Sensing and fluorescence behaviors of complex formation between new lariat crown ethers bearing fluorescence sidearm and metal ions in methanol solution

Fluorescence spectroscopic properties of the complex formation between six new C-pivot16-crown-5 ethers bearing fluorescence side arms and metal ions are studied. Six new C-pivot 16-crown-5 ethers that carry fluorescence side arms were synthesized. The research also included the examination of different fluorescent behavior of the new lariat ethers in the presence of silver and sodium ions (Ag⁺ and Na⁺) in methanol. Because of the good fit of the cavity size of these 16-crown-5 ethers with the Ag⁺ and Na⁺ ions, remarkable change in fluorescent spectra were observed. The results showed that the new lariat crown ethers exhibited enhanced selectivity towards sodium ion, but silver ion show quenching abilities towards the ligands. Cooperative participations of the C-pivot side arm oxygen with the ring oxygen molecules in complexation was also confirmed by the single crystal X-ray crystallography of the complex, (C₂₇H₃₀O₇)·NaClO₄. The freezing of crown ring conformation and the diminishment of the chance of sidearm oscillation that occurred upon complexation with sodium ion are the main causes of fluorescent enhancement. The quenching caused by the addition of silver ion was found to explainable by the photo-induced electron transfer that results in the reduction of silver ions.     

Understanding the polarization signal of spherical particles for microwave limb radiances

This paper presents a simple conceptual model to explain that even spherical scatterers lead to a polarization difference signal for microwave limb radiances. The conceptual model relates the polarization difference measured by a limb-looking sensor situated inside a cloud with the anisotropy of the radiation. In the simulations, it was assumed that the cloud consists of spherical ice particles with a radius of which were situated between 10.6 and 12.3 km altitude. The frequencies 318 and 500 GHz were considered.The results of the conceptual model were compared to the results of the fully polarized scattering model ARTS-1-1. The comparison showed a good qualitative agreement. The polarization difference decreases inside the cloud with increasing height and changes sign. This behavior can be related to a different amount of radiation coming from the atmosphere above and below the cloud, compared to the amount of radiation coming from the sides. The sign of polarization difference of the scattered radiation is opposite for these two radiation sources.     

4,7-二(2-溴代噻吩-5-基)-2,1,3-苯并噻二唑-N-(1-辛基壬烷基)咔唑在ZnS(100)表面吸附的理论研究

采用密度泛函理论中的广义梯度近似(DFT/GGA)方法, 在PW91/DNP水平上研究了4,7-二(2-溴代噻吩-5-基)-2,1,3-苯并噻二唑-N-(1-辛基壬烷基)咔唑(简称PC-DTBT)的低聚合物(PC-DTBT)n(n=1-5)的稳定性和化学活性. 结果表明: 随着聚合度增加, (PC-DTBT)n的稳定性降低, 化学活性增强. 采用密度泛函理论与周期性平板模型相结合的方法, 研究了PC-DTBT单体在ZnS(100)表面的吸附, 通过吸附前后化合物PC-DTBT的Mulliken charge和前线轨道分析表明: 当PC-DTBT吸附在ZnS (100)表面时, ZnS(100)表面向PC-DTBT转移0.200 e电荷, 前线轨道能隙变窄. 理论预测的结果与实验值吻合.     

氮自掺杂Ta_2O_5微球制备及其光催化性能研究

我们采用水热法合成了具有可见光吸收的非金属自掺杂N-Ta_2O_5多孔微球光催化剂.并通过X射线粉末衍射仪(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、紫外可见分光光度计(UV-vis)等多种表征手段对自掺杂N-Ta_2O_5的晶体结构、形貌、组分等进行了测试分析.XRD结果表明,Ta N可以在HF溶液中完全氧化为Ta_2O_5,N掺杂可以通过N与O原子的轨道杂化使Ta_2O_5的带隙从4.0 eV降低为2.2 eV,从而增强其可见光吸收.高催化活性的N-Ta_2O_5可通过调控其结晶度来实现.     

纯Cr2O3包覆Li4Ti5O12微球的制备及其储锂性能研究

The pure Cr₂O₃ coated Li₄Ti₅O₁₂ microspheres were prepared by a facile and cheap solutionbased method with basic chromium(III) nitrate solution (pH=11.9). And their Li-storage properties were investigated as anode materials for lithium rechargeable batteries. The pure Cr₂O₃ works as an adhesive interface to strengthen the connections between Li₄Ti₅O₁₂ particles, providing more electric conduction channels, and reduce the inter-particle resistance. Moreover, LixCr₂O₃, formed by the lithiation of Cr₂O₃, can further stabilize Li₇Ti₅O₁₂ with high electric conductivity on the surface of particles. While in the acid chromium solution (pH=3.2) modification, besides Cr₂O₃, Li₂CrO₄ and TiO₂ phases were also found in the final product. Li₂CrO₄ is toxic and the presence of TiO₂ is not welcome to improve the electrochemical performance of Li₄Ti₅O₁₂ microspheres. The reversible capacity of 1% Cr₂O₃-coated sample with the basic chromium solution modification was 180 mAh/g at 0.1 C, and 134 mAh/g at 10 C. Moreover, it was even as high as 127 mAh/g at 5 C after 600 cycles. At-20℃, its reversible specific capacity was still as high as 118 mAh/g.     

铕(Ⅲ)-2-(5-溴-2-吡啶偶氮)-5-二乙氨基苯酚-溴化十六烷基三甲铵显色反应的研究

研究了铕 ( ) - 5 - Br- PADAP- CTMAB体系的显色反应和光度性质 ,并探讨了其最佳的光度分析条件。在 p H =5 .0的 HAc- Na Ac缓冲溶液中 ,有表面活性剂 CTMAB存在的条件下 ,Eu( )与 5 - Br-PADAP形成了配位比为 1∶ 2的深红色络合物。配合物的最大吸收峰位于 5 98nm,表观摩尔吸光系数为1.5 9× 10 5L· mol-1· cm-1,铕含量在 0— 10μg/ 2 5 m L范围内符合比耳定律。加标回收实验结果令人满意。     

NMR Studies of Drugs. Applications of Achiral and Chiral Lanthanide Shift Reagents to a 5-Substituted-4-thiazolidinone

The 60 MHz ¹H NMR spectra of racemic 5-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-4-thiazolidinone, 1, have been studied in CDCl₃ solution at 28° with the achiral lanthanide shift reagent (LSR), tris (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato)europium (III), 2, and the chiral LSRs, tris[3-(heptafluoropropylhydroxymethylene)- (+)-camphoratojeuropium(III), 3, and tris[3-(trifluoromethylhydroxymethylene-(+) -camphorato]europium (III), 4, Significant enantiomeric shift differences were observed in the presence of added 3, for the aryl protons of 1 that should permit direct determination of enantiomeric excess. Relative magnitudes of lanthanide-induced shift for the different nuclei of 1 with the three LSRs are compared and discussed in terms of preferred LSR binding sites. A favored conformation of 1 with respect to rotation about the C(5)-CH₂ bond is suggested.     

Assignment of the 1H and 13C NMR Chemical Shifts of (3,4-Dihydro-2H-pyran-5-yl)-oxo-acetic Acid Methyl Ester Using the Two Dimensional HMBC Technique

The identification of (3, 4-dihydro-2H-pyran-5-yl)-oxo-acetic acid methyl ester has been realized by combination of two dimensional HETCOR and HMBC techniques. ¹³C and ¹H chemical shifts asignements are described.     

NMR Studies of Drugs. Applications of Achiral and Chiral Lanthanide Shift Reagents to the Analgesic,Famprofazone: “Anomalous Shifts”

The 200 MHz ¹H NMR spectra of the analgesic, famprofazone, 1, have been studied in CDCl₃ solution at ambient temperatures with the achiral lanthanide shift reagent (LSR) tris (6, 6, 7, 7, 8, 8, 8-heptaf luoro-2, 2-dimethyl-3, 5-octanedionato) europium (III), Eu(FOD)₃, 2, for spectral simplification, and with the chiral LSR, tris [3-(heptafluoropropylhydroxymethylene) - (+) camphorato] europium (III), Eu (HFC)₃, 3. Lanthanide induced shift (LIS) magnitudes suggested predominant LSR binding at the carbonyl oxygen. Substantial enantiomeric shift differences were observed for several nuclei of 1 with added 3 which could permit direct determinations of enantiomeric excess.     

Dynamic phase transition and dynamic phase diagrams in the spin-5/2 Blume–Capel model under a time-dependent oscillating external field

We calculate the dynamic phase transition (DPT) temperatures and present the dynamic phase diagrams in the kinetic spin-5/2 Blume–Capel model under the presence of a time-dependent oscillating external magnetic field. First, we employ the Glauber transition rates to construct the mean-field dynamic equation. Then, we study the time variation of the average magnetization to find the phases in the system. We also investigate the behaviour of the dynamic magnetization to characterize the nature (continuous and discontinuous) of transition and to obtain the DPT points. We present the dynamic phase diagrams in two different planes. The phase diagrams include the ferromagnetic-5/2 (f_5/2), the ferromagnetic-1/2 (f_1/2) and paramagnetic (p) fundamental phases. In addition to these fundamental phases, we find 10 mixed phases, depending on the interaction parameters. The phase diagrams display many special points, such as a dynamic tricritical point, a double critical end point, a triple point and a quadruple point.