Determination of configurational isomers in polybutadienes by <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectroscopy

The NMR spectra (600 MHz) of polybutadienes containing different amounts of cis-1,4, trans- 1,4 and 1,2 units are analyzed. The critical consideration of signal assignment and the comparison of ¹H and ¹³C NMR data reveal that there are significant limitations to the quantitative characterization of polybutadienes with the use of NMR spectroscopy.     

<Superscript>13</Superscript>C NMR and mass spectrometry of soil organic matter

Liquid state, high resolution ¹³C NMR spectroscopy and mass spectrometry were used to study the composition and structure of soil organic matter (SOM) using soil extracts from two long-term experiments at the Rothamsted Experimental Station. Both one- and two-dimensional NMR techniques were applied. ¹³C NMR sub-spectra of the CH _n (n=0...3) groups, obtained by the Distortionless Enhancement by Polarisation Transfer (DEPT) technique, were used for the elucidation of the qualitative and quantitative composition of humic and fulvic acids in the soils. The chemical structure of SOM was further analysed at the molecular level through Fast Atom Bombardment Mass Spectrometry (FABMS) and Gas Chromatography-Mass Spectrometry (GC/MS). Humic and fulvic extract results were not only compared to each other, but also to the solid state ¹³C NMR results for the complete soil sample.     

<Superscript>13</Superscript>C NMR analysis of cellulose samples from different preparation methods

Alpha-cellulose is a part of the wooden material that preserves isotopic composition during tree-growth, and therefore provides important indirect data for paleoclimatological studies. For this reason, it is exceptionally important to extract the alpha-cellulose component from plants, e.g. from tree rings of wood. Since the cell wall of plant cells consists of multicomponent polysaccharides, the extraction of cellulose from wood is not an obvious task. In this paper, we describe, evaluate and compare nine methods, based on the literature and experimental observations, for obtaining cellulose from tree rings of wood. We show that the distortionless enhancement by polarization transfer (DEPT-135) variant of liquid-state ¹³C NMR spectroscopy is a powerful analytical method for monitoring the preparation process. Trifluoroacetic acid was applied as solvent for the NMR analysis. We proved that all the preparation methods give pure cellulose samples without hemicellulose and lignin content, and we propose methods resulting in non-fragmented cellulose. ¹³C and ¹⁸O isotope ratio measurements have shown that all the applied extraction methods result in similar isotope ratios, thus they are suitable for paleoclimatological studies.     

<Superscript>29</Superscript>Si NMR Spectroscopy Investigation of Alcoholic Phenyltrimethyl Ammonium Silicate Solutions

²⁹Si NMR spectroscopy is a powerful tool for studies of the silicate species existing in both aqueous and non-aqueous solutions. In this report ²⁹Si NMR spectroscopy was used to characterize species present in alkaline alcoholic silicate solutions. Phenyltrimethylammonium (PTMA) hydroxide was used as a base. The effects of polymerization/depolymerization of silicate anions in alcoholic alkaline solutions were investigated with different alcohols by ²⁹Si NMR spectroscopy. The esterification of monomeric silicate, Si(OH)₄, in the presence of different alcohols was also studied. Esterification depends on the alkyl chain as well as number of hydroxyl groups in the alcohol.     

High-Resolution <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR of Glycyrrhizic Acid and Its Esters

Resonances for protons and C atoms in the ¹H and ¹³C NMR spectra of glycyrrhizic acid and its esters were assigned using high-resolution ¹H (600 MHz) and ¹³C (150 MHz) NMR methods. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 347–350, July–August, 2005.     

Potential and Limitations of 2D <Superscript>1</Superscript>H–<Superscript>1</Superscript>H Spin-Exchange CRAMPS Experiments to Characterize Structures of Organic Solids

Summary.  A brief overview of our recent results concerning the application of 2D CRAMPS experiments to investigate a wide range of materials is presented. The abilities of the 2D ¹H–¹H spin-exchange technique to characterize the structure of organic solids as well as the limitations resulting from segmental mobility and from undesired coherence transfer are discussed. Basic principles of ¹H NMR line-narrowing and procedures for analysis of the spin-exchange process are introduced. We focused to the qualitative and quantitative analysis of complex spin-exchange process leading to the determination of domain sizes and morphology in heterogeneous multicomponent systems as well as the characterization of clustering of surface hydroxyl groups in polysiloxane networks. Particular attention is devoted to the determination of the ¹H–¹H interatomic distances in the presence of local molecular motion. Finally we discuss limitations of the ¹³C–¹³C correlation mediated by ¹H–¹H spin exchange to obtain structural constraints. The application of Lee-Goldburg cross-polarization to suppress undesired coherence transfer is proposed. Corresponding author. E-mail: brus@imc.cas.cz Received May 28, 2002; accepted (revised) July 1, 2002     

Structure of Galactomannans from <Emphasis Type="Italic">Gleditsia delavayi</Emphasis> and <Emphasis Type="Italic">G. aquatica</Emphasis> by <Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR Spectroscopy

The structure of galactomannans isolated from seeds of G. delavayi and G. aquatica was studied by ¹H and ¹³C NMR spectroscopy. It was found that the galactomannans consisted mainly of β-1-4-bound mannopyranoses, a part of which was substituted on the C-6 hydroxyl by terminal units of α-galactopyranose.__________Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 12–13, January–February, 2005.     

Structure of binuclear platinum(III) acetamidate complexes in solutions as probed by <Superscript>195</Superscript>Pt, <Superscript>13</Superscript>C,and <Superscript>1</Superscript>H NMR spectroscopy

¹⁹⁵Pt, ¹H, and ¹³C NMR spectroscopy was used to study the structure of binuclear platinum(III) acetamidate complexes with 1,10-phenanthroline and 2,2′-bipyridine ligands [Pt₂(phen)₂(acam)₄](NO₃)₂ (1) and [Pt₂(bipy)₂(acam)₄](NO₃)₂ (2) in aqueous solutions. The ¹⁹⁵Pt NMR spectra of solutions of complexes 1 and 2 in D₂O exhibit two signals with satellites due to the ¹⁹⁵Pt–¹⁹⁵Pt spin-spin coupling (¹ J(Pt–Pt) ≈ 6345 Hz), whereas their ¹H and ¹³C NMR spectra contain four sets of signals for the protons and the carbon atoms of the heterocyclic and acetamidate ligands. The signals were assigned using the COSY, NOESY, and HSQC/ HMBC experiments and comparing the coordination shifts of the signals for the protons of heterocycles. These data allowed us to draw a conclusion that binuclear complexes 1 and 2 in solution have a head-to-head structure with nonequivalent platinum(III) atoms (coordination cores PtN₅ and PtN₃O₂), the axial-equatorial coordination of the bidentate heterocyclic molecules, and two bridging and two terminal acetamidate ligands.     

Synthesis,radiolabelling and biodistribution of HYNIC-Tyr<Superscript>3</Superscript> octreotide: a somatostatin receptor positive tumour imaging agent

In vivo imaging of tumours using radiolabelled somatostatin (SST) analogues has become an accepted clinical tool in oncology. HYNIC-Tyr³ octreotide and Tyr³ octreotide were synthesized by FMOC solid-phase peptide synthesis using a semi-automated synthesizer. These were analyzed and purified by RP-HPLC, mass spectroscopy, IR spectroscopy, ¹H NMR and ¹³C NMR. The prochelator 6-BOC-HYNIC was also synthesised and characterised indigenously. HYNIC-Tyr³ octreotide was labelled with ^99mTc using Tricine and EDDA as coligand by SnCl₂ method. Labelling with ^99mTc was performed at 100 °C for 15 min and radiochemical analysis by ITLC and HPLC methods. The radiochemical purity of the complex was over 98% and log p value was found to be −1.27 ± 0.12. The stability of radiolabelled peptide complex was checked at 37 °C up to 24 h. Blood clearance and protein-binding study was also performed. In vivo biodistribution studies in rat showed uptake of ^99mTc-HYNIC-TOC in kidney than any other organs. The blood clearance was faster with rapid excretion through kidneys and relatively low uptake in liver.     

Non-empirical and DFT calculations of <Superscript>19</Superscript>F and <Superscript>13</Superscript>C chemical shifts in the NMR spectra of substituted pentafluorobenzenes

Chemical shifts in ¹⁹F and ¹³C NMR spectra of substituted pentafluorobenzenes are calculated by Hartree-Fock and density functional theory methods. The calculated values are compared with the experimental data known from the literature. It is shown that chemical shifts in non-polar solvents can be predicted sufficiently accurately by the GIAO-DFT(PBE/L22) method. This method is used to predict the ¹⁹F and ¹³C chemical shifts of a heptafluorobenzyl cation in the SbF₅ medium. The best agreement between the calculated and experimental values is achieved when the counterion effect is taken into account.     

Vinylimidazole copolymers: coordination chemistry,solubility, and cross-linking as function of Cu<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> complexation

P(1-VIm-co-MMA) copolymers with 4 or 44 wt.% 1-VIm (abbreviated PVM-4 and PVM-44) where polymerized from 1-VIm (1-vinylimidazole) and methylmethacrylate with azobisisobutyronitrile as initiator and reacted with either Cu²⁺ or Zn²⁺. The resulting coordinated polymer complexes were studied using ICP-AES, CP/MAS ¹³C NMR, conductivity measurements, vibrational spectroscopy (mid-FTIR and far-FTIR), DSC, and EPR. It was established by ICP-AES, CP/MAS ¹³C NMR, conductivity, mid-FTIR and EPR measurements that the transition metal ions in the complexes were exclusively coordinated by the imidazole ligand. The coordination geometry is square planar with regard to Cu(II) complexes. The strong interaction between the polymeric imidazole ligand and the transition metal ion cross-links the system, resulting in augmentation of T _g (the glass transition temperature), especially for copolymers with high relative amount of 1-VIm. The effect of changing metal ion is more complicated and depends on both the strength of the coordinate interaction as well as the coordination number. The solubility of the coordinate polymer complex in conventional solvents is low due to the coordinate cross-links. However, the coordinate polymer complexes are soluble in strongly coordinating solvents such as acetonitrile and dimethylsulfoxide.     

Structural Organization of Nickel(II), Zinc(II), and Copper(II) Complexes with Diisobutyldithiocarbamate: EPR, <Superscript>13</Superscript>C and <Superscript>15</Superscript>N CP/MAS NMR,and X-Ray Diffraction Studies

The structures and spectroscopic properties of nickel(II), zinc(II), and copper(II) complexes with dibutyl- and diisobutyldithiocarbamate were studied by EPR and ¹³C and ¹⁵N CP/MAS NMR spectroscopy and X-ray diffraction analysis. According to the EPR data, copper(II) forms mononuclear [^63/65Cu{S₂CNR₂}₂] and heterobinuclear complexes [^63/65CuZn{S₂CNR₂}₄] under magnetic dilution conditions. The isomeric forms of nickel(II) and zinc(II) diisobutyldithiocarbamates were detected by ¹³C and ¹⁵N NMR spectroscopy. The crystalline zinc(II) diisobutyldithiocarbamate was found to have a unique structural organization with alternating mononuclear [Zn{S₂CN(i-C₄H₉)₂}₂] and binuclear molecular forms [Zn₂{ S₂CN(i-C₄H₉)₂}₄] in the 1 : 1 ratio.     

The first (<Superscript>31</Superscript>P, <Superscript>17</Superscript>O,and <Superscript>103</Superscript>Rh) NMR observation complex formation of rhodium(III) with phosphoric acid

³¹P, ¹⁷O, and ¹⁰³Rh NMR spectroscopy shows that rhodium(III) reacts with phosphoric acid to generate polynuclear aquaphosphate complexes in which phosphate ions mostly have a bridging function. Assignment of ¹⁰³Rh NMR signals in dominant rhodium complexes is suggested.     

A <Superscript>1</Superscript>H NMR study of Nile Red solvation

In order to evaluate the capabilities of NMR spectroscopy for investigation of the solvatochromic effect in luminophore solutions, the ¹H NMR chemical shifts of Nile Red in mixtures of solvents with different polarities (benzene, toluene, methanol) has been determined. Their dependence upon the solvent mixture composition has been revealed and binding sites for luminophore and solvent component molecules have been determined. The results of the NMR study are consistent with data on the fluorescence of Nile Red solutions in toluene-ethanol mixtures.     

13C and 15N NMR studies of iron-bound cyanides of heme proteins and related model complexes: sensitive probe for detecting hydrogen-bonding interactions at the proximal and distal sides

Studies of the 13C and 15N NMR paramagnetic shifts of the iron-bound cyanides in the ferric cyanide forms of various heme proteins containing the proximal histidine and related model complexes are reported. The paramagnetic shifts of the 13C and 15N NMR signals of the iron-bound cyanide are not significantly affected by the substitution of the porphyrin side chains. On the other hand, the paramagnetic shifts of both the 13C and 15N NMR signals decrease with an increase in the donor effect of the proximal ligand, and the 13C NMR signal is more sensitive to a modification of the donor effect of the proximal ligand than the 15N NMR signal. With the tilt of the iron-imidazole bond, the paramagnetic shift of the 13C NMR signal increases, whereas that of the 15N NMR signal decreases. The hydrogen-bonding interaction of the iron-bound cyanide with a solvent decreases the paramagnetic shift of both 13C and 15N NMR signals, and the effect is more pronounced for the 15N NMR signal. Data on the 13C and 15N NMR signals of iron-bound cyanide for various heme proteins are also reported and analyzed in detail. Substantial differences in the 13C and 15N NMR shifts for the heme proteins can be explained on the basis of the results for the model complexes and structures around the heme in the heme proteins. The findings herein show that the paramagnetic shift of the 13C NMR signal of the iron-bound cyanide is a good probe to estimate the donor effect of the proximal imidazole and that the ratio of 15N/13C NMR shifts allows the hydrogen-bonding interaction on the distal side to be estimated.     

Crystalline cadmium dialkyl phosphorodithioate complexes: Synthesis and structural organization as probed by multinuclear <Superscript>13</Superscript>C, <Superscript>31</Superscript>P,and <Superscript>113</Superscript>Cd CP/MAS NMR and single-crystal X-ray diffraction

The cadmium O,O′-dethyl (I) and O,O′-di-sec-butyl phosphorodithioate (II) complexes have been synthesized and characterized in detail by ¹³C, ³¹P, and ¹¹³Cd CP/MAS NMR. X-ray crystallography shows that complex II has a binuclear molecular structure [Cd₂{S₂P(O-s-C₄H₉)₂}₄]. For ³¹P and ¹¹³Cd NMR signals, the chemical shift anisotropy δ_aniso and the asymmetry parameter η have been calculated. The ³¹P NMR signals are assigned to the terminal and bridging ligands in the complexes.     

Adducts of zinc and copper(II) dialkyldithiocarbamate complexes with dibutyl-and diisobutylamines: Synthesis,structures, EPR and solid-state natural abundance <Superscript>13</Superscript>C and <Superscript>15</Superscript>N CP/MAS NMR spectra

Crystalline adducts of zinc and copper(II) dithiocarbamate complexes with dibutyl-and diisobutylamines of the general formula [M(NHR′₂)(S₂CNR₂)₂] (M = Zn, ⁶³Cu, and ⁶⁵Cu; R = CH₃ and C₂H₅; R₂ = (CH₂)₄O; R′ = C₄H₉ and i-C₄H₉) were synthesized. Their structures and spectroscopic properties were studied by EPR and solid-state natural abundance ¹³C and ¹⁵N CP/MAS NMR spectroscopy. Experimental EPR data and computer-assisted modeling confirmed the individual character of copper(II) adducts. The geometries of the copper coordination polyhedra were found to be intermediate between a tetragonal pyramid and a trigonal bipyramid (TBP). The contributions from TBP to the geometries of the adducts obtained were calculated from the EPR data. According to the X-ray diffraction data, the adduct of zinc diethyldithiocarbamate with diisobutylamine exists in two isomeric forms. The ¹³C and ¹⁵N CP/MAS NMR signals were assigned to the atomic positions in two crystallographically independent conformer molecules.     

Stereospecificity of <Superscript>13</Superscript>C shielding constants in acetone azine as a tool for configurational assignment of ketone azines

According to the ¹³C NMR data, the chemical shift of the methyl carbon atom in acetone azine in the trans position with respect to the lone electron pair on the neighboring nitrogen atom is lower by 7 ppm than that of the methyl carbon atom in the cis position. The corresponding direct ¹³C-¹³C coupling constant for the trans-methyl groups is lower by 10 Hz as compared to the cis-methyl groups. The experimental spectral data are reproduced well by nonempirical quantum-chemical calculations. The observed stereospecificity of ¹³C chemical shifts and ¹³C-¹³C coupling constants may be used as an effective tool in configurational analysis of various ketone azines.     

Quantitative analysis of hydrogen peroxide by <Superscript>1</Superscript>H NMR spectroscopy

A technique utilizing ¹H NMR spectroscopy has been developed to measure the concentration of hydrogen peroxide from 10^–3 to 10 M. Hydrogen peroxide produces a peak at around 10–11 ppm, depending upon the interaction between solvent molecules and hydrogen peroxide molecules. The intensity of this peak can be monitored once every 30 s, enabling the measurement of changes in hydrogen peroxide concentration as a function of time. ¹H NMR has several advantages over other techniques: (1) applicability to a broad range of solvents, (2) ability to quantify hydrogen peroxide rapidly, and (3) ability to follow reactions forming and/or consuming hydrogen peroxide as a function of time. As an example, this analytical technique has been used to measure the concentration of hydrogen peroxide as a function of time in a study of hydrogen peroxide decomposition catalyzed by iron(III) tetrakispentafluorophenyl porphyrin.Electronic Supplementary Material Supplementary material is available for this article at     

Mechanochemical Changes in the Structure of Layered Silicates according to <Superscript>27</Superscript>Al and <Superscript>29</Superscript>Si NMR Data

Mechanochemical structural changes in layered silicates were studied by ²⁷Al and ²⁹Si NMR spectroscopy.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, p. 344.Original Russian Text Copyright © 2005 by Pashchenko.