Surface studies of aminoferrocene derivatives on gold: electrochemical sensors for chemical warfare agents

The cystamine conjugate [(BocNH)Fc(CO)CSA]2 was prepared by coupling cystamine with the N-protected ferrocene amino acid derivative BocHN-Fc-COOH and was fully characterized by spectroscopic methods and by single-crystal X-ray diffraction. The cystamine conjugate forms films on gold substrates, which upon deprotection of the amino group, react with chemical warfare agent (CWA) mimics, upon which the redox properties of the Fc group are affected significantly. Cyclic voltammetry shows 50(5) mV anodic shifts of the Fc redox potentials after exposure to EtSCH2CH2Cl, a simulant for sulfur mustard HD (MA), and (NC)(EtO)2P(O), a simulant for nerve agent Tabun (NA). Exposure to MA and NA causes an increase in 2.3 and 4.5 ng mass, respectively, in QCM which indicates ca. 70% efficiency in Boc-deprotection. Ellipsometry measured a film thickness increase from 6(+/-1) A for the deprotected film to 10(+/-4) A for the film modified with MA and to 7(+/-2) A for the film modified with NA. AFM measurements show changes in the thickness and morphology of the film after reaction with MA and NA. The surfaces were analyzed by X-ray photoelectron spectroscopy (XPS) and clearly show the attachment of the cystamine conjugate on the surface and its reaction with CWA mimics.     

A new conservation integral for circular arc crack under multiple loads

In this paper, a path independent integral that represents the rate of energy flux at the tip during crack extension in a homogeneous and isotropic material has been derived from the principle of virtual work for a two-dimensional stationary circular arc crack subjected to multiple loads. This integral is an extension of the two-dimensional version of F-integral and includes the presence of the effects of thermal strains, initial strains and body forces, hitherto, unavailable in open literature, to the best of the authors’ knowledge. It has been further demonstrated that Rice’s J-integral, the -integral derived by Kishimoto et al. and the F-integral proposed by Lorentzon et al. are special cases of the generalized integral . The integral has been implemented into a finite element post-processing program for examining the path independence behavior under elastic and elastic-plastic deformation subjected to mechanical loads and thermo-elastic analyses under pure thermal loads. Within the limits of numerical accuracy, the application demonstrates that the solutions for the energy release rate on different contours preserve nearly identical values over the computational range.     

Atmospheric methane: trends and cycles of sources and sinks

For more than 20 years the global emissions and the lifetime of methane have probably been constant, so the buildup of methane in the atmosphere has been slowing down for as long. During this time, there have been periodic events occurring every seven to eight years, when global methane concentrations increased by some 10 ppb and later fell back, in some cases due to temporary increases of emissions from the northern tropics that spread to the global scale. These conclusions are derived from the accumulated global observations that now span 23 years and define the role of human activities in the recent cycle of atmospheric methane.     

RECENT DEVELOPMENTS IN AEROSPACE PROPULSION MATERIALS

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Two novel regions of interstitial deletion on chromosome 8p in colorectal cancer

We have investigated interstitial deletions of chromosome 8 in 70 colorectal carcinomas and 11 colonic adenomas using 11 microsatellite markers, including eight spanning the centromeric region of chromosome 8p (p11.2-p12). Allelic loss or imbalance was observed in 38 (54%) cancers and four (36%) adenomas. Twenty-eight (40%) of the cancers had deletions of 8p11.2-p12. Two distinct and independent regions of interstitial loss were found within this region. Fluorescent in situ hybridization, using an alpha satellite repeat probe to the centromere of 8p and two probes to the P1 region, was performed in four tumours that demonstrated allelic imbalance. Localized heterozygous deletions were confirmed in all four tumours. Eleven (16%) cancers had localized deletion in the region ANK-1 to D8S255 (P1) and a further eleven (16%) cancers had a less well localized deletion in the region defined by the markers D8S87 to D8S259 (P2). Loss of both centromeric loci was identified in a further six (9%) tumours. A functional significance for these two deletion regions was sought by correlation with primary and secondary tumour characteristics. Isolated P2 deletion was associated with 'early' T1 cancers (2p=0.0002), and were also identified in 3/11 adenomas. Conversely, interstitial deletions of the P1 locus were more frequently seen in 'locally invasive' T3/4 cancers (2p=0.015), and isolated P1 deletions were also associated with the presence of liver metastases (2p=0.016). Our data provide evidence of at least two genes within the 8p11.2-p12 region, mutations in which may confer different and independent roles in the pathogenesis of colorectal cancer.     

Chemotactic migration triggers IL-8 generation in neutrophilic leukocytes

Neutrophils recovered from inflammatory exudates possess increased levels of IL-8, but exposure of neutrophils to chemoattractants results in only a modest stimulation of IL-8 generation. This study was undertaken to explore the hypothesis that IL-8 generation in these cells is dependent upon the process of migration. Neutrophils synthesized up to 30 times as much IL-8 during migration in response to a gradient of diverse chemoattractants than they did when stimulated directly by the attractants in the absence of a gradient. This IL-8 response was dependent on migration since it was not observed in cells exposed to concentration gradients of chemoattractants under conditions that prevented cell movement. While actinomycin-D (1 microg/ml) had little influence on the generation of IL-8 during chemotaxis, the protein synthesis inhibitor cycloheximide (10 microg/ml) markedly blunted the accumulation of cell-associated IL-8, suggesting that new protein synthesis from preexisting mRNA was responsible for the effect. Consistent with this interpretation, migrating cells incorporated over 10 times as much [3H]leucine into IL-8 as did nonmotile neutrophils exposed to chemoattractants. A substantial portion of the IL-8 generated during chemotaxis was released upon subsequent metabolic stimulation. Thus, the IL-8 synthesized during chemotaxis is uniquely positioned to exert a regulatory influence on inflammatory processes governed by neutrophilic leukocytes responding to inflammatory and infectious stimuli.     

Factors Influencing Biodegradable Dissolved Organic Carbon Measurement

The inocula requirements and other experimental conditions for the biodegradable dissolved organic carbon (BDOC) procedure have been investigated and optimized to facilitate its use as a routine parameter for characterizing treatment plant performance. Initial inocula of unfiltered secondary effluent, commercial biochemical oxygen demand seed, mixed-liquor suspended solids (MLSS), and incubation temperatures of 20 and 37°C were examined using standard solutions of known DOC, treatment plant effluents, and ozonated treatment plant effluents. Among all inocula tested, MLSS provides the fastest BDOC exertion rate. It is possible to measure BDOC within five days using a larger volume of MLSS inoculum. The results from this research may be used to support the development of a standard BDOC method for water quality assessment.     

The corrosion behavior of TiN coated and uncoated incoloy 800 alloy

Incoloy alloy 800 is used in a variety of applications in industry as well as in domestic appliances for sheeting on electric heating elements. The composition of the alloy enables it to resist deterioration in many corrosive environments. However, resistance of the alloy to corrosion in aqueous media needs to be further examined. The present study examines the corrosion properties of Incoloy 800 alloy of both coated and uncoated workpieces obtained in a 0.1N H₂SO₄ + 0.05N NaCl solution. TiN coating is achieved using a physical vapor deposition (PVD) technique while corrosion tests are carried out using electrochemical polarization methods. Moreover, in order to examine the influence of hydrogen diffusion, reduction of hydrogen at the Incoloy 800 surface is carried out in a solution of 0.1N HNO₃ + 1 g/L thiourea. Tensile tests are conducted on the workpieces to determine the influence of hydrogen embrittlement on the resulting mechanical properties of the substrate. To examine the pit formation and stress induced microcracking, scanning electron microscope (SEM) analysis is carried out. The results show that the corrosion resistance of the alloy improves after TiN coating. In addition, no specific pattern or differentiation on the pit geometry is observed. The pitting rate and its size reduce considerably for TiN coated workpieces.