Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

Preparation of environmental monitoring plan pattern for surface water quality in Iran (Case study: Gharehsou River)

Using water quality management programs is a necessary and inevitable way for preservation and sustainable use of water resources. One of the important issues in determining the quality of water in rivers is designing effective quality control networks, so that the measured quality variables in these stations are, as far as possible, indicative of overall changes in water quality. One of the methods to achieve this goal is increasing the number of quality monitoring stations and sampling instances. Since this will dramatically increase the annual cost of monitoring, deciding on which stations and parameters are the most important ones, along with increasing the instances of sampling, in a way that shows maximum change in the system under study can affect the future decision-making processes for optimizing the efficacy of extant monitoring network, removing or adding new stations or parameters and decreasing or increasing sampling instances. This end, the efficiency of multivariate statistical procedures was studied in this thesis. Multivariate statistical procedure, with regard to its features, can be used as a practical and useful method in recognizing and analyzing rivers’ pollution and consequently in understanding, reasoning, controlling, and correct decision-making in water quality management. This research was carried out using multivariate statistical techniques for analyzing the quality of water and monitoring the variables affecting its quality in Gharasou river, in Ardabil province in northwest of Iran. During a year, 28 physical and chemical parameters were sampled in 11 stations. The results of these measurements were analyzed by multivariate procedures such as: Cluster Analysis (CA), Principal Component Analysis (PCA), Factor Analysis (FA), and Discriminant Analysis (DA). Based on the findings from cluster analysis, principal component analysis, and factor analysis the stations were divided into three groups of highly polluted (HP), moderately polluted (MP), and less polluted (LP) stations Thus, this study illustrates the usefulness of multivariate statistical techniques for analysis and interpretation of complex data sets, and in water quality assessment, identification of pollution sources/factors and understanding spatial variations in water quality for effective river water quality management. This study also shows the effectiveness of these techniques for getting better information about the water quality and design of monitoring network for effective management of water resources. Therefore, based on the results, Gharasou river water quality monitoring program was developed and presented.

Investigating the use of LiDAR scanning as a method for the measurement of timber distortion features

Measuring the extent to which a piece of structural timber has distorted at a macroscopic scale is fundamental to assessing its viability as a structural component. From the sawmill to the construction site, as structural timber dries, distortion can render it unsuitable for its intended purposes. This rejection of unusable timber is a considerable source of waste to the timber industry and the wider construction sector. As such, ensuring accurate measurement of distortion is a key step in addressing ineffciencies within timber processing. Currently, the FRITS frame method is the established approach used to gain an understanding of timber surface profile. The method, while reliable, is dependent upon relatively few measurements taken across a limited area of the overall surface, with a great deal of interpolation required. Further, the process is unavoidably slow and cumbersome, the immobile scanning equipment limiting where and when measurements can be taken and constricting the process as a whole. This thesis seeks to introduce LiDAR scanning as a new, alternative approach to distortion feature measurement. In its infancy as a measurement technique within timber research, the practicalities of using LiDAR scanning as a measurement method are herein demonstrated, exploiting many of the advantages the technology has over current approaches. LiDAR scanning creates a much more comprehensive image of a timber surface, generating input data multiple magnitudes larger than that of the FRITS frame. Set-up and scanning time for LiDAR is also much quicker and more flexible than existing methods. With LiDAR scanning the measurement process is freed from many of the constraints of the FRITS frame and can be done in almost any environment. For this thesis, surface scans were carried out on seven Sitka spruce samples of dimensions 48.5x102x3000mm using both the FRITS frame and LiDAR scanner. The samples used presented marked levels of distortion and were relatively free from knots. A computational measurement model was created to extract feature measurements from the raw LiDAR data, enabling an assessment of each piece of timber to be carried out in accordance with existing standards. Assessment of distortion features focused primarily on the measurement of twist due to its strong prevalence in spruce and the considerable concern it generates within the construction industry. Additional measurements of surface inclination and bow were also made with each method to further establish LiDAR's credentials as a viable alternative. Overall, feature measurements as generated by the new LiDAR method compared well with those of the established FRITS method. From these investigations recommendations were made to address inadequacies within existing measurement standards, namely their reliance on generalised and interpretative descriptions of distortion. The potential for further uses of LiDAR scanning within timber researches was also discussed.

Surface enrichment in gold/silver alloys: effects of temperature studied by atom probe tomography

Bimetallic alloys are increasingly used in heterogeneous catalysis. This interest is explained by the emergence of new features that are absent in the parent single metals. Synergistic effects between the two combined elements create a more efficient catalyst. One of the most challenging aspect of multicomponent materials in catalysis is the ability to fine-tune the catalytic properties of an alloy by controlling the nature and composition of the surface [1]. For example, the gold/silver alloy combines a high activity and a large selectivity for a broad range of oxidation reaction.It is well established that the surface composition of alloys may deviate from that of the bulk phase. Surface enrichment has also important consequences in some applications of heterogeneous catalysis. In some cases, the thermal and chemical treatments can lead to opposite trends regarding the nature of the metal prone to surface enrichment. Using atom probe tomography we aim to link the physicochemical conditions the composition of the very first atomic layers of bimetallic catalysts and eventually to fine-tune the catalytic features of the latter.

Studying the alignment of 5-cyanobiphenyl on a polydimethylsiloxane surface through Molecular Dynamics simulations

For 40 years, at the University of Bologna, a group of researchers coordinated by professor Claudio Zannoni has been studying liquid crystals by employing computational techniques. They have developed effective models of these interesting, and still far from being completely understood, systems. They were able to reproduce with simulations important features of some liquid crystal molecules, such as transition temperature. Then they focused their attention on the interactions that these molecules have with different kinds of surface, and how these interactions affect the alignment of liquid crystals. The group studied the behaviour of liquid crystals in contact with different kinds of surfaces, from silica, either amorphous and crystalline, to organic self assembled monolayers (SAMs) and even some common polymers, such as polymethylmethacrylate (PMMA) and polystyrene (PS). Anyway, a library of typical surfaces is still far from being complete, and a lot of work must be done to investigate the cases which have not been analyzed yet. A hole that must be filled is represented by polydimethylsiloxane (PDMS), a polymer on which the interest of industry has enormously grown up in the last years, thanks to its peculiar features, allowing it to be employed in many fields of applications. It has been observed experimentally that PDMS causes 4-cyano-4’-pentylbiphenyl (well known as 5CB), one of the most common liquid crystal molecules, to align homeotropically (i.e. perpendicular) with respect to a surface made of this polymer. Even though some hypothesis have been presented to rationalize the effect, a clear explanation of this phenomenon has not been given yet. This dissertation shows the work I did during my internship in the group of professor Zannoni. The challenge that I had to tackle was to investigate, via Molecular Dynamics (MD) simulations, the reasons of 5CB homeotropic alignment on a PDMS surface, as the group had previously done for other surfaces.

Comprehensive characterization of snowfall in terms of microphysical features, quantitative precipitation estimation and scavenging properties by in situ and remote sensing observations at an Antarctic coastal site

Snow plays a crucial role in the Earth's hydrological cycle and energy budget, making its monitoring necessary. In this context, ground-based radars and in situ instruments are essential thanks to their spatial coverage, resolution, and temporal sampling. Deep understanding and reliable measurements of snow properties are crucial over Antarctica to assess potential future changes of the surface mass balance (SMB) and define the contribution of the Antarctic ice sheet on sea-level rise. However, despite its key role, Antarctic precipitation is poorly investigated due to the continent's inaccessibility and extreme environment. In this framework, this Thesis aims to contribute to filling this gap by in-depth characterization of Antarctic precipitation at the Mario Zucchelli station from different points of view: microphysical features, quantitative precipitation estimation (QPE), vertical structure of precipitation, and scavenging properties. For this purpose, a K-band vertically pointing radar collocated with a laser disdrometer and an optical particle counter (OPC) were used. The radar probed the lowest atmospheric layers with high vertical resolution, allowing the first trusted measurement at only 105 m height. Disdrometer and OPC provided information on the particle size distribution and aerosol concentrations. An innovative snow classification methodology was designed by comparing the radar reflectivity (Ze) and disdrometer-derived reflectivity by means of DDA simulations. Results of classification were exploited in QPE through appropriate Ze-snow rate relationships. The accuracy of the resulting QPE was benchmarked against a collocated weighing gauge. Vertical radar profiles were also investigated to highlight hydrometeors' sublimation and growth processes. Finally, OPC and disdrometer data allowed providing the first-ever estimates of scavenging properties of Antarctic snowfall. Results presented in this Thesis give rise to advances in knowledge of the characteristics of snowfall in Antarctica, contributing to a better assessment of the SMB of the Antarctic ice sheet, the major player in the global sea-level rise.

High-strength steels manufactured via Laser Powder Bed Fusion: effect of post-process heat treatments and surface finishing on microstructure and mechanical properties

Laser Powder Bed Fusion (LPBF) permits the manufacturing of parts with optimized geometry, enabling lightweight design of mechanical components in aerospace and automotive and the production of tools with conformal cooling channels. In order to produce parts with high strength-to-weight ratio, high-strength steels are required. To date, the most diffused high-strength steels for LPBF are hot-work tool steels, maraging and precipitation-hardening stainless steels, featuring different composition, feasibility and properties. Moreover, LPBF parts usually require a proper heat treatment and surface finishing, to develop the desired properties and reduce the high roughness resulting from LPBF. The present PhD thesis investigates the effect of different heat treatments and surface finishing on the microstructure and mechanical properties of a hot-work tool steel and a precipitation-hardening stainless steel manufactured via LPBF. The bibliographic section focuses on the main aspects of LPBF, hot-work tool steels and precipitation-hardening stainless steels. The experimental section is divided in two parts. Part A addresses the effect of different heat treatments and surface finishing on the microstructure, hardness, tensile and fatigue behaviour of a LPBF manufactured hot-work tool steel, to evaluate its feasibility for automotive and racing components. Results indicated the possibility to achieve high hardness and strength, comparable to the conventionally produced steel, but a great sensitivity of fatigue strength on defects and surface roughness resulting from LPBF. Part B investigates the effect of different heat treatments on the microstructure, hardness, tensile and notch-impact behaviour of a LPBF produced precipitation-hardening stainless steel, to assess its feasibility for tooling applications. Results indicated the possibility to achieve high hardness and strength also through a simple Direct Aging, enabling heat treatment simplification by exploiting the microstructural features resulting from LPBF.

Evaluation Of The Effect Of Different Methods Of Microabrasion And Polishing On Surface Roughness Of Dental Enamel.

The microabrasion technique of enamel consists of selectively abrading the discolored areas or causing superficial structural changes in a selective way. In microabrasion technique, abrasive products associated with acids are used, and the evaluation of enamel roughness after this treatment, as well as surface polishing, is necessary. This in-vitro study evaluated the enamel roughness after microabrasion, followed by different polishing techniques. Roughness analyses were performed before microabrasion (L1), after microabrasion (L2), and after polishing (L3).Thus, 60 bovine incisive teeth divided into two groups were selected (n=30): G1- 37% phosphoric acid (37%) (Dentsply) and pumice; G2- hydrochloric acid (6.6%) associated with silicon carbide (Opalustre - Ultradent). Thereafter, the groups were divided into three sub-groups (n=10), according to the system of polishing: A - Fine and superfine granulation aluminum oxide discs (SofLex 3M); B - Diamond Paste (FGM) associated with felt discs (FGM); C - Silicone tips (Enhance - Dentsply). A PROC MIXED procedure was applied after data exploratory analysis, as well as the Tukey-Kramer test (5%). No statistical differences were found between G1 and G2 groups. L2 differed statistically from L1 and showed superior amounts of roughness. Differences in the amounts of post-polishing roughness for specific groups (1A, 2B, and 1C) arose, which demonstrated less roughness in L3 and differed statistically from L2 in the polishing system. All products increased enamel roughness, and the effectiveness of the polishing systems was dependent upon the abrasive used.

Tuning The Surface Anisotropy In Fe-doped Nio Nanoparticles.

Ni(1-x)FexO nanoparticles have been obtained by the co-precipitation chemical route. X-ray diffraction analyses using Rietveld refinement have shown a slight decrease in the microstrain and mean particle size as a function of the Fe content. The zero-field-cooling (ZFC) and field-cooling (FC) magnetization curves show superparamagnetic behavior at high temperatures and a low temperature peak (at T = 11 K), which is enhanced with increasing Fe concentration. Unusual behavior of the coercive field in the low temperature region and an exchange bias behavior were also observed. A decrease in the Fe concentration induces an increase in the exchange bias field. We argue that these behaviors can be linked with the strengthening of surface anisotropy caused by the incorporation of Fe ions.

The Effect Of Poly(methyl Methacrylate) Surface Treatments On The Adhesion Of Silicone-based Resilient Denture Liners.

Different surface treatment protocols of poly(methyl methacrylate) have been proposed to improve the adhesion of silicone-based resilient denture liners to poly(methyl methacrylate) surfaces. The purpose of this study was to evaluate the effect of different poly(methyl methacrylate) surface treatments on the adhesion of silicone-based resilient denture liners. Poly(methyl methacrylate) specimens were prepared and divided into 4 treatment groups: no treatment (control), methyl methacrylate for 180 seconds, acetone for 30 seconds, and ethyl acetate for 60 seconds. Poly(methyl methacrylate) disks (30.0 × 5.0 mm; n = 10) were evaluated regarding surface roughness and surface free energy. To evaluate tensile bond strength, the resilient material was applied between 2 treated poly(methyl methacrylate) bars (60.0 × 5.0 × 5.0 mm; n = 20 for each group) to form a 2-mm-thick layer. Data were analyzed by 1-way ANOVA and the Tukey honestly significant difference tests (α = .05). A Pearson correlation test verified the influence of surface properties on tensile bond strength. Failure type was assessed, and the poly(methyl methacrylate) surface treatment modifications were visualized with scanning electron microscopy. The surface roughness was increased (P < .05) by methyl methacrylate treatment. For the acetone and ethyl acetate groups, the surface free energy decreased (P < .05). The tensile bond strength was higher for the methyl methacrylate and ethyl acetate groups (P < .05). No correlation was found regarding surface properties and tensile bond strength. Specimens treated with acetone and methyl methacrylate presented a cleaner surface, whereas the ethyl acetate treatment produced a porous topography. The methyl methacrylate and ethyl acetate surface treatment protocols improved the adhesion of a silicone-based resilient denture liner to poly(methyl methacrylate).

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.

Tubular Variant Of Basal Cell Adenoma Shares Immunophenotypical Features With Normal Intercalated Ducts And Is Closely Related To Intercalated Duct Lesions Of Salivary Gland.

The morphological criteria for identification of intercalated duct lesions (IDLs) of salivary glands have been defined recently. It has been hypothesised that IDL could be a precursor of basal cell adenoma (BCA). BCAs show a variety of histological patterns, and the tubular variant is the one that presents the strongest resemblance with IDLs. The aim of this study was to analyse the morphological and immunohistochemical profiles of IDLs and BCAs classified into tubular and non-tubular subtypes, to determine whether or not IDL and tubular BCA represent distinct entities. Eight IDLs, nine tubular BCAs and 19 non-tubular BCAs were studied. All tubular BCAs contained IDL-like areas, which represented 20-70% of the tumour. In non-tubular BCA, IDL-like areas were occasional and small (<5%). One patient presented IDLs, tubular BCAs and IDL/tubular BCA combined lesions. Luminal ductal cells of IDLs and tubular BCAs exhibited positivity for CK7, lysozyme, S100 and DOG1. In the non-tubular BCA group, few luminal cells exhibited such an immunoprofile; they were mainly CK14-positive. Basal/myoepithelial cells of IDLs, tubular BCAs and non-tubular BCAs were positive for CK14, calponin, α-SMA and p63; they were more numerous in BCA lesions. IDL, tubular BCA and non-tubular BCA form a continuum of lesions in which IDLs are related closely to tubular BCA. In both, the immunoprofile of luminal and myoepithelial cells recapitulates the normal intercalated duct. The difference between the adenoma-like subset of IDLs and tubular BCA rests mainly on the larger numbers of myoepithelial cells in the latter. Our findings indicate that at least some BCAs can arise via IDLs.

Effect Of Sodium Hypochlorite And Peracetic Acid On The Surface Roughness Of Acrylic Resin Polymerized By Heated Water For Short And Long Cycles.

To evaluate the surface roughness of acrylic resin submitted to chemical disinfection via 1% sodium hypochlorite (NaClO) or 1% peracetic acid (C2H4O3). The disc-shaped resin specimens (30 mm diameter ×4 mm height) were polymerized by heated water using two cycles (short cycle: 1 h at 74°C and 30 min at 100°C; conventional long cycle: 9 h at 74°C). The release of substances by these specimens in water solution was also quantified. Specimens were fabricated, divided into four groups (n = 10) depending on the polymerization time and disinfectant. After polishing, the specimens were stored in distilled deionized water. Specimens were immersed in 1% NaClO or 1% C2H4O3 for 30 min, and then were immersed in distilled deionized water for 20 min. The release of C2H4O3 and NaClO was measured via visual colorimetric analysis. Roughness was measured before and after disinfection. Roughness data were subjected to two-way ANOVA and Tukey's test. There was no interaction between polymerization time and disinfectant in influencing the average surface roughness (Ra, P = 0.957). Considering these factors independently, there were significant differences between short and conventional long cycles (P = 0.012), but no significant difference between the disinfectants hypochlorite and C2H4O3 (P = 0.366). Visual colorimetric analysis did not detect release of substances. It was concluded that there was the difference in surface roughness between short and conventional long cycles, and disinfection at acrylic resins polymerized by heated water using a short cycle modified the properties of roughness.

[demographic And Clinical Features Of Patients With Rheumatoid Arthritis In Piauí, Brazil--evaluation Of 98 Patients].

Brazilian epidemiological studies on rheumatoid arthritis are scarce, mainly in the northeast; thus many data currently available originate from the international literature. To describe demographic, clinical and serological characteristics of patients with rheumatoid arthritis (RA) followed-up by the same physician, in state of Piauí, Brazil. Data were collected between August 2010 and March 2013, in three health services of Piauí that provided health care in Rheumatology: a university-affiliated hospital, a public outpatient clinic and a private clinic. The numbers represent mean ± SD or percentage: 47.5±11.03 years-old non-Caucasian woman, non-smoker (59.2%), low educational level, mean disease duration of 7.7 years ± 7.6, and major extra-articular manifestations were rheumatoid nodules (19.4%) and sicca syndrome (46.9%). Features of rheumatoid arthritis obtained in this study are similar to those found in some national and international studies, but we observed higher female preponderance and illiteracy rate, in addition to a moderately severe erosive disease on average, with frequent sicca and other extra-articular manifestations.

Laser Printer Attribution: Exploring New Features And Beyond.

With a huge amount of printed documents nowadays, identifying their source is useful for criminal investigations and also to authenticate digital copies of a document. In this paper, we propose novel techniques for laser printer attribution. Our solutions do not need very high resolution scanning of the investigated document and explore the multidirectional, multiscale and low-level gradient texture patterns yielded by printing devices. The main contributions of this work are: (1) the description of printed areas using multidirectional and multiscale co-occurring texture patterns; (2) description of texture on low-level gradient areas by a convolution texture gradient filter that emphasizes textures in specific transition areas and (3) the analysis of printer patterns in segments of interest, which we call frames, instead of whole documents or only printed letters. We show by experiments in a well documented dataset that the proposed methods outperform techniques described in the literature and present near-perfect classification accuracy being very promising for deployment in real-world forensic investigations.