Luminescence of carbazolyl-containing polymers doped with iridium chelates

White light emission is shown to be obtainable at room temperature through the mixing of poly-N-vinylcarbazole (PVC) host fluorescence with fac-tris(2-phenylpyridyl)Ir(III) [Ir(ppy)₃] and bis[2-(2′-benzothienyl)pyridinato-N,C^3′](acetylacetonate)iridium (III) [Btp₂Ir(acac)] dopant phosphorescence whereas at very low temperature through the superposition of poly-N-epoxypropyl-3,6-dibromocarbazole (3,6-DBrPEPC) host and Btp₂Ir(acac) dopant phosphorescence emissions. The balance between basic colors is adjusted by the variation of triplet-emitter dopant concentrations. Spin-allowed singlet-singlet energy transfer from the host to iridium chelate dopants by the Forster mechanism is the dominant process in PVC. Spin-forbidden triplet-singlet transfer by the Forster mechanism from the host to the dopant occurs at low temperatures in 3,6-DBrPEPC due to strong spin-orbit coupling induced by the heavy bromine atoms. Spin-allowed transfer from the same host’s triplet excited state to the iridium chelate occurs via electron exchange at high temperatures. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 324–330, May–June, 2008.     

Luminescence behavior of tetraaza macrocylic nickel (II) complexes and non-linear Stern-Volmer quenching

Macrocylic dicarbinolamine nickel (II) complexes with diimine moiety in their ligand exhibited luminescence, when irradiated at their charge transfer band. The Stern-Volmer (S-V) plots of one of the complexes in DMF medium exhibited positive curvature, when FeC1₃ was used as a quencher, while the same complex showed negative curvature when nitrobenzene was used as a quencher. The mechanism for the luminescence quenching of the macrocyclic complex has also been discussed.     

Tm3+在二苯甲酰基甲基亚砜配合物体系中对Dy3+的荧光增强效应

合成了六种高氯酸掺杂稀土(Dy³⁺,Tm³⁺)与二苯甲酰基甲基亚砜的配合物。经元素分析、稀土络合滴 定、摩尔电导率及差热-热重分析,表明配合物组成为 (Dy_x,Tm_y)L₅(ClO₄)₃·3H₂O(x : y=1.000 : 0.000,0.995 : 0.005,0.990 : 0.010,0.950 : 0.050,0.900 : 0.100,0.800 : 0.200;L=C₆H₅COCH₂SOCH₂COC₆H₅)。并详细讨论了六种稀土配合物的荧光光谱。从配合物的荧光光谱图可以看出,Tm³⁺对Dy³⁺的荧光有增强效应。这可能 是因为在惰性稀土离子Tm³⁺与活性稀土离子Dy³⁺之间有能量的传递。而且当Dy³⁺与Tm³⁺的量比为0.950 : 0.050时,掺杂配合物表现出最佳的发光性质。另外,Tm³⁺对577.4 nm处⁴F_9/2→⁶H_13/2 峰的荧光敏化作用的程度高于对487 nm处⁴F_9/2→⁶H_15/2 峰的荧光敏化作用。⁴F_9/2→⁶H_15/2 峰的荧光强度增强了212％,而⁴F_9/2→⁶H_13/2峰的荧光强度增强了264％。所以,Dy³⁺离子的两个特征峰的发射强度比趋近于1,为1.078,使得配合物在紫外灯下发白色荧光。有可能成为一类发白色荧光的发光材料。     

锌离子对聚乳酸结晶和热性能的影响

本文发现了Zn(II)离子掺杂可以加快聚乳酸的结晶过程. 测试了三种Zn(II)盐(ZnCl₂、ZnSt和ZnOAc),并与其它离子Mg(II)和Ca(II)进行对照. FT-IR以及变温拉曼光谱分析发现,经Zn(II)离子掺杂后,聚乳酸的结晶度和结晶速率均增加,差示扫描量热技术以及X射线衍射分析也进一步证实. 差示扫描量热技术测定PLA/ZnSt-0.4 wt%材料的结晶率达到22.46%,PLA/ZnOAc-0.4 wt%材料的结晶率达到24.83%.     

儿茶酚胺铽敏化发光性质的研究及分析应用

儿茶酚胺（Cas）作为神经递质和激素对人体的生理功能发挥着重要作用。它是一类分子中包含一个胺基和一个邻苯二酚基团的有机化合物，其中邻苯二酚基团由苯环和3, 4位两个羟基组成。生理条件下，儿茶酚胺主要指多巴胺（DA）、去甲肾上腺素（NE）和肾上腺素（E）三种物质。儿茶酚胺性质不稳定，遇光或空气易氧化分解。镧系敏化发光是一种很有前途的临床和药物分析工具，在镧系敏化发光中，镧离子与有机化合物形成络合物，这些络合物具有良好的发光特性，主要用于有机分析物的测定。因此，利用镧系金属离子铽敏化发光法测定儿茶酚胺的关键是待测物与中心离子易形成稳定的络合物。儿茶酚胺与金属离子的络合作用主要依赖于分子中酚羟基解离后的氧作为成键原子，溶液的碱性越强，儿茶酚胺与金属离子的络合能力越强。在碱性介质中，为防止金属离子水解加入乙二胺四乙酸作为协同配体，金属离子铽和协同配体以及儿茶酚胺形成易溶于水的三元络合物，络合物具有良好的稳定性，并表现出较强的铽的特征荧光。加入阳离子表面活性剂十六烷基三甲基氯化铵为增敏剂，可使儿茶酚胺三元络合物体系的荧光强度增加约4～6倍。利用紫外吸收和荧光光谱研究了铽三元络合物的光物理性质以及能量转移机理，结果表明，儿茶酚胺能有效吸收紫外辐射，三元络合物荧光增强机理是配体儿茶酚胺吸收辐射能后通过分子内能量转移将能量转移给铽离子，进而产生铽的特征发射。对影响三元络合物荧光强度的主要因素如溶液酸度、试剂浓度和加入顺序、表面活性剂种类以及干扰物质等进行了讨论。在一定条件下，体系的发光强度与儿茶酚胺的浓度成线性关系。多巴胺、去甲肾上腺素和肾上腺素的线性范围分别为0.080～50.0×10-6， 0.070～50.0×10-6和0.070～50.0×10-6 mol·L-1；相应检出限分别为2.4×10-8, 2.2×10-8和2.1×10-8 mol·L-1。建立的方法用于药物制剂中三种儿茶酚胺的定量测定，结果满意；由于反应体系所得铽络合物具有发射带窄，斯托克斯位移大，以及较长的荧光寿命等优点，该方法有望用于儿茶酚胺的自动分析、临床药代动力学研究以及相关病理的实际诊断，也可用于高效液相色谱和毛细管电泳检测器。     

Studies on Synthesis,Characterization, and Luminescence Properties of A Novel Light Conversion Agent of Eu (III) and Compatibility with PE

A novel light conversion agent (NLCA) has been synthesized that is applicable to polyethylene (PE) film. The composition and structure of the NLCA was characterized by elemental analysis, Fourier transform infrared (FT‐IR) spectroscopy, and nuclear magnetic resonance (NMR) spectrometry. The morphology, particulate dimensions, dispersion property and compatibility of the NLCA were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The results indicate that the average particulate dimension was about 60–100 nm and they were dispersed well in the PE film. The luminescence property of the NLCA was studied via fluorescent spectrometry. The fluorescence spectra of the NLCA show that the NLCA has a highly efficient luminescence.     

以非手性铕化合物为探针的手性氨基醇圆偏振荧光光谱

圆偏振荧光光谱(Circularly Polarized Luminescence,CPL)是一种手性化合物表征与分析的光谱手段,然而,直接CPL检测只适用于具有特征发色团的手性化合物,这极大限制了CPL的应用范围。本文报道了一种利用非手性荧光探针分子间接检测分子手性的CPL方法。以手性氨基醇的检测为例,研究发现:非手性铕化合物Eu(fod)3探针分子可与手性氨基醇相互作用,并使得Eu(fod)3产生诱导CPL(Induced circularly polarized luminescence,ICPL)信号,该ICPL信号不仅具有较高的不对称因子glum,而且其正负性与待测手性氨基醇的手性构型表现出极大的相关性。同时,研究发现ICPL光谱的glum值对不同结构的手性氨基醇表现出不同的变化趋势。以上结果表明以非手性铕化合物Eu(fod)3为探针分子的间接CPL检测方法是手性氨基醇类分子手性构型检测的有效手段。     

IgA免疫复合物微粒的共振散射光谱研究及其分析应用

在pH 6.2的Na₂HPO₄-柠檬酸缓冲溶液中及聚乙二醇4 000存在下,免疫球蛋白A(IgA)与羊抗人免疫球蛋白A通过库力引力、范德华力、氢键结合力、疏水等作用力发生特异性结合形成抗原-抗体免疫复合物微粒。激光散射法测得该微粒的平均粒径约为1 100 nm;而且该微粒在340,390,420,450,470,520 nm有6个共振散射峰。考察了pH值、不同分子量聚乙二醇、羊抗人IgA血清用量、温度及反应时间对共振散射光谱测定IgA的影响。在最佳实验条件下,IgA浓度在0.133～4.67 μg·mL-1范围内与340和470 nm处的共振散射强度均呈线性关系,其回归方程分别为ΔI_{340 nm}=18.61 c_IgA+3.19,ΔI_{470 nm}=18.57 c_IgA+6.51,相关系数分别为0.998 5和0.998 7,检出限分别为0.068和0.072 μg·mL-1。该法用于人血清IgA的测定,相对标准偏差在2.2％～4.2％,并与免疫比浊法测定结果作线性回归分析,其斜率、截距和相关系数分别为1.064,-0.213和0.929 9,结果令人满意。     

新型三元配合物Tb(DPAB)_3IP的制备与发光性能

合成了邻菲罗啉的衍生物咪唑并[5,6-f]邻菲罗啉(IP),并以其为第二配体,二苯胺羰基邻苯甲酸(HDPAB)为第一配体,制备出新型稀土铽三元有机配合物Tb(DPAB)3IP。采用元素分析、红外光谱和紫外光谱对合成的配体及配合物进行了表征。通过荧光光谱研究了配合物的荧光性质,结果表明第二配体IP有较大的共轭体系,在紫外光激发下,配合物中的配体可将吸收的能量传递给稀土Tb3+离子,表现出较强的Tb3+离子的特征发射,且配体Tb(DPAB)3IP的荧光强度明显大于Tb(DPAB)3phen的荧光强度。这说明适宜的第二配体对配合物有很好的敏化发光作用,合成的Tb(DPAB)3IP是一种良好的绿光材料。     

稀土/高分子杂化发光材料的研究

用SiO2为无机组份和以与SiO2具有相似折射率和优良力学性能的丙烯酸类如甲基丙烯酸甲酯（MMA）和甲基丙烯酸羟乙酯（HEMA），在交联剂3－（三甲氧基硅）丙基甲基丙烯酸酯（MSMA）存在下，快速制备了两种杂化基质材料SiO2/P(MMA-MSMA)和SiO2/P(HEMA-MSMA)。分别以盐酸和六次甲基四胺作为酸性催化剂和碱性催化剂，建立了快速制备透明凝胶的两步溶胶－凝胶法，大大缩短了溶胶的成胶时间，所得杂化材料具有良好的光学透明性，利用此方法制备了掺杂稀土配合物的多种发光杂化材料。采用组装的方法，得到了稀土配合物与层次化合物α－磷酸氢锆（α－ZrP)及中孔分子筛材料MCM－41的组装体，并对所制备的杂化材料进行了表征。另外，将稀土配合物通过共价键嫁接于无机SiO2基质中，得到了含有稀土配合物的分子杂化材料。     

Analysis of the ESR Spectrum of a Rhodium (II) Complex

Abstract

Rh(II) complexes are rather scarce¹ and often form dimeric structures, which are diamagnetic. The ESR spectra of definite Rh(II) species have so far been claimed for Rh in ZnWO₃ ², [Rh S₄C₄(CN)₄]^{2 ?}, ^3′4 [Rh(π-C₅H₅)₂]⁵, [(π-C₅H₅)Rh(π-C₂H₄)₂]⁺⁶, and an irradiation produced [RhCπ₂(CN)₄]^{2 ?} complex.⁷ A detailed analysis has been performed on the first², the second⁴ and the last⁷ complexes. The first system shows an almost axial symmetry and the unpaired electron has been assigned to the d_xy orbital² (the x,y,z axes are defined along the octahedral metal-ligand directions). The sulfur ligand complex and the dichlorotetracyano system have their unpaired electron in the d_Z ² orbital. ^4,7 In the course of studies ^8-10 on oxygenation of a Rh(I) complex, [RhCπ(C₈H₁₄)₂]₂, we observed ¹⁰ that a well defined ESR spectrum develops during the reaction in N,N′-dimethylacetamide (DMA) - lithium chloride media. For experimental detail, reference 10 should be consulted. The data summarized in the table refer to the spectrum B in that reference and are attributed to a Rh(II) species.     

The Half Field Line of Tetrakis(Dimethtlglyoximato)Dicopper(II) in Glasses

We have reported recently the finding¹ of triplet state EPR spectra in glasses of tetrakis(dimethylglyoximato)dicopper(II) in ethyl alcohol (a.) at 77°K. Now we wish to report the resolution of the half field band (H_MIN) and the observation of metal and ligand nuclear hyperfine structure on this band. In previous studies of half field lines, the metal nuclear hyperfine has been sufficiently_2,3,4 clear to interpret only in a few cases and the ligand nuclear hyperfine has never been observed before.     

有机-无机杂化材料Eu(BA)3-MCM-41的制备及光学性质

将稀土有机配合物Eu(BA)3组装进介孔MCM-41中,得到有机-无机杂化介孔材料Eu(BA)3-MCM-41。采用XRD、IR、激发、发射光谱等测试方法对其结构和性能进行了分析。结果表明,组装体保持了有序的介孔骨架结构,由组装体IR谱图中波数3451cm-1吸收峰的消失及970cm-1吸收峰强度的降低可知,介孔中Eu(BA)3的引入使得配合物自身含有的结晶水、MCM-41中的吸附水和羟基数目减少,由于Eu(BA)3与—OH在介孔孔道中成键使羟基减少,降低了Eu3 的发光猝灭效应,提高了Eu3 的发光效率。组装体中主客体之间存在较强的相互作用,MCM-41的存在使Eu(BA)3对激发光有更强吸收,且使Eu(BA)3-MCM-41的发光强度较Eu(BA)3有显著的提高。     

Spectroscopic Studies of Oxygen-Bridged Copper (II) Cluster Somplexes; (II) Trinuclear Copper (II) Complex of Pyridine-2-Carbaldehyde Oxime

Abstract

Power electron paramagnetic resonance spectrum of the trinuclear complex Cu3L3 (OM)X2, xH20 (L=pyridine-2-carbaldehyde oxime, X=1/2 S04^2?, x=16.3) was recorded in the X-band region and interpreted in terms of a quarte (S=3/2) spin system.

Vibrational studies of the complex has also been undertaken and an assignment was made of the bands observed it the low frequency infrared and Raman spectra. It was shown that the central metallic core has a C3v syametry. Theoretical calculations of the frequencies of the vibrations related to this skeleton were performed and the results are it agreement with the experimental data.     

青蒿素与氯化血红素作用的荧光研究及分析应用

介绍了吡罗红为指示剂通过荧光降低法研究青蒿素与氯化血红素之间的相互作用。实验发现两者为酶和底物作用模型,作用位点为药物的过氧基团和氯化血红素活性中心的金属离子,其动力学催化常数K_m, V_max和K_cat分别为8.4×10-5 mol·L-1, 7.4×10-6 mol·L-1·s-1及50.23 s-1,催化活性分别受去激活剂和高温影响。在最佳条件下, 荧光降低值ΔF(F₀-F)与青蒿素浓度在0.0～1.27×10-6 mol·L-1范围内成线性关系, 检测限为2.3×10-8 mol·L-1, 该方法已用于测定血浆和尿液介质中的微量青蒿素。     

Synthesis and Luminescence of a Novel Conjugated Europium Complex with 6-Aniline Carbonyl 2-Pyridine Carboxylic Acid

A novel organic ligand, 6-aniline carbonyl 2-pyridine carboxylic acid (HAP), and the corresponding europium complex, tris(6-aniline carbonyl 2-pyridine carboxylato) europium (III) (Eu-AP) have been designed and synthesized. The results showed that Eu-AP was a conjugated complex, emitting strong red luminescence. The lifetimes of ⁵D₀ of Eu³⁺ in the complex were examined using time-resolved spectroscopic analysis, and the lifetime value was 0.55 ± 0.01 ms for solid Eu(AP)₃. Thermogravimetric analysis showed that the europium complex had good thermal stability.     

Study of the Reaction Between the Nucleic Acid and Y-BPMPHD-CTMAB Complex and Its Analytical Application

The fluorescence quenching of the Y-BPMPHD-CTMAB by nucleic acids is reported. It is considered that the Y-BPMPHD-CTMAB can form a large complex with nucleic acid through the electrostatic attraction in the pH range of 4.2-6.8. Under optimal conditions, the difference of fluorescence intensity between the system without and with nucleic acids is proportional to the concentration of nucleic acids over the range of 4.5 x 10(-8)-1.2 x 10(-5) g/mL for fsDNA and 3.2 x 10(-8)-3.0 x 10(-5) g/mL for yRNA, respectively. The detection limits are 14.0 ng/mL for fsDNA and 21.0 ng/mL for yRNA. The method is applied for the determination of nucleic acids in actual sample, and the result obtained is satisfactory.     

The Spectrochemical Properties of Noncubic Transition Metal Complexes in Solutions. VII. Angular Overlap Treatment of the trans-bis(Salicylidene-o-aminopyridine)copper(II) Complex in Various Solvents.

The electronic absorption spectra of trans-[Cu(sap)₂], where (Hsap = salicylidene-o-aminopyridine (Schiff base)), were measured in various solvents at room temperature. The d-d transition energies is used to derive the angular overlap model (AOM) parameters in C_2h symmetry. The experimental curves were resolved by Gaussian analysis. A comparison of the spectra, ligand field parameters and stereochemistries in various solutions was made. The effect of the solvents upon the σ, π-bonding, and bite angle of the bidentate ligand is discussed.