X-ray irradiation

Crystallinity has been studied by x-ray irradiation (85). An initial increase caused by chain scission in the amorphous phase was followed (above 3 kGy or 3 X 10 rad) by a gradual decrease associated with a disordering of the crystallites. The amorphous component showed a maximum of radiation-induced broadening in the nmr at 7 kGy (7 x 10 rad). 

A typical absorption curve for vitreous siUca containing metallic impurities after x-ray irradiation is shown in Eigure 12. As shown, the primary absorption centers are at 550, 300, and between 220 and 215 nm. The 550-nm band results from a center consisting of an interstitial alkah cation associated with a network substituent of lower valency than siUcon, eg, aluminum (205). Only alkaUes contribute to the coloration at 550 nm. Lithium is more effective than sodium, and sodium more effective than potassium. Pure siUca doped with aluminum alone shows virtually no coloration after irradiation. The intensity of the band is deterrnined by the component that is present in lower concentration. The presence of hydrogen does not appear to contribute to the 550-nm color-center production (209). 

The 215-nm band may be intrinsic to sihca. This band can be produced in Coming Code 7940 glass by long-term x-ray irradiation (210). This band is attributed to an E center, which may also be observed in irradiated a-quart2. Stmcturahy, the E center is assumed to be a pyramidal SiO unit having an unpaired electron in the dangling orbital of Si (207). 

Dactinomycin is useful against several tumors especially Wilms tumor of the kidney and rhabdomyosarcoma. Wilms tumor normally requires a combination of surgery, x-ray irradiation, and dactinomycin plus vincristine [57-22-7] or other antitumor agents. Resistance of the multidmg... 

Carbon monoxide also reacts with olefins such as ethylene to produce high molecular weight polymers. The reaction of CO with ethylene can be initiated by an x-ray irradiator (62) or transition-metal cataly2ed reactions (63). The copolymeri2ation of ethylene with carbon monoxide is cataly2ed by cationic Pd (II) complexes such as Pd[P(CgH )2] (CH CN) (BF 2 where n = 1-3. With this catalyst, copolymeri2ation can be carried out at 25°C and pressures as low as 2.1 MPa. 

Degradation of carbon tetrachloride by photochemical, x-ray, or ultrasonic energy produces the trichloromethyl free radical which on dimeri2ation gives hexachloroethane. Chloroform under strong x-ray irradiation also gives the trichloromethyl radical intermediate and hexachloroethane as final product. 

Apart from the application of XPS in catalysis, the study of corrosion mechanisms and corrosion products is a major area of application. Special attention must be devoted to artifacts arising from X-ray irradiation. For example, reduction of metal oxides (e. g. CuO -> CU2O) can occur, loosely bound water or hydrates can be desorbed in the spectrometer vacuum, and hydroxides can decompose. Thorough investigations are supported by other surface-analytical and/or microscopic techniques, e.g. AFM, which is becoming increasingly important. 

Reflectometry is a useful probe with which to investigate the structure of multilayers both in self-supporting films and adsorbed on surfaces [51]. Specular X-ray reflectivity probes the electron density contrast perpendicular to the film. The X-rays irradiate the substrate at a small angle (<5 °) to the plane of the sample, are reflected, and are detected at an equal angle. If a thin film is present on the surface... 

X-ray intensity, see Intensity X-ray irradiance, definition, 6 X-ray methods of analysis, comparative, statistics, 254-256, 280 use of Coolidge tubes in, 6 X-ray Microscope, General Electric, 291-296... 

In a more general application, thermoluminescence is used to study mechanisms of defect annealing in crystals. Electron holes and traps, crystal defects, and color-centers are generated in crystals by isotope or X-ray irradiation at low temperatures. Thermoluminescent emission during the warmup can be interpreted in terms of the microenvironments around the various radiation induced defects and the dynamics of the annealing process (117-118). ... 

As shown in Fig. 21.12, after X-ray irradiation, the BaBPOs crystal shows a few broad, distinct absorption bands from near-infrared to the band gap in the VUV, which indicates the presence of some trapping sites in the crystal and... 

Fig. 21.12 Optical transmittance spectra of the BaBPOs crystal (a) pristine crystal (b) after irradiation by X-rays for 15 min (c) after annealing at 150°C for 1 hour of the X-ray-irradiated sample.

Vo) in the crystal. (Vo) can catch electrons to form F and centers. (Pb) is also able to attract electrons while (Vb)" can trap holes to give rise to color centers. They vdll make a contribution to the X-ray irradiation-induced absorption. Of course, the charge balance of the crystal is kept by charge compensation among these defects. Regretfully, the detailed characterization of these defects is too difficult to cover here and further experiments need to be performed. 

X-Ray irradiation of quartz or silica particles induces an electron-trap lattice defect accompanied by a parallel increase in cytotoxicity (Davies, 1968). Aluminosilicate zeolites and clays (Laszlo, 1987) have been shown by electron spin resonance (e.s.r.) studies to involve free-radical intermediates in their catalytic activity. Generation of free radicals in solids may also occur by physical scission of chemical bonds and the consequent formation of dangling bonds , as exemplified by the freshly fractured theory of silicosis (Wright, 1950 Fubini et al., 1991). The entrapment of long-lived metastable free radicals has been shown to occur in the tar of cigarette smoke (Pryor, 1987). 

E.s.r. showed that, X. ray irradiation of tetraalkyldiphosphine diphosphides gave phosphoranyl radicals with t.b.p. structures (39).114 A structure has been assigned to phosphiny1hydrazy1s (40). The dimethy1 ami no radical was particularly persistent.115 The e.s.r. parameters of the electrogenerated pyrazine radical cations (41) have been recorded.116 The spectra of a stable furanyl phosphate radical adduct117 and a phenalene radical anion which involves injection of spin density into half an attached cyclophosphazene ring,11 are reported. 

Prasad and coworkers60 studied the ESR spectra of cation radicals of dienes, trienes, tetraenes and pentaenes formed in CFCI3 matrix by X-ray irradiation. The structures of the resulting cation radicals were deduced by comparing the experimental coupling constant to those derived from INDO calculation. The unpaired spin density decreases with increasing chain length. 

A second family of MAPKs is referred to as stress-activated protein kinases (SAPKs) [3,14,15]. This includes JNKs, or Jun kinases, named originally for their phosphorylation of the transcription factor c-Jun. SAPKs were first identified in peripheral tissues on the basis of their activation in response to cellular forms of stress, which include X-ray irradiation and osmotic stress. More recently, they have been demonstrated to be activated in brain by several cytokines as well as by synaptic activity [16]. As shown in Figure 23-3, SAPKs are activated by SAPK kinases (SEKs), which are in turn activated by SEK kinases. The Ras-like small G proteins implicated in SEK kinase activation are Rac and Cdc-42. In this case, it appears that Rac/Cdc-42 triggers activation of SEK kinase by stimulating its phosphorylation by still another protein kinase termed p21-activated kinase (PAK). Thus, PAK can be considered a MAPK kinase kinase kinase, which is analogous to the cascade of protein kinases found in yeast (Fig. 23-4). 

A variety of alternating copolymers based on H-allyl- and N-(3-ethynylphenyl)maleimides, with substituted styrenes and vinyl ethers, have been prepared and their response to x-ray irradiation studied. Broadband and monochromatic x-ray exposures were conducted at the Stanford Synchrotron Radiation Laboratory. Sensitivities were observed to correlate with mass absorption coefficients of the copolymers and were found to be as high as 5-10 mJ/cm2. Preliminary fine line lithographic studies indicate 0.5 ion resolution capabilities. 

Fast reactions between pure metal powders (A1 + Ni, A1 + Ti and A1 + Ni + Ti) have been studied by Javel etal. (1997) by using time-resolved X-ray diffraction with the help of synchrotron radiation. The sample (20 X 10 X 2 to 3 mm3 was prepared under purified argon by cold pressing the metal powders mixed in the required proportion. It was then placed in a reaction chamber kept under He gas. A mylar window allows the incident and diffracted X-ray beams to pass in and out. Two small heating devices (tungsten coils on alumina supports) were included. The first one was used to keep the sample at a uniform temperature before ignition and the second one to start the self-propagating reaction at one end of the sample. X-rays irradiated the centre of the specimen. 

Figure 6.4 The absorption spectrum of Eu + ions in NaCl. A weak absorption signal related to the Eu + ions is observed after X-ray irradiation (note the change in the absorption scale) (reproduced with permission from AguUar et al., 1982).

After X-ray irradiation of thermally annealed NaCl crystals, a small percentage of divalent europium ions are converted into trivalent europium ions (Aguilar et al, 1982). This is shown by the appearance of weak and narrow absorption lines at around 460 nm and 520 nm, related to the Fq D2 and Fq Di transitions of Eu + ions, respectively. For our purposes, this example allows us to compare the different band features between (RE) + and (RE) + ions Eu + ions show broad and intense optical bands (electric dipole allowed transitions), while Eu + ions present narrow and weak optical lines (forced electric dipole transitions). 

X-ray irradiation of a matrix containing 2,6-difluorophenylazide in methylene chloride allows fixing the corresponding arylnitrene cation-radical, although such a particle is extremely unstable (Carra et al. 2006). 

Sawada N, IshikawaT, Sekiguchi F, Tanaka Y, IshitsukaH. X-ray irradiation induces thymidine phos-phorylase and enhances the efficacy of capecitabine in human xenografts. Clin Cancer Res 1999 5(10) 2948-2953. 

X ray photoelectron spectroscopy (XPS) is powerful in identifying species present at the surface/interface and atoms or functional groups involved in acid-base interactions [116]. Since XPS measures the kinetic energy of photoelectrons emitted from the core levels of surface atoms upon X ray irradiation of the uppermost atomic layers, it can be used to characterize surface acid sites, in combination with base probe molecules adsorption. 

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