Structural dependence of non-linear optical properties of 4-Dimethylamino-3-cyanobiphenyl

 4-Dimethylamino-3-cyanobiphenyl (4-DMA-3-CB) was characterized with respect to linear and nonlinear optical properties in a crystal as well as in solution. The crystal structure was studied dependent on the crystallization conditions. It is shown that the crystal structure exhibiting NLO-activity can completely be solved by a combination of electron diffraction and computer modeling. There are four molecules per unit cell in the space group Pna2₁ with dimensions a=10.28 Å, b=22.64 Å, c=5.27 Å. From this model structure the values and orientation of the dipole μ and static second order polarizability β can be calculated. Their relevance to the values obtained by a combination of polarization dependent measurements of Electric Field Induced Second Harmonic Generation (EFISH) and Hyper-Rayleigh-Scattering (HRS) in solution are discussed. The molecular second order polarizability tensor was found to be dominated by one single component. The orientations of the dipole and the vectorial parts of the second order polarizability delivered by the semiempirical calculations are in good agreement with the results of the EFISH and HRS-measurements and allow a deeper insight into the nonlinear optical properties of the crystal. Received: 15 April 1996 Accepted: 21 June 1996     

Coherent anti-Stokes Raman Scattering Microscopy.

Coherent anti-Stokes Raman scattering (CARS) microscopy is presented as a new nonlinear optical technique. The combination of vibrational spectroscopy and microscopy allows highly sensitive investigations of unlabelled samples. CARS is an ideal tool for studying a broad variety of samples. The main drawback of the technique is its non-zero-background nature, which implies that the signal has to be detected against a nonresonant background. The need to solve this problem is reflected in the rapid technological developments that have been observed during the last decade. Recent results show that CARS microscopy has the potential to become an important complementary technique that can be used with other well-established microscopic methods. Although it has some limitations, it offers unique access to many problems that cannot be tackled with conventional techniques. For this reason, it can be expected that the impressive growth of the field will continue.     

稀土掺杂的(K, Sr)Cl·SiO2复合凝胶的荧光性能

采用sol gel法制备了单掺铕及共掺铕、铈的(K,Sr)Cl·SiO2复合凝胶,研究了复合凝胶的荧光性能。根据荧光测试结果,复合凝胶中,Eu3+在没有还原剂的作用下,可以与基质作用形成还原态的Eu2+,复合凝胶表现出相应的Eu2+荧光性能;研究认为,Ce3+,Eu3+共掺杂时,复合凝胶激发光谱与发射光谱峰位基本不变,但强度有所不同。330nm处的激发光谱明显增强,且发射光谱随Ce3+的掺杂量增加而增强。当Ce3+掺杂浓度为3.0%(原子分数)时,复合凝胶具有最大的荧光发射强度,表明Ce3+具有很好的敏化作用。在Ce3+,Eu3+共掺杂复合凝胶体系中,复合凝胶荧光强度增大的原因既可能是电子转移过程,也可能是Ce3+→Eu2+的能量传递过程所致。     

Basic Characteristics of Synchrotron Radiation

Many advances have been made in chemical structure research over the past three decades using synchrotron radiation. Synchrotron radiation has a number of unique properties. They include high brightness, high collimation, broad energy spectrum, variable polarization, coherent power, and subnanosecond pulse width. The third-generation storage rings with wiggler and undulator sources and lower electron beam dimensions are delivering over 10¹² times higher brightness than laboratory-based sources. The future of synchrotron sources looks very promising with the development of energy recovery linac sources and free-electron laser sources. These will permit dynamic studies of chemical structure with subpicosecond time resolution. Commensurate with the development of X-ray sources, major progress has occurred in optical schemes to meet the challenging needs of chemical structure research. High-resolution monochromatization and submicron focusing of X rays present new avenues for the future.     

Second‐harmonic response of a series of chiral polyesters: A joint experimental and theoretical study

A series of polyesters with π‐conjugated donor–acceptor segments was synthesized by the condensation of azobenzene‐4,4′‐dicarbonylchloride with 1,4:3,6‐dianhydro‐D‐sorbitol ([α] = + 42.5°) and biphenolic chromophores, bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylmethane and bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylsulfone. The polymers were characterized by spectral methods (IR, ultraviolet–visible, and NMR), thermal methods (thermogravimetry and differential scanning calorimetry), wide‐angle X‐ray scattering, and polarimetry. The polymers containing isosorbide units were optically active and crystalline. They exhibited glass‐transition temperature values between 100 and 160 °C and were stable up to 400 °C. The second‐harmonic generation (SHG) efficiency of the polymers was experimentally verified by a powder‐reflection technique with 2‐methyl‐4‐nitroaniline as a reference. The SHG efficiencies of the polymers were compared to those of the chromophores and explained as a function of the percentage of chiral composition. The hyperpolarizability β values were also determined by a two‐level model solvatochromic method and computational methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2868–2877, 2002     

Electron-transfer in molecular functional materials

We discuss electron-transfer processes that govern the physics of several materials or systems of interest for advanced applications. The discussion touches upon several topics, ranging from solvatochromism to solvent-induced symmetry breaking, from excitonic to cooperative effects in molecular crystals, from phase transitions to vibrational contributions to the dielectric constant in organic materials, from spectroscopy to molecular transport. In all these diverse systems electron transfer (ET) plays a major role and is discussed with reference to simple models for delocalized charges.     

Splitless injection of up to hundreds of microliters of liquid samples in capillary GC: Part II,experimental results

Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point.     

Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.     

大型液相色谱分离过程FAD－SMT数学模型及其数值解

提出大型液相色谱分离过程ＦＡＤ－ＳＭＴ数学模型，把色谱分离连续性方程转变为对流扩散方程和常微分方程组，并提出模型的数值方法，分析了数值解的稳定条件和收敛条件以及空间和时间步长的选取。实验结果表明，ＦＡＤ－ＳＭＴ数学模型计算的液相色谱分离葡萄糖、果糖和分离甘露醇、山梨醇理论与实验流出曲线相吻合。灵敏度分析结果表明：相平衡常数比轴向扩散系数和总传质系数对色谱分离有较大的影响。     

Organophosphorus π-conjugated materials: the rise of a new field

The synthesis and electronic properties of new linear organic π-conjugated systems incorporating phosphole rings are described. Well defined α,α′-(phosphole-thiophene) oligomers possess low HOMO-LUMO gaps and their optical and electrochemical properties can be tuned via chemical modifications of the P-atoms. The physical properties of these compounds make them valuable materials for OLED’s. The coordination ability of phosphole-based dipoles has been exploited for the synthesis of efficient multipolar NLO-phores. Lastly, phospholes have been used for the synthesis of assemblies exhibiting through-bond interaction between two π-systems via P-P σ-skeletons.