C_(60)O_n(n=2,3)异构体的合成和理论计算研究

本文通过臭氧氧化C60得到C60On的混合物,反相高压液相色谱图表明有两种C60O2异构体和两种C60O3异构体,分别标记为C60O2(I)、C60O2(II)和C60O3(I)、C60O3(II),同时得到了它们的UV-vis谱图。为了确定它们的最可能结构,我们对四种最可能的C60O2异构体和九种最可能的C60O3异构体进行了理论计算,从能量、偶极矩、电子光谱方面进行了系统研究,提出了实验得到的C60On(n=2,3)的稳定结构。计算结果与实验吻合良好。     

产生医用放射性核素核数据的测量、理论计算与评价

简要介绍已广泛用于临床的^32P,^89Sr,^90Y,^103Pd,^125I,^131I,^137Cs,^153Sm,^186Re,^188Re,^192Ir和具有很大潜在使用可能性的^64Cu,^67Cu,^67Ga,^86Y,^105Rh,^111In,^114mIn,^124I,^149Pm,^166Ho,^169Yb,^177Lu,^211At,^213Bi,^225Ac 26个放射性核素利用反应堆或加速器或衰变的55种不同途径产生的核数据的测量、理论计算及数据可靠性的初步评价,以改善其在诊断和治疗医用中的安全性、有效性和科学性。The nuclear data measurements and preliminary evaluation as well as alculation for established and emerging 26 radionuclides produced in 55 ways by using reactor or accelerator or decay are briefly introduced in order to keep the safety and validity in medical therapeutic applications. The 11 established radionuclides are ^32P,^89Sr,^90Y,^103Pd,^125I,^131I,^137Cs,^153Sm,^186Re,^188Re,^192Ir and the 15 emerging radionuclides are 64Cu,^67Cu,^67Ga,^86Y,^105Rh,^111In,^114mIn,^124I,^149Pm,^166Ho,^169Yb,^177Lu,^211At,^213Bi,^225Ac.     

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。     

2-(4-氯代苯甲酰基)苯甲酸配合物光致发光研究

以Eu3+,Tb3+为中心离子,2-(4-氯代苯甲酰基)苯甲酸(HCBBA)为第一配体,邻菲咯啉(Phen)、三苯基氧膦(TPPO)、二苯亚砜(DPSO)为第二配体,合成了多种铕铽的二元和三元配合物,并测试其荧光效能,以研究配体的加入对中心离子发光强度的影响。结果表明,合成的配合物均发出Eu(Ⅲ)和Tb(Ⅲ)的特征荧光,但相对强度明显不同。在铕与2-(4-氯代苯甲酰基)苯甲酸根(CBBA)形成的配合物体系中,Phen和DPSO显示了较强的敏化作用,且Phen敏化效果更强,而TPPO则对配合物荧光有猝灭作用。在Tb-CBBA体系中,DPSO表现出很强的敏化作用, Phen和TPPO却对配合物荧光起猝灭作用,且TPPO猝灭效果更强。经红外推测,羧酸根均以双齿桥式与Eu3+和Tb3+配位;在3 200～3 600 cm-1出现水的弱的羟基的伸缩振动吸收峰,表明配合物中含有结晶水。     

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.     

Characterization of microporous aluminophosphate IST-1 using (1)H Lee-Goldburg techniques

The presence of two independent methylamine species in microporous aluminophosphate IST-1 (|(CH(3)NH(2))(4)(CH(3)NH(+)(3))(4)(OH(-))(4)|[Al(12)P(12)O(48)]) has been shown previously by synchrotron powder X-ray diffraction. One of these species, [N(1)-C(1)], links to a six-coordinated framework Al-atom [Al(1)], while the other methylamine [N(2)-C(2)] is protonated and hydrogen-bonded to three O-atoms [O(1), O(2) and O(12)]. We revisit the structure of IST-1 and report the complete assignment of the (1)H NMR spectra by combining X-ray data and high-resolution heteronuclear/homonuclear solid-state NMR techniques based on frequency-switched Lee-Goldburg homonuclear decoupling and (31)P-(31)P homonuclear recoupling. Careful analysis of the 2D (1)H-X homonuclear correlation (X=(1)H) and 2D heteronuclear correlation (X=(13)C, (31)P and (27)Al) spectra allowed the distinction of both methylamine species and the assignment of all (31)P and (13)C resonances. For the first time at a relatively high (9.4 T) magnetic field, symmetric doublet patterns have been observed in the (13)C spectra, caused by the influence of the (14)N second-order quadrupolar interaction.     

吸光度比值-导数光谱法同时测定铜(Ⅱ)和铬(Ⅲ)的研究

提出了运用吸光度比值-导数光谱法同时测定Cr(Ⅲ)与Cu(Ⅱ)含量的新方法。在pH 5.7的HAc-NaAc的缓冲溶液中,Cr3+,Cu2+与铬天青S(CAS)和溴化十六烷基三甲胺(CTMAB)可分别形成蓝色三元络合物。其摩尔吸光系数分别为2.52×105 L·mol-1·cm-1和1.01×105 L·mol-1·cm-1。Cu2+和Cr3+的浓度分别在0.08～1.2 μg·mL-1和0.05～0.52 μg·mL-1范围内符合比尔定律,其检测限分别为0.014和0.013 μg·mL-1。此方法应用于环境水中Cr(Ⅲ),Cu(Ⅱ)的同时测定,取得了满意的结果。     

紫外差光谱测定Gd(Ⅲ), Yb(Ⅲ)与HBED配合物的条件稳定常数

在0.01 mol·L-1 N-2-羟乙基哌嗪-N'-2-乙磺酸(Hepes), pH 7.4, 室温条件下, 应用紫外差光谱滴定观察了Gd(Ⅲ), Yb(Ⅲ)与N, N'-二(2-羟苄基)乙二胺-N, N'-二乙酸(HBED)的结合. 结果表明 Gd(Ⅲ), Yb(Ⅲ)与HBED均形成1∶1的配合物, 其紫外差光谱均于237和291 nm处出现吸收峰, 在237 nm处配合物Gd-HBED与Yb-HBED的摩尔吸光系数分别为 ΔεGd=(22.52±0.20)×103 cm-1·mol-1·L, ΔεYb=(27.15±0.11)×103 cm-1·mol-1·L; 配合物Gd-HBED与Yb-HBED的条件稳定常数分别为 lgKGd-HBED=13.56±0.28, lgKYb-HBED=16.06±0.03, 符合线性自由能关系.     

Spin-glass-like magnetic ordering in Zn substituted magnetite magnetic fluids

Electron spin resonance (ESR) spectra of magnetic fluids involving polydispersed Zn(0.5)Fe(0. 5)Fe(2)O(4) (FZ5) and Zn(0.7)Fe(0. 3)Fe(2)O(4) (FZ7) nanomagnetic particles are scanned from 4.2 to 300K. The FZ7 fluid exhibits certain distinct features below 40K which are different from FZ5 fluid. These include (i) an isotropic shift in resonance field in zero-field-cooled ESR study, (ii) deviation of resonance field from sin(2)theta behavior (where theta is the angle between axis of the particle and field) in field cooled (FC) sample and (iii) abrupt increase in anisotropy field for FC sample. The results are analyzed in light of the core-shell model for nanomagnetic particles.     

Dynamics for Reactions of Ion Pairs in Aqueous Solution: Reactivity of Tosylate Anion Ion Paired with the Highly Destabilized 1-(4-Methylphenyl)-2,2,2-Trifluoroethyl Carbocation

The sum of the rate constants for solvolysis and scrambling of carbon bridging and nonbridging oxygen-18 at 4-MeC(6)H(4)CH(CF(3))OS((18)O(2))Tos in 50/50 (v/v) trifluoroethanol/water, (k(solv) + k(iso)) = 5.4 × 10(-6) s(-1), is 50% larger than k(solv) = 3.6 × 10(-6) for the simple solvolysis reaction of the sulfonate ester. This shows that the ion pair intermediate of solvolysis undergoes significant internal return to form reactant. These data give a value of k(-1) = 1.7 × 10(10) s(-1) for internal return of the carbocation-anion pair to the substrate. This rate constant is larger than the value of k(-1) = 7 × 10(9) s(-1) reported for internal return of an ion pair between the 1-(4-methylphenyl)ethyl carbocation and pentafluorobenzoate anion to the neutral ester (4-MeC(6)H(4)CH(CH(3))O(2)CC(6)F(5)) in the same solvent. The partitioning of ion pairs to the 1-(4-methylphenyl)ethyl carbocation and to the highly destabilized 1-(4-methylphenyl)2,2,2-trifluoroethyl carbocation is compared and contrasted.     

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.     

BaMgAl10O17:Eu2+,Mn2+中Eu2+→Mn2+的能量传递

在还原气氛下采用高温固相法合成了BaMgAl10O17:Mn2 ,BaMgAl10O17:Eu2 ,BaMgAl10O17:Eu2 ,Mn2 粉末样品,测量并研究了它们的激发光谱和发射光谱性质.结果表明:BaMgAl10O17:Eu2 ,Mn2 中,Eu2 的发射光谱和Mn2 的吸收光谱之间的光谱交叠范围较大,两种离子之间发生了明显的交叉弛豫过程,即有较强的共振能量传递过程,导致在紫外光的激发下,样品BaMgAl10O17:Eu2 ,Mn2 发射光谱中以蓝光和绿光为主.     

光度法研究聚乙二醇-硫酸铵-邻苯三酚红体系中铋(Ⅲ), 铁(Ⅲ), 铜(Ⅱ), 镍(Ⅱ), 钴(Ⅱ), 铅(Ⅱ)的萃取分离

本文研究了在聚乙二醇(PEG)-硫酸铵[(NH_4)_2SO_4]-邻苯三酚红(PR)体系中Bi(Ⅲ),Fe(Ⅲ),Cu(Ⅱ),Ni(Ⅱ),Co(Ⅱ),Pb(Ⅱ)的萃取行为。实验结果表明,Bi(Ⅲ)在pH3.5～6.5及Fe(Ⅲ)在pH4.0～7.0范围内可以被PEG相几乎完全萃取,而Cu(Ⅱ),Co(Ⅱ)在pH1.0～7.0,Pb(Ⅱ)在pH2.0～7.0,Ni(Ⅱ)在pH1.0～4.5则不被萃取。从而实现了将Bi(Ⅲ)(pH3.5),Fe(Ⅲ)(pH5.0)与Cu(Ⅱ),Co(Ⅱ),Pb(Ⅱ),Ni(Ⅱ)混合离子的定量分离。同时探讨了PEG相的萃取机理。     

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。     

铕-樟脑酸-1,10-菲咯啉配合物的合成及发光性质

实验合成了稀土铕 樟脑酸 1,10 菲咯啉二元、三元配合物 ,通过元素分析、1 HNMR、中红外光谱、拉曼光谱 ,确定了配合物的组成为Eu2 (CA) 3·2H2 O ,Eu2 (CA) 3(phen) 2 (CA :樟脑酸根 ,phen :1,10 菲咯啉 ) ,另外 ,又合成了铕、镧混配的上述配合物 ,通过三维荧光光谱确定最佳激发波长为 310nm ,最强荧光波长为6 12nm ,即在 310nm光的激发下 ,发射光谱显示Eu3 的特征发射光谱 ,产生 7条谱带 ,分别是 5D0 7F0 (5 79nm) ,5D0 7F1 (5 94nm) ,5D0 7F2 (6 12 ,6 2 0nm) ,5D0 7F3(6 5 0nm) ,5D0 7F4 (6 89,6 97nm) ,其中7F2 和7F4能级发生了分裂。对荧光强度的研究表明 ,镧的掺入并没有降低铕的荧光强度 ,说明镧对铕的荧光发射有增强作用 ,但发射峰的位置基本不变。     

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).     

纳米相氟氧化物玻璃陶瓷中Er3+Yb3+离子对的量子剪裁发光造成的强的光谱调制

研究了纳米相氟氧化物玻璃陶瓷中Er3+Yb3+离子对的量子剪裁发光造成的强的光谱调制现象。测量了Er3+Yb3+双掺纳米相氟氧化物玻璃陶瓷的X射线衍射谱、表面形貌、激发光谱、吸收光谱、和发光光谱;而且也与Tb3+Yb3+双掺纳米相氟氧化物玻璃陶瓷的相对应的光谱参数进行了比较。发现378 nm光激发样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV所导致的652.0 nm红色发光强度为522 nm光激发时的680.85倍和303.80倍;我们还发现378 nm光激发所导致的样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV的 652.0 nm红色发光强度为样品(C) Er(0.5%)∶FOV 的491.05和184.12倍。我们还发现在378 nm光激发时的样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV的{978.0和1 012.0 nm}红外发光强度依次分别为样品(C) Er(0.5%)∶FOV 的{58.00和293.62}倍和{25.11和 67.50}倍。更进一步,对于652.0 nm波长发光的激发谱,发现(A) Er(1%)Yb(8.0%)∶FOV和(B) Er(0.5%)Yb(3.0%)∶FOV的378.5 nm激发谱峰强度是(C) Er(0.5%)∶FOV的大约606.02和199.83倍。同时,也发现样品(A) Er(1%)Yb(8.0%)∶FOV和样品(B) Er(0.5%)Yb(3.0%)∶FOV的一级量子剪裁红外1 012或978 nm发光强度为样品(D) Tb(0.7%)Yb(5.0%)∶FOV的二级量子剪裁红外976 nm发光强度的101.38和29.19倍。发现的该量子剪裁是目前所报道的最强的量子剪裁。因此,相信所发现的氟氧化物纳米玻璃陶瓷中Er3+Yb3+离子对的一级量子剪裁发光是强的可以作为量子剪裁层应用到提高晶硅太阳能电池的发电效率。研究结果也能加速对目前国际热点的下一代环保的光谱调制太阳能电池的探索。     

叶绿素a锰（Ⅲ）和叶绿素a锰（Ⅱ）的合成和光谱

叶绿素ａ锰（Ⅲ）（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）由脱镁叶绿素（Ｐｈｅｏ－ａ）和醋酸锰（Ⅱ）合成而得，用反相高效液相色谱法分离纯化，叶绿素ａ锰（Ⅱ）（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）用Ｎａ２Ｓ２Ｏ４还原时绿素ａ锰（Ⅲ）获得，研究了它们的元素分析（ＥＡ），紫外可见吸附光谱（ＵＶ－Ｖｉｓ）和傅里叶红外吸收光谱（ＦＴ－ＩＲ）证明了此二种配合物的合成，并给出了（Ｍｎ（Ⅲ）－Ｃｈｌ－ａ）与（Ｍｎ（Ⅱ）－Ｃｈｌ－ａ）的组成分     

新型尾式卟啉-吡啶季铵盐对铜(Ⅱ)显色反应研究

研究了三种新型不同链长尾式卟啉 -吡啶季铵盐与Cu2 的显色反应条件 ,其络合物最大吸收波长分别为 4 13nm(Ⅰ ) ,(Ⅱ ) ;4 14nm(Ⅲ )。在相同条件下 ,试剂最大吸收波长分别为 4 4 3 5nm(Ⅰ ) ;4 4 4nm(Ⅱ ) ;4 4 6nm(Ⅲ )。对比度大约 30nm。试剂与铜络合比均为 1∶1,表观摩尔吸光系数为 (Ⅰ ) 3 4× 10 5,(Ⅱ )2 9× 10 5;(Ⅲ ) 2 5× 10 5L·mol-1·cm-1,铜含量分别在 (Ⅰ ) 0～ 0 5 μg·( 10mL) -1;(Ⅱ ) 0～ 0 6 μg·( 10mL) -1;(Ⅲ ) 0～ 1 0 μg·( 10mL) -1内符合比尔定律 ,可用于痕量铜的测定。     

Efficient blue phosphorescent organic light emitting diodes with host engineering

We demonstrate as much as possible blue color and high efficiency phosphorescent organic light-emitting diodes (PHOLEDs) by using well-known iridium(III)bis[(3,5-difluoro-4-cyanophenyl)-pyridinato-N,C′]picolinate (FCNIrpic) dopant and previously reported good host materials. For the control of blue color and efficiency, various host materials, 1,3-bis(carbazole-9-yl)benzene (mCP), 9-(3-(9H-carbazole-9-yl)phenyl)-3-(dibromophenylphosphoryl)-9H-carbazole (mCPPO1), and 2,8-di(9H-carbazol-9-yl)dibenzo[b,d]furan (DFCz), bis(4-(N-carbazole)phenyl)dimethylsilane (2MCBP) are selected and investigated their performances. A maximum external quantum efficiency (EQE) of 23.9% and power efficiency of 30.2 lm/W are achieved from 2MCBP device with Commision Internationale de L'Eclairage color coordinates (CIE_x,y) of (0.14, 0.21). The deepest color with color coordinate of (0.14, 0.19) is obtained for the mCP device.