Determination of propofol by GC/MS and fast GC/MS-TOF in two cases of poisoning

Two cases of suspected acute and lethal intoxication caused by propofol were delivered by the judicial authority to the Department of Sciences for Health Promotion and Mother-Child Care in Palermo, Sicily. In the first case a female nurse was found in a hotel room, where she lived with her mother; four 10 mg/mL vials and two 20 mg/mL vials of propofol were found near the decedent along with syringes and needles. In the second case a male nurse was found in the operating room of a hospital, along with a used syringe. In both cases a preliminary systematic and toxicological analysis indicated the presence of propofol in the blood and urine. As a result, a method for the quantitative determination of propofol in biological fluids was optimized and validated using a liquid-liquid extraction protocol followed by GC/MS and fast GC/MS-TOF. In the first case, the concentration of propofol in blood was determined to be 8.1 \u3bcg/mL while the concentration of propofol in the second case was calculated at 1.2 \u3bcg/mL. Additionally, the tissue distribution of propofol was determined for both cases. Brain and liver concentrations of propofol were, respectively, 31.1 and 52.2 \u3bcg/g in Case 1 and 4.7 and 49.1 \u3bcg/g in Case 2. Data emerging from the autopsy findings, histopathological exams as well as the toxicological results aided in establishing that the deaths were due to poisoning, however, the manner of death in each were different: homicide in Case 1 and suicide in Case 2

Direct evidence for efficient ultrafast charge separation in epitaxial WS₂/graphene heterostructures

We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS2 and graphene. This heterostructure combines the benefits of a direct-gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS2, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electrons remain in the WS2 layer. The resulting charge-separated transient state is found to have a lifetime of ∼1 ps. We attribute our findings to differences in scattering phase space caused by the relative alignment of WS2 and graphene bands as revealed by high-resolution ARPES. In combination with spin-selective optical excitation, the investigated WS2/graphene heterostructure might provide a platform for efficient optical spin injection into graphene

Direct evidence for efficient ultrafast charge separation in epitaxial WS2_2/graphene heterostructure

We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS$_2$ and graphene. This heterostructure combines the benefits of a direct gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS$_2$, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electrons remain in the WS$_2$ layer. The resulting charge transfer state is found to have a lifetime of $\sim1$\,ps. We attribute our findings to differences in scattering phase space caused by the relative alignment of WS$_2$ and graphene bands as revealed by high resolution ARPES. In combination with spin-selective excitation using circularly polarized light the investigated WS$_2$/graphene heterostructure might provide a new platform for efficient optical spin injection into graphene.Comment: 28 pages, 14 figure

Extreme multiplicity in cylindrical Rayleigh-Benard convection: II. Bifurcation diagram and symmetry classification

A large number of flows with distinctive patterns have been observed in experiments and simulations of Rayleigh-Benard convection in a water-filled cylinder whose radius is twice the height. We have adapted a time-dependent pseudospectral code, first, to carry out Newton's method and branch continuation and, second, to carry out the exponential power method and Arnoldi iteration to calculate leading eigenpairs and determine the stability of the steady states. The resulting bifurcation diagram represents a compromise between the tendency in the bulk towards parallel rolls, and the requirement imposed by the boundary conditions that primary bifurcations be towards states whose azimuthal dependence is trigonometric. The diagram contains 17 branches of stable and unstable steady states. These can be classified geometrically as roll states containing two, three, and four rolls; axisymmetric patterns with one or two tori; three-fold symmetric patterns called mercedes, mitubishi, marigold and cloverleaf; trigonometric patterns called dipole and pizza; and less symmetric patterns called CO and asymmetric three-rolls. The convective branches are connected to the conductive state and to each other by 16 primary and secondary pitchfork bifurcations and turning points. In order to better understand this complicated bifurcation diagram, we have partitioned it according to azimuthal symmetry. We have been able to determine the bifurcation-theoretic origin from the conductive state of all the branches observed at high Rayleigh number

Kinematic dynamo action in a sphere. I. Effects of differential rotation and meridional circulation on solutions with axial dipole symmetry

A sphere containing electrically conducting fluid can generate a magnetic field by dynamo action, provided the flow is sufficiently complicated and vigorous. The dynamo mechanism is thought to sustain magnetic fields in planets and stars. The kinematic dynamo problem tests steady flows for magnetic instability, but rather few dynamos have been found so far because of severe numerical difficulties. Dynamo action might, therefore, be quite unusual, at least for large-scale steady flows. We address this question by testing a two-parameter class of flows for dynamo generation of magnetic fields containing an axial dipole. The class of flows includes two completely different types of known dynamos, one dominated by differential rotation (D) and one with none. We find that 36% of the flows in seven distinct zones in parameter space act as dynamos, while the remaining 64% either fail to generate this type of magnetic field or generate fields that are too small in scale to be resolved by our numerical method. The two previously known dynamo types lie in the same zone, and it is therefore possible to change the flow continuously from one to the other without losing dynamo action. Differential rotation is found to promote large-scale axisymmetric toroidal magnetic fields, while meridional circulation (M) promotes large-scale axisymmetric poloidal fields concentrated at high latitudes near the axis. Magnetic fields resembling that of the Earth are generated by D > 0, corresponding to westward flow at the surface, and M of either sign but not zero. Very few oscillatory solutions are found

Capillary electrophoretic and extraction conditions for the analysis of Catha edulis FORKS active principles

A capillary electrophoretic method, which allowed the detection and separation of the active principles of Catha edulis, i.e. cathinone, cathine and phenylpropanolamine, was developed. A suitable internal standard (nicotinamide), which permitted the quantification of the analytes reducing the variability of the migration times due to EOF changes, was identified. The analytical method was validated, assessing linearity, sensitivity and repeatability, showing optimal features for the analysis of the vegetable material. Moreover extraction conditions were investigated to achieve the exhaustion of the plant material in the fastest and most efficient way to meet the requirements of the Court

Kinematic dynamo action in a sphere: Effects of periodic time-dependent flows on solutions with axial dipole symmetry

Choosing a simple class of flows, with characteristics that may be present in the Earth's core, we study the ability to generate a magnetic field when the flow is permitted to oscillate periodically in time. The flow characteristics are parameterised by D, representing a differential rotation, M, a meridional circulation, and C, a component characterising convective rolls. Dynamo action is sensitive to these flow parameters and fails spectacularly for much of the parameter space where magnetic flux is concentrated into small regions. Oscillations of the flow are introduced by varying the flow parameters in time, defining a closed orbit in the space (D,M). Time-dependence appears to smooth out flux concentrations, often enhancing dynamo action. Dynamo action can be impaired, however, when flux concentrations of opposite signs occur close together as smoothing destroys the flux by cancellation. It is possible to produce geomagnetic-type reversals by making the orbit stray into a region where the steady flows generate oscillatory fields. In this case, however, dynamo action was not found to be enhanced by the time-dependence. A novel approach is taken to solving the time-dependent eigenvalue problem, where by combining Floquet theory with a matrix-free Krylov-subspace method we avoid large memory requirements for storing the matrix required by the standard approach.Comment: 22 pages, 12 figures. Geophys. Astrophys. Fluid Dynam., as accepted (2004

Blood cyanide determination in two cases of fatal imtoxication: comparison between headspace gas chromatography and a spectrophotometric method

Blood samples of two cases were analyzed preliminarily by a classical spectrophotometric method (VIS) and by an automated headspace gas chromatographic method with nitrogen-phosphorus detector (HS-GC \u2044 NPD). In the former, hydrogen cyanide (HCN) was quantitatively determined by measuring the absorbance of chromophores forming as a result of interaction with chloramine T. In the automated HS-GC \u2044NPD method, blood was placed in a headspace vial, internal standard (acetonitrile) and acetic acid were then added. This resulted in cyanide being liberated as HCN. The spectrophotometric (VIS) and HS-GC\u2044NPD methods were validated on postmortem blood samples fortified with potassium cyanide in the ranges 0.5\u201310 and 0.05\u20135 lg \u2044 mL, respectively. Detection limits were 0.2 lg \u2044mL for VIS and 0.05 lg \u2044mL for HS-GC\u2044NPD. This work shows that results obtained by means of the two procedures were insignificantly different and that they compared favorably. They are suitable for rapid diagnosis of cyanide in postmortem cases