H MAS NMR monitoring of the C-labeled carbon scrambling for propane in zeolite H-ZSM-5

It has been demonstrated that ¹H MAS NMR spectroscopy can be used as a tool for in situ monitoring the reaction kinetics of ¹³C-labeled carbon scrambling in alkane molecules adsorbed on zeolite catalysts at the reaction temperature of 540–570 K. The accuracy of the results and the time resolution are improved compared to ¹³C MAS NMR spectroscopy.     

原位固体核磁共振研究温和条件下丙烷在镓改性H-ZSM-5上的活化

将价格低廉、储量丰富的低碳烷烃 ( C1～C5)转化为高附加值的工业产品是多相催化研究中的一个重要领域[1～ 6 ] .镓改性的 H-ZSM-5催化剂已被广泛应用于丙烷芳构化的工业化生产中[7,8] .然而 ,由于低碳烷烃中碳碳和碳氢键的高稳定性 ,低碳烷烃的转化通常需要较高的反应温度 ,因     

CP/MAS (13)C NMR study of cellulose and cellulose derivatives. 1. Complete assignment of the CP/MAS (13)C NMR spectrum of the native cellulose

The precise assignments of cross polarization/magic angle spinning (CP/MAS) (13)C NMR spectra of cellulose I(alpha) and I(beta) were performed by using (13)C labeled cellulose biosynthesized by Acetobacter xylinum (A. xylinum) ATCC10245 strain from culture medium containing D-[1,3-(13)C]glycerol or D-[2-(13)C]glucose as a carbon source. On the CP/MAS (13)C NMR spectrum of cellulose from D-[1,3-(13)C]glycerol, the introduced (13)C labeling were observed at C1, C3, C4, and C6 of the biosynthesized cellulose. In the case of cellulose biosynthesized from D-[2-(13)C]glucose, the transitions of (13)C labeling to C1, C3, and C5 from C2 were observed. With the quantitative analysis of the (13)C transition ratio and comparing the CP/MAS (13)C NMR spectrum of the Cladophora cellulose with those of the (13)C labeled celluloses, the assignments of the cluster of resonances which belong to C2, C3, and C5 of cellulose, which have not been assigned before, were performed. As a result, all carbons of cellulose I(alpha) and I(beta) except for C1 and C6 of cellulose I(alpha) and C2 of cellulose I(beta) were shown in equal intensity of doublet in the CP/MAS spectrum of the native cellulose, which suggests that two inequivalent glucopyranose residues were contained in the unit cells of both cellulose I(alpha) and I(beta) allomorphs.     

In situ kinetic study on hydrothermal transformation of D-glucose into 5-hydroxymethylfurfural through D-fructose with 13C NMR

Kinetics of hydrothermal reaction of D-glucose was investigated at 0.02 M over a temperature range of 120-160 °C by applying in situ (13)C NMR spectroscopy. D-Glucose was found to be reversibly transformed first into D-fructose (intermediate) and successively into 5-hydroxymethylfurfural (5-HMF) through dehydration. The carbon mass balance has been kept within the detection limit, and no other reaction pathways are present. The hydrothermal reaction of d-glucose is thus understood as that of D-fructose in the sense that the D-glucose reaction proceeds only through D-fructose. All the isomers of D-glucose and D-fructose were detected by the in situ (13)C NMR in D(2)O: they are the open chains and the pyranoses and furanoses of α- and β-types. The β-forms are the most stable due to the hydration. For both D-glucose and D-fructose, the isomers are in a rapid equilibrium for each monosaccharide, and they are treated collectively in the kinetic analysis of the slower hydrothermal reactions. The reactions are of the first order with respect to the concentrations of D-glucose and D-fructose, and D-glucose converts to 5-HMF on the order of hours. The kinetic parameters were determined by the in situ method.     

Prediction of the 13C NMR chemical shifts of organic species adsorbed on H-ZSM-5 zeolite by the ONIOM-GIAO method

The ONIOM-GIAO method has been used to accurately predict 13C NMR chemical shifts for a series of organic species adsorbed on H-ZSM-5 zeolite. This is useful for the spectroscopic identification of complicated catalytic systems.     

表征固体超强酸性的新方法-正丁烷异构化反应的原位~(13)CMASNMR谱

室温下SO_4~(2-)/ZrO_2催化剂（SZ）上~(13)C标记的丁烷异构化反应的原位 ~(13)C MAS NMR谱研究结果表明：其反应动力学符合Langmuir-Hinshelwood一级可 逆表面反应动力学公式，由该动力学公式计算得到的反应速率常数可以用于衡量固 体催化剂的表面超强酸性。这种新的表征方法显示采用一步-醇热-超临界干燥综合 技术合成的SZ催化剂不仅比表面和硫酸根含量高，而且其超强酸性和异构化反应活 性均明显优于常规法合成的催化剂，具有良好的应用前景。     

Mechanism studies of the conversion of 13C-labeled n-butane on zeolite H-ZSM-5 by using 13C magic angle spinning NMR spectroscopy and GC-MS analysis

By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.     

Automated structure verification based on a combination of 1D (1)H NMR and 2D (1)H - (13)C HSQC spectra

A method for structure validation based on the simultaneous analysis of a 1D (1)H NMR and 2D (1)H - (13)C single-bond correlation spectrum such as HSQC or HMQC is presented here. When compared with the validation of a structure by a 1D (1)H NMR spectrum alone, the advantage of including a 2D HSQC spectrum in structure validation is that it adds not only the information of (13)C shifts, but also which proton shifts they are directly coupled to, and an indication of which methylene protons are diastereotopic. The lack of corresponding peaks in the 2D spectrum that appear in the 1D (1)H spectrum, also gives a clear picture of which protons are attached to heteroatoms. For all these benefits, combined NMR verification was expected and found by all metrics to be superior to validation by 1D (1)H NMR alone. Using multiple real-life data sets of chemical structures and the corresponding 1D and 2D data, it was possible to unambiguously identify at least 90% of the correct structures. As part of this test, challenging incorrect structures, mostly regioisomers, were also matched with each spectrum set. For these incorrect structures, the false positive rate was observed as low as 6%.     

Formation of cyclic compounds and carbenium ions by conversion of methanol on weakly dealuminated zeolite H-ZSM-5 investigated via a novel in situ CF MAS NMR/UV-Vis technique

In studying the conversion of methanol on weakly dealuminated zeolite H-ZSM-5, simultaneously by in situ MAS NMR and in situ UV-Vis spectroscopy under continuous-flow conditions, the formation of cyclic compounds and carbenium ions were found to be formed already at 413 K.     

Influence of catalyst binder on the acidity and activity/selectivity of Ga/H-ZSM-5 zeolite in propane aromatization

The acidity and initial and time-on-stream activity in propane aromatization (at 550°C, space velocity of 3100 cm³g⁻¹ _(zeolite)h⁻¹) of Ga-impregnated H-ZSM-5 zeolite without or with binders (50 wt%), such as silica, alumina and kaolin, have been investigated. Both the acidity and catalytic activity of the zeolite are influenced by the presence of binder in the catalyst, depending upon the binder. The influence is found to be lowest for alumina and highest for kaolin. Among the binders, alumina is the most preferred binder for the zeolite catalyst.     

Line shapes in CP/MAS (13)C NMR spectra of cellulose I

The CP/MAS (13)C NMR line shape of cellulose I has been qualitatively analyzed by direct simulations using the Ornstein-Uhlenbeck stochastic process and the Kubo model. Both approaches describe a anhydroglucose C4 carbon as a oscillator with fluctuating Larmor frequency. The NMR resonance frequency is written omega=omega +omega(t), where the fluctuating part with zero mean was modelled as a stationary Markov diffusion process. The simulation results both motivates the use of multiple line shapes when fitting CP/MAS (13)C NMR spectra recorded on cellulose I and gives some insights into why signals from crystalline cellulose I give rise to Lorentzian line shapes.     

表征固体超强酸性的新方法--正丁烷异构化反应的原位13C MAS NMR谱

室温下SO2 -4/ZrO2 催化剂 (SZ)上13 C标记的正丁烷异构化反应的原位13 CMASNMR谱研究结果表明 :其反应动力学符合Langmuir Hinshelwood一级可逆表面反应动力学公式 ,由该动力学公式计算得到的反应速率常数可以用于衡量固体催化剂的表面超强酸性 .这种新的表征方法显示采用一步 -醇热 -超临界干燥综合技术合成的SZ催化剂不仅比表面和硫酸根含量高 ,而且其超强酸性和异构化反应活性均明显优于常规法合成的催化剂 ,具有良好的应用前景 .     

Crystalline order in polyethylene: A 13C NMR CP/MAS solid-state T1 study

The carbon-13 spin-lattice relaxation times T₁ of the crystalline components of four solid ethylene-octene copolymers have been studied as a function of thermal history, branching number, and branching distribution. Slowly cooled samples (1 deg/min from melt to room temperature) exhibited similar or longer T₁s with respect to the same sample quench cooled (from the melt into 20°C water). The greater the degree of branching and the more homogeneous the branching distribution, the shorter were the observed crystal lattice T₁s. Differences of up to a factor of 3 in T₁ were observed for the same sample undergoing the two thermal treatments. Different degrees of branching homogeneity (for the same total number of branches) resulted in differences approaching a factor of 7 for samples with the same thermal history. These variations were attributed to the differing effects of side-chain disruption of the crystal lattice.     

Supramolecular assembly of dendritic polymers elucidated by 1H and 13C solid-state MAS NMR spectroscopy

Advanced solid-state NMR methods under fast magic-angle spinning (MAS) are used to study the structure and dynamics of large supramolecular systems, which consist of a polymer backbone with dendritic side groups and self-assemble into a columnar structure. The NMR experiments are performed on as-synthesized samples, i.e., no isotopic enrichment is required. The analysis of (1)H NMR chemical-shift effects as well as dipolar (1)H-(1)H or (1)H-(13)C couplings provide site-specific insight into the local structure and the segmental dynamics, in particular, of phenyl rings and -CH(2)O- linking units within the dendrons. Relative changes of (1)H chemical shifts (of up to -3 ppm) serve as distance constraints and allow protons to be positioned relative to aromatic rings. Together with dipolar spinning sideband patterns, pi-pi packing phenomena and local order parameters (showing variations between 30% and 100%) are selectively and precisely determined, enabling the identification of the dendron cores as the structure-directing moieties within the supramolecular architecture. The study is carried out over a representative selection of systems which reflect characteristic differences, such as different polymer backbones, sizes of dendritic side groups, or length and flexibility of linking units. While the polymer backbone is found to have virtually no effect on the overall structure and properties, the systems are sensitively affected by changing the generation or the linkage of the dendrons. The results help to understand the self-assembly process of dendritic moieties and aid the chemical design of self-organizing molecular structures.     

13C and proton NMR spectra of 2(1H)pyrazinones

¹³C and proton NMR spectra data are given for eleven 2(1H)pyraziones. Assignments of chemical shifts were made by methods which included: deuterium exchange with certain protons of 3-alkyl substituents; change of chemical shifts of certain carbon atoms with change in pH; the use of long-range coupling constants for ¹³C to protons; and various correlations among assigned spectra.     

A 1H and 13C NMR study of carminic acid

The ¹H and ¹³C NMR spectra of carminic acid were completely assigned, thus confirming its structure and the conformation of the glucose residue.     

An X-ray and 13C CP/MAS NMR study of C,C-linked bipyrazoles and bispyrazolylmethanes

4,4′-Methylene-bispyrazole (1) crystallizes in the P2₁/n space group with Z = 4, a = 5.4199(8) Å, b = 16.194(6) Å, c = 8.381(5) Å, β = 98.18(5)°. 4,4′-Methylene-bis (3,5-dimethylpyrazole) (2) crystallizes in the Pbca space group with Z = 8, a = 8.350(3) Å, b = 16.078(3) Å and c = 17.154(5) Å. Finally, 3,3′-bipyrazole (4) crystallizes in the P2₁/n space group with Z = 2, a = 5.465(2) Å, b = 5.491(3) Å, c = 10.058(4) Å and sol; = 92.88(2)°. The packing adopted by molecules 1 and 2 is related to the disposition of the pyrazole rings. In compound 4, all the molecules are joined to their neighbors by two double hydrogen bond systems forming zigzag chains. Using solid state ¹³C NMR spectroscopy, no dynamic proton transfer was observed in these crystals, and not on those of 3,5,3′,5′-tetramethyl-4,4′-bipyrazole (3) either.     

Variable temperature CP/MAS13C NMR study of cyclodextrin complexes of benzaldehyde

Fully hydrated as well as dried benzaldehyde complexes of - and -cyclodextrins were studied by using CP/MAS¹³C NMR techniques. Variable temperature studies have shown that below 200 K the guest is rigidly held in the complex, whereas at 328 K, only the aromatic ring performs rapid two-fold flips about the C₁–C₄ axis. In the -Cd complex the benzaldehyde performs more general reorientation. Removal of water causes marked changes in both guest and host spectra, generally consistent with a loss of short-range order and increase in guest motional rate.NRCC No. 27826.