Inverted and suppressed direct response HMQC-TOCSY spectra - a convenient method of spectral editing

HMQC-TOCSY spectra provide a convenient means of establishing proton-proton connectivities in congested spectra of complex aromatic heterocycles. Advantage is taken of the greater dispersion of the ¹³C nmr spectrum to circumvent overlap which would preclude spectral interpretation through the usual COSY spectrum. A recently reported method for inverting direct responses (IDR) in HMQC-TOCSY spectra is demonstrated for [1]benzothieno[2,3-c]naphtho[2,1-g]quinoline. A modification of the IDR-HMQC-TOCSY method is also demonstrated which is capable of fully suppressing direct responses (SDR) without resorting to the timing of the onset of decoupling as in the original report of the HMQC-TOCSY experiment. SDR-HMQC-TOCSY has the further advantage of allowing the use of higher levels of digitization in F₂ than can be attained when broadband heteronuclear decoupling is employed.     

Assignments of the 1H and 13C NMR spectra of pseudo-symmetric heterocyles using the HMQC-TOCSY experiment to differentiate overlapping spin systems

The ¹H nmr spectra of phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline, benzo[f]phenanthro-[9′,10′:4,5]thieno[2,3-c]quinoline and benzo[h]phenanthro[9′,10′:4,5]thieno[2,3-c]quinoline are highly congested. For each compound, all protons abide in an aromatic environment complicated by pseudo-symmetric regions which result in multiple overlap of the different spin systems these molecules contain. We illustrate here the utility of the HMQC-TOCSY experiment to identify spin systems when the proton spectrum is highly congested. To complete the assignment of the ¹H and ¹³C nmr spectra of each compound the HMBC experiment is used to assign the quaternary carbons.     

Total assignment of the proton and carbon NMR spectra of the alkaloid quindoline — utilization of HMQC-TOCSY to indirectly establish protonated carbon-protonated carbon connectivities

The reisolation of the indoloquinoline alkaloid quindoline (also known as norcryptolepine) from Cryptolepis sanguinolenta is reported. The structure was unequivocally confirmed by two-dimensional nmr methods; the proton and carbon spectra were assigned for the first time. Because of congestion in the proton spectrum HMQC-TOCSY was used as an alternative to the more familiar COSY experiment. In addition to establishing proton-proton connectivities, HMQC-TOCSY affords the added benefit of providing, in an indirect sense, connectivity information between protonated carbons.     

Multistep correlations via covariance processing of COSY/GCOSY spectra: opportunities and artifacts

Long-range homonuclear coupling pathways can be observed in COSY or GCOSY spectra by the acquisition of spectra with larger numbers of increments of the evolution period, t(1), than would normally be used. Alternatively, covariance processing of COSY-type spectra acquired with modest numbers of t(1) increments, allows the observation of multistage correlations. In this work results obtained from covariance-processed GCOSY spectra are fully analyzed and compared to normally processed COSY and 80 ms TOCSY spectra. Multistage or 'RCOSY-type' correlations are observed when remote protons both exhibit correlations to the same coupling partner e.g. A --> B and B --> C gives rise to an A --> C correlation. In the strict sense, RCOSY-type responses are artifacts albeit providing useful information. Nonbeneficial artifact correlations are observed when protons couple to other protons that overlap or partially overlap. The origin of artifact responses is also analyzed.     

Molecular dynamics with restrictions derived from optical spectra

The information about molecular structure coded in the optical spectra must often be deciphered by complicated computational procedures. A combination of spectral modeling with the molecular dynamic simulations makes the process simpler, by implicit accounting for the inhomogeneous band broadening and Boltzmann averaging of many conformations. Ideally, geometries of studied systems can be deduced by a direct confrontation of such modeling with the experiment. In this work, the comparison is enhanced by restrictions to molecular dynamics propagations based on the Raman and Raman optical activity spectra. The methodology is introduced and tested on model systems comprising idealized H(2)O(2), H(2)O(3) molecules, and the alanine zwitterion. An additional gradient term based on the spectral overlap smoothed by Fourier transformation is constructed and added to the molecular energy during the molecular dynamics run. For systems with one prevalent conformation the method did allow to enrich the Boltzmann ensemble by a spectroscopically favored structure. For systems with multiconformational equilibria families preferential conformations can be selected. An alternative algorithm based on the comparison of the averaged spectra with the reference enabling iterative updates of the conformer probabilities provided even more distinct distributions in shorter times. It also accounts for multiconformer equilibria and provided realistic spectra and conformer distribution for the alanine.     

Valence electron bands in the gas-phase x-ray photoelectron spectra of acetonitrile and nitromethane

The valence electron bands of the gas-phase X-ray photoelectron spectra were measured on acetonitrile and nitromethane. It is shown that the observed spectra can be interpreted successfully by comparison with the He I photoelectron spectra and the results of CNDO/2 calculations.     

A procedure for analysis of densitometric spectra

Computer-aided quantitative analysis of densitometric spectra is presented. The densitometric spectra are decomposed into component bands using the Powell and Marquardt minimizers. Several different functions for the component bands are utilized. It is shown that the densitometric spectra can be decomposed into component bands with high accuracy only if the proper shapes of the bands are chosen. The method described was used for quantitative analysis of densitometric spectra of DNA cleaved by neocarzinostatin. The procedure is general and can be applied to analyses of autoradiographic films and to direct scans of electrophoretic gels. It is shown that densitometric spectra which show highly overlapped bands are well approximated by asymmetric Cauchy and Gauss functions. Well separated densitometric bands which have substantial asymmetry can be fitted to more sophisticated shapes formed by combinations of symmetric and asymmetric Cauchy and Gauss functions. High accuracy fitting to asymmetric densitometric curves may only be achieved using the cosine function introduced by Mignot and Rondot, J. Appl. Cryst. 1976, 9,460-465.     

Structure,hydrogen bonding and vibrational spectra of pyruvic acid

The complete vibrational spectra of liquid pyruvic acid and the infrared spectrum of crystalline pyruvic acid at about 20 K have been recorded and analyzed. A vibrational assignment is proposed based on these spectra and comparison with spectra of derivatives of pyruvic acid.The spectra of pyruvic acid can best be interpreted in terms of a cyclic hydrogen-bonded dimer structure in which the two carbonyl groups are in a trans configuration in the pure liquid phase. A similar structure has been reported for crystalline pyruvic acid by X-ray diffraction. In dilute solution the structure appears to be monomeric with an internal hydrogen bond, in essential agreement with the structures of the monomer reported from microwave spectroscopic measurements.     

APPLICATION OF HMBC AND HMQC-TOCSY NMR METHODS TO ASSIGN THE STRUCTURES OF BICYCLIC-PEPTIDE MIMETICS

Abstract

The structures of representative bicyclic peptides are confirmed through the NMR methods of HMBC and HMQC-TOCSY. Complete assignment of proton and carbon resonances is afforded by these two-dimensional NMR methods. HMQC-TOCSY is especially useful for assigning spectra in molecules having extensive proton spin systems and in establishing connectivities between protonated carbons. Long-range proton-carbon connectivities obtained by HMBC confirm structure in molecules containing heteroatoms or non-protonated carbons that interrupt proton spin systems.     

Multiplicity-edited broadband HMBC NMR spectra

A new, edited HMBC experiment is introduced that leads to two subspectra according to the number of protons attached to 13C nuclei being even or odd, i.e. one subspectrum with C + CH2 and another with CH + CH3. This experiment can be useful for resolving spectral overlap among the typically large number of peaks in HMBC spectra. It is implemented in a broadband version similar to broadband HMBC and demonstrated on prednisolone [(11beta)-11,17,21-trihydroxypregna-1,4-diene-3,20-dione].     

The lineshape of motion-averaged isotropic Raman spectra

The conventional Kubo model can be used to describe the spectrum modulation by slow to fast motion, i.e. even in the range of applicability of perturbation theory. However, the Kubo model assumes the gaussian shape of static spectra. A model free of this assumption has been used to show that experimental data can be interpreted provided the initial static spectrum has non-gaussian wings.     

Resolution of overlapping mid-infrared spectra using SIMPLISMA and a second-order derivative approach

Matrices of severely overlapping mid-infrared mixture spectra have been resolved into the pure compounds' spectra and concentration profiles using SIMPLISMA and a 2nd order derivative approach. For a three-compound mixture system of organic solvents, SIMPLISMA qualitatively resolves the spectra satisfactorily while it provides only semi-quantitative concentrations. Quantitative results are obtained by applying an additional iterative procedure. Applied to water spectra acquired in the temperature range 2–96°C, SIMPLISMA resolves two spectra. Using a discrete model, these spectra can be interpreted as corresponding to water structures constructed of H₂O molecules with a relatively high and low average number of H-bonds. After an optimising procedure the estimated enthalpy was 2.3 kcal mol⁻¹, which is in accordance with figures found in literature.     

Mass spectra of some alkyl isoxazoles

The mass spectra of several compounds obtained during the process of Stork's isoxazole synthesis9 as well as the related isoxazoles have been investigated. The fragmentations of simple alkyl isoxazoles are nicely formulated via azirine intermediates. A striking difference between the spectra of isoxazoles and those of methylfurans as to the relative abundance of [M — l] peaks is noteworthy. The very low abundance of these peaks in the former reflects the unique character of isoxazole nucleus due to the preferential cleavage of N? O linkage rather than a benzylic C? H bond rupture. If an alkyl substituent is present at 4-position in 3,5-dimethylisoxazoles, strong peaks at m/e 110, 68 and 43 are common in their spectra. The analyses of metastable transitions and high resolution measurements have demonstrated that the formation of these ions can be interpreted by a mechanism involving the cleavage of N? O linkage.     

The vibrational spectra of the elementoorganic starburst dendrimers

The main features of vibrational spectra of starburst dendrimers have been analyzed for the first time. Their spectral pattern, in general, is determined by the ratio of a number of terminal groups to a number of repeating units. This ratio tends to m_r−1 (m_r — branching functionality of repeating unit), and becomes constant, when the generation number of the starburst dendrimer increases higher than 3-5. IR and Raman spectra of twelve generations of the phosphorus-containing dendrimers are represented and interpreted on the basis of the calculation of frequencies of the normal vibrations and band intensities in the IR spectra of ‘molecules’ terminated by dangling methyl groups, which are the fragments of the dendrimer molecule. Tailored spectra of these fragments are then compared with experimental spectra and satisfactory similarity has been obtained. Experimental spectra of generations higher than 4 are very similar, according to the theoretical approach. The results can be used for the analysis of the chemical and physical transformations in starburst dendrimers.     

Carbon-13 nuclear magnetic resonance spectra of some 2-substituted tetrahydropyrans

Fourier transform carbon-13 nuclear magnetic resonance spectra have been obtained and interpreted for some 2-substituted tetrahydropyrans. The effects of the substituents on α, β, γ and δ-carbon atoms are discussed. Using suitable reference compounds the γ-parameter can be used for quantitative conformational analysis.     

An indirect method of X-ray spectra measurement by simultaneous attenuations of the scattered beam

Direct and indirect methods of X-ray spectra determination present obstacles to their practical use since they must position either the collimator-detector assembly or the attenuators-ionization chamber, respectively, along the X-ray beam direction. These arrangements require considerable space and in many instances the detectors promptly saturate. An indirect procedure, which overcomes the aforementioned problems, is developed. It consists of the scattering of the X-ray beam from a carbon disk, which is detected simultaneously by several detectors placed away from the beam. The X-ray flux reaching each of these detectors is attenuated in metal sheets of different thicknesses, thus obtaining simultaneously the attenuation curve values. A set of analytical equations are derived to calculate attenuation curves by taking into account all the absorption and elastic and inelastic scattering processes that a beam of photons undergoes when going from the X-ray tube to the detector. Users, even those who are not well acquainted with computer programming, can easily obtain the X-ray spectrum by a least square fitting of a measured attenuation curve to a previously derived analytical expression. A simulated Monte Carlo program of photon transport from the X-ray tube to the detector provided simulated attenuation curves data. Analytically calculated and simulated attenuation curves for the same input spectrum wholly overlap and furthermore, reconstructed spectra from both sets of curves for different kilovoltages are also in full agreement. Finally, in addition to the importance of having the detectors out of the beam direction, the proposed arrangement features other main advantages, namely, only one X-ray tube shot is needed to obtain the required data, the physical processes involved are very well known, analytical equations are easily interpreted, and the measuring apparatuses can be comparatively simple to assemble and operate.     

Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids

The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.     

Simulation of electron ionization mass spectra of cycloalkyl fluorophosphonates

The mass spectra of highly toxic cycloalkyl alkylfluorophosphonates can be divided into two components: organophosphorus and hydrocarbon. The organophosphorus component is a generalized spectral image of a taxonomic group among those forming a homologous series of cycloalkyl alkylfluorophosphonates. The hydrocarbon component is interpreted as a spectrum of the cycloolefin which is the main product of cycloalkyl alkylfluorophosphonate fragmentation. A method for simulation of the electron ionization mass spectra of these compounds is proposed.     

Vibrational spectra of dimethyl aluminium hydride

The infrared and Raman spectra of dimethyl aluminium hydride and its partially deuterated isotopomers are reported and assigned. On the basis of variable temperature studies, coupled with isotope shifts and normal coordinate analysis, it is shown that the vapour phase infrared spectrum at room temperature may be interpreted as predominantly that of the dimer, with smaller amounts of trimer.     

VUV spectra of the xenon fluorides

The absorption spectra of gaseous XeF₂, XeF₄, and XeF₆ have been accurately measured in the photon energy range from 6 to 35 eV with the use of the synchrotron radiation of DESY. The vibrational structure of several Rydberg transitions could be resolved. The spectra are interpreted and most of the structures could be assigned. From these data, information about the ionized species is obtained. The assignment of the first two IP's of XeF₄ is corrected.