SO_2分子的532nm双光子激发及退激发过程

以纳秒Nd:YAG脉冲激光器的2倍频输出532nm激光作为激发源,采用双光子激发激光诱导色散荧光光谱方法对SO2分子第一激发带粒子的荧光辐射与碰撞弛豫相结合的复杂退激发过程进行了实验研究.结果表明,以215,337nm处荧光包络分别归属于C1B2,B1B1基振动能级到基电子态X1 A1不同振动能级的荧光跃迁,而425nm处荧光包络包既包含有a3B1基振动能级向基电子态X1 A1的荧光跃迁,同时还包含有C1B2基振动能级向A1 A2的荧光跃迁;由规则序列的实验数据可以计算出SO2分子相应电子态的对称振动和弯曲振动模式的基振动角频率及非谐性常数.所得结果对大气污染物SO2的探测及分子物理学研究具有重要意义.     

密度泛函方法研究meso-四苯基卟啉(H2TPP)分子的拉曼光谱

利用密度泛函(DFT)方法计算了m eso-四苯基卟啉(H2TPP)的拉曼活性振动频率.将计算频率乘以因子0.971进行校正,所得结果与实验数据相比,均方根误差小于7.3 cm-1.根据理论计算,参考对卟吩的研究结果,对实验观察到的m eso-四苯基卟啉分子的拉曼振动光谱进行了指认.     

Expression,purification and spectra characterization of neuroglobin

The expression, purification and spectra characterization of recombinant human neuroglobin （NGB） are reported. The pET3a plasmid with the gene of NGB was transformed to E. coli BL21 （DE3） plys cells and expressed in TB culture medium. The results indicated that the expression amount of NGB is about 10 percent of the total protein in cells. The NGB protein was purified by ammonium sulfate precipitation, DEAE-Sepharose anion exchange column, Hiload 16/60 superdex 75 size exclusion chromatography and a Hiprep 16/10 Q FF anion exchange column, and a red soluble protein was obtained which showed a single band in electrophoresis. Electrospray ionization mass spectrometry （ESI-MS） showed that its molecular weight is 16930.0 Da. UV-spectra indicated that the reduced NGB has a strong absorption peak at 425 nm, and two weak peaks at 531 and 559 nm, which can be assigned to γ, β and α bands of porphyrin, respectively, and the oxidized NGB has a strong absorption peak at 413 nm which corresponds to the transition of π electrons in the porphyrin ring. The fluorescence maximal excitation wavelength is at 281 nm and its maximal emission wavelength is at 338 nm. CD spectra indicated that its secondary structure is a typical α helix, and has a positive peak at 410 nm induced by heme, The NGB protein is stable when the pH is higher than 4.     

Distal residues in the oxygen binding site of haemoglobin studied by protein engineering

The geometries of the Fe-O2 and Fe-CO bonds in myoglobin and haemoglobin differ significantly from those in free porphyrin model compounds. It has been suggested that steric hindrance by Val-E11 and His-E7 and a hydrogen bond between His-E7 and oxygen affect the geometry and electronic state of the Fe-ligand bond, and that these interactions may be important in controlling oxygen affinity. We have produced mutant haemoglobins in E. coli having Val(67 beta)E11 replaced by Ala, Met, Leu or Ile and His(58 beta)E7 by Gln, Val or Gly. We have studied the effect of these mutations on the equilibrium and kinetics of ligand binding. The conformation of the new side chains and their effect on the protein structure have been examined by X-ray crystallography, and the vibrational properties of the Fe-CO bond observed by resonance Raman spectroscopy. We found that the steric hindrance of ligand binding by the E11 residue and the polarity of the E7 residue in the beta subunit are critical for fine-tuning ligand affinity.     

诺氟沙星的密度泛函研究

以诺氟沙星为研究对象,采用密度泛函理论的B3LYP/6-311+G(d,p)方法,进行分子结构全优化,并对红外光谱(IR)和拉曼光谱(Raman)、前线轨道(最高占据轨道HOMO、最低空轨道LUMO)、净电荷分布进行了量子力学计算.根据红外光谱(IR)和拉曼光谱(Raman)的计算结果,对振动模式进行了指认;根据前线轨道(HOMO、LUMO)、净电荷分布的计算结果,讨论了诺氟沙星的HOMO、LUMO和分子表面电势的特点.采用密度泛函理论的B3LYP/6-311+G(2d,p)方法,进行分子结构全优化,使用GIAO方法计算得到核磁共振谱(NMR),并对谱图数据进行了分析讨论.     

氯苯的激光拉曼光谱研究

运用群论方法分析氯苯的振动模式,得到各振动模式的对称性和拉曼活性,结果表明,氯苯分子振动拉曼光谱具有30条频率不同的拉曼谱线.采用激光拉曼光谱学技术获得了氯苯的振动拉曼光谱,分析了氯苯拉曼光谱的特点,并对其中16条谱线进行指认,为有机混合物中氯苯分子的识别提供依据.     

Raman spectra of nitrogen-doped tetrahedral amorphous carbon from first principles

The non-resonant vibrational Raman spectra of nitrogen-doped tetrahedral amorphous carbon have been calculated from first principles, including the generation of a structural model, and the calculation of vibrational frequencies, vibrational eigenmodes and Raman coupling tensors. The calculated Raman spectra are in good agreement with the experimental results. The broad band at around 500 cm^-1 arises from mixed bonds. The T peak originates from the vibrations of sp^3 carbon and the G peak comes from the stretching vibrations of sp^2-type bonding of C=C and C=N. The simulation results indicate the direct contribution of N vibrations to Raman spectra.     

键联于核酸的激发态水溶铜卟啉共振拉曼光谱研究

本文测量了键联于核酸的激发态水溶铜卟啉共振拉曼光谱.结果表明,位于1550cm~(-1)和1346cm~(-1)附近的两条谱带归属于受激铜卟啉拉曼带,其强度与核酸和铜卟啉的种类、核酸所含的(AT)_n结构和受激铜卟啉沟槽键联于核酸的能力有关.文中对插入DNA中GC位置上的基态铜卟啉在受激状态下能沟槽键联于—ATAT一位置这一现象作了定性的解释.     

Solvent effects on photophysical properties of copper and zinc porphyrins

The photophysics of Zn（tetraphenylporphyrin,TPP）, Zn（tetra-2,4,6-trimethylphenyl porphyrin, TMP）, Zn （tetra-（o-dichlorophenyl） porphyrin, TPPCI8）, Cu（tetraphenylporphyrin,TPP）, Cu（tetra-2,4,6-trimethyl- phenyl porphyrin,TMP）, and Cu（tetra-（o-dichlorophenyl） porphyrin, TPPCIE, TPPCI8） in several solvents have been investigated on steady state and time-resolved spectroscopy. The Cu（TPPCI8 ） is normal and shows no evidence of CT transition in the visible or near UV regions in nonpolar solvent. However, Cu（TPPCI8）shows a blue shift in the absorption spectrum and intramolecular CT bands at absorption spectra in polar solvent, which shows a fluorescence maximum emission at 650 nm and 8.4 ns lifetime. The reason can be attributed to two points. Firstly, the increase of solvent polarity can enlarge outer reorganisational energy, which is favorable to reduce the activation free energy of charger-transfer transition based on Marcus theory of electron transfer. Moreover, the internal heavy-atom effect on Cu（TPPCIE） is encouraging to stabilize the 2T1 state also, which increases the possibility of population to CT band from 2T1 state. This result is in accord with an earlier estimate of a 10 ns lifetime and CT absorption at 640 nm bands for the CT state of Cu （11） octethylporphyrins. Other possible reasons arousing unusual fluorescence like H-bonding, axial ligands, molecular aggregation are excluded.     

Electrical generation and absorption of phonons in carbon nanotubes

The interplay between discrete vibrational and electronic degrees of freedom directly influences the chemical and physical properties of molecular systems. This coupling is typically studied through optical methods such as fluorescence, absorption and Raman spectroscopy. Molecular electronic devices provide new opportunities for exploring vibration-electronic interactions at the single molecule level. For example, electrons injected from a scanning tunnelling microscope tip into a metal can excite vibrational excitations of a molecule situated in the gap between tip and metal. Here we show how current directly injected into a freely suspended individual single-wall carbon nanotube can be used to excite, detect and control a specific vibrational mode of the molecule. Electrons tunnelling inelastically into the nanotube cause a non-equilibrium occupation of the radial breathing mode, leading to both stimulated emission and absorption of phonons by successive electron tunnelling events. We exploit this effect to measure a phonon lifetime of the order of 10 ns, corresponding to a quality factor of well over 10,000 for this nanomechanical oscillator.     

乙腈分子振动模式和振动光谱的群论方法研究

利用群论的方法可以在不解久期方程的情况下分析分子的振动光谱,本文运用群论方法分析了乙腈分子的简振振动模式,得到了各简振振动模式的对称性,根据振动拉曼光谱选择定则分析了乙腈分子各振动模式的拉曼活性,结果表明乙腈分子振动拉曼光谱有8条频率不同的拉曼谱线,并与实验测定的激光振动拉曼光谱进行比较,理论结果与实验结论吻合很好.     

一种用于光动力治疗的新型Corrole化合物发光特性研究

 通过稳态光谱和皮秒时间分辨的瞬态光谱技术详细研究了一种用于光动力治疗的新型化合物－5,10,15-三（五氟苯基）Corrole（F₁₅TPC）的发光性质。结果表明：F₁₅TPC具有双荧光发射特性;与卟啉相比,F₁₅TPC的S₂态荧光量子产率低,S₁态荧光量子产率高,F₁₅TPC的S₁态荧光寿命为4.8 ns,F₁₅TPC的S₁态具有荧光量子产率高、荧光寿命短的特点。这是由Corrole和卟啉发色团本身的电子结构以及其空间结构和对称性差异引起的。根据实验结果及Corrole和卟啉在光学性质方面的相似性,对Corrole的S₂态电子转移过程进行了类似的讨论。     

Temperature dependence of surface enhanced Raman scattering on C<Subscript>70</Subscript>

The temperature dependence of surface enhanced Raman scattering of the C70 molecule is reported. The Raman scattering of C70 molecules adsorbed on the surface of a silver mirror was measured at different temperatures. The experimental results indicate that the relative intensities of the Raman features vary with the temperature of the sample. When the temperature decreases from room temperature to 0℃, the relative intensifies of certain Raman bands decrease abruptly. If we like the strongest band 1565cm^-1 as a standard value 100, the greatest decrease approaches to 43%. However, with the further decrease in the temperature these relative intensities increase and resume the value at room temperature. And such a temperature dependence is reversible. Our results show that the adsorption state of the C70 molecules on the silver surface around 0℃ changes greatly with the temperature, resulting in a decrease in relative intensities for some main Raman features of C70 molecule. When the temperature is lower than 0℃, the adsorption state changes continually and more slowly. Synchronously, eight new Raman features, which have not ever been reported in fiterature, are observed in our experiment and this enriches the basic information of the vibrational modes for C70 molecule.     

Spectroscopic study on the photophysical properties of chlorine substituted tetraphenylporphyrin-histidine and its zinc(Ⅱ)complexes

The photophysical properties of ortho-CI,meta-CI and para-CI substituted tetraphenylporphy-rin-histidine and their zinc (II) complexes have been studied by means of steady-state absorption and fluo-rescence spectroscopies, as well as time-resolved fluo-rescence spectroscopy. For the cases of both free-base and zinc complexes, it was found that the ortho-chlorine substitution onto the phenyl rings significantly altered the fluorescence quantum yield, thefluorescence lifetime and the ratio between radiative and nonradiative deactivation rates of the porphyrin chromophore, i.e. the photophysical parameters were quite different from those of meta- and para-substituted compounds. On the other hand, however, the introduction of covalently-linked histidine did not exert much effects on the photophysical behavior of the porphyrin chromophore. The results are interpreted interms of the steric effect and the heavy-atom effect from the chlorine atoms substituted onto the phenyl rings.     

Raman spectra of SiC nanorods with different excitation wavelengths

With increasing excitation wavelength from 514 to 782 nm, a significant difference in the Raman spectra of SiC nanorods was observed as compared to bulk material. The intensity ratio of the LO mode to that of the IF mode increases with the excitation wavelength increasing. This has been identified as resonant Raman scattering caused by Fröhlich interaction.     

Identification of a mammalian mitochondrial porphyrin transporter

The movement of anionic porphyrins (for example, haem) across intracellular membranes is crucial to many biological processes, but their mitochondrial translocation and coordination with haem biosynthesis is not understood. Transport of porphyrins into isolated mitochondria is energy-dependent, as expected for the movement of anions into a negatively charged environment. ATP-binding cassette transporters actively facilitate the transmembrane movement of substances. We found that the mitochondrial ATP-binding cassette transporter ABCB6 is upregulated (messenger RNA and protein in human and mouse cells) by elevation of cellular porphyrins and postulated that ABCB6 has a function in porphyrin transport. We also predicted that ABCB6 is functionally linked to haem biosynthesis, because its mRNA is found in both human bone marrow and CD71+ early erythroid cells (by database searching), and because our results show that ABCB6 is highly expressed in human fetal liver, and Abcb6 in mouse embryonic liver. Here we demonstrate that ABCB6 is uniquely located in the outer mitochondrial membrane and is required for mitochondrial porphyrin uptake. After ABCB6 is upregulated in response to increased intracellular porphyrin, mitochondrial porphyrin uptake activates de novo porphyrin biosynthesis. This process is blocked when the Abcb6 gene is silenced. Our results challenge previous assumptions about the intracellular movement of porphyrins and the factors controlling haem biosynthesis.     

NO_2分子5708A带的实验测定及辐射寿命研究

本文报道了我们实验测定的 NO_2分子5708A 附近的一个振动带的光谱结构以及属于该带激发态的辐射寿命,求得了 NO_2分子电子激发态及基态的转动常数以及旋—轨偶合常数,并对实验结果进行了分析讨论。     

苯并三氮唑在铁电极上的光谱电化学研究

苯并三氮唑在硫酸溶液中吸附在铁电极上的极化曲线和表面拉曼光谱研究结果表 明：苯并三氮唑同时抑制了铁的阳极溶解反应和阴极析氢反应;当电位负于腐蚀电位时,苯并三 氮唑以分子或质子化的形式吸附于电极表面．     

Single-pulse coherently controlled nonlinear Raman spectroscopy and microscopy

Molecular vibrations have oscillation periods that reflect the molecular structure, and are hence being used as a spectroscopic fingerprint for detection and identification. At present, all nonlinear spectroscopy schemes use two or more laser beams to measure such vibrations. The availability of ultrashort (femtosecond) optical pulses with durations shorter than typical molecular vibration periods has enabled the coherent excitation of molecular vibrations using a single pulse. Here we perform single-pulse vibrational spectroscopy on several molecules in the liquid phase, where both the excitation and the readout processes are performed by the same pulse. The main difficulty with single-pulse spectroscopy is that all vibrational levels with energies within the pulse bandwidth are excited. We achieve high spectral resolution, nearly two orders of magnitude better than the pulse bandwidth, by using quantum coherent control techniques. By appropriately modulating the spectral phase of the pulse we are able to exploit the quantum interference between multiple paths to selectively populate a given vibrational level, and to probe this population using the same pulse. This scheme, using a single broadband laser source, is particularly attractive for nonlinear microscopy applications, as we demonstrate by constructing a coherent anti-Stokes Raman (CARS) microscope operating with a single laser beam.     

Observation of stimulated emission by direct three-photon excitation

Multiphoton processes, predicted theoretically in 1931, were for a long time considered to be mainly of academic interest. This view changed when it was shown that a two-photon absorption process could, because of a quadratic dependence of excitation on intensity, produce a spatially confined excitation useful for three-dimensional data storage and imaging. Two-photon absorption has received considerable attention recently because of the development of highly efficient two-photon-sensitive materials, leading to numerous technological applications. These successes have created interest in exploring applications based on three-photon excitations. For a three-photon process, a longer excitation wavelength such as those common in optical communications can be used. Also, the cubic dependence of the three-photon process on the input light intensity provides a stronger spatial confinement, so that a higher contrast in imaging can be obtained. Here we report the observation of a highly directional and up-converted stimulated emission as an amplified spontaneous emission, produced in an organic chromophore solution by a strong simultaneous three-photon absorption at 1.3 microm. This achievement suggests opportunities for a three-photon process in frequency-upconversion lasing, short-pulse optical communications, and the emerging field of biophotonics.