectra of metal colloids in function of PANI-EB concentrations showed that gold colloids present a higher degree of aggregation than silver colloids. SERRS of PANI-EB on metal colloids allowed the study of the polymeric species formed primarily on the metallic surface. The polymer formed after the adsorption of PANI-EB on metallic nanoparticles is strongly dependent on the nature of the metal colloids. The oxidation of PANI-EB to pernigraniline occurred for silver colloids, while a doping process of PANI-EB on Au nanoparticles was evidenced through the observation of the characteristic SERRS spectrum of emeraldine salt at 1064nm.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.

Study of a gold electrode modified by trans-[Ru(NH(3))(4)(Ist)SO(4)](+) to produce an electrochemical sensor for nitric oxide

The modification of a gold electrode surface by electropolymerization of trans-[Ru(NH(3))(4)(Ist)SO(4)](+) to produce an electrochemical sensor for nitric oxide was investigated. The influence of dopamine, serotonin and nitrite as interferents for NO detection was also examined using square-wave voltammetry (SWV). The characterization of the modified electrode was carried out by cyclic voltammetry, electrochemical quartz crystal microbalance (EQCM) and SERS techniques. The gold electrode was successfully modified by the trans-[Ru(NH(3))(4)(Ist)SO(4)](+) complex ion using cyclic voltammetry. The experiments show that a monolayer of the film is achieved after ten voltammetric cycles, that NO in solution can coordinate to the metal present in the layer, that dopamine, serotonin and nitrite are interferents for the detection of NO, and that the response for the nitrite is much less significant than the responses for dopamine and serotonin. The proposed modified electrode has the potential to be applied as a sensor for NO. (C) 2011 Elsevier Ltd. All rights reserved.

The origin of the molecular interaction between amino acids and gold nanoparticles: A theoretical and experimental investigation

This study describes the synthesis of novel biological hybrid materials, where 3D structures were obtained using gold nanoparticles (AuNps) and methionine (Met) in a one-step procedure in aqueous media. The type of nanostructure can be controlled by tuning the intermolecular interactions between Met and AuNp, which strongly depends on the pH used for the synthesis. Computational simulation using the density-functional theory (DFT) showed that the AuNp - Met 3D structures are formed upon reorientation of Met molecules so that the backbone amine groups interact via H-bonds. These findings were experimentally confirmed using FTIR and UV-vis spectroscopy. Crown Copyright (C) 2008 Published by Elsevier B. V. All rights reserved.

Effects of a novel calcium aluminate cement on the early events of the progression of osteogenic cell cultures

The present study evaluated the progression of osteogenic cell cultures exposed to a novel calcium aluminate cement (CAC+) in comparison with the gold standard mineral trioxide aggregate (MTA). Cells were enzimatically isolated from newborn rat calvarial bone, plated on glass coverslips containing either CAC+ or a control MTA samples in the center, and grown under standard osteogenic conditions. Over the 10-day culture period, roundening of sample edges was clearly noticed only for MTA group. Although both cements supported osteogenic cell adhesion, spreading, and proliferation, CAC+-exposed cultures showed significantly higher values in terms of total cell number at days 3 and 7, and total protein content and alkaline phosphatase activity at day 10. The present in vitro results indicate that the exposure to CAC+ supports a higher differentiation of osteogenic cells compared with the ones exposed to MTA. Further experimental studies should consider CAC+ as a potential alternative to MTA when the repair of mineralized tissues is one of the desired outcomes in endodontic therapy.

Accuracy of three electronic apex locators in the presence of different irrigating solutions

The present study compared the accuracy of three electronic apex locators (EALs) - Elements Diagnostic®, Root ZX® and Apex DSP® - in the presence of different irrigating solutions (0.9% saline solution and 1% sodium hypochlorite). The electronic measurements were carried out by three examiners, using twenty extracted human permanent maxillary central incisors. A size 10 K file was introduced into the root canals until reaching the 0.0 mark, and was subsequently retracted to the 1.0 mark. The gold standard (GS) measurement was obtained by combining visual and radiographic methods, and was set 1 mm short of the apical foramen. Electronic length values closer to the GS (± 0.5 mm) were considered as accurate measures. Intraclass correlation coefficients (ICCs) were used to verify inter-examiner agreement. The comparison among the EALs was performed using the McNemar and Kruskal-Wallis tests (p < 0.05). The ICCs were generally high, ranging from 0.8859 to 0.9657. Similar results were observed for the percentage of electronic measurements closer to the GS obtained with the Elements Diagnostic® and the Root ZX® EALs (p > 0.05), independent of the irrigating solutions used. The measurements taken with these two EALs were more accurate than those taken with Apex DSP®, regardless of the irrigating solution used (p < 0.05). It was concluded that Elements Diagnostic® and Root ZX® apex locators are able to locate the cementum-dentine junction more precisely than Apex DSP®. The presence of irrigating solutions does not interfere with the performance of the EALs.

Influence of dental metallic artifact from multislice CT in the assessment of simulated mandibular lesions

OBJECTIVE: This study evaluated the influence of metallic dental artifacts on the accuracy of simulated mandibular lesion detection by using multislice technology. MATERIAL AND METHODS: Fifteen macerated mandibles were used. Perforations were done simulating bone lesions and the mandibles were subjected to axial 16 rows multislice CT images using 0.5 mm of slice thickness with 0.3 mm interval of reconstruction. Metallic dental restorations were done and the mandibles were subjected again to CT in the same protocol. The images were analyzed to detect simulated lesions in the mandibles, verifying the loci number and if there was any cortical perforation exposing medullar bone. The analysis was performed by two independent examiners using e-film software. RESULTS: The samples without artifacts presented better results compared to the gold standard (dried mandible with perforations). In the samples without artifacts, all cortical perforation were identified and 46 loci were detected (of 51) in loci number analysis. Among the samples with artifacts, 12 lesions out of 14 were recognized regarding medullar invasion, and 40 out of 51 concerning loci number. The sensitivity in samples without artifacts was 90% and 100% regarding loci number and medullar invasion, respectively. In samples with artifacts, these values dropped to 78% and 86%, respectively. The presence of metallic restorations affected the sensitivity values of the method, but the difference was not significant (p>0.05). CONCLUSIONS: Although there were differences in the results of samples with and without artifacts, the presence of metallic restoration did not lead to misinterpretation of the final diagnosis. However, the validity of multislice CT imaging in this study was established for detection of simulated mandibular bone lesions.

Evaluation of simulated bone lesion in the head of the mandible by using multislice computed tomography

Conventional radiography has shown limitation in acquiring image of the ATM region, thus, computed tomography (CT) scanning has been the best option to the present date for diagnosis, surgical planning and treatment of bone lesions, owing to its specific properties. OBJECTIVE: The aim of the study was to evaluate images of simulated bone lesions at the head of the mandible by multislice CT. MATERIAL AND METHODS: Spherical lesions were made with dental spherical drills (sizes 1, 3, and 6) and were evaluated by using multislice CT (64 rows), by two observers in two different occasions, deploying two protocols: axial, coronal, and sagittal images, and parasagittal images for pole visualization (anterior, lateral, posterior, medial and superior). Acquired images were then compared with those lesions in the dry mandible (gold standard) to evaluate the specificity and sensibility of both protocols. Statistical methods included: Kappa statistics, validity test and chi-square test. Results demonstrated the advantage of associating axial, coronal, and sagittal slices with parasagittal slices for lesion detection at the head of the mandible. RESULTS: There was no statistically significant difference between the types of protocols regarding a particular localization of lesions at the poles. CONCLUSIONS: Protocols for the assessment of the head of the mandible were established to improve the visualization of alterations of each of the poles of the mandible's head. The anterior and posterior poles were better visualized in lateral-medial planes while lateral, medial and superior poles were better visualized in the anterior-posterior plane.

Fine needle aspiration biopsy in the oral cavity and head and neck region

The objective of the current study was to evaluate the sensitivity, specificity and accuracy of fine needle aspiration biopsy (FNAB) of submucous nodules from the oral cavity and head and neck region as an auxiliary diagnostic tool. Fifty patients with nodule lesions in the oral cavity and the head and neck region were selected. All of them were submitted to FNAB and to either incisional or excisional biopsy. The diagnoses from the FNABs were compared with the biopsy diagnosis as the gold standard. All the cases of FNAB were analyzed by a single oral pathologist prior to the biopsy diagnosis. The results showed that the sensitivity of FNAB was 75%, its specificity was 96% and its accuracy was 58.8%. The false positive and false negative rates were 6.7% and 13.3%, respectively. The positive predictive value was 86% and the negative predictive value was 93%. The inconclusive rate was 16/50. FNAB displayed a high success rate for identifying both malignant and benign lesions, but a low accuracy for making a final diagnosis.

Assessment of simulated mandibular condyle bone lesions by cone beam computed tomography

There are many limitations to image acquisition, using conventional radiography, of the temporomandibular joint (TMJ) region. The Computed Tomography (CT) scan is a better option, due to its higher accuracy, for purposes of diagnosis, surgical planning and treatment of bone injuries. The aim of the present study was to analyze two protocols of cone beam computed tomography for the evaluation of simulated mandibular condyle bone lesions. Spherical lesions were simulated in 30 dry mandibular condyles, using dentist drills and drill bits sizes 1, 3 and 6. Each of the mandibular condyles was submitted to cone beam computed tomography (CBCT) using two protocols: 1) axial, coronal and sagittal multiplanar reconstruction (MPR); and 2) sagittal plus coronal slices throughout the longitudinal axis of the mandibular condyles. For these protocols, 2 observers analyzed the CBCT images independently, regarding the presence or not of injuries. Only one of the observers, however, performed on 2 different occasions. The results were compared to the gold standard, evaluating the percentage of agreement, degree of accuracy of CBCT protocols and observers' examination. The z test was used for the statistical analysis. The results showed there were no statistically significant differences between the 2 protocols. There was greater difficulty in the assessment of small-size simulated lesions (drill # 1). From the results of this study, it can be concluded that CBCT is an accurate tool for analyzing mandibular condyle bone lesions, with the MPR protocol showing slightly better results than the sagittal plus coronal slices throughout the longitudinal axis.