两种聚对苯乙炔类衍生物的线性与非线性光学性质

采用吸收光谱、荧光光谱和皮秒Z-扫描等实验方法研究了侧链长度的不同对聚[2-甲氧基-5-(2′-乙基-己氧基)]对苯乙炔(MEH-PPV)和聚(2,5-二辛氧基)对苯乙炔(DO-PPV)两种聚对苯乙炔(PPV)衍生物光学性质的影响,并用π-电子共轭结构理论和共振、非共振增强理论进行了分析。结果表明,侧链较长的MEH-PPV的吸收峰和荧光发射峰比DO-PPV相应的吸收和荧光峰均有所红移;侧链结构及共振增强使得MEH-PPV的三阶非线性极化率比DO-PPV增强了近两个量级,并在532 nm激发时,χ(3)具有最大值9.30×10-10esu。     

双氰基荧光染料的合成、光学性质及其生物成像

设计合成了一种A-π-D-π-A型的双光子荧光染料3,6-双(4-乙烯基苯腈)-9-乙基咔唑,测试了其在二氯甲烷(DCM)、乙酸乙酯(EA)、乙醇(Et OH)、乙腈(ACN)、二甲亚砜(DMSO)和磷酸缓冲盐溶液(PBS)等不同溶剂中的紫外吸收光谱、单光子及双光子荧光光谱。化合物3,6-双(4-乙烯基苯腈)-9-乙基咔唑在紫外吸收光谱中存在两个相似的特征吸收带并呈现出复杂的溶剂化效应,在DMSO中具有最大荧光量子产率(86.02%),其相应的活性吸收截面为12.56 GM。在双光子荧光成像方面,染料分子具有优良的细胞膜通透性并且在双光子荧光显微镜下呈现出明亮的绿色荧光,表现出较好的双光子荧光成像性能。这些数据表明,化合物3,6-双(4-乙烯基苯腈)-9-乙基咔唑可用作一种较为理想的双光子荧光标记染料。     

4-苯乙炔-1, 8-萘酰亚胺荧光化合物的合成及电致发光性能

采用Pd(PPh₃)₂Cl₂-CuI为催化剂,Ph₃P为配体,4-溴-1,8-萘二酸酐为原料,在乙醇溶液中高收率地合成了4-苯乙炔-1,8-萘酰亚胺和4-对甲基苯乙炔-1,8-萘酰亚胺荧光新化合物。光谱研究表明,它们的最大紫外吸收波长(λ_UV,max)分别为374,380 nm,最大荧光发射波长(λ_FL,max)分别为446,462 nm,且有较高的荧光量子效率。电致发光性能测试表明,器件的最大发光亮度达到2250 cd/m²,是一类有潜在应用价值的小分子发光材料。     

Synthesis and Solvent Polarity-Sensitive Photoluminescent Property of 4-Phenylethynyl-4'-Dimethylaminochalcone

以4-溴-4'-二甲氨基查尔酮和苯乙炔为原料,通过Sonogashira钯催化偶联反应合成了4-苯乙炔基-4'-二甲氨基查尔酮,并通过红外光谱和核磁共振氢谱对其结构进行了表征.进一步研究了4-苯乙炔基-4’-二甲氨基查尔酮在不同极性的溶剂中的紫外可见吸收光谱和荧光光谱,结果表明该化合物具有极性敏感的发光特性.     

4-苯乙炔基-4′-二甲氨基查尔酮的合成与溶剂极性敏感的发光特性

以4-溴-4′-二甲氨基查尔酮和苯乙炔为原料,通过Sonogashira钯催化偶联反应合成了4-苯乙炔基-4′-二甲氨基查尔酮,并通过红外光谱和核磁共振氢谱对其结构进行了表征。进一步研究了4-苯乙炔基-4′-二甲氨基查尔酮在不同极性的溶剂中的紫外可见吸收光谱和荧光光谱,结果表明该化合物具有极性敏感的发光特性。     

咔唑-苯并噻唑类衍生物薄膜的线性及非线性光学性质

以咔唑为电子供体,苯并噻唑为电子受体,合成了两种新型咔唑-苯并噻唑衍生物3-(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑和3,6-二(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑,通过核磁共振和分光光度计对其结构进行表征.利用刮刀法制备质量分数为4％的衍生物/聚酰亚胺的复合薄膜.采用透射光谱法和单光束Z-扫描技术分别测试了衍生物的线性和三阶非线性光学特性.Z扫描实验结果表明3-(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑薄膜的非线性吸收系数和非线性折射系数分别为β1=-2.118 9×10-10 cm/W、r1=2.285 2×10-14 cm2/W,具有反饱和吸收特性和自聚焦效应;同时3,6-二(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑薄膜的非线性吸收系数与非线性折射系数分别为β2=-1.275 6×10-9 cm/W、r2=-7.039 9×10-14 cm2/W,具有反饱和吸收特性和自散焦效应.     

咔唑-苯并噻唑类衍生物薄膜的线性及非线性光学性质（英文）

以咔唑为电子供体,苯并噻唑为电子受体,合成了两种新型咔唑-苯并噻唑衍生物3-(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑和3,6-二(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑,通过核磁共振和分光光度计对其结构进行表征.利用刮刀法制备质量分数为4%的衍生物/聚酰亚胺的复合薄膜.采用透射光谱法和单光束Z-扫描技术分别测试了衍生物的线性和三阶非线性光学特性.Z扫描实验结果表明3-(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑薄膜的非线性吸收系数和非线性折射系数分别为β1=-2.118 9×10-10 cm/W、r1=2.285 2×10-14 cm2/W,具有反饱和吸收特性和自聚焦效应;同时3,6-二(2-苯并噻唑-2-基乙烯基)-N-乙基咔唑薄膜的非线性吸收系数与非线性折射系数分别为β2=-1.275 6×10-9 cm/W、r2=-7.039 9×10-14 cm2/W,具有反饱和吸收特性和自散焦效应.     

烷氧取代聚对苯乙炔衍生物的合成及其电致发光性能

用脱氯化氢法制备了可溶性烷氧取代聚对苯乙炔衍生物，聚(2-甲氧基—5—丁氧基)对苯乙炔(PMOBOPV)、聚(2—甲氧基—5—辛氧基)对苯乙炔(PMOOOPV)，该反应具有较高的产率，并且产品具有很好的溶解性和成膜性，同时对其薄膜进行了扫描电镜分析。利用所合成的：PPV衍生物制作了单层及不同结构的多层器件，测试了它们的电致发光性质，同时研究了不同条件对器件的起亮电压、稳定性的影响。结果表明，所制作的器件具有较好的稳定性，单层器件的起亮电压约为4V，发光峰在580nm处。     

一种基于荧光材料的聚合物白光发光二极管

制备了一种基于荧光聚合物共混的单发光层聚合物白光发光二极管.器件结构为铟锡氧化物/苯磺酸掺杂聚乙烯基二氧噻吩/发光层/ 1,3,5-三(N-苯基-2-苯并咪唑-2)苯41/Ba/Al,蓝光材料芴-氟化喹喔啉共聚物(PF-BPFQ5)、绿光材料苯基取代的聚对苯乙炔(P-PPV)和红光材料聚(2-甲氧基-5-(2′-乙基己氧基)-1,4-对苯乙炔)(MEH-PPV)共混为发光层.当PF-BPFQ5,P-PPV,MEH-PPV的质量比例为100∶06∶06时,获得标准的白光,色坐标为（033 关键词： 聚合物发光二极管 白光 共混     

用稀土金属铽的有机配合物Tb(acac)2(AA)phen做发光层的电致发光薄膜的研究

研究了稀土铽的有机配合物(Tb(acac)2(AA)phen的光致发光特性,用Tb(acac)₂(AA)phen做发光层,分别用N,N’-双(3-甲苯)-N,N’-二苯联苯胺(TPD)和聚乙烯基咔唑(PVK)做空穴传输层研制了有机电致发光薄膜器件,研究了它们的电致发光特性.     

Adsorption of 2,4,6-trinitrotoluene on carboxylated porous polystyrene microspheres

Large-pore-size (150 nm) polystyrene (PSt) microspheres were carboxylated with phthalic anhydride (PA) through Friedel-Crafts acetylation to study the adsorption of 2,4,6-trinitrotoluene (TNT) on this material from aqueous solution. The scanning electron microscope (SEM) images and mercury porosimetry measurements (MPM) of the microspheres showed that the pore structure was unchanged during the reaction. High adsorption capacity (11.2 mg g⁻¹ of suction-dried adsorbent) and adsorption rate (33.9 mg g⁻¹ h⁻¹) for TNT were observed during the study. As shown by the adsorption isotherm, the adsorption of TNT on PA-PSt can be described by the Freundlich adsorption equation, indicating heterogeneous adsorption process. On-column adsorption of TNT on PA-PSt and elution indicated that TNT can be completely removed from aqueous solution and condensed into acetone.     

A detailed chemical kinetic model for gas phase combustion of TNT

A detailed chemical kinetic mechanism for gas phase combustion of 2,4,6-tri-nitrotoluene (TNT) has been developed to explore problems of explosive performance and of soot formation during the destruction of munitions. Thermodynamic properties of intermediate and radical species are estimated by group additivity. Reactions for the decomposition and oxidation of TNT and its intermediate products are assembled, based on information from the literature and from analogous reactions where the rate constants are available. The resulting detailed reaction mechanism for TNT is added to existing reaction mechanisms for RDX and for hydrocarbons which can be produced from TNT and RDX. Properties of the reaction mechanism are demonstrated by examining problems of soot formation during open burning of TNT and mixtures of TNT and RDX. Computed results show how addition of oxygen to TNT can reduce the amounts of soot formed in its combustion and why RDX and most mixtures of RDX and TNT do not produce soot during their combustion or incineration.     

Investigation of monolayer dispersion of MoO3 supported on titanate nanotubes

The monolayer dispersion of MoO₃ supported on the surface of titanate nanotubes (TNT) were prepared by heating mechanical mixture of molybdate (HMA) and TNT. The result shows that MoO₃ can disperse spontaneously onto the surface of TNT, and the dispersion capacity is ca. 27 mg MoO₃/g TNT by X-ray diffraction (XRD). On the basis of thermogravimetric (TG) and X-ray photoelectron spectroscopy (XPS) analysis, it was found that the HMA as precursor could not decompose completely into MoO₃ crystal on the surface of TNT around the threshold above decomposed temperature due to the strong interaction between HMA and the surface of TNT.     

基于银胶纳米颗粒的痕量三硝基甲苯的表面增强拉曼光谱的实验研究

近年来对作为典型的硝基苯环类炸药的三硝基甲苯(TNT)的痕量检测受到越来越多的关注。将银胶纳米颗粒作为表面增强拉曼散射(SERS)基底,研究了10-6 mol.L-1的TNT的表面增强拉曼光谱的优化实验条件,重点研究了氯化钠溶液(NaCl)的含量以及碱性水解对TNT的表面增强拉曼光谱的影响。实验发现SERS样品中如果没有加入NaCl溶液,将观察不到TNT的SERS谱。加入的NaCl的含量必须在某一个范围之内才能观察到TNT的SERS谱,而且在这个范围之内,随着NaCl含量的增加,TNT的1 392cm-1处的拉曼峰出现先增大后减小的现象。对NaCl在TNT的SERS中的作用给予了理论解释。研究还发现TNT分子经过碱性水解后,与银纳米颗粒之间的吸附作用增强,其SERS谱的强度明显优于未经碱性水解的SERS结果。     

Increasing 14N NQR signal by 1H-14N level crossing with small magnetic fields

NQR detection of materials, such as TNT, is hindered by the low signal-to-noise ratio at low NQR frequencies. Sweeping small (0-26 mT) magnetic fields to shift the (1)H NMR frequency relative to the (14)N NQR frequencies can provide a significant increase of the (14)N NQR signal-to-noise ratio. Three effects of (1)H-(14)N level crossing are demonstrated in diglycine hydrochloride and TNT. These effects are (1) transferring (1)H polarization to one or more of the (14)N transitions, including the use of an adiabatic flip of the (1)H polarization during the field sweep, (2) shortening the effective (14)N T(1) by the interaction of (1)H with the (14)N transitions, (3) "level transfer" effect where the third (14)N (spin 1) energy level or other (14)N sites with different NQR frequency are used as a reservoir of polarization which is transferred to the measured (14)N transition by the (1)H. The (14)N NQR signal-to-noise ratio can be increased by a factor of 2.5 for one (14)N site in diglycine hydrochloride (and 2.2 in TNT), even though the maximum (1)H frequency used in this work, 111 6 kHz, is only 30% larger than the measured (14)N frequencies (834 kHz for diglycine hydrochloride and 843 kHz for TNT).     

马赫反射效应在炸药爆轰合成金刚石中的应用

 在爆轰法合成超细金刚石中，利用马赫效应提高金刚石得率。用Whitham方法计算马赫杆上的爆轰参数。实验采用中间为TNT药柱、外边包裹TNT/RDX（30/70）的装药，在爆炸罐氮气介质中爆炸，超细金刚石得率为6%，包裹盐后得率超过10%。     

Improving N nuclear quadrupole resonance detection of trinitrotoluene using off-resonance effects

The off-resonance dependence of the amplitudes of the six dominant ¹⁴N nuclear quadrupole resonance (NQR) lines in commercial polymorphic trinitrotoluene (TNT) sample were experimentally determined for a wide range of experimental parameters when irradiated with the spin-lock spin-echo (SLSE) pulse sequence. We find that the amplitudes off-resonance dependence follows a sinc-like function with an additional modulation due to the spacing between the RF pulses. This dependence can be very well modeled with expressions we have derived for a single site ¹⁴N NQR in paranitrotoluene (PNT). The results can be immediately used for the reduction of the number of free parameters used in the robust signal processing models for the TNT NQR detectors.     

Generation of blast waves in a channel by nonideal detonation of aluminum-enriched high-density compositions

The results of experimental studies of the nonideal detonation of high-density, high-energy aluminum-ammonium perchlorate-organic fuel-HE compositions and of the blast waves it generates in a channel filled with air are presented. Aluminum-enriched compositions have high densities (up to 2 g/cm³) and high heats of explosion, nearly twice that for TNT. The studies were performed to work out scientific fundamentals of controlling nonideal detonation and to explore the possibility of creating new high-energy high-density formulations with an enhanced fugacity effect. The factors that enable controlling the nonideal detonation of such charges were determined. It was demonstrated that, at RDX contents above 15%, the detonation velocity increases linearly with the charge density while the critical detonation diameter decreases. Adjusting the density, HE content, ratio of the components makes it possible to vary the detonation velocity in high-density charges over a wide range, from 4 to 7 km/s. The experimental data were compared to the thermodynamically calculated velocity of ideal detonation. For the compositions under study, the pressure- time histories of the blast wave generated in a cylindrical tube by the expanding detonation products at different distances from the charge were measured. The results were compared to analogous data obtained under the same conditions for the detonation of the same mass of TNT (100 g). The parameters of blast waves generated by the test compositions are markedly superior to those characteristic of TNT: the pressure at the leading front of the wave and pressure impulse at a given distance from the charge were found to be 1.5–2.0 (or even more) times those observed for TNT. The TNT equivalency at pressures 30–60 atm has similar values. The TNT equivalencies in pressure and pressure impulse depend nonmonotonically on the distance from the charge, so far unclear why. It was established that the interaction between excess fuel and air oxygen during the expansion of detonation products contributes little to supporting the blast wave.     

Folic Acid as a Bimodal Optical Probe for the Detection of TNT

Rapid and onsite detection of nitroaromatic explosive 2,4,6-trinitrotoluene (TNT) is very crucial for the safety and security of human life as well as for the environment. In this present work, we demonstrate the feasibility for employing Folic Acid (FA) as a fluorescent as well as a colorimetric probe for the detection of TNT. This probe was synthesized by a simple one-step process. The developed probe shows an emission maximum at 490 nm upon excitation at 420 nm. On adding TNT, the fluorescence of the FA probe is quenched. Also, it shows a good selectivity towards TNT over other similar organic compounds such as 4-nitrophenol (4-NP), 2,4-dinitrophenol (2,4-DNP) and picric acid (PA). The limit of detection (LoD) of TNT was found to be 1.9398 µM. Colorimetric detection was conducted and paper strip assay was developed for the practical applications.

Graphical Abstract

     

Electrochemical properties of TiO2 nanotube-Li4Ti5O12 composite anodes for lithium-ion batteries

For application as an anode material in lithium batteries, composite anodes consisting of TiO₂ nanotubes (TNT) and Li₄Ti₅O₁₂ (LTO) nanocrystalline particles are prepared by hydrothermal reaction of rutile TiO₂ particles, physical blending with LTO, and subsequent heat treatment at 300 °C. The TNT-LTO composites with varying the composition are characterized by electron microscopy, X-ray diffraction, potentiostatic cyclic voltammetry, and galvanostatic charge-discharge tests at various current rates. With higher LTO content, short TNTs with the average tube diameter of 10 nm are distributed among the potato-shaped LTO particles with the average diameter of 200 nm. At higher content of TNT, however, the LTO particles are sparsely distributed in the fibrillar aggregates of TNT with more lengthened image. As a result, the samples of TNT:LTO = 2:8 and 4:6 show superior cycle performance and high-rate capability, mainly due to their higher electrode densities to yield nanotubular TNT distributed on and supported by potato-shaped LTO nanoparticles.