Proton transfer and esterification reactions in EMIMOAc-based acidic ionic liquids

Acetate-based ionic liquids (such as 1-ethyl-3-methylimidazolium acetate, EMIMOAc) have potential applications for CO2 absorption and electrochemical reduction, chemical separations and extractions, and Fischer esterification of alcohols, amines, and starch. Both strong and weak organic acids can be dissolved in EMIMOAc and yield interesting proton-rich acidic ionic liquid solutions. We have used GCMS vapor pressure measurements, spectroscopic methods, calorimetry, and viscosity/conductivity measurements to investigate the properties and reactions of various acids dissolved in EMIMOAc. Unique proton transfer and esterification reactions are observed in many of these acidic solutions with carboxylic acids or sulfonic acids as solutes. Some acids react with the acetate anion to produce acetic acid, which provides a measure of acid strength in ionic liquid solvents. In addition, we observed an esterification reaction that might involve the imidazolium cation and the acetate anion to yield methyl acetate

Labeling the human skeleton with 41Ca to assess changes in bone calcium metabolism

Bone research is limited by the methods available for detecting changes in bone metabolism. While dual X-ray absorptiometry is rather insensitive, biochemical markers are subject to significant intra-individual variation. In the study presented here, we evaluated the isotopic labeling of bone using 41Ca, a long-lived radiotracer, as an alternative approach. After successful labeling of the skeleton, changes in the systematics of urinary 41Ca excretion are expected to directly reflect changes in bone Ca metabolism. A minute amount of 41Ca (100nCi) was administered orally to 22 postmenopausal women. Kinetics of tracer excretion were assessed by monitoring changes in urinary 41Ca/40Ca isotope ratios up to 700days post-dosing using accelerator mass spectrometry and resonance ionization mass spectrometry. Isotopic labeling of the skeleton was evaluated by two different approaches: (i) urinary 41Ca data were fitted to an established function consisting of an exponential term and a power law term for each individual; (ii) 41Ca data were analyzed by population pharmacokinetic (NONMEM) analysis to identify a compartmental model that describes urinary 41Ca tracer kinetics. A linear three-compartment model with a central compartment and two sequential peripheral compartments was found to best fit the 41Ca data. Fits based on the use of the combined exponential/power law function describing urinary tracer excretion showed substantially higher deviations between predicted and measured values than fits based on the compartmental modeling approach. By establishing the urinary 41Ca excretion pattern using data points up to day 500 and extrapolating these curves up to day 700, it was found that the calculated 41Ca/40Ca isotope ratios in urine were significantly lower than the observed 41Ca/40Ca isotope ratios for both techniques. Compartmental analysis can overcome this limitation. By identifying relative changes in transfer rates between compartments in response to an intervention, inaccuracies in the underlying model cancel out. Changes in tracer distribution between compartments were modeled based on identified kinetic parameters. While changes in bone formation and resorption can, in principle, be assessed by monitoring urinary 41Ca excretion over the first few weeks post-dosing, assessment of an intervention effect is more reliable ∼150days post-dosing when excreted tracer originates mainly from bon

Standard atomic weights of the elements 2021 (IUPAC Technical Report)

Following the reviews of atomic-weight determinations and other cognate data in 2015, 2017, 2019 and 2021, the IUPAC (International Union of Pure and Applied Chemistry) Commission on Isotopic Abundances and Atomic Weights (CIAAW) reports changes of standard atomic weights. The symbol A r°(E) was selected for standard atomic weight of an element to distinguish it from the atomic weight of an element E in a specific substance P, designated A r(E, P). The CIAAW has changed the values of the standard atomic weights of five elements based on recent determinations of terrestrial isotopic abundances: Ar (argon): from 39.948 ± 0.001 to [39.792, 39.963] Hf (hafnium): from 178.49 ± 0.02 to 178.486 ± 0.006 Ir (iridium): from 192.217 ± 0.003 to 192.217 ± 0.002 Pb (lead): from 207.2 ± 0.1 to [206.14, 207.94] Yb (ytterbium): from 173.054 ± 0.005 to 173.045 ± 0.010 The standard atomic weight of argon and lead have changed to an interval to reflect that the natural variation in isotopic composition exceeds the measurement uncertainty of A r(Ar) and A r(Pb) in a specific substance. The standard atomic weights and/or the uncertainties of fourteen elements have been changed based on the Atomic Mass Evaluations 2016 and 2020 accomplished under the auspices of the International Union of Pure and Applied Physics (IUPAP). A r° of Ho, Tb, Tm and Y were changed in 2017 and again updated in 2021: Al (aluminium), 2017: from 26.981 5385 ± 0.000 0007 to 26.981 5384 ± 0.000 0003 Au (gold), 2017: from 196.966 569 ± 0.000 005 to 196.966 570 ± 0.000 004 Co (cobalt), 2017: from 58.933 194 ± 0.000 004 to 58.933 194 ± 0.000 003 F (fluorine), 2021: from 18.998 403 163 ± 0.000 000 006 to 18.998 403 162 ± 0.000 000 005 (Ho (holmium), 2017: from 164.930 33 ± 0.000 02 to 164.930 328 ± 0.000 007) Ho (holmium), 2021: from 164.930 328 ± 0.000 007 to 164.930 329 ± 0.000 005 Mn (manganese), 2017: from 54.938 044 ± 0.000 003 to 54.938 043 ± 0.000 002 Nb (niobium), 2017: from 92.906 37 ± 0.000 02 to 92.906 37 ± 0.000 01 Pa (protactinium), 2017: from 231.035 88 ± 0.000 02 to 231.035 88 ± 0.000 01 Pr (praseodymium), 2017: from 140.907 66 ± 0.000 02 to 140.907 66 ± 0.000 01 Rh (rhodium), 2017: from 102.905 50 ± 0.000 02 to 102.905 49 ± 0.000 02 Sc (scandium), 2021: from 44.955 908 ± 0.000 005 to 44.955 907 ± 0.000 004 (Tb (terbium), 2017: from 158.925 35 ± 0.000 02 to 158.925 354 ± 0.000 008) Tb (terbium), 2021: from 158.925 354 ± 0.000 008 to 158.925 354 ± 0.000 007 (Tm (thulium), 2017: from 168.934 22 ± 0.000 02 to 168.934 218 ± 0.000 006) Tm (thulium), 2021: from 168.934 218 ± 0.000 006 to 168.934 219 ± 0.000 005 (Y (yttrium), 2017: from 88.905 84 ± 0.000 02 to 88.905 84 ± 0.000 01) Y (yttrium), 2021: from 88.905 84 ± 0.000 01 to 88.905 838 ± 0.00

Geometric conductive filament confinement by nanotips for resistive switching of HfO2-RRAM devices with high performance

Filament-type HfO2-based RRAM has been considered as one of the most promising candidates for future non-volatile memories. Further improvement of the stability, particularly at the "OFF" state, of such devices is mainly hindered by resistance variation induced by the uncontrolled oxygen vacancies distribution and filament growth in HfO2 films. We report highly stable endurance of TiN/Ti/HfO2/Si-tip RRAM devices using a CMOS compatible nanotip method. Simulations indicate that the nanotip bottom electrode provides a local confinement for the electrical field and ionic current density; thus a nano-confinement for the oxygen vacancy distribution and nano-filament location is created by this approach. Conductive atomic force microscopy measurements confirm that the filaments form only on the nanotip region. Resistance switching by using pulses shows highly stable endurance for both ON and OFF modes, thanks to the geometric confinement of the conductive path and filament only above the nanotip. This nano-engineering approach opens a new pathway to realize forming-free RRAM devices with improved stability and reliability

Chemical data evaluation: General considerations and approaches for IUPAC projects and the chemistry community (IUPAC Technical Report)

The International Union of Pure and Applied Chemistry has a long tradition of supporting the compilation of chemical data and their evaluation through direct projects, nomenclature and terminology work, and partnerships with international scientific bodies, government agencies, and other organizations. The IUPAC Interdivisional Subcommittee on Critical Evaluation of Data has been established to provide guidance on issues related to the evaluation of chemical data. In this first report, we define the general principles of the evaluation of scientific data and describe best practices and approaches to data evaluation in chemistryinfo:eu-repo/semantics/publishedVersio

Conductivity, Viscosity, Spectroscopic Properties of Organic Sulfonic Acid solutions in Ionic Liquids

Sulfonic acids in ionic liquids (ILs) are used as catalysts, electrolytes, and solutions for metal extraction. The sulfonic acid ionization states and the solution acid/base properties are critical for these applications. Methane sulfonic acid (MSA) and camphor sulfonic acid (CSA) are dissolved in several IL solutions with and without bis(trifluoromethanesulfonyl)imine (HTFSI). The solutions demonstrated higher conductivities and lower viscosities. Through calorimetry and temperature-dependent conductivity analysis, we found that adding MSA to the IL solution may change both the ion migration activation energy and the number of “free” charge carriers. However, no significant acid ionization or proton transfer was observed in the IL solutions. Raman and IR spectroscopy with computational simulations suggest that the HTFSI forms dimers in the solutions with an N-H-N “bridged” structure, while MSA does not perturb this hydrogen ion solvation structure in the IL solutions. CSA has a lower solubility in the ILs and reduced the IL solution conductivity. However, in IL solutions containing 0.4 M or higher concentration of HTFSI, CSA addition increased the conductivity at low CSA concentrations and reduced it at high concentrations, which may indicate a synergistic effect

Formation of Nano-Bio-Complex as Nanomaterials Dispersed in a Biological Solution for Understanding Nanobiological Interactions

Information on how cells interface with nanomaterials in biological environments has important implications for the practice of nanomedicine and safety consideration of nanomaterials. However, our current understanding of nanobiological interactions is still very limited. Here, we report the direct observation of nanomaterial bio-complex formation (other than protein corona) from nanomaterials dispersed in biologically relevant solutions. We observed highly selective binding of the components of cell culture medium and phosphate buffered saline to ZnO and CuO nanoparticles, independent of protein molecules. Our discoveries may provide new insights into the understanding of how cells interact with nanomaterials

Reading Speed, Comprehension and Eye Movements While Reading Japanese Novels: Evidence from Untrained Readers and Cases of Speed-Reading Trainees

BACKGROUND: A growing body of evidence suggests that meditative training enhances perception and cognition. In Japan, the Park-Sasaki method of speed-reading involves organized visual training while forming both a relaxed and concentrated state of mind, as in meditation. The present study examined relationships between reading speed, sentence comprehension, and eye movements while reading short Japanese novels. In addition to normal untrained readers, three middle-level trainees and one high-level expert on this method were included for the two case studies. METHODOLOGY/PRINCIPAL FINDINGS: In Study 1, three of 17 participants were middle-level trainees on the speed-reading method. Immediately after reading each story once on a computer monitor, participants answered true or false questions regarding the content of the novel. Eye movements while reading were recorded using an eye-tracking system. Results revealed higher reading speed and lower comprehension scores in the trainees than in the untrained participants. Furthermore, eye-tracking data by untrained participants revealed multiple correlations between reading speed, accuracy and eye-movement measures, with faster readers showing shorter fixation durations and larger saccades in X than slower readers. In Study 2, participants included a high-level expert and 14 untrained students. The expert showed higher reading speed and statistically comparable, although numerically lower, comprehension scores compared with the untrained participants. During test sessions this expert moved her eyes along a nearly straight horizontal line as a first pass, without moving her eyes over the whole sentence display as did the untrained students. CONCLUSIONS/SIGNIFICANCE: In addition to revealing correlations between speed, comprehension and eye movements in reading Japanese contemporary novels by untrained readers, we describe cases of speed-reading trainees regarding relationships between these variables. The trainees overall tended to show poor performance influenced by the speed-accuracy trade-off, although this trade-off may be reduced in the case of at least one high-level expert

The importance of context: an exploration of factors influencing the adoption of student-centered teaching among chemistry, biology, and physics faculty

Background: Research at the secondary and postsecondary levels has clearly demonstrated the critical role that individual and contextual characteristics play in instructors’ decision to adopt educational innovations. Although recent research has shed light on factors influencing the teaching practices of science, technology, engineering, and mathematics (STEM) faculty, it is still not well understood how unique departmental environments impact faculty adoption of evidence-based instructional practices (EBIPs) within the context of a single institution. In this study, we sought to characterize the communication channels utilized by STEM faculty, as well as the contextual and individual factors that influence the teaching practices of STEM faculty at the departmental level. Accordingly, we collected survey and observational data from the chemistry, biology, and physics faculty at a single large research-intensive university in the USA. We then compared the influencing factors experienced by faculty in these different departments to their instructional practices. Results: Analyses of the survey data reveal disciplinary differences in the factors influencing adoption of EBIPs. In particular, the physics faculty (n = 15) had primarily student-centered views about teaching and experienced the most positive contextual factors toward adoption of EBIPs. At the other end of the spectrum, the chemistry faculty (n = 20) had primarily teacher-centered views and experienced contextual factors that hindered the adoption of student-centered practices. Biology faculty (n = 25) fell between these two groups. Classroom observational data reflected these differences: The physics classrooms were significantly more student-centered than the chemistry classrooms. Conclusions: This study demonstrates that disciplinary differences exist in the contextual factors teaching conceptions that STEM faculty experience and hold, even among faculty within the same institution. Moreover, it shows that these differences are associated to the level of adoption of student-centered teaching practices. This work has thus identified the critical need to carefully characterize STEM faculty’s departmental environment and conceptions about teaching before engaging in instructional reform efforts, and to adapt reform activities to account for these factors. The results of this study also caution the over generalization of findings from a study focused on one type of STEM faculty in one environment to all STEM faculty in any environment

Forgetting having denied: The "amnesic" consequences of denial

The concept of denial has its roots in psychoanalysis. Denial has been assumed to be effective in blocking unwanted memories. In two experiments, we report that denial has unique consequences for remembering. In two experiments, participants viewed a video of a theft and half of the participants had to deny seeing certain details in the video whereas the other half had to tell the truth. One day later, all participants were given a source monitoring recognition or recall task. In these tasks, they were instructed to indicate (1) whether they could remember talking about certain details and (2) whether they could recollect seeing those details in the video. In both experiments, we found that denial made participants forget that they talked about these details while leaving memory for the video unaffected. This denial-induced forgetting was evident for both the source monitoring recognition and recall tests. Furthermore, when we asked participants after the experiment whether they could still not remember talking about these details, participants who had to deny were most likely to report that they forgot this. In contrast to a widely held belief, we show that denial does not impair memory for the experienced stimuli, but that it has a unique ability to undermine memory for what was talked about