Environmental Levels, Sources, and Cancer Risk Assessment of PAHs Associated with PM2.5 and TSP in Monterrey Metropolitan Area.

In this work, the content of polycyclic aromatic hydrocarbons (PAHs) in total suspended particles and particulate matter with an aerodynamic diameter ≤ 2.5 µm (PM2.5) was analyzed using gas chromatography-mass spectrometry. In addition, a sequential chemical analysis of C-rich particles was performed through the parallel coupling of micro-Raman spectroscopy and scanning electron microscopy with X-ray scattering detection. Samples were collected at four sites in the Monterrey metropolitan area, Mexico. A total of 13 PAHs were quantified; indeno(1,2,3-cd)pyrene, chrysene, and benzo(a)anthracene were the most abundant. The total PAH concentrations at the four sampling sites ranged from 1.34 to 8.76 µg/m3. The diagnostic relation of the PAHs indicates that these compounds were emitted by the burning of gasoline and diesel and by the burning of charcoal and biomass. The sequential analysis correlated the morphology and the elemental/molecular composition of the C-rich particles, associated with the PAHs, with their possible emission sources. The estimated lifetime excess cancer risk for inhalation was higher than that established by the World Health Organization, which clearly makes this a potential health risk for the population.

Metal complexes containing natural and and artificial radioactive elements and their applications.

Recent advances (during the 2007-2014 period) in the coordination and organometallic chemistry of compounds containing natural and artificially prepared radionuclides (actinides and technetium), are reviewed. Radioactive isotopes of naturally stable elements are not included for discussion in this work. Actinide and technetium complexes with O-, N-, N,O, N,S-, P-containing ligands, as well π-organometallics are discussed from the view point of their synthesis, properties, and main applications. On the basis of their properties, several mono-, bi-, tri-, tetra- or polydentate ligands have been designed for specific recognition of some particular radionuclides, and can be used in the processes of nuclear waste remediation, i.e., recycling of nuclear fuel and the separation of actinides and fission products from waste solutions or for analytical determination of actinides in solutions; actinide metal complexes are also usefulas catalysts forcoupling gaseous carbon monoxide,as well as antimicrobial and anti-fungi agents due to their biological activity. Radioactive labeling based on the short-lived metastable nuclide technetium-99m ((99m)Tc) for biomedical use as heart, lung, kidney, bone, brain, liver or cancer imaging agents is also discussed. Finally, the promising applications of technetium labeling of nanomaterials, with potential applications as drug transport and delivery vehicles, radiotherapeutic agents or radiotracers for monitoring metabolic pathways, are also described.

Tapered Optical Fiber Detector for a Red Dye Concentration Measurement.

BACKGROUND: In this work, a detector based on optical fiber covered with Multi-Wall Carbon Nanotubes (MWCNTs) was used for sensing and removal of Alizarin from wastewaters. Alizarin is a strong anionic red dye that is part of the anthraquinone dye group. As a rule, this dye is used in the textile industry as a coloring agent. Experiments showed a good efficiency of wastewater treatment. This development could resolve the problem of water contamination with Alizarin red dye. METHODS: We used a single-mode fiber SMF-28e with a core diameter of 8.2 µm and a cladding diameter of 125 µm as a base for the tapered optical fiber detector. An MWCNTs array was synthesized on the tapered optical fiber detector surface by spray pyrolysis Chemical Vapor Deposition (CVD) method at 800oC for 20 min inside a tubular furnace, using ferrocene solution in toluene as a catalyst precursor. The formed structure was applied for Alizarin detection in water. RESULTS: According to the patent studies, the nanotubes completely covered the optical fiber surface and the array had a high density with minimal distance between nearby nanotubes. Carbon nanotubes were oriented along the radius of the optical fiber. The average diameter of carbon nanotubes was 24 nm. The optical absorbance levels increased as the Alizarin concentration increased from 50 mg/L to 1000 mg/L. MWCNTs on the optical fiber tapered section adsorbed the dye molecules from aqueous solution. Three intensive absorption bands with the wavelength of the 700, 714 and 730 nm appeared and their intensity increased as the Alizarin concentration increased. The accumulated Alizarin can be recovered by multiple immersing clean water. This property may make tapered optical fiber detector reusable and increase the economic expediency of the sensor application. CONCLUSION: The study showed higher Alizarin adsorption efficiency of the tapered optical fiber detector compared with relative detectors. This structure can be reusable for dye detection. Removal efficiency for Alizarin reached 98.6%, which makes the tapered optical fiber detector promising for wastewater treatment and dye elimination.

Sequential SEM-EDS, PLM, and MRS Microanalysis of Individual Atmospheric Particles: A Useful Tool for Assigning Emission Sources.

In this work, the particulate matter (PM) from three different monitoring stations in the Monterrey Metropolitan Area in Mexico were investigated for their compositional, morphological, and optical properties. The main aim of the research was to decipher the different sources of the particles. The methodology involved the ex situ sequential analysis of individual particles by three analytical techniques: scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), polarized light microscopy (PLM), and micro-Raman spectroscopy (MRS). The microanalysis was performed on samples of total suspended particles. Different morphologies were observed for particles rich in the same element, including prismatic, spherical, spheroidal, and irregular morphologies. The sequential microanalysis by SEM-EDS/PLM/MRS revealed that Fe-rich particles with spherical and irregular morphologies were derived from anthopogenic sources, such as emissions from the metallurgical industry and the wear of automobile parts, respectively. In contrast, Fe-rich particles with prismatic morphologies were associated with natural sources. In relation to carbon (C), the methodology was able to distinguish between the C-rich particles that came from different anthopogenic sources-such as the burning of fossil fuels, biomass, or charcoal-and the metallurgical industry. The optical properties of the Si-rich particles depended, to a greater extent, on their chemical composition than on their morphology, which made it possible to quickly and accurately differentiate aluminosilicates from quartz. The methodology demonstrated in this study was useful for performing the speciation of the particles rich in different elements. This differentiation helped to assign their possible emission sources.

Preparation of Tubular Forest-like and Other Carbon Structures Using Distinct Carbon Sources and Catalyst Concentrations.

BACKGROUND: In this work, various carbon nanotubes (MWCNTs) were synthetized by the spray pyrolysis method. Resulting nanoforest-like and bamboo-like carbon nanotubes, as well as Yjunctions of carbon nanotubes, possess different shapes and morphology, depending on the kind of carbon source used and on the number of iron particles on the furnace tube surface, which derives from various concentrations of ferrocene catalyst. METHODS: We used the spray pyrolysis method, using different carbon sources (n-pentane, n-hexane, nheptane, and acrylonitrile) as precursors and two different concentrations of ferrocene as a catalyst. Reactions of hydrocarbon decomposition were carried out at 800oC. The solution (hydrocarbon and catalyst) was introduced with a syringe, with a flow of 1 mL/min and the synthesis time of 20 min. Argon was used as carrier gas (1000 L/min). Preheater and oven temperatures were selected 180°C and 800°C, respectively, for each carbon source. The solution passed into a quartz tube placed in an oven. RESULTS: According to the studies of carbon nanostructures, obtained from different precursors, it can be proposed that the structures synthesized from n-pentane, n-hexane and n-heptane are formed by the root growth method. The growth mechanism of MWCNTs was studied, confirming that the root growth formation of products takes place, whose parameters also depend on furnace temperature and gas flow rate. Dependence of interlayer distance (0.34-0.50 nm) in the formed MWCNTs on precursors and reaction conditions is also elucidated. The formation of carbon nanotubes does not merely depend on carbon precursors but also has strong correlations with such growth conditions as different catalyst concentrations, furnace temperature and gas flow rate. Such parameters as the amount of catalyst and synthesis time are also needed to be considered, since they are important to find minor values of these parameters in the synthesis of forest-like carbon nanotubes and other structures such as bamboo-like carbon nanotubes and Y-junctions in carbon nanotubes. CONCLUSION: As a result of the evaluation of interlayer distance in CNTs formed from different carbon sources, a standard value of interlayer distance normally for CNTs is 0.34 nm and for pentane A (0.5 wt.%), hexane B (1 wt.%), toluene A (0.5 wt.%) the range is from 0.33 to 0.35 nm. In case of pentane and acrylonitrile, under an increase of the catalyst concentration, an increase of the value of interlayer distance takes place from 0.35 and 0.4 to 0.4 and 0.5 nm, respectively, but for hexane, heptane and cyclohexane, an increase of the catalyst concentration maintains the same interlayer distance. This involves the use of lower quantities of raw materials and, therefore less cost for obtaining these materials.

Evaluation of the Conditions for the Synthesis of Silver Nanoparticles from Orange Peels and its Antibacterial Effect.

AIMS: To use an agroindustrial waste (orange peels) as a source of polyphenols as a reducing medium for obtaining silver nanoparticles by greener method. BACKGROUND: Several techniques have been employed for AgNPs synthesis, nevertheless, most of them involve the use of toxic chemicals in the process. The use of fungi, bacteria, and plant extracts as subtracts for green synthesis is an ecofriendly alternative, although hypothetic, route for AgNPs large scale synthesis. In the case of plant extracts, it is believed that polyphenols are the biomolecules responsible for the reduction and stabilization of the Ag+ ions into AgNPs, being a sustainable and ecological option; polyphenols could be obtained from plant waste and agroindustrial subproducts. OBJECTIVE: To develop an efficient, greener, and low-cost method of AgNPs production using natural products. METHODS: The basic principle of silver nanoparticles synthesis is the interaction in a mixture of silver nitrate (source of Ag+ ions) and the orange peel extract (reducing and stabilizing agent) under certain conditions. Five treatments were carried out, evaluating several parameters during AgNPs synthesis such as pH, orange peel extract-silver nitrate ratio, time and conditions of incubation, irradiation of UV light, irradiation of microwave, and temperature. RESULT: The synthesis of silver nanoparticles from an agroindustrial waste as the orange peel was successfully carried out and checked by visual evaluation, UV-Vis spectroscopy, and EDS analysis. The particle size was estimated between 42.82 nm to 151.75 nm, having a spherical and ovoid morphology. DISCUSSION: Through the analysis of several synthesis conditions, it has become possible to establish a suitable treatment to increase antibacterial yield and evaluate morphology and size traits in order to acquire the best conditions for a future industrial scale synthesis. CONCLUSION: The orange peel aqueous extract resulted as a great source of polyphenols, allowing the successful synthesis of silver nanoparticles in mild conditions. Thus, obtained AgNPs revealed an increased antibacterial effect and potential against Gram-positive bacteria such as Staphyloccocus aureus.

Synthesis of Copper(II) Trimesinate Coordination Polymer and Its Use as a Sorbent for Organic Dyes and a Precursor for Nanostructured Material.

Several important synthesis pathways for metal-organic frameworks (MOFs) were applied to determine how the synthesis methods and conditions affect the structure and adsorption capacity of the resulting samples. In the present work, three different synthesis routes were used to obtain copper trimesinate coordination polymer: Slow evaporation (A), solvothermal synthesis using a polyethylene glycol (PEG-1500) modulator (B), and green synthesis in water (C). This MOF was characterized by elemental analysis, infrared spectrometry, X-ray diffraction, scanning electron microscopy, thermogravimetry and volumetric nitrogen adsorption/desorption. The samples have permanent porosity and a microporous structure with a large surface area corresponding to the adsorption type I. The obtained MOF was tested as a sorbent to remove organic dyes methylene blue (МВ), Congo red (CR) and methyl violet (MV) as examples. Dye adsorption followed pseudo-first-order kinetics. The equilibrium data were fitted to the Langmuir and Freundlich isotherm models, and the isotherm constants were determined. Thermodynamic parameters, such as changes in the free energy of adsorption (ΔG0), enthalpy (ΔH0), and entropy (ΔS0), were calculated. Thermolysis of copper trimesinate leads to the formation of carbon materials Cu@C with a high purity.

Development of Sorbent Materials based on Polymer Waste and their Compounds with Nanomaterials for Oil Spill Remediation.

AIMS: The purpose of this work was to obtain a hydrophobic sorbent material with potential applications in oil spill remediation. BACKGROUND: The accidents due to oil spills cause long-term ecological damage, especially in the aquatic environment. The cleaning of oil spills can be carried out by many methods and techniques, being absorbents the most attractive due to the possibility of recovery and complete elimination of the hydrocarbons in situ from the water surface. In recent years, interest in polymeric materials for oil spill remediation has increased due to its low cost, high stability, and recyclability. OBJECTIVE: The objective of this work was the development of sorbent materials based on polymer wastes, such as Polyethylene Terephthalate (PET), obtained from recycled bottles, and recycled Polyurethane (PU), for its application in the recovery of oil spills. METHODS: Sorbent materials were prepared from polymer wastes, using salt molds for the formation of porous materials with a composition of PU of 5, 10 and 15%, which were subsequently hydrophobized using carbon nanotubes or silica nanoparticles by dip-coating technique. RESULTS AND DISCUSSION: The obtained hydrophobic sorbent materials were characterized by Scanning Electron Microscopy (SEM) and Infrared Spectroscopy (FTIR). The resulting absorbent has shown capacity to separate oil from water; the best result was obtained by the sponge of PET-PU (10% PU) hydrophobized with a suspension with low multi-wall carbon nanotubes (MWCNTs) concentration, obtaining an absorption capacity of 2.01 g/g. CONCLUSION: Besides the standard sorption capacity, these cheap sorbent materials had interesting properties like low density, high hydrophobicity and buoyancy, which could be applied in other applications related to solving oil spills.

Hydrophobization of Kraft-type Cellulose and Microfiber Cellulose Obtained from Soybean Husk in Ultrasonic Field.

BACKGROUND: The addition of nanoparticles to cellulose paper can improve its mechanical strength, chemical stability, biocompatibility and hydrophobic properties. Silica nanoparticles are known to be inert, hydrophobic, biocompatible, biodegradable and have a good distribution in being deposited on surfaces. The main characteristics of 20 nm SiO2 nanoparticles are good chemical and thermal stability with a melting point of 1610-1728°3C, a boiling point of 2230°C with a purity of 99.5%. OBJECTIVE: To carry out the hydrophobization of paper based on Kraft cellulose and on cellulose obtained from soybean husk with 20-nm size SiO2 nanoparticles and to study hydrophobicity, morphology and topography of the prepared composites. METHODS: The ground and roasted soybean husk was treated with a NaOH, washed and dried. Hydrophobization of paper was carried in aqueous medium by SiO2 addition in weight ratios "paper-SiO2" of 0.01-0.05 wt.%, stirring, filtration and drying. The obtained cellulose sheet composites were characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), FTIRspectroscopy, Mullen proofs of hydrophobicity, and contact angle measurements. RESULTS: The mechanical properties of paper nanocomposites (tensile strength and compression) increased considerably by varying the concentrations. The tensile strength increased by 41-46% and the compressive strength increased by 55-56%. The existence of fiber nanofoils, good adhesion of 20-nm SiO2 nanoparticles to the paper surface, and their homogeneous distribution were observed. CONCLUSION: Cellulose was successfully obtained from soybean husk, applying the alkaline-based extraction method. A good reinforcement of cellulose fibers is observed due to the outstanding characteristics of the silicon dioxide nanoparticles.

Metal Phthalocyanines as Catalyst Precursors of Metallated Carbon Nanotubes.

BACKGROUND: The addition of nanoparticles to cellulose paper can improve its mechanical strength, chemical stability, biocompatibility and hydrophobic properties. Silica nanoparticles are known to be inert, hydrophobic, biocompatible, biodegradable and have a good distribution being deposited on surfaces. The main characteristics of 20 nm SiO2 nanoparticles are good chemical and thermal stability with a melting point of 1610-1728°C, a boiling point of 2230°C with a purity of 99.5%. OBJECTIVE: To carry out the hydrophobization of paper based on Kraft cellulose and on cellulose obtained from soybean husk with 20-nm size SiO2 nanoparticles and to study hydrophobicity, morphology and topography of the prepared composites. Few relevant patents to the topic have been reviewed and cited. METHODS: The ground and roasted soybean husk was treated with a NaOH, washed and dried. Hydrophobization of paper was carried in aqueous medium by SiO2 addition in weight ratios "paper-SiO2 " of 0.01-0.05 wt.%, stirring, filtration and drying. The obtained cellulose sheet composites were characterized by Scanning Electron Microscopy (SEM), Transmisión Electron Microscopy (TEM), FTIRspectroscopy, Mullen proofs of hydrophobicity, and contact angle measurements. RESULTS: The mechanical properties of paper nanocomposites (tensile strength and compression) increased considerably by varying the concentrations. The tensile strength increased by 41-46% and the compressive strength increased by 55-56%. The existence of fiber nanofoils, good adhesion of 20-nm SiO2 nanoparticles to the paper surface, and their homogeneous distribution were observed. CONCLUSION: Cellulose was successfully obtained from soybean husk, applying the alkaline-based extraction method. A good reinforcement of cellulose fibers is observed due to the outstanding characteristics of the silicon dioxide nanoparticles.

A Comparison of Different Methods of MWCNTs Metalation in a Single Step Using Three Different Silver-containing Compounds.

BACKGROUND: Synthesis and applications of Ag-coated carbon nanotubes are currently under intensive research, resulting in a series of recent patents. Silver nanoparticles are normally obtained from silver nitrate. However, there are also other silver-containing compounds that can facilitate the production of silver nanoparticles, such as silver(I) acetate and silver(II) oxide. Being combined with carbon nanotubes, silver nanoparticles can transfer to them some of their useful properties, such as conductivity and antibacterial properties, and contribute to improving their dispersion in solvents. OBJECTIVE: To apply three different silver-containing precursors of Ag nanoparticles for the decoration of carbon nanotubes and study the morphology of formed composites by several methods. METHOD: Three different silver compounds were used as Ag source to carry out the functionalization and decoration of carbon nanotubes under ultrasonic treatment of the reaction system, containing, commercial carbon nanotubes, organic peroxides as oxidants or hydrazine as a reductant, and a surfactant. Resulting samples were analyzed by XRD and XPS spectroscopy, as well as TEM and SEM microscopy to study the morphology of formed nanocomposites. RESULTS: Silver nanoparticles can be produced without the presence of a reducing agent. Applying hydrazine, as a reducing agent, it is possible to obtain functionalized carbon nanotubes doped with silver nanoparticles, in which their sizes are smaller (1-5 nm) compared to those obtained without using hydrazine. CONCLUSION: Silver nanoparticles having a size range between 2-60 nm can be produced without the presence of a reducing agent. The use of a reducing agent, such as hydrazine, affects the size of silver nanoparticles.

Greener synthesis of chemical compounds and materials.

Modern trends in the greener synthesis and fabrication of inorganic, organic and coordination compounds, materials, nanomaterials, hybrids and nanocomposites are discussed. Green chemistry deals with synthesis procedures according to its classic 12 principles, contributing to the sustainability of chemical processes, energy savings, lesser toxicity of reagents and final products, lesser damage to the environment and human health, decreasing the risk of global overheating, and more rational use of natural resources and agricultural wastes. Greener techniques have been applied to synthesize both well-known chemical compounds by more sustainable routes and completely new materials. A range of nanosized materials and composites can be produced by greener routes, including nanoparticles of metals, non-metals, their oxides and salts, aerogels or quantum dots. At the same time, such classic materials as cement, ceramics, adsorbents, polymers, bioplastics and biocomposites can be improved or obtained by cleaner processes. Several non-contaminating physical methods, such as microwave heating, ultrasound-assisted and hydrothermal processes or ball milling, frequently in combination with the use of natural precursors, are of major importance in the greener synthesis, as well as solventless and biosynthesis techniques. Non-hazardous solvents including ionic liquids, use of plant extracts, fungi, yeasts, bacteria and viruses are also discussed in relation with materials fabrication. Availability, necessity and profitability of scaling up green processes are discussed.

Influence of microwave treatment on the dehydration of crystallohydrates of iron, cobalt and nickel flourides.

Dehydration of inorganic crystallohydrates (Fe2F x 7.1H2O, FeF3 x 3.82O, CoF2 x 4H2O, and NiF2 x 4.4H2O) in the conditions of microwave treatment (MWT) is studied. It is shown that in all cases the MWT changes the defectness of crystals, as well as their thermal stability. The dehydration schemes for the compounds above are presented.

Less-Common Nanostructures: Nanobuds: A Micro-Review.

BACKGROUND: Synthesis, properties, structural peculiarities, and applications of nanobuds and related nanostructures are discussed. In addition, few relevant patents to the topic have been reviewed and cited. According to observed properties and those predicted by DFT calculations, the nanobuds are semiconducting and stable in normal conditions, can accept adatoms and molecules. They contain a relatively chemically inert carbon nanotubes and more active fullerene species and can be compatible with a variety of other materials, in particular polymers. In addition to nanobuds for SWCNTs, the nanobuds with graphene, small fullerenes or metal nanobud-like structures are also known. METHOD: We have undertaken an extensive search of bibliographic databases for peer-reviewed research literature using a focused review question and inclusion/exclusion criteria. The characteristics of screened papers were described and critically compared. RESULTS: Thirty-six papers were included in the review, mainly from high-impact international journals. The published articles correspond to the range 2006-2016; the term "nanobuds" appeared in 2006 after their discovery. The reports included approaches of the synthesis of carbon nanobuds, their formation mechanism, in situ engineering, different modes of attachment of fullerene on carbon nanotubes, DFT and MD calculations, nanobuds containing small fullerenes and graphene nanobuds, information about related noble metal nanobuds, and applications of carbon nanobuds. CONCLUSION: The findings of this review confirm the importance of novel less-common nanostructures on the basis of carbon for fundamental science, their unusual properties and current and possible applications.

Radioactive nanoparticles and their main applications: recent advances.

Selected nanoparticles and nanocomposites on the basis of radioactive elements are reviewed. Isotopes of metallic gold, iodine and technetium salts, CeO2 and other lanthanide and actinide compounds, as well as several p- (P, C, F, Te) and d- (Fe, Co, Cu, Cd, Zn) elements form most common radioactive nanoparticles. Methods for their fabrication, including dopation with radionuclides and neutron/proton/deuteron activation, are discussed. These nanocomposites possess a series of useful applications, in particular in biology and medicine, including cancer therapeutics, drug delivery systems and radiotracers, as well as in the studies of several catalytic processes and materials structure.

The greener synthesis of nanoparticles.

In this review, we examine 'greener' routes to nanoparticles of zerovalent metals, metal oxides, and salts with an emphasis on recent developments. Products from nature or those derived from natural products, such as extracts of various plants or parts of plants, tea, coffee, banana, simple amino acids, as well as wine, table sugar and glucose, have been used as reductants and as capping agents during synthesis. Polyphenols found in plant material often play a key role in these processes. The techniques involved are simple, environmentally friendly, and generally one-pot processes. Tea extracts with high polyphenol content act as both chelating/reducing and capping agents for nanoparticles. We discuss the key materials used in the field: silver, gold, iron, metal alloys, oxides, and salts.

Computational chemistry calculations of stability for bismuth nanotubes, fullerene-like structures and hydrogen-containing nanostructures.

Using molecular mechanics (MM+), semi-empirical (PM6) and density functional theory (DFT) (B3LYP) methods we characterized bismuth nanotubes. In addition, we predicted the bismuth clusters {Bi(20)(C(5V)), Bi(24)(C(6v)), Bi(28)(C(1)), B(32)(D(3H)), Bi(60)(C(I))} and calculated their conductor properties.

State of the art of the bi- and trimetallic nanoparticles on the basis of gold and iron.

Recently reported patents and experimental articles on the synthesis, properties, and main applications of core-shell nanoparticles, containing iron or its oxides and gold, as well as trimetallic systems on their basis, are reviewed. These nanostructures were obtained by a series of methods, including reduction in reverse micelles, decomposition of organometallic compounds, electron-beam, laser and gamma-irradiation, sonolysis and electrochemical methods. (Fe or Fe(X)O(y))/Au nanoparticles are subject to be functionalized with organic moieties, may expand their main applications, which consist of catalysis, biological and biomedical uses.

Synthetic techniques and applications of activated nanostructurized metals: highlights up to 2008.

Main methods for current production of metallic nanoparticles in different forms are reviewed. Metal nanoparticles are generally synthesized in form of nanopowders, nanowires, nanoclusters, nanorods, nanobelts, and nanofilms. Bi- and trimetallic clusters and alloys are also of an interest. Examined techniques for obtaining metal nanoparticles include chemical vapor and electrochemical deposition, use of gamma-, X-ray, laser and UV-irradiation, ultrasonic and microwave treatment, electron- and ion-beams, arc discharge, decomposition and reduction of metal salts and complexes, and biosynthesis. A special attention is paid to Rieke and supported metals.