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Characterizing compositional heterogeneity in Earth’s lower mantle is critical to understanding its dynamics. Three low-nitrogen diamonds from Koffiefontein (South Africa), containing inclusion assemblages of ferropericlase ± orthopyroxene ± magnesite, constrain diamond formation in an Mg-rich lower-mantle environment. Ferropericlase inclusions have Mg# 82.7–88.5 and orthopyroxene inclusions (retrogressed bridgmanite) have Mg# 95.0–95.1 and mantle-like δ18O of +5.6‰ ± 0.2‰. Magnesite included in one diamond implicates carbonated fluids in diamond formation. High Mg# and low Ca, Al, and Na of the assemblage indicate a melt-depleted meta-harzburgitic environment, in contrast to more fertile compositions expected for primitive lower mantle. Extremely low Ca in orthopyroxene inclusions may reflect a combination of melt depletion and low equilibration temperatures at the time of trapping. Inclusion compositions implicate subducted oceanic slab meta-harzburgite as the host for diamond growth. Mantle-like δ18O of the orthopyroxene inclusions indicates unaltered oceanic lithosphere. Similar melt-depleted characteristics in lower-mantle inclusion assemblages worldwide support that meta-harzburgite is the dominant host of lower-mantle diamonds.

Statement of problem Monolithic zirconia has become widely used for single crowns, with the advantages of minimal tooth reduction and good esthetics. However, clinical studies evaluating the performance of and patient satisfaction with posterior monolithic zirconia crowns are sparse. Purpose The purpose of this clinical study was to evaluate the clinical performance of and patient satisfaction with posterior monolithic zirconia crowns. Material and methods Within a prospective cohort study design, participants were recruited from a university dental clinic if they required 1 posterior monolithic zirconia crown. The clinical performance was evaluated at follow-up appointments 1, 2, and 3 years after insertion. Bleeding on probing and pocket probing depths for the crowned teeth were recorded. Overall patient satisfaction was measured by using a visual analog scale (VAS), and quality of life was measured by using the validated German version of the Oral Health Impact Profile 14 (OHIP-G14). Descriptive statistical methods were applied. Mean values were calculated and compared by using the paired t test (α=.05). Results Thirty participants received a monolithic zirconia crown (14 premolars, 16 molars). One biologic complication (vertical root fracture) was identified at the 1-year follow-up. Three years after insertion, 22 participants could be examined, and the crowns were still in function. The gingival and the periodontal status of the crowned teeth had not changed significantly over the 3 years. After insertion, a significant improvement in patient satisfaction was measured up to 3 years Conclusions Posterior monolithic zirconia crowns led to enhanced patient satisfaction up to 3 years after insertion. They provided good middle-term success and offered a promising alternative to conventional metal-ceramic crowns.

Integrating mineralogy with data science is critical to modernizing Earth materials research and its applications to geosciences. Data were compiled on 95,588 garnet sample analyses from a variety of sources, ranging from large repositories (EarthChem, RRUFF, MetPetDB) to individual peer-reviewed literature. An important feature is the inclusion of mineralogical “dark data” from papers published prior to 1990. Garnets are commonly used as indicators of formation environments, which directly correlate with their geochemical properties; thus, they are an ideal subject for the creation of an extensive data resource that incorporates composition, locality information, paragenetic mode, age, temperature, pressure, and geochemistry. For the data extracted from existing databases, we increased the resolution of several key aspects, including petrogenetic and paragenetic attributes, which we extended from generic material type (e.g., igneous, metamorphic) to more specific rock type names (e.g., diorite, eclogite, skarn) and locality information, increasing specificity by examining the continent, country, area, geological context, longitude, and latitude. Likewise, we implemented a broad silica confidence interval to exclude samples of questionable composition from further analysis. This comprehensive dataset of garnet information is an open-access resource available in the Evolutionary System of Mineralogy Database (ESMD) for future mineralogical studies, paving the way for characterizing correlations between chemical composition and paragenesis through natural kinds clustering. We encourage scientists to contribute their own unpublished and unarchived analyses to the growing data repositories of mineralogical information that are increasingly valuable for advancing scientific discovery.

According to retrospective clinical studies periodontal treatment retains teeth. However, evidence on the effectivity of periodontal treatment stemming from the general population is lacking.We analysed data of periodontally treated patients from routine data of a major German national health insurance (BARMER-MV; subsample of the Federal State of Mecklenburg-Vorpommern) and from a clinical cohort (Greifswald Approach to Individualized Medicine, GANI_MED), as well as periodontally untreated and treated participants of the Study of Health in Pomerania (SHIP-TREND) with either ≥2 or ≥4 teeth with pocket depths ≥4 mm. Yearly tooth loss estimates, incidence rates were evaluated.For moderately to severely affected groups, yearly tooth loss and incidence rates were higher in BARMER-MV patients (0.35 and 0.18, respectively) compared to untreated SHIP-TREND controls (0.19 and 0.08, respectively). In line, treated SHIP-TREND participants exhibited higher yearly tooth loss rates than untreated SHIP-TREND controls (0.26 versus 0.19). For severely affected groups, results with respect to tooth loss were inconclusive regarding beneficial effects of periodontal treatment either conducted in the university (GANI_MED data) or in the general practice.Until 2021, periodontal treatment performed in German general dental practices within the national health insurance system was probably not efficient in retaining more teeth in the short- to mid-term. Since reimbursement schemes were changed in 2021 and now cover periodontal treatment to a much larger extent, future will show, whether these new reimbursement codes will improve the quality of periodontal treatment and whether they will lead to more long-term tooth retainment. This article is protected by copyright. All rights reserved.

Hexacoordinate silicon pincer complexes offer promising charge transport and electroluminescent layers for high performance molecular electronic devices. Tuning the structure of the ligands affords good control of the silicon pincer's properties.

Gene expression signatures for a basal-like breast cancer (BLBC) subtype have been associated with poor clinical outcomes, but a molecular basis for this disease remains unclear. Here, we report overexpression of the transcription factor FOXC1 as a consistent feature of BLBC compared with other molecular subtypes of breast cancer. Elevated FOXC1 expression predicted poor overall survival in BLBC (P = 0.0001), independently of other clinicopathologic prognostic factors including lymph node status, along with a higher incidence of brain metastasis (P = 0.02) and a shorter brain metastasis–free survival in lymph node–negative patients (P < 0.0001). Ectopic overexpression of FOXC1 in breast cancer cells increased cell proliferation, migration, and invasion, whereas shRNA-mediated FOXC1 knockdown yielded opposite effects. Our findings identify FOXC1 as a theranostic biomarker that is specific for BLBC, offering not only a potential prognostic candidate but also a potential molecular therapeutic target in this breast cancer subtype. Cancer Res; 70(10); 3870–6. ©2010 AACR.

Supplementary Table from Interleukin 12 Stimulates IFN-γ–Mediated Inhibition of Tumor-Induced Regulatory T-Cell Proliferation and Enhances Tumor Clearance

To define the factors that modulate regulatory T (Treg) cells in the tumor setting, we cocultured various tumor cells with either purified Treg cells, or with unfractionated splenocytes. We found that Treg expansion occurred only with unfractionated splenocytes, suggesting that accessory cells and/or factors produced by them play an essential role in tumor-induced Treg expansion. We performed gene expression profiling on tumor-associated Treg cells to identify candidate signaling molecules and studied their effects on tumor-induced Treg expansion. We inadvertently discovered that interleukin (IL)-12 treatment blocked Treg expansion in an IL-12 receptor–dependent fashion. Additional studies showed that IL-12 acts by stimulating IFN-γ mediated inhibition of Treg cell proliferation, which may partially account for the antitumor effects of IL-12. Furthermore, IL-12 treatment was found to decrease IL-2 production, which may lead to IFN-γ–independent inhibition of Treg cells, as IL-2 is required for their survival and expansion. Mechanistic studies revealed that IFN-γ signaling directly causes cell cycle arrest in Treg cells. This study shows that an IL-12–IFN-γ axis can suppress tumor-induced Treg proliferation. This mechanism may counteract the ability of Treg cells to promote tumor growth in vivo. [Cancer Res 2009;69(22):8700–9]

Supplementary Table Legend from Interleukin 12 Stimulates IFN-γ–Mediated Inhibition of Tumor-Induced Regulatory T-Cell Proliferation and Enhances Tumor Clearance

Supplementary Figures 1-8 from FOXC1 Is a Potential Prognostic Biomarker with Functional Significance in Basal-like Breast Cancer

Supplementary Figures 1-8 from Interleukin 12 Stimulates IFN-γ–Mediated Inhibition of Tumor-Induced Regulatory T-Cell Proliferation and Enhances Tumor Clearance

Supplementary Methods, Tables 1-6, Figure Legends 1-8 from FOXC1 Is a Potential Prognostic Biomarker with Functional Significance in Basal-like Breast Cancer

How and when Earth’s volatile content was established is controversial with several mechanisms postulated, including planetesimal evaporation, core formation and the late delivery of undifferentiated chondrite-like materials. The isotopes of volatile elements such as sulfur can be fractionated during planetary accretion and differentiation and thus are potential tracers of these processes. Using first-principles calculations, we examine sulfur isotope fractionation during core formation and planetesimal evaporation. We find no measurable sulfur isotope fractionation between silicate and metallic melts at core-forming conditions, indicating that the observed light sulfur isotope composition of the bulk silicate Earth relative to chondrites cannot be explained by metal–silicate fractionation. Our thermodynamic calculations show that sulfur evaporates mostly as H2S during planetesimal evaporation when nebular H2 is present. The observed bulk Earth sulfur isotope signature and abundance can be reproduced by evaporative loss of about 90% sulfur mainly as H2S from molten planetesimals before nebular H2 is dissipated. The heavy sulfur isotope composition of the Moon relative to the Earth is consistent with evaporative sulfur loss under 94–98% saturation condition during the Moon-forming giant impact. In summary, volatile evaporation from molten planetesimals before Earth’s formation probably played a key role in establishing Earth’s volatile element content. Earth’s volatile element content was established largely by volatile evaporation from molten planetesimals before Earth’s formation, according to first-principles calculations and examination of sulfur isotope fractionation.

Solution-processable conductive polymers are advantageous materials for making inexpensive, electrical junctions to crystalline semiconductors. We have investigated methods to improve the device performance of hybrid solar cells made from n-type silicon and a conductive polymer glue based on a blend of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and D-sorbitol. The PEDOT:PSS blend behaves like a high work function metal creating a Schottky-type junction. The addition of D-sorbitol increases PEDOT:PSS conductivity and provides adhesive properties, allowing the top contact of the solar cell to be laminated onto the silicon substrate. Unfortunately, the addition of the D-sorbitol to the PEDOT:PSS significantly alters the shape of the measured current-voltage performance curve of a crystalline silicon (n-Si)/PEDOT:PSS junction. Under illumination, this results in a decline in the fill factor (FF) and a drop in photocurrent density (J sc) compared to PEDOT:PSS-only devices. We have discovered that the decline in device performance is likely due to surface trap states caused by D-sorbitol/silicon interaction and/or silicon oxidation. X-ray photoelectron spectroscopic (XPS) analysis shows that surface oxidation quickens, and possible silicon surface functionalization with D-sorbitol occurs while processing the D-sorbitol/PEDOT:PSS contact on H-terminated surfaces. To overcome these interface issues, the silicon surface was chemically modified using surface methylation, making it insensitive to D-sorbitol/silicon interactions and surface oxidation during the processing of the PEDOT:PSS polymer blend contact. This also enabled the crystalline silicon (n-Si)/s-PEDOT:PSS device performance to be maintained for longer periods. Using a silicon surface methylation strategy, good device performance could be achieved without changing the adhesive properties of D-sorbitol/PEDOT:PSS polymer blend.

Zusammenfassung Hintergrund Inanspruchnahme und Ausgaben gehören zu den wichtigsten Kenngrößen von Versorgungssystemen. Sie erlauben auch Rückschlüsse auf die Ausrichtung der praktizierten Zahnmedizin. Ziel der Arbeit Ziel dieser Übersicht ist es, den Status quo der Inanspruchnahme zahnärztlicher Versorgung in Deutschland und der diesbezüglichen Ausgaben anhand vorhandener Routinedaten aus der vertragszahnärztlichen Versorgung zu beschreiben. Material und Methoden Die zugrunde liegenden Analysen wurden den jährlichen Zahnreporten der gesetzlichen Krankenkasse BARMER entnommen. Sie basieren auf deutschlandweiten Abrechnungsdaten von 2010 bis 2018. Ergebnisse Die Inanspruchnahme zahnärztlicher Leistungen liegt in Deutschland mit jährlichen Raten um 70 % überdurchschnittlich hoch. Für Füllungen lag die Inanspruchnahmerate 2018 in den Altersgruppen zwischen 30 und 79 Jahren durchgehend um 30 %, für Neueingliederungen von Zahnersatz und Zahnkronen in den Altersgruppen von 55 bis 84 Jahren bei mindestens 10 %. Im Bereich der Prävention war ein kontinuierlicher Anstieg für Früherkennungsuntersuchungen bei Kindern zu verzeichnen (31,9 % in 2010, 35,2 % in 2018). Bei individualprophylaktischen Maßnahmen bei 6‑ bis 17-Jährigen war kein klarer Trend erkennbar (64,0 % in 2010, 65,4 % in 2018). Die Ausgaben der gesetzlichen Krankenkasse stiegen moderat. Diskussion Durch die hohe Inanspruchnahme sind gute Voraussetzungen für eine präventionsorientierte Zahnmedizin gegeben. Wenn auch eine positive Tendenz zu einer leicht steigenden Inanspruchnahme präventiver Leistungen erkennbar ist, bildet sich im Versorgungsgeschehen nach wie vor eine mehrheitlich auf invasive Intervention orientierte Zahnmedizin ab. Als sinnvolle Instrumente zur Umsetzung eines substanziellen Paradigmenwechsels können unter anderem eine weitere Förderung der Gesundheitskompetenz der Bevölkerung und präventionsfördernde Anreize angesehen werden.

An outstanding goal in planetary science is to understand how terrestrial cores evolved to have the compositions, thermal properties, and magnetic fields observed today. To achieve that aim requires the integration of datasets from space missions with laboratory experiments conducted at high pressures and temperatures. Over the past decade, technological advances have enhanced the capability to conduct in situ measurements of physical properties on samples that are analogs to planetary cores. These challenging experiments utilize large-volume presses that optimize control of pressure and temperature, and diamond-anvil cells to reach the highest pressures. In particular, the current experimental datasets of density, compressional velocity, viscosity, and thermal conductivity of iron alloys are most relevant to the core conditions of small terrestrial planets and moons. Here we review the physical properties of iron alloys measured in the laboratory at conditions relevant to the cores of Mars, the Moon, and Mercury. We discuss how these properties inform models of core composition, as well as thermal and magnetic evolution of their cores. Experimental geochemistry (in particular, metal-silicate partitioning experiments) provides additional insights into the nature and abundance of light elements within cores, as well as crystallization processes. Emphasis is placed on the Martian core to discuss the effect of chemistry on core evolution.

In this article, falling is considered as an existential bodily experience of the youngest children, aged one to three. No toddler can avoid falling; it is simply a condition of being bodily situated in the world. Active toddlers are falling toddlers, but even though the struggle with gravity appears to play a crucial role in the everyday lives of young children, it has been only a limited subject in early childhood research. Therefore, the authors examine the phenomenon of falling on the basis of empirical material collected in a focused ethnographic study carried out in two Danish nurseries. The findings are presented as a kind of typology, which includes analyses of five different fallings situations that were observed and videotaped in planned physical education activities. From an existential point of view, falling can be characterized as a negative experience with which the toddler must reconcile as a consequence of participating in movement activities. Even though it often starts as negative, falling seems to develop productive qualities, such as increased body consciousness or basic wakefulness. Physical active toddlers soon become experienced fallers, and this expertise makes it possible to use falling as a motor skill in playing situations or as a tool for communication. The authors use an existential framework to highlight and discuss the productive qualities of falling with the purpose of making it explicit for work in early childhood education.

In this paper, the complex dielectric function of 2,5-bis(N,N-dibutyl-4-aminophenyl) thiazolo[5,4-d]thiazole is reported. Thin films of this material were obtained by spin coating on a silicon substrate. The samples were investigated using spectroscopic ellipsometry in the spectral range from 354 nm to 1907 nm at multiple angles of incidence. The ellipsometric data were analyzed using a stratified-layer model composed of a thiazolothiazole thin film, a native SiO2 oxide, and a Si substrate. The model dielectric function of the thiazolothiazole thin film was modeled using a series of Tauc-Lorentz and Gaussian oscillators. The best-model calculated data reproduces the experimental data very well. The bandgap of TTz is reported and found to be in good agreement with density functional theory calculations reported earlier.

Organic electronics has developed rapidly over the past 40 years. In 1977, a seminal discovery was reported that showed that a polymer known as polyacetylene could conduct electricity as well as metals could. This was a groundbreaking discovery that led to a Nobel Prize in Chemistry in 2000. The polymers that are used in organic electronics have now been widely studied for use in organic solar cells (OSCs), organic field effect transistors (OFETs), printable electronics, flexible electronics, antistatic coatings, actuators, and more recently in bioelectronics. In particular, the utility of organic electronics is seen in the commercial success of using organic electronic materials in organic light-emitting diodes (OLEDs) where OLED displays can be seen in mobile phones and as flat panel displays. In this paper, we provide a tutorial targeting upper secondary students describing how these special classes of polymers function, and how they can be synthesized. The paper further discusses the use of these materials in two applications: organic solar cells and organic light-emitting diodes. The paper ends with a brief discussion about hands-on activities that can be carried out in the upper secondary student science classroom.

Oral health surveys are considered the gold standard for assessing the caries experience of children. Analyses of routine data offer additional opportunities not yet fully explored. This study aimed at estimating the caries treatment experience by mining an insurance claims database. Comprehensive claims data sets were extracted from the data warehouse of a major health insurance company (BARMER, Germany). A surrogate variable for caries experience was formed that reflected the proportion of children without any former potentially caries-related treatment (filling, root canal treatment, and extraction) at ages from 1 to 14 years. The statistical calculations were based on Kaplan-Meier survival analyses. The evaluation for the permanent dentition comprised N = 593,330 children at 6 years and N = 114,568 at 12 years. At 12 years of age, 66.8% had not yet experienced potentially caries-related treatments. This value hints at a significantly higher caries experience at 12 years compared to available epidemiological data. For the deciduous dentition, the respective rates were 74.0% at 6 years and 45.8% at 10 years. Although various sources of bias have to be taken into account, the potential of routine data mining is evident. The approach is supplemental to oral health surveys. It can be useful in coming closer to reality when estimating the caries experience of children. From our results, we conclude that the oral health of up to 14-year-olds in Germany remains in urgent need of improvement.

Tschauner

The Wollastonite Skarn northeast of Pitcairn has been a productive locality for mineral collectors for nearly 140 years. It is still an active fee locality and one worth visiting. We have detailed ...

Current genetic screening methods for inherited eye diseases are concentrated on the coding exons of known disease genes (gene panels, clinical exome). These tests have a variable and often limited diagnostic rate depending on the clinical presentation, size of the gene panel and our understanding of the inheritance of the disorder (with examples described in this issue). There are numerous possible explanations for the missing heritability of these cases including undetected variants within the relevant gene (intronic, up/down-stream and structural variants), variants harbored in genes outside the targeted panel, intergenic variants, variants undetectable by the applied technology, complex/non-Mendelian inheritance, and nongenetic phenocopies. In this article we further explore and review methods to investigate these sources of missing heritability.

Prepared by William Besse.When our book Collector’s Guide to the Balmat Mining District, St. Lawrence County, New York (Chamberlain et al. 2018) went to press, talc mining had ceased entirely, and ...

Fundamental properties of conjugated copolymers are sensitively linked to their constitution and features of their repeat unit design that govern assembly and organization across multiple length scales, ultimately impacting device performance. Herein we report the efficient synthesis and characterization, and optical, electrochemical and transport properties of complementary pairs of nucleobase-functionalized, fully conjugated copolymers based on benzo[1,2-b:4,5-b′]-dithiophene (BDT) and 3-hexylthiophene (3hT), which is a quintessential low bandgap polymer. Stille cross-coupling polymerizations enable access to high molecular weight, alternating copolymers of modest dispersity containing pendant adenine or thymine groups in each repeating unit, which provide the capacity to direct molecular assembly. Variations in nucleobase type and design of alkyl side chains on BDT units give rise to a strongly red-shifted absorbance onset for the copolymers containing thymine and adenine functionality in comparison to solution and dried films. Higher hole mobilities were also observed and attributed to the tendency of the nucleobase inclusion to heighten organization. The influence of the nucleobases on the organization is further revealed when thermal pre-treatment is used during film formation: modest heating before casting the non-functionalized BDT-3hT copolymers leads to increases in the mobility, optical absorbance and fluorescence, while copolymers with adenine or thymine pendant groups do not show analogous improvements, suggesting that the nucleobases have promoted nanoscale organization, which is consistent with assessments of hydrogen bonding interactions. Given the structure-directing ability of nucleobases through hydrogen bonding, π-stacking, and complementary base pairing, these novel materials engender myriad opportunities to examine how specific molecular-level interactions that cue self-assembly affect optoelectronic properties and device-level performance.

Harzburgites and dunites forming the base of the Late Cretaceous–Paleocene Papuan Ultramafic Belt (PUB) and Marum ophiolites of Papua New Guinea (PNG) are among the most refractory mantle peridotites on Earth. We present a new integrated dataset of major element, bulk plus mineral trace element and Re–Os isotopic analyses aimed at better understanding the genesis of these peridotites. The PUB harzburgites contain olivine (Fo92–93), low-Al enstatite (less than or equal to 0.5 wt. % Al2O3 and CaO), and Cr-rich spinel (Cr# = 0.90–0.95). The Marum harzburgites are less refractory with olivine (Fo91.9–92.7), enstatite (~0.5–1.0 wt. % Al2O3 and CaO), minor clinopyroxene (diopside), and spinel (Cr# = 0.71–0.77). These major element characteristics reflect equivalent or greater levels of melt depletion than that experienced by Archean cratonic peridotites. Whereas bulk-rock heavy rare earth element (HREE) abundances mirror the refractory character indicated by the mineral chemistry and major elements, large-ion lithophile elements indicate a more complex melting and metasomatic history. In situ olivine and orthopyroxene REE measurements show that harzburgites and dunites have experienced distinct melt-rock interaction processes, with dunite channels/lenses, specifically, showing higher abundances of HREE in olivine. Distinctive severe inter-element fraction of platinum group elements and Re result in complex patterns that we refer to as ‘M-shaped’. These fractionated highly siderophile element (HSE) patterns likely reflect the dissolution of HSE-rich phases in highly depleted peridotites by interaction with subduction-related melts/fluids, possibly high-temperature boninites. Osmium isotope compositions of the PNG peridotites are variable (187Os/188Os = 0.1204 to 0.1611), but fall within the range of peridotites derived from Phanerozoic oceanic mantle, providing no support for ancient melt depletion, despite their refractory character. This provides further evidence that highly depleted peridotites can be produced in the modern Earth, in subduction zone environments. The complex geochemistry indicates a multi-stage process for the formation of the PNG mantle peridotites in a modern geodynamic environment. The first stage involves partial melting at low-pressure (

Made available in DSpace on 2022-05-01T11:07:20Z (GMT). No. of bitstreams: 0 Previous issue date: 2022-01-01 These recommendations are specifically for polymers and polymer systems showing a significant response to an electromagnetic field or one of its components (electric field or magnetic field), i.e., for electromagnetic-field-responsive polymer materials. The structures, processes, phenomena and quantities relating to this interdisciplinary field of materials science and technology are herein defined. Definitions are unambiguously explained and harmonized for wide acceptance by the chemistry, physics, polymer and materials science communities. A survey of typical electromagnetic-field-responsive polymers is included. Department of Physical and Macromolecular Chemistry Faculty of Sciences Charles University, Albertov 2030 DF-FC UNESP - Universidade Estadual Paulista, Av. Eng. Luiz Edmundo Carrijo Coube 14-01 Institut des Science Analytiques et Physico-Chimie Pour l'Environnement et les Materiaux CNRS Univ Pau and Pays Adour University of Kent Pi-Conjugated Polymer Unit Okinawa Institute of Science and Technology, Onna-son Organisation Moléculaire Evolution et Matériaux Fluores UMR CNRS 5073 Laboratoire de Chimie Macromoléculaire Université Montpellier II Science et Techniques du Languedoc, Place Eugène Bataillon, Cedex 5 Department of Materials Centre of Plastic Electronics (CPE) Imperial College, Exhibition Road Department of Chemistry University of North Carolina at Charlotte DF-FC UNESP - Universidade Estadual Paulista, Av. Eng. Luiz Edmundo Carrijo Coube 14-01

Two different high-entropy oxide materials were synthesized and studied as Li-ion battery anodes. The two materials have the same active metal constituents but different inactive elements which result in different initial crystalline structures: rock salt for (MgFeCoNiZn)O and spinel for (TiFeCoNiZn)3O4. Local structural studies of the metal elements in these two materials over extended electrochemical cycling reveal that the redox processes responsible for the electrode capacity are independent of the initial crystallographic structure and that the capacity is solely dependent on the initial random distribution of the metal atoms and the amount of active metals in the starting material.

The journal of evidence based dental practice 23(1S), 101794 (2023). doi:10.1016/j.jebdp.2022.101794 special issue: "Dental patient-reported outcomes 2022 Dental PROs / Edited by Fang Hua", Published by Elsevier, Amsterdam [u.a.]

The study of excited-state energy diffusion has had an important impact in the development and optimization of organic electronics. For instance, optimizing excited-state energy migration in the photoactive layer in an organic solar cell device has been shown to yield efficient solar energy conversion. Despite the crucial role that energy migration plays in molecular electronic device physics, there is still a great deal to be explored to establish how molecular orientation impacts energy diffusion mechanisms. In this work, we have synthesized a new library of solution-processable, Zn (alkoxycarbonyl)phenylporphyrins containing butyl (ZnTCB4PP), hexyl (ZnTCH4PP), 2-ethylhexyl (ZnTCEH4PP), and octyl (ZnTCO4PP) alkoxycarbonyl groups. We establish that, by varying the length of the peripheral alkyl chains on the metalloporphyrin macrocycle, preferential orientation and molecular self-assembly is observed in solution-processed thin films. The resultant arrangement of molecules consequently affects the electronic and photophysical characteristics of the metalloporphyrin thin films. The various molecular arrangements in the porphyrin thin films and their resultant impact were determined using UV-Vis absorption spectroscopy, steady-state and time-resolved fluorescence emission lifetimes, and X-ray diffraction in thin films. The films were doped with C60 quencher molecules and the change in fluorescence was measured to derive a relative quenching efficiency. Using emission decay, relative quenching efficiency, and dopant volume fraction as input, insights on exciton diffusion coefficient and exciton diffusion lengths were obtained from a Monte Carlo simulation. The octyl derivative (ZnTCO4PP) showed the strongest relative fluorescence quenching and, therefore, the highest exciton diffusion coefficient (5.29 × 10−3 cm2 s−1) and longest exciton diffusion length (~81 nm). The octyl derivative also showed the strongest out-of-plane stacking among the metalloporphyrins studied. This work demonstrates how molecular self-assembly can be used to modulate and direct exciton diffusion in solution-processable metalloporphyrin thin films engineered for optoelectronic and photonic applications.