Principal eigenvector field segmentation for reproducible diffusion tensor tractography of white matter structures

The study was aimed to test the feasibility of utilizing an algorithmically determinable stable fiber mass (SFM) map obtained by an unsupervised principal eigenvector field segmentation (PEVFS) for automatic delineation of 18 white matter (WM) tracts: (1) corpus callosum (CC), (2) tapetum (TP), (3) inferior longitudinal fasciculus (ILF), (4) uncinate fasciculus (UNC), (5) inferior fronto-occipital fasciculus (IFO), (6) optic pathways (OP), (7) superior longitudinal fasciculus (SLF), (8) arcuate fasciculus (AF), (9) fornix (FX), (10) cingulum (CG), (11) anterior thalamic radiation (ATR), (12) superior thalamic radiation (STR), (13) posterior thalamic radiation (PTR), (14) corticospinal/corticopontine tract (CST/CPT), (15) medial lemniscus (ML), (16) superior cerebellar peduncle (SCP), (17) middle cerebellar peduncle (MCP) and (18) inferior cerebellar peduncle (ICP). Diffusion tensor imaging (DTI)-derived fractional anisotropy (FA) and the principal eigenvector field have been used to create the SFM consisting of a collection of linear voxel structures which are grouped together by color-coding them into seven natural classes to provide PEVFS signature segments which greatly facilitate the selection of regions of interest (ROIs) for fiber tractography using just a single mouse click, as compared with a manual drawing of ROIs in the classical approach. All the 18 fiber bundles have been successfully reconstructed, in all the subjects, using the single ROIs provided by the SFM approach, with their reproducibility characterized by the fact that the ROI selection is user independent. The essentially automatic PEVFS method is robust, efficient and compares favorably with the classical ROI methods for diffusion tensor tractography (DTT).     

The zonal architecture of human articular cartilage described by T2 relaxation time in the presence of Gd-DTPA2-

The depth-wise variation of T(2) relaxation time is known to reflect the collagen network architecture in cartilage, while the delayed Gadolinium Enhanced MRI of Cartilage (dGEMRIC) technique is sensitive to tissue proteoglycan (PG) concentration. As the cartilage PG content varies along the tissue depth, the depth-dependent accumulation of the contrast agent may affect the inherent T(2) of cartilage in a nonconstant manner. Therefore, T(2) and dGEMRIC are typically measured in separate MRI sessions. In the present in vitro MRI study at 9.4 T, depth-wise T(2) profiles and collagenous zone thicknesses as determined from T(2) maps in the absence and presence of Gd-DTPA(2-) (T(2) and T(2Gd), respectively) were compared in samples of intact human articular cartilage (n=65). These T(2) measures were further correlated with birefringence (BF) of polarized light microscopy (PLM) to quantify the ability of MRI to predict the properties of the collagen fibril network. The reproducibility of the T(2) measurement in the current setup was also studied. Typical tri-laminar collagen network architecture was observed both with and without Gd-DTPA(2-). The inverse of BF (1/BF) correlated significantly with both T(2) and T(2Gd) (r=0.91, slope=0.56 and r=0.90, slope=0.63), respectively. The statistically significant linear correlations between zone thicknesses as determined from T(2) and T(2Gd) were r=0.55 (slope=0.49), r=0.74 (slope=0.71) and r=0.95 (slope=0.94) for superficial, middle and deep tissue zones, respectively. Reproducibility of the T(2) measurement was worst for superficial cartilage. Consistent with PLM, T(2) and T(2Gd) measurements reveal highly similar depth-dependent information on collagen network in intact human cartilage. Thus, dGEMRIC and T(2) measurements in one MRI session are feasible for intact articular cartilage in vitro.     

拉曼光谱的16种多环芳烃（PAHs）特征振动光谱辨识

借助密度泛函理论中B3LYP/6-311++G(d, p)方法对美国EPA优先控制污染物中的16种多环芳烃(PAHs)：萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并[a]蒽、稠二萘、苯并[b]荧蒽、苯并[k]荧蒽、苯并[a]芘、二苯并(a, h)蒽、二苯并[g, h, i]芘以及茚苯(1, 2, 3-cd)芘进行结构优化,并计算拉曼光谱振动频率和去偏振度,在此基础上辨识多环芳烃的拉曼特征光谱。研究显示,16种PAHs的拉曼振动主要分布在3个频区：200～1 000 cm-1（指纹区）、1 000～1 700和3 000～3 200 cm-1（基团频率区）,3个频区主要振动归属分别为环变形(ring def),碳碳伸缩(CCStr)、碳氢摇摆(CHw)及其耦合振动(CCStrCCw),碳氢伸缩(CHStr)。进一步分析显示,指纹区16种PAHs的去偏振度随苯环变形振动对称性增强而降低,在该频区去偏振度最小的频移处苯环呼吸振动的对称性最强,指纹区的峰强也在此处出现最大值。任意PAHs在指纹区的最强峰之间的波数差较大,在显微拉曼光谱的可分辨范围内,因而利用指纹区的去偏振度和最强峰可将16种PAHs逐一识别。烷烃、烯烃、炔烃、醇类和酚类、脂肪醚、芳基烷基醚、醛类、酮类、羧酸、酯类、胺类、腈类、酰胺类、酸酐、芳烃的振动频率和峰强分布不完全一致,利用PAHs与这几类物质拉曼频率和峰强分布的差异可以逐一排出干扰。     

A suite of 3D NMR methods for characterizing complex hydrocarbon structure fragments

A suite of triple resonance 3D NMR experiments is presented for the complete connectivity assignment of the hydrocarbon network in complex macromolecular and supramolecular organic structures. These new 3D NMR methods rely only on the presence of a unique set of (13)C resonances (from (13)C(X)) which are separated from the rest of the (13)C NMR spectrum. These experiments take the advantage of region selective excitation and selective inversion by composite pulses to provide correlations among H(A), (13)C(A); H(B), (13)C(B) and neighboring (13)C(X) resonances along three frequency dimensions. These methods include: gHC(A)C(X), gHC(A)C(X)-HH-TOCSY and gHC(A)C(X)-CC-TOCSY experiments. The utility of this approach is illustrated with spectra of selected structure fragments in poly(ethylene-co-n-butyl acrylate-co-carbon monoxide) (polyEBC) prepared from 1,2,3-(13)C(3)-n-butyl acrylate.     

C80n (D2,Ih)的Jahn-Teller畸变和电子光谱

用INDO系列方法研究C80n(D2,Ih)的Jahn-Teller畸变,表明C80(D2)比C80(Ih)稳定,与实验一致;C80n(D2)未发生Jahn-Teller畸变,C80n(Ih)的部分离子发生明显的Jahn-Teller畸变,电荷对C80(Ih)稳定性有显著影响.首次计算其电子光谱,不仅得到C80(D2)与实验一致的吸收峰,还预测了C80n(D2,Ih)的电子光谱,对电子跃迁进行理论指认.C80n(D2)光谱与C80(D2)相比发生吸收峰红移,而C80n(Ih)光谱与C80(Ih)相比发生吸收峰兰移,其原因是C80n(D2)的LUMO-HOMO能隙比C80(D2)小,而C80n(Ih)的能隙则比C80(Ih)的能隙大.     

利用三维荧光结合平行因子算法研究金属离子对溶解性有机物的猝灭和校正

溶解性有机物的荧光组份由于受到金属离子的影响其荧光强度受到变化,从而为溶解性有机物的定量分析带来挑战。利用三维荧光结合平行因子分析方法研究了Cu(Ⅱ), Fe(Ⅲ), Ni(Ⅱ), Sr(Ⅱ), Hg(Ⅱ), K(Ⅰ), Mg(Ⅱ) 和Mn(Ⅱ)八个金属离子对典型溶解性有机物荧光组分的荧光猝灭作用,五个水样来源各不相同。实验表明水样被平行因子成功分解为三个荧光组分(色氨酸、腐殖酸、富里酸),这三个荧光组份的荧光得分随着Fe(Ⅲ), Cu(Ⅱ), Hg (Ⅱ)和 Ni(Ⅱ)浓度的增加呈线性或指数下降。在这四种离子中,Fe(Ⅲ)和Cu(Ⅱ)对腐殖酸和富里酸的荧光猝灭作用明显大于Hg (Ⅱ)和 Ni(Ⅱ)。Sr(Ⅱ), K(Ⅰ), Mg(Ⅱ)和Mn(Ⅱ)基本没有影响。其中Fe(Ⅲ)对于三个荧光组分的荧光猝灭都有较好的分析。由于只考虑Fe(Ⅲ) 和Cu(Ⅱ)的影响,对于含有金属离子的饮用水的荧光强度的校正曲线也被建立。不同来源的饮用水中荧光组份的荧光得分的衰减规律也是不一样的,因此水样的来源也是测量时需要考虑的因素。实验证实了金属离子对溶解性有机物的荧光猝灭作用以及其他因素比如Fe(Ⅲ) 和Cu(Ⅱ)和溶解性有机物本身的多样性都是我们荧光测量典型荧光组份时需要考虑的。表明三维荧光结合平行因子分析方法是一个有效的准确测量溶解性有机物荧光组份的工具。     

Multi-dimensional 1H-13C HETCOR and FSLG-HETCOR NMR study of sphingomyelin bilayers containing cholesterol in the gel and liquid crystalline states

(13)C cross polarization magic angle spinning (CP-MAS) and (1)H MAS NMR spectra were collected on egg sphingomyelin (SM) bilayers containing cholesterol above and below the liquid crystalline phase transition temperature (T(m)). Two-dimensional (2D) dipolar heteronuclear correlation (HETCOR) spectra were obtained on SM bilayers in the liquid crystalline (L(alpha)) state for the first time and display improved resolution and chemical shift dispersion compared to the individual (1)H and (13)C spectra and significantly aid in spectral assignment. In the gel (L(beta)) state, the (1)H dimension suffers from line broadening due to the (1)H-(1)H homonuclear dipolar coupling that is not completely averaged by the combination of lipid mobility and MAS. This line broadening is significantly suppressed by implementing frequency switched Lee-Goldburg (FSLG) homonuclear (1)H decoupling during the evolution period. In the liquid crystalline (L(alpha)) phase, no improvement in line width is observed when FSLG is employed. All of the observed resonances are assignable to cholesterol and SM environments. This study demonstrates the ability to obtain 2D heteronuclear correlation experiments in the gel state for biomembranes, expands on previous SM assignments, and presents a comprehensive (1)H/(13)C NMR assignment of SM bilayers containing cholesterol. Comparisons are made to a previous report on cholesterol chemical shifts in dimyristoylphosphatidylcholine (DMPC) bilayers. A number of similarities and some differences are observed and discussed.     

镜像核13N-13C 和15N-15O中的激发态晕或皮(英文)

用非线性相对论平均场对两对镜像核13N-13C 和15N-15O进行了研究. 发现无论在基态还是激发态， 用两套参数所得的结合能都跟实验值很接近. 计算结果显示13N的第一激发态（2s1/2）和第三激发态（1d5/2）各存在一个非束缚的质子晕， 而13C的第三激发态（1d5/2）存在一个弱束缚的中子皮. 另外研究表明, 在另一对镜像核15N-15O的第二激发态（2s1/2）和第一激发态（2s1/2）分别存在一个中子晕和质子皮. Properties of two pairs of mirror nuclei 13N-13C and15N-15O are investigated by using the nonlinear relativistic mean field theory. It is found that all the calculated binding energies with two different parameter sets are very close to the experimental ones for both the ground states and the excited states. The calculations show that the first excited state (2s1/2) and the third excited state (1d5/2) in 13N are both unbound resonances with proton halo structure, whereas the third excited state (1d5/2) in 13C is weakly bound with a neutron skin. It is also predicted that there has a proton halo in the second excited state (2s1/2) of 15N as well as a neutron skin in the first excited state (2s1/2) of 15O.     

卟啉配合物-巯基棉体系分光光度法测定中药中铅、镉、铜

研究了卟啉与铅、镉、铜的反应及配合物的电子吸收光谱。结合巯基棉分离富集方法 ,将此金属卟啉配合物体系成功地应用于中药中微量铅、镉、铜的测定。方法简便 ,测定体系抗干扰的效果好 ,灵敏度高。实际样品测定的RSD在 3 3%～ 9 6 %之间。样品加标回收率在 90 %～ 1 0 3%之间。     

Diffusion measurements with the aid of nutation spin echoes appearing after two inhomogeneous radiofrequency pulses in inhomogeneous magnetic fields

Nutation echoes are generated by radiofrequency (RF) pulses with an inhomogeneous amplitude, B(1) = B(1)(r), in inhomogeneous magnetic fields, B(0) = B(0)(r). The two gradients of strengths G(1) and G(0), respectively, must be aligned in parallel for a maximum echo signal. After two RF pulses, two echoes appear at times tau(a) = 2 tau(1) + tau(2) + (G(1)/G(0))tau(1) and tau(b) = 2 tau(1) + tau(2) + 2(G(1)/G(0))tau(1), where tau(1) is the RF pulse duration and tau(2) the interpulse interval. It is shown that these echoes can favorably be employed for the determination of self-diffusion coefficients even in the poor experimental situation one often faces in low-resolution or low-field NMR. The signal intensity is comparable to that of ordinary Hahn echoes. Diffusion coefficients and spin-lattice relaxation times can be evaluated from the same experimental data set if both nutation echoes are recorded. Test experiments are in good agreement with literature data. Applications of the technique to "inside out" NMR, well logging NMR, surface coil NMR, toroid cavity NMR, etc., are suggested.     

界面对Fe65Co35薄膜微结构和软磁性的影响

用不同的材料（Co₉₃Fe₇和Fe）作衬底层,利用磁控溅射法成功制备了Fe₆₅Co₃₅（主层）/衬底层结构的双层薄膜．通过X射线衍射和磁性测量发现,在不同的衬底上沉积的Fe₆₅Co₃₅薄膜的织构不同,并且（200）取向的Fe₆₅Co₃₅薄膜的面内各向异性和软磁性优于（110）取向的Fe₆₅Co_{35关键词： 65}Co₃₅薄膜')" href="#">Fe₆₅Co₃₅薄膜 衬底层 界面各向异性 软磁性     

The effects of dissolved oxygen upon amide proton relaxation and chemical shift in a perdeuterated protein

The effects of dissolved molecular oxygen upon amide proton ((1)H(N)) longitudinal and transverse relaxation rates and chemical shifts were studied for a small protein domain, the second type 2 module of fibronectin ((2)F2)-isotopically enriched to 99% (2)H, 98% (15)N. Longitudinal relaxation rate enhancements, R(O(2))((1)H(N)), of individual backbone (1)H(N) nuclei varied up to 14 fold between a degassed and oxygenated (1 bar) solution, indicating that the oxygen distribution within the protein is inhomogeneous. On average, smaller relaxation rate enhancements were observed for (1)H(N) nuclei associated with the core of the protein compared to (1)H(N) nuclei closer to the surface, suggesting restricted oxygen accessibility to some regions. In agreement with an O(2)-(1)H(N) hyperfine interaction in the extreme narrowing limit, the (1)H(N) transverse relaxation rates showed no significant change, up to an oxygen pressure of 9.5 bar (the maximum pressure used in this study). For most (1)H(N) resonances, small deltadelta(O(2))((1)H(N)) hyperfine chemical shifts could be detected between oxygen pressures of 1 bar and 9.5 bar.     

N-(苯基,二茂铁基)甲基-β-羟乙胺与Ni(Ⅱ),Cu(Ⅱ),Zn(Ⅱ),Cd(Ⅱ),Hg(Ⅱ)配合物的红外光谱研究

二茂铁基苯基甲醇与三氟化硼-乙醚溶液在二氯甲烷中作用,形成相应的二茂铁苯基甲基碳正离子,无需从反应混合物中分离出来,该离子便可与乙醇胺作用得到N-(苯基, 二茂铁基)甲基-β-羟乙胺(FcY),用该氨基醇分别与氯化镍,氯化铜,氯化锌,氯化镉,氯化汞反应,制备了氨基醇-镍(Ⅱ)、 氨基醇-铜(Ⅱ)、 氨基醇-锌(Ⅱ)、 氨基醇-镉(Ⅱ)、 氨基醇-汞(Ⅱ)五种二茂铁基氨基醇-重金属配合物(用通式M-FcY表示)。 用Nexus670FTIR红外光谱仪对二茂铁基氨基醇和五种配合物在4 000～400 cm-1范围内测定傅里叶变换红外光谱,对各M-FcY的FTIR主要吸收峰做了经验归属,并将各M-FcY的特征吸收峰与FcY的相应吸收峰作对比分析,结果表明：配合物中—OH , —NH—键的吸收峰位置均向低波数方向移动;C—O, C—N键吸收峰位置向高波数方向移动。说明二茂铁基氨基醇中的氨基、羟基与重金属离子之间形成了配位键。     

直接荧光法和流动注射荧光法测定微量氨的研究

在碱性介质中 ,基于氨与邻苯二甲醛及 2 巯基乙醇反应生成强荧光性吲哚取代衍生物的体系建立测定水溶液中微量氨的直接荧光法和流动注射荧光法。曲通X 10 0 (TritonX 10 0 )对该体系具有良好的增稳作用。在λex=4 15nm ,λem=4 86nm下 ,用直接荧光法测定NH3含量在 0 2～ 1 0 μg·mL- 1 范围内 ,工作曲线的回归方程为ΔI =2 2 2 86 785 71cNH3(μg·mL- 1 ) (I即为Intensity) ,r=0 9995 ;NH3含量在 0 0 2～ 0 10 μg·mL- 1 范围内 ,工作曲线的回归方程为ΔI=- 2 7 4 2 9 2 371 4cNH3(μg·mL- 1 ) ,r=0 996 5。用流动注射法测定的工作曲线的回归方程为ΔI=1188cNH3(μg·mL- 1 ) ,r=0 9998,线性范围为 0～ 0 7μg·mL- 1 ,并对反应机理进行初步探讨。     

铕与4-(4-吡啶甲酰基)苯甲酸配合物的合成与荧光性能研究

以Eu3+为中心离子,4-(4-吡啶甲酰基)苯甲酸(HPFBA)、1,10-菲罗啉(Phen)和三苯基氧膦(TPPO)为配体,合成了新型配合物Eu(PFBA)3(H2O)4,Eu(PFBA)3Phen(H2O)3和Eu(PFBA)3TPPO(H2O)3(PFBA=4-(4-吡啶甲酰基)苯甲酸根).红外光谱表明,形成配合...     

PEG-Na2SO4-PAR体系中Pd(Ⅱ)、U(Ⅵ)、Mo(Ⅵ)的萃取分离

本文研究了在聚乙二醇－２０００（ＰＥＧ）－硫酸钠（Ｎａ２ＳＯ４）－４－（２－吡啶偶氮）－间苯二酚（ＰＡＲ）体系中,Ｐｄ（Ⅱ）、Ｕ（Ⅵ）、Ｌａ（Ⅲ）、Ｍｏ（Ⅵ）的萃取行为。实验结果表明,在ｐＨ４．５￣７．５溶液中,Ｐｄ（Ⅱ）、Ｕ（Ⅵ）、可被ＰＥＧ相几乎完全萃取,Ｌａ（Ⅲ）部分被萃取,而Ｍｏ（Ⅵ）则不被蔺取,从而实现了Ｍｏ（Ⅵ）与Ｐｄ（Ⅱ）、Ｕ（Ⅵ）混合离子间的定量分离,并初步探讨了ＰＥＧ相的萃取机理     

2—溴甲基萘荧光和室温磷光性质研究

研究了２－溴甲基萘（２－ＢｒＭＮ）的荧光及磷光性质。２－溴甲基萘是一种优良的荧光试剂,λｅｘ／λｅｍ＝２７４／３３４ｎｍ,其浓度在１．０×１０＾－６～１．２×１０＾－４ｍｏｌ·Ｌ＾－１范围内与荧光强度呈良好的线性关系,相关系数ｒ＝０．９９９,最低检测限为４．７×１０＾－８ｍｏｌ·Ｌ＾－１。以β－环糊精（β－ＣＤ）作保护剂和１,２－二溴丙烷（ＤＢＰ）为重原子微扰剂的２－ＢｒＭＮ／β－ＣＤ／ＤＢＰ体系     

Emission Spectrometric Analysis of Fresh Waters with U-Shaped D.C. Arc with Aerosol Supply

Abstract

The application of a U-shaped d.c. arc with aerosol supply for analysis of fresh waters has been described. Limits of detection obtained with d.c. plasma compare well with those reported for ICP. A number of spectral lines and molecular bands were examined and the most suitable are selected to ensure the best limits of detection or wide dynamic ranges. Limits of detection in ng ml^?1, given in the parenthesis, following the element symbol, are: Al(0.9), B(0.6), Ba(0.2), Be(0.15), Ca(0.05), Cd(3.5), Co(1.1), Cr(0.2), Fe(2.4), Ga(0.5), Hg(9.0), K(0.3), Li(0.008), Mg(0.4), Mn(0.3), Mo(0.7), Na(0.04), Ni(2.0), P(45), Pb(12), Si(9.0), Sr(0.04), Zn(1.3).     

14N chemical shifts and quadrupole coupling constants of inorganic nitrates

The isotropic chemical shift and the nuclear quadrupole coupling constant for (14)N were obtained for 14 inorganic nitrates by solid-state MAS NMR measurements at two different field strengths, 9.4 and 11.7 T. The compounds studied were polycrystalline powders of AgNO(3), Al(NO(3))(3), Ba(NO(3))(2), Ca(NO(3))(2), CsNO(3), KNO(3), LiNO(3), Mg(NO(3))(2), NaNO(3), Pb(NO(3))(2), RbNO(3), Sr(NO(3))(2), Th(NO(3))(4)center dot4H(2)O, and UO(2)(NO(3))(2)center dot3H(2)O. Even though the spectra show broadening due to (14)N quadrupole interactions, linewidths of a few hundred hertz and a good signal-to-noise ratio were achieved. From the position of the central peaks at the two fields, the chemical shifts and the nuclear quadrupole coupling constants were calculated. The chemical shifts for all compounds studied range from 282 to 342 ppm with respect to NH(4)Cl. The nuclear quadrupole coupling constants range from 429 kHz for AgNO(3) to 993 kHz for LiNO(3). These data are compared with those available in the literature.     

Coupling of simultaneously acquired electrophysiological and haemodynamic responses during visual stimulation

We investigate the relationship between the temporal variation in the magnitude of occipital visual evoked potentials (VEPs) and of haemodynamic measures of brain activity obtained using both blood oxygenation level dependent (BOLD) and perfusion sensitive (ASL) functional magnetic resonance imaging (fMRI). Volunteers underwent a continuous BOLD fMRI scan and/or a continuous perfusion-sensitive (gradient and spin echo readout) ASL scan, during which 30 second blocks of contrast reversing visual stimuli (at 4 Hz) were interleaved with 30 second blocks of rest (visual fixation). Electroencephalography (EEG) and fMRI were simultaneously recorded and following EEG artefact cleaning, VEPs were averaged across the whole stimulation block (120 reversals, VEP₁₂₀) and at a finer timescale (15 reversals, VEP₁₅). Both BOLD and ASL time-series were linearly modelled to establish: (1) the mean response to visual stimulation, (2) transient responses at the start and end of each stimulation block, (3) the linear decrease between blocks, (4) the nonlinear between-block variation (covariation with VEP₁₂₀), (5) the linear decrease within block and (6) the nonlinear variation within block (covariation with VEP₁₅).