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Nanotechnology has profound applications in healthcare and has improved healthcare research to a large extent. The therapeutic benefits of nanotechnology in the field of medicine have resulted in new areas, such as nanomedicine, nanobiotechnology, etc. Researchers in the field are attempting to find an effective nanoformulation to deliver growth factors, supplements or drugs safely and in a sustained manner at the required site. Their task is to attempt a different drug nanoformulation of existing blockbuster drugs that brings improved efficacy and a therapeutic breakthrough. Thus the ultimate objective of these nanotechnological drug-delivery systems is to fine tune the normal profile of potent drug molecules in the body following their administration to significantly improve their efficacy and also minimize potential intrinsic severe adverse effects. For treatment of breast cancer and non-small-cell lung cancer, Abraxane® (paclitaxel) is employed as a nanoparticular formulation, which increases drug delivery up to 70% in comparison with solvent-based paclitaxel delivery. In this novel nanoformulation, Abraxis Bio Sciences have used Bristol-Meyers Squibb’s blockbuster drug paclitaxel (Taxol) and a very common globular protein bovine serum albumin (BSA). There are numerous nanotechnology-based drug-delivery systems such as nanocrystals, nanoemulsions, lipid or polymeric nanoparticles, liposomes and nanofibers. While nanoemulsions and liposomal formulations did not make significant advances, despite huge research spending, the polymeric nanoparticulate systems show more promise. Nanoparticles of a polymeric nature find application as drug-delivery systems and are advantageous due to their scalability, cost, controlled and targeted delivery, compatibility, degradability, etc. Natural biopolymers are even better than the synthetic polymers in terms of biocompatibility and biodegradability. Nanoparticulate drug formulations alter the pharmokinetic profile of the therapeutic entity and program the release of the drug in sustained or controlled manner. Thus, nanoparticle or nanoformulated drugs outperform conventional systemic delivery in terms of delivery of an encapsulated drug and its sustained release. Slowly and surely nanoformulated drugs are coming onto the market, surpassing systemic delivery, which is believed to be the only mode of administration for a wide range of active pharmaceutical ingredients. Nanofibrous drug-delivery systems are being developed as potential scaffolds in tissue regeneration, wound healing and cancer drug-delivery applications. In this chapter we are going to discuss two promising nanotechnology-based drug-delivery tools, namely electrospun micro- and nanofibers and electrosprayed micro- and nanoparticles, which have a common synthetic procedure mediated by an electrical potential difference.
This chapter introduces the fundamental general equations of the dynamics of free liquid jets in Sections 3.1 and 3.2. The applications of these equations encompass practically all fiber-forming processes from melt spinning, as was sketched out in Section 1.2 in Chapter 2 to melt- and solution blowing, and electrospinning of polymer micro- and nanofibers discussed in detail in Chapters 4 and 5, or drawing of optical fibers outlined in Section 6.5 in Chapter 6. They also form the framework for description of several types of instabilities characteristic of the hydrodynamics of free liquid jets in general and of fiber-forming processes in particular. These include capillary instability (Section 3.3), aerodynamically driven bending instability (Section 3.4) and buckling of liquid impinging onto a wall (Section 3.5).
Mass, momentum and moment-of-momentum balance equations
The dynamics of free liquid jets moving in air, which are characteristic of fiber-forming processes, involve growth of various perturbations. The most notable are driven by surface tension and the dynamic interaction with the surrounding air, as well as electrically driven effects. Theoretical/numerical description of the jet evolution in general, and of perturbed jets in particular, is hindered by the fact that such problems typically involve a three-dimensional, time-dependent evolution of flows with free surfaces, the locations in time of which should also be established. Solving such problems in the framework of the rigorous equations of fluid mechanics, say the Navier–Stokes equations, in most cases would be prohibitively time-consuming, even using super-computers. Additional complicating factors arise due to the rheological complexity of polymer solutions used in fiber forming, as well as the temperature-dependent variation of material properties in nonisothermal situations. Accounting for all these factors together in the framework of the rigorous equations of non-Newtonian fluid mechanics would be tremendously difficult. However, these difficulties can be relatively easily overcome in the framework of a quasi-one-dimensional description of liquid motion in the bending jets. In the works of Entov and Yarin (1980, 1984a) and Yarin (1983, 1993) the general quasi-one-dimensional equations of the straight and bending jets were derived from the integral balances of mass, momentum and moment of momentum, as well as by averaging the three-dimensional equations of hydrodynamics over the jet cross-section.
This chapter outlines several applications of electrospun and solution-blown nanofibers and their mats. In the case of filters and membranes (Section 9.1), industrial application has already begun, but a number of research questions are still open. Applications of nanofiber mats as fluffy electrodes beneficial for fuel cells and Li-ion batteries have recently attracted significant attention and are the focus of Section 9.2. Two recent approaches based on nanofibers were proposed in the field of cooling of high-heat flux microelectronics (Section 9.3) and nanofluidics (Section 9.4).
Filters and membranes
Filter materials are used for air, water and blood filtration, while membranes are used in separation processes, in particular, for bioseparation and pathogen removal for direct blood transfusion. Filters can remove particles, droplets, bacteria, viruses or even individual molecules from a carrier fluid flowing through them, or, in principle, possess advanced detection and response features that are practically absent in today’s products (see Chapter 10).
Chemical warfare differs from conventional warfare, such as explosives, in the sense that the toxicity of the chemicals used is very dangerous to the combatants in the battlefield, or to the civil population being affected during a war or as a result of a terrorist attack. The threat is amplified by concealment and low cost and relatively easy production of these agents, which renders them weapons of mass destruction. It becomes essential in such a situation that soldiers wear protective clothing, respirators, face masks, gloves, etc. Initially German troops unleashed chemical warfare agents, such as mustard agent, HD, during World War I in 1915, and this resulted in much more concern during World War II. Thus research on decontamination of chemical and biological warfare agents (CWAs) has been the subject of serious interest in many research laboratories since World War II. Mustard gas or bis(2-chloroethyl) sulfide is one of the highly cytotoxic, readily methylating CWAs that are regulated under the 1993 Chemical Weapons Convention (CWC). It covalently binds to DNA bases or forms disulfide bonds with the thiol groups. This readily leads to programmed cell death or the mutated DNA leads to cancer. The simultaneous danger associated with this toxic agent is its high skin penetration owing to its high lipophilicity, which results in immediate blister formation and huge uptake through skin within a short duration of exposure (Ivarsson et al. 1992).
Conventional modes of decontamination involve activated charcoal or other such heavy physical adsorbants of the contaminant. When compared with technologies employing conventional catalysts and reactive sorbents, which are specific and sometimes time-consuming, nanotechnology-based nanomaterials are highly reactive, nonselective and multifunctional in character. Current development of nanoparticles such as MgO, Al2O3, Fe2O3, ZnO and TiO2 and their incorporation into nanofibers impart enhanced catalytic, disinfection and sensing capabilities, photo-protection capability, and stain-resistance and self-cleaning properties. The testing of these materials in textiles and protective clothing against CWAs showed that they have potential as replacement technology in such applications.
Fiber-forming processes and the resulting fibers have become a key element in many modern technologies. Today, practically everyone is directly or indirectly using these fibers. Manmade macroscopic fibers are widely used in our garments and many other items of everyday life. On the other hand, much smaller microscopic and, especially, nanofibers are only beginning their path to prominence. The chemical, physical and technological aspects of manufacturing of such fibers are still weakly linked and not fully understood. Two main processes associated with formation of micro- and nanofibers are melt- or solution blowing and electrospinning. They require concerted interaction of synthetic chemistry, responsible for polymers used as raw materials, polymer physics, providing a link to their viscoelastic behavior, rheological characterization of flow properties, non-Newtonian fluid dynamics of polymer solutions and melts, aerodynamics, associated with gas blowing, and electrohydrodynamics, in the case of electrospinning. The key element of the fiber-forming processes is a thin jet of polymer solution or melt, which rapidly changes its three-dimensional configuration under the action of the aerodynamic or electric forces applied to its surface and the internal viscous and elastic stresses. There is a definite and imperative need to interpret and rationalize these phenomena, which requires acquisition of extensive experimental data and establishment of an appropriate theoretical framework as an essential element in the further technological design and optimization. In addition to the above-mentioned broad spectrum of disciplines, this involves different aspects associated with materials science, such as the methods developed in polymer crystallography, and elasticity and plasticity theory. Although many aspects of fiber-forming processes can today be considered as uncovered and well described, either experimentally or theoretically/numerically, numerous important details are still to be explored. The importance of this subject is attested by an exponential increase in scientific publications devoted to microscopic and nanofibers and a broad involvement of the industries associated with fiber media, nonwovens, nano-textured materials, novel biomedical and healthcare products and optical fibers, as well as defense applications.
The monoclinic-to-tetragonal phase transition (~70 °C) in vanadium dioxide (VO2) strongly impacts the infrared properties, which enables its use in applications such as smart window devices. Synthesis of VO2 can be challenging due to the variability of vanadium oxide phases that may be formed. We have employed high-temperature X-ray diffraction (HTXRD) to monitor the reaction process of vanadium oxide precursor powders to form the desired tetragonal VO2 phase. Single-phase tetragonal VO2 was formed within 30 min at 420 °C in flowing N2 gas (~50 ppm O2). The monoclinic-to-tetragonal phase transformation was observed via HTXRD at ~70 °C with the typical ~10 °C hysteresis (i.e. approached from above or below the transition).
As a consequence of substantial advances in computer-aided design and manufacturing technology, engineering parts are no longer restricted to combination of simple geometrical shapes. Implementing complex curved surfaces in engineering components in combination with finite-element geometry optimization has become a prevalent means of designing a part. Measuring residual stresses using X-ray diffraction (XRD) on complex curved surfaces requires further development of current measurement methods. Here we investigate how a laboratory XRD system equipped with a five-axis stage and two-dimensional detector can execute sin2ψ residual stress measurements on curved surfaces. Shadowing that blocks the diffracted beam to reach the detector was avoided using proper rotations and tilting of the sample. A standard video-laser alignment system commonly used to manually place the sample in the center of diffraction was used to also generate virtual maps of the sample's curved surfaces on a fine mesh grid. The geometry was then used for setting the required rotations and tilt angles. A set of diffraction frames collected using this method on a model zirconia dental ceramic, afforded the opportunity to superimpose phase and stresses on a complex geometry. This is a step forward for the XRD technology, and its usefulness applies to many different industries.
The crystal structure and powder X-ray diffraction (XRD) patterns for three skutterudite samples, Fe(Sb2+xTe1−x), x = 0.05, 0.10, 0.20, have been determined. These compounds crystallize in the cubic space group $Im\bar 3$. Te was found to randomly substitute in the Sb site. Because of the fact the covalent radius of Sb is greater than that of Te, a trend of increasing lattice parameter has been observed as the x value in Fe(Sb2+xTe1−x) increases [cell parameters range from 9.10432(4) to 9.11120(3) Å for x = 0.0 to 0.2, respectively]. The Fe–Sb/Te bond distance also increases progressively [from 2.5358(4) to 2.5388(4) Å] as the Te content decreases. While average Sb/Te–Sb/Te distances in the four-membered rings are similar in these three compounds, the average Sb/Te–Sb/Te edge distances in the octahedral framework increase progressively from 3.5845(12) to 3.5900(13) Å. Reference XRD patterns of these three phases have been prepared to be included in the Powder Diffraction File (PDF).
Analytical polarized energy-dispersive X-ray fluorescence (PEDXRF) spectrometry (PEDXRFS) represents a substantial advancement over conventional XRF. The higher signal-to-noise commensurate with background lowering and better energy resolution, permits trace analysis for elements with Z ≥ 11. Concomitantly, improvements in analytical software based on the fundamental parameters (FP) approach have improved accuracies and precisions for standard-less analysis (SLA). Two ceramic and soil standard reference materials (SRMs), 98a-Plastic Clay and GSS-1 powders, differed in their intrinsic matrix properties of grain size, bulk, and surface monolayer densities as well as the elemental concentrations. The SRMs were analyzed as powder and as pellets compacted under the same pressure conditions to double the bulk density. Different geometries represented by the sample cup (10, 15, and 24 mm) and pellet (10, 15, and 25 mm) diameters with the same sample thickness (with differing masses and aspect ratios), as well as (for powder samples only) identical low masses (0.5 g) but with varying thicknesses, were analyzed. PEDXRFS combined with TURBOQUANT® (TQ) as SLA-FP enables good quantitative analysis for powders (Z ≥ 13) even for masses significantly lower than recommended, for soil–ceramic samples. Pellets (Z ≥ 12) yielded the best accuracy factor (AF) at high aspect ratio and thicknesses of the matrix analytical depth. Binder in pellets depreciates the AF. TQ needs to adequately quantitate matrix interferences effects, to improve accuracy in the analysis of low atomic numbers, e.g. Na and Mg.
Residual stress measurements on strongly textured materials using the standard sin2ψ evaluation show significant non-linearities. According to EN 15305 there is currently no existing solution for this problem. A method is presented that solves this problem. It is based on two tools. (i) The use of a one-dimensional detector having a large capture angle that yields the full diffraction profiles at each point of the pole figures. Therefore, some hundreds of d-values can be used for the stress calculation. (ii) Data evaluation with the recently developed generalized sin2ψ method. This has the advantage of being based on a flawless theory (Hooke's law in the special form of Dölle–Hauk's equation) and being able to handle any distribution of measurement directions and any number of measured data. The method was successfully tried out at a sheet of brass with significant texture.
The heteroaryl-substituted triazolopyridines 3-phenyl-7-(pyrazin-2-yl)-[1,2,3]triazolo[1,5-a]pyridine (2) and 3-[6-(pyridazin-3-yl)-pyridin-2-yl]-[1,2,3]triazolo[1,5-a]pyridine (4) have been synthesized and characterized (by HRMS, IR, 1H and 13C NMR, XRPD, melting point). The crystal structures have been solved from laboratory powder X-ray diffraction data with the direct-space strategy TALP for molecular compounds based on fast local least-squares minimizations. The crystal structure confirmed the formation of the tridentate compound 4 from a ring chain isomerization process. The almost planar arrangement of atoms in both the structures favors the presence of intermolecular π–π interactions, although weak C–H···N electrostatic interactions seem to be also important for the stabilization of the structure. Powder diffraction data have also proved to be sensible enough to determine the relative rotations of the six-membered rings despite the weak difference in scattering power between C and N atoms.
In recent years, the emerging areas of nanophotonics and, in particular, plasmonics and metamaterials, have seen an explosion of novel ideas. However, transforming revolutionary designs into practical devices requires a significant amount of effort. The constituent materials in plasmonic structures and metamaterials play a crucial role in realizing useful and efficient devices. Similar to the way silicon shaped the nanoelectronics field, finding the best set of materials for plasmonic and metamaterial devices could revolutionize the field of nanophotonics. As a potential solution, alternative plasmonic materials have recently gained significant attention. Metals, despite being essential components of plasmonic and metamaterial devices, pose many technological challenges toward the realization of practical devices—primarily due to their high optical loss, integration, and fabrication limitations. Hence, searching for an alternative is vital to the success of future nanophotonic devices. Several classes of materials, including doped semiconductor oxides and ceramics, are discussed as potential alternatives to metals that could lead to devices with drastically improved performance and new functionalities by providing low intrinsic loss, tunability, and compatibility with standard semiconductor fabrication processes.
The high specific capacity, reactivity, and abundance of magnesium in the earth’s crust and the relatively good safety features of Mg metal, despite its being a reactive metal, drive intensive efforts to develop rechargeable Mg batteries as a follow-up to the success of Li-ion battery technology. However, Mg anodes cannot function in usual non-aqueous electrolyte solutions. Consequently, it is important to develop unique, complex solutions for reversible Mg metal anodes. Also, finding relevant cathode materials that can reversibly insert bivalent Mg ions is a great challenge. In this article, we review the efforts and success in the development of several families of electrolyte solutions for secondary Mg batteries, in which Mg anodes behave fully reversibly, but also exhibit the necessary wide electrochemical window. We also review attempts to develop positive electrodes for rechargeable Mg batteries. The first generation of secondary Mg batteries has already been demonstrated, but their specific energy density remains relatively low. The challenge now is to develop novel Mg battery prototypes that possess high energy density.
The commercialization of lithium-ion batteries has intimately changed our lives and enabled portable electronic devices, which has revolutionized communications, entertainment, medicine, and more. After three decades of commercial development, researchers around the world are now pursuing major advances that would allow this technology to power the next generation of light-duty, electric, and hybrid-electric vehicles. If this goal is to be met, concerted advances in safety and cost, as well as cycle-life and energy densities, must be realized through advances in the properties of the highly correlated, but separate, components of lithium-ion energy-storage systems.
Considering the need for designing better batteries to meet the rapidly growing demand for large-scale energy storage applications, an aspect of primary importance for battery materials is elemental abundance. To achieve sustainable energy development, we must reconsider the feasibility of a sustainable lithium supply, which is essential for lithium(-ion) batteries. Lithium is widely distributed in the Earth, but is not regarded as an abundant element. Therefore, widespread use of large-scale lithium batteries would be inevitably restricted. Sodium(-ion) batteries are thus promising candidates for large-scale applications because sodium is the most advantageous next to lithium considering its atomic weight, standard potential, and natural abundance. Rechargeable sodium-ion batteries consist of two different sodium insertion materials similar to Li-ion batteries. Sodium insertion materials, especially layered oxides, have been studied since the early 1980s, but not extensively for energy storage devices due to the expanded interest in lithium insertion materials in the 1990s. In recent years, materials researchers have again been extensively exploring new sodium insertion materials to enhance battery performance. This article reviews recent advancements and trends in layered sodium transition metal oxides as positive electrode materials for Na-ion batteries.