Potentially Mistaking Enantiomers for Different Compounds Due to the Self-Induced Diastereomeric Anisochronism (SIDA) Phenomenon

The NMR phenomenon of self-induced diastereomeric anisochronism (SIDA) was observed with an alcohol and an ester. The alcohol exhibited large concentration-dependent chemical shifts (δ’s), which initially led us to erroneously consider whether two enantiomers were in fact atropisomers. This highlights a potential complication for the analysis of chiral compounds due to SIDA, namely the misidentification of enantiomers. A heterochiral association preference for the alcohol in CDCl3 was determined by the intermolecular nuclear Overhauser effect (NOE) and diffusion measurements, the same preference as found in the solid state. The ester revealed more subtle effects, but concentration-dependent δ’s, observation of intermolecular NOE’s, as well as distinct signals for the two enantiomers in a scalemic sample all indicated the formation of associates. Intermolecular NOE and diffusion measurements indicated that homochiral association is slightly preferred over heterochiral association in CDCl3, thus masking association for enantiopure and racemic samples of equal concentration. As observed with the alcohol, heterochiral association was preferred for the ester in the solid state. The potential problems that SIDA can cause are highlighted and constitute a warning: Due care should be taken with respect to conditions, particularly the concentration, when measuring NMR spectra of chiral compounds. Scalemic samples of both the alcohol and the ester were found to exhibit the self-disproportionation of enantiomers (SDE) phenomenon by preparative TLC, the first report of SDE by preparative TLC

Oligocene-Miocene biostratigraphy, magnetostratigraphy, and isotopic stratigraphy of the western North Atlantic

Magnetostratigraphic records from western North Atlantic Deep Sea Drilling Project (DSDP) Sites 563 and 558 are correlated with the geomagnetic polarity time scale (GPTS; Berggren et aI., 1984a, 1984b) using marine magnetic anomalies and selected biostratigraphic datum levels. The magnetochronology established is used to make direct magnetobiostratigraphic correlations that agree with previous Oligocene-early Miocene studies. However, we show that Zones NN8 partim and NN9 and associated Epoch 11 correlate with Magnetic Anomaly 5 (= Chron C5n). This contrasts with previous indirect correlations of Epoch 11 with Anomaly 5A and requires an upward adjustment of 1.5-2.0 m.y. for middle-late Miocene calcareous nannofossil zones. We correlate the middle/late Miocene boundary with Zone NN8 and earliest Chron C5n (10.4 Ma)

Late Paleocene event chronology: unconformities, not diachrony

The chronology of the events associated with the late Paleocene thermal maximum (LPTM, Chron C24r) has been established through the construction of a composite reference section that involved chemomagnetobiostratigraphic correlations and assumed minimum diachrony of biostratigraphic events. On this basis, discrepancies between correlations in different sections were explained by inferred unconformities. However, diachrony between distant sections cannot be ruled out. We report here on two geographically close sections drilled onshore New Jersey that yield different records of chemomagnetobiostratigraphic correlations in the interval representing Chron C24r. Because of their proximity (approximately 40 km apart), diachrony of biostratigraphic events between the two sections can be ruled out. In contrast, the marked lithologic disconformities in the sections explain well the different records of events. We thus conclude that the current relative chronology for Chron C24r is firmly based and that the upper Paleocene-lower Eocene stratigraphic record yields multiple unconformities, with Subzone NP9b rarely sampled. We examine the implications that undeciphered unconformities may have on the identification of proxies for paleoceanographic reconstruction, in particular with regard to the identification of the carbon isotope excursion (CIE) that reflects a dramatic latest Paleocene disturbance of the carbon cycle. We propose biostratigraphic means (short-lived calcareous nannoplankton and planktonic foraminifera taxa) that permit the unequivocal identification of the CIE not only in the oceanic realm but also in neritic settings

An Exceptional Chronologic, Isotopic, and Clay Mineralogic Record of the Latest Paleocene Thermal Maximum, Bass River, NJ, ODP 174AX

A thick, apparently continuous section recording events of the latest Paleocene thermal maximum in a neritic setting was drilled at Bass River State Forest, New Jersey as part of ODP Leg l74AX [Miller, Sugarman, Browning et al., 1998]. Integrated nannofossil and magneto-stratigraphy provides a firm chronology supplemented by planktonic foraminiferal biostratigraphy. This chronologic study indicates that this neritic section rivals the best deep-sea sections in providing a complete record of late Paleocene climatic events. Carbon and oxygen isotopes measured on benthic foraminifera show a major (4.0 %o in carbon, 2.3 %o in oxygen) negative shift correlative with the global latest Paleocene carbon isotope excursion (CIE). A sharp increase in kaolinite content coincides with the isotope shift in the Bass River section, analogous to increases found in several other records. Carbon and oxygen isotopes remain low and kaolinite content remains high for the remainder of the depositional sequence above the CIE (32.5 ft, 9.9 m), which we estimate to represent 300-500 k.y. We interpret these data as indicative of an abrupt shift to a warmer and wetter climate along the North American mid-Atlantic coast, in concert with global events associated with the CIE

Phonon Localization in One-Dimensional Quasiperiodic Chains

Quasiperiodic long range order is intermediate between spatial periodicity and disorder, and the excitations in 1D quasiperiodic systems are believed to be transitional between extended and localized. These ideas are tested with a numerical analysis of two incommensurate 1D elastic chains: Frenkel-Kontorova (FK) and Lennard-Jones (LJ). The ground state configurations and the eigenfrequencies and eigenfunctions for harmonic excitations are determined. Aubry's "transition by breaking the analyticity" is observed in the ground state of each model, but the behavior of the excitations is qualitatively different. Phonon localization is observed for some modes in the LJ chain on both sides of the transition. The localization phenomenon apparently is decoupled from the distribution of eigenfrequencies since the spectrum changes from continuous to Cantor-set-like when the interaction parameters are varied to cross the analyticity--breaking transition. The eigenfunctions of the FK chain satisfy the "quasi-Bloch" theorem below the transition, but not above it, while only a subset of the eigenfunctions of the LJ chain satisfy the theorem.Comment: This is a revised version to appear in Physical Review B; includes additional and necessary clarifications and comments. 7 pages; requires revtex.sty v3.0, epsf.sty; includes 6 EPS figures. Postscript version also available at http://lifshitz.physics.wisc.edu/www/koltenbah/koltenbah_homepage.htm

Integrated Late Eocene-Oligocene Stratigraphy of the Alabama Coastal Plain: Correlation of Hiatuses and Stratal Surfaces to Glacioeustatic Lowerings

We integrated strontium and oxygen isotopic, biostratigraphic, and magnetostratigraphic studies of two upper Eocene-Oligocene boreholes drilled near Bay Minette and St. Stephens Quarry (SSQ), Alabama. Continuous coring provided fresh, unweathered material for magnetostratigraphic studies, minimizing problems reported from nearby outcrops. Difficulties with each technique were encountered because of diagenesis, absence of marker fossils, and the presence of unconformities; however, by integrating results from isotopic stratigraphy, biostratigraphy, and magnetostratigraphy, we correlated these relatively shallow-water deposits to the geomagnetic polarity time scale (GPTS). At the SSQ borehole, the upper Eocene to lower Oligocene section is apparently complete within our stratigraphic resolution (0.2-0.5 m.y.), allowing us to estimate the ages of several stratal surfaces. Late Eocene Sr isotope age estimates are as expected at the SSQ borehole, but Oligocene ages are ~1 m.y. older than expected due to diagenesis. At the Bay Minette borehole, a latest Eocene-earliest Oligocene and a late early Oligocene hiatus were detected. We correlate these two hiatuses and stratal surfaces at SSQ with global δ^18O increases inferred to represent glacioeustatic lowerings and with evidence for hiatuses on other continental margins: (1) a distinct disconformity at the base of the Chickasawhay Limestone at both boreholes and a hiatus at Bay Minette correlates with a global δ^18O increase; we revise the age of this surface (equivalent to the TB 1.1 sequence boundary) making it ~2 m.y. older than previously reported; and (2) a surface at the top of the Shubuta Member (lowermost Oligocene) has been interpreted both as a condensed section and a disconformity; this surface at SSQ and a hiatus at Bay Minette correlate with a sharp global δ^18O increase and with hiatuses on the New Jersey and Irish margins. The timing of the hiatuses and stratal surfaces correlates with the inflection of the δ^18O increases and not with the maximum values, supporting models that indicate that unconformities form during the maximum rates of sea level fall

Rapid detection of 2-hydroxyglutarate in frozen sections of IDH mutant tumors by MALDI-TOF mass spectrometry

All isocitrate dehydrogenase (IDH) mutant solid neoplasms exhibit highly elevated levels of D-2-hydroxyglutarate (D-2HG). Detection of 2HG in tumor tissues currently is performed by gas or liquid chromatography-mass spectrometry (GC- or LC-MS) or biochemical detection. While these methods are highly accurate, a considerable amount of time for tissue preparation and a relatively high amount of tissue is required for testing. We here present a rapid approach to detect 2HG in brain tumor tissue based on matrix-assisted laser desorption ionization - time of flight mass spectrometry (MALDI-TOF). We analyzed 26 brain tumor samples with known IDH1 or IDH2 mutation and compared readouts to those from 28 brain tumor samples of wildtype IDH status. IDH mutant samples exhibited a clear positive signal for 2HG which was not observed in any of the IDH wildtype tumors. Our analytical pipeline allowed for 2HG detection in less than 5 min. Data were validated by determining 2HG levels in all tissues with a biochemical assay. In conclusion, we developed a protocol for rapid detection of 2HG levels and illustrate the possibility to use MALDI-TOF for the detection of metabolites on frozen tissue sections in a diagnostic setting

Implementation of the 2017 Berlin Concussion in Sport Group Consensus Statement in contact and collision sports: a joint position statement from 11 national and international sports organisations.

The 2017 Berlin Concussion in Sport Group Consensus Statement provides a global summary of best practice in concussion prevention, diagnosis and management, underpinned by systematic reviews and expert consensus. Due to their different settings and rules, individual sports need to adapt concussion guidelines according to their specific regulatory environment. At the same time, consistent application of the Berlin Consensus Statement's themes across sporting codes is likely to facilitate superior and uniform diagnosis and management, improve concussion education and highlight collaborative research opportunities. This document summarises the approaches discussed by medical representatives from the governing bodies of 10 different contact and collision sports in Dublin, Ireland in July 2017. Those sports are: American football, Australian football, basketball, cricket, equestrian sports, football/soccer, ice hockey, rugby league, rugby union and skiing. This document had been endorsed by 11 sport governing bodies/national federations at the time of being published

Characterisation of Listeria monocytogenes isolates from cattle using a bovine caruncular epithelial cell model

© 2020 Listeria monocytogenes is an important foodborne pathogen in human and veterinary health, causing significant morbidity and mortality including abortion. It has a particular tropism for the gravid uterus, however, the route of infection in reproductive tissues of ruminants (i.e. placentome), is much less clear. In this study, we aimed to investigate a bovine caruncular epithelial cell (BCEC) line as a model for L. monocytogenes infection of the bovine reproductive tract. The BCEC infection model was used to assess the ability of 14 different L. monocytogenes isolates to infect these cells. Lysozyme sensitivity and bacterial survival in 580 μg lysozyme/ml correlated with attenuated ability to proliferate in BCEC (p = 0.004 and p = 0.02, respectively). Four isolates were significantly attenuated compared to the control strain 10403S. One of these strains (AR008) showed evidence of compromised cell wall leading to increased sensitivity to ß-lactam antibiotics, and another (7644) had compromised cell membrane integrity leading to increased sensitivity to cationic peptides. Whole genome sequencing followed by Multi Locus Sequence Type analysis identified that five invasive isolates had the same sequence type, ST59, despite originating from three different clinical conditions. Virulence gene analysis showed that the attenuated isolate LM4 was lacking two virulence genes (uhpT, virR) known to be involved in intracellular growth and virulence. In conclusion, the BCEC model was able to differentiate between the infective potential of different isolates. Moreover, resistance to lysozyme correlated with the ability to invade and replicate within BCEC, suggesting co-selection for surviving challenging environments as the abomasum

Quantification of Internal Stress-Strain Fields in Human Tendon: Unraveling the Mechanisms that Underlie Regional Tendon Adaptations and Mal-Adaptations to Mechanical Loading and the Effectiveness of Therapeutic Eccentric Exercise.

By virtue of their anatomical location between muscles and bones, tendons make it possible to transform contractile force to joint rotation and locomotion. However, tendons do not behave as rigid links, but exhibit viscoelastic tensile properties, thereby affecting the length and contractile force in the in-series muscle, but also storing and releasing elastic stain energy as some tendons are stretched and recoiled in a cyclic manner during locomotion. In the late 90s, advancements were made in the application of ultrasound scanning that allowed quantifying the tensile deformability and mechanical properties of human tendons in vivo. Since then, the main principles of the ultrasound-based method have been applied by numerous research groups throughout the world and showed that tendons increase their tensile stiffness in response to exercise training and chronic mechanical loading, in general, by increasing their size and improving their intrinsic material. It is often assumed that these changes occur homogenously, in the entire body of the tendon, but recent findings indicate that the adaptations may in fact take place in some but not all tendon regions. The present review focuses on these regional adaptability features and highlights two paradigms where they are particularly evident: (a) Chronic mechanical loading in healthy tendons, and (b) tendinopathy. In the former loading paradigm, local tendon adaptations indicate that certain regions may "see," and therefore adapt to, increased levels of stress. In the latter paradigm, local pathological features indicate that certain tendon regions may be "stress-shielded" and degenerate over time. Eccentric exercise protocols have successfully been used in the management of tendinopathy, without much sound understanding of the mechanisms underpinning their effectiveness. For insertional tendinopathy, in particular, it is possible that the effectiveness of a loading/rehabilitation protocol depends on the topography of the stress created by the exercise and is not only reliant upon the type of muscle contraction performed. To better understand the micromechanical behavior and regional adaptability/mal-adaptability of tendon tissue it is important to estimate its internal stress-strain fields. Recent relevant advancements in numerical techniques related to tendon loading are discussed