卟啉及其稀土配合物的紫外可见光谱

合成了稀土卟啉配合物-钇卟啉,研究了卟啉及钇卟啉的电子吸收光谱,讨论了溶剂的性质对其电子吸收光谱的影响,实验结果表明:钇卟啉在丙酮和三氯甲烷中的光稳定性最好,是很好的光敏剂。     

稀土邻菲咯啉双核配合物的光谱研究

合成了 Yx Eu1-x(phen) 2 Cl3· n H2 O、Tbx Eu1-x(phen) 2 Cl3· n H2 O(x=0、0 .2 5、0 .5 0、0 .75 )固体配合物 ,并测定了红外光谱、荧光发射光谱 ,讨论了配合物的组成与发光特性     

吡喃酮类化合物与镱配合物的红外和拉曼光谱研究

采用非水体系中牺牲金属阳极的电化学方法分别合成了稀土金属镱与 3 羟基黄酮及 3 羟基 2 甲基 γ 吡喃酮的配合物。对配合物进行了IR和Raman光谱测定。两种光谱提供了互为补充的信息 ,配体经配位后—OH的伸缩振动谱峰消失 ,部分相关的谱峰频率发生了明显位移 ,特别是羰基伸缩振动红移十分明显 ,在Raman光谱的低波数区间检测到可指认为金属和配体键合的伸缩振动。根据这两种光谱的研究结果推断了所得配合物的可能结构。     

镧系元素双1：11系列杂多蓝的红外光谱和紫外光谱研究

本文首次系统研究了镧系元素钼采双１：１１系列两子杂多蓝ＫｚＨｙ（Ｌｎ（ＸＭｏ１１Ｏ３９０２）．ｎＨ２Ｏ（Ｘ＝Ｐ，Ｌｎ＝Ｌａ，Ｃｅ，Ｐｒ，Ｎｄ，Ｓｍ，Ｇｄ；Ｘ＝Ｓｉ，Ｌｎ＝Ｃｅ，Ｐｒ，Ｓｍ，Ｔｂ，Ｄｙ）的红外光谱和紫外光谱，对特征峰进行指认，并与还原前的杂多酸盐进行比较，发现有的特征峰出现小的位移，有的峰强度稍有变化，所以得出结论，还原前后，杂多阴离子结构基本不变，但有轻微的畸变。     

荧光光谱滴定法研究对磺酸基杯[4]芳烃对吖啶的包结作用

合成了对磺酸基杯[4]芳烃(1),并用荧光光谱滴定法研究了不同温度下(1)在柠檬酸缓冲溶液(pH=5.92,0.1 mol·L-1)中对吖啶的包结行为.在一定的浓度范围内,当加入(1)后,吖啶的荧光峰有红移,且荧光强度随着所加的(1)浓度的增大而发生猝灭.结果显示二者形成了1∶1的稳定包合物.计算了在15.0,20.0,25.0及30.0℃下的包结稳定常数,它们依次为3.08×105,4.45×104,2.58×104和8.90×103,并计算了热力学参数△G,△H和△S.结果说明反应是放热的且是焓变驱动的.其包结机理可能为吖啶部分进入了对磺酸基杯[4]芳烃的空腔中,且吖啶稠环的质子化的N原子与(1)的一个SO3-基团之间以较强的静电作用成键;在此强静电作用的驱动下以及较弱的范德瓦耳斯力、疏水作用的辅助下主客体形成了1∶1的配合物.     

Intensity of the Secondary Transition of Some 1,3-Benzodioxole Derivatives

1,3-benzodioxole derivatives display a charge transfer (C.T.) transition n₀ → π^* _φ, involving the non-bonding electrons of the oxygen atoms (n₀ stands for the pπ orbitals of the oxygen atoms) and a π^* _φ orbital. It has been studied in a preceding paper for derivatives with a strongly perturbating subtituent: X, in para to one of the oxygen atoms (figure 1).¹ These derivatives will be named underneath Bzd-X (for example Bzd-CO₂H). In the present work, we want to study the intensity of the secondary transition which obeys to rules very different from those of the C.T. transition.     

Spectrophotometric Study of Zinc,Cadmium and Lead Complexes with Murexide in Binary Ethanol-Water Mixtures

The complexation reactions between murexide and Zn²⁺, Cd²⁺ and Pb²⁺ ions in C₂H₅OH-H₂ mixtures have been investigated spectrophotometrically. Formation constants of the resulting 1:1 complexes were determined and found to vary in the order Pb²⁺ > Cd²⁺ > Zn²⁺, in all binary ethanol-water mixtures used. There is an inverse relationship between the complex formation constants and amount of water in the mixed solvent. A linear relationship was observed between log K_f for complexes and the mole fraction of ethanol.     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]2HgX4 (X = Br, I)

The crystal structure of [C(NH₂)₃]₂HgBr₄ has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH₂)₃]⁺ and distorted tetrahedral [HgBr₄]^2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr₄]^2? ion. In accordance with the crystal structure, two ⁸¹Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH₂)₃]₂HgI₄ yielded four ¹²⁷I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The ¹H NMR T ₁ measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C₃ reorientations of the planar [C(NH₂)₃]⁺ ions gave the activation energies of 29.8 kJ mol^?1 for the bromide, and 30.2 and 40.0 kJ mol^?1 for the iodide.     

A Double Isotopic Labelling Study of the Infrared Spectra of the Linkage Isomers [Pd(bipy)(SCN)2], [Pd(bipy)(NCS)2] and Related Complexes

Abstract

The IR spectra of the linkage isomers [Pd(bipy)(SCN)₂] and [Pd(bipy)(NCS)₂] have been determined in the C≡N stretching region (2200–2000 cm^?1) and below 500 cm^?1. The band shifts resulting from deuteration of the 2,2′-bipyridine (bipy) ring and ¹⁵NCS-labelling are shown to provide a ready means for distinguishing between the internal ligand modes, the μPd-N(bipy) and μPd-SCN/μPd-NCS vibrations. The assignment technique has been further extended to the complexes [Pt(bipy)(SCN)₂] and [Pd(phen)(SCN)₂] (phen = 1,10-phenanthroline). Finally, a comparison between the IR spectra of [Pd(bipy)(NCO)₂], [Pd(bipy)(NCS)₂] and [Pd(bipy)(SCN)₂] reveals that the frequencies μM-NCO, μM-NCS and μM-SCN decrease in the sequence NCO > NCS > SCN.     

Synthesis and characterization of the Pd/InVO4-TiO2 co-doped thin films with visible light photocatalytic activities

Novel Pd/InVO₄-TiO₂ thin films with visible light photocatalytic activity were synthesized from the Pd and InVO₂ co-doped TiO₂ sol via sol-gel method. The photocatalytic activities of Pd/InVO₄-TiO₂ thin films were investigated based on the oxidative decomposition of methyl orange in aqueous solution. The as-prepared samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectroscopy (UV-vis). The results indicate that the Pd/InVO₄-TiO₂ thin films are compact, uniform and consist of sphere nanoparticles with diameters about 80-100 nm. The UV-vis spectra show that the Pd/InVO₄-TiO₂ thin films extend the light absorption spectrum toward the visible region. XPS results reveal that doped Pd exist in the form of metallic palladium. The photocatalytic experiments demonstrate that Pd doping can effectively enhance the photocatalytic activities of InVO₄-TiO₂ thin films in decomposition of aqueous methyl orange under visible light irradiation. It has been confirmed that Pd/InVO₄-TiO₂ thin films could be excited by visible light (E < 3.2 eV) due to the existence of the Pd and InVO₄ doped in the films.     

Effect of alcohol consumption on the liver detoxication capacity as measured by [13C]methacetin- and [methyl-13C]methionine-breath tests

The aim of this study was to investigate the hepatic microsomal and mitochondrial functions by using the ¹³CO₂-breath test in healthy subjects either before or after the consumption of red wine. Fourteen adults received [¹³C]methacetin and [methyl-¹³C]methionine together with a standardised dinner. Expired air samples were taken over 6 h. After a wash-out period, the subjects consumed 0.4 ml ethanol/kg/day together with dinner over a 10-day period. Thereafter, ¹³C-tracer administration was repeated under identical conditions. The ¹³CO₂-enrichments were measured by isotope ratio mass spectrometry. The mean cumulative percentage ¹³C-dose recovery (CPDR) after administration of [¹³C]methacetin and [methyl-¹³C]methionine either without or with red wine consumption amounted to 38.2±6.3 vs. 36.3±6.7% (p=0.363) and 9.5±3.3 vs. 8.8±2.5% (p=0.47), respectively. Moderate alcohol consumption does not induce significant short-term changes of the microsomal and the mitochondrial functions of the human liver in healthy subjects.     

Dielectric properties and relaxation behavior of [TMA]2Zn0.5Cu0.5Cl4 compound

The [TMA]₂Zn_0.5Cu_0.5Cl₄ hybrid material was prepared and its dielectric spectra were measured in the 10⁻¹ Hz-10⁶ Hz frequency range and 200-305 K temperature interval. The dielectric permittivity showed a ferroelectric-paraelectric phase transition at 293 K. Double relaxation peaks are observed in the imaginary part of the electrical modulus, suggesting the presence of grain and grain boundary in the sample. The frequency dependent conductivity was interpreted in term of Jonscher's law: σ(ω)=σ_dc+Aωⁿ. The temperature dependent of the dc conductivity (σ_dc) was well described by the Arrhenius equation: σ_dcT=σ_o×exp(−E_a/kT).     

1H NMR Studies on the Methylation,Protonation, and Hydration Sites in Some Benzo[b]Naphthyridines (Azaacridines)

Abstract

The 300.13 MHz ¹H NMR spectra of the methylated and protonated 6(9)-methylbenzo[b][1,x] naphthyridines (x=5, 6, 7, 8) (5-methylazaacridines) were collected at 298 K in deuterated dimethyl sulfoxide and chloroform, respectively. The methylation and protonation sites were assigned by comparisons of these data with those of the free bases. The results were compared with similar data for related heterocycles and showed that both methylation and protonation occur at the nitrogen in the outer pyrido ring in all four series.

The hydration site in some 2-and 3-azaacridines was determined by specific line broadening in their ¹H NMR spectra to be the same nitrogen as that involved in methylation and protonation. Variable temperature ¹H NMR demonstrated that the specific line broadening results from some changes of ¹⁴N quadrupolar relaxation produced by the slow chemical exchange between unhydrated and hydrated species. Deuterium exchange experiments indicated that the direct spin-spin interaction of a water proton and the protons alpha to the hydrated nitrogen may also have some contribution.     

Specific Features of Light Scattering in [N(CH3)4]2CuCl4 Crystals with an Incommensurable Phase

We present the results of investigation of the optical birefringence and intensity of the main light beam that passed through an [N(CH₃)₄]₂CuCl₄ crystal under the conditions of viscous interaction of the incommensurable structure with defects. A nonmonotonic temperature dependence of the basic signal is revealed. The observed temperature dependence of the intensity (in the form of irregular steps) is related to different periods of the incommensurable structure. In transitions between adjacent metastable states the periodicity of the incommensurable structure changes. It is shown that in transition regions for the central beam one observes an anomalous decrease in the light intensity due to the appearance of a perturbation lattice with the wave vector q.     

UV-Visible Spectrophotometric Investigations of Charge Transfer Complexes of Some P-N,N-Dimethylaminobenzylidene Ailines with the New Acceptor PFB and CA Acceptor

The CT complexes of PFB and CA acceptors with eleven benzylidene anilines donors have been investigated spectro-photometrically in the uv-visible region for the first time. The values of Ip of these compounds have been estimated from their complexes with CA, the values are in the range of 8.64–8.96 ev. From these values the constants of the new acceptor PFB a, b, c₁, c₂ and Ea have been calculated, the values are 0.91, -5.31, 7.13, 1.97, and 1.37 ev, respectively. The CT parameters of our donors with PFB and CA acceptors, ζCT, ^KCT ΔG° and W have also been estimated and discussed.     

Ultrasonic frequencies correlated with the volume changes of the q[110] mode for the first-order phase transition in NH4CI

We correlate here by means of γ-Grüneisen relations the volume changes with the ultrasonic frequencies of the q[110] mode of NH₄Cl for the first-order phase transition in this crystal. The ultrasonic frequencies were calculated by a method, which we have developed, using the length-change data from the literature at pressures of 0, 0.2, 0.4 and 0.6 kbar in the first-order phase region of NH4Cl.

Our calculated frequencies are in very good agreement with the observed data from the literature for the q[11 0] mode at these pressures. This shows that by correlating the volume changes with the ultrasonic frequencies, the observed behaviour of NH₄Cl can be explained adequately near the first-order phase transition in this crystalline system.     

锂铌比对铪铁铌酸锂晶体全息存储性能的影响

以掺杂4 mol%Hf⁴⁺的LiNbO₃:Fe:Hf系列晶体（[Li]/[Nb]比变化）为研究对象,研究了系列晶体的可见吸收光谱,在632.8nm的写入光下晶体的衍射效率、灵敏度和抗光散射能力在不同[Li]/[Nb]下的变化规律.研究发现Hf⁴⁺的浓度达到阈值浓度后,随着[Li]/[Nb]比的增大,晶体的可见吸收边会发生红移,而且晶格中[Fe²⁺]/[Fe³⁺]也会增加,这就导致随着[Li]/[Nb]比的增加,样品的衍射效率逐渐减小,写入时间缩短,灵敏度增大.同时,在晶体中,随着[Li]/[Nb]的增大,陷阱中心Fe²⁺Li数量增大会使得晶体抗光散射能力减弱.     

DFT study on coupling reaction of carbon dioxide with ethylene oxide catalyzed by 1,4,6-triaza-bicyclo[3.3.0]oct-4-enium bromide (TBO.HBr)

ABSTRACT

Chemical fixation of CO₂ with epoxides catalyzed by organic-base salts were found to be efficient among the various catalysts tested due to synergetic effects of HBDs and halide-ions for ring-opening. In this study, 1,4,6-Triaza–bicyclo[3.3.0]oct-4-enium bromide catalyzed conversion of CO₂ and epoxide into cyclic-carbonate has been studied by using DFT method to understand the reaction mechanism and the catalytic performance of TBO.HBr. Two hypothetical reaction mechanisms were proposed for the coupling reaction. Thermodynamic and kinetic parameters were computed for each steps to determine the more favorable route. Mechanism II is more favorable path whereby Br^- ion first interacts with epoxide to form bromo-alcohol, which directed to form carbonate-ion and finally ring-closure step yielded cyclic-carbonate with catalyst-regeneration. Cyclization step is rate-determining step with reaction barrier of 22.696?kcal/mol in gas phase. Ensuing the favorable mechanism, solvent-effects on the reaction barrier has been investigated using water and THF. Mechanism II is still more favorable reaction path in both THF and water. However, the rate-determining step is found to be ring-opening of the epoxide with reaction barrier of 22.658?kcal/mol (wate) and 21.969?kcal/mol (THF). In this study, TBO.HBr exhibited good catalytic activity for the title reaction investigated in both gas phase and solvents.