Restricted orientational motion of nitroxides in molecular glasses: direct estimation of the motional time scale basing on the comparative study of primary and stimulated electron spin echo decays

A comparative study of anisotropic relaxation in two-pulse primary and three-pulse stimulated electron spin echo decays provides a direct way to distinguish fast (correlation time tau(c)<10(-6) s) and slow (tau(c)>10(-6) s) motions. Anisotropic relaxation is detected as a difference of the decay rates for different resonance field positions in anisotropic electron paramagnetic resonance spectra. For fast motion anisotropic relaxation influences the primary echo decay and does not influence the stimulated echo decay. For slow motion it is seen in both two-pulse echo and three-pulse stimulated echo decays. For nitroxide spin probes dissolved in glassy glycerol only fast motion was found below 200 K. Increase of temperature above 200 K results in the appearance of slow motion. Its amplitude increases rapidly with temperature increase. While in glycerol glass slow motion appears above glass transition temperature T(g), in ethanol glass it is observable below T(g). The scenario of motional dynamics in glasses is proposed which involves the broadening of the correlation time distribution with increasing temperature.     

The EPR dipolar broadening of irradiated solids as detected using FID and ESE following selective hole burning

A novel electron spin echo method employing detection of FID and transient echo shape following selective hole burning in the EPR spectrum has been applied to study γ-irradiated malonic acid. The dipolar lineshapes of stabilized free radicals are separated into bulk and pairwise contributions; both of them have proved to be Lorentzian.     

A comparative investigation of the fatty acid compositions of the seeds of a number of lines of a genetic collection of Gossypium hirsutum

A comparative analysis has been made of the amounts of lipids and their fatty-acid compositions in the seeds of the lines of agenetic collection of cotton plants of the speciesGossypium hirsutum and their hybrids and the variety Tashkent-1. The results obtained on the fatty-acid compositions of some hybrids make it possible to recommend the use of individual lines of cotton plants as donors for improving the food-value indices of cottonseed oil.Institute of Chemsitry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–176, March–April, 1991.     

Water concentration profiles in membranes measured by ESEEM of spin-labeled lipids

Electron spin-echo envelope modulation (ESEEM) spectroscopy of phospholipids spin-labeled systematically down the sn-2 chain was used to detect the penetration of water (D2O) into bilayer membranes of dipalmitoyl phosphatidylcholine with and without 50 mol % cholesterol. Three-pulse stimulated echoes allow the resolution of two superimposed 2H-ESEEM spectral components of different widths, for spin labels located in the upper part of the lipid chains. Quantum chemical calculations (DFT) and ESEEM simulations assign the broad spectral component to one or two D2O molecules that are directly hydrogen bonded to the N-O group of the spin label. Classical ESEEM simulations establish that the narrow spectral component arises from nonbonded water (D2O) molecules that are free in the hydrocarbon chain region of the bilayer membrane. The amplitudes of the broad 2H-ESEEM spectral component correlate directly with those of the narrow component for spin labels at different positions down the lipid chain, reflecting the local H-bonding equilibria. The D2O-ESEEM amplitudes decrease with position down the chain toward the bilayer center, displaying a sigmoidal dependence on position that is characteristic of transmembrane polarity profiles established by other less direct spin-labeling methods. The midpoint of the sigmoidal profile is shifted toward the membrane center for membranes without cholesterol, relative to those with cholesterol, and the D2O-ESEEM amplitude in the outer regions of the chain is greater in the presence of cholesterol than in its absence. For both membrane types, the D2O amplitude is almost vanishingly small at the bilayer center. The water-penetration profiles reverse correlate with the lipid-chain packing density, as reflected by 1H-ESEEM intensities from protons of the membrane matrix. An analysis of the H-bonding equilibria provides essential information on the binding of water molecules to H-bond acceptors within the hydrophobic interior of membranes. For membranes containing cholesterol, approximately 40% of the nitroxides in the region adjacent to the lipid headgroups are H bonded to water, of which ca. 15% are doubly H bonded. Corresponding H-bonded populations in membranes without cholesterol are ca. 20%, of which ca. 6% are doubly bonded.     

Summation of the perturbation theory high order contributions to the correlation correction for the energy levels of the caesium atom

Three dominating subsequences of diagrams are summarized: (1) screening of the residual Coulomb interaction; (2) particle-hole interaction in the polarization operator; (3) chaining of the self-energy correction. An accuracy of 0.1% is obtained for the caesium energy levels.     

多功能两亲梳状聚合物的合成及包覆荧光量子点

利用溶液聚合和成酰胺反应合成了多功能梳状两亲性共聚物,聚(甲基丙烯酸-co-甲基丙烯酸十八酯)-(乙醇胺-乙二胺叶酸)(PSM-EE-FA).用红外光谱(FTIR),核磁共振(1H-NMR)及凝胶渗透色谱(GPC)表征了该聚合物的结构及分子量分布.实验结果证明合成了该聚合物,其数均分子量(Mn)为28600,多分散性为1.375.用该两亲梳状聚合物包覆油溶性CdSe/ZnS量子点,通过相转移作用,得到水溶性靶向量子点(PSM-EE-FA-QDs).该水溶性量子点溶液具有较好的稳定性.通过紫外-可见(UV-Vis)及荧光发射光谱分析对该量子点的光学性质进行研究.结果表明,PSM-EE-FA-QDs的紫外-可见光谱及荧光发射光谱峰形与原量子点基本一致.由于量子点表面聚合物层的形成,峰位发生少量红移.该量子点水溶液的荧光强度是原量子点氯仿溶液的98%,荧光产率是原量子点氯仿溶液的95%.动态光散射(DLS)及透射电镜(TEM)测试结果表明水溶性量子点分布均匀.合成的水溶性量子点不但光学性能稳定,而且聚合物及水溶性量子点的合成方法较为简便.     

Effect of Pumping Pulse Duration on Echo Signal Amplitude in Four-Pulse PELDOR

The impact of pumping pulse duration on four-pulse pulsed electron?Celectron double resonance (PELDOR) data was experimentally studied. For biradicals with known distances between two spin labels, it is shown that refocused echo amplitude decreases with increasing the pumping pulse duration and decreasing the distance between spin labels. The effect becomes substantial when the pumping pulse duration is comparable or exceeds the inverse value of the dipole?Cdipole interaction between spin labels. This effect is essential for determination of distance distribution between labels in double-labeled molecules and for determination of the number of labels in clusters of spin-labeled molecules. PELDOR signal distortion was observed when the pumping pulse position in the time scale coincided with those of the detecting pulses. An approach of signal correction to eliminate this distortion is proposed.     

相对论性核碰撞中Φ介子产生和弦碎裂函数

用强子和弦级联模型LUCIAE系统研究从AGS到SPS,到RHIC,再到LHC能量核–核碰撞中Φ介子产生.采用与能量有关弦碎裂函数,并通过与荷电粒子多重数实验数据的比较确定其中的参数后,LUCIAE模型给出的Φ介子产额与实验数据也都相近,得到的事件平均弦碎裂变量随能量之增趋饱和规律,可能是核穿透性能量行为的定性表示.     

CW EPR, echo-detected EPR, and field-step ELDOR study of molecular motions of nitroxides ino-terphenyl glass: Dynamical transition, dynamical heterogeneity and β-relaxation

Continuous-wave electron paramagnetic resonance (CW EPR), echo-detected (ED) EPR, and field-step electron-electron double resonance (FS ELDOR) were simultaneously applied to study molecular motions of nitroxide spin probes of two different types in glassyo-terphenyl. A strong linear temperature dependence of the overall splitting of the CW EPR lineshape was found for nitroxide Tempone and only a weak one for a phenyl-ring-containing imidasoline nitroxide. The linear temperature dependence of the splitting is explained within the model of harmonic librations. The assessed libration frequency for Tempone is of the order of 3·10¹² rad/s. The observed remarkable difference between the two nitroxides is explained by the different strength of interactions between guest and host molecules and by dynamical heterogeneity of the glass. The nonlinear temperature dependence above 250 K is attributed to the onset of anharmonic motion that is postulated in a number of neutron scattering and Mössbauer spectroscopy studies for molecular glasses and proteins (the so-called dynamical transition). Above 245 K also ED EPR spectra change drastically, which may be explained on the same ground. Magnetization transfer was observed in FS ELDOR for nitroxide Tempone, with a time constant around 10^?5 s. It was found to be almost temperature-independent between 160 K and 265 K and was attributed to the Johari-Goldstein β-relaxation process. For the phenyl-ring-containing imidasoline nitroxide this transfer was not observed, which may be explained again by the dynamical heterogeneity of the glass and by small effectivity of the β-relaxation process in this case.     

以LCD为目标的自动定焦判据选择

在光学综合自动测量中 ,使用液晶显示屏作为分划板可以大大简化结构 ,提高效率 ,真正地实现自动测量。由于液晶显示具有对比度低、噪声大等特点 ,所以根据液晶的这些特点以及图像处理和CCD信号接收的特点选择两种适用的判据进行了分析和试验比较 ,并给出了结果。结果表明 ,这两种判别函数都适用于以液晶显示屏为目标和用图像处理方法进行光学参数测量的系统 ,其中锐度判别函数更优于信息熵判别函数 ,前者具有更好的抗干扰性和稳定性 ,而且其判定结果更接近目视清晰度判别