Search

Background: Despite increased awareness for promoting diversity, orthopaedics remains one of the least diverse specialties. Studying health care providers in women’s professional sports provides a unique opportunity to analyze gender and racial diversity. Hypotheses: There would be low female and minority representation across the various women’s professional sports leagues. There would be an increased number of female head certified athletic trainers (ATCs) when compared with head team physicians (HTPs). Study Design: Cross-sectional study. Methods: We evaluated the perceived race and sex of designated HTPs and ATCs in the Women’s National Basketball Association, National Women’s Soccer League, and National Women’s Hockey League. Type of doctorate degree, specialty, and years in practice were also collected. Kappa (κ) coefficient measurements were used to determine interobserver agreement on race. Categorical and continuous variables were analyzed using chi-square and t tests, respectively. Results: There were significantly more female ATCs than female HTPs (74.1% vs 37.5%; P = .01). Minority representation between HTPs and ATCs was not significantly different (20.8% vs 40.7%; P = .13). Black HTPs (12.5%) and Black ATCs (22.2%) composed the largest proportion among the minority groups. There was high interobserver agreement of perceived race across HTPs (κ = 1.0) and ATCs (κ = 0.95). Conclusion: Although there were more female ATCs than HTPs in women’s professional sports leagues, both cohorts lack perceived racial diversity. These data suggest an opportunity for diversification in medical and training staff of women’s professional sports.

Fetal lymphangioma is an uncommon congenital malformation that is mainly comprised of the subcutaneous tissue of the neck. This malformation can develop in other areas like the thoracic and axillary regions, though rarely. We report 6 consecutive cases of lymphatic malformation in a fetal center in Dominican Republic. In our case series fetal chest lymphangiomas were present in 2 fetuses. In addition, 2 cases of axillary lymphangiomas also involved the thoracic region. Adequate management by a multidiciplinary team is necessary to provide a better approach to delivery.

Background Context The association between low back pain and lumbar disc degeneration is not fully characterized. One potentially overlooked factor of this process is the lumbar multifidus, which plays a role in segmental stabilization and locomotion. Previous reports have shown multifidus degeneration to be associated with disc degeneration. The goal of this study was to develop a mouse model of advanced lumbar disc degeneration to recapitulate the pathology of the human multifidus in patients with lumbar disc degeneration and low back pain. Methods C57BL/6 mice underwent a left anterolateral approach to the lumbar spine and disc puncture with a micro scalpel at L5/6 and L6/S1. Mice underwent behavioral analysis and functional gait testing. A subset of mice underwent 14T T2-weighted MRI to assess disc degeneration and paraspinal muscle quality. At 6 and 15 weeks, mice were sacrificed, and the multifidus muscles were harvested and divided into proximal and distal segments relative to disc injury. Histological analysis was performed to assess muscle degeneration, fiber type, and macrophage density. Fibroadipogenic progenitors (FAPs) were isolated for gene expression analysis with qPCR. Results MRI demonstrated decreased intervertebral disc signal and paraspinal muscle atrophy at 6 weeks, with progressive degeneration and atrophy at 15 weeks. Disc injury resulted in delayed functional recovery and impaired gait. Histology demonstrated progressive multifidus fibrofatty degeneration between 6 and 15 weeks. CD68+ macrophage density was increased at 6 weeks but not 15 weeks. FAPs exhibited increased fibrotic and adipogenic gene expression at 6 weeks compared to sham with less of a difference in gene expression by 15 weeks. Conclusions We have developed a mouse model of disc injury-mediated paraspinal muscle degeneration that recapitulates features of degenerative muscle pathology observed in patients with lumbar disc degeneration, and highlights the role of FAPs in mediating fibrofatty muscle degeneration after disc injury.

Background: Discrepancies in race, ethnicity, and sex among health care providers and their patients have been shown to affect the patient-provider relationship as well as the quality of care. Currently, minority and female representation among orthopaedic surgeons remains low. Given the large proportion of minority athletes and their degree of public visibility, professional sports serves as an important arena within which to analyze the diversity of health care providers. Purpose: To describe and evaluate the current level of diversity of head team physicians (HTPs) and head athletic trainers (ATCs), primarily in terms of race and sex, within men’s professional sports leagues in the United States. Study Design: Cross-sectional study. Methods: Five major US professional sports leagues were evaluated: National Basketball Association, National Football League, National Hockey League, Major League Soccer, and Major League Baseball. Publicly available data were collected to identify the HTPs and head ATCs for each team within these leagues. Two independent observers analyzed photographs and names of these individuals to determine his or her perceived race and sex, with disagreements being resolved by a third independent observer. Other physician data collected included graduate degree(s), specialty, and number of years in practice. Kappa coefficients (κ) were employed to evaluate interobserver reliability. Chi-square, Fisher exact, and t tests were used for statistical comparisons across leagues. Results: The κ values for perceived race were 0.85 for HTPs and 0.89 for head ATCs, representing near-perfect interobserver agreement. Minorities comprised 15.5% of HTPs and 20.7% of ATCs ( P = .24). Women comprised 3.9% of HTPs and 1.3% of head ATCs ( P = .017). The majority of HTPs were orthopaedic surgeons with medical doctorates. Female HTPs had significantly fewer years in practice compared with male HTPs (15.0 ± 4.9 vs 23.1 ± 9.6; P = .04). Conclusion: The lead physicians and athletic training providers for men’s professional sports teams demonstrated low rates of minority and female representation, denoting a highly visible area for discussing the role of increased diversity in health care.

The electricity sector is facing a deep and fast process of change following the energy transition pace. In the next decade, the expected amount of renewables in the system will increase dramatically. One of the main concerns of system operators (such as Red Electrica de Espana -REE-) is the decrease of system inertia and, in general, assuring frequency stability in the future system. This article presents how REE has developed and tuned a model that allows frequency stability accurate analyses about RoCoF, frequency nadir and steady state frequency, in yearly basis taking only as input data the hourly dispatch of market model simulations and considering the peripheral position of the Iberian Peninsula within the Continental Europe system.

The high prevalence of rotator cuff tears poses challenges to individual patients and the healthcare system at large. This orthopedic injury is complicated further by high rates of retear after surgical repair. Outcomes following repair are highly dependent upon the quality of the injured rotator cuff muscles, and it is, therefore, crucial that the pathophysiology of rotator cuff degeneration continues to be explored. Fibro-adipogenic progenitors, a major population of resident muscle stem cells, have emerged as the main source of intramuscular fibrosis and fatty infiltration, both of which are key features of rotator cuff muscle degeneration. Improvements to rotator cuff repair outcomes will likely require addressing the muscle pathology produced by these cells. The aim of this review is to summarize the current rotator cuff degeneration assessment tools, the effects of poor muscle quality on patient outcomes, the role of fibro-adipogenic progenitors in mediating muscle pathology, and how these cells could be leveraged for potential therapeutics to augment current rotator cuff surgical and rehabilitative strategies.

High-cycle fatigue (HCF) tests were conducted on samples fabricated by two powder-bed additive manufacturing techniques. Samples were tested with as-produced surfaces and after various non-contact surface improvement treatments. Ti-6Al-4V samples were made using both electron beam melting (EBM) and selective laser melting (SLM), while Inconel 625 was fabricated using SLM. Ti-6Al-4V was treated with a commercial chemically accelerated vibratory polishing process, with target material removal of approximately 200 µm from each surface for EBM samples and 100 µm for SLM samples. This technique led to increases in both the number of cycles before failure at a given loading condition and endurance limit (at 107 cycles) compared to samples with as-produced surfaces. The results are interpreted as the reduction in elastic stress concentration factor associated with surface defects where fatigue cracks initiate. SLM 625 was treated with both an abrasive polishing method and laser surface remelting. Both methods led to improvements in surface roughness, but these did not lead to improvements in fatigue properties of SLM 625. For abrasive polished samples, the combination of improved measured surface roughness without fatigue property enhancement suggests that surface material is removed, but the roots of surface defects, where fatigue cracks initiate, were left intact. For laser treatment, the remelted surface layer retained a rapidly solidified microstructure that did not increase the number of cycles before crack initiation even though the surface was smoother compared to the surface prior to polishing.

Polymeric nanocomposites have gained attention over the past few decades for their enhanced thermal stability and degradation. However, the reactions involved in a polymer nanocomposite can vary significantly from system to system, making it necessary to investigate novel nanofillers in search for more effective materials. Nanocomposites comprised of alpha-zirconium phosphate (ZrP) nanosheets in poly (methyl methacrylate) (PMMA) were prepared with a wide range of nanoparticle loadings (0, 5, 10, and 30 wt.% ZrP in PMMA). The ZrP nanocomposites were characterized using UV-visible spectroscopy (UV-vis), x-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Nanocomposites were well dispersed and optically transparent as shown by XRD and UV-vis. However in the UV region, transparent ZrP nanocomposites possessed excellent UV scattering properties, significantly reducing the transmittance of UV-light, while remaining transparent to the visual spectrum. Thermal stability studies using TGA and DTG showed the peak mass loss rate (PMLR) was reduced by 10% and simultaneously shifted to higher temperatures by 41 °C. Since the nanocomposites in this work cover such a large range of ZrP loadings, large amounts of high-temperature residuals were encountered after TGA studies, indicating that the high loading ZrP nanocomposites are largely noncombustible. In addition, DSC studies showed that ZrP content does affect the glass transition temperature, but not enough to limit the application in which ZrP nanocomposites could be used. These results point to ZrP nanocomposites being useful as polymer replacements, behaving like polymers until the event of a fire, in which case they are largely noncombustible.

The additive manufacturing (AM) field is growing at an accelerated rate, with new printing techniques and modifications of existing technologies coming out every day. Powder bed fusion (PBF) stands out from the many AM technologies as the main technique to employ when building metal components for aerospace applications. The focus of this chapter will be the texture of the surfaces produced by PBF of metal components and their characterization. The surface texture of these components is highly complex and unique; however, the distinctiveness of these surface textures needs to be understood in order to do an accurate characterization of them. Our discussion will include best practices to characterize the surface texture of PBF-built components based on the surface properties of the printed component, the optimization of the surface textures during the building process, and the use of different surface finishing techniques (post-processing) to yield smooth surfaces.

Molybdocene dichloride (Cp2MoCl2), a metallocene dichloride currently being evaluated as potential anti-cancer drug, has been intercalated into zirconium phosphate, an inorganic layered nanomaterial. Hydrolysis of the chloride ligands appears to occur, leading to the formation of the monocation species ([Cp2Mo(H2O)(OH)]+), which intercalates into the ZrP layers by ion exchange. IR spectroscopy, X-ray powder diffraction (XRPD), UV–Vis spectrophotometry, scanning electron microscopy with energy dispersive X-ray spectroscopy, NMR spectroscopy, and thermogravimetric analysis were used to confirm the presence of the metallocene between the layers of zirconium phosphate. The XRPD data indicates that a new intercalated phase with an expanded interlayer distance of 11.0 A was obtained; thermogravimetric analysis indicates up to 64% loading in the context of molar ratio (0.64 mol per ZrP formula unit) or 32% exchange capacity. Further evidence for intercalation was obtained from 31P MAS NMR experiments. IR spectroscopy confirms the presence of the cyclopentadienyl bearing metallocene in the layers.

Immobilized catalysts can be obtained by using a linker to bind a homogeneous catalyst to a solid support. Ideally, immobilized catalysts combine the advantages of homogeneous and heterogeneous catalysts. Porous supports such as silica result in optimal recyclability, however, the catalytic reactions are slowed down by pore diffusion. Here, non-porous zirconium phosphate nanoplatelets (ZrP) are used as support material to bridge the gap between homogeneous and immobilized catalysts. ZrP nanoplatelets provide sufficient outside surface area, while still being easily separable from the reaction mixtures. First, a phosphine linker containing an ethoxysilyl group, (EtO) 3 Si(CH 2 ) 3 PPh 2 ( 1 ), is reacted with ZrP to give the phosphine-modified 1i . Addition of Wilkinson's catalyst ClRh(PPh 3 ) 3 to 1i gives, via ligand exchange, the immobilized catalyst 1i – Rh . In the absence of pore diffusion the catalytic hydrogenation of 1-dodecene using 1i – Rh proceeds with unprecedented speed and the catalyst can be recovered and recycled 15 times. In the course of the catalytic reaction the mononuclear species forms catalytically active Rh nanoparticles on the surface. Finally it is demonstrated that ClRh(PPh 3 ) 3 can be bound to ZrP directly without linker. However, the catalytic activity of the resulting material ZrP–Rh does not quite match the favorable characteristics of 1i – Rh .

Surface-functionalized zirconium phosphate (ZrP) nanoparticles were synthesized using a combination of ion exchange and self-assembly techniques. The surface of ZrP was used as a platform to deposit tetravalent metal ions by direct ion exchange with the protons of the surface phosphate groups. Subsequently, phosphonic acids were attached to the metal ion layer, effectively functionalizing the ZrP nanoparticles. Use of axially oriented bisphosphonic acids led to the ability to build layer-by-layer assemblies from the nanoparticle surface. Varying the metal ion and ligand used allowed designable architectures to be synthesized on the nanoparticle surface. X-ray powder diffraction, XPS, electron microprobe, solid-state NMR, FTIR, and TGA were used to characterize the synthesized materials.

Two different nickel precursors (NiCl2 or Ni(CH3COCH2COCH3)2) in the presence of 1-dodecanethiol and a mixture of oleylamine and oleic acid were used for a one-pot colloidal synthesis to produce high purity Ni3S4 nanoparticles with controlled shapes in high yields and narrow size distributions. By simply changing the nickel precursors, the shape of Ni3S4 nanocrystals can be readily tuned from triangular nanoprisms to tetrahedra (nanopyramids). The produced nanocrystals were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray powder diffraction, selected area electron diffraction, ultraviolet-visible spectroscopy and superconducting quantum interference device (SQUID). TEM tomography (3D-TEM) was employed to determine details of the particle shapes. SQUID measurements confirmed that particle shape and domain size could dramatically impact their magnetic properties, where tetrahedral nanopyramids of Ni3S4 nanoparticles showed ferromagnetic properties while the Ni3S4 nanoprisms showed random antiferromagnetic interactions between magnetic centers.

The intercalation of inorganic layered materials has resulted in a wide range of applicability. In such cases the applicability of the material is largely dependent upon the species intercalated within the layer, and the layered material acts largely as a host. Recently, the surface modification of inorganic layered materials has been investigated and it has been shown that the exterior layers can be exclusively functionalized. The advent of surface chemistry allows for the synthesis of particles with both a controlled interlayer and surface. This approach can be used to tailor nanoparticles for specific applications. Herein we review the surface chemistry of α-zirconium bis(monohydrogen orthophosphate) monohydrate (Zr(HPO4)2·H2O, α-ZrP) along with some applications of recent interest. Not only can these reactions be applied to α-ZrP, but similar chemistry can also be expanded to other layered materials and systems.

Organically surface-modified α-zirconium phosphate was obtained by reacting the surface P–O–H groups of α-zirconium phosphate nanoparticles (α-ZrP) with octadecyltrichlorosilane (OTS). Surface functionalization of α-ZrP with OTS was accomplished using a one-step synthesis producing highly hydrophobic nanoparticles. The formation of P–O–Si bonds arising from nucleophilic attack of POH to the silane was confirmed by solid-state NMR experiments. The surface coverage of the organic modifier was characterized by TGA, AFM, and FTIR. In addition, we show the applicability of this system with a photoinduced electron-transfer reaction in a nonpolar solvent. Using an organically surface-modified α-ZrP previously loaded with tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)32+), the quenching of the luminescence of Ru(bpy)32+ in the presence of p-benzoquinone was monitored; a static quenching constant (Ks) value of 8.82 × 102 M–1 and a dynamic quenching constant (KD) value of 6.99 × 102 M–1 were obtained.

Nitrosyl hydride, HNO or nitroxyl, is the one-electron reduced and protonated form of nitric oxide. HNO is isoelectronic to singlet O(2), and we have previously reported that deoxymyoglobin traps free HNO to form a stable adduct. In this report, we demonstrate that oxygen-binding hemoglobins from human, soy, and clam also trap HNO to form adducts which are stable over a period of weeks. The same species can be formed in higher yields by careful reduction of the ferrous nitrosyl adducts of the proteins. Like the analogous O(2)-Fe(II) adducts, the HNO adducts are diamagnetic, but with a characteristic HNO resonance in (1)H NMR at ca. 15 ppm that splits into doublets for H(15)NO adducts. The (1)H and (15)N NMR resonances, obtained by HSQC experiments, are shown to differentiate subunits and isoforms of proteins within mixtures. An apparent difference in the reduction rates of the NO adducts of the two subunits of human hemoglobin allows assignment of two distinct nitrosyl hydride peaks by a combination of UV-vis, NMR, and EPR analysis. The two peaks of the HNO-hHb adduct have a persistent 3:1 ratio during trapping reactions, demonstrating a kinetic difference between HNO binding at the two subunits. These results show NMR characterization of ferrous HNO adducts as a unique tool sensitive to structural changes within the oxygen-binding cavity, which may be of use in defining modes of oxygen binding in other heme proteins and enzymes.

This paper describes the development process of the Dynamic Study Model (DSM) for the synchronously interconnected power system of Continental Europe in different simulation tools1. The model was developed by the European Network of Transmission System Operators for Electricity (ENTSO-E) working group System Protection and Dynamics2 and the University of Erlangen-Nuremberg within a collaboration. The paper describes the DSM scope, input and necessary steps towards an adequate basis for the novel dynamic data enhancement process by means of standard dynamic models for generation units and allocation criteria. Through a parameter variation process the DSM has been successively tuned to match a frequency measurement of a system event with respect to system inertia, frequency containment reserve and one of the typical oscillation modes within Continental Europe. Finally, the DSM behavior has been verified by means of previous experience from operation.

This paper examines vertical effects in competition law and regulatory decisions in pay-television markets in France, the United Kingdom and the United States, with a focus on vertical input and customer foreclosure, exclusive dealing, countervailing buyer power and some aspects of the implementation of remedies. Its inception in the discussion surrounding convergence is justified by the importance of vertical effects in consolidation and vertical integration trends between the telecommunication and pay-television industries. Although convergence between these two industries may be considered both from the vertical (vertical integration) and horizontal (service bundling) perspective, this paper only addresses its vertical aspects. Among all types of vertical effects, only those judged more relevant by the authorities, and subject to a greater degree of scrutiny are being addressed, as explained in Section 1. First, we examine the different treatments of buyer power and its use as an argument to justify relaxing requirements for the authorisation of mergers in France and the United Kingdom (countervailing buyer power). Second, we conduct an exhaustive assessment of vertical foreclosure (both input and customer foreclosure) in relation to its regulatory treatment in these countries. In a separate section, exclusive dealing and related competition law practice are assessed in order to discern in which situations it can be pro- or anti-competitive, including future market structures. Finally, a section discusses the pros and cons of having wholesale reference offers for pay-television content against the use of arbitration mechanisms to prevent vertical foreclosure.The overall conclusion of the paper is that, while the United States has been moving away from stringent ex-ante regulation in pay-television markets, justified by an improvement in competition dynamics, France and United Kingdom have only partially succeeded in addressing these concerns – in many ways more serious that in the United States – due to a lack of a legal framework to issue ex-ante regulation. The empirical evidence for this paper is based on an exhaustive assessment of all related competition law and regulatory decisions in pay-television markets in France, the United Kingdom and the United States. The Annex includes a summary of vertical effects in antitrust and merger decisions in these countries from 1996 to 2014.

Communication providers may use bundles of different services (fixed telephony, broadband, pay-television, mobile services) to leverage market power or increase switching costs for consumers, but also as an efficient way to allocate fixed costs across services, reduce offer complexity and provide unified billing and innovative features. Bundles are increasingly important and raise challenges for regulators and policy makers. While the economic literature has extensively addressed bundling, the literature on hedonic price analysis for communication services is relatively limited, and builds on previous applications exploring the relationship between prices and the bundle’s features for automobiles, personal computers or houses (OECD, 2006). The present paper includes two main exercises to show the potential implications of communication bundles for consumer choice and industry performance. First, it estimates a hedonic price function for triple- and quadruple-play communication bundles of the largest operators in France, United Kingdom and the United States. Second, it explores relationship between bundling penetration and firm-level industry performance data (revenues, profits, etc.) in these countries.Section 1 includes a hedonic price analysis model using OLS econometric analysis of 300 offers (April 2014) from 15 operators in France, the United Kingdom and the United States (including standalone, double-, triple- and quadruple-play offers). The collected variables include service price per month, download speed, contract length, data allowance, TV quality index, fixed calls, and mobile plan features. As a novel approach, the quality of the television content has been modeled using an index that takes into account premium content, such as sports and movies, and the number of channels.Section 2 explores the relationship between bundle penetration and firm performance by using a panel of quarterly financial variables from 2010 to 2014 of 13 communication operators. The explanatory variables used in the regression analysis include revenues, profits (EBIT/EBITDA), investment and market share, controlling for country and time fixed effects. As expected, triple-play bundling is more predominant in France than in the United States or the United Kingdom, other factors being equal. Furthermore, the results show that, while revenues (operator’s size) have a very minor (positive) effect on triple-play bundling penetration, investment and market shares prove statistically significant (the former displaying a positive effect, whereas the latter a negative impact on bundling). Nevertheless, given the caveats identified in the dataset and potential endogeneity problems, these results are deemed only exploratory and need to be considered with caution.

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II) ([Ru(phend)(2)bpy](2+)) exchanged into the inorganic layered material zirconium phosphate (ZrP). X-Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)(2)bpy](2+) intercalation from 10.3 Å to 14.2 Å. The UV-vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)(2)bpy](2+). The UV-vis spectrophotometric results indicate that the [Ru(phend)(2)bpy](2+) concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)(2)bpy](2+) exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°' = -38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis -Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.

We fabricated for the first time thermo-sensitive discotic liquid crystals by grafting poly(N-isopropylacrylamide) (PNIPAM) onto zirconium phosphate (ZrP) platelets using pre-irradiated polymerization. The I–N transition was investigated by adjusting the temperature for a single set of samples. We found that soft disks self-assemble into nematic liquid crystals in a wider thickness-over-diameter ratio than do hard disks.

Inorganic-organic hybrid materials were synthesized by covalent attachment of epoxides to the surface of zirconium phosphate (ZrP) nanoplatelets. X-ray powder diffraction, FTIR, and TGA were utilized to confirm the presence of the modifiers and exclusive functionalization of the ZrP surface. NMR experiments were conducted to confirm the formation of P-O-C bonds between surface phosphate groups and epoxide rings. The applicability of the organically modified products was demonstrated by their use as fillers in a polymer matrix. Subsequently, a two step intercalation and surface modification procedure was utilized to prepare polymer nanocomposites that were imparted with functionality through the encapsulation of molecules within the interlayer of surface modified ZrP.

We report the use of zirconium phosphate (ZrP) nanoplatelets for the encapsulation of the anticancer drug cisplatin and its delivery to tumor cells. Cisplatin was intercalated into ZrP by direct ion exchange and was tested in vitro for cytotoxicity in the human breast cancer (MCF-7) cell line. The structural characterization of the intercalated cisplatin in ZrP suggests that during the intercalation process, the chloride ligands of the cisplatin complex were substituted by phosphate groups within the layers. Consequently, a new phosphate phase with the platinum complex directly bound to ZrP (cisPt@ZrP) is produced with an interlayer distance of 9.3 A. The in vitro release profile of the intercalated drug upon a pH stimulus shows that at low pH under lysosomal conditions the platinum complex is released with simultaneous hydrolysis of the zirconium phosphate material, while at higher pH the complex is not released. Experiments with the MCF-7 cell line show that cisPt@ZrP reduced the cell viability up to 40%. The cisPt@ZrP intercalation product is envisioned as a future nanotherapy agent against cancer. Taking advantage of the shape and sizes of the ZrP particles and controlled release of the drug at low pH, it is intended to exploit the enhanced permeability and retention effect of tumors, as well as their intrinsic acidity, for the destruction of malignant cells.

The objective of this study was to evaluate the biocompatibility of zirconium phosphate (ZrP) nanoplatelets (NPs), and their use in drug delivery. ZrP and doxorubicin-intercalated ZrP (DOX:ZrP) NPs were characterized by using X-Ray Powder Diffraction (XRPD), Thermogravimetric Analysis (TGA), Transmission Electron Micrography (TEM), Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Biocompatibility of ZrP NPs was evaluated in human embryonic kidney (HEK-293), breast cancer (MCF-7), metastatic breast cancer (MDA-MB-231), ovarian cancer (OVCAR-3), resistant cancer (NCI-RES/ADR) cells and mouse macrophage (RAW 264.7) cell lines. Hemocompatibility of ZrP NPs was evaluated with human red blood cells. Simulated body fluid (SBF) of pH 7.4 was used to determine the in vitro release of doxorubicin from DOX:ZrP NPs. Cellular uptake and in vitro cytotoxicity studies of DOX:ZrP NPs were determined in MDA-MB-231. The ZrP nanomaterial can be prepared in the 100–200 nm size range with a platelet-like shape. The ZrP NPs themselves are biocompatible, hemocompatible and showed no toxicity to the macrophage cells. ZrP NPs can intercalate high loads (35% w/w) of doxorubicin between their layers. The release of DOX was sustained for about 2 weeks. DOX:ZrP NPs showed higher cellular uptake and increased cytotoxicity than free DOX in MDA-MB-231 cells. ZrP NPs are highly biocompatible, can intercalate large amounts of drugs and sustain the release of drugs. ZrP NPs improved the cellular uptake and cytotoxicity of DOX to MDA-MB-231 cells. ZrP NPs are promising nanocarriers for drug delivery in cancer therapy.

The encapsulation of insulin into different kinds of materials for noninvasive delivery is an important field of study because of the many drawbacks of painful needle and syringe delivery such as physiological stress, infection, and local hypertrophy, among others (Khafagy, E.-S.; et al. Adv. Drug Delivery Rev. 2007, 59 (15), 1521-1546). A stable, robust, nontoxic, and viable noninvasive carrier for insulin delivery is needed. We present a new approach for protein nanoencapsulation using layered zirconium phosphate (ZrP) nanoparticles produced without any preintercalator present. The use of ZrP without preintercalators produces a highly pure material, without any kinds of contaminants, such as the preintercalator, which can be noxious. Cytotoxicity cell viability in vitro experiments for the ZrP nanoparticles show that ZrP is not toxic, or harmful, in a biological environment, as previously reported for rats (Zhu, Z. Y.; et al. Mater. Sci. Forum 2009, 620-622, 307-310). Contrary to previous preintercalator-based methods, we show that insulin can be nanoencapsulated in ZrP if a highly hydrate phase of ZrP with an interlayer distance of 10.3 A (10.3 A-ZrP or θ-ZrP) is used as a precursor. The intercalation of insulin into ZrP produced a new insulin-intercalated ZrP phase with about a 27 A interlayer distance, as determined by X-ray powder diffraction, demonstrating a successful nanoencapsulation of the hormone. The in vitro release profile of the hormone after the intercalation was determined and circular dichroism was used to study the hormone stability upon intercalation and release. The insulin remains stable in the layered material, at room temperature, for a considerable amount of time, improving the shell life of the peptidic hormone. This type of material represents a strong candidate to developing a noninvasive insulin carrier for the treatment of diabetes mellitus.

The direct intercalation reaction of ferrocene (bis(eta5-cyclopentadienyl)iron(II), Fc) with a highly hydrated layered zirconium phosphate (ZrP) resulted in the formation of the ferrocenium ion (Fc+) within the ZrP material. The Fc+-intercalated ZrP material has an interlayer distance of 10.7 A. The intercalated material was used as an electron acceptor for the oxidation of both ferro-cytochrome c and the excited state of tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+). Upon contact of the material with a 1.5 x 10(-5) M solution of ferro-cytochrome c, the UV-vis absorption spectrum shows the successful formation of ferri-cytochrome c. Luminescence spectroscopy shows that the Fc+-intercalated ZrP material quenches the luminescence of [Ru(bpy)3]2+. The excited-state quenching mechanism of [Ru(bpy)3]2+* by Fc+-intercalated ZrP follows a dynamic plus sphere of action model. The second-order dynamic quenching rate constant kq is 2.2 x 10(8) M(-1) s(-1).

The European pollutant release and transfer register (E-PRTR) is the Europe-wide emissions register that provides accessible environmental information about industrial facilities. Reporting of E-PRTR data to the European Commission requires that the member states assess the quality of their data. The errors and omissions in these data should be detected during the review process and corrected, claiming accurate and additional information to the industrial sources. In order to validate E-PRTR data, PRTRval software tool was developed and applied to the Galician industrial facilities. It provides a systematic procedure for the validation of emissions, based on a bottom-up approach to obtain a reference inventory that combines both standard and specific emission factors, and the activity factors yearly reported. The application of this validation procedure to the air pollutants 2010 E-PRTR dataset in Galicia shows that 54% of the emissions need correction or complementary information. The lack of information represented 24% of the errors.

We demonstrate the fabrication of amphiphilic nano-sheets, which are either surface- or edge-modified plates with thickness at the atomic scale, one of the thinnest amphiphilic particles reported so far. They are obtained by exfoliation of functionalized layered crystals, the first time that laminar structures have been utilized to produce such particles. Stable emulsions were made utilizing these nano-sheets. The adsorption of the amphiphilic nano-sheets onto the oil-in-water interfaces and the reduction of surface tension between the PDMS and the amphiphilic nano-sheet suspensions were quantitatively characterized.

Doxorubicin was intercalated into novel zirconium phosphate nano-platelets (ZrP). The obtained doxorubicin intercalated ZrP nano-platelets had an impressive 34.9% (w/w) drug loading. We used this material to deliver doxorubicin to breast cancer cells (MCF-7). Cellular studies with MCF-7 cells showed higher uptake and cytotoxicity of doxorubicin loaded ZrP compared to free doxorubicin.