Influence of Various Soluble Carbonates on the Hydration of Portland Cement studied by X-ray Diffraction.

The effect of limestone on the hydration of Portland cement has been studied by many researchers. However, a possible influence of adding more soluble carbonates was not explained. Therefore we executed a qualitative and quantitative research on the influence of slightly soluble (CaCO3, MgCO3, dolomite), medium soluble (Li2CO3) and highly soluble (K2CO3 and KHCO3) carbonates on the hydration. Blending of Portland cement with differently soluble carbonates was found to influence the hydrate assemblage of the hydrated cement. With the help of the Rietveld analysis, the study indicated that the amount of reacted carbonate in cement hydration at a 15% addition of slightly or medium soluble carbonates does not exceed 5% and is not affected by their solubility; at a 15% addition of the highly soluble carbonate K2CO3 the amount of reacted carbonate was around 6%. An increase in temperature (25 to 40 °C) gradually affects the rate of hydration and the quantity of stable phase assemblage.

Chemistry of Metal-organic Frameworks Monitored by Advanced X-ray Diffraction and Scattering Techniques.

The research on metal-organic frameworks (MOFs) experienced rapid progress in recent years due to their structure diversity and wide range of application opportunities. Continuous progress of X-ray and neutron diffraction methods enables more and more detailed insight into MOF's structural features and significantly contributes to the understanding of their chemistry. Improved instrumentation and data processing in high-resolution X-ray diffraction methods enables the determination of new complex MOF crystal structures in powdered form. By the use of neutron diffraction techniques, a lot of knowledge about the interaction of guest molecules with crystalline framework has been gained in the past few years. Moreover, in-situ time-resolved studies by various diffraction and scattering techniques provided comprehensive information about crystallization kinetics, crystal growth mechanism and structural dynamics triggered by external physical or chemical stimuli. The review emphasizes most relevant advanced structural studies of MOFs based on powder X-ray and neutron scattering.

New Mg-based 4,4'-biphenyldicarboxylate coordination polymer with layered crystal structure.

New magnesium 4,4'-biphenyldicarboxylate (BPDC) was solvothermally synthesized in the presence of N,N'-dimethylformamide (DMF). The crystal structure with formula Mg(3)(BPDC)(3)(DMF)(4) and denoted as NICS-7 was solved in monoclinic symmetry with space group Pn (no. 7) and unit cell parameters a = 12.6433(7) Å, b = 13.3950(5) Å, c = 19.9230(8) A, beta = 107.131(5) °. The structure consists of MgO(6) linear arranged trimers with common vertices connected through BPDC ligands forming extended 2-dimensional layered hybrid structure. Each terminal Mg atom within trimeric clusters is coordinated by two dimethylformamide molecules, respectively. Layers of Mg(3)(BPDC)(3)(DMF)(4) are stabilized by non-coordinated dimethylformamide molecules located within the voids in crystallographically disordered manner. Thermal properties of NICS-7 were determined by thermogravimetric and temperature-programmed X-ray diffraction. The structure remains stable only up to 50 °C. At higher temperatures, the removal of non-coordinated dimethylformamide molecules causes formation of amorphous Mg-BPDC phase.

Spectroscopic evidence for the structure directing role of the solvent in the synthesis of two iron carboxylates.

Crystal engineering: The synthesis of the known compounds MIL-100(Fe) and MIL-45(Fe) is characterized by spectroscopy. The products are obtained under identical conditions by varying the solvent from pure water to a mixture of water and acetone. The starting solution, the gel, and the final reaction product were characterized by X-ray absorption spectroscopy (see picture).

A new layered Ca-succinate coordination polymer.

A new layered Ca-succinate coordination polymer, poly[µ(3)-succinato-calcium(II)], [Ca(C(4)H(5)O(4))](n), was synthesized by reaction of CaCl(2)·2H(2)O and succinic acid in an aqueous medium under hydrothermal microwave conditions. The structure contains infinite layers of edge-sharing calcium pentagonal-bipyramidal polyhedra forming six-membered rings connected through succinate ligands. Such an assembly of inorganic building units is unique for calcium metal-organic framework-type structures. Adjacent layers are packed into a final pseudo-three-dimensional structure through weak C-H···O hydrogen bonds.

The phase (trans)formation and physical state of a model drug in mesoscopic confinement.

Compounds embedded into mesoporous or even microporous matrices are interesting for many emerging applications, such as novel catalysts, sensors, batteries, hydrogen storage materials or modern drug delivery devices. We report on two unexpected phenomena regarding the structural and dynamic properties of a model drug substance (indomethacin) when confined in mesoscopic matrices. Firstly, we show that the confinement directs the crystallization of the drug into a stable polymorph that is not otherwise formed at all; its relative amount depends on the pore size. This phenomenon is also explained theoretically using a modified classical heterogeneous nucleation theory. Secondly, we demonstrate that--even at relatively low volume fractions--the confined drug forms a condensed phase in a way that obstructs the passage of the pore channels. This may have far-reaching consequences for understanding the mechanisms of drug release from porous matrices.

Solid-state NMR spectroscopy and first-principles calculations: a powerful combination of tools for the investigation of polymorphism of indomethacin.

Two polymorphs of indomethacin were investigated by 1H MAS and CRAMPS, and 1H-13C CPMAS and HETCOR NMR techniques. The obtained spectra clearly elucidated the structural differences between the polymorphs, especially the different numbers of indomethacin molecules within the crystallographic asymmetric units and the different schemes of hydrogen bonding among the molecules. Known structure of indomethacin gamma was used in first-principles DFT/GIPAW calculations of 1H and 13C isotropic chemical shifts. Two packages, freely available Quantum Espresso and commercially available CASTEP, were employed. They both provided values that excellently agreed with the measured values, and thus allowed unambiguous assignment of 1H and 13C spectral lines.

MnO(x) nanoparticles supported on a new mesostructured silicate with textural porosity.

A two-step synthesis of a novel mesostructured silicate, KIL-2, and its manganese-containing analogue, Mn/KIL-2, has been developed. KIL-2 possesses interparticle mesopores with pore dimensions between 5 and 60 nm and a surface area of 448 m(2). The mesopores are formed by the aggregation of silica nanoparticles, which creates a network with interparticle voids. The particle size and the pore diameters depend on the temperature of the ageing step (first step) and on the solvothermal treatment in ethanol (second step), respectively. Mn/KIL-2 contains octahedrally coordinated Mn(3+) (80%) and tetrahedrally coordinated Mn(2+) (20%) ions. Mn(3+) ions are present in the extra-framework MnO(x) nanoparticles with typical dimensions of 2 nm, which are homogeneously distributed throughout the material. Mn(2+) ions occur as isolated manganese framework sites. The material is also able to retain its structure characteristics after the hydrothermal treatment in boiling water. Because of its non-toxic nature and cost-effective synthesis, Mn/KIL-2 thus exhibits properties that are needed for an environment-friendly catalyst.

Removal of aqueous manganese using the natural zeolitic tuff from the Vranjska Banja deposit in Serbia.

The natural zeolite tuff from the Vranjska Banja deposit (Serbia) has been studied as sorbent for Mn(II) ions from aqueous solutions. The zeolite sample containing mainly clinoptilolite (more than 70%) removes Mn(II) ions by ion-exchange process, which was confirmed by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray analysis (EDXS). XPS showed that there is no surface accumulation of Mn but an almost uniform distribution inside the sorbent; EDXS confirmed that Mn(II) replaced the clinoptilolite Na counter ions. The sorption isotherms were studied at 298 K by batch experiments showing that the Mn(II) removal is best described by the Langmuir-Freundlich or Sips model. The kinetics followed the pseudo-second-order model, the activation energy being 128 kJ mol(-1). The intra-particle diffusion is not the rate-controlling step in the sorption of Mn(II) on clinoptilolite. Thermodynamic data suggest spontaneity of the endothermic ion-exchange process in the 298-338 K range.

Measuring distances between half-integer quadrupolar nuclei and detecting relative orientations of quadrupolar and dipolar tensors by double-quantum homonuclear dipolar recoupling nuclear magnetic resonance experiments.

We studied the possibility of using double-quantum homonuclear dipolar recoupling magic angle spinning nuclear magnetic resonance experiments for structural analysis of systems of half-integer quadrupolar nuclei. We investigated symmetry-based recoupling schemes R2(2) (1) and R2(2) (1)R2(2) (-1) and showed that the obtained double-quantum filtered signals depend substantially on magnitudes and relative orientations of dipolar and quadrupolar tensors. Experimental results measured on aluminophosphate molecular sieve AlPO(4)-14, containing dipolar-coupled spin-52 aluminum nuclei, were compared to results of time-consuming numerical simulations. The comparison for short mixing times allowed us to roughly measure internuclear Al-Al distances, if constraints about relative tensor orientations were available. Inspection of relative orientations of dipolar and quadrupolar tensors, using known distances between nuclei, required experimental and simulated data for long mixing times and yielded less accurate results. Two experimental protocols were employed for measuring double-quantum filtered curves, the symmetric protocol, in which excitation and reconversion periods are incremented simultaneously, and the asymmetric protocol, in which only the length of the excitation period is incremented and the length of the reconversion period is kept constant. The former experimental protocol was more convenient for the detection of internuclear distances, and the latter one was more appropriate for the inspection of relative orientations of interaction tensors.

31P NMR as a tool for studying incorporation of Ni, Co, Fe, and Mn into aluminophosphate zeotypes.

The incorporation of moderate amounts of Ni(II), Co(II), Fe(II/III), and Mn(II/III) into aluminophosphate zeotype AlPO4-34 and Fe(II/III) into aluminophosphate zeotype AlPO4-36 was studied by broadline 31P NMR. The technique provided direct evidence on isomorphous substitution of framework aluminum by transition metals and allowed us to determine the extent of the substitution. 31P NMR proved to be complementary to other spectroscopic techniques such as X-ray absorption spectroscopy (XAS), Mössbauer, electron paramagnetic resonance (EPR), and electron nuclear double resonance (ENDOR) spectroscopies. The position of the NMR signal belonging to phosphorus in the P(OAl)3(OMe) environment depended mostly on the magnitude of the hyperfine interaction between a phosphorus nucleus and an unpaired electron, which was delocalized from the transition metal atom Me by covalent bonding. The width of the NMR signal was dominated by dipolar coupling among phosphorus nuclei and nearest paramagnetic centers. In addition, broadline NMR of ethylenediamine-templated manganese phosphate (C2H10N2)[Mn2(HPO4)3(H2O)], which was used as a model compound, showed that on the basis of line positions and line widths different 31P signals could easily be assigned to different phosphorus crystallographic sites. The technique could thus be applied to extract valuable structural information about metal phosphates as well.

Enhancing sensitivity or resolution of homonuclear correlation experiment for half-integer quadrupolar nuclei.

We have recently introduced double-quantum homonuclear correlation NMR experiment for half-integer quadrupolar nuclei in solids, which was based on rotary resonance recoupling [J. Chem. Phys. 120 (2004) 2835]. In this contribution we show on two 23Na (I=3/2) containing samples, Na2SO4 and Na2HPO4, that the efficiency of the experiment can be substantially enhanced by adding rotor assisted population transfer (RAPT) and Carr-Purcell-Meiboom-Gill (CPMG) sequences to it. We also present an upgraded two-dimensional experiment, in which double- and six-quantum coherences are correlated during t1 evolution period, yielding a high-resolution isotropic spectrum along an indirectly detected dimension. The sensitivity of the upgraded experiment is, however, greatly reduced compared to the sensitivity of the original experiment, so that its application is feasible only when RAPT and CPMG can be used as well.

Atomic force microscopy study of the molecular sieve MnAPO-50.

Atomic force microscopy (AFM) imaging of MnAPO-50 reveals multiply-nucleated, elliptical terraces, oriented in registry with the facet edges with step heights ranging from one to six template repeat distances on the [100] facets and terraces with step heights ranging from one to thirty three times the c unit cell parameter on the [001] facets.

Synthesis, structural and spectroscopic properties of two new ethylenediamine-templated gallophosphate-oxalate layered materials.

Two new layered gallophosphate-oxalate materials have been prepared hydrothermally using ethylenediamine and oxalic acid as structure-directing agents. The compounds (C2N2H10)2[Ga2(C2O4)2(HPO4)3].H2O 1 and (C2N2H10)3- [Ga4(C2O4)4(HPO4)4(H2PO4)2] 2 are closely related, consisting of anionic double chains built of alternating paris of GaO6 and HPO4 polyhedra. These double chains are linked via bridging HPO4 or H2PO4 tetrahedra to form corrugated layers containing eight-membered rings. The oxalate group acts as a bidentate ligand to each of the GaO6 octahedron. The corrugated layers are held together by strong to weak hydrogen-bonding interactions between oxalate groups, water and diprotonated ethylenediamine molecules, and the framework components. The compounds were characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and infrared and Raman spectroscopy. Crystal data for 1: monoclinic, space group P21/C (No. 14), a = 6.355(1) A, b = 39.362(8) A, c = 9.249(2) A, beta = 106.7(1) degrees, Z = 2. Crystal data for 2: triclinic, space group P1 (No. 2), a = 8.730(1) A, b = 11.575(1) A, c = 11.696(1) A, alpha = 115.12(1) degree, beta = 90.07(1) degree, gamma = 111.23(1) degree, Z = 2.