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Martensitic Ni 50 Ti 50 wires and sheets with different textures were tensile tested in the temperature range between −100 °C and 60 °C. The effect of texture and temperature on reorientation of martensite variants was investigated. After deformation, all material states were heated into the austenite regime to study their shape memory behavior. During room temperature tensile testing, in-situ digital image correlation revealed that the reorientation of martensite variants is associated with the nucleation and propagation of a macroscopic Lüders band. A comparison between the mechanical data obtained for wire and sheet specimens revealed a strong effect of texture. The plateau stresses of sheets were found to be 25–33% larger and their recoverable strains were 30% lower than for wires. However, the product of plateau stress and recoverable strain, which represents the external work per unit volume required for martensite variants reorientation does not depend on texture. The tensile tests performed at different temperatures revealed that in the temperature range considered the recoverable strain does not depend significantly on temperature. In contrast, the plateau stress as well as the external work required to reorient martensite decrease with increasing testing temperature. We use a thermodynamic approach involving the elastic strain energy associated with the growth of reoriented martensite variants to rationalize these temperature dependencies. [ABSTRACT FROM AUTHOR]

Due to their high work output and good mechanical properties, actuators made from shape memory alloys (SMAs) are used in numerous applications. Unfortunately, SMAs such as nickel–titanium (Ni–Ti) can only be employed at temperatures up to about 100 °C. Lately, high-temperature shape memory alloys (HT SMAs) have been introduced to overcome this limitation. Ternary systems based on Ni–Ti have been intensively characterized and alloys are available that can operate at elevated temperatures. However, these alloys either contain substantial amounts of expensive noble elements like platinum and palladium, or the materials are brittle. The titanium–tantalum (Ti–Ta) system has been developed to overcome these issues. Binary Ti–Ta provides relatively high M S temperature combined with excellent workability, but it suffers from fast cyclic degradation. By alloying with third elements this drawback can be overcome: The ternary Ti–Ta–Al alloy shows overall promising properties as will be shown in the present work. In-situ thermo-mechanical cycling experiments were conducted and allowed for evaluation of the factors affecting the functional and structural fatigue of this alloy. Functional fatigue is dominated by ω-phase evolution, while structural fatigue is triggered by an interplay of ω-phase induced embrittlement and deformation constraints imposed by unsuitable texture. In addition, a concept for fatigue life extension proposed very recently for binary Ti–Ta, is demonstrated to be also applicable for the ternary Ti–Ta–Al. [ABSTRACT FROM AUTHOR]

Abstract: Crack extension in pseudoelastic binary NiTi shape memory alloy (SMA) compact tension (CT) specimens was examined during static loading. The material composition of 50.7at.% Ni (austenitic, pseudoelastic) was investigated using high-energy synchrotron X-ray diffraction. A miniature CT specimen was developed, which is small enough to allow in situ testing in a synchrotron beam line to identify phases, textures and lattice strains in front of a crack tip. Stress-induced martensite in pseudoelastic NiTi SMAs was mapped in front of the crack of a CT specimen during static loading using synchrotron radiation. The phase volume fraction and lattice microstrain results are discussed and compared with results from thermographic measurements. The Poisson effect is observed by comparing the lattice strains in the loading direction and transverse to the loading direction. [Copyright &y& Elsevier]

Abstract: The high-temperature and low-stress creep (1293K, 160MPa) of the single-crystal Ni-based superalloy LEK 94 is investigated, comparing the tensile creep behavior of miniature creep specimens in [001] and [110] directions. In the early stages of creep, the [001]-direction loading shows higher minimum creep rates, because a greater number of microscopic crystallographic slip systems are activated, the dislocation networks at γ/γ′ interfaces accommodate lattice misfit better, and γ channels are wider. After the creep rate minimum, creep rates increase more strongly as a function of strain for [110] tensile loading. This may be related to the nature of rafting during [110] tensile creep, which results in a more open topology of the γ channels. It may also be related to more frequent γ′ cutting events compared with [100] tensile creep. [Copyright &y& Elsevier]

Abstract: Nickel–Titanium shape memory alloys (NiTi-SMA) are of biomedical interest due to their unusual range of pure elastic deformability and their elastic modulus, which is closer to that of bone than any other metallic or ceramic material. Newly developed porous NiTi, produced by Selective Laser Melting (SLM), is currently under investigation as a potential carrier material for human mesenchymal stem cells (hMSC). SLM enables the production of highly complex and tailor-made implants for patients on the basis of CT data. Such implants could be used for the reconstruction of the skull, face, or pelvis. hMSC are a promising cell type for regenerative medicine and tissue engineering due to their ability to support the regeneration of critical size bone defects. Loading porous SLM-NiTi implants with autologous hMSC may enhance bone growth and healing for critical bone defects. The purpose of this study was to assess whether porous SLM-NiTi is a suitable carrier for hMSC. Specimens of varying porosity and surface structure were fabricated via SLM. hMSC were cultured for 8days on NiTi specimens, and cell viability was analyzed using two-color fluorescence staining. Viable cells were detected on all specimens after 8days of cell culture. Cell morphology and surface topography were analyzed by scanning electron microscopy (SEM). Cell morphology and surface topology were dependent on the orientation of the specimens during SLM production. The Nickel ion release can be reduced significantly by aligned laser processing conditions. The presented results clearly attest that both dense SLM-NiTi and porous SLM-NiTi are suitable carriers for hMSC. Nevertheless, before carrying out in vivo studies, some work on optimization of the manufacturing process and post-processing is required. [Copyright &y& Elsevier]

Abstract: The present work investigates the effect of grain boundary chemistry and crystallography on creep and on creep damage accumulation in Cu–0.008wt.% Bi and Cu–0.92wt.% Sb at stresses ranging from 10 to 20MPa and temperatures between 773 and 873K. Small additions of Bi and Sb significantly reduce the rupture strain and rupture time during creep of Cu. High stress exponents (Cu–Bi) and high apparent activation energies for creep (Cu–Bi and Cu–Sb) are obtained. Sb promotes creep cavitation on random high-angle grain boundaries. Bi, on the other hand, causes brittle failure when small crack-like cavities cause decohesion. Both elements suppress dynamic recrystallization, which occurs during creep of Cu at high stresses and temperatures. [Copyright &y& Elsevier]

Advanced methods for the repair of single-crystalline (SX) Ni-based superalloys are of special interest for the gas turbine industry. Polycrystalline repair approaches show promising results, while the repair of SX materials is still challenging. Directional annealing experiments resulted in large columnar grains by imposing thermal gradients at the abnormal grain growth temperature of a specific Ni-based superalloy. A numerical model of the Bridgman process is applied to provide an insight into the temperature evolution during zone annealing of the Vacuum-Plasma-Spray (VPS) repair coatings with the aim of promoting grain growth from the SX substrate. The results presented here suggest that this is a promising approach to repair or manufacture SX turbine blades. Unlabelled Image • Abnormal grain growth behavior of vacuum plasma sprayed superalloy coatings. • Directional annealing of fine-grained repair coating results in columnar grains. • FEM simulation of a Bridgeman furnace for directional annealing • Single crystalline repair by simulating grain growth from single crystal substrate [ABSTRACT FROM AUTHOR]

Abstract Turbine blades in aviation engines and land based gas-turbines are exposed to extreme environments. They suffer damage accumulation associated with creep, oxidation and fatigue loading. Therefore, advanced repair methods are of special interest for the gas-turbine industry. In this study, CMSX-4 powder is sprayed by Vacuum Plasma Spray (VPS) on single-crystalline substrates with similar compositions. The influence of the substrate temperature is investigated altering the temperature of the heating stage between 850 °C to 1000 °C. Different spray parameters were explored to identify their influence on the microstructure. Hot isostatic pressing (HIP) featuring fast quenching rates was used to minimize porosity and to allow for well-defined heat-treatments of the coatings. The microstructure was analysed by orientation imaging scanning electron microscopy (SEM), using electron backscatter diffraction (EBSD). The effects of different processing parameters were analysed regarding their influence on porosity and grain size. The results show that optimized HIP heat-treatments can lead to dense coatings with optimum γ/γ′ microstructure. The interface between the coating and the substrate is oxide free and shows good mechanical integrity. The formation of fine crystalline regions as a result of fast cooling was observed at the single-crystal surface, which resulted in grain growth during heat-treatment in orientations determined by the crystallography of the substrate. Graphical abstract Unlabelled Image Highlights • Vacuum plasma spray is used for the deposition of CMSX-4 powder on heated single crystalline CMSX-4 substrates. • Coatings with different spray parameters were produced to identify the condition for optimum mechanical properties. • A HIP is used to promote grain growth, decrease the porosity and achieve the desired microstructure. • The microstructure of the interface region and the coating was characterised in the as-spayed and the HIP condition. [ABSTRACT FROM AUTHOR]

This extensive AWMF 085-002 S2e-guideline "First Trimester Diagnosis and Therapy @ 11-13 +6 Weeks of Gestation" has systematically analyzed high-quality studies and publications and the existing evidence (evidence tables) and produced recommendations (level of recommendation, level of evidence, strength of consensus).This guideline deals with the following topics in the context of the 11-13 +6 weeks scan: the legal basis, screening for anatomical malformations, screening for chromosomal defects, quality assessment and audit, screening for preeclampsia and FGR, screening for preterm birth, screening for abnormally invasive placenta (AIP) and placenta accreta spectrum (PAS), screening for velamentous cord insertion and vasa praevia, screening for diabetes mellitus and LGA.Screening for complications of pregnancy can best be carried out @ 11-13+6 weeks of gestation. The issues of how to identify malformations, chromosomal abnormalities and certain disorders of placentation (high blood pressure and proteinuria, intrauterine growth retardation) have been solved. The problem of how to identify placenta percreta and vasa previa has been partially solved. What is still unsolved is how to identify disorders of glucose metabolism and preterm birth.In the first trimester, solutions to some of these problems are available: parents can be given extensive counselling and the risk that a pregnancy complication will manifest at a later stage can be delayed and reduced. This means that screening is critically important as it helps in decision-making about the best way to manage pregnancy complications (prevention and intervals between follow-up examinations).If no treatment is available and if a termination of pregnancy is considered, the intervention can be carried out with far lower complications compared to the second trimester of pregnancy. In most cases, further examinations are not required and the parents can be reassured. A repeat examination at around week 20 of gestation to complete the screening for malformations is recommended. NOTE:: The guideline will be published simultaneously in the official journals of both professional societies (i.e. Ultraschall in der Medizin/European Journal of Ultrasound for the DEGUM and Geburtshilfe und Frauenheilkunde for the DGGG)., Competing Interests: See also the long version of the guideline: https://register.awmf.org/de/leitlinien/detail/085-002, (Thieme. All rights reserved.)

This extensive AWMF 085-002 S2e-guideline "First Trimester Diagnosis and Therapy @ 11-13 +6 Weeks of Gestation" has systematically analyzed high-quality studies and publications and the existing evidence (evidence tables) and produced recommendations (level of recommendation, level of evidence, strength of consensus).This guideline deals with the following topics in the context of the 11-13 +6 weeks scan: the legal basis, screening for anatomical malformations, screening for chromosomal defects, quality assessment and audit, screening for preeclampsia and FGR, screening for preterm birth, screening for abnormally invasive placenta (AIP) and placenta accreta spectrum (PAS), screening for velamentous cord insertion and vasa praevia, screening for diabetes mellitus and LGA.Screening for complications of pregnancy can best be carried out @ 11-13 +6 weeks of gestation. The issues of how to identify malformations, chromosomal abnormalities and certain disorders of placentation (high blood pressure and proteinuria, intrauterine growth retardation) have been solved. The problem of how to identify placenta percreta and vasa previa has been partially solved. What is still unsolved is how to identify disorders of glucose metabolism and preterm birth.In the first trimester, solutions to some of these problems are available: parents can be given extensive counselling and the risk that a pregnancy complication will manifest at a later stage can be delayed and reduced. This means that screening is critically important as it helps in decision-making about the best way to manage pregnancy complications (prevention and intervals between follow-up examinations).If no treatment is available and if a termination of pregnancy is considered, the intervention can be carried out with far lower complications compared to the second trimester of pregnancy. In most cases, further examinations are not required and the parents can be reassured. A repeat examination at around week 20 of gestation to complete the screening for malformations is recommended. NOTE: The guideline will be published simultaneously in the official journals of both professional societies (i.e. Ultraschall in der Medizin/European Journal of Ultrasound for the DEGUM and Geburtshilfe und Frauenheilkunde for the DGGG)., Competing Interests: See also the long German-language version of the guideline: https://register.awmf.org/de/leitlinien/detail/085–002, (Thieme. All rights reserved.)

This extensive AWMF 085-002 S2e-guideline "First Trimester Diagnosis and Therapy @ 11 - 13 +6 Weeks of Gestation" has systematically analyzed high-quality studies and publications and the existing evidence (evidence tables) and produced recommendations (level of recommendation, level of evidence, strength of consensus). This guideline deals with the following topics in the context of the 11 - 13 +6 weeks scan: the legal basis, screening for anatomical malformations, screening for chromosomal defects, quality assessment and audit, screening for preeclampsia and FGR, screening for preterm birth, screening for abnormally invasive placenta (AIP) and placenta accreta spectrum (PAS), screening for velamentous cord insertion and vasa praevia, screening for diabetes mellitus and LGA. Screening for complications of pregnancy can best be carried out @ 11 - 13 +6 weeks of gestation. The issues of how to identify malformations, chromosomal abnormalities and certain disorders of placentation (high blood pressure and proteinuria, intrauterine growth retardation) have been solved. The problem of how to identify placenta percreta and vasa previa has been partially solved. What is still unsolved is how to identify disorders of glucose metabolism and preterm birth. In the first trimester, solutions to some of these problems are available: parents can be given extensive counselling and the risk that a pregnancy complication will manifest at a later stage can be delayed and reduced. This means that screening is critically important as it helps in decision-making about the best way to manage pregnancy complications (prevention and intervals between follow-up examinations). If no treatment is available and if a termination of pregnancy is considered, the intervention can be carried out with far lower complications compared to the second trimester of pregnancy. In most cases, further examinations are not required and the parents can be reassured. A repeat examination at around week 20 of gestation to complete the screening for malformations is recommended. Note: The guideline will be published simultaneously in the official journals of both professional societies (i.e. Ultraschall in der Medizin/European Journal of Ultrasound for the DEGUM and Geburtshilfe und Frauenheilkunde for the DGGG)., Competing Interests: Conflict of Interest See also the long German-language version of the guideline: https://register.awmf.org/de/leitlinien/detail/085-002, (Thieme. All rights reserved.)

This extensive AWMF 085-002 S2e-guideline "First Trimester Diagnosis and Therapy @ 11 - 13 +6 of Gestation" has systematically analyzed high-quality studies and publications and the existing evidence (evidence tables) and produced recommendations (level of recommendation, level of evidence, strength of consensus). This guideline deals with the following topics in the context of the 11 - 13 +6 weeks scan: the legal basis, screening for anatomical malformations, screening for chromosomal defects, quality assessment and audit, screening for preeclampsia and FGR, screening for preterm birth, screening for abnormally invasive placenta (AIP) and placenta accreta spectrum (PAS), screening for velamentous cord insertion and vasa praevia, screening for diabetes mellitus and LGA. Screening for complications of pregnancy can best be carried out @ 11 - 13 +6 weeks of gestation. The issues of how to identify malformations, chromosomal abnormalities and certain disorders of placentation (high blood pressure and proteinuria, intrauterine growth retardation) have been solved. The problem of how to identify placenta percreta and vasa previa has been partially solved. What is still unsolved is how to identify disorders of glucose metabolism and preterm birth. In the first trimester, solutions to some of these problems are available: parents can be given extensive counselling and the risk that a pregnancy complication will manifest at a later stage can be delayed and reduced. This means that screening is critically important as it helps in decision-making about the best way to manage pregnancy complications (prevention and intervals between follow-up examinations). If no treatment is available and if a termination of pregnancy is considered, the intervention can be carried out with far lower complications compared to the second trimester of pregnancy. In most cases, further examinations are not required and the parents can be reassured. A repeat examination at around week 20 of gestation to complete the screening for malformations is recommended. Note: The guideline will be published simultaneously in the official journals of both professional societies (i.e. Ultraschall in der Medizin/European Journal of Ultrasound for the DEGUM and Geburtshilfe und Frauenheilkunde for the DGGG)., Competing Interests: Conflict of Interest See also the long version of the guideline: https://register.awmf.org/de/leitlinien/detail/085-002, (Thieme. All rights reserved.)

Description of the Problem. Gamification is used in pharmacy education as an innovative learning strategy to engage learners with educational content. The March Medication Madness activity used bracketology, a type of gamification not previously described in pharmacy education literature, to increase student engagement and knowledge of key disease states. The Innovation. The activity was developed for use in a capstone course during the final semester of the didactic pharmacy curriculum. Students created medication-related pearls that were placed in a tournament-style bracket. Students then completed brackets to predict the winning pearls and voted biweekly to determine the most clinically significant pearl. Student knowledge was assessed pre- and post-activity along with a post-activity perception assessment. Critical Analysis. Of the 52 student participant responses, most agreed or strongly agreed that the activity increased understanding and stimulated interest in course material, while adding a fun element to the course. There was a statistically significant increase ( P = .002) in the average percentage of multiple-choice questions students answered correctly from the pre-test (57.7% ± 1.5%) to the posttest (63.1% ± 1.9%). Pearls that received the most votes were no more likely to be associated with an increase in knowledge than pearls receiving fewer votes. Next Steps. Implementation of a bracketology activity was perceived by students as fun, engaging, and beneficial in understanding course material. However, increase in knowledge was limited. This shows the importance of structuring gamification in a way that provides educational value and underscores the need to modify the activity to promote student learning., (© Individual authors.)

The goal of this study was to examine how regular physical activity before and during pregnancy affected life quality throughout pregnancy. Between July 2020 and May 2021, 218 pregnant women were recruited from 11 outpatient clinics for this survey. Data were collected prospectively in a panel format beginning with the 10th gestational week over a 20-week period. Prior to pregnancy, a previous time point was also defined. The International Physical Activity Questionnaire, the EQ-5D-3L questionnaire, and the EQ-VAS questionnaire were used to collect data on the duration and intensity of daily physical exercises, as well as to assess health-related quality of life and self-estimated health status. The final survey included data from 113 women. During pregnancy, physical activity decreased dramatically. The duration of strenuous activities, but not moderate activities, was significantly reduced. Continuous physical activity independently predicted higher life quality scores at all points of assessment. Cases who participated in moderate and strenuous activities on a regular basis had higher self-estimated health status scores than cases who only participated in moderate activity. Instead of focusing solely on specific types of physical activity, we believe that strategies for motivating all pregnant women to be constantly active should be developed.

Introduction: This study characterized faculty perceptions of student barriers to achieving an Entrustable Professional Activities (EPA) level 2 or higher in the Patient Care Provider domain., Methods: Pharmacy skills laboratory faculty participated in a nominal group technique (NGT) session. Participants reflected on two questions: "What behaviors would result in a student not achieving a rank of EPA readiness level 2 or higher?" and "What knowledge and skills would result in a student not achieving a rank of EPA readiness level 2 or higher?" Participants developed a ranked list using silent brainstorming, idea generation, clarification, and discussion., Results: Two NGT sessions were conducted. Group 1 reported (lack of) professionalism, (inability to perform) physical skills, (lack of) critical thinking and interpreting data gathered during physical skills, and (inability to achieve) programmatic outcomes and mile makers exams as barriers. Group 2 ranked behaviors as lack of independence, not taking roles and responsibilities seriously, inability to follow instructions, lack of classroom engagement, and disorganized and unable to prioritize. Group 2 ranked knowledge and skills of significant errors when making medication recommendations, inability to identify accurate medication history, inability to perform tasks with time constraints, poor patient communication, and inability to identify resources., Conclusions: Pharmacy skills laboratory faculty can identify behaviors, knowledge, or skills that may prevent a student from achieving an EPA readiness level 2 or higher such as lack of professionalism and poor critical thinking skills and should be empowered to identify early warning signs for students' success and progression to experiential education., Competing Interests: Declaration of Competing Interest None., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Alkenylbenzenes are naturally occurring secondary plant metabolites. While some of them are proven genotoxic carcinogens, other derivatives need further evaluation to clarify their toxicological properties. Furthermore, data on the occurrence of various alkenylbenzenes in plants, and especially in food products, are still limited. In this review, we tempt to give an overview of the occurrence of potentially toxic alkenylbenzenes in essential oils and extracts from plants used for flavoring purposes of foods. A focus is layed on widely known genotoxic alkenylbenzenes, such as safrole, methyleugenol, and estragole. However, essential oils and extracts that contain other alkenylbenzenes and are also often used for flavoring purposes are considered. This review may re-raise awareness of the need for quantitative occurrence data for alkenylbenzenes in certain plants but especially in final plant food supplements, processed foods, and flavored beverages as the basis for a more reliable exposure assessment of alkenylbenzenes in the future.

Background: Individuals with high sensory processing sensitivity (SPS) ("highly sensitive persons") are thought to be easily excitable and overwhelmed, highly attentive to aesthetic impressions, and particularly sensitive to sensory stimulation. Public discourse suggests that those who describe themselves as highly sensitive see themselves as fundamentally different from others, and view their personality as a gift and a burden. From a clinical personality perspective, high sensitivity could be considered to have substantial overlaps with hypersensitive narcissism, or generally vulnerable narcissism., Method: We investigated the associations and shared nomological networks between high sensitivity and hypersensitive narcissism in two studies using convenience and representative samples (n 1  = 280, n 2  = 310)., Results: There is evidence for replicable associations between SPS and hypersensitive (.53 ≤ r ≤ .54) as well as vulnerable narcissism (.44 ≤ r ≤ .54), associations were not attributable to general neuroticism. Nomological networks were similar and pointed to a neurotic-introverted personality profile with reduced personality functioning. Latent class analyses further pointed to substantial and practically relevant person-level covariance., Conclusion: Sensory processing sensitivity and hypersensitive narcissism are substantially related constructs. For clinicians, this points to the importance of being attentive to narcissistic self-regulatory strategies in individuals presenting as highly sensitive., (© 2022 The Authors. Journal of Clinical Psychology published by Wiley Periodicals LLC.)

Purpose: Clinical efficiency is a key component of the value-based care model and a driver of patient satisfaction. The purpose of this study was to identify and address inefficiencies at a high-volume radiation oncology clinic., Methods and Materials: Patient flow analysis (PFA) was used to create process maps and optimize the workflow of consultation visits in a gastrointestinal radiation oncology clinic at a large academic cancer center. Metrics such as cycle times, waiting times, and rooming times were assessed by using a real-time patient status function in the electronic medical record for 556 consults and compared between before vs after implementation of the PFA recommendations., Results: The initial PFA revealed four inefficiencies: (1) protracted rooming time, (2) inefficient communications, (3) duplicated tasks, and (4) ambiguous clinical roles. We analyzed 485 consult-visits before the PFA and 71 after the PFA. The PFA recommendations led to reductions in overall median cycle time by 21% (91 min vs 72 min, p < 0.001), in cumulative waiting times by 64% (45 min vs 16 min; p < 0.001), which included waiting room time (14 min vs 5 min; p < 0.001) and wait for physician (20 min vs. 6 min; p < 0.001). Slightly less than one-quarter (22%) of consult visits before the PFA lasted > 2 h vs. 0% after implementation of the recommendations (p < 0.001). Similarly, the proportion of visits requiring < 1 h was 16% before PFA vs 34% afterward (p < 0.001)., Conclusions: PFA can be used to identify clinical inefficiencies and optimize workflows in radiation oncology consultation clinics, and implementing their findings can significantly improve cycle times and waiting times. Potential downstream effects of these interventions include improved patient experience, decreased staff burnout, financial savings, and opportunities for expanding clinical capacity., (© 2022. The Author(s).)

Effective teamwork in the online environment is essential to patient care and safety. The need for training health professionals to work together on a virtual interprofessional team has become even more important since the start of the COVID-19 pandemic as telehealth, or the provision of virtual healthcare to patients, has become more common. This resource describes the development of an online escape room activity using free online resources. The activity aimed to enhance health profession students' abilities to communicate effectively, work together to complete a task, and develop knowledge of the unique roles of healthcare team members in a course dedicated to interprofessional education. Teams of five to seven students met online and completed seven puzzles to escape a virtual room. Results obtained from the pre-post surveys of 176 students across six disciplines showed the activity aided in increasing participants perceptions of their ability to communicate respectfully and work together to complete a task, while developing knowledge of the unique roles of members of the healthcare team, all components of the Interprofessional Education Collaborative (IPEC) Core Competencies. This activity lays the groundwork for collaborative, interprofessional activities, such as telehealth, which students will be exposed to in their futures, and the results infer that the activity can help to build collaboration among team members, even team members that are not in the same physical space., (© 2022 Elsevier Inc. All rights reserved.)

Interfacing neurons persistently to conductive matter constitutes one of the key challenges when designing brain-machine interfaces such as neuroelectrodes or retinal implants. Novel materials approaches that prevent occurrence of loss of long-term adhesion, rejection reactions, and glial scarring are highly desirable. Ion doped titania nanotube scaffolds are a promising material to fulfill all these requirements while revealing sufficient electrical conductivity, and are scrutinized in the present study regarding their neuron-material interface. Adsorption of laminin, an essential extracellular matrix protein of the brain, is comprehensively analyzed. The implantation-dependent decline in laminin adsorption is revealed by employing surface characteristics such as nanotube diameter, ζ-potential, and surface free energy. Moreover, the viability of U87-MG glial cells and SH-SY5Y neurons after one and four days are investigated, as well as the material's cytotoxicity. The higher conductivity related to carbon implantation does not affect the viability of neurons, although it impedes glial cell proliferation. This gives rise to novel titania nanotube based implant materials with long-term stability, and could reduce undesirable glial scarring.

The global pandemic has dramatically impacted how pharmacists connect with patients. Telepharmacy and telehealth technologies are being used by pharmacists in a multitude of settings to positively influence the health and wellbeing of patients. Having pharmacists that are prepared to deliver services using telepharmacy and telehealth necessitates that Doctor of Pharmacy (PharmD) students receive tele-education. Tele-education topics may include telepharmacy and telehealth, audio and visual technologies, etiquette, law, reimbursement, and privacy and confidentiality. In many cases, the pandemic has required pharmacy programs to incorporate tele-education into curriculums quickly, resulting in limited and underdeveloped experiences for students. Tele-education should be purposefully incorporated into curriculums through a combination of didactic, simulation, and experiential training. Programs should evaluate how tele-education is taught within their curriculum and share those experiences with the Academy as pharmacy graduates will likely be providing patient care services using telepharmacy and telehealth., (© 2021 American Association of Colleges of Pharmacy.)

Ni-based single crystal superalloys contain microstructural regions that are separated by low-angle grain boundaries. This gives rise to the phenomenon of mosaicity. In the literature, this type of defect has been associated with the deformation of dendrites during Bridgman solidification. The present study introduces a novel serial sectioning method that allows to rationalize mosaicity on the basis of spatial dendrite growth. Optical wide-field micrographs were taken from a series of cross sections and evaluated using quantitative image analysis. This allowed to explore the growth directions of close to 2500 dendrites in a large specimen volume of approximately 450 mm 3 . The application of tomography in combination with the rotation vector base-line electron back-scatter diffraction method allowed to analyze how small angular differences evolve in the early stages of solidification. It was found that the microstructure consists of dendrites with individual growth directions that deviate up to ≈4° from the average growth direction of all dendrites. Generally, individual dendrite growth directions coincide with crystallographic <001> directions. The quantitative evaluation of the rich data sets obtained with the present method aims at contributing to a better understanding of elementary processes that govern competitive dendrite growth and crystal mosaicity.

Biosurfactants have been investigated as potential alternatives for synthetic surfactants in several areas, for example, in environmental and pharmaceutical fields. In that regard, extensive research has been carried out with sophorolipids and rhamnolipids that also present various biological properties with therapeutic significance. These biosurfactants are obtained as complex mixtures of slightly different molecules, and thus when studying these microbial glycolipids, the ability to identify and purify the produced compounds is of extreme importance. This study aimed to develop improved methodologies for the identification, separation, and purification of sophorolipids and rhamnolipids. Therefore, an ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was modified to ensure faster characterization of both sophorolipids and rhamnolipids, enabling the identification and fragmentation pattern description of 10 and 13 congeners, respectively. The separation and purification of these biosurfactants was achieved with novel reversed-phase solid-phase extraction methods guaranteeing the isolation of different glycolipids, including those considered for their significant biological activity (e.g. antimicrobial, anticancer). It was possible to isolate sophorolipids and rhamnolipids with purity of 94% and 99%, respectively. The methods presented herein can be easily implemented and are expected to make purification of these biosurfactants easier, facilitating the study of their individual properties in further works.

The Cr-Co-Ni system was studied by combining experimental and computational methods to investigate phase stability and mechanical properties. Thin-film materials libraries were prepared and quenched from high temperatures up to 700 °C using a novel quenching technique. It could be shown that a wide A1 solid solution region exists in the Cr-Co-Ni system. To validate the results obtained using thin-film materials libraries, bulk samples of selected compositions were prepared by arc melting, and the experimental data were additionally compared to results from DFT calculations. The computational results are in good agreement with the measured lattice parameters and elastic moduli. The lattice parameters increase with the addition of Co and Cr, with a more pronounced effect for the latter. The addition of ∼20 atom % Cr results in a similar hardening effect to that of the addition of ∼40 atom % Co.

This study analyzes the local deformation behavior of austenitic stainless steel 316L, manufactured conventionally by casting and additively by laser metal deposition (LMD). We produced directionally solidified 316L specimens with most grains showing (001) orientations parallel to the longitudinal specimen axis. We conducted nanoindentation and scratch experiments for local mechanical characterization and topography measurements (atomic force microscopy and confocal laser scanning microscopy) of indentation imprints and residual scratch grooves for the analysis of the deformation behavior and, in particular, of the pile-up behavior. The local mechanical properties and deformation behavior were correlated to the local microstructure investigated by scanning electron microscopy with energy dispersive X-ray spectroscopy and electron backscatter diffraction analysis. The results show that the local mechanical properties, deformation behavior, and scratch resistance strongly depend on the crystallographic orientation. Nearly (001)-oriented grains parallel to the surface show the lowest hardness, followed by an increasing hardness of nearly (101)- and (111)-oriented grains. Consequently, scratch depth is the greatest for nearly (001)-oriented grains followed by (101) and (111) orientations. This tendency is seen independently of the analyzed manufacturing route, namely Bridgman solidification and laser metal deposition. In general, the laser metal deposition process leads to a higher strength and hardness, which is mainly attributed to a higher dislocation density. Under the investigated loading conditions, the cellular segregation substructure is not found to significantly and directly change the local deformation behavior during indentation and scratch testing.

Introduction: A novel continuing professional education CPE training program and simulation were used to teach pharmacists and pharmacy technicians about continuous quality improvement and how to identify, report, and communicate information regarding medication related errors using root cause analysis., Methods: Pharmacists and pharmacy technicians attending a statewide pharmacy association meeting voluntary attended a CPE training program and simulation. During the simulation, learners investigated and identified medication related errors in three different pharmacy settings. A collection of items found at each pharmacy and audio recordings were used by learners to identify the medication related error. After each simulation, facilitators led a debriefing to discuss the learners' experiences. Data was collected using online surveys. Descriptive statistics and chi-square tests were used to analyze the data., Results: Fourteen months following the program, 15 of the 67 participants responded to an anonymous survey. Of the 15 responding participants, 73.3% (11/15) were confident or very confident they could establish or maintain a high-quality continuous quality improvement plan at their practice site. Sixty percent (9/15) felt the experience reinforced their current practices, 13.3% (2/15) had implemented changes to their practice, and 13.3% (2/15) felt they needed more information before considering changes to their practice. Reported barriers to establishing a continuous quality improvement program were time constraints, 40.0% (6/15), system constraints, 26.7% (4/15), or lack of staff 20.0% (3/15)., Conclusion: A CPE training program and simulation reinforced practice for pharmacy personnel, resulted in changes to practice, and positively increased participants' confidence in establishing a continuous quality improvement plan in the workplace., Competing Interests: Conflicts of interest: None, (© Individual authors.)

Background and Purpose: All 50 states have implemented policies to improve access to naloxone through community pharmacies. Many states require naloxone-based training for pharmacists before participating in these activities. The purpose of this study was to determine the effects of an opioid misuse and overdose training program on students' knowledge, self-efficacy, and value of pharmacists' role in preventing overdose., Educational Activity and Setting: The training program was implemented with third-year professional pharmacy students. Students participated in a 50-min lecture followed by a two-hour hands-on laboratory activity. Students took a pre-survey immediately before the lecture and a post-survey immediately following the laboratory activity., Findings: Seventy students completed the pre- and post-surveys. Students showed a significant (p < 0.05) gain in self-efficacy and value after completing the training program, and a significant gain in knowledge from six of the eight related survey items. There was a significant correlation between students' self-efficacy and perceived value of the pharmacists' role in preventing opioid overdose., Summary: A training program implemented for third-year pharmacy students increases students' knowledge, self-efficacy, and perceived value. Specifically, the strong correlation seen between self-efficacy and perceived value after completing the training program is important to note as we prepare future pharmacists for their role in fighting the opioid epidemic., (Copyright © 2019 Elsevier Inc. All rights reserved.)

By a combination of electron paramagnetic resonance spectroscopy, finite-temperature ab initio simulations, and electronic structure analyses, the activation of molecular dioxygen at the interface of gold nanoparticles and titania in Au/TiO 2 catalysts is explained at the atomic scale by tracing processes down to the molecular orbital picture. Direct evidence is provided that excess electrons in TiO 2 , for example created by photoexcitation of the semiconductor, migrate to the gold particles and from there to oxygen molecules adsorbed at gold/titania perimeter sites. Superoxide species are formed more efficiently in this way than on the bare TiO 2 surface. This catalytic effect of the gold nanoparticles is attributed to a weakening of the internal O-O bond, leading to a preferential splitting of the molecule at shorter bond lengths together with a 70% decrease of the dissociation free energy barrier compared to the non-catalyzed case on bare TiO 2 . The findings are an important step forward in the clarification of the role of gold in (photo)catalytic processes.

Introduction: The purpose of this study is to evaluate longitudinal changes in professionalism of pharmacy students across the curriculum using a validated instrument that minimizes ceiling effect., Methods: The Professionalism Assessment Tool (PAT) was administered to first, second, and third year PharmD students twice throughout the first and second professional year (P1 and P2) and three times throughout the third professional year (P3)., Results: Longitudinal increases in all five domains of professionalism of the PAT were noted as students progressed through each year of the didactic curriculum. Most demographic categories (sex, age, employment in a pharmacy, and number of other degrees held) of respondents did not affect self-assessment results. Two demographic categories, the number of student organizations and age group, had statistically significant impact on self-reported professionalism., Conclusions: This pilot study showed longitudinal improvement in student self-assessment of professionalism over the course of the didactic curriculum at one school. Self-assessment of pharmacy student professionalism increased over the course of the didactic curriculum and was not affected by most demographics., (Copyright © 2017. Published by Elsevier Inc.)

Performing ab initio molecular dynamics simulations of open systems, where the chemical potential rather than the number of both nuclei and electrons is fixed, still is a challenge. Here, drawing on bicanonical sampling ideas introduced two decades ago by Swope and Andersen [ J. Chem. Phys. 1995 , 102 , 2851 - 2863 ] to calculate chemical potentials of liquids and solids, an ab initio simulation technique is devised, which introduces a fictitious dynamics of two superimposed but otherwise independent periodic systems including full electronic structure, such that either the chemical potential or the average fractional particle number of a specific chemical species can be kept constant. As proof of concept, we demonstrate that solvation free energies can be computed from these bicanonical ab initio simulations upon directly superimposing pure bulk water and the respective aqueous solution being the two limiting systems. The method is useful in many circumstances, for instance for studying heterogeneous catalytic processes taking place on surfaces where the chemical potential of reactants rather than their number is controlled and opens a pathway toward ab initio simulations at constant electrochemical potential.

Introduction: To describe current methods used to assess SOAP notes in colleges and schools of pharmacy., Methods: Members of the American Association of Colleges of Pharmacy Laboratory Instructors Special Interest Group were invited to share assessment tools for SOAP notes. Content of submissions was evaluated to characterize overall qualities and how the tools assessed subjective, objective, assessment, and plan information., Results: Thirty-nine assessment tools from 25 schools were evaluated. Twenty-nine (74%) of the tools were rubrics and ten (26%) were checklists. All rubrics included analytic scoring elements, while two (7%) were mixed with holistic and analytic scoring elements. A majority of the rubrics (35%) used a four-item rating scale. Substantial variability existed in how tools evaluated subjective and objective sections. All tools included problem identification in the assessment section. Other assessment items included goals (82%) and rationale (69%). Seventy-seven percent assessed drug therapy; however, only 33% assessed non-drug therapy. Other plan items included education (59%) and follow-up (90%)., Discussion and Conclusions: There is a great deal of variation in the specific elements used to evaluate SOAP notes in colleges and schools of pharmacy. Improved consistency in assessment methods to evaluate SOAP notes may better prepare students to produce standardized documentation when entering practice., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Ti-Ta alloys are attractive materials for applications in actuators as well as biomedical implants. When fabricated as thin films, these alloys can potentially be employed as microactuators, components for micro-implantable devices and coatings on surgical implants. In this study, Ti 100-x Ta x (x = 21, 30) nanocolumnar thin films are fabricated by glancing angle deposition (GLAD) at room temperature using Ti 73 Ta 27 and Ta sputter targets. Crystal structure, morphology and microstructure of the nanostructured thin films are systematically investigated by XRD, SEM and TEM, respectively. Nanocolumns of ∼150-160 nm in width are oriented perpendicular to the substrate for both Ti 79 Ta 21 and Ti 70 Ta 30 compositions. The disordered α″ martensite phase with orthorhombic structure is formed in room temperature as-deposited thin films. The columns are found to be elongated small single crystals which are aligned perpendicular to the [Formula: see text] and [Formula: see text] planes of α″ martensite, indicating that the films' growth orientation is mainly dominated by these crystallographic planes. Laser pre-patterned substrates are utilized to obtain periodic nanocolumnar arrays. The differences in seed pattern, and inter-seed distances lead to growth of multi-level porous nanostructures. Using a unique sputter deposition geometry consisting of Ti 73 Ta 27 and Ta sputter sources, a nanocolumnar Ti-Ta materials library was fabricated on a static substrate by a co-deposition process (combinatorial-GLAD approach). In this library, a composition spread developed between Ti 72.8 Ta 27.2 and Ti 64.4 Ta 35.6 , as confirmed by high-throughput EDX analysis. The morphology over the materials library varies from well-isolated nanocolumns to fan-like nanocolumnar structures. The influence of two sputter sources is investigated by studying the resulting column angle on the materials library. The presented nanostructuring methods including the use of the GLAD technique along with pre-patterning and a combinatorial materials library fabrication strategy offer a promising technological approach for investigating Ti-Ta thin films for a range of applications. The proposed approaches can be similarly implemented for other materials systems which can benefit from the formation of a nanocolumnar morphology.

Release of Ni(1+) ions from NiTi alloy into tissue environment, biological response on the surface of NiTi and the allergic reaction of atopic people towards Ni are challengeable issues for biomedical application. In this study, composite coatings of hydroxyapatite-silicon multi walled carbon nano-tubes with 20wt% Silicon and 1wt% multi walled carbon nano-tubes of HA were deposited on a NiTi substrate using electrophoretic methods. The SEM images of coated samples exhibit a continuous and compact morphology for hydroxyapatite-silicon and hydroxyapatite-silicon-multi walled carbon nano-tubes coatings. Nano-indentation analysis on different locations of coatings represents the highest elastic modulus (45.8GPa) for HA-Si-MWCNTs which is between the elastic modulus of NiTi substrate (66.5GPa) and bone tissue (≈30GPa). This results in decrease of stress gradient on coating-substrate-bone interfaces during performance. The results of nano-scratch analysis show the highest critical distance of delamination (2.5mm) and normal load before failure (837mN) as well as highest critical contact pressure for hydroxyapatite-silicon-multi walled carbon nano-tubes coating. The cell culture results show that human mesenchymal stem cells are able to adhere and proliferate on the pure hydroxyapatite and composite coatings. The presence of both silicon and multi walled carbon nano-tubes (CS3) in the hydroxyapatite coating induce more adherence of viable human mesenchymal stem cells in contrast to the HA coated samples with only silicon (CS2). These results make hydroxyapatite-silicon-multi walled carbon nano-tubes a promising composite coating for future bone implant application., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Shape Memory Alloys (SMA) using elastocaloric cooling processes have the potential to be an environmentally friendly alternative to the conventional vapor compression based cooling process. Nickel-Titanium (Ni-Ti) based alloy systems, especially, show large elastocaloric effects. Furthermore, exhibit large latent heats which is a necessary material property for the development of an efficient solid-state based cooling process. A scientific test rig has been designed to investigate these processes and the elastocaloric effects in SMAs. The realized test rig enables independent control of an SMA's mechanical loading and unloading cycles, as well as conductive heat transfer between SMA cooling elements and a heat source/sink. The test rig is equipped with a comprehensive monitoring system capable of synchronized measurements of mechanical and thermal parameters. In addition to determining the process-dependent mechanical work, the system also enables measurement of thermal caloric aspects of the elastocaloric cooling effect through use of a high-performance infrared camera. This combination is of particular interest, because it allows illustrations of localization and rate effects - both important for efficient heat transfer from the medium to be cooled. The work presented describes an experimental method to identify elastocaloric material properties in different materials and sample geometries. Furthermore, the test rig is used to investigate different cooling process variations. The introduced analysis methods enable a differentiated consideration of material, process and related boundary condition influences on the process efficiency. The comparison of the experimental data with the simulation results (of a thermomechanically coupled finite element model) allows for better understanding of the underlying physics of the elastocaloric effect. In addition, the experimental results, as well as the findings based on the simulation results, are used to improve the material properties.

Highly sensitive and efficient biosensors play a crucial role in clinical, environmental, industrial, and agricultural applications, and tremendous efforts have been dedicated to advanced electrode materials with superior electrochemical activities and low cost. Here, we report a three-dimensional binder-free Cu foam-supported Cu2O nanothorn array electrode developed via facile electrochemistry. The nanothorns growing in situ along the specific direction of <011> have single crystalline features and a mesoporous surface. When being used as a potential biosensor for nonenzyme glucose detection, the hybrid electrode exhibits multistage linear detection ranges with ultrahigh sensitivities (maximum of 97.9 mA mM(-1) cm(-2)) and an ultralow detection limit of 5 nM. Furthermore, the electrode presents outstanding selectivity and stability toward glucose detection. The distinguished performances endow this novel electrode with powerful reliability for analyzing human serum samples. These unprecedented sensing characteristics could be ascribed to the synergistic action of superior electrochemical catalytic activity of nanothorn arrays with dramatically enhanced surface area and intimate contact between the active material (Cu2O) and current collector (Cu foam), concurrently supplying good conductivity for electron/ion transport during glucose biosensing. Significantly, our findings could guide the fabrication of new metal oxide nanostructures with well-organized morphologies and unique properties as well as low materials cost.

Isoprene emissions from poplar (Populus spp.) plantations can influence atmospheric chemistry and regional climate. These emissions respond strongly to temperature, [CO2], and drought, but the superimposed effect of these three climate change factors are, for the most part, unknown. Performing predicted climate change scenario simulations (periodic and chronic heat and drought spells [HDSs] applied under elevated [CO2]), we analyzed volatile organic compound emissions, photosynthetic performance, leaf growth, and overall carbon (C) gain of poplar genotypes emitting (IE) and nonemitting (NE) isoprene. We aimed (1) to evaluate the proposed beneficial effect of isoprene emission on plant stress mitigation and recovery capacity and (2) to estimate the cumulative net C gain under the projected future climate. During HDSs, the chloroplastidic electron transport rate of NE plants became impaired, while IE plants maintained high values similar to unstressed controls. During recovery from HDS episodes, IE plants reached higher daily net CO2 assimilation rates compared with NE genotypes. Irrespective of the genotype, plants undergoing chronic HDSs showed the lowest cumulative C gain. Under control conditions simulating ambient [CO2], the C gain was lower in the IE plants than in the NE plants. In summary, the data on the overall C gain and plant growth suggest that the beneficial function of isoprene emission in poplar might be of minor importance to mitigate predicted short-term climate extremes under elevated [CO2]. Moreover, we demonstrate that an analysis of the canopy-scale dynamics of isoprene emission and photosynthetic performance under multiple stresses is essential to understand the overall performance under proposed future conditions., (© 2015 American Society of Plant Biologists. All Rights Reserved.)

The increase of extended- spectrum β-lactamase-producing Enterobacteriaceae (ESBL-E) in humans and in food-producing animals is of public health concern. The latter could contribute to spreading of these bacteria or their resistance genes to humans. Several studies have reported the isolation of third generation cephalosporin resistant bacteria in livestock animals. However, the number of samples and the methodology used differ considerably between studies limiting comparability and prevalence assessment. In the present study, a total of 564 manure and dust samples were collected from 47 pig farms in Northern Germany and analysed to determine the prevalence of ESBL-E. Molecular typing and characterization of resistance genes was performed for all ESBL-E isolates. ESBL-E isolates were found in 55.3% of the farms. ESBL-Escherichia coli was found in 18.8% of the samples, ESBL-Klebsiella pneumoniae in 0.35%. The most prevalent ESBL genes among E. coli were CTX-M-1 like (68.9%), CTX-M-15 like (16%) and CTX-M-9 group (14.2%). In 20% of the latter two, also the OXA-1 like gene was found resulting in a combination of genes typical for isolates from humans. Genetic relation was found between isolates not only from the same, but also from different farms, with multilocus sequence type (ST) 10 being predominant among the E. coli isolates. In conclusion, we showed possible spread of ESBL-E between farms and the presence of resistance genes and STs previously shown to be associated with human isolates. Follow-up studies are required to monitor the extent and pathways of ESBL-E transmission between farms, animals and humans.

During the last two decades density functional based linear response approaches have become the de facto standard for the calculation of optical properties of small- and medium-sized molecules. At the heart of these methods is the solution of an eigenvalue equation in the space of single-orbital transitions, whose quickly increasing number makes such calculations costly if not infeasible for larger molecules. This is especially true for time-dependent density functional tight binding (TD-DFTB), where the evaluation of the matrix elements is inexpensive. For the relatively large systems that can be studied the solution of the eigenvalue equation therefore determines the cost of the calculation. We propose to do an oscillator strength based truncation of the single-orbital transition space to reduce the computational effort of TD-DFTB based absorption spectra calculations. We show that even a sizable truncation does not destroy the principal features of the absorption spectrum, while naturally avoiding the unnecessary calculation of excitations with small oscillator strengths. We argue that the reduced computational cost of intensity-selected TD-DFTB together with its ease of use compared to other methods lowers the barrier of performing optical property calculations of large molecules and can serve to make such calculations possible in a wider array of applications.

Methanol synthesis is one of the landmarks of heterogeneous catalysis due to the great industrial significance of methanol as a clean liquid fuel and as a raw material for industry. Understanding in atomistic detail the properties of the underlying metal/oxide catalyst materials as a function of temperature and composition of the reactive gas phase is of utmost importance in order to eventually improve the production process. By performing extensive density functional theory based slab calculations in combination with a thermodynamic formalism we establish an atomistic understanding of gas phase-induced changes of surface morphology, redox properties and reactivity of ZnO supported Cu nanocatalysts. Extending our recent insights [Phys. Rev. Lett., 2013, 110, 086108], we explore surface stabilization mechanisms and site-dependent redox states of both catalyst components as well as the pronounced electronic charge transfer processes across the metal-support interface. Moreover, ab initio molecular dynamics simulations unveil the vital role played by dynamical shape fluctuations of the deposited Cu8 cluster. The pronounced structural flexibility of the metal nanoparticle is found to enhance CO2 activation over Cu8 at the elevated temperature conditions of the industrial methanol synthesis process, in addition to activation of CO2via electronic charge transfer from the ZnO support.

Methanol synthesis from CO and H2 over ZnO, which requires high temperatures and high pressures giving rise to a complex interplay of physical and chemical processes over this heterogeneous catalyst surface, is investigated using ab initio simulations. The redox properties of the surrounding gas phase are known to directly impact on the catalyst properties and thus, set the overall catalytic reactivity of this easily reducible oxide material. In Paper III of our series [J. Kiss, J. Frenzel, N. N. Nair, B. Meyer, and D. Marx, J. Chem. Phys. 134, 064710 (2011)] we have qualitatively shown that for the partially hydroxylated and defective ZnO(0001¯) surface there exists an intricate network of surface chemical reactions. In the present study, we employ advanced molecular dynamics techniques to resolve in detail this reaction network in terms of elementary steps on the defective surface, which is in stepwise equilibrium with the gas phase. The two individual reduction steps were investigated by ab initio metadynamics sampling of free energy landscapes in three-dimensional reaction subspaces. By also sampling adsorption and desorption processes and thus molecular species that are in the gas phase but close to the surface, our approach successfully generated several alternative pathways of methanol synthesis. The obtained results suggest an Eley-Rideal mechanism for both reduction steps, thus involving "near-surface" molecules from the gas phase, to give methanol preferentially over a strongly reduced catalyst surface, while important side reactions are of Langmuir-Hinshelwood type. Catalyst re-reduction by H2 stemming from the gas phase is a crucial process after each reduction step in order to maintain the catalyst's activity toward methanol formation and to close the catalytic cycle in some reaction channels. Furthermore, the role of oxygen vacancies, side reactions, and spectator species is investigated and mechanistic details are discussed based on extensive electronic structure analysis.

A rigorous characterization of a wealth of molecular species adsorbed at oxygen defects on ZnO(0001) is given. These defects represent the putative active sites in methanol synthesis from CO and H2. The oxidation state of the ZnO catalyst and thus the preferred charge state and the reactivity of the oxygen vacancies depend on the gas phase temperature and pressure conditions. Considering charge states of oxygen vacancies relevant at the reducing conditions of the industrial process, i.e., F(++)/H2, F(0), F(0)/H2, and F(--), as well as the F(++) center which is abundant at UHV conditions and therefore important to allow for comparison with surface science experiments, we have investigated the structure, energetics, and vibrational frequencies of an exhaustive catalog of reaction intermediates using electronic structure calculations. After having identified the characteristic adsorption modes of CO, formate, formic acid, hydroxymethylene, formyl, formaldehyde, dioxomethylene, hydroxymethyl, hydroxymethoxide, methoxide, as well as methanol itself, the thermodynamic stability of all species with respect to the charge state of the oxygen vacancy and their electronic stabilization is discussed in detail and summarized in an energy level diagram.

By calculation of a thermodynamic phase diagram we provide an atomistic understanding of the morphological changes in ZnO-supported Cu nanocatalysts, which are subject to strong metal-support interactions, in response to the redox properties of the surrounding gas phase, i.e., depending on temperature and pressure. The reactivity, and thus the strong metal-support interactions, of this catalyst is traced back to a redox-state dependent occupation of delocalized ZnO substrate bands and localized Cu cluster states at the Fermi level. It is shown that at the conditions of industrial methanol synthesis complex electronic charge transfer processes across the metal-support interface, driven by morphological and electronic changes, explain the enhanced catalytic reactivity toward CO(2).

The interplay of physical and chemical processes in the heterogeneous catalytic synthesis of methanol on the ZnO(0001) surface with oxygen vacancies is expected to give rise to a complex free energy landscape. A manifold of intermediate species and reaction pathways has been proposed over the years for the reduction of CO on this catalyst at high temperature and pressure conditions as required in the industrial process. In the present study, the underlying complex reaction network from CO to methanol is generated in the first place by using ab initio metadynamics for computational heterogeneous catalysis. After having "synthesized" the previously discussed intermediates in addition to finding novel species, mechanistic insights into this network of surface chemical reactions are obtained based on exploring the global free energy landscape, which is refined by investigating individual reaction pathways. Furthermore, the impact of homolytic adsorption and desorption of hydrogen at the required reducing gas phase conditions is probed by studying such processes using different charge states of the F-center.

Background: Peptide patterns of bronchoalveolar lavage fluid (BALF) were assumed to reflect the complex pathology of acute lung injury (ALI)/acute respiratory distress syndrome (ARDS) better than clinical and inflammatory parameters and may be superior for outcome prediction., Methodology/principal Findings: A training group of patients suffering from ALI/ARDS was compiled from equal numbers of survivors and nonsurvivors. Clinical history, ventilation parameters, Murray's lung injury severity score (Murray's LISS) and interleukins in BALF were gathered. In addition, samples of bronchoalveolar lavage fluid were analyzed by means of hydrophobic chromatography and MALDI-ToF mass spectrometry (MALDI-ToF MS). Receiver operating characteristic (ROC) analysis for each clinical and cytokine parameter revealed interleukin-6>interleukin-8>diabetes mellitus>Murray's LISS as the best outcome predictors. Outcome predicted on the basis of BALF levels of interleukin-6 resulted in 79.4% accuracy, 82.7% sensitivity and 76.1% specificity (area under the ROC curve, AUC, 0.853). Both clinical parameters and cytokines as well as peptide patterns determined by MALDI-ToF MS were analyzed by classification and regression tree (CART) analysis and support vector machine (SVM) algorithms. CART analysis including Murray's LISS, interleukin-6 and interleukin-8 in combination was correct in 78.0%. MALDI-ToF MS of BALF peptides did not reveal a single identifiable biomarker for ARDS. However, classification of patients was successfully achieved based on the entire peptide pattern analyzed using SVM. This method resulted in 90% accuracy, 93.3% sensitivity and 86.7% specificity following a 10-fold cross validation (AUC = 0.953). Subsequent validation of the optimized SVM algorithm with a test group of patients with unknown prognosis yielded 87.5% accuracy, 83.3% sensitivity and 90.0% specificity., Conclusions/significance: MALDI-ToF MS peptide patterns of BALF, evaluated by appropriate mathematical methods can be of value in predicting outcome in pneumonia induced ALI/ARDS.

The concept of reticular chemistry is investigated to explore the applicability of the formation of Covalent Organic Frameworks (COFs) from their defined individual building blocks. Thus, we have designed, optimized and investigated a set of reported and hypothetical 2D COFs using Density Functional Theory (DFT) and the related Density Functional based tight-binding (DFTB) method. Linear, trigonal and hexagonal building blocks have been selected for designing hexagonal COF layers. High-symmetry AA and AB stackings are considered, as well as low-symmetry serrated and inclined stackings of the layers. The latter ones are only slightly modified compared to the high-symmetry forms, but show higher energetic stability. Experimental XRD patterns found in literature also support stackings with highest formation energies. All stacking forms vary in their interlayer separations and band gaps; however, their electronic densities of states (DOS) are similar and not significantly different from that of a monolayer. The band gaps are found to be in the range of 1.7-4.0 eV. COFs built of building blocks with a greater number of aromatic rings have smaller band gaps.

The aluminosilicate mineral imogolite is composed of single-walled nanotubes with stoichiometry of (HO)(3)Al(2)O(3)SiOH and occurs naturally in soils of volcanic origin. In the present work we study the stability and the electronic and mechanical properties of zigzag and armchair imogolite nanotubes using the density-functional tight-binding method. The (12,0) imogolite tube has the highest stability of all tubes studied here. Uniquely for nanotubes, imogolite has a minimum in the strain energy for the optimum structure. This is in agreement with experimental data, as shown by comparison with the simulated X-ray diffraction spectrum. An analysis of the electronic densities of states shows that all imogolite tubes, independent on their chirality and size, are insulators.

The cellular defense of Müller cells against oxidative and nitrosative stress was examined after the addition of the nitric oxide donor papanonoate. Glucose concentrations of > or = 550 microM efficiently protected the Müller cells from cell death by maintaining high ATP and glutathione and allowing only a moderate increase of free radicals. Fluorescence-activated cell sorting (FACS) analysis showed that 22% of the cells underwent apoptosis whereas necrosis was strongly suppressed. Under glucose deprivation, the intracellular concentration of ATP declined to 15% after 1 h; glutathione dropped to 50% within 2 h after papanonoate addition. Both the number of cells containing excess free radicals and the mean concentration of free radicals increased twofold at 0.5-2 h of incubation with papanonoate. Cell death switched from prevailing apoptosis to massive necrosis and cell viability decreased drastically. Several metabolites of glycolysis, gluconeogenesis, and the pentose phosphate pathway were tested with respect to their capability to protect the stressed Müller cells. 2 mM pyruvate was found to enhance cell viability 1.6-fold predominantly by reducing the necrotic cell demise. It could be shown that pyruvate did not act by improving the energy status of Müller cells but by scavenging excess free radicals. Inhibition of the monocarboxylate transporters in Müller cells by alpha-cyano-4-hydroxycinnamate abolished this effect. Other 2-ketoacids, like oxalacetate, 2-ketoglutarate and 2-ketobutyrate had a similar protecting effect as pyruvate. Lactate, glutamate, 2-deoxyglucose, and ribose 5-phosphate did not protect Müller cells against oxidative and nitrosative stress., (Copyright 2005 Wiley-Liss, Inc.)

Objectives: AVE0118 is a novel blocker of the K(+) channels K(v)1.5 and K(v)4.3 which are the molecular basis for the human cardiac ultrarapid delayed rectifier potassium current (I(Kur)) and the transient outward current (I(to)). The objective of this study was to investigate the effect of AVE0118 on atrial refractoriness (ERP), left atrial vulnerability (LAV) and on left atrial monophasic action potentials (MAP) in pentobarbital anesthetized pigs in comparison to the selective I(Kr) blocker dofetilide in order to assess the therapeutic potential of the novel K(+) channel blocker for atrial fibrillation., Methods: Atrial ERP was determined with the S1-S2-stimulus method in the free walls of left and right atrium at 240, 300 and 400 ms basic cycle length (BCL). The inducibility of mostly nonsustained atrial tachyarrhythmias by the premature S2 extrastimulus, which is very high in the left pig atrium and referred to as LAV, was evaluated before and after drugs. Left atrial epicardial MAP was recorded to study the influence of the potassium channel blockers on the time course of repolarization. Left ventricular epicardial MAP, ERP and QT interval were measured to investigate a possible effect of AVE0118 on ventricular repolarization., Results: ERPs determined at 240, 300 and 400 ms BCL were significantly shorter in the left vs. right atrium (99+/-3, 106+/-4 and 113+/-3 ms vs. 133+/-4 ms, 142+/-4 and 149+/-5, respectively; p<0.001; n=21). AVE0118 administered i.v. dose-dependently prolonged the atrial ERP independent from rate and inhibited LAV (100% at 0.5 and 1 mg/kg) while having no effect at all on the corrected QT (QTc) interval. At 1 mg/kg (n=5) AVE0118 prolonged left vs. right atrial ERP by 49.6+/-4.1 ms vs. 37.7+/-9.7 ms (means+/-SEM of changes at 240, 300, and 400 ms BCL), respectively, corresponding to a relative increase of 53.2+/-6.2% vs. 27.6+/-6.8% (p<0.05 for percent increase of left vs. right atrial ERP). In a separate group of pigs (n=5) AVE0118 had no effect on left ventricular ERP at 333, 400 and 500 ms BCL and no effect on MAP duration and QT at 600 ms BCL. After 1 mg/kg of AVE0118 the atrial MAP was significantly prolonged already at 10% repolarization (P<0.05; n=7) reaching the maximum at 40% repolarization. In contrast to AVE0118 the effect of dofetilide (10 microg/kg) on atrial MAP started to become significant only at 60% repolarization (n=6) with a maximum increase at 90%. Dofetilide, which prolonged the QTc interval by 16.9% (P<0.001), had a significantly stronger effect on right (34.7+/-5 ms) vs. left atrial ERP (23.5+/-7 ms) at 300 ms BCL, respectively, but did not significantly inhibit LAV (14%; n=6)., Conclusion: The novel K(+) channel blocker AVE0118 prolonged atrial ERP and showed strong atrial antiarrhythmic efficacy with no apparent effect on ventricular repolarization in pigs in vivo.

Bacterial effects on in vitro mineralization of human periodontal fibroblasts (HPF) have not yet been examined in great detail. In our study, we investigated the effects of soluble extracts of the periodontopathic bacteria Porphyromonas gingivalis, Bacteroides forsythus and, Treponema denticola on cell proliferation, mineralization, as well as on osteoblastic markers present in HPF cultured in vitro, such as alkaline phosphatase (ALP) activity and collagen content. Periodontal fibroblasts stimulated by B-glycerophosphate, ascorbic acid and dexamethasone (BAD) or by dexamethasone and ascorbic acid (DA) were compared to unstimulated cells. During the cultivation period, the stimulation of HPF by combined dexamethasone and ascorbic acid (DA) had a strong inductive effect on proliferation, ALP activity and collagen formation. The extracts obtained from the periodontal pathogens had a suppressing effect on the proliferation rate of HPF. The extracts from P. gingivalis, B. forsythus and T. denticola caused a decrease in ALP activity within 24 h of application. While extracts obtained from P. gingivalis and B. forsythus induced a reduction in collagen content in BAD- and DA-stimulated HPF cells, T. denticola extracts led to an increase in collagen. Our data suggest that specific periodontopathic bacteria may suppress tissue regeneration in vivo not only by activating host defense mechanisms but also directly via a suppression of growth and differentiation of HPF and a reduction in the extracellular collagen matrix. For the process of pocket formation, not even the direct influence of viable bacteria seems to be necessary. Additionally, long-distance effects of bacteria harboured in periodontal pockets or in root canals may be of importance.