Marko Bertmer

Dephasing of spin echoes by multiple heteronuclear dipolar interactions in rotational echo double resonance NMR experiments.

The application of rotational echo double resonance (REDOR) nuclear magnetic resonance (NMR) for accurate distance measurements has thus far been largely restricted to isolated heteronuclear two-spin systems. In the present paper, the informational content of REDOR curves is explored for systems characterized by multi-spin interactions. To this end, numerical REDOR simulations are presented for cases in which single observe spins S are dipolarly coupled to groups of spins I in distinct geometries. To develop the utility of REDOR for characterizing dipolar couplings in unknown and/or ill-defined geometries, the validity ranges and systematic errors of certain analytical approximations are studied. In the limit of short dipolar evolution times where 0 < deltaS/S0 < or = 0.2 to 0.3, the REDOR difference signal intensity increases approximately proportional to the square of the dipolar evolution time. Here, the curvature depends simply on the second moment M2 characterizing the overall strength of the heterodipolar coupling, irrespective of specific molecular geometries. Fitting experimental REDOR data in this manner produces slight systematic underestimates of M2. However, these errors tend to be counterbalanced by additional systematic errors made by neglecting weak couplings to more remote spins and distribution effects caused by disorder. Based on these findings, the results suggest a convenient method of obtaining site-resolved second moment information in disordered materials.

Fabrication of alginate–gelatin crosslinked hydrogel microcapsules and evaluation of the microstructure and physico-chemical properties

Microencapsulation of cells by using biodegradable hydrogels offers numerous attractive features for a variety of biomedical applications including tissue engineering. This study highlights the fabrication of microcapsules from an alginate-gelatin crosslinked hydrogel (ADA-GEL) and presents the evaluation of the physico-chemical properties of the new microcapsules which are relevant for designing suitable microcapsules for tissue engineering. Alginate di-aldehyde (ADA) was synthesized by periodate oxidation of alginate which facilitates crosslinking with gelatin through Schiffs base formation between the free amino groups of gelatin and the available aldehyde groups of ADA. Formation of Schiffs base in ADA-GEL and aldehyde groups in ADA was confirmed by FTIR and NMR spectroscopy, respectively. Thermal degradation behavior of films and microcapsules fabricated from alginate, ADA and ADA-GEL was dependent on the hydrogel composition. The gelation time of ADA-GEL was found to decrease with increasing gelatin content. The swelling ratio of ADA-GEL microcapsules of all compositions was significantly decreased, whereas the degradability was found to increase with the increase of gelatin ratio. The surface morphology of the ADA-GEL microcapsules was totally different from that of alginate and ADA microcapsules, observed by SEM. Two different buffer solutions (with and without calcium salt) have an influence on the stability of microcapsules which had a significant effect on the gelatin release profile of ADA-GEL microcapsules in these two buffer solutions.

Deactivation and regeneration of a naphtha reforming catalyst

Abstract A series of naphtha reforming catalysts from different stages of the deactivation (coking) and the regeneration (decoking) processes were investigated by NMR and chemical engineering methods. The dependence of the tortuosity on the coke content was determined for both processes by NMR measurements of the intraparticle self-diffusion coefficients of adsorbed liquid n -heptane. The shrinkage of the accessible pore volume as a function of increasing coke content due to the deactivation process is compared to nitrogen adsorption (BET) measurements which show an equivalent behavior. A crude model was adapted to predict qualitatively the relationship between the tortuosity and the average pore diameter. Longitudinal ( T 1 ) and transverse ( T 2 ) NMR relaxation times measured for protons of adsorbed liquid n -heptane, provide information on the pore morphology changes which can be corroborated by the tortuosity measurements. The chemical composition of the coke layer, which was investigated by 1 H magic angle spinning (MAS) and 13 C cross polarization (CP)/MAS NMR spectroscopy, is shown to change during both deactivation and decoking processes. Moreover, the micro-structure of the fresh catalyst and the fully regenerated catalyst was investigated by scanning electron microscopy (SEM). The experimental results indicate that a full recovery of the activity of the clean catalyst is not achieved by the regeneration process, and that the quality of regeneration depends on the coke content reached during the deactivation/regeneration cycle.

Water-mediated proton conduction in a robust triazolyl phosphonate metal-organic framework with hydrophilic nanochannels.

The development of water-mediated proton-conducting materials operating above 100 °C remains challenging because the extended structures of existing materials usually deteriorate at high temperatures. A new triazolyl phosphonate metal-organic framework (MOF) [La3L4(H2O)6]Cl⋅x H2O (1, L(2-) = 4-(4H-1,2,4-triazol-4-yl)phenyl phosphonate) with highly hydrophilic 1D channels was synthesized hydrothermally. Compound 1 is an example of a phosphonate MOF with large regular pores with 1.9 nm in diameter. It forms a water-stable, porous structure that can be reversibly hydrated and dehydrated. The proton-conducting properties of 1 were investigated by impedance spectroscopy. Magic-angle spinning (MAS) and pulse field gradient (PFG) NMR spectroscopies confirm the dynamic nature of the incorporated water molecules. The diffusivities, determined by PFG NMR and IR microscopy, were found to be close to that of liquid water. This porous framework accomplishes the challenges of water stability and proton conduction even at 110 °C. The conductivity in 1 is proposed to occur by the vehicle mechanism.

Combined proton NMR wideline and NMR relaxometry to study SOM-water interactions of cation-treated soils

Abstract Focusing on the idea that multivalent cations affect SOM matrix and surface, we treated peat and soil samples by solutions of NaCl, CaCl2 or AlCl3. Water binding was characterized with low field 1H-NMR-relaxometry (20 MHz) and 1H wideline NMR spectroscopy (400 MHz) and compared to contact angles. From 1H wideline, we distinguished mobile water and water involved in water molecule bridges (WaMB). Large part of cation bridges (CaB) between SOM functional groups are associated with WaMB. Unexpectedly, 1H NMRrelaxometry relaxation rates suggest that cross-linking in the Al-containing peat is not stronger than that by Ca. The relation between percentage of mobile water and WaMB water in the context of wettability and 1H NMR relaxation times confirms that wettability controls the water film surrounding soil particles. Wettability is controlled by WaMB-CaB associations fixing hydrophilic functional groups in the SOM interior. This can lead to severe water repellency. Wettability decreases with increasing involvement of functional groups in CaB-WaMB associations. The results demonstrate the relevance of CaB and WaMB for the dynamics of biogeochemical and hydrological processes under field conditions, as only a few percent of organic matter can affect the physical, chemical, and biological functioning of the entire 3-phase ecosystem.

Restructuring of a Peat in Interaction with Multivalent Cations: Effect of Cation Type and Aging Time

It is assumed to be common knowledge that multivalent cations cross-link soil organic matter (SOM) molecules via cation bridges (CaB). The concept has not been explicitly demonstrated in solid SOM by targeted experiments, yet. Therefore, the requirements for and characteristics of CaB remain unidentified. In this study, a combined experimental and molecular modeling approach was adopted to investigate the interaction of cations on a peat OM from physicochemical perspective. Before treatment with salt solutions of Al3+, Ca2+ or Na+, respectively, the original exchangeable cations were removed using cation exchange resin. Cation treatment was conducted at two different values of pH prior to adjusting pH to 4.1. Cation sorption is slower (>>2 h) than deprotonation of functional groups (<2 h) and was described by a Langmuir model. The maximum uptake increased with pH of cation addition and decreased with increasing cation valency. Sorption coefficients were similar for all cations and at both pH. This contradicts the general expectations for electrostatic interactions, suggesting that not only the interaction chemistry but also spatial distribution of functional groups in OM determines binding of cations in this peat. The reaction of contact angle, matrix rigidity due to water molecule bridges (WaMB) and molecular mobility of water (NMR analysis) suggested that cross-linking via CaB has low relevance in this peat. This unexpected finding is probably due to the low cation exchange capacity, resulting in low abundance of charged functionalities. Molecular modeling demonstrates that large average distances between functionalities (∼3 nm in this peat) cannot be bridged by CaB-WaMB associations. However, aging strongly increased matrix rigidity, suggesting successive increase of WaMB size to connect functionalities and thus increasing degree of cross-linking by CaB-WaMB associations. Results thus demonstrated that the physicochemical structure of OM is decisive for CaB and aging-induced structural reorganisation can enhance cross-link formation.

Hydroisomerization of long-chain paraffins over nano-sized bimetallic Pt–Pd/H-beta catalysts

The hydroisomerization of long-chain n-paraffins was studied in the temperature range of 205–230 °C at pH2 = 50 bar using a pilot-scale trickle-bed continuous-flow reactor over bimetallic catalysts consisting of mixtures of platinum and palladium supported on commercially available nano-sized zeolite beta (nSi/nAl = 12.5 and 25, respectively) extruded with an alumina binder. For n-hexadecane conversion, high yields of isomers (25 and 45 wt.% of mono- and multibranched isomers, respectively) without extensive cracking (>10 wt.%) were obtained at a conversion of 80%. Long-term tests with n-hexadecane and blends of solid n-paraffins for 30–60 days on-stream clearly indicate that a minor loss in catalyst activity can easily be compensated for by increasing the reaction temperature from 220 °C to 225 °C. The zeolite with a “mild acidity” exhibits a low hydrocracking activity with isomerization yields of up to 70 wt.% and high stability over more than 60 days on-stream. Carbonaceous deposits formed during n-paraffin hydroisomerization were investigated by elemental analysis, TGA, ATR-FTIR and 13C MAS NMR spectroscopy, showing the formation of hydrogen-rich coke which leads to pore blocking.

Alkali metal copper acetylides ACuC2 (A = Na-Cs): synthesis, crystal structures and spectroscopic properties

Abstract By reaction of CuI and A2C2 (A = K, Rb, Cs) suspended in liquid ammonia and subsequent heating of the remaining residue in vacuum ternary alkali metal copper acetylides ACuC2 were accessible. NaCuC2 could be obtained by decomposing NaCu5C6, which was synthesized from NaC2H and CuI in liquid ammonia. The crystal structures were determined by both X-ray and neutron powder diffraction. In all compounds 1 ∞ [ Cu ( C 2 ) 2/2 − ] chains are the characteristic structural motif. In NaCuC2 and β-RbCuC2 these chains are orientated parallel to the c axis of a tetragonal unit cell (KAgC2 type, P4/mmm, Z=1), whereas in KCuC2, α-RbCuC2 and CsCuC2 these chains are arranged in layers perpendicular to the c axis of a tetragonal unit cell (CsAgC2 type, P42/mmc, Z=2). These layers are staggered along the c axis by rotating them by 90° to each other. The alkali metal ions separate the copper carbon chains. Raman spectroscopic investigations indicate the existence of CC triple bonds, as the frequencies of the CC stretching vibration are comparable to those found for acetylene and ternary silver and gold acetylides. In the 13C MAS NMR spectra of KCuC2, RbCuC2 and CsCuC2 the isotropic signals are complicatedly split due to the coupling to the nearby quadrupolar copper nuclei, but the chemical shifts are in the range found for other acetylides with CC triple bonds.

Size effects of aromatic substitution in the ortho position on the photodimerization kinetics of alpha-trans cinnamic acid derivatives. A solid-state NMR study.

The photoreaction of two alpha-cinnamic acid derivatives, alpha-o-methoxy and alpha-o-ethoxy cinnamic acid, was studied by (13)C CPMAS solid-state NMR spectroscopy in order to elucidate effects of aromatic substitution and substituent size on the kinetics of the [2+2] photodimerization. The reactants and products can be clearly differentiated and a detailed spectroscopic characterization was carried out, including 2D PASS spectra, at a low spinning frequency to determine the principal values of the chemical shift tensor. Density functional theory (DFT) calculations of chemical shifts and chemical shift anisotropy tensors were found to be in good agreement with the experimental results and helped in the individual assignments of reactant and photoproduct carbon atoms. The photoreaction kinetics show no systematic variation with substituent size, in that the alpha-o-methoxy cinnamic acid progresses at a slower rate than unsubstituted alpha-cinnamic acid, but alpha-o-ethoxy cinnamic acid at a faster one. Interestingly, the distance between reacting double bonds is not a good indicator of photoreaction rate. The observed trend is in part due to a larger degree of reorientation of the aromatic ring for the o-methoxy cinnamic acid, and a more dominant interaction appears to be the p-orbital overlap between two reacting double bonds in determining the reaction kinetics.

113Cd solid-state NMR for probing the coordination sphere in metal-organic frameworks.

Spectroscopic techniques are a powerful tool for structure determination, especially if single-crystal material is unavailable. (113)Cd solid-state NMR is easy to measure and is a highly sensitive probe because the coordination number, the nature of coordinating groups, and the geometry around the metal ion is reflected by the isotropic chemical shift and the chemical-shift anisotropy. Here, a detailed investigation of a series of 27 cadmium coordination polymers by (113)Cd solid-state NMR is reported. The results obtained demonstrate that (113)Cd NMR is a very sensitive tool to characterize the cadmium environment, also in non-single-crystal materials. Furthermore, this method allows the observation of guest-induced phase transitions supporting understanding of the structural flexibility of coordination frameworks.