Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.

Synthesis and Characterization of Gold/Alanine Nanocomposites with Potential Properties for Medical Application as Radiation Sensors

Radiation dose assessment is essential for several medical treatments and diagnostic procedures. In this context, nanotechnology has been used in the development of improved radiation sensors, with higher sensitivity as well as smaller sizes and energy dependence. This paper deals with the synthesis and characterization of gold/alanine nanocomposites with varying mass percentage of gold, for application as radiation sensors. Alanine is an excellent stabilizing agent for gold nanoparticles because the size of the nanoparticles does not augment with increasing mass percentage of gold, as evidenced by UV-vis spectroscopy, dynamic light scattering, and transmission electron microscopy. X-ray diffraction patterns suggest that the alanine crystalline orientation undergoes alterations upon the addition of gold nanoparticles. Fourier transform infrared spectroscopy indicates that there is interaction between the gold nanoparticles and the amine group of the alanine molecules, which may be the reason for the enhanced stability of the nanocomposite. The application of the nanocomposites as radiation detectors was evaluated by the electron spin resonance technique. The sensitivity is improved almost 3 times in the case of the nanocomposite containing 3% (w/w) gold, so it can be easily tuned by changing the amount of gold nanoparticles in the nanocomposites, without the size of the nanoparticles influencing the radiation absorption. In conclusion, the featured properties, such as homogeneity, nanoparticle size stability, and enhanced sensitivity, make these nanocomposites potential candidates for the construction of small-sized radiation sensors with tunable sensitivity for application in several medical procedures.

Neutral Gold Complexes with Tridentate SNS Thiosemicarbazide Ligands

Na[AuCl4].2H(2)O reacts with tridentate thiosemicarbazide ligands, H(2)L1, derived from N-[N',N'-dialkylamino(thiocarbonyl)]benzimidoyl chloride and thiosemicarbazides under formation of air-stable, green [AuCl(L1)] complexes. The organic ligands coordinate in a planar SNS coordination mode. Small amounts of gold(I) complexes of the composition [AuCl(L3)] are formed as side-products, where L3 is an S-bonded 5-diethylamino-3-phenyl-1-thiocarbamoyl-1,2,4-triazole. The formation of the triazole L3 can be explained by the oxidation of H(2)L1 to an intermediate thiatriazine L2 by Au3+, followed by a desulfurization reaction with ring contraction. The chloro ligands in the [AuCl(L1)] complexes can readily be replaced by other monoanionic ligands such as SCN- or CN- giving [Au(SCN)(L1)] or [Au(CN)(L1)] complexes. The complexes described in this paper represent the first examples of fully characterized neutral Gold(III) thiosemicarbazone complexes. All the [AuCl(L1)] compounds present a remarkable cell growth inhibition against human MCF-7 breast cancer cells. However, systematic variation of the alkyl groups in the N(4)-position of the thiosemicarbazone building blocks as well as the replacement of the chloride by thiocyanate ligands do not considerably influence the biological activity. On the other hand, the reduction of Au-III to Au-I leads to a considerable decrease of the cytotoxicity.

Silver-gold nanotubes containing hot spots on their surface: facile synthesis and surface-enhanced Raman scattering investigations

We report the synthesis of silver-gold nanotubes containing hot spots along their surface. The Ag-Au nanotubes exhibited exceptional SERS properties compared to silver nanowires, enabling the detection of crystal violet in the 10(-10) M regime, as well as 9-nitroanthracene and benzo[a] pyrene at 3.3 x 10(-7) M.

Annealing effects on nanostructured gold-polymethylmethacrylate composites: Small-angle x-ray scattering analysis

Composites formed of a polymer-embedded layer of sub-10 nm gold nanoclusters were fabricated by very low energy (49 eV) gold ion implantation into polymethylmethacrylate. We used small angle x-ray scattering to investigate the structural properties of these metal-polymer composite layers that were fabricated at three different ion doses, both in their original form (as-implanted) and after annealing for 6 h well above the polymer glass transition temperature (150 degrees C). We show that annealing provides a simple means for modification of the structure of the composite by coarsening mechanisms, and thereby changes its properties. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720464]

Implant Stability Measurements of Two Immediate Loading Protocols for the Edentulous Mandible: Rigid and Semi-rigid Splinting of the Implants

Aim: Primary and secondary stabilities of immediately loaded mandibular implants restored with fixed prostheses (FP) using rigid or semirigid splinting systems were clinically and radiographically evaluated. Methods: Fifteen edentulous patients were rehabilitated using hybrid FP; each had 5 implants placed between the mental foramens. Two groups were randomly divided: group 1-FP with the conventional rigid bar splinting the implants and group 2-semi-rigid cantilever extension system with titanium bars placed in the 2 distal abutment cylinders. Primary stability was evaluated using resonance frequency analysis after installation of the implant abutments. The measurements were made at 3 times: T0, at baseline; T1, 4 months after implant placement; and T2, 8 months after implant placement. Presence of mobility and inflammation in the implant surrounding regions were checked. Stability data were submitted to statistical analysis for comparison between groups (P, 0.05). Results: Implant survival rate for the implants was of 100% in both groups. No significant differences in the mean implant stability quotient values were found for both groups from baseline and after the 8-month follow-up. Conclusion: The immediate loading of the implants was satisfactory, and both splinting conditions (rigid and semi-rigid) can be successfully used for the restoration of edentulous mandibles. (Implant Dent 2012;21:486-490)

Focusing surface plasmons on Er3+ ions through gold planar plasmonic lenses

Gold plasmonic lenses consisting of a planar concentric rings-groove with different periods were milled with a focused gallium ion beam on a gold thin film deposited onto an Er3+-doped tellurite glass. The plasmonic lenses were vertically illuminated with an argon ion laser highly focused by means of a 50x objective lens. The focusing mechanism of the plasmonic lenses is explained using a coherent interference model of surface plasmon-polariton (SPP) generation on the circular grating due to the incident field. As a result, phase modulation can be accomplished by the groove gap, similar to a nanoslit array with different widths. This focusing allows a high confinement of SPPs that can excite the Er3+ ions of the glass. The Er3+ luminescence spectra were measured in the far-field (500-750 nm wavelength range), where we could verify the excitation yield via the plasmonic lens on the Er3+ ions. We analyze the influence of the geometrical parameters on the luminescence spectra. The variation of these parameters results in considerable changes of the luminescence spectra.

Use of a gold microelectrode for discrimination of gunshot residues

Gunshot residues (GSR) can be used in forensic evaluations to obtain information about the type of gun and ammunition used in a crime. In this work, we present our efforts to develop a promising new method to discriminate the type of gun [four different guns were used: two handguns (0.38 revolver and 0.380 pistol) and two long-barrelled guns (12-calibre pump-action shotgun and 0.38 repeating rifle)] and ammunition (five different types: normal, semi-jacketed, full-jacketed, green, and 3T) used by a suspect. The proposed approach is based on information obtained from cyclic voltammograms recorded in solutions containing GSR collected from the hands of the shooters, using a gold microelectrode; the information was further analysed by non-supervised pattern-recognition methods [(Principal Component Analysis (PCA) and Hierarchical Cluster Analysis (HCA)]. In all cases (gun and ammunition discrimination), good separation among different samples in the score plots and dendrograms was achieved. (C) 2012 Elsevier B.V. All rights reserved.

The impact of healing time before loading on orthodontic mini-implant stability: a histomophometric study in minipigs

Objective: To evaluate healing time before loading, areas compression and tension and location of insertion on mini-implant stability. Design: Six minipigs were used. Each animal received 3 mini-implants in each quadrant: 1 mini-implant was used as an unloaded control (G1, n = 24); the other 2 were loaded with 150 g-force at three time intervals (G2: immediate loading, G3: after 15 days and G4: after 30 days), with 16 mini-implant in each experimental group. After 120 days, tissue blocks of the areas of interest were harvested. Clinical analysis (exact Fisher test) determined the survival rate. Histological analysis (Kontron KS 300TM, Zeiss) quantified the fractional bone-toimplant contact (%BIC) and bone area (%BA) at each healing time point, areas of interest, and insertion site (ANOVA and t tests for dependent and independent samples). Results: The mini-implant survival rates were G1: 71%, G2: 50%, G3: 75% and G4: 63%, with no statistical differences between them. The groups presented similar %BIC and %BA. There were no differences between the compression and tension sides or maxillary and mandibular insertion sites. Conclusions: These results suggest that low-intensity immediate or early orthodontic loading does not affect mini-implant stability, because similar histomorphometric results were observed for all the groups, with partial osseointegration of the mini-implants present.

The effect of CCL3 and CCR1 in bone remodeling induced by mechanical loading during orthodontic tooth movement in mice

Bone remodeling is affected by mechanical loading and inflammatory mediators, including chemokines. The chemokine (C–C motif) ligand 3 (CCL3) is involved in bone remodeling by binding to C–C chemokine receptors 1 and 5 (CCR1 and CCR5) expressed on osteoclasts and osteoblasts. Our group has previously demonstrated that CCR5 down-regulates mechanical loading-induced bone resorption. Thus, the present study aimed to investigate the role of CCR1 and CCL3 in bone remodeling induced by mechanical loading during orthodontic tooth movement in mice. Our results showed that bone remodeling was significantly decreased in CCL3−/− and CCR1−/− mice and in animals treated with Met-RANTES (an antagonist of CCR5 and CCR1). mRNA levels of receptor activator of nuclear factor kappa-B (RANK), its ligand RANKL, tumor necrosis factor alpha (TNF-α) and RANKL/osteoprotegerin (OPG) ratio were diminished in the periodontium of CCL3−/− mice and in the group treated with Met-RANTES. Met-RANTES treatment also reduced the levels of cathepsin K and metalloproteinase 13 (MMP13). The expression of the osteoblast markers runt-related transcription factor 2 (RUNX2) and periostin was decreased, while osteocalcin (OCN) was augmented in CCL3−/− and Met-RANTES-treated mice. Altogether, these findings show that CCR1 is pivotal for bone remodeling induced by mechanical loading during orthodontic tooth movement and these actions depend, at least in part, on CCL3.

Study of an anisotropic polymeric cellular material under compression loading

This paper emphasizes the influence of micro mechanisms of failure of a cellular material on its phenomenological response. Most of the applications of cellular materials comprise a compression loading. Thus, the study focuses on the influence of the anisotropy in the mechanical behavior of cellular material under cyclic compression loadings. For this study, a Digital Image Correlation (DIC) technique (named Correli) was applied, as well as SEM (Scanning Electron Microscopy) images were analyzed. The experimental results are discussed in detail for a closed-cell rigid poly (vinyl chloride) (PVC) foam, showing stress-strain curves in different directions and why the material can be assumed as transversely isotropic. Besides, the present paper shows elastic and plastic Poisson's ratios measured in different planes, explaining why the plastic Poisson's ratios approach to zero. Yield fronts created by the compression loadings in different directions and the influence of spring-back phenomenon on hardening curves are commented, also.

Effects of specimen geometry and loading mode on crack growth resistance curves of a high-strength pipeline girth weld

This work presents an investigation of the ductile tearing properties for a girth weld made of an API 5L X80 pipeline steel using experimentally measured crack growth resistance curves. Use of these materials is motivated by the increasing demand in the number of applications for manufacturing high strength pipes for the oil and gas industry including marine applications and steel catenary risers. Testing of the pipeline girth welds employed side-grooved, clamped SE(T) specimens and shallow crack bend SE(B) specimens with a weld centerline notch to determine the crack growth resistance curves based upon the unloading compliance (UC) method using the single specimen technique. Recently developed compliance functions and η-factors applicable for SE(T) and SE(B) fracture specimens with homogeneous material and overmatched welds are introduced to determine crack growth resistance data from laboratory measurements of load-displacement records.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Synthesis of self-assembled tubes in direct conjugated porphyrin-gold nanohybrid solution

We report on the formation of self-assembled meso-tetrakis (p-sulfonatofenyl) porphyrin (H2 TPP'S POT. 4-''IND. 4') tubes stabilized by gold nanoparticles (NPs) in basic solution and on their spectroscopic chareterization. The role of the gold NPs in the aggregation dynamics of free-base sulfonated porphyrin (H2TPP'S POT. 4-''IND. 4') is also investigated. The direct conjugation of the gold NPs to the H2TPPS4 molecule quenches the fluorescence intensity, while absorption peaks are blue-shifted, indicating predominant H-type aggregation. It is observed that porphyrin molecules adsorbed on the surface of the gold NP interact and form tubes of maximum diameter ∼1.5 μm and length >100 μm. Steady-state and time-resolved spectroscopic techniques confirm nonradiative energy transfer from porphyrin to gold NP.

In vivo photothermal tumour ablation using gold nanorods

Less invasive and more effective cancer treatments have been the aim of research in recent decades, e.g. photothermal tumour ablation using gold nanorods. In this study we investigate the cell death pathways activated, and confirm the possibility of CTAB-coated nanoparticle use in vivo. Nanorods were synthesized by the seeding method; some of them were centrifuged and washed to eliminate soluble CTAB. The MTT cytotoxicity test was performed to evaluate cytotoxicity, and the particles' viability after their synthesis was assessed. Once it had been observed that centrifuged and washed nanorods are harmless, and that nanoparticles must be used within 48 h after their synthesis, in vivo hyperthermic treatment was performed.After irradiation, a tumour biopsy was subjected to a chemiluminescence assay to evaluate membrane lipoperoxidation, and to a TRAP assay to evaluate total antioxidant capacity. There was a 47 ºC rise in temperature observed at the tumour site. Animals irradiated with a laser (with or without nanorods) showed similar membrane lipoperoxidation, more intense than in control animals. The antioxidant capacity of experimental animal tumours was elevated. Our results indicate that necrosis is possibly the cell death pathway activated in this case, and that nanorod treatment is worthwhile.