The effects of nitrogen mustard on plasma membrane function

The antitumour bifunctional alkylating agent nitrogen mustard (HN2) inhibited the unidirectional influx of the potassium congener, 86 rubidium, into murine PC6A plasmacytoma cells and L1210 leukaemia cells. The proliferation of L1210 cells in vitro was characterised and shown to be sentitive to HN2. 86Rubidium influx into cells from rapidly-dividing cultures was more sensitive to inhibition by HN2 than that of cells from stationary cultures. Three components of unidirectional 86Rb+ & K+ influx into proliferating L1210 cells were identified pharmacologically: approximately 40% was active to the Na+ K+ ATPase inhibitor ouabain (10-3M), 40% was sensitive to the `loop' diuretics bumetanide (10-4M) and furosemide (10-3M) and the remainder was insensitive to both ouabain and furosemide. HN2 (10-5M) selectively inhibited the diuretic-sensitive component, which was entirely dependent upon extracellular Na+ and Cl- ions, and was presumed to represent Na+ K+ Cl- cotransport activity. The system did not mediate K+ /K+ exchange or unidirectional 86Rb+ efflux; accordingly, 86Rb+ efflux was insensitive to HN2. Inhibition of 86Rb & K+ influx by 10-5M HN2 was accompanied by approximately 35% of cell volume under isosmotic conditions; thus intracellular Na+ and K+ concentrations remained unchanged. These effects followed lethal damage to the cells but preceded actual cell death; other cellular functions were maintained including accumulation of cycloleucine, transmembrane potential, permeability to trypan blue, intracellular pH, total intracellular glutathione and calcium concentrations. No evidence was found that elevated cAMP levels or reduced ATP levels were involved in modulation of 86Rb+ & K+ influx. However, the Na+ - depedent transport of an amino acid was inhibited in a manner which appeared to be independent of 86Rb & K+ influx. An HN2-resistant L1210R cell line was also resistant to furosemide, and lacked a component of 86Rb+ & K+ influx which was sensitive to furosemide (10-3M). The results strongly suggest that the Na+ K+ Cl- costransporter of L1210 cells is a cellular target for HN2. This lesion is discussed with reference to the cytotoxic effects of the agent.

A study in the reduction of efficiency of nitrogen oxide removal catalysts for automobiles

Automotive catalysts are the most effective short-term answer to air pollution from automobiles. Since strict control of exhaust emissions is, or will be,covered by legislation in most developed countries in the world, catalytic devices will be increasingly fitted to cars. There is consequently an urgent need for the development of catalysts that will not compete for scarce precious metal resources. A number of problems have already been identified in connection with base metal catalysts but quantitative investigations are lacking. The base metal reduction catalysts developed by Imperial Chemical Industries Limited, catalysts and Chemical Group, in collaboration with the Air Pollution Control Laboratory, B L Cars Limited for automotive emission control, are susceptible to de-activation by three major mechanisms. These are: physical loss of the wash-coat (a high surface area coating which supports the active species), aggregation of the active species and poisoning by fuel and engine oil additives. This thesis is especially concerned with the first two of these and attempts to indicate the relative magnitude .of their effect on the activity of. the catalysts. Aggregation of the active species or sintering, as it is loosely called, was studied by using impregnated granules to overcome effects due to the loss of the wash-coat. Samples were aged in a synthetic exhaust gas, free from poisons, and metal crystallite sizes were measured by scanning-electron microscopy. The increase in particle size was correlated with the loss in catalytic activity. In order to maintain a link with the real conditions of service a number of monolithic catalysts were tested in an engine-dynamometer and several previously tested endurance catalysts were examined. A mechanism is proposed for the break-up and subsequent 10s.5 of the wash-coat and suggestions for improved resistance to loss of the' coating and active species are proposed.

Large scale fabrication of nitrogen vacancy-embedded diamond nanostructures for single-photon source applications

Some color centers in diamond can serve as quantum bits which can be manipulated with microwave pulses and read out with laser, even at room temperature. However, the photon collection efficiency of bulk diamond is greatly reduced by refraction at the diamond/air interface. To address this issue, we fabricated arrays of diamond nanostructures, differing in both diameter and top end shape, with HSQ and Cr as the etching mask materials, aiming toward large scale fabrication of single-photon sources with enhanced collection efficiency made of nitrogen vacancy (NV) embedded diamond. With a mixture of O2 and CHF3 gas plasma, diamond pillars with diameters down to 45 nm were obtained. The top end shape evolution has been represented with a simple model. The tests of size dependent single-photon properties confirmed an improved single-photon collection efficiency enhancement, larger than tenfold, and a mild decrease of decoherence time with decreasing pillar diameter was observed as expected. These results provide useful information for future applications of nanostructured diamond as a single-photon source.

Nitrogen implantation of tool steels and engineering coatings

Ion implantation modifies the surface composition and properties of materials by bombardment with high energy ions. The low temperature of the process ensures the avoidance of distortion and degradation of the surface or bulk mechanical properties of components. In the present work nitrogen ion implantation at 90 keV and doses above 1017 ions/cm2 has been carried out on AISI M2, D2 and 420 steels and engineering coatings such as hard chromium, electroless Ni-P and a brush plated Co-W alloy. Evaluation of wear and frictional properties of these materials was performed with a lubricated Falex wear test at high loads up to 900 N and a dry pin-on-disc apparatus at loads up to 40 N. It was found that nitrogen implantation reduced the wear of AISI 420 stainless steel by a factor of 2.5 under high load lubricated conditions and by a factor of 5.5 in low load dry testing. Lower but significant reductions in wear were achieved for AISI M2 and D2 steels. Wear resistance of coating materials was improved by up to 4 times in lubricated wear of hard Cr coatings implanted at the optimum dose but lower improvements were obtained for the Co-W alloy coating. However, hardened electroless Ni-P coatings showed no enhancement in wear properties. The benefits obtained in wear behaviour for the above materials were generally accompanied by a significant decrease in the running-in friction. Nitrogen implantation hardened the surface of steels and Cr and Co-W coatings. An ultra-microhardness technique showed that the true hardness of implanted layers was greater than the values obtained by conventional micro-hardness methods, which often result in penetration below the implanted depth. Scanning electron microscopy revealed that implantation reduced the ploughing effect during wear and a change in wear mechanism from an abrasive-adhesive type to a mild oxidative mode was evident. Retention of nitrogen after implantation was studied by Nuclear Reaction Analysis and Auger Electron Spectroscopy. It was shown that maximum nitrogen retention occurs in hard Cr coatings and AISI 420 stainless steel, which explains the improvements obtained in wear resistance and hardness. X-ray photoelectron spectroscopy on these materials revealed that nitrogen is almost entirely bound to Cr, forming chromium nitrides. It was concluded that nitrogen implantation at 90 keV and doses above 3x1017 ions/cm2 produced the most significant improvements in mechanical properties in materials containing nitride formers by precipitation strengthening, improving the load bearing capacity of the surface and changing the wear mechanism from adhesive-abrasive to oxidative.

The effects of ionising radiation on polypropylene

The interaction of ionising radiation with polymers is described and the literature relating; to the effects on polypropylene is reviewed. Oxidative and free radical reactions are discussed with particular reference to post-irradiationeffects.Isotactic and atactic polypropylene were δ and electron irradiated to doses of up to 20 megarad. Irradiations weremainly made in air. A series of other polymers were also irradiated in a preliminary survey. Molar mass measurements are used to measure the radiationyield for chain scission G (s). Irradiation at room temperature causes significantly more chain scission than at 195K. Additional chain scission occurs on storage following irradiation at 195 K. Free radical concentrations are determined by electron spin resonance, and the decay rates measured. The radical formed in air is a peroxy radical and in vacuo is a hydrocarbon radical. At77K in vacuo the radical is -CH2 - C* (CH3) - CH2 - but additional radicals are produced on warning to room temperature. The effects of increasing tenparature on radicals formed in air are described. Electron spin resonance studies on atactic polypropylene,and isotactic polypropylene in hydrogen, sulphur dioxide and nitric oxide are reported.. The melting temperatures, spherulite growth rates, and isothermal crystallisation rates of irradiated polypropylene are compared to those of the non-irradiated polymer. Crystallisation is found to proceed with an Avrami integer n = 2. At a given crystallisation temperature, the overall crystallisation rate of irradiated polymer is less than the non-irradiated, but spherulite growth rates are identical. Thermogravimetric analysis is used to assess the thermal stability of irradiated polypropylene in nitrogen, air and oxygen. Hydroperoxide analysis is used to show that several molecules of oxygen are absorbed for each initial radical, and that hydroperoxides continue to be formed for a long period following irradiation. Possible solutions for minimising irradiation and post-irradiation degradation are suggested, together with some problems for further study.

High rate growth of nanocrystalline diamond films using high microwave power and pure nitrogen/methane/hydrogen plasma

In this work, we investigate the impact of minute amounts of pure nitrogen addition into conventional methane/hydrogen mixtures on the growth characteristics of nanocrystalline diamond (NCD) films by microwave plasma assisted chemical vapour deposition (MPCVD), under high power conditions. The NCD films were produced from a gas mixture of 4% CH4/H2 with two different concentrations of N2 additive and microwave power ranging from 3.0 kW to 4.0 kW, while keeping all the other operating parameters constant. The morphology, grain size, microstructure and texture of the resulting NCD films were characterized by using scanning electron microscope (SEM), micro-Raman spectroscopy and X-ray diffraction (XRD) techniques. N2 addition was found to be the main parameter responsible for the formation and for the key change in the growth characteristics of NCD films under the employed conditions. Growth rates ranging from 5.4 μm/h up to 9.6 μm/h were achieved for the NCD films, much higher than those usually reported in the literature. The enhancing factor of nitrogen addition on NCD growth rate was obtained by comparing with the growth rate of large-grained microcrystalline diamond films grown without nitrogen and discussed by comparing with that of single crystal diamond through theoretical work in the literature. This achievement on NCD growth rate makes the technology interesting for industrial applications where fast coating of large substrates is highly desirable.

Impact of high microwave power on hydrogen impurity trapping in nanocrystalline diamond films grown with simultaneous nitrogen and oxygen addition into methane/hydrogen plasma

In this work, we study for the first time the influence of microwave power higher than 2.0 kW on bonded hydrogen impurity incorporation (form and content) in nanocrystalline diamond (NCD) films grown in a 5 kW MPCVD reactor. The NCD samples of different thickness ranging from 25 to 205 μm were obtained through a small amount of simultaneous nitrogen and oxygen addition into conventional about 4% methane in hydrogen reactants by keeping the other operating parameters in the same range as that typically used for the growth of large-grained polycrystalline diamond films. Specific hydrogen point defect in the NCD films is analyzed by using Fourier-transform infrared (FTIR) spectroscopy. When the other operating parameters are kept constant (mainly the input gases), with increasing of microwave power from 2.0 to 3.2 kW (the pressure was increased slightly in order to stabilize the plasma ball of the same size), which simultaneously resulting in the rise of substrate temperature more than 100 °C, the growth rate of the NCD films increases one order of magnitude from 0.3 to 3.0 μm/h, while the content of hydrogen impurity trapped in the NCD films during the growth process decreases with power. It has also been found that a new H related infrared absorption peak appears at 2834 cm-1 in the NCD films grown with a small amount of nitrogen and oxygen addition at power higher than 2.0 kW and increases with power higher than 3.0 kW. According to these new experimental results, the role of high microwave power on diamond growth and hydrogen impurity incorporation is discussed based on the standard growth mechanism of CVD diamonds using CH4/H2 gas mixtures. Our current experimental findings shed light into the incorporation mechanism of hydrogen impurity in NCD films grown with a small amount of nitrogen and oxygen addition into methane/hydrogen plasma.