Laser photodissociation of trimethylaluminum and trimethylindium on a quartz substrate: Laser–induced fluorescence study

Laser photodissociation of trimethylaluminum and trimethylindium at 248 nm on a quartz substrate was studied by detecting aluminum and indium atoms appearing as reaction intermediates by laser–induced fluorescence. Photodissociation occurred predominantly in the adsorbed state in the experimental conditions. Kinetic energy distributions of the atoms were measured and were simulated by Maxwell–Boltzmann distributions in order to discuss photodissociation mechanisms.     

Capacitive Discharge Graphite Furnace Laser-Excited Atomic Fluorescence of Thallium

For the first time, an anisotropic graphite furnace heated by capacitive discharge was used for laser-excited atomic fluorescence spectrometry. A detection limit of 5 fg for thallium was obtained with a laser repetition rate of 500 Hz and a peak integration time of 80 ms. The use of a capacitive discharge furnace allows for a shorter integration time, which in turn should allow for integration of less background noise, and improved detection limits. Theoretically, the magnitude of the shot noise should be proportional to the square root of the integration time, and inversely proportional to the square root of the laser repetition rate. Experimental data illustrated the effect of laser repetition rate, but were inconclusive with respect to integration time. The linear dynamic range of the calibration curve was six orders of magnitude, which was comparable to that normally obtained for laser-excited atomic fluorescence in modern commercial graphite furnaces. Thallium was accurately determined in NIST biological samples at levels one to two orders of magnitude below the detection limit of electrothermal atomic absorption spectrometry, with an analytical precision between 8 and 20%. The interference effects of calcium, sodium chloride, and potassium chloride on the thallium signal were investigated and shown to be similar to both laser-excited atomic fluorescence in a conventional furnace and capacitive discharge furnace atomic absorption results reported in the literature.     

Highly Sensitive Spectrofluorimetric Determination of Trace Amounts of Indium with 5-Bromine-Salicylaldehyde Salicyloylhygrazone

The fluorescence reaction of 5-bromine-salicylaldehyde salicyloylhydrazone (5-Br-SASH) with indium was studied in detail. Based on this chelating reaction, a sensitive spectrofluorimetric method was developed for the determination of indium in a water–ethanol (63%) medium at PH 4.6. Under these conditions, the In-5-Br-SASH complex has excitation and emission maxima at 395 nm and 461 nm, respectively. The linear range of the method is from 0 to 1000 ng mL^–1and the detection limit is 2.4 ng mL^–1of indium. The molar ratio of indium to the reagent is 1 : 3. Interferences from other ions were studied. The method was successfully applied to the determination of indium in lead, tin, spelter, zinc sulfide using the standard additions method.     

Use of (130)Te(2) for frequency referencing and active stabilisation of a violet extended cavity diode laser

This paper reports on the use of (130)Te(2) absorption lines in active laser-locking, and in frequency referencing, of the emission of a violet extended cavity diode laser with a wavelength of around 410 nm. We note the existence of closely spaced tellurium absorption lines, suitable for referencing purposes in gas sensing applications, at wavelengths below the lower limit (417 nm) of the spectral region covered by the tellurium atlas [J. Cariou, P. Luc, Atlas du spectre d'Absorption de la Molecule de Tellure, CNRS, Paris, 1980]. The absolute positions of the lines in the acquired spectra were estimated by comparison to a simultaneously acquired fluorescence spectrum of atomic indium, and were identified using calculations based on fundamental spectroscopic data. The laser frequency was stabilised within a range of 40 MHz, which is negligible compared to typical transition widths at atmospheric pressure.     

铟酞菁功能化的四臂星型聚甲基丙烯酸甲酯的合成及三阶非线性光学性质

以四(2-氯丙酰胺基)氯代铟酞菁[InClPc(NHCOCHClCH3)4]为引发剂,通过原子转移自由基聚合(ATRP)法制得一种新型的以氯代铟酞菁为核的四臂星型聚甲基丙烯酸甲酯(PMMA-InClPc).通过傅里叶红外光谱(FTIR)、紫外-可见光谱(UV-Vis)和核磁共振氢谱(1H NMR)表征了PMMA-InClPc的结构;通过凝胶渗透色谱(GPC)测定了聚合物的分子量及分子量分布;研究了所制备聚合物的聚合反应动力学,其聚合过程符合一级反应动力学.使用调Q倍频Nd∶YAG脉冲激光系统,在输出激光波长为532 nm,脉冲宽度为21ps条件下,通过Z扫描测试研究了聚合物的三阶非线性光学性质.通过计算可知,当PMMA-InClPc的分子量为2902时,其三阶非线性极化率值最大,为7.216×10-10esu.     

Laser-induced fluorescence of cyclohexadienyl (c-C6H7) radical in the gas phase

A laser-induced fluorescence spectrum was observed in the 500-560 nm region when a mixture of 1,4-cyclohexadiene and oxalyl chloride was photolyzed at 193 nm. The observed excitation spectrum was assigned to the A (2)A(2)<--X (2)B(1) transition of the cyclohexadienyl radical c-C6H7, produced by abstraction of a hydrogen atom from 1,4-cyclohexadiene by Cl atoms. The origin of the A<--X transition of c-C(6)H(7) was at 18 207 cm(-1). From measurements of the dispersed fluorescence spectra and ab initio calculations, the frequencies of several vibrational modes in both the ground and excited states of c-C(6)H(7) were determined: nu(5)(C-H in-plane bend)=1571, nu(8)(C-H in-plane bend)=1174, nu(10)(C-C-C in-plane bend)=981, nu(12)(C-C-C in-plane bend)=559, nu(16)(C-C-C out-of-plane bend)=375, and nu(33)(C-C-C in-plane bend)=600 cm(-1) for the ground state and nu(8)=1118, nu(10)=967, nu(12)=502, nu(16)=172, and nu(33)=536 cm(-1) for the excited states.     

Use of Te2 for frequency referencing and active stabilisation of a violet extended cavity diode laser

This paper reports on the use of ¹³⁰Te₂ absorption lines in active laser-locking, and in frequency referencing, of the emission of a violet extended cavity diode laser with a wavelength of around 410 nm. We note the existence of closely spaced tellurium absorption lines, suitable for referencing purposes in gas sensing applications, at wavelengths below the lower limit (417 nm) of the spectral region covered by the tellurium atlas [J. Cariou, P. Luc, Atlas du spectre d’Absorption de la Molecule de Tellure, CNRS, Paris, 1980]. The absolute positions of the lines in the acquired spectra were estimated by comparison to a simultaneously acquired fluorescence spectrum of atomic indium, and were identified using calculations based on fundamental spectroscopic data. The laser frequency was stabilised within a range of 40 MHz, which is negligible compared to typical transition widths at atmospheric pressure.     

Axial halogen ligand effect on photophysics and optical power limiting of some indium naphthalocyanines

Three axially substituted complexes, 2,3-octa(3,5-di-tert-butylphenoxy)-2,3-naphthalocyaninato indium chloride (1a), 2,3-octa(3,5-di-tert-butylphenoxy)-2,3-naphthalocyaninato indium bromide (1b), and 2,3-octa(3,5-di-tert-butylphenoxy)-2,3-naphthalocyaninato indium iodide (1c) have been synthesized and their photophysical properties have been investigated. Optical power limiting of nanosecond (ns) and picosecond (ps) laser pulses at 532 nm using these complexes has been demonstrated. All complexes display strong Q(0,0) absorption and measurable emission in the near-infrared region and exhibit strong excited-state absorption in the range of 470-700 nm upon ns laser excitation. The different axial ligands show negligible effect on the linear absorption, emission, and transient difference absorption spectra. However, the excited-state lifetime, triplet excited-state quantum yield, and efficiency to generate singlet oxygen are affected significantly by the heavier axial ligand. Brominated and iodinated complexes 1b and 1c show higher triplet excited-state quantum yield, while chlorinated complex 1a has longer excited-state lifetime and is more efficient in generating singlet oxygen. The iodinated complex 1c displayed the best optical limiting due to the higher ratio of excited-state absorption cross section to ground state absorption cross section (sigma(eff)/sigma(0)).     

Synthesis of indium nanoparticles: digestive ripening under mild conditions

Here we report the synthesis of monodispersed indium nanoparticles by evaporation/condensation of indium shot using the solvated metal atom dispersion (SMAD) technique, followed by digestive ripening in low boiling point (BP 38 °C) methylene chloride and in a high boiling point (BP 110 °C) toluene solvent. The as-prepared SMAD indium nanoparticles are polydispersed with particle size ranging from 25 to 50 nm, but upon digestive ripening (heating of colloidal material at the boiling point of solvent in presence of excess surface active ligands) in methylene chloride, a remarkable reduction of particle size was achieved. In higher boiling solvent (toluene), where the indium nanoparticles at reflux temperature are probably melted, it does not allow the best result, and less monodispersity is achieved. We employed different surface active ligands (amine, phosphine, and mixed ligands) to passivate these indium nanoparticles. The temporal evolution of the surface plasmon of indium nanoparticles was monitored by in situ UV-vis spectroscopy, and particles were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The merits of this synthesis procedure are the use of bulk indium as starting material, tuning the particle size in low boiling point solvent, particle size adjustment with the choice of ligand, and a possible scale up.     

Tunable diode laser spectroscopy of copper,cadmium, and indium at 325 nm

A tunable frequency-doubled external-cavity diode laser has been recently developed for atomic absorption spectroscopy in the wavelength range from 320 to 327 nm. The line width of the laser is 0.003 pm. In this work the light source has been applied to the laser absorption spectroscopy of copper at 324.754 nm, cadmium at 326.106 nm, and indium at 325.609 nm and 325.856 nm. The Cu transition was measured in three different environments: in a direct current plasma, a diffusion flame, and in a low-pressure hollow-cathode discharge. Both the plasma and the flame were at atmospheric pressure. The Cd and In transitions were measured in the diffusion flame. A Voigt profile was fit to the measured spectra taking into account the hyperfine structure. From the measured absorption lines spectral reference data for Cu is extracted.     

Highly Sensitive Spectrofluorimetric Determination of Trace Amounts of Indium(Ⅲ) with Salicylaldehyde Salicyloylhydrazone

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｒｅｃｅｎｔｙｅａｒｓ ,ａｒｏｙｌｈｙｄｒａｚｏｎｅｓｗｈｉｃｈｃｏｎｔａｉｎｇｒｏｕｐ—ＣＯＮＨＮ ＣＨ—ｈａｖｅｂｅｅｎｔｅｓｔｅｄａｓｆｌｕｏｒｉ ｍｅｔｒｉｃｒｅａｇｅｎｔｓｆｏｒｔｈｅｄｅｔｅｒｍｉｎａｔｉｏｎｏｆａｌｕｍｉｎｕｍ ,ｇａｌｌｉｕｍ ,ｓｃａｎｄｉｕｍ ,ｚｉｎｃ ,ｃｏｐｐｅｒａｎｄｏｔｈｅｒｍｅｔａｌｉｏｎｓ[17] .Ｔｈｅｒｅａｃｔｉｏｎｏｆａｍｅｔａｌｉｏｎｗｉｔｈａｃｈｅｌａｔｉｎｇａｇｅｎｔｐｒｏｄｕｃｅｓａｒｉｇｉｄｍｏｌｅｃｕｌｅｗｉｔｈａ…     

Resonance fluorescence spectroscopy in laser-induced cavitation bubbles

Laser-induced breakdown spectroscopy (LIBS) in liquids using a double-pulse Q-switched Nd:YAG laser system has provided reliable results that give trace detection limits in water. Resonant laser excitation has been added to enhance detection sensitivity. A primary laser pulse (at 532 nm), transmitted via an optical fiber, induces a cavitation bubble and shockwave at a target immersed in a 10 mg l⁻¹–100 mg l⁻¹ indium (In) water suspension. The low-pressure rear of the shockwave induces bubble expansion and a resulting reduction in cavity pressure as it extends away from the target. Shortly before the maximum diameter is expected, a secondary laser pulse (also at 532 nm) is fed into the bubble in order to reduce quenching processes. The plasma field generated is then resonantly excited by a fiber-guided dye laser beam to increase detection selectivity. The resulting resonance fluorescence emission is optically detected and processed by an intensified optical multichannel analyzer system.      

Determination of Fluorine, Chlorine, and Bromine by Molecular Absorption Spectrometry

Fluorine was determined by molecular absorption spectrometry (MAS) in a graphite tube furnace, and fluorine, chlorine, and bromine were determined in a flame. For the fluorine work, aluminum nitrate was added as a reagent to produce aluminum fluoride molecules whose absorbance was monitored with emission from a platinum hollow cathode lamp (HCL) at 227.45 nm. A deuterium arc lamp was employed for background correction. For the furnace work, barium nitrate was used as a chemical modifier to increase the absorption signal. After optimization of the chemical and furnace conditions, a detection limit of 160 pg F was obtained, with a linear dynamic range of two orders of magnitude. Graphite furnace MAS was used to accurately determine fluoride in dental rinse and National Institute of Standards and Technology oyster tissue, but the precision was between 21 and 23%. Low recoveries were obtained for the determination of trifluoroacetic acid and l,2,2,3-tetrafluoropropan-1-ol by graphite furnace MAS. The detection limit for F by flame MAS was 13 mg liter⁻¹ which is a factor of 5 lower than the best reported flame MAS detection limit. Chlorine was determined by flame MAS with the aluminum chloride molecule. Excitation was done at 261.4 nm with a lead HCL. and a detection limit of 180mg liter⁻¹ was obtained. Flame MAS of bromine was done by use of AlBr (excitation at 279.0 nm with an arsenic HCL) and InBr (excitation at 284.3 nm with a chromium HCL), but very poor detection limits were obtained: 24.5 g liter⁻¹ and 500mg liter⁻¹, respectively.     

三苯胺-噁二唑超支化共轭聚合物的多光子泵浦绿色荧光

采用钯催化Heck反应制备了一种新型三苯胺-噁二唑超支化荧光聚合物PI. 用飞秒Ti:sapphire激光研究了PI的三光子和双光子上转换荧光光谱, 激发波长位于近红外区(800~1350 nm). 在1280 nm和80 fs激光激发下, PI的三光子上转换荧光发射波长分别为525 nm(THF), 534 nm(CH2Cl2)和578 nm(DMF). 在800 nm和150 fs激光激发下, PI的双光子上转换荧光发射波长分别为527 nm(THF), 532 nm(CH2Cl2)和573 nm(DMF). 采用非线性透过率法测定荧光聚合物PI的三光子和双光子吸收系数. 系统研究了PI的线性吸收和透过、单光子荧光、荧光寿命、前线轨道能级及热稳定性. 实验结果表明, 三苯胺-噁二唑超支化共轭聚合物的多光子吸收和上转换荧光发射性能比树型分子或线型聚合物更为优异.     

注射成型掺酞菁铟反饱和吸收材料的研究

反饱和吸收是指介质的吸收系数随输入光强的增加而增大的一种现象。反饱和吸收材料在全光开关、光计算与通信以及光限幅和光稳幅等光电子领域中都有着广泛的应用前景。酞菁类化合物以其较大的非共振三阶极化率、内在的快速响应和良好的化学和热稳定性倍受关注。目前所研究的反饱和吸收材料多是溶液和薄膜样品，在实用化方面存在较大困难，并且一些反饱和吸收性能好的酞菁化合物在溶剂中易于分解，给薄膜制备和溶液的稳定带来了困难。本文采用注射成型方法将酞菁铟掺杂到聚甲基丙烯酸甲酯（PMMA）中，研究了样品的反饱和吸收性能，国内外鲜见相关报道。     

Photoinduced redox cycle of riboflavin at a water/oil interface.

A photoinduced redox reaction cycle of Riboflavin (RF) at a water/CCl4 interface was studied directly by means of both steady-state and time-resolved total internal reflection (TIR) fluorescence spectroscopies. The TIR fluorescence spectrum of RF observed at the water/CCl4 interface with the maximum wavelength of 517 nm was assigned to the pi-pi* transition from the excited singlet-state of the isoalloxazine chromophore in RF. Upon prolonged laser irradiation (400 nm) in the presence of N,N-dioctadecyl-[1,3,5]triazine-2,4,6-triamine (DTT) as a guest for RF in the CCl4 phase, on the other hand, a new TIR fluorescence band appeared at around 480 nm. Furthermore, the fluorescence intensity at around 480 nm increased in the presence of acetic acid in the water phase. Detailed studies demonstrated that the new fluorescence band should be ascribed to 1,5-dihydoroflavin (RFH2). The present results indicated that RFH2 was produced through the photoreaction of the RF-DTT hydrogen-bonded complex formed at the water/CCl4 interface, whose reaction mechanisms were discussed on the basis of the results observed by fluorescence spectra/dynamics measurements under the TIR conditions as well as by transient absorption spectroscopy.     

基于共轭聚合物的纳米粒子用于肿瘤的近红外二区荧光成像及光热治疗

为提高生物组织荧光成像质量以及对肿瘤的高效光热治疗,设计合成了一种新型的窄带隙共轭聚合物(BDT-TTQ),并通过纳米沉积的方式将聚合物制备成水溶性纳米粒子(BDT-TTQ NPs).该共轭聚合物纳米粒子在1000~1200 nm近红外二区范围具有较好的吸收,在1064 nm的激发光下能实现1200~1400 nm的近红外二区荧光成像. BDT-TTQ NPs纳米粒子粒径分布较窄,形貌呈规则的球形且分散均匀,具有好的生物相容性.该纳米粒子既可以在体外实现较高的近红外二区荧光成像穿透深度,又可以实现对小鼠活体血管的高清晰度的近红外二区荧光成像.此外,BDT-TTQ NPs纳米粒子在1064 nm激光下展现出优异的光热转换效率,具有较高的光毒性,对体外的肿瘤细胞以及小鼠的异质瘤具有高的光热杀伤能力.     

UV laser removal of varnish on tempera paints with nanosecond and femtosecond pulses

Two laser cleaning approaches based on ablation by ultraviolet laser pulses of femtosecond (fs) and nanosecond (ns) durations for the removal of shellac varnish from egg-yolk based tempera paints are investigated. Laser irradiation effects, induced on the varnish layer and on the underlying temperas by multiple pulses in the fs domain at 398 and 265 nm and single pulses in the ns domain at 213 nm, were examined following a spectroanalytical approach. By using optical microscopy, colorimetry and laser induced fluorescence it was found that irradiation of the varnished temperas with fs pulses changes the texture of the varnish surface and results in degradation of the underlying coloured paint. In contrast, operating with pulses of 15 ns at the highly absorbed wavelength of 213 nm, controlled micrometric layer removal of the varnish is possible without noticeable modification of the coloured temperas. These results widen the choice of laser conditions for painting restoration.     

反式-4,4’-二（邻甲氧基苯乙烯基）联苯化合物的合成、结构及光物理性能

以Wittig-Homer反应合成了反式对称的4,4’-二(邻甲氧基苯乙烯基)联苯化合物, X射线衍射分析测定了化合物的晶体结构. 测定了其在不同溶剂中的线性吸收光谱、荧光发射光谱及荧光量子产率. 飞秒激光做光源研究了化合物的双光子光物理性能. 测试结果表明: 该化合物在蓝光波段有较强的荧光发射, 化合物具有较高的荧光量子产率和较大的双光子吸收截面, 具有双光子诱导蓝光发射光学特性.