Minimal analytical characterization of engineered nanomaterials needed for hazard assessment in biological matrices.

Abstract This paper presents the outcomes from a workshop of the European Network on the Health and Environmental Impact of Nanomaterials (NanoImpactNet). During the workshop, 45 experts in the field of safety assessment of engineered nanomaterials addressed the need to systematically study sets of engineered nanomaterials with specific metrics to generate a data set which would allow the establishment of dose-response relations. The group concluded that international cooperation and worldwide standardization of terminology, reference materials and protocols are needed to make progress in establishing lists of essential metrics. High quality data necessitates the development of harmonized study approaches and adequate reporting of data. Priority metrics can only be based on well-characterized dose-response relations derived from the systematic study of the bio-kinetics and bio-interactions of nanomaterials at both organism and (sub)-cellular levels. In addition, increased effort is needed to develop and validate analytical methods to determine these metrics in a complex matrix.

Structural Characterization of UHPC Waffle Bridge Deck and Connections, TR-614, 2014

The AASHTO strategic plan in 2005 for bridge engineering identified extending the service life of bridges and accelerating bridge construction as two of the grand challenges in bridge engineering. These challenges have the objective of producing safer and more economical bridges at a faster rate with a minimum service life of 75 years and reduced maintenance cost to serve the country’s infrastructure needs. Previous studies have shown that a prefabricated full-depth precast concrete deck system is an innovative technique that accelerates the rehabilitation process of a bridge deck, extending its service life with reduced user delays and community disruptions and lowering its life-cycle costs. Previous use of ultra-high performance concrete (UHPC) for bridge applications in the United States has been considered to be efficient and economical because of its superior structural characteristics and durability properties. Full-depth UHPC waffle deck panel systems have been developed over the past three years in Europe and the United States. Subsequently, a single span, 60-ft long and 33-ft wide prototype bridge with full-depth prefabricated UHPC waffle deck panels has been designed and built for a replacement bridge in Wapello County, Iowa. The structural performance characteristics and the constructability of the UHPC waffle deck system and its critical connections were studied through an experimental program at the structural laboratory of Iowa State University (ISU). Two prefabricated full-depth UHPC waffle deck (8 feet by 9 feet 9 inches by 8 inches) panels were connected to 24-ft long precast girders, and the system was tested under service, fatigue, overload, and ultimate loads. Three months after the completion of the bridge with waffle deck system, it was load tested under live loads in February 2012. The measured strain and deflection values were within the acceptable limits, validating the structural performance of the bridge deck. Based on the laboratory test results, observations, field testing of the prototype bridge, and experience gained from the sequence of construction events such as panel fabrication and casting of transverse and longitudinal joints, a prefabricated UHPC waffle deck system is found to be a viable option to achieve the goals of the AASHTO strategic plan.

Biofuel Co-Product Uses for Pavement Geo-Materials Stabilization, TR-582, 2010

The production and use of biofuels has increased in the present context of sustainable development. Biofuel production from plant biomass produces not only biofuel or ethanol but also co-products containing lignin, modified lignin, and lignin derivatives. This research investigated the utilization of lignin-containing biofuel co-products (BCPs) in pavement soil stabilization as a new application area. Laboratory tests were conducted to evaluate the performance and the moisture susceptibility of two types of BCP-treated soil samples compared to the performance of untreated and traditional stabilizer-treated (fly ash) soil samples. The two types of BCPs investigated were (1) a liquid type with higher lignin content (co-product A) and (b) a powder type with lower lignin content (co-product B). Various additive combinations (co-product A and fly ash, co-products A and B, etc.) were also evaluated as alternatives to stand-alone co-products. Test results indicate that BCPs are effective in stabilizing the Iowa Class 10 soil classified as CL or A-6(8) and have excellent resistance to moisture degradation. Strengths and moisture resistance in comparison to traditional additives (fly ash) could be obtained through the use of combined additives (co-product A + fly ash; co-product A + co-product B). Utilizing BCPs as a soil stabilizer appears to be one of the many viable answers to the profitability of the bio-based products and the bioenergy business. Future research is needed to evaluate the freeze-thaw durability and for resilient modulus characterization of BCP-modified layers for a variety of pavement subgrade and base soil types. In addition, the long-term performance of these BCPs should be evaluated under actual field conditions and traffic loadings. Innovative uses of BCP in pavement-related applications could not only provide additional revenue streams to improve the economics of biorefineries, but could also serve to establish green road infrastructures.

Precursor nanoscale modulations in ferromagnets: Modeling and thermodynamic characterization

Using a Ginzburg-Landau model for the magnetic degrees of freedom with coupling to disorder, we demonstrate through simulations the existence of stripelike magnetic precursors recently observed in Co-Ni-Al alloys above the Curie temperature. We characterize these magnetic modulations by means of the temperature dependence of local magnetization distribution, magnetized volume fraction, and magnetic susceptibility. We also obtain a temperature-disorder strength phase diagram in which a magnetic tweed phase exists in a small region between the paramagnetic and dipolar phases.

A Quantitative method for the characterization of lytic metastases of the bone from radiographic images

The aim of our study was to assess the diagnostic usefulness of the gray level parameters to distinguish osteolytic lesions using radiological images. Materials and Methods: A retrospective study was carried out. A total of 76 skeletal radiographs of osteolytic metastases and 67 radiographs of multiple myeloma were used. The cases were classified into nonflat (MM1 and OL1) and flat bones (MM2 and OL2). These radiological images were analyzed by using a computerized method. The parameters calculated were mean, standard deviation, and coefficient of variation (MGL, SDGL, and CVGL) based on gray level histogram analysis of a region-of-interest.Diagnostic utility was quantified bymeasurement of parameters on osteolyticmetastases andmultiplemyeloma, yielding quantification of area under the receiver operating characteristic (ROC) curve (AUC). Results: Flat bone groups (MM2 and OL2) showed significant differences in mean values of MGL ( = 0.048) and SDGL ( = 0.003). Their corresponding values of AUC were 0.758 for MGL and 0.883 for SDGL in flat bones. In nonflat bones these gray level parameters do not show diagnostic ability. Conclusion: The gray level parametersMGL and SDGL show a good discriminatory diagnostic ability to distinguish between multiple myeloma and lytic metastases in flat bones.

Vanadium-modified molecular sieves: preparation, characterization and catalysis

Vanadium-containing molecular sieves are redox catalysts and are good candidates as substitutes for oxide-supported V2O5 in a number of reactions. These materials have the advantage of presenting better dispersion of vanadium species, as well as shape-selective properties and controllable acidities. They may be prepared by one-pot synthesis or by post-synthesis methods and a number of techniques such as diffuse reflectance UV-visible spectroscopy, 51V nuclear magnetic resonance and electron paramagnetic resonance, to name but a few, have been used to characterize these materials. In this review, methods of preparation of vanadium-modified molecular sieves, their characterization and applications in catalysis are discussed.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Synthesis, characterization and application of ion imprinted poly(vinylimidazole) for zinc ion extraction/preconcentration with faas determination

In this paper, we describe the synthesis of an ion imprinted polymer (IIP) by homogeneous polymerization and its use in solid-phase to extract and preconcentrate zinc ions. Under optimal conditions (pH 5.0, preconcentration flow rate of 12.0 mL min-1, and eluted with 1.0 mol L-1 HNO3) this procedure allows the determination of zinc with an enrichment factor of 10.2, and with limits of detection and quantification of 1.5 and 5.0 µg L-1, respectively. The accuracy of our results was confirmed by analysis of tap water and certified reference materials: NIST 1570a (Spinach leaves) and NIST 1515 (Apple leaves).

ISOLATION AND CHARACTERIZATION OF NANOFIBRILLATED CELLULOSE FROM OAT HULLS

The objectives of this work were to investigate the microstructure, crystallinity and thermal stability of nanofibrillated cellulose obtained from oat hulls using bleaching and acid hydrolysis at a mild temperature (45 ºC) followed by ultrasonication. The oat hulls were bleached with peracetic acid, and after bleaching, the compact structure around the cellulosic fibers was removed, and the bundles became individualized. The extraction time (30 or 60 min) did not affect the properties of the nanofibrillated cellulose, which presented a higher crystallinity index and thermal stability than the raw material (oat hulls). The nanocellulose formed interconnected webs of tiny fibers with diameters of 70-100 nm and lengths of several micrometers, producing nanofibers with a relatively high aspect ratio, thus indicating that these materials are suitable for polymer reinforcement.

Synthesis and characterization of Fe(III)-doped ceramic membranes of titanium dioxide and its application in photoelectrocatalysis of a textile dye

Pure and Fe(III)-doped TiO2 suspensions were prepared by the sol gel method with the use of titanium isopropoxide (Ti(OPri)4) as precursor material. The properties of doped materials were compared to TiO2 properties based on the characterization by thermal analysis (TG-DTA and DSC), X-ray powder diffractometry and spectroscopy measurements (FTIR). Both undoped and doped TiO2 suspensions were used to coat metallic substrate as a mean to make thin-film electrodes. Thermal treatment of the precursors at 400ºC for 2 h in air resulted in the formation of nanocrystalline anatase TiO2. The thin-film electrodes were tested with respect to their photocatalytic performance for degradation of a textile dye in aqueous solution. The plain TiO2 remains as the best catalyst at the conditions used in this report.

System-level characterization of Th2 cell development and immune cell responses to ZnO and TiO2 nanoparticles

Asthma and allergy are common diseases and their prevalence is increasing. One of the hypotheses that explains this trend is exposure to inhalable chemicals such as traffi c-related air pollution. Epidemiological research supports this theory, as a correlation between environmental chemicals and allergic respiratory diseases has been found. In addition to ambient airborne particles, one may be exposed to engineered nanosized materials that are actively produced due to their favorable physico-chemical properties compared to their bulk size counterparts. On the cellular level, improper activity of T helper (Th) cells has been connected to allergic reactions. Th cells can differentiate into functionally different effector subsets, which are identifi ed according to their characteristic cytokine profi les resulting in specifi c ability to communicate with other cells. Th2 cells activate humoral immunity and stimulate eradication of extracellular pathogens. However, persistent predominance of Th2 cells is involved in a development of number of allergic diseases. The cytokine environment at the time of antigen recognition is the major factor determining the polarization of a naïve Th cell. Th2 cell differentiation is initiated by IL4, which signals via transcription factor STAT6. Although the importance of this pathway has been evaluated in the mouse studies, the signaling components involved have been largely unknown. The aim of this thesis was to identify molecules, which are under the control of IL4 and STAT6 in Th cells. This was done by using system-level analysis of STAT6 target genes at genome, mRNA and protein level resulting in identifi cation of various genes previously not connected to Th2 cell phenotype acquisition. In the study, STAT6-mediated primary and secondary target genes were dissection from each other and a detailed transcriptional kinetics of Th2 cell polarization of naïve human CD4+ T cells was collected. Integration of these data revealed the hierarchy of molecular events that mediates the differentiation towards Th2 cell phenotype. In addition, the results highlighted the importance of exploiting proteomics tools to complement the studies on STAT6 target genes identifi ed through transcriptional profi ling. In the last subproject, the effects of the exposure with ZnO and TiO2 nanoparticles was analyzed in Jurkat T cell line and in primary human monocyte-derived macrophages and dendritic cells to evaluate their toxicity and potential to cause infl ammation. Identifi cation of ZnO-derived gene expression showed that the same nanoparticles may elicit markedly distinctive responses in different cell types, thus underscoring the need for unbiased profi ling of target genes and pathways affected. The results gave additional proof that the cellular response to nanosized ZnO is due to leached Zn2+ ions. The approach used in ZnO and TiO2 nanoparticle study demonstrated the value of assessing nanoparticle responses through a toxicogenomics approach. The increased knowledge of Th2 cell signaling will hopefully reveal new therapeutic nodes and eventually improve our possibilities to prevent and tackle allergic infl ammatory diseases.

Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

Phenolics of the Inner Bark of Silver Birch: Characterization and Intraspecific Variation

This thesis describes work related to the in-depth characterization of the phenolic compounds of silver birch (Betula pendula) inner bark. Phenolic compounds are the most ubiquitous class of plant secondary compounds. The unifying feature of this structurally diverse group is an aromatic ring containing at least one hydroxyl group. Due to the structural diversity, phenolics have various roles in the plant defense against biotic and abiotic stresses. In addition, they can confer several health-promoting properties to humans. Furthermore, the structural diversity of this class of compounds causes challenges for their analysis. The study species in the present work, silver birch, is economically the most important hard wood species in northern Europe. Its inner bark contains a high level of phenolic compounds and it has shown one of the strongest antioxidant activities among 92 Finnish plant materials. The literature review surveys the diversity and organ specific distribution of phenolic compounds in silver birch as well as the proposed ecological functions of phenolic compounds in nature. In addition, the basis for the characterization of phenolics by mass spectrometry (MS), nuclear magnetic resonance spectroscopy (NMR), and circular dichroism spectroscopy (CD) are reviewed. The objective of the experimental work was to extract, purify, characterize, and quantify the inner bark phenolic compounds. Overall 36 compounds were characterized by MS and ultraviolet spectroscopy (UV). 24 compounds were isolated and their structures confirmed by NMR and CD spectroscopy. Five novel natural compounds were identified. Special emphasis was placed on the establishment of a method for the characterization of proanthocyanidins (PAs). Hydrophilic interaction liquid chromatography (HILIC) was utilized because of its high resolution power and predictable elution order of oligomeric and polymeric PAs according to an increasing degree of polymerization. The combination of HILIC and high-resolution MS detection allowed the identification of procyanidin (PC) polymers up to the degree of polymerization of 22. In addition, a series of oligomeric and polymeric PC monoxylosides were observed for the first time in nature. Season and genotype influenced the quantities of the main inner bark phenolics, yet qualitative differences were not observed. However, manual wounding of the inner bark induced the production of ellagitannins (ETs) in the wounded tissues, i.e. callus. Since ETs were not detected in the intact inner bark, this finding may reflect the capacity of silver birch to exploit ellagitannins in its defense.

Surface characterization of chemically modified fiber, wood and paper

Inorganic-organic sol-gel hybrid coatings can be used for improving and modifying properties of wood-based materials. By selecting a proper precursor, wood can be made water repellent, decay-, moisture- or UV-resistant. However, to control the barrier properties of sol-gel coatings on wood substrates against moisture uptake and weathering, an understanding of the surface morphology and chemistry of the deposited sol-gel coatings on wood substrates is needed. Mechanical pulp is used in production of wood-containing printing papers. The physical and chemical fiber surface characteristics, as created in the chosen mechanical pulp manufacturing process, play a key role in controlling the properties of the end-use product. A detailed understanding of how process parameters influence fiber surfaces can help improving cost-effectiveness of pulp and paper production. The current work focuses on physico-chemical characterization of modified wood-based materials with surface sensitive analytical tools. The overall objectives were, through advanced microscopy and chemical analysis techniques, (i) to collect versatile information about the surface structures of Norway spruce thermomechanical pulp fiber walls and understand how they are influenced by the selected chemical treatments, and (ii) to clarify the effect of various sol-gel coatings on surface structural and chemical properties of wood-based substrates. A special emphasis was on understanding the effect of sol-gel coatings on the water repellency of modified wood and paper surfaces. In the first part of the work, effects of chemical treatment on micro- and nano-scale surface structure of 1st stage TMP latewood fibers from Norway spruce were investigated. The chemicals applied were buffered sodium oxalate and hydrochloric acid. The outer and the inner fiber wall layers of the untreated and chemically treated fibers were separately analyzed by light microscopy, atomic force microscopy and field-emission scanning electron microscopy. The selected characterization methods enabled the demonstration of the effect of different treatments on the fiber surface structure, both visually and quantitatively. The outer fiber wall areas appeared as intact bands surrounding the fiber and they were clearly rougher than areas of exposed inner fiber wall. The roughness of the outer fiber wall areas increased most in the sodium oxalate treatment. The results indicated formation of more surface pores on the exposed inner fiber wall areas than on the corresponding outer fiber wall areas as a result of the chemical treatments. The hydrochloric acid treatment seemed to increase the surface porosity of the inner wall areas. In the second part of the work, three silane-based sol-gel hybrid coatings were selected in order to improve moisture resistance of wood and paper substrates. The coatings differed from each other in terms of having different alkyl (CH3–, CH3-(CH2)7–) and fluorocarbon (CF3–) chains attached to the trialkoxysilane sol-gel precursor. The sol-gel coatings were deposited by a wet coating method, i.e. spraying or spreading by brush. The effect of solgel coatings on surface structural and chemical properties of wood-based substrates was studied by using advanced surface analyzing tools: atomic force microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion spectroscopy. The results show that the applied sol-gel coatings, deposited as thin films or particulate coatings, have different effects on surface characteristics of wood and wood-based materials. The coating which has a long hydrocarbon chain (CH3-(CH2)7–) attached to the silane backbone (octyltriethoxysilane) produced the highest hydrophobicity for wood and wood-based materials.

Characterization Of Process Efficiency Improvement In Laser Additive Manufacturing

Laser additive manufacturing (LAM), known also as 3D printing, has gained a lot of interest in past recent years within various industries, such as medical and aerospace industries. LAM enables fabrication of complex 3D geometries by melting metal powder layer by layer with laser beam. Research in laser additive manufacturing has been focused in development of new materials and new applications in past 10 years. Since this technology is on cutting edge, efficiency of manufacturing process is in center role of research of this industry. Aim of this thesis is to characterize methods for process efficiency improvements in laser additive manufacturing. The aim is also to clarify the effect of process parameters to the stability of the process and in microstructure of manufactured pieces. Experimental tests of this thesis were made with various process parameters and their effect on build pieces has been studied, when additive manufacturing was performed with a modified research machine representing EOSINT M-series and with EOS EOSINT M280. Material used was stainless steel 17-4 PH. Also, some of the methods for process efficiency improvements were tested. Literature review of this thesis presents basics of laser additive manufacturing, methods for improve the process efficiency and laser beam – material- interaction. It was observed that there are only few public studies about process efficiency of laser additive manufacturing of stainless steel. According to literature, it is possible to improve process efficiency with higher power lasers and thicker layer thicknesses. The process efficiency improvement is possible if the effect of process parameter changes in manufactured pieces is known. According to experiments carried out in this thesis, it was concluded that process parameters have major role in single track formation in laser additive manufacturing. Rough estimation equations were created to describe the effect of input parameters to output parameters. The experimental results showed that the WDA (width-depth-area of cross-sections of single track) is correlating exponentially with energy density input. The energy density input is combination of the input parameters of laser power, laser beam spot diameter and scan speed. The use of skin-core technique enables improvement of process efficiency as the core of the part is manufactured with higher laser power and thicker layer thickness and the skin with lower laser power and thinner layer thickness in order to maintain high resolution. In this technique the interface between skin and core must have overlapping in order to achieve full dense parts. It was also noticed in this thesis that keyhole can be formed in LAM process. It was noticed that the threshold intensity value of 106 W/cm2 was exceeded during the tests. This means that in these tests the keyhole formation was possible.