Authentication of Fennel, Star Anise, and Anise Essential Oils by Gas Chromatography (GC/MS) and Stable Isotope Ratio (GC/IRMS) Analyses.

The aromatic compound (E)-anethol is widely used in the flavor, fragrance, and medicinal industries. This compound is commonly produced through steam distillation of fennel, star anise, and anise seed. Given the cost of production, these natural and authentic essential oils are commonly adulterated with lower-cost natural materials or synthetic alternatives. The current study investigates essential oil profiles (gas chromatography/mass spectrometry) and stable isotope ratios (gas chromatography/isotope ratio mass spectrometry) of the abundant compound (E)-anethol in both authentic reference standards (n = 15) and commercially available samples (n = 30). This multifaceted analytical approach establishes techniques for ensuring the authenticity of essential oil sources of (E)-anethol and was then used to evaluate the current essential oil market sources of (E)-anethol. These findings report that adulteration of (E)-anethol-containing natural products takes various forms, and a multifaceted analytical approach is recommended for authentication. Of the commercial samples analyzed for this report, 27% were adulterated.

Analysis of Cation Composition in Dolomites on the Intact Particles Sampled from Asteroid Ryugu.

Characterization of the elemental distribution of samples with rough surfaces has been strongly desired for the analysis of various natural and artificial materials. Particularly for pristine and rare analytes with micrometer sizes embedded on specimen surfaces, non-invasive and matrix effect-free analysis is required without surface polishing treatment. To satisfy these requirements, we proposed a new method employing the sequential combination of two imaging modalities, i.e., microenergy-dispersive X-ray fluorescence (micro-XRF) and Raman micro-spectroscopy. The applicability of the developed method is tested by the quantitative analysis of cation composition in micrometer-sized carbonate grains on the surfaces of intact particles sampled directly from the asteroid Ryugu. The first step of micro-XRF imaging enabled a quick search for the sparsely scattered and micrometer-sized carbonates by the codistributions of Ca2+ and Mn2+ on the Mg2+- and Fe2+-rich phyllosilicate matrix. The following step of Raman micro-spectroscopy probed the carbonate grains and analyzed their cation composition (Ca2+, Mg2+, and Fe2+ + Mn2+) in a matrix effect-free manner via the systematic Raman shifts of the lattice modes. The carbonates were basically assigned to ferroan dolomite bearing a considerable amount of Fe2+ + Mn2+ at around 10 atom %. These results are in good accordance with the assignments reported by scanning electron microscopy-energy-dispersive X-ray spectroscopy, where the thin-sectioned and surface-polished Ryugu particles were applicable. The proposed method requires neither sectioning nor surface polishing; hence, it can be applied to the remote sensing apparatus on spacecrafts and planetary rovers. Furthermore, the non-invasive and matrix effect-free characterization will provide a reliable analytical tool for quantitative analysis of the elemental distribution on the samples with surface roughness and chemical heterogeneity at a micrometer scale, such as art paintings, traditional crafts with decorated shapes, as well as sands and rocks with complex morphologies in nature.

Water circulation in Ryugu asteroid affected the distribution of nucleosynthetic isotope anomalies in returned sample.

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred [Formula: see text] after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water.

Non-contingent affective outcomes influence judgments of control.

Our main goal in these experiments was to examine whether affective valence plays a role in judgments of control (JoC) in intentional action. To test this, we asked participants to completevariationsofasimple aiming task in which words appeared in place of clicked targets. The affective content of the words was manipulated during the experiments but was not contingent on participants' performance. Throughout the task, participants were periodically asked to judge their JoC.Thus, JoC judgments in this task included contributions of a well-established cue to judgments of control, task performance, and a source of affect that was not related to task performance. We found thatmetacognitions of controlvaried consistentlyacross levels of affect, with stronger judgments of being in control for conditions with positive outcome words (e.g., 'puppy') and the weaker judgments of being in control for conditions with negative outcome words (e.g.,'killer').These results suggestaffective outcomes can influence JoC, even though the outcomes are not related to performance.

Abundant presolar grains and primordial organics preserved in carbon-rich exogenous clasts in asteroid Ryugu.

Preliminary analyses of asteroid Ryugu samples show kinship to aqueously altered CI (Ivuna-type) chondrites, suggesting similar origins. We report identification of C-rich, particularly primitive clasts in Ryugu samples that contain preserved presolar silicate grains and exceptional abundances of presolar SiC and isotopically anomalous organic matter. The high presolar silicate abundance (104 ppm) indicates that the clast escaped extensive alteration. The 5 to 10 times higher abundances of presolar SiC (~235 ppm), N-rich organic matter, organics with N isotopic anomalies (1.2%), and organics with C isotopic anomalies (0.2%) in the primitive clasts compared to bulk Ryugu suggest that the clasts formed in a unique part of the protoplanetary disk enriched in presolar materials. These clasts likely represent previously unsampled outer solar system material that accreted onto Ryugu after aqueous alteration ceased, consistent with Ryugu's rubble pile origin.

Nasal continuous positive pressure versus simple face mask oxygenation for adult obese and obstructive sleep apnea patients undergoing colonoscopy under propofol-based general anesthesia without tracheal intubation: A randomized controlled trial.

STUDY OBJECTIVE: To determine if a nasal positive airway pressure (nasal CPAP) mask would decrease the number of hypoxemic events in obese and obstructive sleep apnea patients undergoing colonoscopy. DESIGN: Single-center prospective randomized controlled trial. SETTING: Tertiary academic center. PATIENTS: We enrolled 109 patients with diagnosis of obesity and/or obstructive sleep apnea scheduled to undergo colonoscopy under propofol general anesthesia without planned tracheal intubation. INTERVENTION: Patients were randomly allocated (1:1 ratio) to receive supplementary oxygen at a flow of 10 L/min, either through a nasal CPAP or a simple facemask. MEASUREMENTS: The primary endpoint was the difference in the mean percentage of time spent with oxygen saturation below 90% between the two groups. Secondary outcomes included the need for airway maneuvers/interventions, average SpO2 during the case, duration and severity of oxygen desaturation, incidence and duration of procedural interruptions, and satisfaction and tolerance scores. MAIN RESULTS: 54 were allocated to the simple face mask and 55 to the nasal CPAP mask arms, respectively. A total of 6 patients experienced a hypoxemic event. Among these patients, the difference in the percentage of time spent with oxygen saturation below 90% was not clinically relevant (p = 1.0). However, patients in the nasal CPAP group required less chin lift (20% vs. 42.6%; p = 0.01) and oral cannula insertion (12.7% vs.29.6%; p = 0.03). The percentage of patients with at least one airway maneuver was higher in the simple face mask arm (68.5% vs. 41.8%; p = 0.005). Patient tolerance to device score was lower in the nasal CPAP group (8.85 vs. 9.56; p = 0.003). CONCLUSIONS: A nasal CPAP did not prevent hypoxemia and should not be used routinely for colonoscopy in obese or OSA patients if a simple face mask is an alternative therapy. However, potential advantages of its use include fewer airway maneuvers or interventions, which may be desirable in certain clinical settings. TRIAL REGISTRATION: Clinicaltrials.gov, identifier: NCT05175573.

Essential Oil Composition and Enantioselective Profile of Agastache urticifolia (Lamiaceae) and Monardella odoratissima (Lamiaceae) from Utah.

Two species within the Lamiaceae (mint) family, Agastache urticifolia and Monardella odoratissima, are aromatic plants that are native to the Intermountain Region (USA). Essential oil produced through steam distillation was examined to establish the essential oil yield and both the achiral and chiral aromatic profiles of both plant species. The resulting essential oils were analyzed by GC/MS, GC/FID, and MRR (molecular rotational resonance). For A. urticifolia and M. odoratissima, achiral essential oil profiles were largely composed of limonene (71.0%, 27.7%), trans-ß-ocimene (3.6%, 6.9%), and pulegone (15.9%, 4.3%), respectively. Between the two species, eight chiral pairs were analyzed and, interestingly, the dominant enantiomer (calculated as ee%) of limonene and pulegone switched between the two species. Where enantiopure standards were not commercially available, MRR was used as a reliable analytical technique for chiral analysis. This study verifies the achiral profile for A. urticifolia and, for the first time to the authors' knowledge, establishes the achiral profile for M. odoratissima and chiral profile for both species. Additionally, this study confirms the utility and practicality of using MRR for determining chiral profiles in essential oils.

Meteorites have inherited nucleosynthetic anomalies of potassium-40 produced in supernovae.

Meteorites record processes that occurred before and during the formation of the Solar System in the form of nucleosynthetic anomalies: isotopic compositions that differ from the Solar System patterns. Nucleosynthetic anomalies are rarely seen in volatile elements such as potassium at bulk meteorite scale. We measured potassium isotope ratios in 32 meteorites and identified nucleosynthetic anomalies in the isotope potassium-40. The anomalies are larger and more variable in carbonaceous chondrite (CC) meteorites than in noncarbonaceous (NC) meteorites, indicating that CCs inherited more material produced in supernova nucleosynthesis. The potassium-40 anomaly of Earth is close to that of the NCs, implying that Earth's potassium was mostly delivered by NCs.

Samples returned from the asteroid Ryugu are similar to Ivuna-type carbonaceous meteorites.

Carbonaceous meteorites are thought to be fragments of C-type (carbonaceous) asteroids. Samples of the C-type asteroid (162173) Ryugu were retrieved by the Hayabusa2 spacecraft. We measured the mineralogy and bulk chemical and isotopic compositions of Ryugu samples. The samples are mainly composed of materials similar to those of carbonaceous chondrite meteorites, particularly the CI (Ivuna-type) group. The samples consist predominantly of minerals formed in aqueous fluid on a parent planetesimal. The primary minerals were altered by fluids at a temperature of 37° ± 10°C, about [Formula: see text] million (statistical) or [Formula: see text] million (systematic) years after the formation of the first solids in the Solar System. After aqueous alteration, the Ryugu samples were likely never heated above ~100°C. The samples have a chemical composition that more closely resembles that of the Sun's photosphere than other natural samples do.

Oxygen isotopes of anhydrous primary minerals show kinship between asteroid Ryugu and comet 81P/Wild2.

The extraterrestrial materials returned from asteroid (162173) Ryugu consist predominantly of low-temperature aqueously formed secondary minerals and are chemically and mineralogically similar to CI (Ivuna-type) carbonaceous chondrites. Here, we show that high-temperature anhydrous primary minerals in Ryugu and CI chondrites exhibit a bimodal distribution of oxygen isotopic compositions: 16O-rich (associated with refractory inclusions) and 16O-poor (associated with chondrules). Both the 16O-rich and 16O-poor minerals probably formed in the inner solar protoplanetary disk and were subsequently transported outward. The abundance ratios of the 16O-rich to 16O-poor minerals in Ryugu and CI chondrites are higher than in other carbonaceous chondrite groups but are similar to that of comet 81P/Wild2, suggesting that Ryugu and CI chondrites accreted in the outer Solar System closer to the accretion region of comets.

Ryugu's nucleosynthetic heritage from the outskirts of the Solar System.

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune.

Essential Oil Composition and Stable Isotope Profile of Osmorhiza occidentalis Torr. (Apiaceae) from Utah.

Osmorhiza occidentalis Torr. is an essential-oil-bearing plant in the Apiaceae family. Volatile oil was produced through steam distillation (n = 3) of the above ground plant parts and was analyzed by gas chromatography (GC/FID, GC/MS), and gas chromatography/isotope ratio mass spectrometry (GC/IRMS) to establish the essential oil composition and stable isotope profile. The resulting essential oils were found to be comprised of 33 volatile compounds. Prominent volatile compounds include methyl chavicol (avg. 61.6%), (Z)-ß-ocimene (avg. 14.7%), sabinene (avg. 10.5%), and γ-terpinene (avg. 2.8%). Stable isotope values were determined for prominent volatile compounds, including methyl chavicol, (Z)-ß-ocimene, sabinene, and γ-terpinene. Values for δ2H range from -393.479 (avg. sabinene) to -171.516 (avg. methyl chavicol). Those for δ13C range from -35.957 (avg. methyl chavicol) to -30.820 (avg. (Z)-ß-ocimene). The essential oil yield was 0.12% (w/w). The current study establishes for the first time, to the best knowledge of the authors, the essential oil yield, essential oil composition, and stable isotope profile of prominent volatile compounds extracted from the above-ground portions of O. occidentalis. These results provide insight into the volatile chemical composition produced by the plant and provide fundamental data for substantiation of ethnobotanical applications.

Essential Oil Composition and Stable Isotope Profile of Cultivated Ocimum campechianum Mill. (Lamiaceae) from Peru.

Ocimum campechianum Mill. (Peruvian basil) is an essential oil-bearing plant of the Lamiaceae family. Volatile oil produced through steam distillation of Peruvian basil was examined to establish the aromatic and stable isotope profiles of samples (n = 9) from three different cultivated plots in Peru. The resulting essential oils were analyzed by GC/FID, GC/MS, and GC/IRMS. In accordance with findings from other researchers, multiple chemotypes, defined by the most abundant aromatic compounds, exist within these populations. Overall, 55% of samples are the eugenol chemotype (values ranging 15.4-30.2%), 33% are the methyl eugenol chemotype (values ranging 68.1-68.7%), and a single sample is a mixture of both chemotypes, containing high levels of both eugenol (38.1%) and methyl eugenol (8.6%). Stable isotope ratios, δ2H and δ13C, performed on prominent compounds provide supporting data for distinguishing chemotypes. Complete aromatic profiles, stable isotope ratios, and essential oil yield are established for each sample. This study confirms the existence of multiple chemotypes and, for the first time, to the author's best knowledge, establishes stable isotope ratios for O. campechianum essential oil, which proves a useful tool in further investigating plant metabolism and determining essential oil authenticity.

Pneumonia is a common and early complication of the Severe Alcohol Withdrawal Syndrome (SAWS).

BACKGROUND: Pneumonia (PNA) may complicate the Severe Alcohol Withdrawal Syndrome (SAWS), with ICU admission, mechanical ventilation (MV), prolonged length of stay (LOS), and adverse events. OBJECTIVES: To examine the onset, features and courses of PNA in patients with SAWS to aid management. METHODS: A 33 month contiguous review of SAWS and PNA was conducted at an urban public hospital. RESULTS: There were 279 episodes of Alcohol Withdrawal Syndrome (AWS) among 255 patients. Males predominated (91%) with a mean age of 45.8 years (range 23-73), of whom 31% (87/279) developed SAWS with ICU management. Direct ICU admission occurred for 62 patients; 25 were transferred for delirium, seizures, escalating sedation, PNA or other complications. PNA was identified for 34 ICU direct admissions and 13 ward patients. Ten transfers to the ICU also developed PNA for an ICU total of 44/87 (51%), of whom 82% (36/44) required MV. Another 10 ICU patients without PNA received MV for high dose sedation or respiratory failure. Most ICU patients (72/87 (83%)), including all with MV, required IV infusion of sedation. MV prolonged LOS, but LOS for PNA with MV was similar to all MV. ICU transfers had longer LOS with greater use of MV than direct admits (p<0.05). PNA was identified before ICU admission or transfer for 73% (32/44 (p<0.05)), and usually before intubation. Most PNA was Community Acquired Pneumonia (CAP) with P. Pneumoniae frequently cultured. CONCLUSIONS: PNA with SAWS is predominately CAP and occurs early. Focused ICU admission with respiratory support are priorities of initial management.

Alcohol Withdrawal Syndrome in Women vs Men: Analysis of 1496 Cases at a Single Site.

BACKGROUND: Studies of alcohol withdrawal syndrome indicate a higher prevalence in men than in women. However, it is unknown how the condition differs between the sexes. OBJECTIVE: To assess alcohol withdrawal syndrome in women versus men at a single site. METHODS: All cases of alcohol withdrawal syndrome at a public hospital from 2010 to 2014 were reviewed retrospectively. For all 1496 episodes, age, sex, and admission to a general care unit (ward) versus the medical intensive care unit were ascertained, along with patient survival. A detailed analysis was performed of 437 cases: all 239 patients admitted to the medical intensive care unit, all 99 female patients admitted to the ward, and 99 randomly selected male patients admitted to the ward. Also analyzed were administration of benzodiazepines, disease course, length of stay, and complications. RESULTS: Men accounted for 92% of all cases (1378 of 1496; P < .001) and medical intensive care unit admissions (220 of 239; P < .05). Sixteen percent of both men and women were admitted to the medical intensive care unit. Men were older (mean age, 45.6 vs 43.9 years; P < .01), and women required more benzodiazepines. Similar rates of complications occurred in both sexes, although women had a higher rate of pancreatitis and men had higher rates of pneumonia, higher rates of sepsis, and longer stays. CONCLUSIONS: Men and women with alcohol withdrawal syndrome have similar complications, courses, and intensive care unit admission rates, although men are more prone to pneumonia and have longer stays.

What am I doing? It depends: agency and action identification.

Actions can be identified at a range of levels, from higher level, outcome-related descriptions to lower level, movement-related descriptions. But how do these levels of identification influence the experience of control (agency) over a task? We addressed the relation between the level of action identification and agency using a hierarchical task modeled from typing. Participants memorized letter sequences and reported them by moving a cursor to targets that contained letters. To manipulate lower level (aiming) difficulty, the targets were either large or small. To manipulate higher level (memory) difficulty, the letter sequences were either constant or random within a block. We found effects of higher and lower level difficulty on agency and action identification. Moreover, we found interactive effects of higher and lower level difficulty on performance. We discuss these findings in terms of contributions to the study of agency, and some differences from the results of previous studies of action identification.

Rapid Transition to Buprenorphine in a Patient With Methadone-Related QTc Interval Prolongation.

BACKGROUND: Patients with opioid use disorder (OUD) who are managed on methadone often require transition to buprenorphine therapy. Current recommendations require months to gradually taper off of methadone; however, in some cases, the need to transition is urgent. Only a few rapid methadone-to-buprenorphine transitions have been reported and there are no established protocols to guide clinicians in these cases. CASE PRESENTATION: A 43-year-old man on 95 mg methadone for opioid use disorder experienced cardiac arrest attributable to ventricular fibrillation caused by QTc interval prolongation from methadone. In the hospital, a gradual taper of methadone was initiated but proved intolerable; the patient requested to restart his home dose of methadone and leave against medical advice. A rapid transition was initiated instead. Naltrexone (25 mg) was used to precipitate acute withdrawal followed 1 hour later by a "rescue" with buprenorphine/naloxone (16 mg/4 mg). The Clinical Opiate Withdrawal Score (COWS) peaked at 21 post-naltrexone and fell quickly to 15 within a half-hour of buprenorphine/naloxone administration. The patient was maintained on a total daily dose of 16 mg/4 mg buprenorphine/naloxone through the time of discharge. CONCLUSIONS: A patient requiring an urgent taper off of methadone due to adverse cardiac effects successfully transitioned to buprenorphine/naloxone within 2 hours by using naltrexone to precipitate withdrawal followed by a "rescue" with buprenorphine/naloxone. A relatively high dose of 16 mg/4 mg buprenorphine/naloxone successfully arrested withdrawal symptoms. With further refinement, this protocol may be an important technique for urgent methadone-to-buprenorphine transitions in the inpatient setting.

Tungsten-182 evidence for an ancient kimberlite source.

Globally distributed kimberlites with broadly chondritic initial 143Nd-176Hf isotopic systematics may be derived from a chemically homogenous, relatively primitive mantle source that remained isolated from the convecting mantle for much of the Earth's history. To assess whether this putative reservoir may have preserved remnants of an early Earth process, we report 182W/184W and 142Nd/144Nd data for "primitive" kimberlites from 10 localities worldwide, ranging in age from 1,153 to 89 Ma. Most are characterized by homogeneous µ182W and µ142Nd values averaging -5.9 ± 3.6 ppm (2SD, n = 13) and +2.7 ± 2.9 ppm (2SD, n = 6), respectively. The remarkably uniform yet modestly negative µ182W values, coupled with chondritic to slightly suprachondritic initial 143Nd/144Nd and 176Hf/177Hf ratios over a span of nearly 1,000 Mya, provides permissive evidence that these kimberlites were derived from one or more long-lived, early formed mantle reservoirs. Possible causes for negative µ182W values among these kimberlites include the transfer of W with low µ182W from the core to the mantle source reservoir(s), creation of the source reservoir(s) as a result of early silicate fractionation, or an overabundance of late-accreted materials in the source reservoir(s). By contrast, two younger kimberlites emplaced at 72 and 52 Ma and characterized by distinctly subchondritic initial 176Hf/177Hf and 143Nd/144Nd have µ182W values consistent with the modern upper mantle. These isotopic compositions may reflect contamination of the ancient kimberlite source by recycled crustal components with µ182W ≥ 0.

Essential Oil Profile and Yield of Corolla, Calyx, Leaf, and Whole Flowering Top of Cultivated Lavandula angustifolia Mill. (Lamiaceae) from Utah.

Lavandula angustifolia Mill. (lavender) is an essential-oil-bearing plant in the Lamiaceae family. Volatile oil produced through the steam distillation of lavender was examined to establish the essential oil yield and aromatic profile from each portion of the plant-namely, the corolla, calyx, leaf, and whole flowering top. The resulting essential oils were analyzed by GC-FID and GC-MS. The different plant parts generally shared similar compounds but in varying relative percentages. Aromatic profiles of the whole flowering top and calyx were similar, with prominent compounds being linalool acetate (34.3%, 32.0%), linalool (26.5%, 32.9%), lavandulyl acetate (5.6%, 4.9%), terpinen-4-ol (5.3%, 7.0%), and (Z)-ß-ocimene (4.5%, 5.4%), respectively. Aromatic profiles for the corolla and leaf were unique. Prominent aromatic compounds of the corolla included linalool acetate (18.4%), linalool (10.8%), epi-α-cadinol (10.0%), borneol (7.3%), and lavandulyl acetate (6.3%). Prominent aromatic compounds of the leaf included epi-α-cadinol (19.8%), γ-cadinene (11.0%), borneol (6.0%), caryophyllene oxide (4.9%), and bornyl acetate (4.8%). Complete profiles and essential oil yields of corolla, calyx, leaf, and whole flowering top were established. This study establishes the influence the corolla, calyx, and leaf exert on the aromatic profile of the whole flowering top and provides insight into authentication of lavender essential oil.