A coded support for use in analysis of aerosols by different spectroscopic methods

A device used for localization of solid atmospheric microparticles on silicon wafers is described. Dimensions of the device are 5.04 mm × 5.0809 mm. This support facilitates the analysis by other instruments of particles previously located by scanning electron microscopy (SEM). The area of the wafer is divided into tables and cells identified by microlithographic alphanumeric characters. These characters are made of an alloy of aluminium, silicon and copper which can be visualized by imaging secondary-ion mass spectrometry (SIMS). The quality of the image produced by SIMS is worse than that obtained with SEM, mainly because of the bigger diameter of the SIMS ion beam, but the symbols and patterns used are still easily legible. Examples are given of images obtained from SEM, SIMS and secondary electron ion-induced microscopy (SEIIM).     

Molecular self-assembly inhibition leads to basket-shaped cyclophane formation with chiral dynamics

Planar perylene derivatives form macrocyclic dimers and concatenated dimer-dimer rings under the action of molecular self-assembly. If this underpinning principle is true, highly twisted perylene derivatives should be more frustrated toward formation of multimeric cyclic compounds such as macrocyclic dimers and concatenated dimer-dimers because of perturbation resulting from intermolecular pi-pi stacking. Indeed, 1,6,7,12- tetraphenoxy-substituted perylene is highly twisted and undergoes unimolecular cyclization rather than bimolecular or multimolecular cyclization. The resulting monocyclic monomer exhibits interesting conformation switching from one chiral structure (left-handedness) to another chiral structure (right-handedness) at room temperature. NMR studies of conformational dynamics reveal that such configuration change between the two enantiomers can be frozen at low temperature (-45 degrees C). An activation enthalpy barrier of 13.4 +/- 0.5 kcal.mol-1 for twisting the perylene plane in order to convert from one enantiomer to the other has been found.     

Manufacturing Man‐Made Magnetosomes: High‐Throughput In Situ Synthesis of Biomimetic Magnetite Loaded Nanovesicles

A new synthetic method for the production of artificial magnetosomes, i.e., lipid‐coated vesicles containing magnetic nanoparticles, is demonstrated. Magnetosomes have considerable potential in biomedical and other nanotechnological applications but current production methods rely upon magnetotactic bacteria which limits the range of sizes and shapes that can be generated as well as the obtainable yield. Here, electrohydrodynamic atomization is utilized to form nanoscale liposomes of tunable size followed by electroporation to transport iron into the nanoliposome core resulting in magnetite crystallization. Using a combination of electron and fluorescence microscopy, dynamic light scattering, Raman spectroscopy, and magnetic susceptibility measurements, it is shown that single crystals of single‐phase magnetite can be precipitated within each liposome, forming a near‐monodisperse population of magnetic nanoparticles. For the specific conditions used in this study the mean particle size is 58 nm (±8 nm) but the system offers a high degree of flexibility in terms of both the size and composition of the final product.

     

Chemical knockout of pantothenate kinase reveals the metabolic and genetic program responsible for hepatic coenzyme A homeostasis

Coenzyme A (CoA) is the major acyl group carrier in intermediary metabolism. Hopantenate (HoPan), a competitive inhibitor of the pantothenate kinases, was used to chemically antagonize CoA biosynthesis. HoPan dramatically reduced liver CoA and mice developed severe hypoglycemia. Insulin was reduced, glucagon and corticosterone were elevated, and fasting accelerated hypoglycemia. Metabolic profiling revealed a large increase in acylcarnitines, illustrating the role of carnitine in buffering acyl groups to maintain the nonesterified CoASH level. HoPan triggered significant changes in hepatic gene expression that substantially increased the thioesterases, which liberate CoASH from acyl-CoA, and increased pyruvate dehydrogenase kinase 1, which prevents the conversion of CoASH to acetyl-CoA. These results identify the metabolic rearrangements that maintain the CoASH pool which is critical to mitochondrial functions, including gluconeogenesis, fatty acid oxidation, and the tricarboxylic acid and urea cycles.     

Magnetoresistance in granular films formed by CoFe and phase change material

Magnetoresistance having a field and current dependence like that of GMR (but a rather small magnitude) has been observed in Co₇₀Fe₃₀/GeTe and Co₇₀Fe₃₀/Ge₂Sb₂Te₅ granular films. Film stacks were fabricated using tandem (multilayer) deposition and annealing was required for the films to develop the GMR-type response. This GMR-type behavior is distinct from AMR, which is observed before annealing. With films having the structure [CoFe 4 nm/GeTe 6 nm]₁₀, a magnetoresistance (MR) of 0.19 %, which has the GMR-type character can be observed after an optimal annealing temperature of 450 °C. TEM and X-ray reflectometry suggest that columnar granules with layered Fe form during deposition and with annealing. Magnetoresistive transport is believed to be between the discontinuous layers in each columnar grain. These discontinuous layers are observed to be superparamagnetic in SQUID ZFC-FC measurements measured from 5–300 K. Magnetoresistance can be fitted by the quadratic relation appropriate for GMR in granular films, especially at higher GeTe compositions. When Ge₂Sb₂Te₅ is used instead of GeTe, higher anneal temperatures are required before the MR with GMR character appears. This GMR type response does not appear when pure Fe is used instead of the CoFe alloy, with the samples showing only AMR in this case. This is due to the absence of Co which seems to cause a more granular growth.     

A simple proof that third-order quadrupole perturbations of the NMR central transition of half-integral spin nuclei are zero

It has been known for a long time that the third-order quadrupole corrections to transitions from mz=-n/2 to mz=+n/2 are zero in the NMR of half-integer nuclei. However, the derivation has relied on deriving the corrections to the energy levels through somewhat laborious calculations. Only when the transitions between the levels were calculated was it revealed that the corrections to the transition frequency were zero. In this paper, we use Liouville-space methods to work with the transitions directly. Application of a recently published [A.D. Bain, Exact calculation, using angular momentum, of combined Zeeman and quadrupolar interactions in NMR, Mol. Phys. 101 (2003) 3163-3175] selection rule for the quadrupole coupling leads to a very simple proof that third-order corrections to the central and other symmetrical transitions are zero. The simplicity of the proof suggests there is a fundamental symmetry involved.     

TRPM5-expressing microvillous cells in the main olfactory epithelium

Background  

The main olfactory epithelium (MOE) in the nasal cavity detects a variety of air borne molecules that provide information regarding the presence of food, predators and other relevant social and environmental factors. Within the epithelium are ciliated sensory neurons, supporting cells, basal cells and microvillous cells, each of which is distinct in morphology and function. Arguably, the least understood, are the microvillous cells, a population of cells that are small in number and whose function is not known. We previously found that in a mouse strain in which the TRPM5 promoter drives expression of the green fluorescent protein (GFP), a population of ciliated olfactory sensory neurons (OSNs), as well as a population of cells displaying microvilli-like structures is labeled. Here we examined the morphology and immunocytochemical properties of these microvillous-like cells using immunocytochemical methods.     

Nickel(II) and copper(II) complexes of 5-substituted-salicylaldehyde thiosemicarbazones

Binuclear nickel(II) and copper(II) complexes with four 5-methoxysalicylaldehyde N(3)-substituted thiosemicarbazones and nickel(II) complexes of four 5-nitro-salicylaldehyde N(3)-substituted thiosemicarbazones have been prepared and characterized. I.r., electronic, and e.s.r. spectra of the complexes, as well as i.r., electronic, and 1H- and 13C-n.m.r spectra of the thiosemicarbazones, have been obtained. None of these compounds show significant growth inhibitory activity against the fungi Aspergillus niger and Paecilomyces variotii.     

Rates of Mass Transfer and Adsorption of Hexadecyltrimethylammonium Bromide at an Expanding Air-Water Interface

An overflowing cylinder (OFC) provides a convenient method for studying nonequilibrium liquid interfaces under steady-state conditions. In the presence of surfactants in solution, large accelerations in the surface velocity are observed as a result of Marangoni effects. The surface expansion rate is approximately uniform over the surface of the OFC and falls in the range of 1-10 s(-1). In this paper, a quantitative model is presented for the mass transport to the expanding surface of the OFC. The model is then used to analyze experimental measurements of surface expansion rates and surface excess for solutions of a cationic surfactant, hexadecyltrimethylammonium bromide (CTAB), obtained by laser Doppler scattering and neutron reflection, respectively. The experimental results are in satisfactory agreement with the predictions of diffusion-controlled adsorption close to the critical micelle concentration (cmc). At concentrations well above and well below the cmc, kinetic barriers to adsorption appear to exist. The data at low concentrations are discussed in terms of a model for mass transport through the electrical double layer. At high concentrations, double-layer effects are negligible and steric barriers to adsorption are postulated. Copyright 2000 Academic Press.     

Copper(II) complexes of 2-formyl-, 6-methyl-2-formyl- and 2-benzoylpyridine N(4)-(2-methylpyridinyl)-,N(4)-(2-ethylpyridinyl)-and N(4)-methyl(2-ethylpyridinyl)thiosemicarbazones

Summary The title complexes of general formula [Cu(HL)Cl₂] or [Cu(L)Cl] have been isolated and characterized by ¹H and ¹³C-n.m.r., i.r. and electronic spectra. The i.r., electronic and e.s.r. spectral data for the Cu^II complexes are compared with those of previously studied complexes. The antitumour and antiviral activities of the thiosemicarbazones and their complexes are discussed.