Experiments concerning resonance-enhanced multiphoton ionization probe measurements of flame-species profiles

Resonance-enhanced multiphoton ionization (REMPI) detection of radical species in low-pressure laboratory flames is a promising tool for the development and refinement of combustion models. For accurate REMPI species concentration measurements in flame zones with inherently high background ionization levels, an understanding of the influence of plasma sheaths on REMPI probe response is required. Proper probe response is found to depend on careful control of probe-biasing and laserfocusing conditions. Only negatively biased probes are suitable, because of the influences of secondary ionization on the response of positively biased probes. In situ probe calibration procedures with the (2 + 2) REMPI of N(2) at 270.6 nm are described. Detection of O atoms in a stoichiometric 20-Torr methane-oxygen flame permits a precise comparison of both laser-induced fluorescence and REMPI measurements with flame-modeling results.     

Effects of excited-state absorption on two-photon absorbing materials

Many chromophores with a large two-photon absorptive cross section are hybrid materials where the two-photon absorption (TPA) is coupled to an excited-state absorption (ESA). We develop a numerical technique to investigate hybrid two-photon processes in nonlinear absorbers. Our numerical method compares well with published results. In addition to customary calculation of the transmission curve, we demonstrate the importance of the ESA following the TPA, which may cause significant temporal and radial distortion. We also show that improvements in the transmission can result in significant radial and temporal pulse distortion, which may actually reduce the material effect.     

Excited-state absorption and anisotropy properties of two-photon absorbing fluorene derivatives

The electronic structure of fluorene derivatives N-(7-benzothiazol-2-yl-9,9-bis-decyl-9H-fluoren-2-yl)-acetamide (1); 9,9-didecyl-2,7-bis-(N,N-benzothiazoyl)fluorene (2); 4,4'-{[9,9-bis(ethyl)-9H-fluorene-2,7-diyl]di-2,1-ethenediyl}bis(N,N-diphenyl)benzeneamine (3); and 4,4',4"{[9,9-bis(ethyl)-9H-fluorene-2,4,7-triyl]tri-2,1-ethenediyl}tris(N,N-diphenyl)benzeneamine (4) were investigated by a steady-state spectral technique, quantum-chemical calculations, and a picosecond pump-probe method. These derivatives are of interest for their relatively high two-photon absorption. The steady-state excitation anisotropy spectra reveal the nature of the ground-state absorption bands. Semiempirical quantum-chemical calculations of the fluorene derivatives (AM1, ZINDO/S) show good agreement with experimental data. The spectral positions and alignment of various electronic transitions of derivatives 1-4 were estimated from their excited-state absorption and anisotropy spectra.     

多重响应性大分子荧光探针的合成与性能

由偶氮二异丁腈(AIBN)引发N-异丙基丙烯酰胺(NIPAM)和N-丙烯酰氧基丁二酰亚胺(NA-SI)及3-丙烯酰氧基荧光素(Ac-Flu)进行三元共聚,得到P(Flu-co-NASI-co-NIPAM)三元共聚物。进而在碱性条件下使荧光小分子9-氨基吖啶(9AA)与共聚物中的丁二酰亚胺酯基反应,制得了温度和pH值多重响应性大分子荧光探针P(Flu-co-9AA-co-NIPAM)。利用FT-IR、1 H NMR、GPC、UV-Vis等对大分子荧光探针的结构及分子量进行表征,并用荧光光谱测定其水溶液的荧光强度。结果表明,当体系温度和pH值变化时,荧光颜色均可发生可逆转变,T<33℃(LCST)或pH值=8.9时呈现黄绿色,当T≥33℃或pH值=3.1时呈蓝色,该大分子荧光探针具有多重响应性。     

比率型CN-检测荧光探针的合成与应用

利用CN-诱导的迈克尔加成反应阻断探针的分子内电荷转移过程(ICT),成功设计合成一种新型的荧光比率型CN-荧光探针。该探针对CN-具有显著的荧光比率响应,其荧光光谱蓝移128 nm。相对于其他干扰离子,探针对CN-具有较高的选择性和专一性。通过以上实验为监测CN-浓度提供一个简单有效并具有较高灵敏度的分析方法。     

Reflectionless absorption of electromagnetic radiation incident at an angle upon a clarified absorbing substrate

The conditions for the occurrence of complete reflectionless absorption of an electromagnetic wave when it is incident at an angle upon an absorbing substrate of infinite thickness with a layer of nonabsorbing dielectric applied to it have been found. The dependence of these conditions on the thickness of the layer of clarifying coating, angle of wave incidence, and the dielectric properties of the substrate and coating materials is investigated. __________ Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 81, No. 2, pp. 223–228, March–April, 2008.     

An easy method to monitor lactide polymerization with a boron fluorescent probe

Fluorescence spectroscopy has been widely used to monitor different polymer processes such as polymerization kinetics, chain entanglements, and thermal transitions. The solvent-free controlled ring-opening polymerization (ROP) of lactide is significant both commercially and for research; thus, monitoring this process with a simple fluorescence method can be very useful. Here, a fluorescent dye, difluoroboron 4-methoxydibenzoylmethane (BF(2)dbmOMe) is employed to probe lactide bulk ROP by measuring the emission from solidified reaction aliquots at room temperature. It was found that, through the course of polymerization, the fluorescence of BF(2)dbmOMe in the solid-state aliquots exhibited a systematic shift from yellow to green and then to blue, accompanied by a gradual reduction in the decay lifetime. The fluorescence color change is sensitive to the monomer percent conversion, not the polymer molecular weight. On the basis of these observations and experimental data, we propose that the long-wavelength emission with perceivably longer lifetimes arises from BF(2)dbmOMe dye aggregates (ground and/or excited states), while the dissolved individual dye molecules are responsible for the blue fluorescence with a shorter lifetime. This demonstration of the utility of BF(2)dbmOMe as a fluorescent probe for lactide polymerization could have important practical implications.     

Electromagnetic and absorption properties of carbonyl iron/rubber radar absorbing materials

We measured the effective complex magnetic permeability /spl mu//sub eff//sup */ and dielectric permittivity /spl epsiv//sub eff//sup */ spectra in rubber radar absorbing material (RAM) with various carbonyl iron volume fractions by using the transmission/reflection method with a vector network analyzer. We studied the effects of carbonyl iron content and rubber thickness on the microwave absorption properties in the frequency range of 2.6 to 18 GHz. Our mathematical analysis is based on electromagnetic theory. The results indicate that the effective complex magnetic permeability and dielectric permittivity values of the RAM increase as the carbonyl iron volume fraction increases. For sample thickness of 3.0 mm, an increase in carbonyl iron content reduces the minimum reflection loss from -1.3 to -23.9 dB and shifts the frequency of the minimum reflection loss from 15.5 to 3.5 GHz. For an equal volume fraction of carbonyl iron, the frequency of the minimum reflection loss decreases as the thickness is increased. However, the dip in the reflection loss plot (in decibels) initially decreases to a minimum value before it increases with a further increase in thickness. We determined the value of the reflection loss for the samples by the impedance matching degree (reflection coefficient), which depends on the thickness and composition of the RAM.     

用于检测生物硫醇的新型萘酰亚胺荧光探针的合成与应用

该文利用硫醇诱导的2,4-二硝基苯磺酰基基团的断裂反应生成具有供-吸电能力的荧光团,成功设计合成一种基于萘酰亚胺识别硫醇的荧光探针。相对于其他氨基酸,该探针在生理p H(7.40)值下,对于含硫醇的氨基酸具有高度的选择性和灵敏度。探针对硫醇具有显著的荧光增强响应,其荧光强度可以恢复197倍。此外,细胞内硫醇的荧光成像实验,证明该荧光探针具有潜在检测细胞内生物硫醇的能力。     

Surface-modified CdS nanoparticles as a fluorescent probe for the selective detection of cysteine

We present a novel method for the selective detection of cysteine, a sulfur-containing amino acid, which plays a crucial role in many important biological functions such as protein folding. Surface-modified colloidal CdS nanoparticles have been used as a fluorescent probe to selectively detect cysteine in the presence of other amino acids in the micromolar concentration range. Cysteine quenches the emission of CdS in the 0.5-10?μM concentration range, whereas the other amino acids do not affect its emission. Among the other amino acids, histidine is most efficient in quenching the emission of the CdS nanoparticles. The sulfur atom of cysteine plays a crucial role in the quenching process in the 0.5-10?μM concentration range. Cysteine is believed to quench the emission of the CdS nanoparticles by binding to their surface via its negatively charged sulfur atom. This method can potentially be applied for its detection in biological samples.     

Plano-concave microcuvette for measuring the absorption coefficient of highly absorbing liquids

A powerful and simple method based on the use of a plano-concave microcuvette was investigated for measuring the absorption coefficient of highly absorbing liquids. A plano-convex lens put on a plane-parallel plate formed a microcuvette with small, continuously varying thicknesses. This microcuvette was filled with liquid and illuminated by a homogeneous beam. The parabolic variation of the liquid thickness generates a Gaussian spatial intensity distribution behind the cuvette. This Gaussian profile, detected by a CCD camera, was used to determine the absorption coefficient of the liquid. An absorption coefficient as high as 1.54 x 10(4) cm(-1) was measured by use of high-concentration malachite green dye solutions. A comparison of the results with data extrapolated from those of conventional methods showed good agreement.     

Assessment of multiphoton absorption in inert gases for the measurement of gas temperatures

A spatially resolved optical technique to measure gas temperature was assessed. The technique relies on multiphoton absorption in inert gases. In contrast to laser-induced fluorescence, absorption is insensitive to collisional deactivation, and, in contrast to one-photon absorption, multiphoton absorption only occurs around the focus point of a typical laser beam. Multiphoton absorption features both the merits of being insensitive to quenching and of being a spatially resolved technique. In a case study we assessed two-photon absorption in xenon upon exciting the 5p6 1S0-->5p56p[5/2]2 transition in xenon at a wavelength of 256 nm. The amount of light absorbed by xenon is related to the number density of the gas, and if the gas pressure is known then the gas temperature can be inferred from the number density. Two-photon absorbance was measured as a function of xenon number density and was used to validate a theoretical model of the absorption process. We discuss the circumnavigation of experimental challenges in applying this technique and analyze its precision in terms of the inferred gas temperature.     

Practical formula for the evaluation of high-order multiphoton absorption in thin nonlinear media

We present an analytical formula for the fast and accurate evaluation of nonlinear absorption in materials exhibiting an admixture of different multiphoton processes. This approach is specifically addressed for its use in thin films when the slowly varying envelope approximation applies. The contribution of absorptions of distinct order is conveniently averaged in order to use well-known expressions for a single multiphoton process. In the latter case, therefore, our simple expression is reduced toward the exact solution.     

吸波剂含量和涂层厚度对微波吸收性能的影响

以具有强磁损耗特性的磁粉、电阻型和电介质型物质作为吸波剂,制备出了具有阻抗渐变结构的3层复合雷达吸波涂层,研究了吸波剂用量和涂层厚度对吸波性能的影响.结果表明,增加表层、中层或底层吸波剂含量及涂层厚度,均能使吸波性能曲线向低频端方向移动,反之,吸波性能曲线向高频端方向移动;选择适当的吸波剂含量或者一定厚度的涂层才能拓宽、加深吸波性能.制得的试样中反射损耗可达-35.74和-39.25dB,其频宽(＜-10dB)分别为3.52和2.84GHz.     

Detection of enzymatically generated hydrogen peroxide by metal-based fluorescent probe

We developed a metal-based fluorescent probe for H(2)O(2) called MBFh1, which has an iron complex as a reaction site for H(2)O(2) and a 3,7-dihydroxyphenoxazine derivative as the fluorescent reporter unit. The iron complex reacts quickly with H(2)O(2) to form oxidants, and then the oxidants convert the closely appended nonfluorescent 3,7-dihydroxyphenoxazine moiety to resorufin in an intramolecular fashion. The quick response to H(2)O(2) allows us to plot the enzymatic evolution of H(2)O(2). A combination of N-acetyl-3,7-dihydroxyphenoxazine and horseradish peroxidase has been frequently used to detect enzymatically generated H(2)O(2), but this method has interference with phenol derivatives. The use of MBFh1 overcomes this drawback.     

Finite-difference time-domain solution of light scattering and absorption by particles in an absorbing medium

The three-dimensional (3-D) finite-difference time-domain (FDTD) technique has been extended to simulate light scattering and absorption by nonspherical particles embedded in an absorbing dielectric medium. A uniaxial perfectly matched layer (UPML) absorbing boundary condition is used to truncate the computational domain. When computing the single-scattering properties of a particle in an absorbing dielectric medium, we derive the single-scattering properties including scattering phase functions, extinction, and absorption efficiencies using a volume integration of the internal field. A Mie solution for light scattering and absorption by spherical particles in an absorbing medium is used to examine the accuracy of the 3-D UPML FDTD code. It is found that the errors in the extinction and absorption efficiencies from the 3-D UPML FDTD are less than approximately 2%. The errors in the scattering phase functions are typically less than approximately 5%. The errors in the asymmetry factors are less than approximately 0.1%. For light scattering by particles in free space, the accuracy of the 3-D UPML FDTD scheme is similar to a previous model [Appl. Opt. 38, 3141 (1999)].     

Influence of absorption coefficient fluctuations on the heating of a weakly absorbing medium by intense optical radiation

The problem of heating the opacity fluctuations in a transparent solid medium by powerful optical radiation is numerically solved. The dependence of the absorption coefficient of the medium on the thermoelastic stresses is taken into account.Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 36, No. 2, pp. 327–330, February, 1979.     

Optical absorption and fluorescent behaviour of titanium ions in silicate glasses

Titanium in normal melting conditions in air atmosphere present as Ti⁴⁺ ion in basic silicate glasses exhibited an ultra-violet cut-off in silicate glasses, viz. soda-magnesia-silica, soda-magnesia-lime-silica and soda-lime-silica glasses. This indicates that Ti⁴⁺ ion can be a good replacement for Ce⁴⁺ ion in producing UV-absorbing silicate glasses for commercial applications. The wavelength maxima at which the infinite absorption takes place in glasses was found to be around 310 nm against Ti-free blank glass in UV-region. The mechanism of electronic transition from O^2- ligands to Ti⁴⁺ ion was suggested as L→ M charge transfer. The low energy tails of the ultra-violet cut-off were found to obey Urbach’s rule in the optical range 360–500 nm. The fluorescence spectra of these glasses were also studied and based on the radiative fluorescent properties it was suggested that the soda-lime-silica glass containing Ti⁴⁺ ion with greater emission cross-section would emit a better fluorescence than the corresponding soda-magnesia-lime-silica and sodamagnesia-silica glasses. The shift of emission wavelengths maxima towards longer wavelength in titania introduced silicate glasses was observed on replacement of MgO by CaO which may be attributed due to an increase in basicity of the glass system.