Sealed Samples Research Articles

In Situ and Time-Resolved SAXS Studies of Pd Nanoparticle Formation in a Template of Block Copolymer Microdomain Structures

Time-resolved small-angle X-ray scattering (SAXS) measurements were performed to study in-situ formation of palladium (Pd) nanoparticles in block copolymer microdomains. The nanoparticles were reduced in a reaction medium containing a fixed composition of polyisoprene-block-poly(2-vinylpyridine) (PI-b-P2VP), palladium acetylacetonate, Pd(acac)2, and benzyl alcohol as a solvent and a reducing agent. The polymer concentration is high enough so that it forms swollen ordered lamellae before reduction. The reduction was induced by a rapid temperature jump, and the polymer concentration was kept constant in a sealed sample cell. It was clearly elucidated that the formation of Pd nanoparticles occurred in the templates of the swollen lamellar microdomains. By fitting the theoretical scattered intensity for spherical particles to the observed SAXS profiles, we analyzed time evolution of mean radius, standard deviation of radius, and total volume of Pd nanoparticles in concentrated PI-b-P2VP solutions after T-jump...

Tissue Distribution of Perfluorinated Chemicals in Harbor Seals (Phoca vitulina) from the Dutch Wadden Sea

Perfluorinated acids (PFAs) are today widely distributed in the environment, even in remote arctic areas. Recently, perfluorooctane sulfonate (PFOS) has been identified in marine mammals all over the world, but information on the compound-specific tissue distribution remains scarce. Furthermore, although longer perfluorinated carboxylic acids (PFCAs) are used in industry and were shown to cause severe toxic effects, still little is known on potential sources or their widespread distribution. In this study, we report for the first time on levels of longer chain PFCAs, together with some short chain PFAs, perfluorobutane sulfonate (PFBS) and perfluorobutanoate (PFBA), in liver, kidney, blubber, muscle, and spleen tissues of harbor seals (Phoca vitulina) from the Dutch Wadden Sea. PFOS was the predominant compound in all seal samples measured (ranging from 89 to 2724 ng/g wet weight); however, large variations between tissues were monitored. Although these are preliminary results, it is, to our knowledge, the first time that PFBS could be found at detectable concentrations (2.3 +/- 0.7 ng/g w wt) in environmental samples. PFBS was only detected in spleen tissue. PFCA levels were much lower than PFOS concentrations. The dominant PFCA in all tissues was PFNA (perfluorononanoic acid), and concentrations generally decreased in tissues for all other PFCA homologues with increasing chain length. No clear relationship between PFOS levels in liver and kidney was observed. Furthermore, hepatic PFDA (perfluorodecanoic acid) levels increased with increasing body length, but in kidney tissue, PFDA levels showed an inverse relationship with increasing body length. These data suggest large differences in tissue distribution and accumulation patterns of perfluorinated compounds in marine organisms.

Biological CO oxidation in the Sargasso Sea and in Vineyard Sound, Massachusetts

In situ dissolved carbon monoxide (CO) in oligotrophic waters follows a diel cycle varying from 0.3 to 0.5 nmol L™1 before dawn to 2.5 to 3 nmol L™1 in early afternoon, when photo-production of CO exceeds biological CO oxidation and other sinks. Coastal waters may contain up to 15 nmol L™1 [CO] in the daytime. Assays to measure the rate of CO bio-oxidation typically involve the addition of labeled CO to sealed samples, resulting in CO concentrations that are above ambient levels during incubation (up to 9 nmol L™1 CO). We find that biological oxidation of CO obeys first-order kinetics when incubated with up to 4 nmol L™1 [CO] in coastal water samples and up to between 4 and 10.8 nmol L™1 in oligotrophic waters. At higher [CO], kinetic behavior transitions to zero-order or saturation kinetics. CO-oxidation rate coefficients obtained in dark incubations were not representative of the entire diurnal period, as others have assumed. Biological CO-oxidation rate coefficients kco measured in dark incubations of Sargasso Sea surface water in summer were 0.020 ± 0.002 h™1 (mean ± standard deviation) and an order of magnitude greater than those measured in situ during daylight hours (0.002 ± 0.001 h™1). Dark and in situ rate coefficients in early spring were 0.006 ± 0.004 h™1 and 0.003 ± 0.001 h™1, respectively. In dark incubations of Vineyard Sound water, kco was 0.127 ± 0.038 h™1. The apparent half-saturation constant Kapp for CO ranged from 2.04 to 5.44 nmol L™1 CO in both environments.

Mössbauer spectroscopic studies of the disintegration of hexavalent iron compounds (BaFeO 4 and K 2FeO 4)

Mössbauer spectroscopic studies of BaFeO 4 and K 2FeO 4 as prepared, then either sealed, or exposed to air, or exposed to moist air for a period up to more than one year, were performed at room temperature as a function of time. Some of the samples were studied as a function of temperature down to 4.2 K. K 2FeO 4 and BaFeO 4 after preparation, exhibit a pure Fe 6+ spectrum. K 2FeO 4 shows low stability. After a period of 14 months in a sealed sample holder, the spectrum exhibits 83% noncrystalline Fe 3+, as Fe 2O 3 nanoparticles, and only 17% of the original Fe 6+. BaFeO 4 sealed, or exposed to dry air disintegrates slowly, exhibiting a spectrum composed of three subspectra. In addition to the original Fe 6+ and final Fe 3+ subspectra, a subspectrum, of an intermediate stage of a crystalline Fe 4+ system, is present. In the first month the increase of the Fe 3+ subspectrum is 15%, and that of the Fe 4+ is 8%. BaFeO 4 exposed to moist air, disintegrates at a very fast rate. The Fe 3+ subspectrum, due to Fe 2O 3 nanoparticles, increases in the first days at the rapid rate of ∼13%/day, and there is no evidence for Fe 4+ in the spectrum. The Fe 6+ in BaFeO 4, Fe 3+ and Fe 4+ in the disintegrated systems are all magnetically ordered at 4.2 K. Above 90 K the Fe 3+ subspectra exhibit a superposition of a paramagnetic doublet and a diffuse magnetic sextet, with relative intensities changing with temperature, and changing from sample to sample according to their blocking temperatures, which are determined by the distribution in size of the nanoparticles.

Analysis of organochlorines in harbor seal (Phoca vitulina) tissue samples from Alaska using gas chromatography/ion trap mass spectrometry by an isotopic dilution technique

A gas chromatography/ion trap mass spectrometry (GC/ITMS) method was developed for the determination of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in harbor seal (Phoca vitulina) tissues. Tissue samples were homogenized, lyophilized and fortified with (13)C-PCBs 28, 123, 169 and 170, and then extracted with an accelerated solvent extractor with a mixture of hexane and methylene chloride (1:1, v/v). After lipid removal using a 40% H(2)SO(4)-modified silica gel column, all organochlorines were collected in one fraction and further fractionated with an activated carbon/silica gel (1:20) column into a first fraction containing OCPs, non-coplanar PCBs and (13)C-PCBs 28, 123 and 170, and a second containing PCNs, coplanar PCBs and (13)C-PCB 169. Prior to GC/MS/MS analysis, (13)C-PCB 169 was added into the first fraction as an injection standard and (13)C-PCB 170 into the second fraction to calibrate the recoveries of the fortified internal standards. This method can effectively eliminate matrix interferences, and has high selectivity and sensitivity. Recoveries averaged 45-86% for OCPs with relative standard deviations (RSDs) of 2-14%, 52-137% for PCBs with RSDs of 3-29% and 36-152% for PCNs with RSDs of 7-29% from lard and chicken heart samples, which were used as alternative matrices to harbor seal samples in recovery studies. The limits of detection for OCPs, PCBs and PCNs were 0.7-1.9, 1.5-8.9 and 0.5-10 pg/g dry weight, respectively. This method can be used to analyze OCPs, PCBs and PCNs in harbor seal blubber, liver and kidney samples.

Automated PrPres amplification using indirect sonication

Prions, which mainly consist of the scrapie isoform of the prion protein (PrP Sc), induce the misfolding of the physiological prion protein (PrP C). The Protein Misfolding Cyclic Amplification (PMCA), a process consisting of sonication and incubation, is one of the few methods thought to model autocatalytic prion replication and generation of proteinase K (PK)-resistant PrP (PrPres) in vitro. Here we show for the first time that the amplification may be achieved through direct as well as indirect sonication (water bath sonication using sealed sample containers), allowing the PMCA method to be automated. The automated method may serve as a valuable tool in high throughput screening for the diagnosis or compound identification for treatment of prion disease. The in vitro amplification process is weakly facilitated by divalent cations such as Mn, Zn and Ni, but not Cu, however, the presence of metal ions decreases the stability of PrPres against proteinase K digestion.

High-temperature DTA studies of A xM F 3 compounds ( [formula omitted], Rb, Cs; [formula omitted], Cr; and [formula omitted

A x VF 3 ( A = K , Rb, Cs; x = 0 – 1.0 ) and A x CrF 3 compounds were sealed inside high-temperature DTA molybdenum sample cups using electron beam welding techniques. Melting temperatures of the A x VF 3 compounds ranged from 1050 to 1400 °C; those of A x CrF 3 from 850 to 1200 °C. Reconstructive transitions were observed for A x VF 3 compounds between 650 and 950 °C, and for A x CrF 3 compounds between 550 and 825 °C. A displacive transition was observed to occur in VF 3 at 490 °C. Order–disorder transitions were determined by X-ray diffraction techniques. In the A x VF 3 compounds, electronic ordering and ordering of partially filled A + sites were observed to occur between 100 and 300 °C. Ordering phenomena in the A x CrF 3 compounds (in addition to electronic ordering and ordering of partially filled A + sites) included Jahn–Teller cooperative ordering. These compounded transitions occurred between 300 and 500 °C.

Synthesis and Characterization of Amorphous Hydrated Alkali Thio‐Hydroxogermanates.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis and Characterization of Amorphous Hydrated Alkali Thio-Hydroxogermanates

The synthesis, structure, and nonhumidified proton conductivity of the hydrated alkali thio-hydroxogermanates, denoted as MxGeSx(OH)4-x·yH2O (1 ≤ x ≤ 4, 0 < y < 8) for M = Na, K, Rb, and Cs, are reported. These materials are generally X-ray amorphous when produced by a low-temperature (∼75 °C) aqueous solution evaporation−precipitation route. Raman and IR spectroscopies indicate mixed chalcogenide germanium central anions with distinct asymmetric Ge−O and symmetric Ge−S stretching modes observable around 820−754 and 500−325 cm-1, respectively. These thio-oxoanions possess a combination of thermally stable hydroxyl groups and hydrophilic alkali associated with the nonbridging sulfurs. Alternating current impendence measurements performed under anhydrous conditions on low-pressure sealed pellets reveal fast ionic conductivity, 10-3−10-2 S/cm, for typical temperatures between 100 and 275 °C. The observed falloff in conductivity at higher temperatures is consistent with the appearance of endothermic transitions in differential scanning calorimetry measurements of hermetically sealed samples, presumably from the “boiling” or sublimation of a crystalline water sublattice. Corresponding onset temperatures were observed between 150 and 275 °C and dependent on the alkali and composition. Under dry atmosphere conditions, thermogravimetric analysis mass loss measurements indicate continuous mass loss above the preparation temperature of ∼75 °C.

Improved Differential Scanning Calorimetric Measurement Method for the Small Reaction Heat Capacities

Abstract Heat capacities of the different rubber states are important features for the engineering calculation of rubber manufacturing. The heat capacity change Δcp due to the vulcanization process has been measured with a differential scanning calorimeter (DSC) only after reducing the standard error of a Δcp measurement under 5 J kg−1 K−1. For this purpose, we used sealed (up to 150 bar) DSC sample pans which avoid mass losses. Heat capacities before and after vulcanization were measured on the same samples using special DSC procedure and reversible thermal effects due to rubber components were corrected. For natural rubber vulcanized with sulfur at t=40…110 °C we found, in J/(kg S)−1 K−1: Δcp=76+11 t, whatever the temperature vulcanization between 100 and 160 °C.

Thermal and optical evolution of gas in vacuum glazing

The mechanisms associated with gas evolution in vacuum glazing have been studied. When sealed samples of vacuum glazing are stored at a high temperature or under sunlight, the pressure within these devices is observed to increase. When the temperature of a thermally stored sample is reduced, the internal pressure is observed to recover, at least partially. In contrast, after removal of an optically exposed sample from the sunlight, the evolved gases remain in the evacuated space causing a permanent pressure increase. Mass spectroscopic analysis has shown that the gases evolved during storage of vacuum glazing at high temperature and under sunlight are, respectively, water vapour and carbon oxides. These results suggest that totally different underlying physical mechanisms are responsible for the two processes. The observed time dependence of pressure in sealed samples of vacuum glazing during optical and thermal studies has been related to the gas evolution that occurs during the evacuation and outgassing stages of the manufacture of the samples. In both cases, the evolution of gas in vacuum glazing can be reduced significantly by outgassing the samples at high temperatures (>350 °C) during manufacture.

Xenon NMR measurements of permeability and tortuosity in reservoir rocks

In this work we present measurements of permeability, effective porosity and tortuosity on a variety of rock samples using NMR/MRI of thermal and laser-polarized gas. Permeability and effective porosity are measured simultaneously using MRI to monitor the inflow of laser-polarized xenon into the rock core. Tortuosity is determined from measurements of the time-dependent diffusion coefficient using thermal xenon in sealed samples. The initial results from a limited number of rocks indicate inverse correlations between tortuosity and both effective porosity and permeability. Further studies to widen the number of types of rocks studied may eventually aid in explaining the poorly understood connection between permeability and tortuosity of rock cores.

Reproductive rates of ringed seals and survival of pups in Northwestern Hudson Bay, Canada, 1991?2000

Reproductive parameters were determined from a sample of ringed seals collected by Inuit hunters during their annual open water harvest in autumn at Arviat, Nunavut, on the western coast of Hudson Bay, Canada, in 1991–1992 and 1998–2000. Ovulation rates of adult females were high and similar to rates recorded from studies of ringed seals in other geographic areas. However, pregnancy rates averaged only 55% and were significantly lower than in other studies, and the proportions of young-of-the-year were only 4.8, 4.2, 7.5, 4.1, and 23% for the mentioned years, respectively, instead of being >30% as expected. These results appear to indicate that reproductive parameters of ringed seals and survival of their young are exhibiting long-term shifts rather than short-term fluctuations, and that the trend is downward. Furthermore, these downward trends in reproduction, in conjunction with changes in the proportions of different seal species in the diet of polar bears, climatic warming in western Hudson Bay, and progressively earlier breakup of sea ice over the last 25 years, suggest that major changes are occurring in the marine ecosystem of Hudson Bay. The pathways involved are poorly understood and merit further study.

Occurrence of Microbial Indicators and Clostridium perfringens in Wastewater, Water Column Samples, Sediments, Drinking Water, and Weddell Seal Feces Collected at McMurdo Station, Antarctica

McMurdo Station, Antarctica, has discharged untreated sewage into McMurdo Sound for decades. Previous studies delineated the impacted area, which included the drinking water intake, by using total coliform and Clostridium perfringens concentrations. The estimation of risk to humans in contact with the impacted and potable waters may be greater than presumed, as these microbial indicators may not be the most appropriate for this environment. To address these concerns, concentrations of these and additional indicators (fecal coliforms, Escherichia coli, enterococci, coliphage, and enteroviruses) in the untreated wastewater, water column, and sediments of the impacted area and drinking water treatment facility and distribution system at McMurdo Station were determined. Fecal samples from Weddell seals in this area were also collected and analyzed for indicators. All drinking water samples were negative for indicators except for a single total coliform-positive sample. Total coliforms were present in water column samples at higher concentrations than other indicators. Fecal coliform and enterococcus concentrations were similar to each other and greater than those of other indicators in sediment samples closer to the discharge site. C. perfringens concentrations were higher in sediments at greater distances from the discharge site. Seal fecal samples contained concentrations of fecal coliforms, E. coli, enterococci, and C. perfringens similar to those found in untreated sewage. All samples were negative for enteroviruses. A wastewater treatment facility at McMurdo Station has started operation, and these data provide a baseline data set for monitoring the recovery of the impacted area. The contribution of seal feces to indicator concentrations in this area should be considered.

Two new sealed sample cells for small angle x-ray scattering from macromolecules in solution and complex fluids using synchrotron radiation

Two different vacuum tight sample cells for in situ temperature dependent small angle scattering from liquids are presented in this article. In the first one, the sample fills a 1 mm thickness gap sealed on both sides by two thin parallel mica windows (volume 300 μl). In the second one, the liquid is injected into a 1 mm cylindrical capillary tube (volume 130 μl). The cells are lodged into temperature controlled chambers directly connected to the beamline vacuum path. Several important improvements with respect to similar instrumentation previously reported are: (1) versatile application of the mica cell, that can be used for all types of samples (gels, liquid crystals, and dispersions in organic solvents) and (2) the design of the chamber for the capillary cell allows registration of wider angle data and a convenient replacement of the capillary tube after each experiment. Signal to background ratio and data reproducibility were tested using protein solutions. We give a brief report of scattering experiments performed with different protein samples and two-dimensional data collection.

A Case Study on Forensic Polymer Analysis by DIOS-MS: The Suspect Who Gave Us the SLIP®

New technology was used to identify traces of a commercial barrier/spermicide in evidence from a case of a man accused of rape of a minor. Examination of vaginal swabs performed by another laboratory had been negative for seminal fluid or other sources of DNA from the suspect and we were asked to examine the remaining swabs for any traces that might have originated from the commercial product. Encare consists of vaginal inserts having a suppository-like shape. They contain the spermicide, nonoxynol-9, in a matrix consisting of approximately two parts polyethylene glycol (PEG) 1000 to one part PEG 1450, plus minor inorganic components added to produce foaming. Portions of the cotton from vaginal swabs from the victim and penile swabs from the suspect were extracted with methanol and subsequently examined by desorption ionization on silicon time-of-flight mass spectrometry (DIOS TOF MS). Low levels of PEG in the same mass range as Encare were found on two separate vaginal swabs from the victim and one penile swab from the suspect. Subsequent to these findings, the suspect (through his attorneys) provided us with a sample of SLIP Plus, a commercial sexual lubricant that also contains nonoxynol-9. Traces of PEG in the same mass range as Encare were found in this sample, while no PEG was found in a sealed sample of SLIP Plus provided by the manufacturer. At trial the suspect's attorneys stipulated that their client had added some Encare to the SLIP Plus sample he had provided.

Surface Characterization and Experimental Design for Testing of a Radial Lip Seal

In radial lip seals, it is generally accepted that sealing occurs through microasperities that form on the surface of the elastomer. It is most often thought that these asperities form during the first few hours of operation due to the stresses and wear in the seal. Thus, the formation of these asperities is highly dependent upon the specific operating conditions of the seal. This article studies the size, shape, and quantity of the asperities that are present on a specific seal design, when run at a certain set of operating conditions. From this analysis it has been determined that the hydrodynamic pumping aids that are present on the seal significantly affect the formation of microasperities. Radial lip seal samples affected by pumping aids had more distinct microasperities, but these asperities are clustered on the edges of the sealing zone, which is not the case for samples unaffected by pumping aids.

Polybrominated diphenyl ethers and organochlorines in archived northern fur seal samples from the Pacific coast of Japan, 1972-1998.

The present study clearly indicated possible prolonged and chronic marine pollution by polybrominated diphenyl ethers (PBDEs) unless the international regulatory measures are reinforced substantially. Fat tissues of female northern fur seals (Callorhinus ursinus), collected at 10 time periods between 1972 and 1998 from the Pacific coast of northern Japan, were analyzed for PBDEs and organochlorine compounds (OCs). PCBs and DDTs were the predominant contaminants in the fur seal samples. PBDEs were detected in all the samples analyzed, the values ranging from 0.33 to 100 ng/g lipid wt. with predominance of BDE-47. The lowest PBDE levels were in the fur seals collected in 1972, with the peak concentration around 1991-1994 and then decreased to about 50% in 1997-1998. Compositions of higher brominated congeners increased since 1972, while some lower brominated congeners decreased, implying a change in the pattern of use, particularly the increased use of highly brominated diphenyl ethers during 1972-1998. In the meantime, PCB compositions in fur seals showed no temporal variation, suggesting a continuous input of PCBs into the marine environment in significant quantities. As peak concentrations of PBDEs occurred later than OCs, it is essential to follow up the patterns of PBDEs pollution that may be of great concern in the future. To our knowledge, this is the first report on the contamination by PBDEs in marine mammals from the Asia-Pacific waters.

Development of a unidirectional cooling technique for synthesizing compound semiconductors in 10 m drop tower

The solidification process and structures of CdTe solidified in microgravity were studied using the unidirectional cooling apparatus in a 10 m drop tower. Since the drop tower provides 1.4 seconds of microgravity, the unidirectional cooling apparatus cools samples rapidly by cooling gas. The system adopts a Pt heater, which accurately heats samples to a maximum of 1300°C. The sample is placed in an ampoule under vacuum conditions. A flat wall in the ampoule divides the inner sealed sample from the outer open side. A nozzle blowing cooling gas is directed on to the outer wall, and cools the sample until solidification. The cooling properties were measured during CdTe solidification in microgravity. The result shows that solidification occurred between 0.9 and 1.3 seconds after release, so solidification is completed in microgravity. Optical microscope (OM) observation of the sample solidified in microgravity revealed that it produces CdTe and Te phases with segregation patterns, and the structures are ordered along the cooling direction, whereas no order is observed in the structures of the terrestrial sample solidified under 1 g.

Determination of residual monomer in polymer latex by full evaporation headspace gas chromatography

This study demonstrated a full evaporation (FE) headspace gas chromatographic technique for the determination of residual monomer in methyl methacrylate (MMA) polymer latex. A very small amount (∼10–30 mg) of latex was added to a sealed headspace sample vial (20 ml). A near-complete monomer mass transfer from both liquid (aqueous phase) and solid phase (polymer particles) to the vapor phase (headspace) is achieved within 5 min at a temperature of 110 °C. The method eliminates sample pretreatment procedures such as the solvent extraction. Thus, it avoids the risk of polymer deposition on the GC system caused by a directly injection of extraction solvent in the conventional GC monomer analysis. The present method is simple, rapid, and accurate.