Search

Valence shell electron pair repulsion theory (VSEPR) as explained in most textbooks predicts that substituents bonded to a central atom in AX[subscript n]E[subscript z][superscript c] species (A = main-group central atom, X = substituent, E = lone pair on central atom, c = charge) will change their X-A-X angles to bend away from the lone pairs. Exceptions have appeared in the literature, commonly arising from steric repulsions between very large substituents and less commonly from electronic factors such as multiple bonding and bond polarization. We have conducted extensive computational studies of hypercoordinate main-group molecules and ions AX[subscript n]E[subscript z][superscript c] and AO[subscript m]X[subscript n]E[subscript z][superscript c], where X = halide, and found that VSEPR-based predictions of such bending for those species containing heavier halides are likely incorrect. Indeed, despite the fact that cases where X = F usually conform to the prediction, we find that IOF[subscript 4][overbar]/XeOF[subscript 4] and IO[subscript 2]F[subscript 2][overbar]/XeO[subscript 2]F[subscript 2] should not. Calculations of the electron localization function indicate that the root cause of the difference is the migration of lone pairs closer to the central atom. We recommend that presentation of VSEPR in general chemistry and inorganic chemistry textbooks be revisited and provide suggested language incorporating this phenomenon.

Exposure to ultraviolet (UV) radiation from the sun has both harms and benefits for human health. The best-known benefit of sun exposure is the generation of vitamin D within the skin and the best-known harm is malignant skin cancer. Australia and New Zealand have very high ambient UV radiation, resulting in high rates of skin cancer incidence and mortality, yet there is an appreciable prevalence of vitamin D deficiency (defined as blood 25-hydroxyvitamin D (25(OH)D) < 50 nmol/L) in both populations. The purpose of this study was to create a microsimulation model to replicate population 25(OH)D concentrations of people living in Australia and New Zealand, thus enabling the effect of different population-wide interventions to be estimated. We used large population datasets containing data on sun behaviours and socio-demographic variables, and environmental data on UV radiation, ozone, and solar zenith angle. Latitude, weather and time of day were accounted for. We simulated the conversion of daily UV radiation to a standard vitamin D dose (SDD) (100 J/m2 vitamin D-weighted UV) and monthly accumulation of SDD to 25(OH)D concentration. The model was calibrated to match the seasonal prevalence of vitamin D deficiency. This report describes the Sun Exposure (SUNEX) microsimulation model, its development, data inputs and calibration against population prevalence of vitamin D deficiency.

The way high school chemistry curricula are structured has the potential to convey consequential messages about knowledge and knowing to students and teachers. If a curriculum is built around practicing skills and recalling facts to reach ''correct'' answers, it is unlikely class activities will be seen (by students or the teacher) as opportunities to figure out causes for phenomena. Our team of teachers and researchers is working to understand how enactment of transformed curricular materials can support high school chemistry students in making sense of perplexing, relatable phenomena. Given this goal, we were surprised to see that co-developers who enacted our materials overwhelmingly emphasized the importance of acquiring true facts/skills when writing weekly reflections. Recognition that teachers' expressed aims did not align with our stated goal of ''supporting molecular-level sensemaking'' led us to examine whether the tacit epistemological commitments reflected by our materials were, in fact, consistent with a course focused on figuring out phenomena. We described several aspects of each lesson in our two-semester curriculum including: the role of phenomena in lesson activities, the extent to which lessons were 3-dimensional, the role of student ideas in class dialogue, and who established coherence between lessons. Triangulation of these lesson features enabled us to infer messages about valued knowledge products and processes materials had the potential to send. We observed that our materials commonly encouraged students to mimic the structure of science practices for the purpose of being evaluated by the teacher. That is, students were asked to ''go through the motions'' of explaining, modeling etc. but had little agency regarding the sorts of models and explanations they found productive in their class community. This study serves to illustrate the importance of surfacing the tacit epistemological commitments that guide curriculum development. Additionally, it extends existing scholarship on epistemological messaging by considering curricular materials as a potentially consequential sources of messages.

This study investigates the associations between countermovement rebound jump (CMRJ) performance metrics and various independent measures of athletic performance, including the isometric mid-thigh pull (IMTP), 20 m linear sprint, and 505 change-of-direction (COD) speed tests. Pearson’s correlations were used to analyse the relationship between the CMRJ measures with athletic performance, with significance being set at p ≤ 0.006. Results showed large significant positive relationships between IMTP peak force and force at 300 milliseconds with the first jump height of the CMRJ (JH-1, r = 0.54 to 0.55, p ≤ 0.002). Additionally, inverse relationships were observed between reactive strength index modified (RSImod) and reactive strength index (RSI) with 20 m sprint total and split times (r = −0.55 to −0.66, p ≤ 0.001), and the 10 m and total sprint times were significantly correlated with JH-1 (r = −0.54, p = 0.003), indicating that greater vertical explosive power and reactive strength are associated with faster sprint performance. Finally, a significant inverse relationship was identified between CMRJ metrics (two JH values and RSImod) and 505 COD times in both the left and right sides (r = −0.51 to −0.68, p ≤ 0.006). These findings suggest that CMRJ performance metrics are valuable indicators of lower-limb explosive force production, with a strong link to both linear sprint and COD performance. The finding underscores the importance of including CMRJ assessments in athletic performance evaluations due to their dual assessment capacity of slow and fast stretch–shortening cycle mechanics.

Abstract Manganese(III/IV) oxide is a promising pseudocapacitive material for supercapacitor electrodes due to favorable attributes such as its chemical resilience, high earth abundance and low specific cost. Herein, the morphological, compositional and electrochemical characteristics of co‐precipitated manganese(III/IV) oxide products, each described by the general formula NaxKyMnOz, are investigated to establish how these properties are influenced by synthesis conditions. NaxKyMnOz growths in low‐temperature (

The COVID-19 pandemic disrupted chemistry teaching practices globally as many courses were forced online, necessitating adaptation to the digital platform. The biggest impact was to the practical component of the chemistry curriculum--the so-called wet lab. Naively, it would be thought that computer-based teaching laboratories would have little problem in making the move. However, this is not the case as there are many unrecognized differences between delivering computer-based teaching in-person and virtually: software issues, technology, and classroom management. Consequently, relatively few "hands-on" computational chemistry teaching laboratories are delivered online. In this paper, we describe these issues in more detail and how they can be addressed, drawing on our experience in delivering a third-year computational chemistry course as well as remote hands-on workshops for the Virtual Winter School on Computational Chemistry and the European BIG-MAP project.

Competition between attractive and repulsive interactions between colloidal particles drives the formation of complex assemblies. Here, the authors exploit the dual functionality of magnetic nanoparticle dispersions to simultaneously drive attraction and repulsion between suspended non-magnetic microspheres, allowing for precise tuning of the interaction energy landscape of colloidal particles.

Coincidence experiments at free-electron lasers enable time resolved site-specific investigations of molecular photochemistry at high signal rates, but isolating individual dissociation processes still poses a considerable technical challenge. Here, the authors use electron-ion partial covariance imaging to isolate otherwise elusive chemical shifts in UV-induced photofragmentation pathways of the prototypical chiral molecule 1-iodo-2-methylbutane.

The kinetic analysis of joint work and joint contribution provides practitioners with information regarding movement characteristics and strategies of any jump test that is undertaken. This study aimed to compare joint works and contributions, and performance metrics in the countermovement jump (CMJ), drop jump (DJ), and countermovement rebound jump CMRJ. Thirty-three participants completed 18 jumps across two testing sessions. Jump height and strategy-based metrics (time to take-off [TTTO], countermovement depth [CM depth], and ground contact time [GCT]) were measured. Two-way analysis of variance assessed systematic bias between jump types and test sessions (α = 0.05). Reliability was evaluated via intraclass correlation coefficient [ICC] and coefficient of variation [CV]. Jump height and strategy-based metrics demonstrated good to excellent reliability (ICC = 0.82–0.98) with moderate CV (≤8.64%). Kinetic variables exhibited moderate to excellent reliability (ICC = 0.64–0.93) with poor to moderate CV (≤25.04%). Moreover, apart from TTTO (p ≤ 0.027, effect size [ES] = 0.49–0.62) that revealed significant differences between jump types, CM depth (p ≤ 0.304, ES = 0.27–0.32) and GCT (p ≤ 0.324, ES = 0.24) revealed nonsignificant trivial to small differences between three jumps in both sessions. Finally, the negative and positive hip and knee works, and positive ankle contribution measured in the CMRJ showed significant differences from the CMJ and DJ (p ≤ 0.048, g ≤ 0.71), with no significant difference observed in other kinetic variables between the three jump actions (p ≥ 0.086). Given the consistent joint works and joint contributions between jump types, the findings suggest that practitioners can utilize the CMRJ as a viable alternative to CMJ and DJ tests, and the CMRJ test offers valuable insights into movement characteristics and training suggestions.

Adding to the versatile class of ionic liquids, we report a new series of hydrophilic polyethylene glycol-functionalized room-temperature ionic liquids, offering interesting thermo- and electrochemical behavior as well as remarkable surface properties. A scalable and generally applicable synthetic procedure for the preparation of N,N’-bis(polyethylene glycol)imidazolium salts, generally abbreviated as [(mPEGn)2Im][A] (n = 2‒6, A = I‒, OMs‒, PF6‒, NTf2‒) was developed. These ionic liquids were studied concerning their thermo- and electrochemical properties, such as phase transition behavior, decomposition temperature, viscosity, and density, as well as electrical conductivity and electrochemical stability, using i.a. differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), electrochemical impedance spectroscopy (EIS) and linear sweep voltammetry (LSV). Additionally, the surface properties were investigated by angle-resolved X-ray photoelectron spectroscopy (ARXPS) and the pendant drop method. Molecular dynamics simulations complement the studies and provide insight into the molecular structure of the ionic liquids and their specific orientation at the liquid-vacuum interface.

CyMe4-BTPhen and CyMe4-BTBP are the principal ligand systems used in Europe for the separation of actinides from lanthanides as a part of the SANEX process for nuclear recycling and reprocessing. We present a new approach to the synthesis of the CyMe4 fragment beginning from readily available hydroxypivalic acid. It features a cobalt-catalysed homocoupling of a neopentyl bromide to provide the key bisester precursor, thereby avoiding the requirement for technically challenging low-temperature LDA-mediated aldol chemistries.

Abstract This mini-review assesses supercritical carbon dioxide (scCO2) extraction and high-pressure carbon dioxide pre-treatment technologies for valorisation of corn stover agricultural residues with particular focus on showing how these can aid in the creation of a holistic biorefineries. Corn stover is currently the largest source of agriculture residues in the USA, as such there is significant potential for exploitation to yield valuable chemicals. ScCO2 extraction could lead to the recovery of a variety of different chemicals which include flavonoids, sterols, steroid ketones, hydrocarbons, saturated fatty acids, unsaturated fatty acids, fatty alcohols, phenolics and triterpenoids. Importantly, recent studies have not only demonstrated that supercritical extraction can be utilized for the recovery of plant lipids for use in consumer products, including nutraceuticals and personal care, but the processing of treated biomass can lead to enhanced yields and recovery of other products from biorefinery processes. Despite the great potential and opportunities for using scCO2 and high-pressure systems in a biorefinery context their real-world application faces significant challenges to overcome before it is widely applied. Such challenges have also been discussed in the context of this mini-review.

Grazing management to reduce soil erosion is paramount for preserving and enhancing grassland health under pastoral livestock production systems. However, as the focus of these production systems is to increase productivity, the inclusion of the soil and its complexity in grazing management has been usually neglected. Detailed consideration of the soil spatio-temporal susceptibility to erosion may be best approached with simulation modelling. To understand and explore the spatio-temporal impact of grazing strategies on soil surface erosion, this work used a geospatial model approach in a high-country pastoral livestock production system in New Zealand as a case study. We modelled 45 scenarios characterized by different stock densities and occupation periods applied for each season of the year and for different livestock types: sheep, beef, and deer, producing a total of 540 scenarios. In addition, we included scenarios to represent ungrazed pastures for each season and the current grazing management of the case study station as the baseline for comparisons (resulting in a total of 545 scenarios). Spatio-temporal variation of natural soil superficial erosion from ungrazed pastures appears to be more relevant than the impact of manipulating grazing intensity and indicates that paddocks in our study area have different capacities to support grazing which also changes during seasons. Increases in occupation period seem more detrimental to soil erosion compared to increases in stock density, and cattle are the most detrimental stock type compared to sheep and deer. Our results suggest that grassland health can be enhanced in LUMGS by applying context-adjusted grazing management strategies according to the station spatio-temporal heterogeneity and susceptibility to erosion.

Small-scale science activities provide an opportunity for engagement of diverse, large audiences at settings such as 4-H fairs. We present practical information for implementation of small-scale food science experiences in the Extension education context. Our focus is description of a tool for adaptation of activities for inquiry-based learning and tips for miniaturization of activities to save on costs and resources.

Membrane fusion events allow enveloped viruses to enter and infect cells. The study of these processes has led to the identification of a number of proteins that mediate this process. These proteins are classified according to their structure, which vary according to the viral genealogy. To date, three classes of fusion proteins have been defined, but current evidence points to the existence of additional classes. Despite their structural differences, viral fusion processes follow a common mechanism through which they exert their actions. Additional studies of the viral fusion proteins have demonstrated the key role of specific proteinogenic subsequences within these proteins, termed fusion peptides. Such peptides are able to interact and insert into membranes for which they hold interest from a pharmacological or therapeutic viewpoint. Here, the different characteristics of fusion peptides derived from viral fusion proteins are described. These criteria are useful to identify new fusion peptides. Moreover, this review describes the requirements of synthetic fusion peptides derived from fusion proteins to induce fusion by themselves. Several sequences of the viral glycoproteins E1 and E2 of HCV were, for example, identified to be able to induce fusion, which are reviewed here.

In natural friction melts, or pseudotachylites, clast textures and glass compositions can influence the frictional behavior of faults hosting pseudotachylites, and are, in turn, sensitive to the processes involved in pseudotachylite formation. Quantification of these parameters in situations where the host rock composition and formation conditions are well-constrained, such as analogue experiments, may yield calibrations that can be employed in analysis of natural pseudotachylites. In this paper, we experimentally-generated pseudotachylites in granitoid rocks (tonalite and Westerly granite) at Pconf = 40 MPa and slip rates of ∼0.1 m s−1, comparable to the conditions under which natural pseudotachylite is known to form in Earth’s upper crust. We find variations in both clast textures and glass compositions that reflect formation processes, and probably influence the frictional behavior of similar natural faults hosting pseudotachylite. Quantification of particle size and shape distribution with a semi-automatic image analysis method, combined with analysis of glass and host-rock composition of these experimentally generated pseudotachylites, reveals that the textures of pseudotachylite material evolved by combinations of 1) comminution, 2) heterogeneous frictional flash melting, and 3) homogeneous (diffusive) clast melting and/or marginal decrepitation. Fractal dimensions of pseudotachylite-hosted clasts (D ∼ 3) that are greater than those of marginal fragmented host rock particles (gouge, D ∼ 2.4), reflect an increase of the intensity of comminution by slip localisation during a pre-melting phase. Chemical analyses demonstrate that these pseudotachylite glasses were generated by frictional flash melting, where host rock phases melt individually. Biotite is the least resistant to melting, feldspar intermediate, and quartz is the most resistant. The peudotachylite glass generated in these experiments has an alkaline composition, is depleted in SiO2 compared to the bulk host-rock, and shows heterogeneous compositions in a single sample related to proximity to host-rock minerals. The percentage contributions of host rock phases to the melt, calculated by a mixing model, shows that glass compositions are dominated by plagioclase and biotite. Within the melt, margins of clasts were dissolved uniformly by diffusion and/or affected by marginal decrepitation, resulting in convex and round shapes with convexities averaging ∼0.8 and circularities averaging ∼0.65.

In severe cases of total knee arthroplasty, where off-the-shelf implants are not suitable or available anymore (i.e., in cases with extended bone defects or periprosthetic fractures), custom-made knee implants represent one of the few remaining treatment options. Design verification and validation of such custom-made implants is very challenging. The aim of this study is to support surgeons and engineers in their decision on whether a developed design is suitable for the specific case. A novel method for the pre-clinical testing of custom-made knee implants is suggested, which relies on the biomechanical test and finite element analysis (FEA) of a comparable reference implant. The method comprises six steps: (1) identification of the main potential failure mechanism and its corresponding FEA quantity of interest, (2) reproduction of the biomechanical test of the reference implant via FEA, (3) identification of the maximum value of the corresponding FEA quantity of interest at the required load level, (4) definition of this value as the acceptance criterion for the FEA of the custom-made implant, (5) reproduction of the biomechanical test with the custom-made implant via FEA, (6) conclusion, whether the acceptance criterion is fulfilled or not. Two exemplary cases of custom-made knee implants were evaluated with this method. The FEA acceptance criterion derived from the reference implants was fulfilled in both custom-made implants. Subsequent biomechanical tests verified the FEA results. The suggested method allows a quantitative evaluation of the biomechanical properties of a custom-made knee implant without performing a biomechanical test with it. This represents an important contribution in the pre-clinical testing of custom-made implants in order to achieve a sustainable treatment of complex revision total knee arthroplasty patients in a timely manner.

Objectives: Vitamin B6 deficiency is associated with a wide spectrum of clinical syndromes. While vitamin B6 status is primarily assessed by measuring the biologically active form of the vitamin, pyridoxal 5-phosphate (PLP), concurrent measurement of the final metabolite 4-pyridoxic acid (PA) can provide additional information regarding supplement intake and hypophosphatasia. The aim of this study is to develop a simple method traceable to the NIST standard reference material 3950 for simultaneous detection of PLP and PA. Design & methods: A one-step reverse phase HPLC method with fluorescence detection was developed by evaluating different derivatization conditions, the use of an internal standard and different calibration strategies. The assay analytical performance was evaluated. Results: Pre-column derivatization with semicarbazide showed the best overall performance in terms of signal to noise ratio, retention time and peak shape when compared to pre- or post-column derivatization with chlorite, pre-column or in-mobile phase derivatization using sodium bisulfite. The final method provided an analytical measurement range from 7.8 to 350 ​nmol/L for PLP and 3.3–339 ​nmol/L for PA, total imprecision

The introduction of two distinct dopants in a microporous zeotype framework can lead to the formation of isolated, or complementary catalytically active sites. Careful selection of dopants and framework topology can facilitate enhancements in catalysts efficiency in a range of reaction pathways, leading to the use of sustainable precursors (bioethanol) for plastic production. In this work we describe our unique synthetic design procedure for creating a multi-dopant solid-acid catalyst (MgSiAPO-34), designed to improve and contrast with the performance of SiAPO-34 (mono-dopant analog), for the dehydration of ethanol to ethylene. We employ a range of characterization techniques to explore the influence of magnesium substitution, with specific attention to the acidity of the framework. Through a combined catalysis, kinetic analysis and computational fluid dynamics (CFD) study we explore the reaction pathway of the system, with emphasis on the improvements facilitated by the multi-dopant MgSiAPO-34 species. The experimental data supports the validation of the CFD results across a range of operating conditions; both of which supports our hypothesis that the presence of the multi-dopant solid acid centers enhances the catalytic performance. Furthermore, the development of a robust computational model, capable of exploring chemical catalytic flows within a reactor system, affords further avenues for enhancing reactor engineering and process optimisation, toward improved ethylene yields, under mild conditions.

The demand for flexible large area optoelectronic devices such as organic light-emitting diodes (OLEDs) and organic photovoltaics (OPVs) is growing. Roll-to-roll (R2R) printing enables cost-efficient industrial production of optoelectronic devices. The performance of electronic devices may significantly suffer from local electrical defects. The dark lock-in infrared thermography (DLIT) method is an effective non-destructive testing (NDT) tool to identify such defects as hot spots. In this study, a DLIT inspection system was applied to visualize the defects of R2R printed silver conductors on flexible plastic substrates. A two-stage automated defect recognition (ADR) methodology was proposed to detect and localize two types of typical electrical defects, which are caused by complete or partial breaks on the printed conductive wires, based on localized segmentation and thresholding methods.

Background: Irreversible electroporation (IRE) is an ablation technique based on the application of short, high-voltage pulses between needle electrodes (diameter: ~1.0 × 10−3 m). A Finite Difference-based software simulating IRE treatment generally uses rectangular grids, yielding discretization issues when modeling cylindrical electrodes and potentially affecting the validity of treatment planning simulations. Aim: Develop an Electric-Potential Estimation (EPE) method for accurate prediction of the electric-potential distribution in the vicinity of cylindrical electrodes. Methods: The electric-potential values in the voxels neighboring the cylindrical electrode voxels were corrected based on analytical solutions derived for coaxial/cylindrical electrodes. Simulations at varying grid resolutions were validated using analytical models. Low-resolution heterogeneous simulations at 2.0 × 10−3 m excluding/including EPE were compared with high-resolution results at 0.25 × 10−3 m. Results: EPE significantly reduced maximal errors compared to analytical results for the electric-potential distributions (26.6–71.8%→0.4%) and for the electrical resistance (30%→1–6%) at 3.0 × 10−3 m voxel-size. EPE significantly improved the mean-deviation (43.1–52.8%→13.0–24.3%) and the calculation-time gain (>15,000×) of low-resolution compared to high-resolution heterogeneous simulations. Conclusions: EPE can accurately predict the potential distribution of neighboring cylindrical electrodes, regardless of size, position, and orientation in a rectangular grid. The simulation time of treatment planning can therefore be shortened by using large voxel-sized models without affecting accuracy of the electric-field distribution, enabling real-time clinical IRE treatment planning.

Abstract A one-pot, direct reductive acetylation of aldehydes was achieved under mild conditions using 1-hydrosilatrane as a safe and easily accessible catalyst. Described herein is a facile synthesis that produces acylated primary alcohols that can serve as valuable building blocks for organic synthesis. The method has good functional group tolerance and works for a range of aryl aldehydes, with the notable exception of electron-rich arenes. A library of esters was isolated by flash chromatography in yields as high as 92%.

The purpose of this computational study was to analyze the effects of different mobile-bearing (MB) total knee replacement (TKR) designs on knee joint biomechanics. A validated musculoskeletal model of the lower right extremity implanted with a cruciate-retaining fixed-bearing TKR undergoing a squat motion was adapted for three different MB TKR design variants: (I) a commercially available TKR design allowing for tibial insert rotation about the tibial tray with end stops to limit the range of rotation, (II) the same design without end stops, and (III) a multidirectional design with an additional translational degree-of-freedom (DoF) and end stops. When modeling the MB interface, two modeling strategies of different joint topologies were deployed: (1) a six DoF joint as a baseline and (2) a combined revolute-prismatic joint (two DoF joint) with end stops in both DoF. Altered knee joint kinematics for the three MB design variants were observed. The commercially available TKR design variant I yielded a deviation in internal-external rotation of the tibial insert relative to the tray up to 5° during knee flexion. Compared to the multidirectional design variant III, the other two variants revealed less femoral anterior-posterior translation by as much as 5 mm. Concerning the modeling strategies, the two DoF joint showed less computation time by 68%, 80%, and 82% for design variants I, II, and III, respectively. However, only slight differences in the knee joint kinematics of the two modeling strategies were recorded. In conclusion, knee joint biomechanics during a squat motion differed for each of the simulated MB design variants. Specific implant design elements, such as the presence of end stops, can impact the postoperative range of knee motion with regard to modeling strategy, and the two DoF joint option tested accurately replicated the results for the simulated designs with a considerably lower computation time than the six DoF joint. The proposed musculoskeletal multibody simulation framework is capable of virtually characterizing the knee joint dynamics for different TKR designs.

Well-developed, problem-solving skills are essential for any student enrolled in a science, technology, engineering, and mathematics (STEM) course as well as for graduates in the workforce. One of the most essential skills is the ability to monitor one's own progress and understanding while solving a problem. Successful monitoring during the entire solution allows a solver to identify errors within a solution and make adjustments as necessary. To highlight this aspect of problem solving, the authors developed a framework that introduces students to monitoring (M) alongside the more traditional aspects of problem solving models: analyzing the task (A), creating a plan (C), and executing the plan (E). This ACE-M framework has been successfully implemented in lower division chemistry, mathematics, and physics courses. Students enrolled in courses where ACE-M was used as the foundation for problem solving instruction reported improved problem-solving self efficacy and more monitoring while solving problems. With this explicit instruction on self-monitoring, students are now introduced to expert problem-solving skills that will benefit them in their STEM careers.

Although simulation models are heavily used in biomechanical research and testing of TKA implants, pre-clinical tools for a holistic estimation of implant performance under dynamic loading conditions are rare. The objective of this study was the development of an efficient pre-clinical test method for analyzing knee contact mechanics and kinematics based on a dynamic FE model and to evaluate the effects of the proximo-distal patella position and the patellar tendon stiffness on the patellar kinematics. A finite element-based workflow for knee prostheses designs was developed based on standardized in vivo load data, which included the tibial forces and moments. In a new research approach, the tibial forces are used as input for the model, whereas the tibial moments were used to validate the results. For the standardized sit down, stand up, and knee bend load cycles, the calculated tibial moments show only small deviations from the reference values—especially for high flexion angles. For the knee bend cycle, the maximum absolute value of patellar flexion decreases for higher patellar tendon stiffness and more distally placed patellar components. Therefore, patella-related clinical problems caused by patella baja may also arise if the patellar tendon is too weak for high tibiofemoral flexion angles.

The Polymers and Cross-Linking experiment is presented via a new three phase learning cycle: CORE (Chemical Observations, Representations, Experimentation), which is designed to model productive chemical inquiry and to promote a deeper understanding about the chemistry operating at the submicroscopic level. The experiment is built on two familiar activities often used in public outreach: mixing solutions of poly(vinyl alcohol) and sodium borate, producing the substance known as "slime", and linking paper clips as an analogy to represent polymers. In phase 1 of the CORE experiment, students prepare slime, and explore the properties of the separate solutions and slime. In phase 2, students use analogical reasoning to think about a representation for considering the chemistry at the submicroscopic level. The analogy activity includes using an Analog to Target Worksheet to carefully consider similarities and differences between the analog (paper clip chains) and target (polymers). Phase 3 begins with pairs of students designing experiments in response to this question: How do different proportions of the two reactants, poly(vinyl alcohol) and sodium borate, affect the material properties of the new polymer that is formed? In a recent JCE paper, we report the capacity for students to engage in using analogical reasoning when conducting the Polymer and Cross-Linking experiment. In this paper, we include an analysis of a postlab question, asking students to propose an alternative analogy that could be used in the lab experiment. Detailed analysis of a subset (23 out of 312) of student-generated alternative analogies is provided in Supporting Information. Together with the previously published paper, the data provides insight into student thinking about using analogical reasoning in the Polymers and Cross-Linking CORE experiment.

Understanding the origin of reactive species following ionization in aqueous systems is an important aspect of radiation–matter interactions as the initial reactive species lead to production of radicals and subsequent long-term radiation damage. Tunable ultrafast X-ray free-electron pulses provide a new window to probe events occurring on the sub-picosecond timescale, supplementing other methodologies, such as pulse radiolysis, scavenger studies, and stop flow that capture longer timescale chemical phenomena. We review initial work capturing the fastest chemical processes in liquid water radiolysis using optical pump/X-ray probe spectroscopy in the water window and discuss how ultrafast X-ray pump/X-ray probe spectroscopies can examine ionization-induced processes more generally and with better time resolution. Ultimately, these methods will be applied to understanding radiation effects in complex aqueous solutions present in high-level nuclear waste.

We designed a low-cost wrist-worn prototype for simultaneously measuring environmental, behavioral, and physiological domains of influencing factors in healthcare. Our prototype continuously monitors ambient elements (sound level, toxic gases, ultraviolet radiation, air pressure, temperature, and humidity), personal activity (motion tracking and body positioning using gyroscope, magnetometer, and accelerometer), and vital signs (skin temperature and heart rate). An innovative three-dimensional hardware, based on the multi-physical-layer approach is introduced. Using board-to-board connectors, several physical hardware layers are stacked on top of each other. All of these layers consist of integrated and/or add-on sensors to measure certain domain (environmental, behavioral, or physiological). The prototype includes centralized data processing, transmission, and visualization. Bi-directional communication is based on Bluetooth Low Energy (BLE) and can connect to smartphones as well as smart cars and smart homes for data analytic and adverse-event alerts. This study aims to develop a prototype for simultaneous monitoring of the all three areas for monitoring of workplaces and chronic obstructive pulmonary disease (COPD) patients with a concentration on technical development and validation rather than clinical investigation. We have implemented 6 prototypes which have been tested by 5 volunteers. We have asked the subjects to test the prototype in a daily routine in both indoor (workplaces and laboratories) and outdoor. We have not imposed any specific conditions for the tests. All presented data in this work are from the same prototype. Eleven sensors measure fifteen parameters from three domains. The prototype delivers the resolutions of 0.1 part per million (PPM) for air quality parameters, 1 dB, 1 index, and 1 °C for sound pressure level, UV, and skin temperature, respectively. The battery operates for 12.5 h under the maximum sampling rates of sensors without recharging. The final expense does not exceed 133€. We validated all layers and tested the entire device with a 75 min recording. The results show the appropriate functionalities of the prototype for further development and investigations.

An autonomous underwater vehicle (AUV) under payload control (PC) was used to map the movements of juvenile Chinook salmon (Oncorhynchus tshawytscha) tagged with acoustic transmitters. After detecting a tag, the AUV deviated from its pre-programmed route and performed a maneuver designed to enhance the location estimate of the fish and to move closer to collect proximal environmental data. Nineteen fish were released into marine waters of southeastern Alaska. Seven missions with concurrent AUV and vessel-based surveys were conducted with two to nine fish present in the area per mission. The AUV was able to repeatedly detect and estimate the location of the fish, even when multiple individuals were present. Although less effective at detecting the fish, location estimates from the vessel-based surveys helped verify the veracity of the AUV data. All of the fish left the area within 48 h of release. Most fish exhibited localized movements (milling behavior) before leaving the area. Dispersal rates calculated for the fish suggest that error associated with the location estimates was minimal. The average movement rate was 0.62 body length per second and was comparable to marine movement rates reported for other Chinook salmon stocks. These results suggest that AUV-based payload control can provide an effective method for mapping the movements of marine fish.

Olive trees (Olea europaea) and their processed products, such as olive oil, play a major role in the Mediterranean way of life. Their positive impact on human health is being intensely investigated. One research topic is the identification of new application areas of olive mill wastewater (OMWW). OMWW is characterized by the high content of polyphenols possessing many positive health effects. Thus, the phenol-enriched OMWW extract offers the potential for the treatment of skin disorders and for cosmetic application. The aim of the present study was to evaluate cell viability and proliferation, the anti-inflammatory and anti-oxidative properties of a phenol-enriched OMWW extract on an immortal keratinocyte cell line (HaCaT cells). Moreover, the influence on the growth of various microorganisms was investigated; furthermore, the effects on normal human epidermal keratinocytes (NHEK) and human melanoma cells (A375) were studied in a commercially available tumor invasion skin model. The phenol-enriched OMWW extract showed excellent antimicrobial activity. Moreover, a noticeable reduction in reactive oxygen species formation as well as Interleukin-8 release in HaCaT cells were observed. Finally, the inhibited growth of A375 melanoma nodules in the melanoma skin model could be shown. Our results indicate that the OMWW extract is a promising ingredient for dermal applications to improve skin health and skin protection as well as having a positive impact on skin ageing.

Our group is interested in applying supramolecular host systems as catalysts for challenging transformations. Although a variety of supramolecular containers has been described in literature, their use as reaction chambers is still underexplored. We herein describe our first steps in this exciting interdisciplinary field of research.

Fascination with fireworks and pyrotechnics can be used for educational purposes. Several aspects of pyrochemistry such as redox reactions, flame colors, or the theory of combustion can be incorporated in the curriculum to illustrate some basic chemical principles, guaranteeing a lesson that will be engaging and memorable. Beyond classic pyrochemistry, this paper also deals with the environmental pollution caused by fireworks and recent developments toward greener pyrotechnics. Safety and health aspects of pyrotechnics are discussed. (Contains 3 figures, 3 tables, and 2 notes.)

The mechanical and electrical characteristics of films, buckypapers and fiber materials from combinations of clay, carbon nanotubes (CNTs) and chitosan are described. The rheological time-dependent characteristics of clay are maintained in clay–carbon nanotube–chitosan composite dispersions. It is demonstrated that the addition of chitosan improves their mechanical characteristics, but decreases electrical conductivity by three-orders of magnitude compared to clay–CNT materials. We show that the electrical response upon exposure to humid atmosphere is influenced by clay-chitosan interactions, i.e., the resistance of clay–CNT materials decreases, whereas that of clay–CNT–chitosan increases.

An experiment is conducted to ascertain trace-level Pb in samples of bovine liver or muscle by applying graphite furnace atomic absorption spectrophotometry (GFAAS). The primary objective is to display the effects of physical and spectral intrusions in determining trace elements, and project the usual methods employed to minimize accuracy errors caused by such intrusions.

Prenyl ethyl ether (PEE) was previously described as the cause for a solvent-like off-note in ground hazelnuts, but its origin remained unclear. Investigations were carried out by analytical groups of Coop and Givaudan over four years to elucidate this phenomenon. From mouldy citrus fruits a strain of Penicillium digitatum was isolated and found to form PEE. Formation on citrus and other fruits was prominent and contributed to the particular smell of decayed fruits. Several strains of P. digitatum formed PEE, while other fungal species did not. In contrast to citrus fruit, prenyl methyl ether (PME) was formed as dominant prenyl ether on hazelnuts while only small amounts of PEE were found. PME has not been previously described as volatile metabolite of fungi or as a food-taint. Spiking experiments with deuterated ethanol showed that the ethyl group is likely incorporated into PEE via the aldehyde form. On hazelnuts strongly decayed by P. digitatum yet another prenyl ether was tentatively identified: Prenyl isopropyl ether. Prenyl ethers present a novel group of volatile metabolites of P. digitatum. They are likely typical for this species and have not been described before. Prenyl ethers seem to play a significant role in the smell of food decayed by P. digitatum and should be considered in cases of off-notes and taints.

A Monte Carlo method is used to generate interactive pointillist displays of electron density in hydrogenic orbitals. The Web applet incorporating Jmol viewer allows for clear and accurate presentation of three-dimensional shapes and sizes of orbitals up to "n" = 5, where "n" is the principle quantum number. The obtained radial probability distributions can be compared with theoretical curves on two-dimensional plots. The applet also produces orbital cross sections and contour plots and their three-dimensional isometric projections, illustrating the standing-wave nature of the orbitals. The classical boundary surfaces with various predetermine cutoffs may also be displayed for size comparisons. Nodal surfaces are available for all displays. (Contains 1 figure.)

A simple and direct method for measuring the absorption of carbon dioxide by two different substances is described. Lithium hydroxide has been used for decades to remove the gas from enclosed living spaces, such as spacecraft and submarines. The ratio of the mass of carbon dioxide absorbed to the mass of lithium hydroxide used obtained from this static method compares favorably with results in the literature that use a more complex constant-flow method. The method also works well for ethanolamine, another commonly used carbon dioxide absorber. The experiment for the general chemistry laboratory serves both quantitative and qualitative learning goals. Students compare stoichiometric calculations that assume a complete reaction with their experimental results to motivate use of the latter in predicting the amount of lithium hydroxide required for space missions. They use the ideal gas law to determine the mass of carbon dioxide absorbed. Their data allow a comparison of the performance characteristics of the two absorbers on the basis of their absorption capacity and the reversibility of their reactions with carbon dioxide. Students can also enhance their knowledge of descriptive chemistry by connecting qualitative observations during the reactions with species in the chemical equations. (Contains 1 table and 1 figure.)

Gamma hydroxybutyric acid (GHB) is a regulated therapeutic drug, which naturally occurs in mammalian brain tissues as an intermediate of the GABA (gamma aminobutyric acid) neurotransmitter metabolism. The increasing misuse of GHB as a narcotic or abusing drug in recent years calls for the development of a simple and rapid screening method as an alternative to the currently available, technically demanding diagnostic methods. We have developed a rapid enzymatic assay based on the GHB dehydrogenase of Ralstonia eutropha. The enzyme is expressed as a recombinant protein in Escherichia coli and characterized in terms of reaction mechanism and kinetic parameters for the catalysis of conversion of GHB into succinic semialdehyde (SSA). The concomitant NADH production enables spectrophotometric monitoring of the reaction and the quantification of GHB in physiological fluids depending on initial velocities. We have tested a panel of twelve serum and urine samples containing GHB concentrations from 0.0 to 2.1 mmol/L. GHB dehydrogenase activity obeys a non classical bi bi ping pong mechanism exhibiting substrate inhibition by NAD+. With an optimal NAD+ concentration of 3.7 mmol/L in the reaction, the enzyme yields a KM of 1.0 mmol/L for GHB and a Vmax of 3.37 mmol/min/mg. The assay shows a linear standard curve from 0.1 to at least 1 mmol/L of GHB. Spiking experiments result in mean recoveries of 92% for urine and 114% for serum, respectively. The comparison to an ion chromatographic reference method exhibits a mean difference of 10% divergence from the target values in urine and 9% in serum, respectively.

A sequence of exercises for the isolation and characterization of invertase (E.C. 3.1.2.26) from baker's yeast obtained from a local grocery store is outlined. Because the enzyme is colorless, the use of colored markers and the sequence of purification steps are designed to "visualize" the process by which a colorless protein is selectively detected and isolated from a mixture of many different proteins. Students then compare their product from each stage of the purification against a commercial standard of purified invertase using both qualitative (SDS-PAGE) and quantitative (specific activity) techniques. The equipment and materials required for this 4-week exercise are either already available in most undergraduate departments or are not cost prohibitive. Our experience suggests that this project is well suited to undergraduate institutions limited to a one-semester course in biochemistry that caters to a large and diverse student enrollment. (Contains 2 tables and 2 figures.)

Points out the health and legal implications related to laboratory substances that could cause allergic reactions. Presents a list of potential cosmetic allergens and irritants. Includes precautionary measures dealing with allergy situations. (ML)

Presented three algorithms to university students in an introductory laboratory chemistry course and found that differences in the effects of representation modes--flow charts, lists, and standard prose--were complex and changed over 10 lab sessions. There was no evidence that representation mode affected critical thinking ability or final grade. (Author/JEG)

Explained is a representation of the three categories of spectra. Discusses what a lesson on spectra should include, background information, and equipment needed. Provided is a diagram of an absorption box. (RT)