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Measuring the isotopic composition of trace Zr in presolar stardust grains allows us to study the environment of slow neutron-capture nucleosynthesis in asymptotic giant branch stars. Here, we present a newly characterized Zr resonance ionization scheme that can be saturated with state-of-the-art titanium-sapphire lasers and yields a useful yield of (5.4 ± 0.4)%. Resonance ionization is achieved in two steps: after first being excited with a photon at 319.215 nm, neutral Zr atoms are then ionized with a photon at 388.988 nm, where both wavelengths are reported as in vacuum. [ABSTRACT FROM AUTHOR]

A 3D flower-shaped bimetallic nanocomposite zirconium magnesium oxide (ZMO) was prepared first time by the controlled solution combustion method using triethanolamine (TEA) as a fuel and chelating agent. The composite material was used to remove excess fluoride via adsorption. The thermal stability of the adsorbent was characterized by thermogravimetric analysis (TGA). Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX), and X-ray diffraction (XRD) were used to characterize the adsorbent. The surface charge of the nano adsorbent was determined by Zeta Sizer. The surface area and pore volume of the adsorbent were determined by Brunauer-Emmett-Teller (BET) isotherm and Barrett-Joyner-Halenda (BJH) methods. The adsorption behavior of fluoride was studied systematically varying the pH, contact time, adsorbent dose, and initial fluoride concentration. The adsorption followed the Langmuir isotherm model with a maximum adsorption capacity of 42.14 mg/g. The pseudo-second-order kinetic model was confirmed by the adsorption study. The maximum adsorption efficiency was in the 6-10 pH range. The reaction mechanism was mainly based on ion exchange between hydroxy and fluoride ions which was proven by X-ray photoelectron spectroscopy (XPS). Real water tests indicated that ZMO could be used as a potential defluoridation agent for fluoride containing groundwater treatment., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The present systematic review and meta-analysis aimed to assess the characteristics and consequences of post-processing methods after grinding procedures in YSZ ceramics on its surface roughness and flexural strength. The protocol of this review was made prospectively and is available online in the PROSPERO database (link). Literature searches on PubMed/MEDLINE, EMBASE, Lilacs, Web of Science and Scopus were conducted on December 2022 to select in vitro studies written in English, without publishing-date restrictions, that considered surface characteristics and mechanical properties of YSZ ceramics submitted to grinding and subsequent post-processing surface treatments as an attempt to revert the effect induced by grinding. Two authors independently selected the studies, extracted the data and assessed the risk of bias. Mean differences (Rev-Man 5.1, random effects model, α= 0.05) were obtained by comparing flexural strength and surface roughness values of ground surfaces with at least one post-processing surface treatment (global analysis). Subgroup analyses were performed considering the most prevalent categories of post-processing methods. A total of 33 (out of 4032) studies were eligible and included in the analysis. In the global analysis, ground surfaces showed higher flexural strength than when post-processing methodologies were employed (p< 0.0001). The subgroup analysis showed that only polishing was able to enhance the flexural strength after grinding (p= 0.001); however, when other protocols were used, the ground surface was always superior in terms of flexural strength (p< 0.0001). Post-processing techniques in both the global and sub-group analyses were able to reduce the surface roughness after grinding in YSZ ceramics (p< 0.00001). High heterogeneity was found in all the meta-analyses. Concerning the risk of bias analysis, the included studies had mixed scores for the considered factors. In conclusion, in terms of improving flexural strength and restoring surface roughness after grinding, polishing protocols can be considered the best indication as post-processing treatment after YSZ ceramics adjustments/grinding., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The biosynthesis of metal oxide nanoparticles provides an excellent alternative to the chemical synthesis approach. The aim of the current study was a green and eco-friendly synthesis of zirconium nanoparticles (ZrNPs) from fruit peels of Punica granatum (Pomegranate). The synthesis of ZrNPs was confirmed using a UV-visible spectrophotometer. The functional groups present on surface of ZrNPs were analyzed using FTIR. The average size of obtained ZrNPs was analyzed using SEM and DLS and it was around 20-60 nm. The antimicrobial activity of obtained ZrNPs was tested against Gram-positive strains (Bacillus subtilis and Staphylococcus aureus), Gram-negative strains (Escherichia coli and Klebsiella pneumoniae) and Fungi (Aspergillus niger) by agar well diffusion method. ZrNPs showed maximum zone of inhibition against S. aureus (19 mm) and A. niger (18 mm) at the maximum concentration of 200 μg/mL. The antioxidant scavenging activity of obtained ZrNPs was analyzed using the following methods: DPPH radical scavenging activity, Hydroxyl radical scavenging activity, Ferric reducing antioxidant power and hydrogen peroxide radical scavenging activity. This the first and foremost study on ZrNPs synthesized using P. granatum fruit peel extract reporting their efficacy as antimicrobial agents against Bacteria and Fungi. Considering the tolerance of zirconium towards human body, it can also be used as antimicrobial coating material on human implants., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Purpose: The purpose of this study was to evaluate the effect of veneering and aging on the translucency of newly introduced extra and high translucent zirconia with different thickness., Materials and Methods: One hundred forty disk-shaped specimens were fabricated from two translucent zirconia blocks (VITA YZ XT and VITA YZ HT), and they are milled with CAD/CAM system. Then, specimens were divided into nonveneered (XT, HT) and veneered groups (XTV, HTV). Nonveneered groups were prepared with four different thicknesses (0.5-1-1.5-2 mm). Veneered groups were divided into three subgroups ( n = 10) for veneering with base dentin ceramic with thicknesses of 0.5 + 0.5, 0.5 + 1, and 0.5 + 1.5 mm. A spectrophotometer was used to calculate the translucency parameter (TP) and contrast ratio (CR) of all specimens before and after aging. Statistical analysis was performed using 3-way ANOVA and Tukey HSD tests ( p < 0.05)., Results: TP values were significantly affected by thickness of specimens ( p < 0.001). VITA YZ XT was significantly found more translucent than VITA YZ HT. The highest translucency was observed in the XT-0.5 mm group. There is no significant difference between translucency of the veneered and nonveneered groups in the same thickness for XT. On the contrary, veneering significantly affected translucency of HT. TP values significantly decreased after aging for all groups. After aging, translucency value difference before and after aging was the highest in the XT-0.5 mm group whereas the HTV-2 mm group showed the lowest difference after aging. TP decreased significantly as thickness of specimen increases regardless of the material type. Extra translucent and nonveneered zirconia groups are more prone to hydrothermal aging., Conclusions: The translucency parameter of zirconia ceramics was significantly influenced by both material type and veneering. Also, extra translucent and nonveneered zirconia groups are more susceptible to hydrothermal aging., Competing Interests: The authors report no conflict of interest., (Copyright © 2021 Sevki Cinar and Bike Altan.)

The megalithic jar sites of Laos (often referred to as the Plain of Jars) remain one of Southeast Asia's most mysterious and least understood archaeological cultures. The sites, recently inscribed as UNESCO World Heritage, host hollowed stone jars, up to three metres in height, which appear scattered across the landscape, alone or clustered in groups of up to more than 400. Until now, it has not been possible to estimate when the jars were first placed on the landscape or from where the stone was sourced. Geochronological analysis using the age of detrital zircons demonstrates a likely quarry source for one of the largest megalithic jar sites. Optically Stimulated Luminescence (OSL) dating suggests the jars were positioned at the sites potentially as early as the late second millennium BC. Radiocarbon dating of skeletal remains and charcoal samples places mortuary activity around the jars from the 9-13th century AD, suggesting the sites have maintained ritual significance from the period of their initial placement until historic times., Competing Interests: The authors have declared that no competing interests exist.

Background: Monolithic restorations made of translucent yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) have become popular over the past few decades. However, whether aging affects the color and translucency of monolithic translucent Y-TZP is unclear., Objective: The aim of this systematic review and meta-analysis of in vitro studies was to evaluate the effects of aging on the color and translucency of monolithic translucent Y-TZP ceramics., Materials and Methods: This systematic review/meta-analysis was reported according to the PRISMA statement and registered in the OSF registries (https://osf.io/5qjmu). Four databases including Medline via the PubMed, Embase, and Web of Science databases and the Cochrane Library were searched using no publication year and language limits. The last search was executed on November 20, 2020. In vitro studies comparing the translucency and/or color of monolithic translucent Y-TZP ceramics before and after simulated aging were selected. Meta-analyses were performed using Review Manager software (version 5.3, Cochrane Collaboration, Oxford, UK) with random-effects models at a significance level of 0.05. A risk-of-bias assessment was also performed for the included studies., Results: Of the 188 potentially relevant studies, 13 were included in the systematic review. The hydrothermal aging duration ranged from 1 to 100 h at relatively similar temperatures (~134°C). In the general meta-analyses, the aged Y-TZP ceramics exhibited similar translucency parameter (TP), L ∗ , and b ∗ values compared with the nonaged controls ( P = .73, P = .49, and P = .62, respectively). Moreover, there was a significant difference between the aged and nonaged Y-TZP ceramics in the a ∗ value ( P = .03; MD = -0.26; 95% CI = -0.51 to - 0.02), favoring the nonaged Y-TZP ceramics. The subgroup analyses showed that the duration of aging contributed to changes in the translucency and color of the Y-TZP ceramics., Conclusions: The optical properties of monolithic translucent Y-TZP ceramics were stable after hydrothermal aging at 134°C and 0.2 MPa for ≤20 h. Moreover, clinically unacceptable changes in the translucency and color of monolithic translucent Y-TZP ceramics were found after hydrothermal aging for >20 h., Competing Interests: The authors declare that they have no conflicts of interest., (Copyright © 2021 Chang-yuan Zhang et al.)

Ischaemic heart disease evokes a complex immune response. However, tools to track the systemic behaviour and dynamics of leukocytes non-invasively in vivo are lacking. Here, we present a multimodal hot-spot imaging approach using an innovative high-density lipoprotein-derived nanotracer with a perfluoro-crown ether payload ( 19 F-HDL) to allow myeloid cell tracking by 19 F magnetic resonance imaging. The 19 F-HDL nanotracer can additionally be labelled with zirconium-89 and fluorophores to detect myeloid cells by in vivo positron emission tomography imaging and optical modalities, respectively. Using our nanotracer in atherosclerotic mice with myocardial infarction, we observed rapid myeloid cell egress from the spleen and bone marrow by in vivo 19 F-HDL magnetic resonance imaging. Concurrently, using ex vivo techniques, we showed that circulating pro-inflammatory myeloid cells accumulated in atherosclerotic plaques and at the myocardial infarct site. Our multimodality imaging approach is a valuable addition to the immunology toolbox, enabling the study of complex myeloid cell behaviour dynamically.

Nanotherapy has recently emerged as an experimental treatment option for atherosclerosis. To fulfill its promise, robust noninvasive imaging approaches for subject selection and treatment evaluation are warranted. To that end, we present here a positron emission tomography (PET)-based method for quantification of liposomal nanoparticle uptake in the atherosclerotic vessel wall. We evaluated a modular procedure to label liposomal nanoparticles with the radioisotope zirconium-89 ( 89 Zr). Their biodistribution and vessel wall targeting in a rabbit atherosclerosis model was evaluated up to 15 days after intravenous injection by PET/computed tomography (CT) and PET/magnetic resonance imaging (PET/MRI). Vascular permeability was assessed in vivo using three-dimensional dynamic contrast-enhanced MRI (3D DCE-MRI) and ex vivo using near-infrared fluorescence (NIRF) imaging. The 89 Zr-radiolabeled liposomes displayed a biodistribution pattern typical of long-circulating nanoparticles. Importantly, they markedly accumulated in atherosclerotic lesions in the abdominal aorta, as evident on PET/MRI and confirmed by autoradiography, and this uptake moderately correlated with vascular permeability. The method presented herein facilitates the development of nanotherapy for atherosclerotic disease as it provides a tool to screen for nanoparticle targeting in individual subjects' plaques.

Background: Forms of interstitial pneumonia secondary to exposure to an air-contaminant are varied and so far, insufficiently described., Objectives/methods: We report here a case of a 57-year-old patient managed in our department for the exploration of MRC grade 2 dyspnoea and interstitial pneumonia. He mentioned multiple occupational and domestic exposures such as hens' excrements, asbestos and metal particles; he also had a previous history of smoking., Results: High-resolution computed tomography showed ground glass opacities predominating in posterior territories and surrounding cystic lesions or emphysematous destruction. The entire etiological assessment revealed only macrophagic alveolitis with giant multinucleated cells on the bronchoalveolar lavage. A surgical lung biopsy allowed us to refine the diagnosis with evidence of desquamative interstitial pneumonia and pulmonary granulomatosis. Finally, the analysis of the mineral particles in the biopsy revealed abnormally high rates of Zirconium and Aluminium. We were therefore able to conclude to a desquamative interstitial pneumonia associated with pulmonary granulomatosis linked to metal exposure (Aluminium and Zirconium). The clinical, functional and radiological evolution was favorable after a systemic corticosteroid treatment with progressive decay over one year., Conclusion: This presentation reports the first case to our knowledge of desquamative interstitial pneumonitis related to exposure to Zirconium and the third one in the context of Aluminium exposure. The detailed analysis of the mineral particles present on the surgical lung biopsy allows for the identification of the relevant particle to refine the etiological diagnosis, to guide the therapeutic management and to give access to recognition as an occupational disease. (Sarcoidosis Vasc Diffuse Lung Dis 2020; 37 (1): 79-84) ., (Copyright: © 2020 SARCOIDOSIS VASCULITIS AND DIFFUSE LUNG DISEASES.)

Background and Objectives : All-ceramic prosthesis is widely used in modern dental practice because of its improved physico-mechanical and optical properties. These restorations are exposed to coloring agents from various nutrition and beverages in the oral cavity. Long-term color stability is critical for the success of these restorative materials. The purpose of this in vitro study was to assess the effect of common beverages and mouthwash on the color stability of lithium disilicate (LD), monolithic zirconia (MZ) and bilayer zirconia (BZ) surfaces. Materials and Method : Thirty disc-shaped specimens from each material were fabricated; each group was subdivided ( n = 10) according to coffee, green tea and chlorhexidine immersion solutions. The baseline color of ceramic discs was recorded according to the CIE L*a*b* system with a portable spectrophotometer. The second measurement was recorded after 3000 thermocycling and immersion in coloring agents for 7 days. The mean color difference was calculated and data were compared with Kruskal-Wallis and Mann-Whitney post hoc tests (0.05). Results : ΔE values for LD with the immersion of coffee, tea, and Chlorhexidine gluconate (CHG) were 1.78, 2.241 and 1.58, respectively. Corresponding ΔE values for MZ were 5.60, 5.19, and 4.86; marginally higher than the clinically acceptable level of 3.5. Meanwhile, BZ showed better color stability compared to MZ with ΔE values of 4.22, 2.11 and 1.43. Conclusions : Among the ceramics evaluated, LD ceramic was found to be more color stable, while MZ ceramics displayed a higher susceptibility to discoloration. MZ and BZ ceramic colors were significantly altered with coffee immersion, while LD ceramics were more affected by green tea.

The suitability of a reference element or normalizer used in assessing soil contamination levels using enrichment factor (EF) is important for soil quality assessment and monitoring. This study evaluated the results of using three reference elements Ti, Fe, and Zr for EF determination of Rb and Sr in soils within treated wastewater discharge vicinity, Central Botswana. The upper continental crust (UCC), world average values (WAV), and the local background values (LBV) were used in EF assessment of eight pedons. The elemental concentrations of the soils were determined with portable X-ray fluorescence (pXRF) analyzer. Relationships between the elements were strongly significant between Rb and Ti (r = 0.600, p < 0.01), Rb and Fe (r = 0.735, p < 0.01), Sr and Ti (r = 0.545, p < 0.01), and Sr and Fe (r = 0.841, p < 0.01). Second-level correlation analysis between contamination factor (CF) and EF levels showed Zr as the best reference element for Rb and Sr in the soils. Results from this study provide baseline knowledge necessary for contamination assessment and monitoring of soils with similar environmental conditions.

This paper documents the first U-Pb zircon ages for Ashfall Fossil Beds (Nebraska, USA), a terrestrial Konservat-Lagerstätte mass-death assemblage that is arguably the most diverse of its type and age. The Ashfall tephra was correlated with ignimbrites from the Bruneau-Jarbidge volcanic field (12.7-10.5 Ma) in southwest Idaho based on geochemical analysis. The methods and geochemical data supporting the original age assessment of the ash bed, however, were never published, and there has been a persistent misconception that dateable heavy minerals (e.g., zircon) are absent. Notwithstanding, we recovered abundant zircons from Ashfall Fossil Beds, and from an ash bed ~6 km to the southeast at Grove Lake, Nebraska, and analyzed them through LA-ICP-MS. Our new zircon U-Pb age of 11.86 ± 0.13 Ma substantiates correlation of the Ashfall Fossil Beds deposit to tuffs originating from the Bruneau-Jarbidge caldera (~12.7-10.5 Ma). Our U-Pb zircon age of 6.42 ± 0.06 Ma for the Grove Lake ash bed coincides with supervolcanic activity in the Heise volcanic field (6.6-4.3 Ma) in eastern Idaho. These new dates improve age constraints of strata comprising the Ogallala Group and the important paleontological site. Moreover, we find that detrital and airfall zircons are unevenly distributed in the stratified ash beds we describe herein and presumably in similar deposits worldwide. Therefore, a higher-resolution sampling scheme is necessary in such cases., Competing Interests: The authors have declared that no competing interests exist.

Hydrosphere interactions and alteration of the terrestrial crust likely played a critical role in shaping Earth's surface, and in promoting prebiotic reactions leading to life, before 4.03 Ga (the Hadean Eon). The identity of aqueously altered material strongly depends on lithospheric cycling of abundant and water-soluble elements such as Si and O. However, direct constraints that define the character of Hadean sedimentary material are absent because samples from this earliest eon are limited to detrital zircons (ZrSiO 4 ). Here we show that concurrent measurements of Si and O isotope ratios in Phanerozoic and detrital pre-3.0 Ga zircon constrain the composition of aqueously altered precursors incorporated into their source melts. Phanerozoic zircon from (S)edimentary-type rocks contain heterogeneous δ 18 O and δ 30 Si values consistent with assimilation of metapelitic material, distinct from the isotopic character of zircon from (I)gneous- and (A)norogenic-type rocks. The δ 18 O values of detrital Archean zircons are heterogeneous, although yield Si isotope compositions like mantle-derived zircon. Hadean crystals yield elevated δ 18 O values (vs. mantle zircon) and δ 30 Si values span almost the entire range observed for Phanerozoic samples. Coupled Si and O isotope data represent a constraint on Hadean weathering and sedimentary input into felsic melts including remelting of amphibolites possibly of basaltic origin, and fractional addition of chemical sediments, such as cherts and/or banded iron formations (BIFs) into source melts. That such sedimentary deposits were extensive enough to change the chemical signature of intracrustal melts suggests they may have been a suitable niche for (pre)biotic chemistry as early as 4.1 Ga., Competing Interests: The authors declare no conflict of interest.

Tumor angiogenesis has attracted increasing attention because of its potential as a valuable marker in the differential diagnosis of brain tumors as well as a novel therapeutic target. Prostate-specific membrane antigen (PSMA) is expressed by the neovasculature endothelium of some tumors, with little to no expression by the tumor cells or normal vasculature endothelium. The aim of this study was to investigate the potential of PSMA for the evaluation of the tumor neovasculature of various brain tumors and the possibility of detecting PSMA expression in brain tumors using PET imaging with 89 Zr-Df-IAB2M (anti-PSMA minibody). Eighty-three tissue specimens including gliomas, metastatic brain tumors, primary central nervous system lymphomas (PCNSL), or radiation necroses were analyzed by immunohistochemical staining with PSMA antibody. 89 Zr-Df-IAB2M PET scans were performed in three patients with recurrent high-grade gliomas or metastatic brain tumor. PSMA was highly expressed in the vascular endothelium of high-grade glioma and metastatic brain tumor, whereas PSMA was poorly expressed in the vascular endothelium of PCNSL and radiation necrosis. PSMA expression in high-grade gliomas and a metastatic brain tumor was clearly visualized by PET imaging with 89 Zr-Df-IAB2M. Furthermore, a trend toward a positive correlation between the degree of 89 Zr-Df-IAB2M uptake and PSMA expression levels in tumor specimens was observed. PET imaging of PSMA using 89 Zr-Df-IAB2M may have potential value in the differential diagnosis of high-grade glioma from PCNSL or radiation necrosis as well as in the prediction of treatment efficacy and assessment of treatment response to bevacizumab therapy for high-grade glioma.

Granular zirconium-aluminum hybrid adsorbent (GZAHA) was fabricated for efficient defluoridation of groundwater in filter application. GZAHA was formed through the aggregation of massive Zr/Al oxide nanoparticles with an amorphous pattern. This adsorbent has a satisfactory mechanical strength, a specific surface area of 29.55 m 2 /g, and numerous hydroxyl groups on the surface. F adsorption equilibrium could be achieved within 12 h, and the sorption process followed a pseudo-second-order reaction rate. The maximum adsorption capacity of F estimated from the Langmuir model was 65.07 mg/g at 25 °C, being greater than most of other granular adsorbents. The removal efficiency of F could be maintained in a wide pH range of 5~9. The presence of phosphate posed an adverse effect on F adsorption due to the competition mechanisms. The saturated adsorbents could be regenerated and reused for four times by using sodium hydroxide solution as an eluent, and the adsorption capacity remained around 80%. Besides electrostatic attraction and Al-F complex, surface complexation and anion exchange were also involved in the adsorption process. Continuous adsorption experiments illustrated that 808 bed volumes of F-contaminated water (F = 5 mg/L) were treated successfully by a GZAHA-packed column without second pollution.

This study aimed to evaluate and compare the effect of different surface post-processing treatments (polishing, heat treatment, glazing, polishing + heat treatment and polishing + glazing) on the superficial characteristics (micromorphology and roughness), phase transformation and fatigue strength of a Y-TZP ceramic ground with diamond bur. Discs of Y-TZP ceramic were manufactured (ISO:6872-2015; final dimensions of 15mm in diameter and 1.2 ± 0.2mm in thickness) and randomly allocated according to the surface condition: Ctrl - as-sintered; Gr - ground with coarse diamond bur; Gr+HT - ground and subjected to the heat treatment; Gr+Pol - ground and polished; Gr+Pol+HT - ground, polished and heat treated; Gr+Gl - ground and glazed; Gr+Pol+Gl - ground, polished and glazed. The following analyses were performed: roughness (n = 25), surface topography (n = 2), phase transformation (n = 2) and fatigue strength by staircase method (n = 20). All treatments influenced to some extent the surface characteristics of Y-TZP, being that polishing reduced the surface roughness, the m-phase content and improved the fatigue strength; glazing led to the lowest roughness values (Ra and Rz), although it showed the worst fatigue strength; heat treatment showed limited effect on surface roughness, led to complete reversion of the existing m-phase content to t-phase, without enhancing fatigue performance. Thus, a polishing protocol after clinic adjustment (grinding) of monolithic restorations based on polycrystalline zirconia material is mandatory for surface characteristics and fatigue performance improvements., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

To study the tetragonal-to-monoclinic (T-M) phase transformation behavior under different strain rates and indentation depths, nanoindentation tests were performed on stabilized zirconia ceramics with Continuous Stiffness Measurements. The results indicate decreased phase transformation velocities at both lower and higher strain rates, but increased velocity under medium strain rate during loading. The phase transformation process is sensitive to Ṗ/P but the final volume fractions are almost identical (45%). Furthermore, most of the phase transformation is completed during a short initial time followed by slight linear increase of the M-phase volume fraction with holding time. The phase transformation continuously slowed with increasing indentation depth when indented with a constant strain rate., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Ti-13Nb-(0-6)Zr alloys were fabricated by conventional powder metallurgy sintering method. Their microstructure, phase transformation temperature and mechanical properties were investigated by optical microscopy, scanning electron microscope, X-ray diffraction, differential scanning calorimetry and compression test. It was found that with more Zr addition, the content of β phase increased while the content of precipitated α phase reduced. With 1 at% Zr increase, the Ms of Ti-13Nb-(0~6)Zr alloys decreased linearly by around 10°C. The compression test results revealed that sintered Ti-13Nb-2Zr owned a recoverable strain as high as 3.7% at room temperature, and Ti-13Nb-4Zr and Ti-13Nb-6Zr exhibited a remarkable recoverable strain of 4.4% at their Ms temperature which was lower than room temperature, indicating that these two alloys have a higher intrinsic recoverable strain and may be further optimized., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The Zr, Hf, Y and lanthanide (REE) distribution in biological tissues of Sabella spallanzanii and Styela plicata species collected from two harbours from the northern Sicily is studied for providing information regarding the Zr, Hf and REE uptake from the environment. Previous studies determined the fractionation of dissolved REE scavenged on binding sites onto biological surfaces. By comparing the recognised shale-normalised REE patterns of studied samples with evidence from reference data, the observed behaviour of these elements in biological tissues of Sabella spallanzanii and Styela plicata is interpreted to result from the preferential uptake of intermediate REE onto carboxylic sites. Moreover, the relationship observed between the Fe content and Zr/Hf ratio suggests that preferential Hf accumulation occurs via siderophore-like binding sites. Features of the REE bioaccumulation factors (BAF), in addition to the absolute La, Ce and Sm contents and Zr-Hf fractionation, allow definition of the different origins of studied elements in the investigated localities. Higher BAF values for La and Ce associated with larger REE contents and lower Zr/Hf values strongly suggest that the environmental REE distribution in the Termini Imerese harbour is influenced by the delivery of particles from industrial sources and power plants. On the contrary, the REE contents of biological tissues collected in the Cala tourist harbour are affected by the dust dissolution from automotive traffic. These results suggest that the geochemical behaviour of REE and Zr/Hf signature can be used in environmental studies of biological tissues for reconstructing the nature of anthropogenic contaminations., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The objective of this study is to compare the mechanical behaviour of thermally oxidised commercially pure titanium (CP-Ti) and commercially pure zirconium (CP-Zr). For this purpose, these two bio-metals were thermally oxidised under the same condition (650°C for 6h) and the oxidised specimens were characterised using various analytical and experimental techniques, including oxygen uptake analysis, layer thickness and hardness measurements, scratch tests, dry sliding friction and wear tests and tribocorrosion tests in Ringer's solution. The results show that under the present thermal oxidation condition, 4 times more oxygen is introduced into CP-Zr than into CP-Ti and the oxide layer produced on CP-Zr is nearly 6 times thicker than that on CP-Ti. Thermally oxidised CP-Zr possesses a higher hardness, a deeper hardening depth and better scratch resistance than thermally oxidised CP-Ti. Under dry sliding and tribocorrosion conditions, thermally oxidised CP-Zr also possesses much better resistance to material removal and a higher load bearing capacity than thermally oxidised CP-Ti. Thus, thermally oxidised Zr possesses much better mechanical behaviour than thermally oxidised Ti., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

In joint arthroplasty one of the main issues related to the failure of prosthetic implants is due to the wear of the ultra-high molecular weight polyethylene (UHMWPE) component. Surface treatments and coatings have been recognized as enhancing methods, able to improve the tribological properties of the implants. Therefore, the main objective of this work was to investigate the possibility to fabricate yttria-stabilized zirconia (YSZ) coatings on a metal (AISI 316-L) substrate by means of Pulsed Electron Deposition, in order to improve the tribological behavior of the polymer-metal coupling, by reducing the initial wear of the UHMWPE component. In order to optimize the coating characteristics, the effects of working gas pressure on both its morphological and tribological properties were analyzed. Morphological characterization of the films was evaluated by Atomic Force Microscopy (AFM). Coating wettability was also estimated by contact angle (CA) measurement. Tribological performance (coupling friction and wear of UHMWPE) was evaluated by using a ball-on-disc tribometer during highly-stressing tests in dry and lubricated (i.e. NaCl and serum) conditions; friction and wear were specifically evaluated at the initial sliding distances - to highlight the main effect of coating morphology - and after 100m - where the influence of the intrinsic materials properties prevails. AFM analysis highlighted that the working pressure heavily affected the morphological characteristics of the realized films. The wettability of the coating at the highest and lowest deposition pressures (CA ~ 60°, closed to substrate value) decreased for intermediate pressures, reaching a maximum CA of ~ 90°. Regarding tribological tests, a strong correlation was found in the initial steps between friction coefficient and wettability, which decreased as the distance increased. Concerning UHMWPE wear associated to coated counterpart, at 100m a reduction rate of about 7% in dry, 12% in NaCl and 5% in presence of serum was obtained compared to the uncoated counterpart. Differently from what highlighted for friction, no correlation was found between wear rate and morphological parameters. These findings, in agreement with literature, underlined the effect of the deposition pressure on the morphological properties, but suggested that physical characteristics are influenced too. Further research on the deposition process will be required in order to improve the tribological performance of the coating at long distances, addressing - above all - orthopedic applications., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Objectives: To determine the fatigue limits of three-unit monolithic zirconia fixed dental prosthesis (FDPs) before and after grinding of the gingival areas of connectors with diamond burs., Material and Methods: FDPs were milled from pre-sintered blocks of zirconia simulating the absence of the first mandibular molar. Half of the specimens were subjected to grinding, simulating clinical adjustment, and all of them were subjected to glazing procedure. Additional specimens were manufactured for roughness analysis. FDPs were adhesively cemented onto glass-fiber reinforced epoxy resin abutments. Fatigue limits and standard deviations were obtained using a staircase fatigue method (n=20, 100,000 loading cycles/5Hz). The initial test load was 70% of the mean load-to-fracture (n=3) and load increments were 5% of the initial test load for both the control and ground specimens. Data were compared by Student's T-test (α≤0.05)., Results: Both the control and ground groups exhibited similar values of load-to-fracture and fatigue limits. Neither the surface treatments nor ageing affected the surface roughness of the specimens., Conclusions: The damage induced by grinding with fine-grit diamond bur in the gingival area of the connectors did not decrease the fatigue limit of the three-unit monolithic zirconia FDP., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The aim of the present study was to evaluate the influence of intra-oral aging on the tetragonal-to-monoclinic (t→m) phase transformation of two Y-TZP dental ceramics - Lava Frame (Frame) and Lava Plus (Plus) - and determine the impact of this response on their microstructures and mechanical properties: flexural strength, Young's modulus, microhardness and fracture toughness. Standardized ceramic specimens were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). After the baseline analysis, the specimens were attached to personalized intra-oral resin appliances and exposed to the oral cavity of 20 subjects for 60 days and then analyzed again. Specimens produced for mechanical properties evaluation were also analyzed before and after the 60-day intra-oral aging. The data were analyzed using two-way ANOVA and Tukey HSD's post hoc test (α=0.05). Weibull analysis was used to evaluate the strength reliability. Both Y-TZP ceramics suffered t→m phase transformation after 60-day intra-oral aging (Plus=4.7%/Frame=7.7%). SEM and AFM analyses showed dislodgement of ZrO 2 grains and a significant increase in roughness after intra-oral aging for both ceramics. Both Y-TZP ceramics suffered a decrease on flexural strength, Young's modulus and fracture toughness after intra-oral aging (p<0.05). Only Plus presented a decrease of microhardness after intra-oral aging (p<0.05). Intra-oral aging for 60 days produced t→m phase transformation, changed the microstructure and decreased the mechanical properties of two Y-TZP dental ceramics., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This study evaluated the effects of different pre-sintering fabrication processing techniques of Y-TZP ceramic (CAD/CAM Vs. in-lab), considering surface characteristics and mechanical performance outcomes. Pre-sintered discs of Y-TZP ceramic (IPS e.max ZirCAD, Ivoclar Vivadent) were produced using different pre-sintering fabrication processing techniques: Machined- milling with a CAD/CAM system; Polished- fabrication using a cutting device followed by polishing (600 and 1200 SiC papers); Xfine- fabrication using a cutting machine followed by grinding with extra-fine diamond bur (grit size 30 μm); Fine- fabrication using a cutting machine followed by grinding with fine diamond bur (grit size 46 μm); SiC- fabrication using a cutting machine followed by grinding with 220 SiC paper. Afterwards, the discs were sintered and submitted to roughness (n=35), surface topography (n=2), phase transformation (n=2), biaxial flexural strength (n=20), and biaxial flexural fatigue strength (fatigue limit) (n=15) analyses. No monoclinic-phase content was observed in all processing techniques. It can be observed that obtaining a surface with similar characteristics to CAD/CAM milling is essential for the observation of similar mechanical performance. On this sense, grinding with fine diamond bur before sintering (Fine group) was the best mimic protocol in comparison to the CAD/CAM milling., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

An increasing interest in zirconium-89 ( 89 Zr) can be attributed to the isotope's half-life which is compatible with antibody imaging using positron emission tomography (PET). The goal of this work was to develop an efficient means of production for 89 Zr that provides this isotope with high radionuclidic purity and specific activity. We investigated the irradiation of yttrium sputtered niobium coins and compared the yields and separation efficiency to solid yttrium coins. The sputtered coins were irradiated with an incident beam energy of 17.5MeV or 17.8MeV providing a degraded transmitted energy through an aluminum degrader of 12.5MeV or 12.8MeV, respectively, with various currents to determine optimal cyclotron conditions for 89 Zr production. Dissolution of the solid yttrium coin took 2h with 50mL of 2M HCl and dissolution of the sputtered coin took 15-30min with 4mL of 2M HCl. During the separation of 89 Zr from the solid yttrium coins, 77.9 ± 11.2% of the activity was eluted off in an average of 7.3mL of 1M oxalic acid whereas for the sputtered coins, 91 ± 6% was eluted off in an average of 1.2mL of 1M oxalic acid with 100% radionuclidic purity. The effective specific activity determined via DFO-SCN titration from the sputtered coins was 108±7mCi/μmol as compared to 20.3mCi/μmol for the solid yttrium coin production. ICP-MS analysis of the yttrium coin and the sputtered coins showed 99.99% yttrium removed with 178μg of yttrium in the final solution and 99.93-100% of yttrium removed with remaining range of 0-42μg of yttrium in the final solution, respectively. The specific activity calculated for the solid coin and 3 different sputtered coins using the concentration of Zr found via ICP-MS was 140±2mCi/μmol, 300±30mCi/μmol, 410±60mCi/μmol and 1719±5mCi/μmol, respectively. Labeling yields of the 89 Zr produced via sputtered targets for 89 Zr- DFO-trastuzumab were >98%. Overall, these results show the irradiation of yttrium sputtered niobium coins is a highly effective means for the production of 89 Zr., (Copyright © 2017 Elsevier Inc. All rights reserved.)

The catastrophic disruption of the L chondrite parent body in the asteroid belt c. 470 Ma initiated a prolonged meteorite bombardment of Earth that started in the Ordovician and continues today. Abundant L chondrite meteorites in Middle Ordovician strata have been interpreted to be the consequence of the asteroid breakup event. Here we report a zircon U-Pb date of 467.50±0.28 Ma from a distinct bed within the meteorite-bearing interval of southern Sweden that, combined with published cosmic-ray exposure ages of co-occurring meteoritic material, provides a precise age for the L chondrite breakup at 468.0±0.3 Ma. The new zircon date requires significant revision of the Ordovician timescale that has implications for the understanding of the astrogeobiologic development during this period. It has been suggested that the Middle Ordovician meteorite bombardment played a crucial role in the Great Ordovician Biodiversification Event, but this study shows that the two phenomena were unrelated., Competing Interests: The authors declare no competing financial interests.

Ceramics are materials of choice for hip joint implants because of their excellent biocompatibility and mechanical properties. Wear of the bearing couple (femoral head and cup) remains one of the main concerns of hip implants. Although ceramics are known for their good tribological properties, shocks due to micro-separation, friction and hydrothermal ageing in physiological environment remain the three main sources of wear. It has been recently suggested that shock effects dominate but the three degradation mechanisms were so far simulated separately. We developed a procedure that combines sequences of shocks, hydrothermal ageing in an autoclave and friction on hip-walking simulator to investigate their combined effects on Zirconia Toughened Alumina (ZTA) implants. Our results confirm that shocks can be considered as the key phenomenon causing wear, and that their effect is independent of friction and hydrothermal degradation. The analysis of retrieved femoral heads reveals wear features comparable to the ones created experimentally by shocks. Standards (ASTM or ISO) could be improved by including shock tests, which are more relevant than wear tests currently performed on hip simulators at least for Ceramic-on- Ceramic couplings., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Objective: To investigate the effect of aging on phase transformation and mechanical properties of yttria-tetragonal zirconia polycrystal (Y-TZP)., Materials and Methods: Fully-sintered Y-TZP slabs, IPS E-max ZirCAD (ZC - Ivoclar) and Z-5 ceramic (Z5 - C5 Medical Werks), were artificially aged in autoclave for: 0, 30, 60 or 90min. Flexural strength (FS), crystalline changes (X-ray diffraction analysis - XRD) and surface topography were analyzed. 0 and 90min-aged samples were evaluated by nanoindentation to measure hardness and modulus, and results were compared using Wilcoxan Mann Whitney rank sum test (p≤0.05). FS results were compared using two-way ANOVA and Tukey HSD (α=0.05)., Results: Material factor had significant effect (p=0.001) on flexural strength (Z5=966.95MPa; ZC=847.82MPa), but aging did not. Nanoindentation showed incidence of typical load/depth curves combined with some exhibiting features compatible with cracking. When typical curves were considered, aging had no effect on the modulus and hardness, but hardness was dependent on material type. A steady increase in the m phase related to aging time was observed for ZC samples. The maximum incidence of m phase was 6.56% for Z5/60min., Significance: Flexural strength is not affected by surface transformation in dental Y-TZP. Hydrothermal aging has an effect on m content and surface topography of different zirconia brands, but mechanical tests that can precisely characterize surface changes in aged Y-TZP are still missing., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This paper studied the surface quality (damage, morphology, and phase transformation) of yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) in CAD/CAM milling, and subsequent polishing, sintering and sandblasting processes applied in dental restorations. X-ray diffraction and scanning electron microscopy (SEM) were used to scan all processed surfaces to determine phase transformations and analyse surface damage morphology, respectively. The average surface roughness (R a ) and maximum roughness (R z ) for all processed surfaces were measured using desk-top SEM-assisted morphology analytical software. X-ray diffraction patterns prove the sintering-induced monoclinic-tetragonal phase transformation while the sandblasting-induced phase transformation was not detected. The CAD/CAM milling of pre-sintered Y-TZP produced very rough surfaces with extensive fractures and cracks. Simply polishing or sintering of milled pre-sintered surfaces did not significantly improve their surface roughness (ANOVA, p>0.05). Neither sintering-polishing of the milled surfaces could effectively improve the surface roughness (ANOVA, p>0.05). The best surface morphology was produced in the milling-polishing-sintering process, achieving R a =0.21±0.03µm and R z =1.73±0.04µm, which meets the threshold for bacterial retention. Sandblasting of intaglios with smaller abrasives was recommended as larger abrasive produced visible surface defects. This study provides technical insights into process selection for Y-TZP to achieve the improved restorative quality., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The aim of this study was to evaluate the effects of different cooling procedures and a new composite interlayer composition on the flexural strength, and veneer delamination resistance, of an all-ceramic veneered translucent Y-TZP core. One hundred twenty bar-shaped specimens of a translucent Y-TZP ceramic were prepared and divided into three groups: (1) no composite interlayer; (2) a glass interlayer (silica-based glass); (3) a mixed composite interlayer of glass and porcelain veneer material. A veneering porcelain (with and without a composite interlayer) was applied on the specimen surface and sintered. Each core-veneer group was cooled using a rapid or a slow cooling rate. All specimens were tested in four-point bending. Data were statistically analyzed using two-way ANOVA, followed by Post-Hoc tests with Bonferroni correction (α=0.05) and Weibull analysis. The group with no interlayer using the rapid cooling technique exhibited the highest flexural strength. However, with low reliability and the greatest delaminated area of porcelain under tension. A glass interlayer between porcelain veneer and zirconia core presents as a good alternative for maintaining flexural strength and porcelain veneer delamination resistance in zirconia based restorations., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The effect of frictional sliding on the surface degradation of commercially available zirconia-toughened alumina (ZTA) femoral heads was studied using a pin-on-ball wear tester under three different lubricating conditions: dry, water, and squalene. Water and squalene were employed under boundary lubrication regimes. Despite the unique (non-standard) character of this apparatus, standard loading conditions could be applied, which effectively determined dynamic friction coefficients as basic material properties. Two types of surface degradation were observed: (i) the polymorphic tetragonal-to-monoclinic (t→m) transformation of the zirconia (ZrO 2 ) dispersoids, and (ii) the off-stoichiometry drift caused by oxygen vacancy formation within the alumina matrix. Scanning laser microscopy (SLM), Raman spectroscopy (RS), scanning electron microscopy (SEM), cathodoluminescence (CL), and X-ray photoelectron spectroscopy (XPS) were utilized to evaluate the fractions of transformed zirconia phase and the stoichiometric evolution of the oxygen sub-lattice at the surface of wear-tested ZTA components. Wear tracks on the surface of the femoral heads were only detected under dry conditions. Dry wear also showed the highest frictional forces and the most pronounced formation of oxygen vacancies among the tested conditions. Conversely, equivalent or greater amounts of the t→m transformation were observed with water and squalene lubrication when compared to the dry wear condition., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This study aimed to determine the effects of grinding and low temperature aging on the biaxial flexural strength, structural reliability (Weibull analysis), surface topography, roughness analysis, and phase transformation (t→m) of an yttrium-stabilized tetragonal zirconia polycrystalline ceramic. Ceramic discs (15.0×1.2±0.2mm, VITA In-Ceram YZ) were prepared and randomly assigned into six groups according to 2 factors (n=30): 'grinding' (Ctrl - without treatment, as-sintered; Xfine - grinding with extra fine diamond bur - 30µm; Coarse - grinding by coarse diamond bur - 151µm), and 'aging' (without or with aging: Ctrl LTD ; Xfine LTD ; Coarse LTD ). Grinding was performed in an oscillatory motion with a contra-angle handpiece under constant water-cooling. Low temperature degradation (LTD) was simulated in an autoclave at 134°C, under 2bar pressure, for 20h. The roughness (R a and R z parameters) significantly increased after grinding in accordance with bur grit-size (Coarse>Xfine>Ctrl), and aging promoted distinct effects (Ctrl=Ctrl LTD ; Xfine>Xfine LTD ; Coarse=Coarse LTD ). Grinding increased the m-phase, and aging led to an increase in the m-phase in all groups. However, different susceptibilities to LTD were observed. Weibull analysis showed a significant increase in the characteristic strength after grinding (Coarse=Xfine>Ctrl), while aging did not lead to any deleterious impact. Neither grinding nor aging resulted in any deleterious impact on material reliability (no statistical decrease in the Weibull moduli). Thus, neither grinding nor aging led to a deleterious effect on the mechanical properties of the evaluated Y-TZP ceramic although a high m-phase content and roughness were observed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Background: Immediately-loaded, narrow-diameter implants can be a less invasive alternative for the implant-supported fixed rehabilitation of narrow, posterior crests., Purpose: To determine the stability and marginal bone level (MBL) changes of narrow-diameter, titanium-zirconium (TiZr) implants placed with flapless surgery and loaded immediately in the posterior region., Materials and Methods: Thirty-eight TiZr implants (3.3 mm diameter, 10 mm length, Roxolid, Straumann AG) were placed in the posterior crests of 14 patients with computer-guided flapless surgery as a support of 3-unit posterior bridges. Eighteen implants were loaded immediately, and 20 implants were loaded conventionally. The implant stability quotients were determined at the 1, 2, 4, and 8. weeks of healing before conventional loading, and at the 3, 6, and 12. months after loading by resonance frequency analysis. The MBL changes were measured by digital radiography., Results: The surgical protocols were accomplished without any biological complications. There was no significant difference in the stability changes of TiZr implants between the loading groups (p > .05). The MBL changes were -0.18 ± 0.27 mm and -0.24 ± 0.27 mm at the 12. month of immediate and conventional loading, respectively, which was not statistically significant (p > .05)., Conclusion: The stability and MBL changes of TiZr implants supporting posterior 3-unit bridges were clinically acceptable at the first year of loading., (© 2016 Wiley Periodicals, Inc.)

The aim of this study was to systematically review the literature to assess the effect of grinding on the mechanical properties, structural stability and superficial characteristics of Y-TZP ceramics. The MEDLINE via PubMed and Web of Science (ISI - Web of Knowledge) electronic databases were searched with included peer-reviewed publications in English language and with no publication year limit. From 342 potentially eligible studies, 73 were selected for full-text analysis, 30 were included in the systematic review with 20 considered in the meta-analysis. Two reviewers independently selected the studies, extracted the data, and assessed the risk of bias. Statistical analyses were performed using RevMan 5.1, with random effects model, at a significance level of 0.05. A descriptive analysis considering phase transformation, Y-TZP grain size, Vickers hardness, residual stress and aging of all included studies were executed. Four outcomes were considered in the meta-analyses (factor: grinding x as-sintered) in global and subgroups analyses (grinding tool, grit-size and cooling) for flexural strength and roughness (Ra) data. A significant difference (p<0.05) was observed in the global analysis for strength, favoring as-sintered; subgroup analyses revealed that different parameters lead to different effects on strength. In the global analysis for roughness, a significant difference (p<0.05) was observed between conditions, favoring grinding; subgroup analyses revealed that different parameters also lead to different effects on roughness. High heterogeneity was found in some comparisons. Generally grinding promotes decrease in strength and increase in roughness of Y-TZP ceramics. However, the use of a grinding tool that allows greater accuracy of the movement (i.e. contra angle hand-pieces coupled to slowspeed turbines), small grit size (<50μm) and the use of plenty coolant seem to be the main factors to decrease the defect introduction and allow the occurrence of the toughening transformation mechanism, decreasing the risk of deleterious impact on Y-TZP mechanical properties., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Objectives: In this study on 90 individuals we aimed at evaluating the microRNAs (miRNAs) expression profile associated with personal levels of Titanium (Ti) and Zirconium (Zr) traced in hair samples. Ti and Zr materials are broadly used for dental implants but the biological reactions triggered by a long term presence of these materials in the oral cavity still need to be assessed. MiRNAs are mechanisms that need to be investigated as they play a fundamental role in the control of gene expression following external stimuli and contribute to a wide range of pathophysiological processes., Methods: Using the TaqMan® Low-Density Array, we assessed the expression levels of 377 human miRNAs in peripheral blood of 90 subjects. Hair samples were analyzed for Ti and Zr content using Inductively Coupled Plasma-Mass Spectrometry. We performed multivariable regression analysis to investigate the effects of Ti and Zr exposure on miRNA expression levels. We used the Ingenuity Pathway Analysis (IPA) software to explore the functional role of the investigated miRNAs and the related target genes., Results: Seven miRNAs (miR-99b, miR-142-5p, miR-152, miR-193a-5p, miR-323-3p, miR-335, miR-494) resulted specifically associated with Zr levels. The functional target analysis showed that miRNAs are involved in mechanisms such as inflammation, skeletal and connective tissue disorders., Conclusions: Our data suggest that Zr is more bioactive than Ti and show that miRNAs are relevant molecular mechanisms sensitive to Zr exposure., Competing Interests: The authors have declared that no competing interests exist.

Metal oxide nanoparticles (NP) are applied in the fields of biomedicine, pharmaceutics, and in consumer products as textiles, cosmetics, paints, or fuels. In this context, the functionalization of the NP surface is a common method to modify and modulate the product performance. A chemical surface modification of NP such as an amino-functionalization can be used to achieve a positively charged and hydrophobic surface. Surface functionalization is known to affect the interaction of nanomaterials (NM) with cellular macromolecules and the responses of tissues or cells, like the uptake of particles by phagocytic cells. Therefore, it is important to assess the possible risk of those modified NP for human health and environment. By applying Raman microspectroscopy, we verified in situ the interaction of amino-modified ZrO2 NP with cultivated macrophages. The results demonstrated strong adhesion properties of the NP to the cell membrane and internalization into the cells. The intracellular localization of the NP was visualized via Raman depth scans of single cells. After the cells were treated with sodium azide (NaN3) and 2-deoxy-glucose to inhibit the phagocytic activity, NP were still detected inside cells to comparable percentages. The observed tendency of amino-modified ZrO2 NP to interact with the cultivated macrophages may influence membrane integrity and cellular functions of alveolar macrophages in the respiratory system. Graphical abstract Detection of ZrO2 NM at subcellular level.

The present study investigated the essential and non-essential elements in cultivated and wild mussels and assessed the health risk arising from their consumption as an impact of rapid growth and intensive production of Mytilus galloprovincialis in the mussel farms of the Boka Kotorska Bay. The concentrations of macro, micro, nonessential and even the small amounts of potentially toxic elements in the cultivated and wild mussels were influenced by industry, tourism and the geohydrology of the Bay. In the case of cultivated mussels, the limiting factor, i.e., the element the elevated concentration of which restricts mussels consumption, was Zr, while in the case of wild mussels the limiting factors were Cr and As. The sites with cultivated mussels stand out as sites with the highest calculated element pollution index, the total hazard index and with higher estimated risk to the health of consumers., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Benthic foraminifera are single-celled eukaryotes that make a protective organic, agglutinated or calcareous test. Some agglutinated, single-chambered taxa, including Psammophaga Arnold, 1982, retain mineral particles in their cytoplasm, but the selective mechanism of accumulation is not clear. Here, we report the ability of a foraminiferal species to select and accumulate zircons and other heavy minerals in their cytoplasm. In particular, the use of Scanning Electron Microscope coupled with an Energy Dispersive X-ray microanalysis system (SEM-EDS) enabled a representative overview of the mineral diversity and showed that the analysed Psammophaga zirconia sp. nov. individuals contained dominantly crystals of zircon (51%), titanium oxides (27%), and ilmenite (11%) along with minor magnetite and other minerals. The studied specimens occur in the shallow central Adriatic Sea where the sediment has a content of zircon below 1% and of other heavy minerals below 4%. For that reason we hypothesize that: (i) P. zirconia may be able to chemically select minerals, specifically zircon and rutile; (ii) the chemical mechanism allowing the selection is based on electrostatic interaction, and it could work also for agglutinated foraminifera (whether for ingestion, like Xenophyophores, or incorporation in the test as in many other described taxa). In particular, this aptitude for high preferential uptake and differential ingestion or retention of zircon is reported here for the first time, together with the selection of other heavy minerals already described in members of the genus Psammophaga. They are generally counted among early foraminifera, constructing a morphologically simple test with a single chamber. Our molecular phylogenetic study confirms that P. zirconia is a new species, genetically distinctive from other Psammophaga, and occurs in the Adriatic as well as in the Black Sea., (© 2016 John Wiley & Sons Ltd.)

For PET radionuclides, the radioactivity of a sample can be conveniently measured by a dose calibrator. These devices depend on a "calibration setting number", but many recommended settings from manuals were interpolated based on standard sources of other radionuclide(s). We conducted HPGe gamma-ray spectroscopy, resulting in a reference for determining settings in two types of vessels containing one of several PET radionuclides. Our results reiterate the notion that in-house, experimental calibrations are recommended for different radionuclides and vessels., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The flocculation efficiency of a cationic polyelectrolyte with quaternary ammonium salt groups in the backbone, namely PCA5 was evaluated on zirconium silicate (kreutzonit), kaolin, K- feldspar and zinc oxide (ZnO) suspensions prepared either with each pollutant or with their mixture. The effect of several parameters such as settling time, polymer dose and the pollutant type on the separation efficacy was evaluated and followed by optical density and zeta potential measurements. Except for ZnO, the interactions between PCA5 and suspended particles led to low residual turbidity values (around 4% for kreutzonit, 5% for kaolin and 8% for K-feldspar) as well as to the reduction of flocs settling time (from 1200 min to 30 min and 120 min in case of kaolinit and K-feldspar, respectively), that meant a high efficiency in their separation. The negative value of the zeta potential and flocs size measurements, at the optimum polymer dose, point to contribution from charge patch mechanism for the particles flocculation. A good efficiency of PCA5 in separation of paraffin oil (a minimum residual turbidity of 9.8%) has been also found., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

It is well-known that proximity-dependent probes containing an analyte recognization site and a signal formation domain could be assembled specifically into a sandwich-like structure (probe-analyte-probe) via introducing an analyte. In this work, using the design for zirconium ion (Zr(4+)) detection as the model, we develop a novel and reliable proximity-dependent DNA-scaffolded silver nanocluster (DNA/AgNC) probe for Zr(4+) detection via target-induced emitter proximity. The proposed strategy undergoes the two following processes: target-mediated emitter pair proximity as target recognition implement and the synthesis of DNA/AgNCs with fluorescence as a signal reporter. Upon combination of the rationally designed probe with Zr(4+), the intact templates were obtained according to the -PO3(2-)-Zr(4+)-PO3(2-)- pattern. The resultant structure with an emitter pair serves as a potent template to achieve highly fluorescent DNA/AgNCs. To verify the universality of the proposed proximity-dependent DNA/AgNC probe, we extend the application of the proximity-dependent probe to DNA and adenosine triphosphate (ATP) detection by virtue of a specific DNA complementary sequence and ATP aptamer as a recognition unit, respectively. The produced fluorescence enhancement of the DNA/AgNCs in response to the analyte concentration allows a quantitative evaluation of the target, including Zr(4+), DNA, and ATP with detection limits of ∼3.00 μM, ∼9.83 nM, and ∼0.81 mM, respectively. The proposed probe possesses good performance with simple operation, cost-effectiveness, good selectivity, and without separation procedures.

Detrital zircon studies are providing new insights on the evolution of sedimentary basins but the role of sedimentary recycling remains largely undefined. In a broad region of northwestern North America, this contribution traces the pathway of detrital zircon sand grains from Proterozoic sandstones through Phanerozoic strata and argues for multi-stage sedimentary recycling over more than a billion years. As a test of our hypothesis, integrated palynology and detrital zircon provenance provides clear evidence for erosion of Carboniferous strata in the northern Cordillera as a sediment source for Upper Cretaceous strata. Our results help to calibrate Earth's sedimentary cycle by showing that recycling dominates sedimentary provenance for the refractory mineral zircon.

Evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ∼ 3.5 billion years (Ga), the chemofossil record arguably to ∼ 3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in a crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ(13)CPDB of -24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ∼ 300 My earlier than has been previously proposed.

Objective: The objective of this 5-year cohort investigation was to determine the survival and success rate of all-ceramic reconstructions on zirconia oral implants., Material and Methods: Ninety-three patients received 122 one-piece zirconia implants. One hundred seventeen implants were restored with 63 single crowns (SCs) and 27 three-unit bridges (fixed dental prostheses, FDPs) fabricated using zirconia frameworks (Procera(®) Zirconia, Nobel Biocare(®), Göteborg, Sweden) hand-layered with a silicate ceramic (NobelRondo(™) Zirconia, Nobel Biocare(®)). With any occurrence of chipping regarded as an event, Kaplan-Meier success curves were plotted. Covariates (gender, location, manufacturing date) were estimated by the use of log-rank tests., Results: Eighty-nine patients received prosthetic reconstructions. Sixty-three of them were seen at the 5-year follow-up, with a mean observation time of 58.2 months (47 patients with SCs, 16 patients with FDPs). Reasons for the decreasing number of patients at the follow-up sessions included dropouts due to implant loss (n = 21), moving (n = 3), missed appointments (n = 1), and severe illness (n = 1). Over half of the SCs (57.2%) and 38% of the FDPs were successful after an observation time of 5 years (overall success rate of 51.7%). The performed log-rank tests revealed no statistically significant differences for the success curves regarding the above-mentioned covariates. Among the 63 restorations that completed the study, 11 of 47 SCs and one of 16 FDPs had to be replaced due to the severity of the observed chipping. This results in survival rates of 76.6% for the SCs and 93.8% for the FDPs. No framework fractures or decementations were observed in any group., Conclusion: Hand-layering of zirconia-based SCs and FDPs with NobelRondo(™) Zirconia restoring one-piece zirconia implants did not show acceptable survival and success rates. Meanwhile, the material has been recalled from the market. It is advised that new materials should undergo adequate preclinical evaluation before coming to the market., (© 2014 Wiley Periodicals, Inc.)

Purpose: Peri-implantitis is a disease characterized by soft tissue inflammation and continued loss of supporting bone, which can result in implant failure. Peri-implantitis is a multifactorial disease, and one of its triggering factors may be the presence of excess cement in the soft tissues surrounding an implant. This descriptive study evaluated the composition of foreign particles from 36 human biopsy specimens with 19 specimens selected for analysis. The biopsy specimens were obtained from soft tissues affected by peri-implantitis around cement-retained implant crowns and compared with the elemental composition of commercial luting cement., Materials and Methods: Nineteen biopsy specimens were chosen for the comparison, and five test cements (TempBond, Telio, Premier Implant Cement, Intermediate Restorative Material, and Relyx) were analyzed using scanning electron microscopy equipped with energy dispersive x-ray spectroscopy. This enabled the identification of the chemical composition of foreign particles embedded in the tissue specimens and the composition of the five cements. Statistical analysis was conducted using classification trees to pair the particles present in each specimen with the known cements., Results: The particles in each biopsy specimen could be associated with one of the commercial cements with a level of probability ranging between .79 and 1. TempBond particles were found in one biopsy specimen, Telio particles in seven, Premier Implant Cement particles in four, Relyx particles in four, and Intermediate Restorative Material particles in three., Conclusion: Particles found in human soft tissue biopsy specimens around implants affected by peri-implant disease were associated with five commercially available dental cements.

Purpose: We evaluated the dosimetry of [(89)Zr]rituximab, an anti-CD20 immunoPET tracer to image B cell non-Hodgkin's lymphoma (NHL) using a humanized transgenic mouse model that expresses human CD20 transgenic mice (huCD20TM)., Procedures: Rituximab was conjugated to desferrioxamine (Df) for radiolabeling of Zirconium-89. [(89)Zr]rituximab (2.8 ± 0.2 MBq) was tail vein-injected into huCD20T mice. Positron emission tomography (PET)/CT imaging was performed on the two groups of mice (blocking = 2 mg/kg pre-dose of rituximab and non-blocking; n = 5) at eight time points (1, 4, 24, 48, 72, 96, 120, and 168 h) post injection., Results: The novel [(89)Zr]rituximab PET tracer had good immunoreactivity, was stable in human serum, and was able to specifically target human CD20 in mice. The human equivalents of highest dose (mean ± SD) organs with and without pre-dose are liver (345 ± 284 μSv/MBq) and spleen (1165 ± 149 μSv/MBq), respectively., Conclusions: Dosimetry of the human patient whole-body dose was found to be 145 MBq per annum, and the patient dose-limiting organ will be the liver (with rituximab pre-dose blocking) and spleen for non-blocking. The [(89)Zr]rituximab (t½ = 78.4 h) imaging of B cell NHL patients could permit the observation of targeting lesions in NHL patients over an extended period due to longer half-life as compared to the [(64)Cu] rituximab (t½ = 12.7 h).

Granitoids are silicic rocks that make up the majority of the continental crust, but different models arise for the origins of these rocks. One classification scheme defines different granitoid types on the basis of materials involved in the melting/crystallization process. In this end-member case, granitoids may be derived from melting of a preexisting igneous rock, while other granitoids, by contrast, are formed or influenced by melting of buried sedimentary material. In the latter case, assimilated sedimentary material altered by chemical processes occurring at the near surface of Earth-including biological activity-could influence magma chemical properties. Here, we apply a redox-sensitive calibration based on the incorporation of Ce into zircon crystals found in these two rock types, termed sedimentary-type (S-type) and igneous-type (I-type) granitoids. The ∼400 Ma Lachlan Fold Belt rocks of southeastern Australia were chosen for investigation here; these rocks have been a key target used to describe and explore granitoid genesis for close to 50 years. We observe that zircons found in S-type granitoids formed under more reducing conditions than those formed from I-type granitoids from the same terrain. This observation, while reflecting 9 granitoids and 289 analyses of zircons from a region where over 400 different plutons have been identified, is consistent with the incorporation of (reduced) organic matter in the former and highlights one possible manner in which life may modify the composition of igneous minerals. The chemical properties of rocks or igneous minerals may extend the search for ancient biological activity to the earliest period of known igneous activity, which dates back to ∼4.4 billion years ago. If organic matter was incorporated into Hadean sediments that were buried and melted, then these biological remnants could imprint a chemical signature within the subsequent melt and the resulting crystal assemblage, including zircon.