Experimentally determined stress-intensity factors for single-edge-crack round bars loaded in bending

Dimensionless stress-intensity factors were determined for single-edge-crack solid and hollow round bars loaded in bending. These factors were calculated from experimental compliance (inverse slope of load-displacement curve) measurements made on round bars loaded in three-point bending. The compliance specimens had span to diameter ratios of 6.67 and 3.33, and measurements were made over a range of dimensionless crack lengths from 0.002 to 0.70. The tests were made using 3-in. (76-mm) and 6-in. (152-mm) solid and hollow round bars notched on one side; the hollow bars had an inner to outer diameter ratio of 0.33. A comparison was made with data in the literature for rectangular bars; for ana/D of 0.0001, the dimensionless stress-intensity factor for a solid round bar is 1.3 vs. 2.0 for a rectangular bar.     

Native-Like and Denatured Cytochrome <Emphasis Type="Italic">c</Emphasis> Ions Yield Cation-to-Anion Proton Transfer Reaction Products with Similar Collision Cross-Sections

The relationship between structures of protein ions, their charge states, and their original structures prior to ionization remains challenging to decouple. Here, we use cation-to-anion proton transfer reactions (CAPTR) to reduce the charge states of cytochrome c ions in the gas phase, and ion mobility to probe their structures. Ions were formed using a new temperature-controlled nanoelectrospray ionization source at 25 °C. Characterization of this source demonstrates that the temperature of the liquid sample is decoupled from that of the atmospheric pressure interface, which is heated during CAPTR experiments. Ionization from denaturing conditions yields 18+ to 8+ ions, which were each isolated and reacted with monoanions to generate all CAPTR products with charge states of at least 3+. The highest, intermediate, and lowest charge-state products exhibit collision cross-section distributions that are unimodal, multimodal, and unimodal, respectively. These distributions depend strongly on the charge state of the product, although those for the intermediate charge-state products also depend on that of the precursor. The distributions of the 3+ products are all similar, with averages that are less than half that of the 18+ precursor ions. Ionization of cytochrome c from native-like conditions yields 7+ and 6+ ions. The 3+ CAPTR products from these precursors have slightly more compact collision cross-section distributions that are indistinguishable from those for the 3+ CAPTR products from denaturing conditions. More broadly, these results indicate that the collision cross-sections of ions of this single domain protein depend strongly on charge state for charge states greater than ~4.

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Anomalies in the physical properties of the α form of bismuth oxide

Several of the physical properties of α-Bi₂O₃ have been studied in the temperature region above room temperature: the thermal expansion, the thermally stimulated current, the permittivity, the electrical resistance, and the specific heat. X-ray diffraction measurements and a thermogravimetric analysis have also been carried out. Several unusual properties in the physical properties of bismuth oxide have been detected in the temperature interval 450–570 K: exothermic maxima on the DTA and DSC curves, a small maximum and a sharp increase of the permittivity of the single crystal, a jump and a change of sign in the thermally stimulated current, and a sharp falloff of the electrical resistance of ceramic samples. At the same time, no appreciable changes in the monoclinic structure of α-Bi₂O₃ have been recorded in the indicated temperature interval. Fiz. Tverd. Tela (St. Petersburg) 39, 865–870 (May 1997)     

Pyroelectric effects in magnetoelectric multilayer composites

Magnetoelectric and pyroelectric properties have been investigated in heterostructures of nickel zinc ferrite (NZFO)-lead zirconate titanate (PZT) and lanthanum calcium manganite (LCMO)-PZT. The magnetoelectric (ME) coupling, mediated by mechanical strain, is found to be two orders of magnitude stronger in NZFO-PZT than in LCMO-PZT. The pyroelectric effect is investigated by measuring the current through the sample as the temperature is varied at 0.1 K/s. For NZFO-PZT the pyroelectric coefficient is in the range 0.2-15 nC/cm² K, depending on the temperature. A much weaker current is observed in LCMO-PZT. A reversal in the current direction is detected when the thermal cycle is switched from heating to cooling. The pyroelectric coefficient is found to scale with the strength of ME interactions. A clear correlation between pyroelectric current and ME interactions is evident from the results.     

Structures of cationized proline analogues: evidence for the zwitterionic form

The structures of lithiated and sodiated alpha-methyl-proline (alpha-Me-Pro) and structural isomers, both with and without a water molecule, are investigated using blackbody infrared radiative dissociation (BIRD) and density functional theory. From the BIRD kinetic data measured as a function of temperature, combined with master equation modeling of these data, threshold dissociation energies for the loss of a water molecule from these clusters are obtained. These energies are 77.5 +/- 0.5 and 53 +/- 1 kJ/mol for lithiated and sodiated alpha-Me-Pro, respectively. For the nonzwitterionic isomer, proline methyl ester, these values are 3.0-4.5 kJ/mol higher. These results provide compelling experimental evidence that alpha-Me-Pro is zwitterionic in these clusters. Theory at the temperature corrected B3LYP/6-311++G**//B3LYP/6-31++G** level indicates that the salt-bridge or zwitterionic forms of lithiated and sodiated alpha-Me-Pro are between 17 and 23 kJ/mol lower in energy than the nonzwitterionic or charge-solvated forms and that attachment of a single water molecule does not significantly change the structure or the relative energies of these clusters. The proton affinity of proline is 8 kJ/mol higher than that of alpha-Me-Pro, indicating that lithiated and sodiated singly hydrated proline should also be zwitterionic.     

Reduction of silicon halides and alkoxides with diisobutylaluminum hydride. Stereochemistry-rate law correlations for the SNiSi and SN2Si mechanisms

Stereochemistry-rate law correlations are given for the reduction of R₃Si*X compounds with i-Bu₂ AlH in either and n-hexane.     

An integrated mass spectrometry imaging and digital pathology workflow for objective detection of colorectal tumours by unique atomic signatures

Tumours are abnormal growths of cells that reproduce by redirecting essential nutrients and resources from surrounding tissue. Changes to cell metabolism that trigger the growth of tumours are reflected in subtle differences between the chemical composition of healthy and malignant cells. We used LA-ICP-MS imaging to investigate whether these chemical differences can be used to spatially identify tumours and support detection of primary colorectal tumours in anatomical pathology. First, we generated quantitative LA-ICP-MS images of three colorectal surgical resections with case-matched normal intestinal wall tissue and used this data in a Monte Carlo optimisation experiment to develop an algorithm that can classify pixels as tumour positive or negative. Blinded testing and interrogation of LA-ICP-MS images with micrographs of haematoxylin and eosin stained and Ki67 immunolabelled sections revealed Monte Carlo optimisation accurately identified primary tumour cells, as well as returning false positive pixels in areas of high cell proliferation. We analysed an additional 11 surgical resections of primary colorectal tumours and re-developed our image processing method to include a random forest regression machine learning model to correctly identify heterogenous tumours and exclude false positive pixels in images of non-malignant tissue. Our final model used over 1.6 billion calculations to correctly discern healthy cells from various types and stages of invasive colorectal tumours. The imaging mass spectrometry and data analysis methods described, developed in partnership with clinical cancer researchers, have the potential to further support cancer detection as part of a comprehensive digital pathology approach to cancer care through validation of a new chemical biomarker of tumour cells.

Digital pathology and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) imaging reveals a unique elemental signature of colorectal cancer.     

Decoding neural events from fMRI BOLD signal: A comparison of existing approaches and development of a new algorithm

Neuroimaging methodology predominantly relies on the blood oxygenation level dependent (BOLD) signal. While the BOLD signal is a valid measure of neuronal activity, variances in fluctuations of the BOLD signal are not only due to fluctuations in neural activity. Thus, a remaining problem in neuroimaging analyses is developing methods that ensure specific inferences about neural activity that are not confounded by unrelated sources of noise in the BOLD signal. Here, we develop and test a new algorithm for performing semiblind (i.e., no knowledge of stimulus timings) deconvolution of the BOLD signal that treats the neural event as an observable, but intermediate, probabilistic representation of the system's state. We test and compare this new algorithm against three other recent deconvolution algorithms under varied levels of autocorrelated and Gaussian noise, hemodynamic response function (HRF) misspecification and observation sampling rate. Further, we compare the algorithms' performance using two models to simulate BOLD data: a convolution of neural events with a known (or misspecified) HRF versus a biophysically accurate balloon model of hemodynamics. We also examine the algorithms' performance on real task data. The results demonstrated good performance of all algorithms, though the new algorithm generally outperformed the others (3.0% improvement) under simulated resting-state experimental conditions exhibiting multiple, realistic confounding factors (as well as 10.3% improvement on a real Stroop task). The simulations also demonstrate that the greatest negative influence on deconvolution accuracy is observation sampling rate. Practical and theoretical implications of these results for improving inferences about neural activity from fMRI BOLD signal are discussed.