Electron Paramagnetic Resonance Imaging of the Spatial Distribution of Free Radicals in PMR-15 Polyimide Resins

Prior studies have shown that free radicals generated by heating polyimides above 300 C are stable at room temperature and are involved in thermo-oxidative degradation in the presence of oxygen gas. Electron Paramagnetic Resonance Imaging (EPRI) is a technique to determine the spatial distribution of free radicals. X-band (9.5 GHz) EPR images of PMR-15 polyimide were obtained with a spatial resolution of about 0.18 mm along a 2 mm dimension of the sample. In a polyimide sample that was not thermocycled, the radical distribution was uniform along the 2 mm dimension of the sample. For a polyimide sample that was exposed to thermocycling in air for 300 one-hour cycles at 335 C, one-dimensional EPRI showed a higher concentration of free radicals in the surface layers than in the bulk sample. A spectral-spatial two-dimensional image showed that the EPR lineshape of the surface layer remained the same as that of the bulk. These EPRI results suggest that the thermo-oxidative degradation of PMR-15 resin involves free radicals present in the oxygen-rich surface layer

Use of Rapid-Scan EPR to Improve Detection Sensitivity for Spin-Trapped Radicals

AbstractThe short lifetime of superoxide and the low rates of formation expected in vivo make detection by standard continuous wave (CW) electron paramagnetic resonance (EPR) challenging. The new rapid-scan EPR method offers improved sensitivity for these types of samples. In rapid-scan EPR, the magnetic field is scanned through resonance in a time that is short relative to electron spin relaxation times, and data are processed to obtain the absorption spectrum. To validate the application of rapid-scan EPR to spin trapping, superoxide was generated by the reaction of xanthine oxidase and hypoxanthine with rates of 0.1–6.0 μM/min and trapped with 5-tert-butoxycarbonyl-5-methyl-1-pyrroline-N-oxide (BMPO). Spin trapping with BMPO to form the BMPO-OOH adduct converts the very short-lived superoxide radical into a more stable spin adduct. There is good agreement between the hyperfine splitting parameters obtained for BMPO-OOH by CW and rapid-scan EPR. For the same signal acquisition time, the signal/noise ratio is >40 times higher for rapid-scan than for CW EPR. Rapid-scan EPR can detect superoxide produced by Enterococcus faecalis at rates that are too low for detection by CW EPR

Impact of Electron-Electron Spin Interaction on Electron Spin Relaxation of Nitroxide Diradicals and Tetraradical in Glassy Solvents Between 10 and 300 K

To determine the impact of electron-electron spin-spin interactions on electron spin relaxation rates, 1/T1 and 1/Tm were measured for nitroxide monoradical, diradical, and tetraradical derivatives of 1,3-alternate calix[4]arenes, for two pegylated high-spin nitroxide diradicals, and for an azine-linked nitroxide diradical. The synthesis and characterization by SQUID (superconducting quantum interference device) magnetometry of one of the high-spin diradicals, in which nitroxides are conformationally constrained to be coplanar with the m-phenylene unit, is reported. The interspin distances ranged from about 5-9 Å, and the magnitude of the exchange interaction ranged from \u3e150 to \u3e0.1 K. 1/T1 and 1/Tm were measured by long-pulse saturation recovery, three-pulse inversion recovery, and two-pulse echo decay at X-band (9.5 GHz) and Q-band (35 GHz). For a diradical with interspin distance about 9 Å, relaxation rates were only slightly faster than for a monoradical with analogous structure. For interspin distances of about 5-6 Å, relaxation rates in glassy solvents up to 300 K increased in the order monoradical \u3c diradical \u3c tetraradical. Modulation of electron-electron interaction enhanced relaxation via the direct, Raman, and local mode processes. The largest differences in 1/T1 were observed below 10 K, where the direct process dominates. For the three diradicals with comparable magnitude of dipolar interaction, 1/Tm and 1/T1 were faster for the molecules with more flexible structures. Relaxation rates were faster in the less rigid low-polarity sucrose octaacetate glass than in the more rigid 4:1 toluene/chloroform or in hydrogen-bonded glycerol glasses, which highlights the impact of motion on relaxation

A Spirocyclohexyl Nitroxide Amino Acid Spin Label for Pulsed EPR Distance Measurements

Site-directed spin labeling (SDSL) and electron paramagnetic resonance (EPR) spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α-amino acid and its N-(9- fluorenylmethoxycarbonyl) (Fmoc) derivative, has been synthesized that exhibit slow enough spin echo dephasing to permit accurate distance measurements by pulse EPR at temperatures up to 125 K in 1:1 water:glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR to the study of structure and conformation for peptides and proteins

A Spirocyclohexyl Nitroxide Amino Acid Spin Label for Pulsed EPR Distance Measurements

Site-directed spin labeling (SDSL) and electron paramagnetic resonance (EPR) spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α-amino acid and its N-(9- fluorenylmethoxycarbonyl) (Fmoc) derivative, has been synthesized that exhibit slow enough spin echo dephasing to permit accurate distance measurements by pulse EPR at temperatures up to 125 K in 1:1 water:glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR to the study of structure and conformation for peptides and proteins

The Chinese Tea Culture in The behavior of Post-consumption Times ----Based on tea packaging design to the construction of the brand value

中国传统文化在茶和茶事中渗透和发展形成了独具特色的茶文化。茶叶的整体包装是茶文化的物质载体，同时茶文化赋予茶包装以灵魂和性格。在后消费时代的背景下，物质极大丰裕，消费者可选择的余地空前加大，在新的消费格局形成发展中，占领消费者的心智资源是企业迫切要实现的目标，即将商品的品质特征、文化特性传达给消费者。茶行业近年来取得了长足的发展，茶叶的健康特质、精神韵味的文化内涵已深入人心，并涌现出一大批先进茶企。然而我国茶行业仍处于“有名品无名牌”的尴尬境地，市场鱼龙混杂，消费者在挑选时感到无所适从。茶叶产量大国走向茶叶贸易大国的必由之路：提升产品的附加值。品牌化之路是中国茶企的必由之路，以传统茶文化为基础...A unique feature culture was established by the Chinese traditional culture, which was formed and permeated in the development of tea and tea event. Tea packaging is the corporeal carrier of tea culture , meanwhile tea culture gives soul and character to tea packaging. Under the background of the consumer age , items is abundant. Consumers can choose freely. Before the new consumption pattern is c...学位：文学硕士院系专业：艺术教育学院美术系_设计艺术学学号：1862008115353

Room-Temperature Distance Measurements of Immobilized Spin-Labeled Protein by DEER/PELDOR

Nitroxide spin labels are used for double electron-electron resonance (DEER) measurements of distances between sites in biomolecules. Rotation of gem-dimethyls in commonly used nitroxides causes spin echo dephasing times (Tm) to be too short to perform DEER measurements at temperatures between ∼80 and 295 K, even in immobilized samples. A spirocyclohexyl spin label has been prepared that has longer Tm between 80 and 295 K in immobilized samples than conventional labels. Two of the spirocyclohexyl labels were attached to sites on T4 lysozyme introduced by site-directed spin labeling. Interspin distances up to ∼4 nm were measured by DEER at temperatures up to 160 K in water/glycerol glasses. In a glassy trehalose matrix the Tm for the doubly labeled T4 lysozyme was long enough to measure an interspin distance of 3.2 nm at 295 K, which could not be measured for the same protein labeled with the conventional 1-oxyl-2,2,5,5-tetramethyl-3-pyrroline-3- (methyl)methanethio-sulfonate label

Room-Temperature Distance Measurements of Immobilized Spin-Labeled Protein by DEER/PELDOR

Nitroxide spin labels are used for double electron-electron resonance (DEER) measurements of distances between sites in biomolecules. Rotation of gem-dimethyls in commonly used nitroxides causes spin echo dephasing times (Tm) to be too short to perform DEER measurements at temperatures between ∼80 and 295 K, even in immobilized samples. A spirocyclohexyl spin label has been prepared that has longer Tm between 80 and 295 K in immobilized samples than conventional labels. Two of the spirocyclohexyl labels were attached to sites on T4 lysozyme introduced by site-directed spin labeling. Interspin distances up to ∼4 nm were measured by DEER at temperatures up to 160 K in water/glycerol glasses. In a glassy trehalose matrix the Tm for the doubly labeled T4 lysozyme was long enough to measure an interspin distance of 3.2 nm at 295 K, which could not be measured for the same protein labeled with the conventional 1-oxyl-2,2,5,5-tetramethyl-3-pyrroline-3- (methyl)methanethio-sulfonate label

Imaging thiol redox status in murine tumors in vivo with rapid-scan electron paramagnetic resonance

Thiol redox status is an important physiologic parameter that affects the success or failure of cancer treatment. Rapid scan electron paramagnetic resonance (RS EPR) is a novel technique that has shown higher signal-to-noise ratio than conventional continuous-wave EPR in in vitro studies. Here we used RS EPR to acquire rapid three-dimensional images of the thiol redox status of tumors and normal tissues in living mice. This work presents, for the first time, in vivo RS EPR images of the kinetics of the reaction of 2H,15N-substituted disulfide-linked dinitroxide (PxSSPx) spin probe with intracellular glutathione. The cleavage rate is proportional to the intracellular glutathione concentration. Feasibility was demonstrated in a FSa fibrosarcoma tumor model in C3H mice. Similar to other in vivo and cell model studies, decreasing intracellular glutathione concentration by treating mice with L-buthionine sulfoximine (BSO) markedly altered the kinetic images

Rapid-Scan EPR of Immobilized Nitroxides

X-band electron paramagnetic resonance spectra of immobilized nitroxides were obtained by rapid scan at 293 K. Scan widths were 155 G with 13.4 kHz scan frequency for 14N-perdeuterated tempone and for T4 lysozyme doubly spin labeled with an iodoacetamide spirocyclohexyl nitroxide and 100 G with 20.9 kHz scan frequency for 15N-perdeuterated tempone. These wide scans were made possible by modifications to our rapid-scan driver, scan coils made of Litz wire, and the placement of highly conducting aluminum plates on the poles of a Bruker 10 magnet to reduce resistive losses in the magnet pole faces. For the same data acquisition time, the signal-to-noise for the rapid-scan absorption spectra was about an order of magnitude higher than for continuous wave first-derivative spectra recorded with modulation amplitudes that do not broaden the lineshapes