scholarly journals Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time 13C CP-MAS solid-state NMR characterization

2015 ◽  
Vol 11 ◽  
pp. 2785-2794 ◽  
Author(s):  
Isabelle Mallard ◽  
Davy Baudelet ◽  
Franca Castiglione ◽  
Monica Ferro ◽  
Walter Panzeri ◽  
...  
Keyword(s):  
Solid State ◽  
Contact Time ◽  
Magic Angle Spinning ◽  
Proton Spin ◽  
Fine Tuning ◽  
Spin Lattice Relaxation ◽  
Molar Ratio ◽  
Magic Angle ◽  
Cross Polarization ◽  
Nmr Characterization

The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state 13C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices.

A Cross-Polarization Magic-Angle Spinning 13C NMR Characterization of the Stable Solid-State Forms of Cimetidine

1997 ◽  
Vol 86 (12) ◽  
pp. 1400-1402 ◽  
Author(s):  
David A. Middleton ◽  
Cecile S. Le Duff ◽  
Frederic Berst ◽  
David G. Reid
Keyword(s):  
Solid State ◽  
13C Nmr ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
Cross Polarization ◽  
Nmr Characterization ◽  
Angle Spinning

scholarly journals CP MAS kinetics and impedance spectroscopy studies of local disorder in low-dimensional H-bonded proton-conducting materials

2019 ◽  
Vol 59 (3) ◽  
Author(s):  
Laurynas Dagys ◽  
Sergejus Balčiūnas ◽  
Jûras Banys ◽  
Feliksas Kuliešius ◽  
Vladimir Chizhik ◽  
...  
Keyword(s):  
Impedance Spectroscopy ◽  
Spin Diffusion ◽  
Lattice Relaxation ◽  
Magic Angle Spinning ◽  
Proton Spin ◽  
Spin Lattice Relaxation ◽  
Magic Angle ◽  
Coupling Constant ◽  
Spin Lattice ◽  
Local Disorder

The 1H–13C cross-polarization magic angle spinning (CP MAS) kinetics was studied in poly(vinyl phosphonic acid) (pVPA), i.e. material with high degrees of freedom of proton motion along H-bonded chains. It has been shown that the CP kinetic data for the adjacent 1H–13C spin pairs can be described in the frame of the isotropic spin-diffusion approach. The rates of spin diffusion and spin-lattice relaxation as well as the parameters accounting for spin coupling and the effective size of spin clusters have been determined. The local order parameter S ≈ 0.63±0.02, determined as the ratio of the measured dipolar 1H–13C coupling constant and the calculated static dipolar coupling constant, is significantly lower than the values deduced for related sites in other polymers and in series of amino acids. This means that the local disorder of the C–H bonds in pVPA is between those for rather rigid C–H bond configurations having S = 0.8–1.0 and highly disordered –CH3 groups (S ~ 0.4). This effect can be attributed to the presence of the proton transfer path where proton motion is easy to activate. The activation energy for the proton motion Ea = 59±7 kJ/mol was determined from the impedance spectroscopy data analysing the temperature and frequency dependences of the complex dielectric permittivity of pVPA. The rates of proton spin-lattice relaxation and spin diffusion are of the same order and both run in the time scale of milliseconds.

scholarly journals New Condensation Polymer Precursors Containing Consecutive Silicon Atoms—Decaisopropoxycyclopentasilane and Dodecaethoxyneopentasilane—And Their Sol–Gel Polymerization

Polymers ◽  
2019 ◽  
Vol 11 (5) ◽  
pp. 841
Author(s):  
Sung Jin Park ◽  
Myong Euy Lee ◽  
Hyeon Mo Cho ◽  
Sangdeok Shim
Keyword(s):  
Solid State ◽  
Sol Gel ◽  
Magic Angle Spinning ◽  
Magic Angle ◽  
Cross Polarization ◽  
Reaction Conditions ◽  
Polymer Precursors ◽  
Sol Gel Process ◽  
Angle Spinning ◽  
Magnetic Resonances

The sol–gel polymerization of alkoxysilanes is a convenient and widely used method for the synthesis of silicon polymers and silicon–organic composites. The development of new sol–gel precursors is very important for obtaining new types of sol–gel products. New condensation polymer precursors containing consecutive silicon atoms—decaisopropoxycyclopentasilane (CPS) and dodecaethoxyneopentasilane (NPS)—were synthesized for the preparation of polysilane–polysiloxane material. The CPS and NPS xerogels were prepared by the sol–gel polymerization of CPS and NPS under three reaction conditions (acidic, basic and neutral). The CPS and NPS xerogels were characterized using N2 physisorption measurements (Brunauer–Emmett–Teller; BET and Brunauer-Joyner-Halenda; BJH), solid-state CP/MAS (cross-polarization/magic angle spinning) NMRs (nuclear magnetic resonances), TEM, and SEM. Their porosity and morphology were strongly affected by the structure of the precursors, and partial oxidative cleavage of Si-Si bonds occurred during the sol–gel process. The new condensation polymer precursors are expected to expand the choice of approaches for new polysilane–polysiloxane.

Applications of high-resolution 13C and 15N n.m.r. of solids

1981 ◽  
Vol 299 (1452) ◽  
pp. 593-608 ◽  
Keyword(s):  
High Resolution ◽  
Spin Diffusion ◽  
Magic Angle Spinning ◽  
Spin Lattice Relaxation ◽  
Spatial Proximity ◽  
Magic Angle ◽  
Rotating Frame ◽  
Cross Polarization ◽  
Relaxation Rates ◽  
Relaxation Parameters

The combination of cross polarization, dipolar decoupling and magic angle spinning results in liquid-like high-resolution 13 C and 15 N n.m.r. spectra of a wide variety of solid materials. Structural determinations based on such 13 C n.m.r. spectra include the measurement of the extent to which pyrolysed polyacrylonitrile fibres (Orion) retain aliphatic character during the first step of the production of a carbon fibre, the determination of the chemical identity of the cross links formed from an acetyleneterminated polyimide resin, and the characterization of the metabolic products of a bacterial fermentation of wood lignin. All of these non-destructive analyses are performed on intact heterogeneous samples. The high resolution of the carbon experiment can also be exploited by obtaining proton spin-lattice relaxation parameters for chemically different protons in solids. Because of spin diffusion, these parameters are dependent on spatial proximity and so are helpful in measuring the homogeneity of solid blends of polymers such as poly(phenylene oxide) and polystyrene. High-resolution 13 C n.m.r. spectra of polymers can also be used for measuring microscopic chain dynamics. 13 C rotating-frame relaxation parameters observed for polycarbonate and poly (ethylene terephthalate) are related to the effects on motion of annealing, additives and structural substitutions. Individual relaxation rates are observed for individual carbons, so the behaviour of side groups is cleanly separated from that of the main chain. All of the line-narrowing and sensitivity-enhancing techniques applied to 13 C n.m.r. of solids work equally well for 15 N n.m.r. Use of 15 N rotating-frame and cross-polarization parameters leads to the assessment of the relative concentrations of 13 C - 15 N and 12 C - 15 N pair concentrations in the main chains of multiply labelled proteins. Such measurements can be used to characterize the rate of protein turnover in fully expanded soybean leaves, as well as the details of protein synthesis in cultured soybean cotyledons.

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