Hybrid E-cinnamate- and Z-cinnamate-intercalated layered double hydroxides (Mg2Al- E- or Z-Cin LDH and Zn2Al- E- or Z-Cin LDH) were prepared by the co-precipitation method, and structurally characterised by powder X-ray diffractometry, UV–Vis, FT-IR and 13C CP MAS solid-state NMR spectroscopies to gain further insights on the arrangement of the organic anions in the interlamellar domain. UV light irradiation induced E–Z isomerisation reaction was subsequently attempted in the solid state and in methanolic suspension. Although reaction was observed in the solid state; however, E–Z isomerisation mainly occurred in the slurry phase. The fact that there was no isomerisation when E-Cin was solely adsorbed on the surfaces of pristine LDHs highlights that the reaction took place in the interlayer region. Similar behaviour was observed for the two LDH compositions proving that the LDH structures acted as nanoreactors confining the photoinduced isomerisation.

Nowadays there is a growing need for user friendly workflow editors in all fields of scientific research. A special interest group is present at big physics research facilities where instrumentation is mostly controlled by a robust and reliable low level control software solution. Different types of specific experiments using predetermined automated protocols and on-line data processing with real-time feedback require a more flexible and abstract high level control system[1]. Beside flexibility and dynamism, easy usability is also required for researchers collaborating from several different fields. Tentatively, to test the ease and flexible usability, the Kepler workflowengine was integrated with TANGO[2]. It enables researchers to automate and document experiment protocols without any programming skill. The X-ray crystallography laboratory at the Biological Research Center of Hungarian Academy of Science (BRC) has implemented an example crystallographic workflow to test the integrated system. This development was performed in cooperation with ELI-ALPS.

The single-crystal structures of calcium D-gluconate and calcium α-D-isosaccharinate have been determined using X-ray diffraction at 100 K. Surprisingly, given its significance in industrial and medical applications, the structure of calcium D-gluconate has not previously been reported. Unexpectedly, the gluconate crystal structure comprises coordination polymers. Unusually, the calcium coordination number is nine. Adjacent metal centres are linked by three μ-oxo bridges, with a metal–metal separation of 3.7312 (2) Å. One of the gluconate ligands contradicts a suggestion from 1974 that a straight chain conformation is associated with an intramolecular hydrogen bond. This ligand binds to three adjacent metal centres. The use of synchrotron radiation provided an improved crystal structure with respect to that previously reported for the isosaccharinate complex, allowing the location of the hydroxy hydrogen sites to be elucidated. In contrast to the gluconate structure, there are no μ-oxo bridges in the isosaccharinate coordination polymer and the isosaccharinate bridging coordination is such that the distance between adjacent metal centres, each of which is eight-coordinate, is 6.7573 (4) Å. Complementing the crystal structure determinations, modelling studies of the geometries and coordination modes for the aqueous [CaGluc] + and [CaIsa] + complexes are presented and discussed.

General method for the naming of the studied cinnamic acids:A few examples for the shortened names: E3Ph -cinnamic acid (E-3-phenylpropenoic acid (1/E))Z2Ph33P -Z-2-phenyl-3-(3-pyridyl)propenoic acid Z -"Z" instead of "E" before the shorthand names of the materials listed above, means the Z isomer M -at the end of the shorthand names of the materials listed above, means the individual monomer D -at the end of the shorthand names of the materials listed above, means the dimer kept together by double hydrogen bonds between the carboxylic groups T -at the end of the shorthand names of the materials listed above, means the tetramer built up from two dimers via (aromatic)C-H…X hydrogen bond between the aromatic rings Me -at the end of the shorthand names of the materials listed above, means the methyl ester of the corresponding cinnamic acid derivative O -at the end of the shorthand names of the materials listed above, means the octylester of the corresponding cinnamic acid derivative ZW -at the end of the shorthand names of the materials listed above, means that the pyridyl derivatives are in the zwitterionic forms EWG -electron withdrawing group List of Abbreviations VIII Ar -aromatic group Ph -phenyl group R -substituent X -heteroatom (O,N,S) Hlg -halogen (F, Cl, Br, I) Ac -acetyl group Me -methyl group Et -ethyl group Pr -propyl group MeO -methoxy group EtO -ethoxy group TEA -triethylamine THF -tetrahydrofuran DMSO -dimethyl sulfoxide DMF -N,N-dimethylformamide MeOH -methanol EtOH -ethanol AcOH -acetic acid EtOAc -ethyl acetate Ac2O -acetic anhydride KHMDS -potassium bis(trimethylsilyl)amide t-BuOK -potassium tert-butoxide DMAP -4-(dimethylamino)pyridine PPE -polyphosphate ester TBAB -tetrabutylammonium bromide TMS -tetramethylsilane TMSO -trimethylsilyloxy group DSS -4,4-dimethyl-4-silapentane-1-sulphonic acid METHODS MALDI-MS -matrix-assisted laser desorption/ionization mass

The conformational as well as the structure-forming properties of E-3-(x-pyridyl)propenoic acids (x=2, 3 or 4) have been studied with a combination of computational and spectroscopic methods. IR spectroscopy revealed that in the solid state the zwitterionic species predominate, while NMR measurements showed that dimers, kept together by strong CO⋯HO hydrogen bonds, were formed in a dipolar aprotic solvent (DMSO). In concentrated solution, extended aggregation occurred through the cooperative effect of (aromatic) CH⋯N weak hydrogen bonds. Conformational search was performed at the HF/6-31G(d,p) level of theory. Comparison with experimental values as well as benchmarking calculations at several different levels of theory to probe the performance of the methods, B3LYP/6-31G++(d,p) method was found to be able to provide reasonable geometries as well as quantitative formation energies for the dimers and the tetramers, too.

Following a preliminary exploration of the conformational space by the PM3 and HF/6-31 G* ab initio methods the conformational characteristics of the scarcely available Z isomer of an α-pyridyl-substituted cinnamic acid dimer [Z-2(3′-pyridyl)-3-phenylpropanoic acid] was studied by NMR spectroscopy (NOESY measurements) in DMSO(d6), methanol(d4) and chloroform(d1). Calculations predicted that full conjugation was overruled by steric interactions and the rotation of the pyridyl ring was not restricted. NOESY measurements verified indeed that in all three solvents the pyridyl group was virtually freely rotating, while some restriction applied for that of the phenyl group.

Self-assembling layers were formed from sulfur-containing cinnamic acid analogues over polycrystalline Au surface. The horizontal organising forces were strong O–H⋯O and weaker C–H⋯S hydrogen bonds (the former interaction kept together the acid dimers serving as the fundamental unit, while the latter was crucial in the construction of the 2D layers), while the vertical organisation forces were provided by Au–S covalent bonds. Measurements by atomic force, scanning electron, infrared and Raman microscopies attested that the dimers were situated in a nearly perpendicular fashion to the Au surface providing a ∼30–40nm thick organic “carpet” and out of this layer occasionally, peaks with height of ∼100–120nm grew out. The outgrowth of these surface structures were most probably governed by the defects of the polycrystalline metal surface.

Supported gold catalysts are highly active in oxidation reactions. Beside the most frequently studied CO oxidation, they are readily applied in the epoxidation of more or less complex olefinic compounds using air or oxygen directly or other oxidants like peroxides of various kinds. Less frequently though, the reverse reaction, ring opening with single or double C–O scission is also investigated. These and other ring making and breaking reactions are reviewed, and the catalytic roles of gold species are described.

Various propenoic acid stereoisomers 2,3-disubstituted with thienyl and/or phenyl groups were synthesised and their aggregation behaviour was studied both in solution and in the solid state by experimental (mid-range FT-IR spectroscopy) and computational (semiempirical and ab initio) methods. Experimental approach embraced the identification of potential hydrogen bonding sites through finding the relevant IR bands and monitoring their displacement upon increasing the acid concentration in solution and on going from solution to the solid state. In solution OH⋯O hydrogen bonds were only found providing short-range ordering, while in the solid state CH⋯S hydrogen bonds were identified. Hydrogen bonding sites could be assigned and relevant aggregate models could be built. Molecular modelling allowed obtaining good estimates for hydrogen bond lengths and angles and visualisation of the geometric arrangements.

Self-assembling layers of Z-2(3′-pyridyl)-3-phenyl propenoic acid molecules were built on silver and gold films prepared by pulsed laser deposition. The dip-coating technique was used for depositing the organic material onto the metals. The clean metal surfaces were studied by scanning electron microscopy, and the organic structures formed over the metal surfaces were investigated by FT-IR microspectroscopy and atomic force microscopy. Various surface structures were identified and their rationalisation was attempted.