CARBON-13 NMR STUDY ON MOLECULAR MOTION OF 1, 2-POLYBUTADIENE——TEMPERATURE DEPENDENCE OF MOLECULAR MOTION

Proton-decoupled, ~(13)C FT-NMR (operating at 50.3 MHz) is used to determine spin-latticerelaxation time (T_1), nuclear Overhauser enhancement (NOE), linewidth and chemical shift of 1,2-polybutadiene as a function of temperature in CDCl_3 solution and the temperature dependence ofmolecular motion of 1,2-polybutadiene has been investigated with these NMR relaxation parameters.It is found that jumps of NOE and linewidth vs. temperature appear between-1℃and -30℃. Theminimum of nT_1 vs. temperature for all carbons occur at about -45℃.     

Quantitative NMR measurements in copolymers of vinylidene chloride and acrylonitrile: The effect of saturation and varying nuclear Overhauser enhancements

Spin-lattice relaxation times and nuclear Overhauser enhancements (NOE) for ¹³C nuclei in copolymers of acrylonitrile and vinylidene chloride were measured at 20.1 and 67.9 MHz. In the ? CCl₂? region of the spectrum T₁ and NOE values of the various resonances are equal within experimental error and are invariant to changes in composition. The T₁ and NOE values of the ? CCl₂? region, however, are not equal to those of the ? CH? or ? CN region. As a result compositions cannot be calculated by direct comparison of the areas in the ? CCl₂? region and either the ? CH? or the ? CN region. Discrepancies can be corrected for the ? CH? resonances by multiplication of the area by an empirical constant. A similar constant for the ? CN region is composition-dependent at 20.1 and 67.9 MHz. A chemical shift anisotropy mechanism is postulated as important for relaxation of the ? CN resonances. The overall influence of variable T₁ and NOE values on quantitative determination of polymer composition is considered.     

Nuclear magnetic relaxation of α-13C nuclei of helical poly(γ-hexyl-L-glutamate) and poly(γ-benzyl-L-glutamate)

Spin-lattice relaxation times (T₁), spin-spin relaxation times (T₂), and nuclear Overhauser enhancements (NOE), at 75.5 MHz are reported for α-¹³C nuclei of poly (γ-benzyl-L -glutamate) in deuterated dimethylformamide at 60°C and of poly(γ-hexyl-L -glutamate) in cyclohexanone at 48 and 79°C. It is shown that for molecular weights above 10⁵, the polypeptides cannot be considered as essentially rigid helices with internal librational motions; additional backbone flexing motions contribute to the relaxation behavior.     

13C NMR spectroscopic study of epoxidized 1,4-polyisoprene and 1,4-polybutadiene

Partly epoxidized cis- and trans-1,4-polyisoprenes and cis-and trans-1,4-polybutadienes were prepared, and their ¹³C NMR spectra examined. All the prominent resonances in the spectra of the epoxidized polymers were assigned by using lanthanide shift reagent and off-resonance decoupling experiments. A ¹³C NMR method of quantitative assessment of the epoxide content was developed following determination of relative spin-lattice relaxation time (T₁) and nuclear Overhauser effect (NOE) parameters of the various carbons in the epoxidized polyisoprenes and polybutadienes.     

Direct structure determination of the self-condensation product of 1-phenylpentane-2,4-dione using T1 and NOE measurements from 13C NMR spectroscopy

The nuclear Overhauser effect (NOE) is known to depend on molecular dynamics and structure. However, in some cases the values obtained for selective homonuclear and heteronuclear NOE are much too small, considering that the nuclei involved are located within a short distance of each other in space. A quantitative treatment of the NOE values allows a clear explanation of this apparent anomaly, and allows the possibility of using T₁ and NOE values measured with broad-band proton irradiation. The corresponding relationship is useful for solving many structural problems in organic chemistry, and has the great advantage of employing the typical high resolution of fully decoupled spectra. The method was used in this work for the structure determination of the self-condensation product of 1-phenylpentane-2,4-dione, and it was concluded that the previous assignment of the ¹³C NMR spectrum was erroneous. An independent proof of the new assignment is given using the selective collapse of the fine structure under low-power irradiation of the methyl protons.     

Coupling NMR to NOM

This work itemizes and critically assesses several 1D and multi-dimensional nuclear magnetic resonance (NMR) techniques, in both the liquid (solvent suppression, APT, DEPT, INEPT, COSY, TOCSY, HSQC, HMQC, HMBC, NOESY, ROESY and others) and solid states (DP, SACP, RAMP-CP, CP-TOSS, MQ-DEPT, 2D ¹H–¹³C HETCOR and others), which are relevant to the characterization of natural organic matter (NOM). The pros and cons of many of the discussed techniques are compared in an effort to provide guidance to the most beneficial utilization of these NMR instrumental techniques for researchers interested in gaining insight into various aspects of NOM.Abbreviations 1D One dimensional - 2D Two dimensional - APT Attached proton test - BIRD Bilinear rotation decoupling - CP Cross polarization - COSY Correlation spectroscopy - CSA Chemical shift anisotropy - DEPT Distortionless enhancement by polarization transfer - DMSO Dimethyl sulfoxide - DOSY Diffusion ordered spectroscopy - DP Direct polarization - DQ Double quantum - FID Free induced decay - FT Fourier transform - FT-ICR-MS Fourier transform-ion cyclotron resonance-mass spectroscopy - HETCOR Heteronuclear correlation - HH Hartmann–Hahn - HMBC Heteronuclear multiple bond correlation - HMQC Heteronuclear multiple quantum coherence - HSQC Heteronuclear single quantum coherence - INEPT Insensitive nuclei enhanced by polarization transfer - LR-COSY Long-range COSY - MAS Magic-angle spinning - MQ Multiple quantum - MS Mass spectroscopy - NMR Nuclear magnetic resonance - NOE Nuclear Overhauser enhancement - NOESY Nuclear Overhauser enhanced spectroscopy - NOM Natural organic matter - PASS Phase adjustment of spinning sidebands - RAMP Ramped amplitude - RESTORE Restoration of spectra via T _CH and T one rho (T _1H) editing - r.f. Radio frequency - ROESY Rotating frame Overhauser enhancement spectroscopy - SACP Single amplitude cross polarization - SOM Soil organic matter - SS Spinning sideband - TMS Tetramethylsilane - TOCSY Total correlation spectroscopy - TOSS Total suppression of sidebands - TPPM Two-pulse phase modulation - VCT Variable contact time - VSL Variable spin lock - WATERGATE Water suppression by gradient tailored excitation     

Anisotropy of local relaxation properties of macromolecules. Spin-lattice relaxation of 13C nuclei,the nuclear overhauser effect and the estimation of parameters of an equivalent ellipsoid for kinetic segments of polymer chains

The expressions for the functions of spectral density at different orientations of the components of the internuclear vector with respect to the chain backbone, the frequency dependences of the spin-lattice relaxation time of ¹³C nuclei (T_1C) and the values of the nuclear Overhauser effect (NOE) were obtained for the tetrahedral lattice model of a polymer chain with three-unit kinetic elements. It was shown that peculiar features of the behavior of T_1C and NOE reflect the characteristic properties of the spectra of relaxation (correlation) times for “longitudinal” and “transverse” components of the internuclear vector. It was established that in the range of relatively short times of the relaxation spectrum the dynamics of an anisotropic kinetic segment of the chain may be described with the aid of a simple model of an elongated ellipsoid of rotation with an axial ratio of about 10. It is shown that the equivalent-ellipsoid model leads to significant differences from a more specific model of chain dynamics when a broad frequency range is considered.     

Cellulose organic solutions: A nuclear magnetic resonance investigation

Four solvents of cellulose have been studied by using ¹³C-NMR spectroscopy. All these solvents, N-methyl morpholine-N-oxide, methylamine, hydrazine, and paraformaldehyde (PF), contained dimethyl sulfoxide (DMSO) as a cosolvent. Oligomers of cellulose of DP = 10 soluble in hot DMSO have been used as model compounds. ¹³C chemical shifts and line shapes show that three of the mentioned solvents are “true solvents” of cellulose. On the other hand, dissolution of cellulose in DMSO-PF system occurs by the formation of a statistical derivative of cellulose. Enriched ¹³C bacterial cellulose on C-1 and C-6 positions have been used to identify the ¹³C positions mainly in DMSO-N-methyl morpholine-N-oxide system. This solvent has been found to be degradative for the macromolecule when the solution is kept at 100°C over a long period. Viscosity measurements show a reduction of the molecular weight in these conditions. Polarimetry indicates that no glucose is present in solution and hence there is a statistical break of the chain. Enriched cellulose solution in DMSO–N-methyl morpholine-N-oxide has been also used for relaxation time (T₁) determination both of the solvent and of the enriched carbons of the polymer. Nuclear Overhauser enhancement (NOE) was found to be 1.8 for C-1 and 2.1 for C-6 showing that relaxation phenomenon is not purely dipolar. T₁ values of 97 and 65 msec are found for C-1 and C-6 of cellulose, in good agreement with the values known for polysaccharides. Determination of T₁ for the different carbon atoms of the solvent DMSO-N-methyl morpholine-N-oxide with and without cellulose shows a large reduction of T₁ for N-methyl morpholine-N-oxide molecule. This denotes a slower molecular motion of this molecule and a preferential interaction with the cellulose macromolecule.     

Local chain motions of poly(β-hydroxyoctanoate) in the bulk. 13C NMR relaxation study

Variable-temperature ¹³C NMR spin-lattice relaxation times (T₁) and Nuclear Overhauser Enhancements (NOE) at two magnetic fields have been used to study the dynamics of the amorphous part of a semicrystalline sample (33% of crystallinity) of poly(β-hydroxyoctanoate) (PHO). The interpretation of the relaxation data of the backbone carbons was made by employing a number of motional models. Among these, the DLM model offered the best interpretation of the relaxation data in terms of conformational transitions and librational motions of the backbone C? H vectors, and proved to be superior to unimodal distribution functions. The interpretation of temperature- and frequency-dependent T₁ and NOE data of the carbon nuclei in the n-pentyl side chain was made by employing a newly developed composite spectral density function for multiple internal C? C bond rotations of restricted amplitude and chain segmental motion. The temperature dependence of the linewidths of the various protonated carbon resonances of PHO has been discussed in terms of the semicrystalline character of this polymer. © 1995 John Wiley & Sons, Inc.     

Natural abundance nitrogen-15 n.m.r. spectroscopy. Spin–lattice relaxation in organic compounds

The small negative magnetogyric ratio (γ) of the ¹⁵N nucleus decreases the efficiency of ¹⁵N? ¹H dipole-dipole relaxation to about 25% of that for an analogous ¹³C nucleus. This may lead to greater competition from other relaxation mechanisms in ¹⁵N n.m.r. and consequent partial or total quenching of the negative nuclear Overhauser effect (NOE). In unfavorable circumstances nulling of the ¹⁵N resonance can occur. Previous ¹⁵N relaxation studies have examined isotopically enriched, low molecular weight compounds. The present study examines several small to intermediate size organic compounds containing nitrogen at natural isotopic abundance. In contrast to some of the earlier studies, ¹⁵N? ¹H dipolar relaxation was found to be dominant for protonated nitrogen atoms, even for two tertiary nitrogens (the tertiary amine nitrogen in 1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a] quinolizine and the oxime nitrogen in 3-methyl-2-pentanone ketoxime). The magnitude of the NOE and the moderate value of T₁ indicate effective dipolar relaxation from neighboring but not directly bonded protons in these cases. Nitro groups were found, as expected, to have predominant contributions from non-dipolar mechanisms, and in one case (2-methyl-2-nitro-1, 3-propanediol) signal nulling (NOE of η = ?1) was observed. The effect of paramagnetic impurities was demonstrated for ethanolamine, which contains a basic nitrogen. In this case T₁^DD(¹⁵N? ¹H) = 4·3 s; added Ni(acac)₂ at 1 × 10^?4 Molar reduced the ¹⁵N T₁ to 0·065 s and consequently the NOE to η = 0.     

The Stereostructure of Porphyra‐334: An Experimental and Calculational NMR Investigation. Evidence for an Efficient ‘Proton Sponge’

The mycosporine‐like amino acid (MAA) porphyra‐334 ( 1 ) is subjected to extensive ¹H‐ and ¹³C‐NMR analysis as well as to density‐functional‐theory (DFT) calculations. All ¹H‐ and ¹³C‐NMR signals of 1 are assigned, as well as the resonances of prochiral proton pairs. This is achieved by 500‐MHz standard COSY, HMQC, and HMBC experiments, as well as by one‐dimensional (DPFGSE‐NOE) and two‐dimensional (NOESY) NOE experiments. Diffusion measurements (DOSY) confirm that 1 is monomeric in D₂O solution. DFT Calculations yield ¹³C‐NMR chemical shifts which are in good agreement for species 6 which is the imino N‐protonated form of 1 . An exceptionally high proton affinity of 265.7 kcal/mol is calculated for 1 , indicating that 1 may behave as a very powerful ‘proton sponge’ of comparable strength as synthetic systems studied so far. Predictions of ¹³C‐NMR chemical shifts by the ‘NMRPredict’ software are in agreement with the DFT data. The absolute configuration at the ring stereogenic center of 1 is concluded to be (S) from NOE data as well as from similarities with the absolute configuration (S) found in mycosporine‐glycine 16 . This supports the assumption that 1 is biochemically derived from 3,3‐O‐didehydroquinic acid ( 17 ). The data obtained question the results recently published by a different research group claiming that the configuration at the imino moiety of 1 is (Z), rather than (E) as established by the here presented study.     

Chain mobility of some terephthalic acid polyesters in solution. A 13C spin-relaxation study

Carbon-13 spin-lattice relaxation times (T₁), nuclear Overhauser enhancements (NOE), and resonance linewidths (Δp) have been measured for a series of terephthalic acid polyesters containing ethyl, butyl, hexyl, and isopropyl groups between neighboring terephthalate units. The relaxation parameters of all carbons in the terephthalate groups are independent of the length of the separating alkyl chain. Reduced NOE's are seen for all carbons. The data are interpreted in terms of a log X²distribution of correlation times of constant width, but variable average mobility. The average mobility in the alkyl chain increases with increasing distance from the terephthalate group in a given polymer. For a given position in the chain. mobility increases with increasing chain length. This behavior is consistent with the presence of independently reorienting, highly solvated terephthalate groups.     

CARBON-13 NMR STUDY OF MOLECULAR MOTION OF 1, 2-POLYBUTADIENES IN SOLUTION Ⅰ. STRUCTURE DEPENDENCE OF MOLECULAR MOTIOM

Proton decoupled, partially relaxed, Fourier-transform 50.3 MHz carbon-13 NMR in naturalabundance was used to determine spin-lattice times (T_1) and nuclear Overhauser enhancement fac-tors (NOE) of individual carbon of a serics of 1,2-polybutadienes with different structures in solutionin CDCl_2 The structure dependence of molecular metion and the internal motion of vinyl group in1,2-polybutadiene have been studied by nT_1 and NOE values. The nT_1 values of the carbons in cis-1,4-units are the highest and those of the carbons in 1.2-units are the lowest in three types of units in1,2-polybutadiene. The nT_1 values of carbons in the same unit become greater when the adjacent1,2-units are replaced by 1,4-units, and nT_1 values of the carbons in all units decrease sharply withthe increase of content of 1,2-units in the polymers. The fact that nT_1 values of --CH=are larger than those of=CH_2 in vinyl group impliesthat there are complex internal motions of vinyl group. It is shown by calculation that the dominantfactor causing the difference in nT_1 of--CH=and=CH_2 in vinyl group is a swing of vinyl group ina plane peopndicular to the chain backbone.     

Spin‐Labeled Heparins as Polarizing Agents for Dynamic Nuclear Polarization

A potentially biocompatible class of spin‐labeled macromolecules, spin‐labeled (SL) heparins, and their use as nuclear magnetic resonance (NMR) signal enhancers are introduced. The signal enhancement is achieved through Overhauser‐type dynamic nuclear polarization (DNP). All presented SL‐heparins show high ¹H DNP enhancement factors up to E=?110, which validates that effectively more than one hyperfine line can be saturated even for spin‐labeled polarizing agents. The parameters for the Overhauser‐type DNP are determined and discussed. A striking result is that for spin‐labeled heparins, the off‐resonant electron paramagnetic resonance (EPR) hyperfine lines contribute a non‐negligible part to the total saturation, even in the absence of Heisenberg spin exchange (HSE) and electron spin‐nuclear spin relaxation (T_1ne). As a result, we conclude that one can optimize the use of, for example, biomacromolecules for DNP, for which only small sample amounts are available, by using heterogeneously distributed radicals attached to the molecule.     

1H bridging and terminal hydride T1 values. Comments on classical vs non-classical hydride identification using T1 criteria

Hydride ¹H T₁ values are reported for a selected series of ruthenium, iridium and platinum complexes. These T₁ values range from 6.9 to 0.05 s with the shortest value, 0.05 s, assigned to a complex containing both hydride and coordinated molecular hydrogen, i.e. “M(H₂)”. There are nuclear Overhauser enhancements arising both from protons on coordinated ligands and other hydride ligands. It is suggested that the molecular weight of the complex and the measurement conditions can be important factors for T₁.     

13C NMR spectra of benzo[b]thiophene and 1-(X-benzo[b]thienyl)ethyl acetate derivatives

Carbon-13 chemical shift assignments are reported for benzo[b]thiophene and 1-(X-benzo[b]thienyl)ethyl acetate derivatives, where X=? CH(OAc)CH₃ substituted at positions 2-7. Substituent chemical shift (SCS) effects for the ethyl acetate group are additive at all positions. A substantial upfield shift was observed at C-3, arising from the peri interaction of H-3 and the 4-ethyl acetate substituent. Carbon-13 relaxation times (T₁) and nuclear Overhauser enhancements (η) have been measured for benzo[b]thiophene and its derivatives, and the contributions of dipolar, T^DD₁, and spin rotation, T^SR₁, relaxation have been determined. Intramolecular dipole–dipole interactions are found to provide by far the most important spin-lattice relaxation mechanism whenever protons are bound directly to the carbons under investigation. Nonprotonated ring carbons are relaxed by both DD and SR mechanisms. Anisotropic motion has an easily observable effect on the DD contribution to T₁, and can form the basis for spectral assignments, as in 1-phenylethyl acetate. Long-range ¹³C? ¹H coupling constants were observed both between ring carbons and between ring carbons with ring side-chain hydrogens. These results have been used for the structure determination of the title compounds.     

Carbon-13 NMR. The analysis of the relaxation times T1 of benzofuran and of a series of its methyl derivatives. Correlations between molecular motions and structural properties

Carbon-13 relaxation times (T₁) and nuclear Overhauser enhancements (η) have been measured for benzofuran and a series of its methyl derivatives. The contributions of dipolar (T₁ ^DD) and spin rotation (T₁^SR) mechanisms have both been determined. The temperature dependence of T₁ has been studied. The relationships between molecular motions and structural properties have been emphasized. The overall motional anisotropy of the benzofuran molecule is increased by substitution in positions 2 and 5. The internal rotation of a methyl group may change depending on its position in the molecule and on the influence of other methyl groups in its close neighbourhood.     

13C Spin-Lattice Relaxation Times and the Mobility of Organic Molecules in Solution

While the chemical shifts and coupling constants of ¹³C NMR belong to the most powerful tools available to the organic chemist for the solution of structural problems, increasing interest is being shown in ¹³C spin-lattice relaxation times T₁ as structural parameters. Together with the nuclear Overhauser effects arising by proton decoupling of ¹³C NMR spectra, the T₁ values of ¹³C nuclei in a molecule permit conclusions to be drawn with regard to relaxation mechanisms. They reflect the inter- and intramolecular mobility of a molecule, and thus complement the results of temperature-dependent NMR spectroscopy. The T₁ differences within a molecule show, for instance, whether the molecular motion is anisotropic in solution, whether the internal motion of groups is subject to steric hindrance, the extent to which strong intermolecular or interionic interactions affect the flexibility of the molecule, and which parts of the molecule are rigid and which are flexible. Finally, differences between the T₁ values measured for the ¹³C nuclei of a molecule frequently provide a reliable aid in the assignment of ¹³C NMR spectra, particularly in cases of signal crowding and multiplet overlapping.     

STEREOELECTRONIC PROPERTIES OF PHOTOSYNTHETIC AND RELATED SYSTEMS—VI. AB INITIO CONFIGURATION INTERACTION CALCULATIONS ON THE GROUND AND LOWER EXCITED SINGLET AND TRIPLET STATES OF ETHYL BACTERIOCHLOROPHYLLIDE-a AND ETHYL BACTERIOPHEOPHORBIDE-a‡

Abstract— Ab initio quantum mechanical calculations on ethyl bacteriochlorophyllide-a (Et-BChl-a) and ethyl bacteriopheophorbide-a (Et-BPheo-a) are presented, including self-consistent-field (SCF) molecular orbital studies on the ground states using the molecular fragment procedure, and configuration interaction (CI) calculations on the low-lying singlet and triplet states and absorption spectra. A characterization and comparison of many of the higher-lying molecular orbitals obtained from the SCF studies is presented. The estimated first ionization potentials are 5.66 and 5.97 eV for Et-BChl-a and Et-BPheo-a, respectively. Excited state calculations show that the visible spectrum of both molecules consists of an intense, y-polarized S₁← S₀ transition and a weakly-allowed, x-polarized S₂← S₀ transition. Both S₁ and S₂ states are ¹(π, π*) in character, and are described by a four-orbital model. Transitions to the remaining calculated states, S₃-S₁₂, appear in the Soret region of the spectrum of both molecules. However, only transitions to S₉(‘x’), S₁₀(‘x’) and S₁₁(‘y’) of Et-BChl-a, and S₇(‘x’) and S₁₀(‘y’) of Et-BPheo-a are of high intensity. The composition of the high intensity Soret states is ¹(π, π*) and strongly “four-orbital” in nature. The lowest triplet state, T₁, is predicted to lie 9752 cm^-1 and 7880 cm^-1 above S₀ for Et-BPheo-a and Et-BChl-a, respectively. In each molecule T₂ and S₁ are nearly degenerate, suggesting a favorable pathway for intersystem crossing. Calculated T_n← T₁ transitions indicate that the y-polarized T₁₂← T₁ transition in Et-BChl-a corresponds to the observed intense 24,400 cm^-1 absorption in the triplet-triplet spectrum of BChl-a. A similar type spectrum is also predicted for BPheo-a.