Theoretical analysis of the structure of excited electronic states, Raman, and resonance Raman spectra of indole in the isolated state and aqueous solution

The structure of the first excited electronic states of indole has been calculated for the isolated state and aqueous solution. The vibrational spectra of isolated indole have been calculated by the DFT method in the harmonic and anharmonic approximations. The resonance Raman spectra of indole have been calculated quantum mechanically in the Herzberg-Teller approximation. The effect of hydrogen bonds on the structure and vibrational (Raman and resonance Raman) spectra of indole has been analyzed.     

Absorption,fluorescence, and fluorescence excitation spectra of free molecules of indole and its derivatives

We have obtained and analyzed the absorption, fluorescence, and fluorescence excitation spectra of indole vapor, N-acetyl-L-tryptophan vapor, and 3-indole aldehyde vapor. From analysis of the dependence of the fluorescence spectrum of the free indole molecules on the wavelength of the exciting radiation λ_ex, it follows that emission of fluorescence occurs when the molecules undergo a transition from the one electronically excited state ¹L_b. The fluorescence spectra of the studied compounds are insignificantly different, suggesting a major role for the indole chromophore in formation of the compounds. The absorption spectrum of N-acetyl-L-tryptophan, in which the group of atoms is added to the indole ring through a-C-C bond, is similar to the spectrum of indole, while the spectrum of 3-indole aldehyde is significantly different from the indole spectrum due to the effect of the C=O group conjugated with the indole ring. The fluorescence excitation spectra are considerably different from the absorption spectra. This is associated with the strong dependence of the quantum yield for the free molecules on λ_ex. Qualitatively, they are mirror-symmetric to the fluorescence spectra of the stodied compounds. Analysis of the data obtained provides a basis for assuming that in the case of free molecules of indole and its derivatives, the ¹L_a absorption in the extreme long-wavelength region of the spectrum does not overlap ¹L_b absorption. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 218–222, March–April, 2007.     

Polarized Fluorescence of Jet-Cooled indole and Carbazole and Their Complexes with Water

The spectra of the fluorescence excitation within the rotational contours of the bands of the pure electronic long-wavelength S ₀-S ₁ transitions of jet-cooled indole and carbazole molecules and their complexes with water are measured. For the carbazole-water complex, a contour with three maxima is registered, which is possibly related to the occurrence of two isomers, differing in a slight displacement of hydrogen between the nitrogen atom of the imine group of carbazole and the oxygen atom of the water molecule. The degrees of polarization of integral fluorescence upon excitation within the rotational contours of the S ₀-S ₁ electronic transition bands of the above molecules and their complexes with water are determined for the first time. The coincidence of the calculated (7.7%) and measured (7.3%) values of the degree of polarization upon excitation in the rotational Q branch of the ^b L ₁-A electronic transition of indole confirms the accepted intramolecular orientation of the transition dipole moment at an angle of 38.3° with respect to the principal axis of inertia A. Upon excitation of indole, its complex with water, and carbazole into the P and R branches, the measured and calculated degrees of polarization are also close to each other and amount to 2–3%. This confirms the occurrence of contributions to the fluorescence polarization due to the rotations of the indole molecules around the principal axes of inertia A and C.     

Quantum-mechanical calculation of the intensity distributions in spectra of resonance hyper-Raman scattering and two-photon absorption of indole and skatole

We have performed a quantum-mechanical calculation of the relative intensities of lines in the spectra of resonance hyper-Raman scattering and two-photon absorption of isolated indole, indole in an aqueous solution, isolated skatole, and skatole-water complex. The effects of hydrogen bonds and intermolecular interaction on the spectra have been considered. Particular features of the intensity distributions in the spectra of indole and skatole have been compared.     

Red-Edge Excitation Study of Nonexponential Fluorescence Decay of Indole in Solution and in a Protein

Proteins are known to be heterogeneous systems with a hierarchy of internal motions. However, those properties are often ignored when the complex fluorescence decay of tryptophan residues is compared to model studies with indole derivatives in solution. Here two simple models are presented, which illustrate different aspects of protein organization: (1) Trp zwitterion in buffer exemplifies ground-state heterogeneity and (2) indole in water/glycerol mixture exemplifies excited-state reconfiguration of solvate. Both systems are known to produce nonexponential fluorescence decay, attributed to the existence of multiple species (rotamers) or to the effects of slow dipolar relaxation, for (1) and (2), respectively. In the latter case a substantial dependence of decay on the excitation wavelength is expected. Indeed such dependence is observed for indole in water/glycerol mixture but not for Trp zwitterion in buffer. Therefore, excitational dependence can be used as a criterion to distinguish effects of multiple conformations in the ground state from effects of excited state reactions on tryptophan decays in proteins. The example of the bee venom peptide melittin indicates that both phenomena are important for interpretation of heterogeneity of decay, and therefore, caution should be exercised when assigning individual decay components to conformational subspecies in proteins.     

Annihilation Delayed Fluorescence of Indole and Carbazole in Liquid Solutions at Room Temperature

Optics and Spectroscopy - The spectra of long-lasting luminescence of indole and carbazole in neutral (cyclohexane) and polar (ethanol) solvents are obtained. The spectra of long-lasting...     

Chemical shift imaging without water suppression at 3 T

Purpose

Proton magnetic resonance spectroscopy without water suppression is possible but is hampered by the presence of sideband artifacts. The aim of this study was to develop a chemical shift imaging method without water suppression for clinical routine with reduced sideband artifacts.

Materials and Methods

Spectra from ten healthy volunteers were acquired using a 3T (TimTrio, Siemens, Erlagen, Germany) scanner with a Point RESolved Spectroscopy sequence for volume selection. Postprocessing was performed in three steps: correcting the water peak position in all spectra (chemical shift correction), subtracting the Gaussian convolution of all free induction decay signals (FIDs) (water signal reduction), and subtracting the FID of a water phantom from the volunteer's FID signal (reduction of sidebands). For the postprocessing customized software was developed with Matlab 2007b.

Results

The described technique provides spectra with reduced water signal and sidebands. Quantitative analysis showed that there is a good agreement between spectra obtained with water suppressing radiofrequency pulses and the new method. Moreover, spectra obtained with the new method do not need phase correction.

Conclusion

The new method offers sufficient reduction of the water peak and sidebands. Its simplicity allows its use in clinical applications.     

Calculation and interpretation of the absorption and fluorescence spectra of indole in the isolated state and aqueous solution

We have calculated the vibronic absorption and fluorescence spectra of the first (¹ L _b ) and second (¹ L _a ) electronic transitions of indole in the isolated state and aqueous solution. The vibrational structure of the absorption and fluorescence spectra has been interpreted. The influence of the aqueous solution on the vibronic spectra has been shown.     

13C NMR and 2D (H,H and H,C COSY) Spectra of Triazolo-triazino-indole Derivatives and the Conformational Analysis of the Respective C-Nucleoside Analogues

¹³C NMR and 2D (H,H and H,C COSY) spectra of selected examples of sugar (5H-1,2,4-triazino[5,6-b]-indol-3-yl) hydrazones, peracetylated sugar-1-acetyl -1- (5-acetyl-1,2,4-triazino[5,6-b]indol-3-yl)hydrazones, and 10-acetyl-3-(per-0-acetylalditol-1-yl)-1,2,4-triazolo[4′, 3′:2,3][1,2,4]triazino[5,6-b]indole have been reported. The conformation of the latter C-nucleoside analogues have been determined by analysis of their ¹H NMR spectra. The D-galacto, D-manno and L-arabino isomers are preponderantly existing in the planar zigzag arrangement of carbon atoms.     

Interaction of Electrons with Indole,Tryptophan, and their Derivatives in the Gas Phase

The electron energy loss spectra (EELS) of indole, 3-indolyl propionic acid, 3-indolealdehyde, 3-dimethylaminomethylindole, tryptophan, and N-acetyl-L-tryptophan in the gas phase upon excitation by monokinetic electrons with an energy of E₀ = 11–50 eV are obtained. The structure of EELS is determined in the main by the indole chromophore; the side groups, except for the C=O group of 3-indolealdehyde, exert an insignificant influence. The energy of the lower triplet level ³L_a is 3.3 eV for indole and its derivatives and 3.2 eV for tryptophan and N-acetyl-L-tryptophan. Four singlet transitions in the region of 4.4–7.2 eV have been identified. The molecules studied, except for tryptophan, fluoresce in the gas phase on excitation by electrons. At low values of E₀ (10–25 eV), the fluorescence spectra are similar and are due to the indole fluorophore. Just as in the case of optical excitation, fluorescence on excitation by electrons is associated with the ¹L_b-S₀ transitions. An increase in the energy E₀ up to 60–80 eV leads to dissociation of a portion of the indole molecules and to the appearance of additional bands in the fluorescence spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 468–472, July–August, 2005.     

The effect of temperature on the fluorescence of aromatic amino acid solutions

The temperature dependence of the fluorescence and the absorption spectra, as well as the duration of the excited state of indole, aromatic amino acids, and glycyl-trytophane in dipolar glassy solvents were studied. It was established that for indole, tryptophane, and glycyl-tryptophane, the temperature shifts of the spectra can be explained on the basis of a relaxation mechanism of an orientational interaction.In conclusion, the authors express their gratitude to A. N. Sevchenko for his continuous interest in the work.     

A Spectroscopic Study of the Interaction of the Fluorescent β-Carboline-3-carboxylic Acid N-methylamide with DNA Constituents: Nucleobases, Nucleosides and Nucleotides

Interaction between beta-carboline-3-carboxylic acid N-methylamide, betaCMAM, and nucleobases, nucleosides and nucleotides is studied in the ground state with UV-visible, (1)H NMR and (31)P NMR spectroscopies and in the first excited state, with steady-state and time-resolved fluorescence spectroscopy. Job plots show a predominant 1:1 interaction in both electronic states. Association constants are estimated from changes in the absorption spectra, and show that the strongest interaction is produced with the nucleosides: 2'-deoxyadenosine (dAdo) and thymidine (Thd), and with the mononucleotides: 2'-deoxycytidine 5'- monophosphate (5'-dCMP) and uridine 5'- monophosphate (5'-UMP). These results are corroborated by the upfield shifts of two (1)H NMR resonances of the betaCMAM indole group. The (31)P NMR resonance of nucleotides is shifted downfield, suggesting the presence of electrostatic or hydrogen bond interaction with betaCMAM. In the first electronic singlet excited state, static and dynamic quenching of betaCMAM emission is achieved upon addition of nucleobases, nucleosides and nucleotides. This has been analysed using Stern-Volmer kinetics.     

A theoretical investigation of the effect of water on the structure and fluorescence spectra of L-tryptophan

Fluorescence spectra of two long-wavelength electron transitions S₀ ← ¹L_b and S₀ ← ¹L_a in uncharged and zwitterionic forms of L-tryptophan (Trp) in aqueous solution and in the complex of Trp with water molecule were calculated using the Frank–Condon approximation. Geometric parameters of Trp in electronically excited states were determined, and the vibrational structure of vibronic spectra was analyzed. It was shown that the relative position of structural fragments of alanine (R-Ala) and indole (R-In) could have a determining effect on the fluorescence and formation of the vibrational structure of electronic spectra. The increase of the rotation angle between the R-Ala and R-In, which depends on the Trp environment, results in the Trp fluorescence originating only from the singlet excited state ¹L_a.     

迭代最小二乘法气体光谱自动水汽差减算法

傅里叶红外光谱法具有测量速度快、信噪比高、检测范围广等优势,在针对污染源废气排放的快速检测及长时间在线监测中具有巨大的发展潜力。水汽是红外光谱污染气体检测中的主要干扰物,影响NO_X,SO₂等重要污染物的检测,差减水汽背景谱消除光谱中水汽干扰可提高这些污染物的检测精度,具有重要意义。气体光谱中水汽吸收峰由于受到水分子团簇、仪器线型函数等影响,通过数值方法对其计算的误差较大;为此,水汽背景谱一般需采用同一台光谱仪实测获得。主要有两种方法： 第一种是通过反复调节水汽/氮气混合气中的水汽浓度,使水汽背景谱中的水汽吸收峰与污染气体光谱中水汽吸收峰相同,此方法耗时较长,且受环境条件制约很难在现场检测中使用;第二种方法是预先测量不同浓度的水汽光谱,在检测污染气体时选取两幅与污染气体光谱中水汽吸收峰最为接近且将其夹在中间的水汽光谱作为参考谱,使用这两幅参考谱线性拟合与污染气体光谱中水汽吸收峰相同的水汽背景谱,此方法可获得高度近似的水汽背景谱,但当前缺乏相关自动算法妨碍了其在快速自动消除水汽干扰方面的应用。为此,提出一种选取水汽参考谱及拟合水汽背景谱的自动算法,用于自动差减消除水汽干扰。在参考谱选取中,使用污染气体光谱依次减去浓度由低至高的水汽光谱,依据差减后光谱中水汽吸收峰所在波数的吸光度正负性来选取参考谱。在水汽背景谱计算中,基于迭代最小二乘法逐步剔除光谱中受污染物吸收峰干扰的波数,采用剩余波数上的数据拟合水汽背景谱,使其与污染气体光谱中水汽吸收峰相一致。使用水汽背景谱对污染气体光谱进行差减即可消除污染气体光谱中的水汽干扰。对含有NO₂的污染气体光谱进行了差减消除水汽干扰实验,结果表明所提出的自动算法可快速准确消除水汽干扰;NO₂在消除水汽干扰后可由其位于1 629 cm-1的强吸收峰检测,相比消除水汽干扰前使用不受水汽干扰的位于2 917 cm-1的弱吸收峰检测,其检出限得到了大幅提高。     

Study on the Synthesis and Spectra of a Novel Kind of Carbozole Benzothiazole Indole Styryl Cyanine Dye with a Carbazole Bridged Chain

Based on the frequently-used cyanine dye probe thiazole orange (TO) and Cy3, a novel kind of styryl cyanine dye was designed and synthesized. Carbazole was inserted into the structures of two cyanine dyes, TO and Cy3, to act as a bridge to link the benzothiazole and indole. This modification resulted in a novel kind of carbozole benzothiazole indole cyanine dye with a carbazole-bridged chain. The dyes were characterized by HNMR and MS. The spectra of the novel dyes were also studied and the results showed that the fluorescence wavelength of novel carbazole benzothiazole indole cyanine dye shifted red, the Stokes shift and Fluorescence quantum yields increased and the fluorescence intensity was enhanced compared to that of TO. These results indicated that the novel dye could be used as an excellent fluorescent probe in biological labeling.     

New method for photoelectron spectroscopy of solutions

A new method of rather general scope is reported for the determination of the photoionization (PI) spectra of solutions. Spectra thus obtained correspond to PI for ejection of quasi-free electrons into the liquid phase. The method is based upon photoelectron emission (PEE) into vacuum by the solution upon irradiation with adjustable photon energy. A new instrument is described which features irradiation (up to 10 eV) of a film of the solution on the rim of a rotating disk target (72 r.p.m.). Two types of data are obtained: PEE quantum yield per incident photon as a function of photon energy; energy distribution curve (EDC) of electrons emitted into vacuum at given photon energies. The PI cross-section is obtained as a function of photon energy by the previously developed method of EDC superposition. The method is applicable even when the contribution by the solvent to total PEE is dominant. Application is made to PI by 0.4 M indole in glycol for irradiation from 6.5 to 10 eV. Experimental results include: the effect of equilibrium vapor pressure (3.5 × 10^?3 ? 4.6 × 10^?2 torr) on EDC's; PEE spectral response of solvent and solution; EDC's from 6.5 to 10 eV. Interpretation covers these results and also includes: attenuation of the photon flux in the gas phase; PI in the gas phase; changes of temperature and solute concentration caused by evaporation. The PI spectrum of indole in glycol at ?7 °C exhibits a band for bound-continuum transitions (rising segment up to ≈ 7.0 eV) and a superimposed band (maximum at ≈ 7.6 eV) for PI via autoionization of excited bound states. Systematic development of the photoionization spectroscopy of solutions up to 10 eV is made possible by this approach. Application of the rotating disk methodology to higher photon energies (HeI, ESCA) may be of interest.     

Synthesis and Spectra of a Kind of Novel Longer-Wavelength Benzoxazole Indole Styryl Cyanine Dye with a Carbazole-Bridged Chain

Based on cyanine dye probe oxazole yellow (YO) and Cy₃, a series of novel styryl cyanine dyes were designed and synthesized. Carbazole was inserted into the structures of YO and Cy₃ to act as a bridge to link the benzoxazole and indole group. This modification resulted in a novel kind of benzoxazole indole styryl cyanine dye with a carbazole-bridged chain. The dyes were characterized by ¹HNMR and MS. The spectra of the novel dyes were also performed and the results showed that the maximum emission wavelength of the carbazole styryl cyanine dye was shifted red, the Stokes shift increased and the fluorescence intensity enhanced compared with those of YO and Cy₃. These results indicated that the novel dye could be used as an excellent fluorescent probe in biological labeling.     

光谱二阶差分Gabor展开法土壤铜铅污染鉴别

土壤是人类生存环境的重要载体,因此,土壤重金属污染问题一直备受关注。随着遥感技术的发展,高光谱遥感在土壤重金属研究中取得了大量的成果,但是,基本上是根据土壤中有机质、铁、粘土矿物等的光谱吸收特征和反演土壤中重金属含量,而不能够区分土壤重金属污染光谱之间的微弱差异。通过盆栽土壤不同浓度铜(Cu)、铅(Pb)污染实验得到不同浓度Cu和Pb污染下盆栽土壤光谱曲线、土壤含水率和有机质含量,提出了一种光谱二阶差分Gabor展开方法探测不同浓度Cu和Pb污染下土壤光谱曲线之间的微弱差异。以二阶差分为基础,首先将土壤光谱转换为稀疏光谱,然后结合土壤稀疏光谱与Gabor展开理论,在频率域中检测不同浓度土壤重金属污染光谱之间的微弱差异,因此,摆脱了单纯通过土壤光谱反射率信息反演土壤重金属含量的研究,而是对土壤重金属污染光谱信息进行时频分析,最终达到检测土壤重金属污染瞬时光谱存在的目的。结果表明：受Cu和Pb污染的盆栽土壤光谱二阶差分Gabor展开系数尺度及等高线分布有较大的差异,Cu污染的盆栽土壤光谱二阶差分Gabor展开系数尺度分布存在两个较高的峰值,且等高线在第1 800~3 600项之间稀疏分布,Pb污染的盆栽土壤光谱二阶差分Gabor展开系数尺度分布存在一个较高的峰值,且等高线在第3 200~3 600项之间密集分布;二阶差分Gabor展开法检测的土壤Cu和Pb污染结果与土壤Cu和Pb含量、土壤含水率、土壤有机质是密切相关的,由于土壤Cu和Pb含量、有机质含量、含水率的不同,土壤Cu和Pb污染二阶差分Gabor展开光谱尺度分布而不同。根据相关性分析结果,分别将土壤Cu和Pb污染划分为三组：Cu(50)~Cu(300),Cu(400)~Cu(800),Cu(1 000)以上;Pb(50)以下,Pb(100)~Pb(300),Pb(400)~Pb(1 200)。     

水驱油过程的核磁共振二维谱研究

岩心水驱油过程中油水分布状况是岩心多孔介质的重要性质. 水驱油过程的研究是进一步进行提高采收率研究的基础. 核磁共振扩散-弛豫二维谱提供了岩心中流体性质的多方面信息,与核磁共振一维弛豫谱相比极大地提高了区分油水的能力. 该文通过2组岩心水驱油实验,从不同含油饱和度的扩散-弛豫二维谱中提取出水的一维弛豫谱,在原油粘度比较高的情况下获得了驱替过程中油水在不同孔隙中的分布状况以及润湿性等信息, 解决了单独用一维弛豫谱方法难以区分油水的问题. 该文的研究方法对油田提高采收率的研究有比较大的参考价值.     

Quantitation of phosphorus metabolites in newborn human brain using internal water as reference standard

A new method for noninvasive, in vivo quantitation of cerebral phosphorus (³¹P) metabolites is described. The technique employs point-resolved spectroscopy (PRESS) to obtain both ³¹P-metabolite and proton (¹H) water spectra: brain water is used as an internal concentration reference. Spin-spin relaxation times (T₂s) of cerebral ³¹P metabolites are much longer than the minimum echo time (TE) usable on a spectrometer equipped with actively shielded gradient coils. With short-TE (≈10 ms) ³¹P PRESS, T₂ relaxation is minimal and phase modulation of the nucleotide triphosphate (NTP) multiplets can be accounted for. ¹H water spectra were acquired using several TEs so that extra- and intracellular water signals could be separated from that due to cerebrospinal fluid. Prior calibration of the ³¹P and ¹H spectrometer channels and an assumed brain-water concentration enabled estimations of metabolite concentrations. Using this method, mean ³¹P metabolite concentrations in the brains of eight normal infants of gestational plus postnatal age 34 to 39 wk were: phosphomonoester (PME) 5.6 (SD 0.9); inorganic phosphate 1.4 (0.4); mobile phosphodiester 2.3 (0.6); phosphocreatine 2.9 (0.3); nucleotide triphosphate 2.8 (0.6); and total mobile phosphate 21.4 (2.8) mmol/kg wet.