Cyclic polyamide oligomers extracted from nylon 66 membrane filter disks as a source of contamination in liquid chromatography/mass spectrometry

Background interferences are perhaps an unavoidable part of analytical detection schemes, particularly when analyzing trace level samples or when using detectors with high levels of sensitivity. In liquid chromatography, mobile phase solvents are routinely filtered using membrane filter disks to trap particulates in hopes of minimizing contamination, providing improvements in data output and instrumental operation. In this study, we report that one such filter disk leads to a significant level of contamination in LC and LC/MS experiments. Extractable compounds from nylon membrane filters generate significant background signals in UV absorption chromatograms at 214 nm, and are also detected by electrospray ionization mass spectrometry, with nominal m/z values of 453 and 679. It is shown that rinsing the nylon membranes before their use can reduce, but will not eliminate, the extractable contaminants from the mobile phase. Through MS and tandem MS analysis, we have identified these contaminants as cyclic oligomers of polyamide 66. Based on these results, it is recommended that nylon membrane filters be avoided when conducting trace level analysis, particularly when conducting LC/MS experiments.     

Determination of ppb concentrations of transition metals by radioisotope-excited energy-dispersive X-ray spectrometry

Using ammonium pyrrolidine dithiocarbamate as precipitant and iron as a carrier, ppb concentrations of the following elements were coprecipitated from fresh water: vanadium, chromium, manganese, nickel, copper, zinc, selenium, mercury, and lead. Precipitates were collected on membrane filters then element concentrations were determined using energy dispersive X-ray fluorescence spectrometry. Calibration curves indicate sensitivities ranging from 0.4 ppb for V, Zn, As and Hg to 1.2 ppb for Pb. It is likely that this method of preconcentration can be directly incorporated into field sampling procedures, thus eliminating the problems of sample contamination or trace element losses by absorption on container walls.     

Neutron activation analysis of ultrapure water in a 500 ml silicon single crystal irradiation flask

Trace element analysis of ultrapure liquids requires the avoidance of contamination not only during preparation but also during irradiation of the sample. Double subboiling distilled water activated within flasks made out of synthetic quartz shows a significant correlation between irradiation time, quality of the flasks and the determined trace element concentration. The resulting falsification of the analysis and limitation of sensitivity seems to be caused by diffusion-like processes during irradiation. Even though single crystal FZ-silicon is rather brittle, it has been possible to fabricate a 500 ml irradiation flask out of this extremely pure material. The flask as well as its application in the analysis of double subboiling distilled water are discussed in the article.     

Einige Aspekte der Instrumentellen Neutronen-Aktivierungsanalyse Biologischer Materialien

The use of low temperature irradiation, lyophilisation and synthetic multielement standards in the INAA of biological samples are described. Changes of trace element concentration during the growth of a tumour and between normal, gastritic and tumourous mucous membrane of the stomach are demonstrated. Trace elements are also determined in histone fractions.      

The long-time reactor irradiation of biological material at reduced temperature

When biological material in closed quartz ampoules is irradiated gaseous reaction products are formed as a result of radiation damage and thermal decomposition. The pressure thus created in the ampoules puts a limit to the time of irradiation or the sample mass and thereby to the detection limit of neutron activation analysis. The investigation will show how the internal pressure of the ampoules is reduced by cooling the sample containers in a nitrogen bath during irradiation so that a number of trace elements also in fresh biological material can be detected by means of neutron activation analysis with long-time irradiation. It will further contain a methodical study of the mechanical strength of quartz ampoules used as sample containers and the change in sample temperature using different sample containers and cooling through different media. The results of two irradiation studies of biological material in the low temperature irradiation unit of the reactor Melusine of the CENG Grenoble will be discussed.     

Sublethal effects of ultraviolet A radiation on Enterobacter cloacae

We report the sublethal effects of ultraviolet A (UVA) on Enterobacter cloacae in comparison with those produced in Escherichia coli. UVA-induced sublethal effects were investigated in either bacterial membrane and at tRNA level. Limited dependence on oxygen concentration for photoinduced inhibition of biochemical membrane functions and low levels of oxidative damage during the irradiation period were found in En. cloacae. On the other hand, ultraviolet spectroscopy and reversed-phase HPLC analysis of hydrolysed tRNA showed that radio induced damage to tRNA is similar in En. cloacae and E. coli. Nevertheless, growth delay induced by UVA in En. cloacae was shorter than that found in E. coli submitted to the same experimental conditions. A limited post-irradiation ppGpp accumulation and the absence of any influence of the membrane damage on the growth delay extent seem to be responsible for the shortness of this effect in En. cloacae. Most of the differences between En. cloacae and E. coli could be attributed to an increased ability of En. cloacae to overcome oxidative stress during UVA exposure.     

Advantages of boron filters in instrumental epithermal neutron activation analysis of biological materials

Boron carbide (B₄C) and boron nitride (BN) irradiation filters have been constructed and used for epithermal neutron activation analysis of biological materials. The major advantage offered by these filters in this application is the substantial reduction of interfering matrix activities. Consequently some trace elements of interest can be determined instrumentally with minimum delay. The filters are particulary beneficial if utilized in short reactor irradiations for rapid analysis of biological materials.     

Gamma ray decomposition of dissolved organic substances in river water without compositional change of metallic elements

A river water sample was irradiated with 60Co gamma-rays under aerobic conditions, and the changes of the organic substances in the sample were examined by the analyses of the dissolved organic carbon (DOC), organic composition, UV spectrum and molecular-weight distribution. By the irradiation, the DOC decreased with irradiation dose following the first-order kinetics. In addition, the changes of UV absorption and molecular-weight distribution showed that the considerable decomposition of polymeric aromatic structure, which is the characteristic of humic substances, took place by irradiation of relatively low dose. Since the gamma-ray decomposition does not require any oxidizing agents and pH control, it will cause no compositional change of metallic elements in the water samples and has less chance of contamination. Therefore the method will be useful in, for example, geochemical studies of trace metals in natural waters.     

Experience with the sources of contamination when preparing samples for the analysis of trace elements

Summary Modern analysis of trace elements has been carried out for many years. The quality of analysis results however still leaves a lot to be desired. Problems arise from contaminations caused by ubiquitous distribution of the trace elements during preparation of the samples. It is shown where in the laboratory sources of contamination are to be found and how they can be avoided. Experience with sample preparation, a decomposition system with low contamination and cleaning methods are described.

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Erfahrung mit Verunreinigungen bei der Probenvorbereitung für die Spurenelementanalyse

     

Neutron activation analysis of snow and ice in Antarctica

In order minimize the possible contamination during storing and pre-treatment of such pure samples as ice and snow collected in Antarctica, trace elements in experimental tools such as bottles, beakers, tubings and filters were determined by neutron activation analysis. By using well certified tools, ice and snow samples from Antarctica and high mountains in China and in Japan were analyzed. Relative concentrations of volatile elements such as Zn, Cd, As, Sb or Ag to Al or Fe which are major components in the earth crust were found to be 10 to 1000 times higher than in the ordinary soil for the samples from Antarctica and Mt. Naimonanyi in China.     

The application of neutron activation analysis to the determination of trace elements in pollen and sporopollenins

Neutron activation analysis has been used to assay the trace elements Co, Fe, Sc, Rb and Zn in pollen and derived sporopollenins. The method is capable of high precision and avoids the necessity for sample ashing and the introduction of reagent contamination. Rubidium was completely removed during the chemical isolation of sporopollenins and the remaining elements which survived chemical treatment were found in reduced amounts. The ratio of Sc: Fe in pollen and in several derived sporopollenins was found to be approximately constant. Results are discussed with reference to the possibilities of anomalous chemical behaviour of the elements resulting from irradiation.     

On the combination of photodynamic therapy with ionizing radiation

Ehrlich ascites carcinoma growth and cell damage have been examined after photodynamic therapy (PDT), radiotherapy (RT) and combined treatment. Haematoporphyrin dimethyl ether (HPde) is used as a photosensitizer for PDT and tested as a radiosensitizer for RT. For PDT a non-coherent light source (370 < lambda < 680 nm) equipped with filters is used. gamma-Irradiation consists of 60Co irradiation at a dose of 2 Gy. Both PDT and RT induce a significant delay and inhibition in tumour growth (33 and 38%, respectively). Nevertheless cell damage after these treatments is different: after PDT the cell membrane integrity is damaged and no serious chromosomal aberrations are observed; whereas after gamma-irradiation there is no cell membrane integrity damage, but more significant DNA injuries are observed. It seems evident that HPde is able to act as a photosensitizer as well as a radiosensitizer. Combining PDT and RT produces an additive effect, not dependent on the sequence in which the two treatments are given, when a 1 h time window is used.     

Photostabilization of butyl methoxydibenzoylmethane (Avobenzone) and ethylhexyl methoxycinnamate by bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), a new UV broadband filter

It is now well documented that chronic UVA exposure induces damage to human skin. Therefore, modern sunscreens should not only provide protection from both UVB and UVA radiation but also maintain this protection during the entire period of exposure to the sun. UVA filters, however, are rare and not sufficiently photostable. We investigated the effect of the introduction of a new UV filter, bis-ethylhexyloxyphenol methoxyphenyl triazine (Tinosorb S), in oil in water sunscreen formulations on the photostability of butyl methoxydibenzoylmethane (Avobenzone [AVB]) after irradiation with an optically filtered Xenon arc source (UV irradiance adjusted at 1 mean effective dose [MED]/min). With spectrophotometrical methods to assess the sun protection factor (SPF) and UVA ratio and chromatographical methods to determine the amount of UV filters recovered after irradiation we showed that Tinosorb S prevented the photodegradation of AVB in a concentration-dependent way, leading to a sustained SPF and UVA ratio even after irradiation with doses of up to 30 MED. Since AVB was shown to destabilize ethylhexyl methoxycinnamate (EHM) we tested the effect of Tinosorb S in sunscreens containing this UV filter combination. Here too Tinosorb S showed photoprotective properties toward both UV filters. Thus, Tinosorb S can be used successfully to improve the photostability and efficiency of sunscreens containing AVB and EHM.     

High-Flux Irradiation of Open Samples

The irradiation of large samples of biological material in a high neutron flux enables the extention of trace element analysis into the ng to pg range, but raises several problems as gamma heating and radiolysis degrade the samples. Gamma heating increases the pressure to a point where either a very large irradiation container is necessary or a container which can endure the high pressure. Several methods to overcome these problems have been published. The irradiation of open samples was performed as an alternative to these methods. Temperature effects on biological material during irradiation in a high and in a low neutron flux were compared. As an example, wheat was irradiated in open containers allowing simultaneous temperature measurement in the sample during irradiation.     

CORTICOSTEROID (METHYLPREDNISOLONE) MODULATION OF PHOTOPEROXIDATION BY ULTRAVIOLET LIGHT IN LIPOSOMES

Abstract— UV irradiation of ovolecithin liposomes produced a dose dependent wave of peroxidation which reached a peak and then fell again coincident with substrate exhaustion. This correlated well with subsequent increases in membrane permeability. There was a progressive loss of unsaturated fatty acids, and when cholesterol was incorporated into liposomes, the UV produced a progressive loss of this steroid.
Methylprednisolone sodium succinate, a synthetic corticosteroid, was found to inhibit this peroxidation in a dose dependent manner, also ameliorating membrane permeability increases when present during irradiation, but not able to compensate for pre-existing damage. When cholesterol was present in the liposomes, methylprednisolone sodium succinate was also able to protect this steroid from UV peroxidative damage.
The rates of reaction in this system suggested that polyunsaturated fatty acids, even when present in extremely small concentrations, underwent an initial rapid wave of peroxidation, which served to initiate the slower rate of lipoperoxidation within the bulk of mono- and di-"unsaturates". At low concentrations, the corticosteroid preferentially blocked damage to mono- and di-unsaturated fatty acids, affecting the polyunsaturated fatty acids as well, at higher concentrations.
This study suggests that the corticosteroid, methylprednisolone sodium succinate, possesses antioxidant properties in lipid systems subjected to free radical peroxidation.     

Titanium nitride as a coating for surgical instruments used to collect human tissue for trace metal analysis

When metallic surgical instruments are used to collect human tissue, metal contamination may occur, making accurate ultra-trace metal determinations very difficult. In order to reduce this risk as much as possible, surgical instruments made from a stainless-steel core covered by a film of titanium nitride, a very hard compound with high chemical stability and very good wear resistance, were prepared. The degree of risk from trace metal contamination during sample collection was investigated by neutron activation analysis and a radio-release in vitro serum test. As examples of their application, the titanium nitride coated instruments were used to determine Co, Cr and W in the skin of unexposed subjects and of uraemic patients under regular dialysis treatment.     

Instrumental neutron activation analysis of silicon wafers using the silicon matrix as the comparator

For the instrumental neutron activation analysis of trace impurities in high purity silicon wafer, a modified single comparator method has been applied. The energy distribution of the neutrons at the irradiation position was measured using the two flux monitors, Au and Co, and elemental contents were calculated using the silicon matrix in the wafer as a comparator. This has advantage of reducing the cross contamination from an external monitor during sample preparation and irradiation, the uncertainties from the non-homogeneity of the neutron flux and the error on the weight of comparators. Determination limits for 49 elements were presented under the condition of 72 hours irradiation at a neutron flux of 3.7·10¹³ n·cm^-2·s^-1 and 4000 s measurement. The analytical results obtained by this method and the conventional single comparator method were compared and were found to agree well within 5%.     

A review of contamination-resistant antireflective sol–gel coatings

Sol–gel derived silica antireflective (AR) coatings have been widely used as the optical components for high peak power laser systems because of their excellent optical properties and high laser-induced damage thresholds. However, the sol–gel derived coatings have a high surface area that is more susceptible to be contaminated by absorption of trace amounts of water vapor and other volatile organic compounds from the environment. In this paper, the major approaches to fabricate contamination resistant sol–gel derived silica AR coatings have been extensively reviewed. Different approaches, including solution-phase and vapor-phase silanization, ammonia–water vapor treatment and fluorine modification have been discussed. The optical properties and laser-induced damage thresholds of modified coatings have also been evaluated. The improved sol–gel AR coatings have been shown to possess superior contamination resistance to work in vacuum systems compare to the traditional sol–gel AR coatings.     

Effects of Irradiation on the Structure-activity Relationship of Konjac Glucomannan Molecular Chain Membrane

To know the effects of irradiation on the konjac glucomannan (KGM) molecular chain membrane, KGM membrane solution was treated with the irradiation dose of 0-20 kGy in this study, and the structure and properties of KGM membrane were analyzed with Infrared spectrum, Raman spectrum, X-ray, SEM scanning and so on. The results revealed that the effects of different irradiation doses on the KGM molecular chain structure were different. Higher irradiation dose (20 kGy) resulted in partial damage against KGM membrane crystal structure, and there was no obvious change for the amorphous structure; with membrane property test, the tensile strength of KGM membrane gradually increased with the increase of irradiation dose and its elongation at break reduced, but these changes were not significant, WVP value reduced; with SEM, the membrane surface treated with irradiation was smoother even than the membrane without treatment. In addition, when increasing the irradiation dose, membrane surface became more even, and arrangement was more orderly and compact. Irradiation modification could effectively improve the KGM membrane properties, and it is an ideal modification method.     

Photodecarbonylation of 1,3-dithiophenyl propanone: using nanocrystals to overcome the filtering effect of highly absorbing trace impurities

Irradiation of crystalline 2,4-dimethyl-2,4-di(thiophen-3-yl)pentan-3-one (1) resulted in photodecarbonylation and radical combination to give 2 with >99% selectivity. However, extended irradiation led to no more than ca. 8% conversion due to highly absorbing unidentified trace impurities that act as filters. We report here a simple procedure to improve the reaction efficiency by taking advantage of nanocrystalline suspensions prepared by the reprecipitation method, which leads to shorter reaction times and quantitative yields.