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Robust chronologies and time equivalent tephra markers are essential to better understand spatial palaeoenvironmental response to past abrupt climatic changes. Identification of well-dated and widely dispersed volcanic ash by tephra and cryptotephra (microscopic volcanic ash) provides time synchronous tie-points and strongly reduces chronological uncertainties. Here, we present the major, minor and trace element analyses of cryptotephra shards in the Dead Sea Deep Drilling sedimentary record (DSDDP 5017-1A) matching the Campanian Ignimbrite (CI). This geochemical identification expands the known dispersal range of the CI to the southeastern Mediterranean, over 2300 km from the volcanic source. Due to the CI eruption occurring near-synchronous with North Atlantic ice surge of Heinrich Event 4 (HE4), this tephra provides insights into regional responses to large-scale climatic change in the Mediterranean. In the Dead Sea, the CI layer is associated with wetter climatic conditions. This contrasts with the contemporaneous occurrence of the CI deposition and dry conditions in the central and eastern Mediterranean suggesting a possible climate time-transgressive expansion of HE4. Our finding underscores the temporal and spatial complexity of regional climate responses and emphasises the importance of tephra as a time marker for studying large-scale climatic changes verses regional variations., (© 2024. The Author(s).)

Lanthanide based ceria nanomaterials are important practical materials due to the redox properties that are useful in the avenues pertaining to technology and life sciences. Sub 10 nm spherical and highly monodisperse Ce 1- x Yb x O 2- y (0.04 ≤ x ≤ 0.22) nanoparticles were synthesized by thermal decomposition, annealed separately at 773 K and 1273 K for 2 hours and characterized. Elemental mapping for Yb 3+ doped ceria nanoparticles shows homogeneous distribution of Yb 3+ atoms in the ceria with low Yb 3+ content annealed at 773 K and 1273 K for 2 hours. However, clusters are observed for 773 K annealed ceria samples with high concentration of Yb 3+ . These clusters are not detected in 1273 K annealed nanomaterials. Introducing small amounts of Yb 3+ ions into the ceria lattice as spectroscopic probes can provide detailed information about the atomic structure and local environments allowing the monitoring of small structural changes, such as clustering. The emission spectra observed at room temperature and at 4 K have a manifold of bands that corresponds to the 2 F 5/2 → 2 F 7/2 transition of Yb 3+ ions. Some small shifts are observed in the Stark splitting pattern depending on the sample and the annealing conditions. The deconvolution by PARAFAC analysis yielded luminescence decay kinetics as well as the associated luminescence spectra of three species for each of the low Yb 3+ doped ceria samples annealed at 773 K and one species for the 1273 K annealed samples. However, the ceria samples with high concentration of Yb 3+ annealed at the two temperatures showed only one species with lower decay times as compared to the low Yb 3+ doped ceria samples., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

New TiO 2 hybrid composites were prepared from kaolin clay, predried and carbonized biomass, and titanium tetraisopropoxide and explored for tetracycline (TET) and bisphenol A (BPA) removal from water. Overall, the removal rate is 84% for TET and 51% for BPA. The maximum adsorption capacities ( q m ) are 30 and 23 mg/g for TET and BPA, respectively. These capacities are far greater than those obtained for unmodified TiO 2 . Increasing the ionic strength of the solution does not change the adsorption capacity of the adsorbent. pH changes only slightly change BPA adsorption, while a pH > 7 significantly reduces the adsorption of TET on the material. The Brouers-Sotolongo fractal model best describes the kinetic data for both TET and BPA adsorption, predicting that the adsorption process occurs via a complex mechanism involving various forces of attraction. Temkin and Freundlich isotherms, which best fit the equilibrium adsorption data for TET and BPA, respectively, suggest that adsorption sites are heterogeneous in nature. Overall, the composite materials are much more effective for TET removal from aqueous solution than for BPA. This phenomenon is assigned to a difference in the TET/adsorbent interactions vs the BPA/adsorbent interactions: the decisive factor appears to be favorable electrostatic interactions for TET yielding a more effective TET removal., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Eight d-metal-containing N -butylpyridinium ionic liquids (ILs) with the nominal composition (C 4 Py) 2 [Ni 0.5 M 0.5 Cl 4 ] or (C 4 Py) 2 [Zn 0.5 M 0.5 Cl 4 ] (M = Cu, Co, Mn, Ni, Zn; C 4 Py = N -butylpyridinium) were synthesized, characterized, and investigated for their optical properties. Single crystal and powder X-ray analysis shows that the compounds are isostructural to existing examples based on other d-metal ions. Inductively coupled plasma optical emission spectroscopy measurements confirm that the metal/metal ratio is around 50 : 50. UV-Vis spectroscopy shows that the optical absorption can be tuned by selection of the constituent metals. Moreover, the compounds can act as an optical sensor for the detection of gases such as ammonia as demonstrated via a simple prototype setup., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Fifteen N-butylpyridinium salts - five monometallic [C 4 Py] 2 [MBr 4 ] and ten bimetallic [C 4 Py] 2 [M 0.5 a M 0.5 ] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10 b Br 4 ] (M=Co, Cu, Mn, Ni, Zn) - were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10 -5 and 10 -6  S cm -1 at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.-4  S cm -1 at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Dual-energy computed tomography (DECT) is an imaging technique that combines nondestructive morphological cross-sectional imaging of objects and the quantification of their chemical composition. However, its potential to assist investigations in paleontology has not yet been explored. This study investigates quantitative DECT for the nondestructive density- and element-based material decomposition of fossilized bones. Specifically, DECT was developed and validated for imaging-based calcium and fluorine quantification in bones of five fossil vertebrates from different geological time periods and of one extant vertebrate. The analysis shows that DECT material maps can differentiate bone from surrounding sediment and reveals fluorine as an imaging marker for fossilized bone and a reliable indicator of the age of terrestrial fossils. Moreover, the jaw bone mass of Tyrannosaurus rex showed areas of particularly high fluorine concentrations on DECT, while conventional CT imaging features supported the diagnosis of chronic osteomyelitis. These findings highlight the relevance of radiological imaging techniques in the natural sciences by introducing quantitative DECT imaging as a nondestructive approach for material decomposition in fossilized objects, thereby potentially adding to the toolbox of paleontological studies., (© 2022. The Author(s).)

Purpose: To describe the perfusion patterns of peripheral pulmonary granulomatous lesions (PPGLs) by contrast-enhanced ultrasound (CEUS) and their correlation with vascularization patterns (VPs) represented by immunohistochemical (CD34) endothelial staining., Patients and Methods: From January 2007 until September 2020, 10 consecutive patients with histologically confirmed PPGLs were investigated by CEUS. The time to enhancement, classified as early pulmonary-arterial (PA) pattern of enhancement versus delayed bronchial-arterial (BA) pattern of enhancement, the extent of enhancement, classified as marked or reduced, the homogeneity of enhancement, classified as homogeneous or inhomogeneous, and the decrease of enhancement, classified as rapid washout (<120 seconds) or a late washout (≥120 seconds), were analyzed retrospectively. Furthermore, the tissue samples from the study patients and as a control group, 10 samples of normal lung tissue obtained by autopsy, and 10 samples of lung tissue with acute pneumonia obtained by autopsy were immunohistochemically stained with CD34 antibody. The presence of avascular areas (AAs) and the VPs were evaluated in all tissue samples., Results: On CEUS, all PPGLs showed a reduced inhomogeneous BA pattern of enhancement and a rapid washout (<120 seconds). On CD34 staining, all PPGLs showed central AAs in granulomas and a chaotic VP similar to angiogenesis in lung tumors. The lung tissue in control groups revealed on CD34 staining a regular alveolar VP., Conclusion: The PPGLs on CEUS show an identical perfusion pattern similar to those of malignant lesions. Furthermore, for the first time, neoangiogenesis was demonstrated as a histopathological correlate to BA pattern of enhancement on CEUS., (© 2021 The Authors. Journal of Ultrasound in Medicine published by Wiley Periodicals LLC on behalf of American Institute of Ultrasound in Medicine.)

The imagination of clearly separated core-shell structures is already outdated by the fact, that the nanoparticle core-shell structures remain in terms of efficiency behind their respective bulk material due to intermixing between core and shell dopant ions. In order to optimize the photoluminescence of core-shell UCNP the intermixing should be as small as possible and therefore, key parameters of this process need to be identified. In the present work the Ln(III) ion migration in the host lattices NaYF 4 and NaGdF 4 was monitored. These investigations have been performed by laser spectroscopy with help of lanthanide resonance energy transfer (LRET) between Eu(III) as donor and Pr(III) or Nd(III) as acceptor. The LRET is evaluated based on the Förster theory. The findings corroborate the literature and point out the migration of ions in the host lattices. Based on the introduced LRET model, the acceptor concentration in the surrounding of one donor depends clearly on the design of the applied core-shell-shell nanoparticles. In general, thinner intermediate insulating shells lead to higher acceptor concentration, stronger quenching of the Eu(III) donor and subsequently stronger sensitization of the Pr(III) or the Nd(III) acceptors. The choice of the host lattice as well as of the synthesis temperature are parameters to be considered for the intermixing process.

Activated carbons (ACs) were prepared from dried spent coffee (SCD), a biological waste product, to produce adsorbents for methylene blue (MB) and methyl orange (MO) from aqueous solution. Pre-pyrolysis activation of SCD was achieved via treatment of the SCD with aqueous sodium hydroxide solutions at 90 °C. Pyrolysis of the pretreated SCD at 500 °C for 1 h produced powders with typical characteristics of AC suitable and effective for dye adsorption. As an alternative to the rather harsh base treatment, calcium carbonate powder, a very common and abundant resource, was also studied as an activator. Mixtures of SCD and CaCO 3 (1:1 w / w ) yielded effective ACs for MO and MB removal upon pyrolysis needing only small amounts of AC to clear the solutions. A selectivity of the adsorption process toward anionic (MO) or cationic (MB) dyes was not observed.

Thirteen N-butylpyridinium salts, including three monometallic [C 4 Py] 2 [MCl 4 ], nine bimetallic [C 4 Py] 2 [M 1-x a M x ] and one trimetallic compound [C b Cl 4 ] and one trimetallic compound [C 4 Py] 2 [M 1-y-z a ] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 °C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10 y b M z c Cl 4 ] (M=Co, Cu, Mn; x=0.25, 0.50 or 0.75 and y=z=0.33), were synthesized and their structure and thermal and electrochemical properties were studied. All compounds are ionic liquids (ILs) with melting points between 69 and 93 °C. X-ray diffraction proves that all ILs are isostructural. The conductivity at room temperature is between 10 -4 and 10 -8 at 70 °C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V.-1 . Some Cu-based ILs reach conductivities of 10 -2  S cm -1 , which is, however, probably due to IL dec. This correlates with the optical bandgap measurements indicating the formation of large bandgap semiconductors. At elevated temperatures approaching the melting points, the conductivities reach up to 1.47×10 -1  S cm -1 at 70 °C. The electrochemical stability windows of the ILs are between 2.5 and 3.0 V., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Covellite-phase CuS and carrollite-phase CuCo 2 S 4 nano- and microstructures were synthesized from tetrachloridometallate-based ionic liquid precursors using a novel, facile, and highly controllable hot-injection synthesis strategy. The synthesis parameters including reaction time and temperature were first optimized to produce CuS with a well-controlled and unique morphology, providing the best electrocatalytic activity toward the oxygen evolution reaction (OER). In an extension to this approach, the electrocatalytic activity was further improved by incorporating Co into the CuS synthesis method to yield CuCo 2 S 4 microflowers. Both routes provide high microflower yields of >80 wt %. The CuCo 2 S 4 microflowers exhibit a superior performance for the OER in alkaline medium compared to CuS. This is demonstrated by a lower onset potential (∼1.45 V vs RHE @10 mA/cm 2 ), better durability, and higher turnover frequencies compared to bare CuS flowers or commercial Pt/C and IrO 2 electrodes. Likely, this effect is associated with the presence of Co 3+ sites on which a better adsorption of reactive species formed during the OER (e.g., OH, O, OOH, etc.) can be achieved, thus reducing the OER charge-transfer resistance, as indicated by X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy measurements.

An amendment to this paper has been published and can be accessed via the original article.

Bullous pemphigoid (BP) is the most prevalent autoimmune skin blistering disease and is characterized by the generation of autoantibodies against the hemidesmosomal proteins BP180 (type XVII collagen) and BP230. Most intriguingly, BP is distinct from other autoimmune diseases because it predominantly affects elderly individuals above the age of 75 years, raising the question why autoantibodies and the clinical lesions of BP emerges mostly in this later stage of life, even in individuals harboring known putative BP-associated germline gene variants. The mitochondrial genome (mtDNA) is a potential candidate to provide additional insights into the BP etiology; however, the mtDNA has not been extensively explored to date. Therefore, we sequenced the whole mtDNA of German BP patients ( n = 180) and age- and sex-matched healthy controls ( n = 188) using next generation sequencing (NGS) technology, followed by the replication study using Sanger sequencing of an additional independent BP ( n = 89) and control cohort ( n = 104). While the BP and control groups showed comparable mitochondrial haplogroup distributions, the haplogroup T exhibited a tendency of higher frequency in BP patients suffering from neurodegenerative diseases (ND) compared to BP patients without ND (50%; 3 in 6 BP with haplogroup T). A total of four single nucleotide polymorphisms (SNPs) in the mtDNA, namely, m.16263T>C, m.16051A>G, and m.16162A>G in the D-loop region of the mtDNA, and m.11914G>A in the mitochondrially encoded NADH:ubiquinone oxidoreductase core subunit 4 gene ( MT-ND4 ), were found to be significantly associated with BP based on the meta-analysis of our NGS data and the Sanger sequencing data ( p = 0.0017, p = 0.0129, p = 0.0076, and p = 0.0132, respectively, Peto's test). More specifically, the three SNPs in the D-loop region were negatively, and the SNP in the MT-ND4 gene was positively associated with BP. Our study is the first to interrogate the whole mtDNA in BP patients and controls and to implicate multiple novel mtDNA variants in disease susceptibility. Studies using larger cohorts and more diverse populations are warranted to explore the functional consequences of the mtDNA variants identified in this study on immune and skin cells to understand their contributions to BP pathology., (Copyright © 2019 Russlies, Fähnrich, Witte, Yin, Benoit, Gläser, Günter, Eming, Erdmann, Gola, Gupta, Holtsche, Kern, König, Kiritsi, Lieb, Sadik, Sárdy, Schauer, van Beek, Weidinger, Worm, Zillikens, Schmidt, Busch, Ibrahim and Hirose.)

Background: Electrical stimulation of peripheral nerves is used in a variety of applications such as restoring motor function in paralyzed limbs, and more recently, as means to provide intuitive sensory feedback in limb prostheses. However, literature on the safety requirements for stimulation is scarce, particularly for chronic applications. Some aspects of nerve interfacing such as the effect of stimulation parameters on electrochemical processes and charge limitations have been reviewed, but often only for applications in the central nervous system. This review focuses on the safety of electrical stimulation of peripheral nerve in humans., Methods: We analyzed early animal studies evaluating damage thresholds, as well as more recent investigations in humans. Safety requirements were divided into two main categories: passive and active safety. We made the distinction between short-term (< 30 days) and chronic (> 30 days) applications, as well as between electrode preservation (biostability) and body tissue healthy survival (harmlessness). In addition, transferability of experimental results between different tissues and species was considered., Results: At present, extraneural electrodes have shown superior long-term stability in comparison to intraneural electrodes. Safety limitations on pulse amplitude (and consequently, charge injection) are dependent on geometrical factors such as electrode placement, size, and proximity to the stimulated fiber. In contrast, other parameters such as stimulation frequency and percentage of effective stimulation time are more generally applicable. Currently, chronic stimulation at frequencies below 30 Hz and percentages of effective stimulation time below 50% is considered safe, but more precise data drawn from large databases are necessary. Unfortunately, stimulation protocols are not systematically documented in the literature, which limits the feasibility of meta-analysis and impedes the generalization of conclusions. We therefore propose a standardized list of parameters necessary to define electrical stimulation and allow future studies to contribute to meta-analyses., Conclusion: The safety of chronic continuous peripheral nerve stimulation at frequencies higher than 30 Hz has yet to be documented. Precise parameter values leading to stimulation-induced depression of neuronal excitability (SIDNE) and neuronal damage, as well as the transition between the two, are still lacking. At present, neural damage mechanisms through electrical stimulation remain obscure.

A new micro/mesoporous hybrid clay nanocomposite prepared from kaolinite clay, Carica papaya seeds, and ZnCl 2 via calcination in an inert atmosphere is presented. Regardless of the synthesis temperature, the specific surface area of the nanocomposite material is between ≈150 and 300 m 2 /g. The material contains both micro- and mesopores in roughly equal amounts. X-ray diffraction, infrared spectroscopy, and solid-state nuclear magnetic resonance spectroscopy suggest the formation of several new bonds in the materials upon reaction of the precursors, thus confirming the formation of a new hybrid material. Thermogravimetric analysis/differential thermal analysis and elemental analysis confirm the presence of carbonaceous matter. The new composite is stable up to 900 °C and is an efficient adsorbent for the removal of a water micropollutant, 4-nitrophenol, and a pathogen, E. coli, from an aqueous medium, suggesting applications in water remediation are feasible.

New mesoporous silk fibroin (SF)/silica hybrids were processed via a one-pot soft and energy-efficient sol-gel chemistry and self-assembly from a silica precursor, an acidic or basic catalyst, and the ionic liquid 1-butyl-3-methylimidazolium chloride, acting as both solvent and mesoporosity-inducer. The as-prepared materials were obtained as slightly transparent-opaque, amorphous monoliths, easily transformed into powders, and stable up to ca. 300 °C. Structural data suggest the formation of a hexagonal mesostructure with low range order and apparent surface areas, pore volumes, and pore radii of 205-263 m 2 g -1 , 0.16-0.19 cm 3 g -1 , and 1.2-1.6 nm, respectively. In all samples, the dominating conformation of the SF chains is the β-sheet. Cytotoxicity/bioactivity resazurin assays and fluorescence microscopy demonstrate the high viability of MC3T3 pre-osteoblasts to indirect (≥99 ± 9%) and direct (78 ± 2 to 99 ± 13%) contact with the SF/silica materials. Considering their properties and further improvements, these systems are promising candidates to be explored in bone tissue engineering. They also offer excellent prospects as electrolytes for solid-state electrochemical devices, in particular for fuel cells., Competing Interests: The authors declare no competing financial interest.

Hexagonal p-type semiconductor CuS nanoplates were synthesized via a hot injection method from bis(trimethylsilyl)sulfide and the ionic liquid precursor bis( N -dodecylpyridinium) tetrachloridocuprate(ii). The particles have a broad size distribution with diameters between 30 and 680 nm and well-developed crystal habits. The nanoplates were successfully incorporated into organic photovoltaic (OPV) cells as hole conduction materials. The power conversion efficiency of OPV cells fabricated with the nanoplates is 16% higher than that of a control device fabricated without the nanoplates.

Background: Metal recycling factories (MRFs) have developed rapidly in Nigeria as recycling policies have been increasingly embraced. These MRFs are point sources for introducing potentially toxic elements (PTEs) into environmental media., Objectives: The aim of this study was to determine the constituents (elemental and mineralogy) of the wastes (slag and particulate matter, (PM)) and soils around the MRFs and to determine the level of pollution within the area., Methods: Sixty samples (30 slag samples, 15 soil samples and 15 PM samples) were collected for this study. The soils, slag and PM samples were analyzed for elemental constituents using inductively coupled plasma optical emission spectrometry. Mineralogy of the PM was determined using scanning electron microscope-energy dispersive spectroscopy (SEM-EDS), and soil mineralogy was determined by an X-ray diffractometer (XRD)., Results: The results of the soil analyses revealed the following concentrations for the selected metals in mg/kg include lead (Pb) (21.0-2399.0), zinc (Zn) (56.0-4188.0), copper (Cu) (10.0-1470.0), nickel (Ni) (6.0-215.0), chromium (Cr) (921.0-1737.0) and cadmium (Cd) (below detectable limit (Bdl)-18.1). For the slags the results were Pb (68.0-.333.0), Zn (1364.0-3062), Cu (119.0-1470.0), Ni (12.0-675.0), Cr (297-1737) and Cd (Bdl-15.8). The results in μg/g for the metal analysis in PM were Pb (4.6-160.0), Zn (18.0-471.0), Cu (2.5-11.0), Ni (0.8-4.2), and Cr (2.5-11.0), while Cd was undetected. The slags are currently utilized for filling the foundations of buildings and roads, providing additional pathways for the introduction of PTEs into the environment from the suspended materials generated from mechanical breakdown of the slags., Conclusions: The MRFs were found to have impacted the quality of environmental media through the introduction of PTEs, impairing soil quality, in addition to PM, which can have detrimental health consequences. Further studies on the health implications of these pollutants and their impacts on human health are needed., Competing Interests: The authors declare no competing financial interests.

The article describes the surface modification of 3D printed poly(lactic acid) (PLA) scaffolds with calcium phosphate (CP)/gelatin and CP/chitosan hybrid coating layers. The presence of gelatin or chitosan significantly enhances CP co-deposition and adhesion of the mineral layer on the PLA scaffolds. The hydrogel/CP coating layers are fairly thick and the mineral is a mixture of brushite, octacalcium phosphate, and hydroxyapatite. Mineral formation is uniform throughout the printed architectures and all steps (printing, hydrogel deposition, and mineralization) are in principle amenable to automatization. Overall, the process reported here therefore has a high application potential for the controlled synthesis of biomimetic coatings on polymeric biomaterials., Competing Interests: The authors declare no conflict of interest. The funding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO 2 )/gold(Au)/ Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m 2 /g. The diameter of the TiO 2 nanoparticles (NPs) - mainly anatase with a minor fraction of brookite - and the Au NPs are on the order of 5 and 7-18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.

Hybrid clay composites were prepared from Kaolinite clay and Carica papaya seeds via modification with chitosan, Alum, NaOH, and ZnCl 2 in different ratios, using solvothermal and surface modification techniques. Several composite adsorbents were prepared, and the most efficient of them for the removal of gram negative enteric bacteria was the hybrid clay composite that was surface-modified with chitosan, Ch-nHYCA 1:5 (Chitosan: nHYCA = 1:5). This composite adsorbent had a maximum adsorption removal value of 4.07 × 10 6 cfu/mL for V. cholerae after 120 min, 1.95 × 10 6 cfu/mL for E. coli after ∼180 min and 3.25 × 10 6 cfu/mL for S. typhi after 270 min. The Brouers-Sotolongo model was found to better predict the maximum adsorption capacity ( q max ) of Ch-nHYCA 1:5 composite adsorbent for the removal of E. coli with a q max of 103.07 mg/g (7.93 × 10 7 cfu/mL) and V. cholerae with a q max of 154.18 mg/g (1.19 × 10 8 cfu/mL) while the Sips model best described S. typhi adsorption by Ch-nHYCA 1:5 composite with an estimated q max of 83.65 mg/g (6.43 × 10 7 cfu/mL). These efficiencies do far exceed the alert/action levels of ca. 500 cfu/mL in drinking water for these bacteria. The simplicity of the composite preparation process and the availability of raw materials used for its preparation underscore the potential of this low-cost chitosan-modified composite adsorbent (Ch-nHYCA 1:5 ) for water treatment.

Understanding the mechanisms responsible for generating different phases and morphologies of calcium phosphate by elastin-like recombinamers is supreme for bioengineering of advanced multifunctional materials. The generation of such multifunctional hybrid materials depends on the properties of their counterparts and the way in which they are assembled. The success of this assembly depends on the different approaches used, such as recombinant DNA technology and click chemistry. In the present work, an elastin-like recombinamer bearing lysine amino acids distributed along the recombinamer chain has been cross-linked via Huisgen [2 + 3] cycloaddition. The recombinamer contains the SN A 15 peptide domains inspired by salivary statherin, a peptide epitope known to specifically bind to and nucleate calcium phosphate. The benefit of using click chemistry is that the hybrid elastin-like-statherin recombinamers cross-link without losing their fibrillar structure. Mineralization of the resulting hybrid elastin-like-statherin recombinamer hydrogels with calcium phosphate is described. Thus, two different hydroxyapatite morphologies (cauliflower- and plate-like) have been formed. Overall, this study shows that crosslinking elastin-like recombinamers leads to interesting matrix materials for the generation of calcium phosphate composites with potential applications as biomaterials.

In this work, we report three isostructural 3D frameworks, named IFP-11 (R = Cl), IFP-12 (R = Br), and IFP-13 (R = Et) (IFP = Imidazolate Framework Potsdam) based on a cobalt(II) center and the chelating linker 2-substituted imidazolate-4-amide-5-imidate. These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under microwave (MW)-assisted conditions in DMF. Structure determination of these IFPs was investigated by IR spectroscopy and a combination of powder X-ray diffraction (PXRD) with structure modeling. The structural models were initially built up from the single-crystal X-ray structure determination of IFP-5 (a cobalt center and 2-methylimidazolate-4-amide-5-imidate linker based framework) and were optimized by using density functional theory calculations. Substitution on position 2 of the linker (R = Cl, Br, and Et) in the isostructural IFP-11, -12, and -13 allowed variation of the potential pore window in 1D hexagonal channels (3.8 to 1.7 Å). The potential of the materials to undergo specific interactions with CO2 was measured by the isosteric heat of adsorption. Further, we resynthesized zinc based IFPs, namely IFP-1 (R = Me), IFP-2 (R = Cl), IFP-3 (R = Br), and IFP-4 (R = Et), and cobalt based IFP-5 under MW-assisted conditions with higher yield. The transition from a nucleation phase to the pure crystalline material of IFP-1 in MW-assisted synthesis depends on reaction time. IFP-1, -3, and -5, which are synthesized by MW-assisted conditions, showed an enhancement of N2 and CO2, compared to the analogous conventional electrical (CE) heating method based materials due to crystal defects.

Poly(ethylene oxide) (PEO) has long been used as an additive in toothpaste, partly because it reduces biofilm formation on teeth. It does not, however, reduce the formation of dental calculus or support the remineralization of dental enamel or dentine. The present article describes the synthesis of new block copolymers on the basis of PEO and poly(3-sulfopropyl methacrylate) blocks using atom transfer radical polymerization. The polymers have very large molecular weights (over 10(6) g/mol) and are highly water-soluble. They delay the precipitation of calcium phosphate from aqueous solution but, upon precipitation, lead to relatively monodisperse hydroxyapatite (HAP) spheres. Moreover, the polymers inhibit the bacterial colonization of human enamel by Streptococcus gordonii, a pioneer bacterium in oral biofilm formation, in vitro. The formation of well-defined HAP spheres suggests that a polymer-induced liquid precursor phase could be involved in the precipitation process. Moreover, the inhibition of bacterial adhesion suggests that the polymers could be utilized in caries prevention.

Cellulose/calcium phosphate hybrid materials were synthesized via an ionic liquid-assisted route. Scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis/differential thermal analysis show that, depending on the reaction conditions, cellulose/hydroxyapatite, cellulose/chlorapatite, or cellulose/monetite composites form. Preliminary studies with MC3T3-E1 pre-osteoblasts show that the cells proliferate on the hybrid materials suggesting that the ionic liquid-based process yields materials that are potentially useful as scaffolds for regenerative therapies.

The genus Arcobacter is composed of 17 species which have been isolated from various sources. Of particular interest are A. butzleri, A. cryaerophilus, and A. skirrowii, as these have been associated with human cases of diarrhea, the probable transmission routes being through the ingestion of contaminated drinking water and food. To date, only limited studies of virulence traits in this genus have been undertaken. The present study used 60 Arcobacter strains isolated from different sources, representing 16 of the 17 species of the genus, to investigate their ability to adhere to and invade the human intestinal cell line Caco-2. In addition, the presence of five putative virulence genes (ciaB, cadF, cj1349, hecA, and irgA) was screened for in these strains by PCR. All Arcobacter species except A. bivalviorum and Arcobacter sp. strain W63 adhered to Caco-2 cells, and most species (10/16) were invasive. The most invasive species were A. skirrowii, A. cryaerophilus, A. butzleri, and A. defluvii. All invasive strains were positive for ciaB (encoding a putative invasion protein). Other putative virulence genes were present in other species, i.e., A. butzleri (cadF, cj1349, irgA, and hecA), A. trophiarum (cj1349), A. ellisii (cj1349), and A. defluvii (irgA). No virulence genes were detected in strains which showed little or no invasion of Caco-2 cells. These results indicate that many Arcobacter species are potential pathogens of humans and animals.

We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-1-4, IFP = imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R = Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.0-1.7 Å), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and (1)H MAS and (13)C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345-400 °C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO(2) was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH(4) (at 298 K), CO(2) (at 298 K) and H(2) (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO(2) is physisorbed on IFP-1-4 under dry conditions and that both CO(2) and H(2)O are physisorbed on IFP-1 under moist conditions., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The sensing potential of CuO nanoparticles synthesized via precipitation from a water/ionic liquid precursor (ILP) mixture was investigated. The particles have a moderate surface area of 66 m(2)/g after synthesis, which decreases upon thermal treatment to below 5 m(2)/g. Transmission electron microscopy confirms crystal growth upon annealing, likely due to sintering effects. The as-synthesized particles can be used for ethanol sensing. The respective sensors show fast response and recovery times of below 10 s and responses greater than 2.3 at 100 ppm of ethanol at 200 °C, which is higher than any CuO-based ethanol sensor described so far.

Functional hybrid materials on the basis of inorganic hosts and ionic liquids (ILs) as guests hold promise for a virtually unlimited number of applications. In particular, the interaction and the combination of properties of a defined inorganic matrix and a specific IL could lead to synergistic effects in property selection and tuning. Such hybrid materials, generally termed ionogels, are thus an emerging topic in hybrid materials research. The current article addresses some of the recent developments and focuses on the question why silica is currently the dominating matrix used for (inorganic) ionogel fabrication. In comparison to silica, matrix materials such as layered simple hydroxides, layered double hydroxides, clay-type substances, magnetic or catalytically active solids, and many other compounds could be much more interesting because they themselves may carry useful functionalities, which could also be exploited for multifunctional hybrid materials synthesis. The current article combines experimental results with some arguments as to how new, advanced functional hybrid materials can be generated and which obstacles will need to be overcome to successfully achieve the synthesis of a desired target material., (This journal is © The Royal Society of Chemistry 2011)

Polymer brushes on thiol-modified gold surfaces were synthesized by using terminal thiol groups for the surface-initiated free radical polymerization of methacrylic acid and dimethylaminoethyl methacrylate, respectively. Atomic force microscopy shows that the resulting poly(methacrylic acid) (PMAA) and poly(dimethylaminoethyl methacrylate) (PDMAEMA) brushes are homogeneous. Contact angle measurements show that the brushes are pH-responsive and can reversibly be protonated and deprotonated. Mineralization of the brushes with calcium phosphate at different pH yields homogeneously mineralized surfaces, and preosteoblastic cells proliferate on both the nonmineralized and mineralized surfaces. The number of living cells on the mineralized hybrid surfaces is ca. 3 times (PDMAEMA) and 10 times (PMAA) higher than on the corresponding nonmineralized brushes.

Background: Living autologous vascular grafts with the capacity for regeneration and growth may overcome the limitations of contemporary artificial prostheses. Particularly in congenital cardiovascular surgery, there is an unmet medical need for growing replacement materials. Here we investigate growth capacity of tissue-engineered living pulmonary arteries in a growing lamb model., Methods and Results: Vascular grafts fabricated from biodegradable scaffolds (ID 18+/-l mm) were sequentially seeded with vascular cells. The seeded constructs were grown in vitro for 21 days using biomimetic conditions. Thereafter, these tissue-engineered vascular grafts (TEVGs) were surgically implanted as main pulmonary artery replacements in 14 lambs using cardiopulmonary bypass and followed up for < or = 100 weeks. The animals more than doubled their body weight during the 2-year period. The TEVG showed good functional performance demonstrated by regular echocardiography at 20, 50, 80, and 100 weeks and computed tomography-angiography. In particular, there was no evidence of thrombus, calcification, stenosis, suture dehiscence, or aneurysm. There was a significant increase in diameter by 30% and length by 45%. Histology showed tissue formation reminiscent of native artery. Biochemical analysis revealed cellularity and proteoglycans and increased collagen contents in all of the groups, analogous to those of native vessels. The mechanical profiles of the TEVG showed stronger but less elastic tissue properties than native pulmonary arteries., Conclusions: This study provides evidence of growth in living, functional pulmonary arteries engineered from vascular cells in a full growth animal model.

Objective: To detect myocardial damage in severe systemic inflammation by cTnI measurements in patients without acute coronary syndromes., Design: Prospective case control study., Setting: Tertiary referral center., Participants: Twenty patients with sepsis, septic shock, and systemic inflammatory response syndrome (SIRS) were examined and compared to controls without coronary artery disease or myocarditis., Measurements and Results: cTnI levels were assessed in patients with SIRS, sepsis, and septic shock. Eight patients (two female/six male) suffered from septic shock, nine (three female/six male) from sepsis without shock, and three (three male) from SIRS. Seventeen patients (85%) showed elevated cTnI (median 0.57 microg/l; 0.17-15.4), whereas no patient in the control group showed elevated cTnI (P < 0.0001). Six patients (30%),--three with septic shock and three with sepsis--died during hospitalization, five of them with elevated cTnI. Four out of five autopsies showed normal coronary arteries. Coronary angiography, autopsy, and stress echocardiography ruled out significant coronary artery disease in ten cTnI-positive patients (59%). In 41 % of cTnI-positive patients, Streptococcus pneumoniae could be cultured, whereas no cTnI-negative or control patient showed signs of infection due to S. pneumoniae., Conclusion: Cardiac troponin I was elevated in 85% of patients with sepsis, septic shock or SIRS in our study. A high percentage showed infection caused by S. pneumoniae. In what way microorganisms cause cTnI elevations is not yet understood.

Echocardiography is the most important non-invasive test for many cardiovascular diseases. Morphologic and haemodynamic evaluation can be performed in a short time. In this review we will discuss the most common and the most important indications for an echocardiographic assessment. A detailed list for a quick reference is included at the end.