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1.
电子俘获材料Zn4B6O13:Dy3+的热释光特性研究   总被引:4,自引:0,他引:4  
通过高温固相扩散反应合成了稀土元素镝掺杂的Zn4-xB6O13:xDy3+磷光体.测定了该化合物在高能60Co伽玛射线辐照下的热释发光曲线和三维热释光谱.三维热释光谱表明,位于大约480nm和580nm的发光谱带来自于Dy3+离子的f-f跃迁.基质中掺杂的Dy3+离子浓度的变化能够改变陷阱的相对分布,随着Dy3+浓度的增加,发光峰温向高温方向移动,这可提高剂量器的热稳定性.当辐照剂量增加时,发光峰温亦向高温方向移动,即陷阱加深.确定了Zn3.86B6O13:0.16Dy3+样品主峰的陷阱深度E=0.73eV,频率因子S=2.43×109s-1.在1~100Gy治疗级范围内,Zn3.86B6O13:0.16Dy3+对60Co伽玛射线辐照的热释光剂量响应呈良好的线性关系.实验结果表明,Zn3.86B6O13:0.16Dy3+是一个潜在的应用于临床医疗的伽玛射线电离辐射热释光剂量计材料.  相似文献   

2.
The French National Reference Laboratory (NRL) for heavy metals in foodstuffs of animal origin at the French Food Safety Agency (AFSSA) regularly organises proficiency tests schemes (PTS) focused on the quantification of the three elements lead (Pb), cadmium (Cd) and mercury (Hg), for the 23 departmental laboratories of the network of laboratories, under its responsibility. The NRL prepares test materials to promote comparability of data and support harmonisation of official analytical procedures in the case of routine analysis. When target values for the analytes are set, the PTS also provide an objective assessment and improvement of the analytical trueness in the daily work of the laboratories.The long-term performance of the network was examined using results of 10 years of PTS in various matrices from different foodstuffs of animal origin (fish, meat and milk products), with 3 different official methods, using Flame- and Electro-Thermal-AAS techniques. In all cases, participants were requested to carry out 3 independent measurements of Pb, Cd and Hg. Moreover, the assessment of the PTS was based on the Z-score approach. From 1998 to 2008, this evaluation applied to 690 results obtained in 41 PTS indicated a frequency distribution of the Z-score value for the three elements Pb, Cd and Hg of 89.2%, 94.5% and 97.7% of acceptable results, respectively. The results of this balance sheet indicated the homogeneity and ability of the laboratories network to provide comparable results of similar quality. Comparison with results obtained by a primary method were presented as complementary information to determine the interest to organize, in the future, PTS based on a certified value.  相似文献   

3.
A novel supramolecular mixed ligand complex of formula [Cu(PTS)2(Him)2(H2O)2] (C20H26CuN4O8S2,PTS=p-toluenesulfonate,Him=imidazole) has been synthesized in aqueous solution and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The compound crystallizes in the monoclinic system,space group P21/n,Z=2,a=5.650(2),b=14.671(3),c=14.638(3),β=100.10(3)°,V=1194.60(4)3,Dc=1.607 g/cm3,μ(MoKα)=1.143 mm-1,F(000)=598,R=0.0615 and wR=0.1503 for 1752 observed reflections with I 2σ(I).The copper(II) ion in the complex adopts a slightly distorted octahedral coordination geometry and is six-coordinated with N2O4 donor set consisting of two nitrogen atoms and four oxygen atoms provided by the ligands of two imidazole molecules,two water molecules and two p-toluenesulfonate ions.The sulfonate group of the PTS ligand remains weak-coordinated and forms a number of hydrogen bonds with water molecules and imidazole ligands.X-ray structural analysis reveals that the coordination molecules are connected to form a 3-D supramolecular framework by electrostatic interaction,weak van der Waals forces,hydrogen bonding and π-π interaction.The thermal behaviour of the title complex was investigated by using DSC and TG-DTG techniques.  相似文献   

4.
Visible-light Photochemistry and Phototoxicity of Thiarubrines   总被引:2,自引:0,他引:2  
Abstract. Thiarubrines, a group of intensely red, sulfur-containing pigments produced by asteraceous plants, are photola-bile, yielding thiophenes and elemental sulfur upon exposure to UV or visible light. The mechanism of this light-induced conversion for thiarubrines A (la), B (lb) and D (lc), isolated from the roots of Ambrosia chamis-sonis (Asteraceae), was investigated. Visible-light irradiation of thiarubrines resulted in the formation of novel 2,6-dithiabicyclo[3.1.0]hex-3-ene polyyne photointerme-diates (photosulfides) that rapidly undergo desulfuriza-tion to yield thiophenes. Six photosulfides, photosulfides 3a and 3a' from thiarubrine A (la), photosulfides 3b and 3b' from thiarubrine B (lb) and photosulfides 3c and 3c' from thiarubrine D (lc) were characterized. Thiarubrine photointermediates are short-lived and unstable, with the photosulfides formed from thiarubrine A having a half-life of 12.3 min at room temperature. While the immediate fate of the extruded sulfur is unknown, we identified cyclooctasulfur (S8) in photolysis solutions of thiarubrine A using electron impact mass spectrometry. Visible-light irradiation of Candida albicans cell suspensions treated with thiarubrine A led to a 99% decrease in cell viability, suggesting that the photosulfides, or other molecules generated by the exposure of thiarubrines to light, have significant toxicity.  相似文献   

5.
The effects of neutron scattering by matrix hydrogen in geological samples were examined in order to accurately determine their chemical compositions by neutron-induced prompt gamma-ray analysis (PGA). Three different matrix materials including basaltic reference rock sample (JB-2) mixed with chemical reagents including H-containing ones were analyzed by using thermal and/or cold neutron-guided beams of JRR-3 at Japan Atomic Energy Agency. The sensitivity change of elements with the variation of the H concentrations was evaluated for disk and spherical target geometries. The results show that the analytical sensitivities of B, Cl and Cd in disk samples seem to increase with increasing the matrix H concentrations by the irradiation of both thermal and cold-neutron beams. The sensitivity enhancement of B for disk-shaped JB-2 mixed with up to 2% mass H is within the analytical uncertainty associated with PGA with a thermal-neutron beam.  相似文献   

6.
The aim of this work was to implement and to validate the k 0 standardization method in neutron activation analysis (k 0-NAA) at the Moroccan TRIGA Mark II research reactor. This technique was used in order to determine, the calibration of several HPGe detectors and calibration of neutron flux parameters in the typical irradiation channels [rotary specimen rack (RSR) and the pneumatic tube system (PTS) facilities]. Calibrations and calculations of k 0-NAA results were carried out using the k 0-IAEA program. The two parameters of neutron flux in the selected irradiation channels used for elemental concentration calculation, f (thermal-to-epithermal ratio) and α (deviation from the 1/E distribution), have been determined as well in the PTS as in the RSR facilities using the zirconium bare triple method. Results obtained for f and α in two irradiation channels show that f parameter determined in this way is different in the RSR and the PTS facilities. This can be explained by the fact that the RSR channel is situated in a graphite reflector and is relatively far from the reactor core, while the PTS is in the core. Five reference materials of different origin obtained from USGS (basalt BE-N, bauxite BX-N, biotite mica-Fe, granite GS-N) and IAEA (Soil-7) were used to evaluate the validity of this method in our laboratory by analyzing the elemental concentrations with respect to the certified values. In general, good agreement was obtained between results of this work and values in certificates of the individual reference materials, thus proving the accuracy of our results and successful implementation of the method for analysis of real samples.  相似文献   

7.
The near-infrared (NIR) absorption of toluene-sulfonate-diacetylene crystals (PTS) has been investigated during thermal polymerization. It is shown by comparative NIR and IR spectroscopy of deuterated and of protonated PTS at various temperatures, that these absorptions are vibronic in nature. They can be assigned unambiguously to distinct parts of the molecule. No low-lying electronic state has been found.  相似文献   

8.
Partial Synthesis of Grandidones A, 7-Epi-A, B, 7-Epi-B, C, D and 7-Epi-D, from 14-Hydroxytaxodione Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved. Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved. Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved. Oxydative addition of coleon U ( 6 ) to 14-hydroxytaxodione ( 5 ) in the presence of Fétizon's reagent mainly leads to grandidone A ( 1a ) and 7-epigrandidone A ( 1b ) (ca. 15:1), whereas coleon V ( 7 ) and 5 under the same conditions yield grandidone B ( 2a ) and 7-epigrandidone B ( 2b ) (ca. 3:1). Dimerization of 14-hydroxytaxodione ( 5 ) gives grandidone C ( 3 ; ca. 40%), grandidone D ( 4a ; ca. 50%) and 7-epigrandidone D ( 4b ; ca. 10%). All these compounds obtained by partial synthesis are in every respect identical with the natural products, thus establishing their absolute configurations. The thermal transformation of grandidone C ( 3 ) to grandidone D ( 4a )/7-epigrandidone D ( 4b ) and interconversions of 4a and 4b were achieved.  相似文献   

9.
Nine new diterpenes, neovibsanin D (1), 7-epi-neovibsanin D (2), 15-O-methylneovibsanin F (3), 14-epi-15-O-methylneovibsanin F (4), 15-O-methyl-18-oxoneovibsanin F (5), 2-O-methylneovibsanin H (6), 2-O-methylneovibsanin I (7), neovibsanin G (8), and 14-epi-neovibsanin G (9), were isolated from a methanol extract of the leaves of Viburnum awabuki. Their structures were elucidated to be uniquely rearranged vibsane-type diterpenes by spectroscopic analyses and comparison of NMR data with those of previously reported vibsane-type diterpenes. In addition, irradiation of vibsanin B (12) in methanol with a high-pressure Hg lump led to the direct formation of neovibsanins A (14) and B (15). These results gave a clue to understanding of the biogenetic interconversion of 11-membered vibsanins into neovibsanins.  相似文献   

10.
Thermal degradation of two poly(acyl sulfide) polymers, poly(adipoyl sulfide) (PADS) and poly(terephthaloyl sulfide) (PTS) was investigated by direct pyrolysis mass spectrometry (DPMS). The structures of pyrolysis products detected in the DPMS analysis of both PADS and PTS indicate that the thermal degradation takes place mainly through a loss of carbon monoxide and carbonyl oxysulfide leading to the formation of cyclics. In the case of PADS, linear products with thioacid end groups were formed through hydrogen transfer reactions. In the case of PTS, almost equal proportions of linear products with phenyl end groups and cyclic products were formed. The mechanism of formation of degradation products has also been addressed.  相似文献   

11.
Abstract— Laser micro-irradiation was used to study the uptake of low levels of strain (Janus Green B) by the mitochondria of tissue culture cells and the selective lesions induced by the irradiation. A comparison of the thermal effects produced in the cells and in a stained model system (albumin), permitted the calculation of the degree of concentration of stain in the mitochondria from the staining media (approximately 500 fold). Evaluation of the various parameters of Laser irradiation, particularly thermal events, resulted in optimal irradiation times for measurement of local stain concentration, as well as for the selective destruction of the stained mitochondria. For the studies of the latter phenomenon a lower limit for irradiation duration is set by optical saturation and dielectric breakdown.  相似文献   

12.
A 2D layered spin crossover complex, [FeIIH3L(Me)]Cl.I3, has been synthesized from the reaction of FeIIICl3, a tripod ligand (H3LMe = tris[2-(((2-methylimidazoyl-4-yl)methylidene)amino)ethyl]amine), and NaI in methanol. The compound showed an abrupt spin transition between the HS (S = 2) and LS (S = 0) states at T(1/2) = 110 K without hysteresis. The crystal structures of the HS and LS states were determined at 180 and 90 K. A 2D layered structure is composed of NH...Cl- hydrogen bonds between the Cl- ion and three neighboring imidazole groups of [FeIIH3LMe]2+. The green light irradiation at 5 K induced the LIESST effect, and the thermal relaxation process from the HS to LS state showed a sigmoid curve at T > 55 K.  相似文献   

13.
The photoreduction process of PtCl(6)2- to Pt nanoparticles in poly(N-vinyl-2-pyrrolidone) solutions upon UV light irradiation was investigated by monitoring the change in the diffusion coefficient (D). The D values of chemical species during UV irradiation was measured by the laser-induced transient grating (TG) method. The TG signal of the PtCl(6)2- solution before UV irradiation was composed of three kinds of contributions, the thermal grating, the species grating due to the creation of PtCl4(2-), and the species grating due to the depletions of PtCl6(2-). Upon UV irradiation of the solution, the species grating signal due to PtCl6(2-) diminished and then the TG signal of Pt nanoparticles gradually appeared. This result indicates that the gradual clustering of Pt0 atoms into Pt nanoparticles occurs after all PtCl(6)2- ions are photochemically reduced to PtCl(4)2- and subsequently transformed to Pt0 atoms with a short delay. With increasing time of the UV irradiation, the TG signal intensity increased, while D of the Pt nanoparticles did not change. This suggests that the number of Pt nanoparticles increases, but the size of the Pt nanoparticles with the polymer layer is unchanged, in the course of the UV irradiation.  相似文献   

14.
Cloisite 30B as a modified kind of nanoclay was utilized for the formation of 3D network based on novolac resin with high thermal stable properties. Two types of phenolic resins including neat novolac (NR) and modified novolac resin were used to create a compatible matrix with nanoclay. For this purpose, NR modified with (3‐chloropropyl)triethoxysilane (CPTES) to form SiNR. For improvement of thermal behaviors, Cloisite 30B was dispersed in matrix via ultrasonic waves and cured with hexamethylenetetramine (HMTA) to form 3D network. X‐ray diffraction (XRD) analysis was used to measure the d‐spacing in intercalated systems and results indicated the optimum amount of clay for appropriate thermal properties. Investigation of the thermal properties of the samples by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the presence of Cloisite 30B in matrix resulted in much higher thermal stability and char yield with respect to modification of novolac resin originated from formation of 3D Si–O–Si network. Also, cured modified resin and its nanocomposites showed much higher thermal stability than cured NR and its nanocomposites. Such nanocomposite materials with high thermal stability have potential applications in advanced fields such electronic, industrial molds, coatings, adhesives, and aerospace composites.  相似文献   

15.
This work elucidates photoinduced two-dimensional (2D) gratings in dye-doped cholesteric liquid crystal films. The helical pitch is increased by green-beam-induced trans-cis isomerization and a concomitant thermal effect. Two-dimensional gratings appear when the green beam is turned off. Grating formation results from elastic instability caused by restored strain arising from helical pitch reduction. Grating lifetime increases as green beam intensity increases and declines under irradiation with a strong red beam. Variation in grating spacing with green intensity with various pitches is also examined.  相似文献   

16.
From polytitanosiloxanes (PTS), SiO2–TiO2 oxide fibers with fairly good tensile strength were prepared, and their mechanical and thermal properties were investigated. The precursor fibers PTS-0.5 and PTS-1.0 were obtained by dry spinning of a highly viscous PTS solution which were formed as the reaction mixture of silicic acid (SA) with bis(2,4-pentanedionato)titanium diisopropoxide (PTP) in the molar ratios (SA/PTP) of 0.5 and 1.0. The precursor fibers PTS-0.5 were too brittle to measure their tensile strength, whereas PTS-1.0 and the heat-treated fibers were found to have tensile strength of 130 (precursor), 540 (500°C), and 450 (900°C) MPa, respectively. Heat-treatment of the fibers PTS-1.0 at above 1000°C forms anatase and rutile of titanium dioxide. The crystallization is resulted from the unreacted PTP which is not incorporated into the polymer network.  相似文献   

17.
Induction of apoptosis is a function of external stimuli and cellular gene expression. Many cells respond to DNA damage by the induction of apoptosis, which depends on a functional p53 protein and is signaled by elevation of p53 levels. In this study, we found that a prior exposure to mild stress (42 degrees C) can protect HepG2 (p53+/+) cells from a subsequent UVC-induced apoptosis determined by DNA fragmentation and ratio of sub-G1 peak, but no heat-enhanced protection was found in Hep3B (p53-/-) cells. Although a similar inductive pattern of HSP70 protein and mRNA was detected in the two cell lines under thermal stress, the effect of thermal stress on UVC-induced apoptosis in HepG2 and Hep3B cells was obviously different. Overexpression of HSP70 by transient transfection of HSP70 expression vector in HepG2 cells significantly inhibited UVC-induced cell death; however, this inhibitory effect did not occur in transfected-Hep3B cells. Treatment of HepG2 cells with p53-specific antisense oligonucleotide could effectively block the antiapoptotic effect of thermal stress on UVC-induced apoptosis and increase of intracellular wild-type p53 protein by transfecting wtp53 expression plasmid into Hep3B cells yielded more resistance to UVC irradiation after prior thermal stress exposure. The results reveal an involvement of p53 in the antiapoptotic effect of thermal stress on UVC irradiation. Finally, a p53 protein increase was detected in UVC-treated HepG2 cells and could be coimmunoprecipitated with HSP70 after a thermal stress treatment. Prolonged p53 binding activity and enhanced expression of p53-controlled genes such as G1 arrest and DNA damage 45 and wild-type p53 activation factor 1/Cdk-interacting protein 1 by thermal stress are also observed in UVC-irradiated HepG2 cells. Based on these results, we propose that the antiapoptotic effect of thermal stress is mediated by increasing HSP70 and modulating intracellular p53 function.  相似文献   

18.
We have previously shown that keratinocytes in vitro can convert biologically inactive vitamin D3 to the hormone calcitriol. The present study was initiated to test whether ultraviolet B (UVB)-induced photolysis of provitamin D3 (7-dehydrocholesterol, [7-DHC]) which results in the formation of vitamin D3 also leads to the generation of calcitriol in keratinocytes. Submerged monolayers of HaCaT keratinocytes were preincubated with 7-DHC (25 microM) at 37 degrees C and irradiated with monochromatic UVB at different wavelengths (effective UV-doses: 7.5-60 mJ/cm2), or a narrow-band fluorescent lamp Philips TL-01 (UVB-doses: 125-1500 mJ/cm2). Irradiation with both sources of UVB resulted in the generation of different amounts of previtamin D3 in our in vitro model followed by time-dependent isomerization to vitamin D3 and consecutive formation of calcitriol in the picomolar range. Unirradiated cultures or cultures exposed to wavelengths > 315 nm generated no or only trace amounts of calcitriol. The conversion of vitamin D3 generated after UVB irradiation to calcitriol is inhibited by ketoconazole indicating the involvement of P450 mixed function oxidases in this chemical reaction. The generation of calcitriol was wavelength- and UVB dose dependent and reached approximately 18-fold higher levels after irradiation at 297 nm than at 310 nm (effective UVB dose: 30 mJ/cm2). Hence, keratinocytes may be a potential source of biologically active calcitriol within epidermis, when irradiated with therapeutical doses of UVB.  相似文献   

19.
本文利用微波法合成了2,5-二(2′-苯并咪唑)吡啶,采用水热合成技术得到了它的单晶(1)及其锌的配合物[Zn(C19H12N5)2(H2O)2].5H2O(2)。IR和X-射线单晶衍射实验测定和结构解析结果表明,化合物1由2,5-二(2′-苯并咪唑)吡啶和晶格水组成,化合物2中Zn2+离子与2,5-二(2′-苯并咪唑)吡啶的N原子配位,通过氢键作用形成1D链状结构,再通过配体间π-π作用形成三维结构。此外,TG和荧光测定分析表明化合物2具有良好的热稳定性和荧光性能。  相似文献   

20.
We have studied the adducts formed by eosin (E) with a fourth generation dendrimer (D) that comprises 30 tertiary amine units in the interior and 32 naphthyl and 32 trans azobenzene units in the periphery. We have found that: (i) the all trans dendrimer D(32t) can be converted by irradiation with 365 nm light (Phi=0.12) into species containing, as an average, 4 trans and 28 cis azobenzene units, D(4t28c), that at 313 K undergoes a D(4t28c) --> D(32t) thermal back reaction (k = 7.0 x 10(-5) s(-1)); (ii) D(32t) and D(4t28c) extract 8 and, respectively, 6 eosin molecules from water at pH 7, yielding the species D(32t) subset 8E and D(4t28c) subset 6E; (iii) eosin uptake is significantly faster for D(32t) than for D(4t28c); (iv) irradiation at 365 nm of the D(32t) subset 8E species at 298 K leads to the release of two eosin molecules with formation of a photostable D(15t17c) subset 6E species (Phi = 0.15) that is also obtained from the back thermal reaction of D(4t28c) subset6E at 313 K (k = 2.7 x 10(-5) s(-1)); (v) thermal release of E from D(32t) subset 6E is much faster than from D(4t28c) subset 6E; and (vi) excitation of E in the adducts sensitizes the cis --> trans (but not the trans --> cis) isomerization. The results obtained show that the isomerization of the 32 peripheral azobenzene units controls to some extent the hosting capacity of the dendrimer and, viceversa, eosin molecules hosted in the dendrimer affect the isomerization process of its azobenzene units.  相似文献   

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