Sensitive analysis of aconitine, hypaconitine, mesaconitine and jesaconitine in human body fluids and Aconitum tubers by LC/ESI-TOF-MS

The Aconitum species (Ranunculaceae) are widely distributed in northern Asia and North America. Their roots are popularly used in herbal medicines in China and Japan. Many cases of accidental, suicidal and homicidal intoxication with this plant have been reported; some of these were fatal because the toxicity of Aconitum is very high. It is thus important to detect and quantify Aconitum alkaloids in body fluids, with high sensitivity. We have developed a simple and sensitive method for measuring four kinds of Aconitum alkaloids (aconitine, hypaconitine, jesaconitine and mesaconitine) by LC/electrospray (ESI)-time-of-flight (TOF)-MS. For all of them, only molecular ions were observed at an orifice voltage of 75 V; at 135 V, base peaks corresponding to [M - 60 + H]+ ions were observed. These four compounds and methyllycaconitine (internal standard) in human plasma samples were purified by solid-phase extraction. The four extracted compounds were completely separated in mass chromatograms; the calibration curves showed good linearity in the range 10-300 ng/ml, and the detection limits were estimated to be 0.2-0.5 ng/ml. Using our method, we also determined the amounts of these compounds in tuber samples. The present method is applicable in clinical and forensic toxicology.     

Relationship between the shape of tibial spurs on X-ray and meniscal changes on MRI in early osteoarthritis of the knee

OBJECTIVE: The purpose of this study was to evaluate the relationship between the shape of tibial spurs on plain X-rays and the meniscal changes on magnetic resonance imaging (MRI) in early osteoarthritis of the knee. MATERIALS AND METHODS: Sixty-three patients (age range, 40 to 59 years; average, 51.8) underwent X-ray and MRI examinations of their knees. Ligament injuries caused by trauma and Kellgren Radiographic Grades III and IV on X-ray were excluded. The shapes of the medial and lateral tibial spurs on X-ray were classified into four types: (a) normal type; (b) horizontal type, in which the spur protruded horizontally; (c) upward type, in which the spur protruded upward; and (d) downward type, in which the spur protruded downward. The femorotibial angle (FTA) on the X-rays was also measured. The medial and lateral meniscal displacement rates on MRI were measured by the proportion by which the meniscal lesion protruded from the edge of the tibial joint surface to the overall meniscal width. The medial and lateral meniscal signal changes on MRI were classified into three types: (a) normal type; (b) intrameniscal type, which showed a high signal within the meniscus; and (c) tear type, which showed a high signal extending to the tibial joint surface. The relationships between the shape of the medial and lateral tibial spur classification on X-ray, the medial and lateral meniscal displacement rates on MRI, the medial and lateral meniscal signal changes on MRI and the FTA were evaluated statistically. RESULTS: Statistically significant correlations were observed between the medial tibial spur classification on X-ray, the medial meniscal displacement rate on MRI and the medial meniscal signal change classification on MRI. In the downward type of medial tibial spur, the medial meniscal displacement rate (50.46+/-17.95%) and the percentage (8 out of 8 cases; 100%) involving the tear type of medial meniscus were greater than the other types. Statistical significance was not observed among the lateral tibial spur classification on X-ray, the lateral meniscal displacement rate on MRI and the lateral meniscal signal change classification on MRI. However, in the horizontal type of lateral tibial spur, the percentage (7 out of 10 cases; 70%) involving the tear type of lateral meniscus was greater than the other types. Correlations tended to be observed between the medial meniscal displacement rate on MRI and the FTA. CONCLUSIONS: In this study, there was a relationship between the shape of the tibial spur on X-ray and the meniscal changes on MRI in early osteoarthritis of the knee. The shape of the medial tibial spur on X-ray can be a useful indicator for predicting the progression of osteoarthritis of the knee. A downward type of medial tibial spur classification on X-ray may be a risk factor for developing severe osteoarthritis of the knee.     

Surface analysis of traces stained with discharge on plane electrode in atmospheric pressure negative corona

The surface deposits of the traces stained with discharges on the brass plate electrode in atmospheric pressure DC negative corona have been analyzed. The surface analysis showed that the major deposits on the traces originate from nitrogen oxide ions NO_x^? and neutrals NO_x, or carbon clusters C_n. The relationship between the plane positions and resulting deposits obtained with the point-to-plane electrodes with arbitrary needle angle to the plane provided the information about the general behavior of negative ions NO_x^? and neutral species NO_x occurring in stationary inhomogeneous electric fields.     

Planar-chiral metal complexes comprised of square-planar metal and achiral tetradentate ligands: design, optical resolution, and thermodynamics

Planar-chiral palladium complexes {[[N,N'-[1,4-butanediylbis(oxy-7,1-naphthalenediyl)]bis(2-pyridinecarboxamidato)](2-)-κN(1),κN(1)',κN(2),κN(2)']palladium (PdL(4)) and [[2,2'-[1,4-butanediylbis[[(oxy-7,1-naphthalenediyl)imino]methyl]]dipyrrolato](2-)-κN(1),κN(1)',κN(2),κN(2)']palladium (PdL(5))} were synthesized from achiral tetradentate ligands N,N'-[1,4-butanediylbis(oxy-7,1-naphthalenediyl)]bis(2-pyridinecarboxamide) (H(2)L(4)) and N,N'-bis[(1H-pyrrol-2-yl)methylidene]-7,7'-(1,4-butanediyldioxy)bis(1-naphthalenamine) (H(2)L(5)) bearing two dissymmetric bidentate units at both ends and a Pd(II) ion, respectively. The palladium complexes were crystallized in the monoclinic space group P2(1)/n with the unit cell parameters a = 16.5464(6) ?, b = 11.3534(4) ?, c = 17.6697(7) ?, β = 115.5300(10)°, and Z = 4 for PdL(4) and a = 17.2271(8) ?, b = 10.1016(5) ?, c = 17.9361(9) ?, β = 105.6310(10)°, and Z = 4 for PdL(5). The planar-chiral structures of PdL(4) and PdL(5) were confirmed by single-crystal X-ray analyses, resulting in the fact that the crystals were racemic mixtures. The racemic mixtures were successfully resolved by using chiral high-performance liquid-chromatography techniques. Racemizations of the complexes were found to be drastically dependent on the arrangement of the charged or uncharged metal-binding N atoms of the ligands.     

Core temperature and density profile measurements in inertial confinement fusion implosions

We have measured time-integrated and time-gated electron temperature (T_e) and density (N_e) spatial profiles from indirect-drive implosions. In our experiments, we used a multiple-pinhole two-dimensional imaging spectrometer to obtain multispectral X-ray images of the imploded core. Quantitative comparisons between quasi-monochromatic images in different energy bands allowed T_e and N_e spatial profiles to be determined using two independent and validated techniques: a multi-objective search and reconstruction analysis, and an analytical analysis. We then compared the results to a simple one-dimensional (1D) mix-free hydrodynamics simulation in order to evaluate the ability of such a model to predict our experiments. Our data show spatial T_e profiles that are qualitatively consistent with the predictions of our 1D simulations, but we observe central cores that are 10–25% cooler and emit X-rays as late as 200 ps after peak compression. We infer time-gated spatial N_e profiles that are consistent with our 1D simulations near the times of peak compression, but we find significant disagreement between time-integrated data and 1D simulation predictions at large radii. Careful analysis of the time-gated and time-integrated T_e and N_e spatial profiles, together with streaked X-ray emission spectra from core and shell dopants, suggests mixing of shell material into the core is an important process that our 1D hydrodynamics simulations fail to capture, and comparison between image data and a simple analytical model suggests that 2–5 μm of the initial inner shell thickness mixes into the core during the time period of significant X-ray emission. This mix width is consistent with the predictions of a growth-factor analysis that treats instability growth seeded by capsule surface roughness, and points to the need to consider time-dependent mixing effects when interpreting T_e and N_e spatial profiles derived from multispectral X-ray image data, particularly at large radii where mixing effects will be most significant.     

Computer-Aided Detection of Quantitative Signatures for Breast Fibroepithelial Tumors Using Label-Free Multi-Photon Imaging

Fibroadenomas (FAs) and phyllodes tumors (PTs) are major benign breast tumors, pathologically classified as fibroepithelial tumors. Although the clinical management of PTs differs from FAs, distinction by core needle biopsy diagnoses is still challenging. Here, a combined technique of label-free imaging with multi-photon microscopy and artificial intelligence was applied to detect quantitative signatures that differentiate fibroepithelial lesions. Multi-photon excited autofluorescence and second harmonic generation (SHG) signals were detected in tissue sections. A pixel-wise semantic segmentation method using a deep learning framework was used to separate epithelial and stromal regions automatically. The epithelial to stromal area ratio and the collagen SHG signal strength were investigated for their ability to distinguish fibroepithelial lesions. An image segmentation analysis with a pixel-wise semantic segmentation framework using a deep convolutional neural network showed the accurate separation of epithelial and stromal regions. A further investigation, to determine if scoring the epithelial to stromal area ratio and the SHG signal strength within the stromal area could be a marker for differentiating fibroepithelial tumors, showed accurate classification. Therefore, molecular and morphological changes, detected through the assistance of computational and label-free multi-photon imaging techniques, enable us to propose quantitative signatures for epithelial and stromal alterations in breast tissues.     

Copper-Catalyzed Oxidative Benzylic C(sp3)−H Cyclization for the Synthesis of β-Lactams

β-Lactams are important structural motifs because of their ubiquity in natural products and pharmaceuticals. We report herein a Cu-catalyzed intramolecular oxidative C(sp³)−H amidation for the synthesis of β-lactams using tBuOOtBu. This method is based on Kharasch–Sosnovsky amidation and does not require prefunctionalization of C(sp³)−H bonds or the installation of a directing group, thereby allowing for the straightforward synthesis of β-lactams. Our intramolecular functionalization protocol can be extended to diverse benzylic C(sp³)−H bonds and shows excellent functional-group tolerance.     

Stereocontrolled glycosidations using a heterogeneous solid acid, sulfated zirconia, for the direct syntheses of α- and β-manno- and 2-deoxyglucopyranosides

Novel α- and β-stereocontrolled glycosidations using a heterogeneous solid acid, sulfated zirconia (SO₄/ZrO₂), as an activator have been developed. The glycosidations of manno- and 2-deoxyglucopyranosyl α-fluorides with several alcohols using SO₄/ZrO₂ in MeCN proceeded α-stereoselectively, while those with the same activator in the presence of MS 5A in Et₂O occurred with β-stereoselectivity. Thus, both the α- and β-manno- and 2-deoxyglucopyranosides were effectively obtained by the present glycosidations.     

Microradiographic strain measurement using markers

A method for measuring strain on interior planes of some real structural materials is presented. X-ray images are formed of small (10–40 micron) gold markers placed on selected interior planes of optically opaque X-ray transparent materials. The use of well collimated monochromatic synchrotron radiation makes possible high contrast images of the small markers. Images of the particles before and after straining are recorded photographically. Photographs are enlarged 33X and measured using a simple electro-optical setup. In calibration experiments using approximately a 300-micron gage length, the strain measured by this method agreed with extensometer measured strains to within 100 microstrain. Example applications in a graphite-epoxy composite are presented, including measurement of the strain drop off near the free edge, strain concentration around a hole, and the strain field on a particular plane near a hole after local delamination. The technique is currently limited to materials no less X-ray transparent than titanium.Paper was presented at the 1992 SEM Spring Conference on Experimental Mechanics held in Las Vegas, NV on June 8–11.