对苯二胺和N-取代衍生物正离子自由基的共振喇曼光谱研究

本文中报道了对苯二胺和四种N-烷基取代衍生物正离子自由基的共振喇曼光谱, 揭示了自由基是具有明显C=C和C=N双键性质的半醌式结构, N原子上给电子基团的取代引起上述化学键振动峰低频移动, 反映出结构一端N上有烷基的自由基中与取代基直接相连的N原子失去一个p电子带正电荷, 并吸引环上的π电子形成一定程度C=N双键. 共振喇曼光谱随激发光波长的变化表明, 自由基的两个可见电子吸收带分别主要产生于环结构的π→π*和包含N原子结构的n→π*电子跃迁。     

Proton-electron double resonance: Spectroscopy and imaging in very low magnetic fields

Proton-electron double resonance, also named dynamic nuclear polarization (DNP) is characterized by an enhancement of the proton NMR signal when the electron resonance of a free radical coupled to water protons is saturated. In very low magnetic fields, new EPR transitions are allowed. The complete theory of DNP in nitroxide solutions is recalled, in order to interpret the experimental spectra. Proton-electron double resonance images (PEDRI) were obtained with 7 out of the 10 EPR transitions allowed in low fields. Field cycled PEDRI were obtained in magnetic fields as low as 0.6 G. The optimum field strength for PEDRI is discussed according to the theoretical and experimental results of DNP obtained with nitroxide solutions.     

Non-standard base pairing and stacked structures in methyl xanthine clusters

We present resonant two-photon ionization and IR-UV double resonance spectra of methylated xanthine derivatives including 7-methylxanthine dimer and theobromine dimer seeded in a supersonic jet by laser desorption. For 7-methylxanthine, theophylline and theobromine monomer we assign the lowest energy tautomer based on comparison with IR-UV double resonance spectra and calculated IR frequencies. For the 7-methylxanthine dimer, we observe hydrogen bonding on the N3H position suggesting 3 possible combinations, one that is reverse Watson-Crick type and two that are reverse Hoogsteen type. For the theobromine dimer, we observe a stacked structure. For trimethylxanthine dimers we infer a stacked structure as well.     

Raman spectra of carotenoids in natural products

Resonance Raman spectra of naturally occurring carotenoids have been obtained from nautilus, periwinkle (Littorina littorea) and clam shells under 514.5 nm excitation and these spectra are compared with the resonance Raman spectra obtained in situ from tomatoes, carrots, red peppers and saffron. The tomatoes, carrots and red peppers gave rise to resonance Raman spectra exhibiting a nu1 band at ca. 1520 cm(-1), in keeping with its assignment to carotenoids with ca. nine conjugated carbon-carbon double bonds in their main chains, whereas the resonance Raman spectrum of saffron showed a nu1 band at 1537 cm(-1) which can be assigned to crocetin, having seven conjugated carbon-carbon double bonds. A correlation between nu1 wavenumber location and effective conjugated chain length has been used to interpret the data obtained from the shells, and the wavenumber position (1522 cm(-1)) of the nu1 band of the carotenoid in the orange clam shell suggests that it contains nine conjugated double bonds in the main chain. However, the black periwinkle and nautilus shells exhibit nu1 bands at 1504 and 1496 cm(-1), respectively. On the basis of the correlation between nu1 wavenumber location and effective conjugated chain length, this indicates that they contain carotenoids with longer conjugated chains, the former having ca. 11 double bonds and the latter ca. 13 or even more. Raman spectra of the nautilus, periwinkle and clam shells also exhibited a strong band at 1085 cm(-1) and a doublet with components at 701 and 705 cm(-1), which can be assigned to biogenic calcium carbonate in the aragonite crystallographic form.     

IR-UV double resonance spectroscopy of xanthine

We present resonant two-photon ionization (R2PI), UV-UV, and IR-UV double resonance spectra of xanthine seeded in a supersonic jet by laser desorption. We show that there is only one tautomer of xanthine which absorbs in the wavelength range of 36 700 to 37 700 cm(-1). The IR-UV double resonance spectrum shows three strong bands at 3444, 3485, and 3501 cm(-1), all of which we assign as N-H stretching vibrations. Comparison of the IR-UV double resonance spectrum with frequencies and intensities obtained from density functional theory (DFT) and second order M?ller Plesset (MP2) calculations suggests that the observed xanthine is the diketo N(7)H tautomer.     

Two-color double resonance in the four-photon ionization of nitric oxide

We have measured the two-color double resonance enhanced four-photon ionization and the fluorescence de-enhanced spectra of nitric oxide by using two tunable pulsed dye lasers. The spectra show clear structure in the third-photon (8.2 eV) region. Also discussed is the multiphoton ionization mechanism in the resonance state.     

Ionen-Cyclotron-Resonanzuntersuchungen an Ionen–Molekül-Komplexen von Anisol und Anisolhomologen

The ion cyclotron resonance spectra of anisol, 3-methylanisol, phenetol, 3-methylphenetol and thioanisol at pressures of 10^?6 Torr resemble the normal mass spectra. Above 10^?5 Torr the spectra show signals due to product ions. As seen from double resonance measurements most product ions are formed by the reaction of a fragment ion with a neutral ether molecule under elimination of alkyl, alkoxy alkylthioradicals or of ethylene. Apart from the molecular ion radical ions do not participate in ion-molecule reactions.     

Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.

A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins.     

Ionen-Cyclotron-Resonanz-Messungen von Ion/Molekül-Reaktionen bei Chinonen

At a pressure of 10^?6 Torr the ion cyclotron resonance spectra of p-benzoquinone, methyl-p-benzoquinone, tetramethyl-p-benzoquinone and tetrafluoro-p-benzoquinone are identical to the normal mass spectra. Above 10^?5 Torr the spectra show a variety of signals for product ions. From double resonance measurements it was shown that all the product ions are formed by addition of the molecular ion or of a fragment ion to a neutral quinone molecule. In most cases the addition is accompanied by the elimination of carbon monoxide.     

Does double electron capture lead to the formation of biradicals? An ECD-SORI-CID study on lacticin 481

We studied lacticin 481, a small lantibiotic with three lanthionine bridges, by electron capture dissociation (ECD) in a Fourier transform ion cyclotron resonance (FTICR) mass spectrometer. Following electron capture, very little fragmentation was observed, but species formed by nondissociative single and multiple electron capture were abundant. Ions formed by double electron capture were subjected to sustained off resonance irradiation collision induced dissociation (SORI-CID) to determine whether stable biradicals were formed. In the SORI-CID spectra of the ions formed by double electron capture, some, but minor, H* radical loss was observed, which was not observed at all for regularly protonated ions. A small part of the ions formed by double electron capture are thus long-lived biradicals. Apart from the observed H* loss, the SORI-CID spectra of ions that captured two electrons was similar to that of regularly protonated ions and quite different from the SORI-CID spectra of radical ions formed by single electron capture. This implies that recombination of the two radical sites is the dominant process in biradical lacticin 481 ions, at least on the time scale of our SORI-CID experiments.     

Raman spectroscopy as a tool for the analysis of carbon-based materials (highly oriented pyrolitic graphite,multilayer graphene and multiwall carbon nanotubes) and of some of their elastomeric composites

Raman spectra of highly oriented pyrolitic graphite, multilayer graphene and multiwall carbon nanotubes are carried out at different laser powers and different excitation energies. The effects of the laser heating and the double resonance Raman scattering are investigated as a prerequisite for a correct interpretation of the Raman spectra of carbon materials-based composites. The Raman spectra of multilayer graphene and multiwall carbon nanotubes embedded in a silicone matrix are also analyzed in an attempt to get some insights into the polymer–filler interface.     

Surface-enhanced Raman scattering and enhanced fluorescence of dyes on silver chloride sols

The enhanced fluorescence and enhanced Raman spectra of dye-1555 molecules adsorbed on silver chloride sols are detected for the first time. The enhanced fluorescence is attributed to the double resonance effect proposed by Chew and Wang. The enhanced Raman spectra indirectly support the energy-transfer model of spectral sensitization of dyes, one of two competing mechanisms of spectral sensitization in the photographic process.     

L-tryptophan radical cation electron spin resonance studies: connecting solution-derived hyperfine coupling constants with protein spectral interpretations

Fast-flow electron spin resonance (ESR) spectroscopy has been used to detect a free radical formed from the reaction of l-tryptophan with Ce (4+) in an acidic aqueous environment. Computer simulations of the ESR spectra from l-tryptophan and several isotopically modified forms strongly support the conclusion that the l-tryptophan radical cation has been detected by ESR for the first time. The hyperfine coupling constants (HFCs) determined from the well-resolved isotropic ESR spectra support experimental and computational efforts to understand l-tryptophan's role in protein catalysis of oxidation-reduction processes. l-Tryptophan HFCs facilitated the simulation of fast-flow ESR spectra of free radicals from two related compounds, tryptamine and 3-methylindole. Analysis of these three compounds' beta-methylene hydrogen HFC data along with equivalent l-tyrosine data has led to a new computational method that can distinguish between these two amino acid free radicals in proteins without dependence on isotope labeling, electron-nuclear double resonance, or high-field ESR. This approach also produces geometric parameters (dihedral angles for the beta-methylene hydrogens) that should facilitate protein site assignment of observed l-tryptophan radicals as has been done for l-tyrosine radicals.     

Electron spin resonance on carbon nanotubes–polymer composites

Electron spin resonance investigations on styrene–polyisoprene–polystyrene block copolymer loaded with various amounts of multiwalled carbon nanotubes are reported. The temperature dependence of resonance line parameters in the range 290–425 K was analyzed. It was proved that the main resonance line represents a bottleneck of localized and delocalized electrons residing on carbon nanotubes. The temperature dependence of the g-factor and double integral of resonance spectra confirmed this interpretation. The temperature dependence of the resonance linewidth of composites containing various concentrations of nanotubes was explained by the thermally activated narrowing of the resonance spectra. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3406–3412, 2005     

OPTICAL-MICROWAVE DOUBLE RESONANCE SPECTROSCOPY OF IN VIVO CHLOROPHYLL

At low temperatures, chloroplast and subchloroplast preparations exhibit complex fluorescence spectra. Emission bands can be attributed to photosystem (PS) particles and various antenna-chl proteins as well as solubilized chls. Initial results from a systematic study of the components of these fluorescence spectra via optical-microwave double resonance spectroscopy are presently reported. Conclusions regarding possible structural features are discussed. Experiments on triplet sublevel decay rates yielded data consistent with an interpretation of triplet energy transfer within antenna fragments.     

The long-lived molecular ion of propionitrile: An ion cyclotron resonance study

Evidence has been reported that primary loss of H and of HCN from the molecular ions of propionitrile, isobutyronitrile and butyronitrile in the mass spectrometer is preferentially preceded by hydrogen migration from C-2 to C-1. Ion cyclotron double resonance spectra of proton (or deuteron-) transfer products derived from propionitrile-2-d2 and -3-d3 and a series of bases provide evidence that such migration occurs also in long-lived propionitrile molecular ions.     

AC Stark detection of optical-optical double resonance in CH2

A new scheme for the detection of double resonance spectra of chemical intermediates involves negligible population transfer but the detection of electric field-induced energy shifts in unpopulated levels.     

14N quadrupole coupling in thermochromic N-5-chlorosalicylideneaniline

The temperature dependence on the proton—¹⁴N double resonance spectra demonstrates that thermochromism in solid N-5-chlorosalicylideneaniline is accompanied by intramolecular proton transfer and an enol—keto transformation.     

Pulse EPR Methods for Studying Chemical and Biological Samples Containing Transition Metals

This review discusses the application of pulse EPR to the characterization of disordered systems, with an emphasis on samples containing transition metals. Electron nuclear double‐resonance (ENDOR), electron‐spin‐echo envelope‐modulation (ESEEM), and double electron–electron resonance (DEER) methodologies are outlined. The theory of field modulation is outlined, and its application is illustrated with DEER experiments. The simulation of powder spectra in EPR is discussed, and strategies for optimization are given. The implementation of this armory of techniques is demonstrated on a rich variety of chemical systems: several porphyrin derivatives that are found in proteins and used as model systems, otherwise highly reactive aminyl radicals stabilized with electron‐rich transition metals, and nitroxide–copper–nitroxide clusters. These examples show that multi‐frequency continuous‐wave (CW) and pulse EPR provides detailed information about disordered systems.     

The photochemical primary step and the potential in the proton bridge of the chromophore of visual pigments and bacteriorhodopsin

The primary photochemical step in the mechanism of vision is likely to involve cis → trans isomerization as well as proton transfer. Our understanding of this is connected with the problem as to whether the nitrogen of the chromophore Schiff base is protonated or not. More precisely we need to know the shape of the potential in the C?N···H⁺···X group, where X is a proton donor. It is proposed that this potential is double well. The consequences of this relating to the resonance Raman spectra are discussed.