Phase modulation in dipolar-coupled A2 spin systems: effect of maximum state mixing in H NMR in vivo

Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (A_n system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time.     

Thermal treatment on composite γ-zirconium phosphate-silica

The prepared amorphous γ-ZrP\SiO₂ composite had a complicated composition, since a part of γ-ZrP is converted to α-form during the exfoliation of it. The γ-ZrP\SiO₂ composite have specific surface area of 421 m²g^–1. The acidic P–OH groups of the lamellae species placed on the surface (it is ≈1.0 meq g^–1), do not destroy until the temperature of 1030 K. During the thermal treatment the total mass loss of 7.79% was found. This value corresponds to 0.42 mole of H₂O per molecule unit. The water loss process was found very slow, because of the placing of bilamellar species in the composite.     

正丁基苝四羧酸二酰亚胺的晶型和性能研究

文章合成了N,N'-二正丁基苝四羧酸二酰亚胺,并纯化、调晶,进行了IR、元素分析、X射线等测定.分析该化合物在DMF中的紫外光谱(最大吸收波长524.80 nm)、荧光光谱(最大发射波长539.0 nm)、Stokes位移(数值15 nm)等光谱性质.在400～700 nm范围内,α晶型薄膜紫外-可见吸收出现很强的吸收峰,且由β型变为α型,最大吸收波长有明显的红移(545 nm变为580 nm).X射线粉末衍射也反映出α晶型的2θ在26.0°处衍射峰CPS为2 508,β型在25.2°为1 891.α,β晶型作为电荷产生材料制得的功能分离型有机光导体,在光源滤波波长λ=532 nm曝光下,测得含α,β感光体达到饱和电位的时间分别为46,93.98 s,光衰电位(5.3千伏电压负充电电晕,1～2 s后的表面电位)分别为727和525 V,半衰曝光量分别为4.32,4.34μJ·cm-2,残余电位分别为30和45 V等光导性能数值.     

用离子速度影象技术研究n-C4H9Br的光解

利用离子速度影象技术研究了正一溴丁烷(n-C4H9Br)在231~267 nm波段的光解,得出了如下结论:正一溴丁烷(n-C4H9Br)在231~267 nm波段的吸收源于基态到三个最低激发态的跃迁,这三个激发态标识为1A″、2A′和3A′;发生在这三个排斥态的势能面(PES)上的光解最终导致C4H9 Br(2P3/2)或C4H9 Br*(2P1/2)的产生;2A′和3A′态之间存在避免交叉(Avoided crossing)会影响最终的光解产物;从基态1A′到激发态1A″的跃迁矩垂直于对称面,也就垂直于C-Br键;从基态1A′到激发态3A′的跃迁矩平行于对称面,同时平行于C-Br键;从基态1A′到激发态2A′的跃迁矩在对称面内,且与C-Br键成53.1°夹角.我们也讨论了正一溴丁烷(n-C4H9Br)在234 nm和267 nm附近光解时的避免交叉几率(Avoided crossingprobability),以及它对单通道相对产额(Relative fraction of the individual pathways)的影响.     

若干具有[(PO4)2Mo5O15]簇骼的化合物的光谱研究

本文对所合成的具有 [(PO4 ) 2 Mo5O1 5]簇骼的 3种新颖的有机 磷钼酸盐簇合物(NH3CH2 CH2 NH3) 2 5[(PO4 ) (HPO4 )Mo5O1 5]·7 5H2 O (Ⅰ ) ,(H3NCH2 CH2 NH3) 3·[(PO4 ) 2 Mo5O1 5]·3H2 O (Ⅱ )和(H3NCH2 CH2 NH3) 2 ·[Cu(en) ][(PO4 ) 2 Mo5O1 5]·5H2 O (Ⅲ )用FTIR ,NIR Raman ,紫外 可见漫反射光谱 (UV VisDRS)和荧光光谱等研究手段 ,对其进行光谱研究 ,探讨其结构和性能的关系。在这些化合物中 ,化合物Ⅰ和Ⅱ具有孤立的 [(PO4 ) 2 Mo5O1 5]簇骼基元 ,而化合物Ⅲ的 [(PO4 ) 2 Mo5O1 5]簇骼基元是由 [Cuen]基团桥联成链 ;磷钼酸盐的特征振动频率和这些化合物的结构相关 ;UV VisDRS显示 ,在 2 0 0和 2 6 0nm左右有两个杂多化合物的特征吸收谱带 ;化合物的稳态荧光光谱中 ,观察到以 2 4 0nm激发 ,在大约 4 0 0nm附近出现的由金属氧簇Oμ→Mo跃迁激发所引起的较强的发射峰 ,在化合物 (Ⅲ )中 ,还观察到通过 [Cuen]的荷移跃迁的以 5 70nm激发所产生的 6 0 4nm的发射峰。     

Structures and syntheses of layered and framework amine-bearing uranyl phosphate and uranyl arsenates

Two hydrated uranyl arsenates and a uranyl phosphate were synthesized by hydrothermal methods in the presence of amine structure-directing agents and their structures determined: (N₂C₆H₁₄)[(UO₂)(AsO₄)]₂(H₂O)₃, DabcoUAs, {NH(C₂H₅)₃}[(UO₂)₂(AsO₄)(AsO₃OH)], TriethUAs, and (N₂C₄H₁₂)(UO₂)[(UO₂)(PO₄)]₄(H₂O)₂, PiperUP. Intensity data were collected at room temperature using MoKα X-radiation and a CCD-based area detector. The crystal structures were refined by full-matrix least-squares techniques on the basis of F² to agreement indices (DabcoUAs, TriethUAs, PiperUP) wR₂=5.6%, 8.3%, 7.2% for all data, and R₁=2.9%, 3.3%, 4.0%, calculated for 1777, 5822, 9119 unique observed reflections (|F_o|?4σ_F), respectively. DabcoUAs is monoclinic, space group C2/m, Z=2, a=18.581(1), b=7.1897(4), c=7.1909(4) Å, β=102.886(1)°, V=936.43(9) Å³, D_calc=3.50 g/cm³. TriethUAs is monoclinic, space group P2₁/n, Z=4, a=9.6359(4), b=18.4678(7), c=10.0708(4) Å, β=92.282(1)°, V=1790.7(1) Å³, D_calc=3.41 g/cm³. PiperUP is monoclinic, space group Pn, Z=2, a=9.3278(4), b=15.5529(7), c=9.6474(5) Å, β=93.266(1)°, V=1397.3(1) Å³, D_calc=4.41 g/cm³. The structure of DabcoUAs contains the autunite-type sheet formed by the sharing of vertices between uranyl square bipyramids and arsenate tetrahedra. The triethylenediammonium cations are located in the interlayer along with two H₂O groups and are disordered. Both TriethUAs and PiperUP contain sheets formed of uranyl pentagonal bipyramids and tetrahedra (arsenate and phosphate, respectively) with the uranophane sheet-anion topology. In TriethUAs, triethlyammonium cations are located in the interlayer. In PiperUP, the sheets are connected by a uranyl pentagonal bipyramid that shares corners with phosphate tetrahedra of adjacent sheets, resulting in a framework with piperazinium cations and H₂O groups in the cavities of the structure.     

Thermoanalytical investigation of layered titanium salts

The investigated materials have similar routes of thermal decomposition; i.e. they lose their crystal water first, then at a higher temperature their structural one. At least the result TiP₂O₇ goes through a phase change at about 1000 K. The amorphous titanium phosphate lost its crystal and structural water at higher temperature than those of crystalline forms. Both α- and γ-titanium phosphates and also their transition metal containing forms have layered structure. In case of α- and γ-forms after the loss of crystal water a phase change occurs which is followed by the decomposition of the molecule. Various transition metals containing γ-titanium phosphates lose their crystal water at the same temperature, with the exception of Ni containing ones. The process is finished in this case at temperature 90 K higher than that of the others. This revised version was published online in July 2006 with corrections to the Cover Date.     

电流密度对钙磷沉积层组成和结构的影响(英文)

用X射线衍射、激光拉曼光谱以及等离子体原子发射光谱等技术研究了电化学沉积钙磷陶瓷过程中 ,电流密度对电沉积层组成和结构的影响 .实验表明阴极表面得到的沉积物是几种钙磷盐组成的混合物 ,且其成份随电流密度的改变而发生较大的变化 .在电解液温度为 75℃条件下 ,当控制电流密度较低时 ,沉积层主要由CaHPO4· 2H2 O (DCPD)和Ca8H2 (PO4) 6· 5H2 O (OCP)组成 ;随着电流密度的增加 ,阴极表面逐渐生成Ca3 (PO4) 2 ·nH2 O (TCP)和Ca10 (PO4) 6(OH) 2 (HAP) .当电流密度大于 5mA/cm2 时 ,电沉积层的主要成份为羟基磷灰石 (HAP) .     

Thermal decomposition of struvite

Struvite (NH₄MgPO₄·6H₂O) is a mineral often found in urinary tracts and kidneys. Thermal decomposition using slow low heating shows that the 'kidney' stone can be decomposed at temperatures below 40°C. At this temperature both ammonia and water are evolved. If more rapid heating is employed the decomposition occurs at around 80°C. The implication of this work rests with the use of low slow heat for the decomposition of the kidney stones. This revised version was published online in July 2006 with corrections to the Cover Date.