Decomposition odour analysis involves the chemical profiling of volatile organic compounds produced by decomposing remains. This is important for areas of forensic science that rely on the detection of decomposition odour such as insect attraction to carrion, positive alerts of cadaver dogs to decomposing remains, and the development of field instrumentation for search and recovery procedures. Traditionally decomposition odour analysis has been performed using gas chromatography–quadrupole mass spectrometry (GC–qMS); however, the use of comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC×GC–TOFMS) is rapidly becoming more prevalent. The objective of this study was to compare GC–qMS and GC×GC–TOFMS for decomposition odour profiling based on inter-year replicate field studies using decomposing porcine remains. The increased peak capacity, sensitivity and selectivity afforded by GC×GC–TOFMS allowed peak co-elutions, chromatographic artefacts, and dynamic range to be more easily addressed and managed. Furthermore, the software associated with GC×GC–TOFMS provided several additional benefits including improved peak alignment between samples and increased consistency of reported results, overall allowing for additional statistical tests to be applied following data processing. Future GC–qMS results could be improved by implementing some of these software-associated procedures, potentially reducing the magnitude of variation observed between GC–qMS and GC×GC–TOFMS studies. One-dimensional GC analysis may also benefit substantially from coupling with TOFMS detection to provide an indirect increase in peak capacity using deconvolution. However, the wealth of information gained by using GC×GC–TOFMS in decomposition odour profiling is undoubtedly an asset in this field of research.
Lithium is used in the treatment and prophylaxis of manic-depressive illness. A narrow therapeutic range of lithium (0.4-1.2 meq/l) requires constant monitoring of these levels to avoid neurotoxicity and overdose. It is general practice to measure plasma lithium levels as a guide to monitor the therapy. Efforts to predict the concentration of Li at its active sites in the brain have led to the use of red blood cells (RBCs) because they are similar to neuronal cells. Thus RBC lithium is a very relevant clinical parameter for monitoring therapy and to observe the changes at intracellular levels under varying treatment conditions. A measure of both plasma and RBC lithium may be of significant value to physicians and researchers as lithium profile for RBCs correlate more closely with the brain lithium than plasma lithium. Although methods to measure lithium in blood such as atomic absorption or flame photometry exist, a complete quantitation of both plasma and RBC lithium requires a tedious physical separation of the two components prior to chemical analysis. On the other hand, lithium MR technique, via the use of shift reagents, can provide both plasma and RBC lithium in a single study. Here we have performed a correlation study of lithium results obtained from MR with the vitros dry-slide method on blood samples from rats treated with lithium. The results show a high degree of correlation between the two methods. Additionally, the MR measurements made on dilute samples of blood indicate that small blood samples with lithium concentration in the neighborhood of 0.08 meq/l can be measured with high accuracy and reproducibility needed for clinical purposes. 相似文献
The synthesis, structure, and magnetic properties of a ligand-modified Mn(4) dicubane single-molecule magnet (SMM), [Mn(4)(Bet)(4)(mdea)(2)(mdeaH)(2)](BPh(4))(4), are presented, where the cationic SMM units are significantly separated from neighboring molecules in the crystal lattice. There are no cocrystallized solvate molecules, making it an ideal candidate for single-crystal magnetization hysteresis and high-frequency electron paramagnetic resonance studies. Increased control over intermolecular interactions in such materials is a crucial factor in the future application of SMMs. 相似文献
Magnetically dilute samples of complexes Dy(H(2)BPz(Me2)(2))(3) (1) and U(H(2)BPz(2))(3) (3) were prepared through cocrystallization with diamagnetic Y(H(2)BPz(Me2)(2))(3) (2) and Y(H(2)BPz(2))(3). Alternating current (ac) susceptibility measurements performed on these samples reveal magnetic relaxation behavior drastically different from their concentrated counterparts. For concentrated 1, slow magnetic relaxation is not observed under zero or applied dc fields of several hundred Oersteds. However, a 1:65 (Dy:Y) molar dilution results in a nonzero out-of-phase component to the magnetic susceptibility under zero applied dc field, characteristic of a single-molecule magnet. The highest dilution of 3 (1:90, U:Y) yields a relaxation barrier U(eff) = 16 cm(-1), double that of the concentrated sample. These combined results highlight the impact of intermolecular interactions in mononuclear single-molecule magnets possessing a highly anisotropic metal center. Finally, dilution elucidates the previously observed secondary relaxation process for concentrated 3. This process is slowed down drastically upon a 1:1 molar dilution, leading to butterfly magnetic hysteresis at temperatures as high as 3 K. The disappearance of this process for higher dilutions reveals it to be relaxation dictated by short-range intermolecular interactions, and it stands as the first direct example of an intermolecular relaxation process competing with single-molecule-based slow magnetic relaxation. 相似文献
The ligands KS(2)CN(Bz)CH(2)CH(2)N(Bz)CS(2)K (K(2)L(1)), N(CH(2)CH(2)N(Me)CS(2)Na)(3) (Na(3)L(2)), and the new chelates {(CH(2)CH(2))NCS(2)Na}(3) (Na(3)L(3)) and {CH(2)CH(2)N(CS(2)Na)CH(2)CH(2)CH(2)NCS(2)Na}(2) (Na(4)L(4)), react with the gold(I) complexes [ClAu(PR(3))] (R = Me, Ph, Cy) and [ClAu(IDip)] to yield di-, tri-and tetragold compounds. Larger metal units can also be coordinated by the longer, flexible linker, K(2)L(1). Thus two equivalents of cis-[PtCl(2)(PEt(3))(2)] react with K(2)L(1) in the presence of NH(4)PF(6) to yield the bimetallic complex [L(1){Pt(PEt(3))(2)}(2)](PF(6))(2). The compounds [NiCl(2)(dppp)] and [MCl(2)(dppf)] (M = Ni, Pd, Pt; dppp = 1,3-bis(diphenylphosphino)propane, dppf = 1,1'-bis(diphenylphosphino)ferrocene) also yield the dications, [L(1){Ni(dppp)}(2)](2+) and [L(1){Ni(dppf)}(2)](2+) in an analogous fashion. In the same manner, reaction between [(L'(2))(AuCl)(2)] (L'(2) = dppm, dppf; dppm = bis(diphenylphosphino)methane) and KS(2)CN(Bz)CH(2)CH(2)N(Bz)CS(2)K yield [L(1){Au(2)(L'(2))}(2)]. The molecular structures of [L(1){M(dppf)}(2)](PF(6))(2) (M = Ni, Pd) and [L(1){Au(PR(3))}(2)] (R = Me, Ph) are reported. 相似文献
Neutron reflectivity (NR) measurements of ultrathin surface films (below 30 nm) composed of Bombyx mori silk fibroin protein in combination with atomic force microscopy and ellipsometry were used to reveal the internal structural organization in both dry and swollen states. Reconstituted aqueous silk solution deposited on a silicon substrate using the spin-assisted layer-by-layer (SA-LbL) technique resulted in a monolayer silk film composed of random nanofibrils with constant scattering length density (SLD). However, a vertically segregated ordering with two different regions has been observed in dry, thicker, seven-layer SA-LbL silk films. The vertical segregation of silk multilayer films indicates the presence of a different secondary structure of silk in direct contact with the silicon oxide surface (first 6 nm). The layered structure can be attributed to interfacial β-sheet crystallization and the formation of well-developed nanofibrillar nanoporous morphology for the initially deposited silk surface layers with the preservation of less dense, random coil secondary structure for the layers that follow. This segregated structure of solid silk films defines their complex nonuniform behavior in the D(2)O environment with thicker silk films undergoing delamination during swelling. For a silk monolayer with an initial thickness of 6 nm, we observed the increase in the effective thickness by 60% combined with surprising decrease in density. Considering the nanoporous morphology of the hydrophobic silk layer, we suggested that the apparent increase in its thickness in liquid environment is caused by the air nanobubble trapping phenomenon at the liquid-solid interface. 相似文献
An integrated suite of synthesis and characterisation techniques that includes synchrotron-based single crystal, powder X-ray diffraction, nuclear magnetic resonance and electron diffraction have been employed to uncover two new distinct structures in the Ca(x)Ba(2-x)P(2)O(7) polymorphic phosphate system. These materials have particular relevance for their application as both biomaterials and phosphors. Calcium barium pyrophosphate, CaBaP(2)O(7), was shown by a combination of spectroscopic and diffraction techniques to have two polymorphs distinct in structure from all of the five previously reported polymorphs of Ca, Sr and Ba pyrophosphate. A high temperature polymorph HT-CaBaP(2)O(7) prepared at 1200 °C is orthorhombic, of space group P(212121) with a = 13.0494 ?, b = 8.9677 ?, c = 5.5444 ?. A low temperature polymorph LT-CaBaP(2)O(7), prepared below 1000 °C, is monoclinic with space group P2(1)/c and dimensions a = 12.065 ?, b = 10.582 ?, c = 9.515 ?, β = 94.609°. 相似文献
Research on informal statistical inference has so far paid little attention to the development of students?? expressions of uncertainty in reasoning from samples. This paper studies students?? articulations of uncertainty when engaged in informal inferential reasoning. Using data from a design experiment in Israeli Grade 5 (aged 10?C11) inquiry-based classrooms, we focus on two groups of students working with TinkerPlots on investigations with growing sample size. From our analysis, it appears that this design, especially prediction tasks, helped in promoting the students?? probabilistic language. Initially, the students oscillated between certainty-only (deterministic) and uncertainty-only (relativistic) statements. As they engaged further in their inquiries, they came to talk in more sophisticated ways with increasing awareness of what is at stake, using what can be seen as buds of probabilistic language. Attending to students?? emerging articulations of uncertainty in making judgments about patterns and trends in data may provide an opportunity to develop more sophisticated understandings of statistical inference. 相似文献
The ability to locate and quantify elemental distributions in plants is crucial to understanding plant metabolisms, the mechanisms
of uptake and transport of minerals and how plants cope with toxic elements or elemental deficiencies. High-resolution secondary
ion mass spectrometry (SIMS) is emerging as an important technique for the analysis of biological material at the subcellular
scale. This article reviews recent work using the CAMECA NanoSIMS to determine elemental distributions in plants. The NanoSIMS
is able to map elemental distributions at high resolution, down to 50 nm, and can detect very low concentrations (milligrams
per kilogram) for some elements. It is also capable of mapping almost all elements in the periodic table (from hydrogen to
uranium) and can distinguish between stable isotopes, which allows the design of tracer experiments. In this review, particular
focus is placed upon studying the same or similar specimens with both the NanoSIMS and a wide range of complementary techniques,
showing how the advantages of each technique can be combined to provide a fuller data set to address complex scientific questions.
Techniques covered include optical microscopy, synchrotron techniques, including X-ray fluorescence and X-ray absorption spectroscopy,
transmission electron microscopy, electron probe microanalysis, particle-induced X-ray emission and inductively coupled plasma
mass spectrometry. Some of the challenges associated with sample preparation of plant material for SIMS analysis, the artefacts
and limitations of the technique and future trends are also discussed. 相似文献