Temperature induced rotation in a [4.4]cyclophane

The synthesis, the X-ray, NMR and molecular modeling structure determination of a new orthopara[4.4]cyclophane are reported. The similarity of the π(CO)-π(Ar) driven conformational equilibrium of this compound to the work of an amusement ride machinery is also revealed.     

Protein–Inorganic Array Construction: Design and Synthesis of the Building Blocks

Herein we describe the design and synthesis of the first series of di‐functional ligands for the directed construction of inorganic‐protein frameworks. The synthesized ligands are composed of a metal‐ion binding moiety (terpyridine‐based) conjugated to an epoxysuccinyl peptide, known to covalently bind active cysteine proteases through the active‐site cysteine. We explore and optimize two different conjugation chemistries between the di‐functionalized metal‐ion ligand and the epoxysuccinyl‐containing peptide moiety: peptide‐bond formation (with limited success) and Cu^I‐catalysed click chemistry (with good results). Further, the complexation of the synthesized ligands with Fe^II and Ni^II ions is investigated: the di‐functional ligands are confirmed to behave similarly to the parent terpyridine. As designed, the peptidic moiety does not interfere with the complexation reaction, in spite of the presence of two triazole rings that result from the click reaction. ES‐MS together with NMR and UV/Vis studies establish the structure, the stoichiometry of the complexation reactions, as well as the conditions under which chemically sensitive peptide‐containing polypyridine ligands can undergo the self‐assembly process. These results establish the versatility of our approach and open the way to the synthesis of di‐functional ligands containing more elaborated polypyridine ligands as well as affinity labels for different enzyme families. As such, this paper is the first step towards the construction of robust supramolecular species that cover a size‐regime and organization level previously unexplored.     

Adsorption behavior of 4-methoxypyridine on gold nanoparticles

We demonstrate a phase transfer method to create stable colloidal solutions of Au nanoparticles with 4-methoxypyridine ligands. We then investigate the adsorption behavior of 4-methoxypyridine onto gold surfaces by Raman spectroscopy, DFT calculations, and (1)H NMR. In contrast to unsubstituted pyridine and the frequently used (N,N-dimethylamino)pyridine (DMAP), a flat adsorption of 4-methoxypyridine on gold was found.     

Identification and characterisation of the E951 artificial food sweetener by vibrational spectroscopy and theoretical modelling

Aspartame (E951), a very well‐known dipeptide sweetener, approximately 150–200 times sweeter than sugar, is widely used in a variety of applications, especially in soft drinks. A drawback of E951 is its relatively low stability at high pH values and at high temperatures, thereby limiting its use. The changes observed in the very strong bands from the 1600–1300 cm⁻¹ spectral region, characteristic to the υ(CO) mode coupled with the NH bending mode, allows to establish the species present in the Raman and SERS solutions at different concentrations and pH values. More exactly, a molecule protonation at the amino group was detected on going from basic to acidic pH values. The DFT calculated geometry, harmonic vibrational modes and Raman scattering activities of E951 were in good agreement with the experimental data and helped establish its SERS behaviour on silver surfaces. According to the DFT calculations performed, E951 can give rise to an intramolecular hydrogen bonding network, with lengths in the same range as the hydrogen bonds in the peptide unit moieties. Copyright © 2009 John Wiley & Sons, Ltd.     

FTIR and FT‐Raman spectra and density functional computations of the vibrational spectra,molecular geometry and atomic charges of the biomolecule: 5‐bromouracil

FTIR and FT‐Raman spectra of 5‐bromouracil in the powder form were recorded in the region 400–4000 cm⁻¹ and 50–4000 cm⁻¹, respectively. The observed wavenumbers were analysed and assigned to different normal modes of vibration of the molecule. Quantum chemical calculations were performed to support the assignments of the observed wavenumbers. The performance of the B3LYP hybrid density functional (DFT) method was compared with other methods. With the 6–31 G** and 6–311 + G(2d,p) basis sets, the calculated geometry, dipole moments and harmonic vibrations were determined. A comparison with the uracil molecule was made, and specific scale factors were deduced and employed in the predicted wavenumbers of 5‐bromouracil. The total atomic charges and thermodynamic parameters were calculated, and are discussed briefly. Structure and harmonic vibrations of 5‐bromouracil were also calculated in the presence of water within a simple model with one molecule. It is observed that the bromine atom at position 5 exhibits smaller inductive effects than the fluorine atom, producing a small distortion of the electrostatic potential around the ring and a reduction of the molecular dipole moment. Copyright © 2007 John Wiley & Sons, Ltd.     

Molecular rotors: design, synthesis, structural analysis, and silver complex of new [7.7]cyclophanes

New molecular rotors, [7.7](2,6)pyridinocyclophanes (monomers and dimers) embedding 1,3-dioxanes in the bridges, were investigated by variable-temperature NMR, molecular modeling, and single-crystal X-ray diffractometry. The nitrogen-inside rotation of the pyridine ring is more hindered in the derivatives with longer distance between the bridges (i.e., para > meta and 2,6-pyridylene > ortho) and can be chemically stopped by complexation with CF(3)SO(3)Ag. [structure: see text]     

Synthesis of fused dihydro-pyrimido[4,3-d]coumarins using Biginelli multicomponent reaction as key step

A new efficient approach for the synthesis of functionalized dihydro-pyrimido[4,3-d]coumarins is described. Use of benzyl- or tert-butyl acetoacetate and various salicyl aldehydes in typical Biginelli multicomponent reactions provides esters that can be easily deprotected to yield the corresponding hydroxy acids. Annelation of the latter leads to the target dihydro-pyrimido[4,3-d]coumarins. Formation of some unexpected oxo-bridged tetrahydro-pyrimidines is also described. Spectral properties of the synthesized dihydro-pyrimido[4,3-d]coumarins indicate the necessity to revisit some compounds previously reported as products of direct one-pot Biginelli condensation involving 4-hydroxycoumarin as dicarbonyl component.     

Theoretical and spectroscopic studies of 5‐aminoorotic acid and its new lanthanide(III) complexes

The complexes of cerium(III) and neodymium(III) were synthesized by reaction of the respective inorganic salts with 5‐aminoorotic acid (H₄L) in amounts equal to the metal:ligand molar ratio of 1:3. The structures of the final complexes were determined by means of spectral (IR, Raman, ¹H NMR and ¹³C NMR) and elemental analysis. Significant differences in the IR spectra of the complexes were observed as compared to the spectrum of the ligand. A comparative analysis of the Raman spectra of the complexes with that of the free H₄L allowed a straightforward assignment of the vibrations of the ligand groups involved in coordination. The geometry of H₄L was computed and optimized for the first time with the Gaussian03 program using the B3PW91/6‐311++G**, B3PW91/LANL2DZ, B3LYP/6‐311++G** and B3LYP/LANL2DZ methods. The experimental IR and Raman bands of the ligand were assigned to normal modes on the basis of DFT calculations. The vibrational analysis performed for the studied species, H₄L and its complexes, helped to explain the vibrational behavior of the ligand vibrational modes sensitive to interaction with the lanthanides. The vibrational study gave evidence for the coordination mode of the ligand to lanthanide ions and was in agreement with the other theoretical prediction. Copyright © 2006 John Wiley & Sons, Ltd.     

“Geländer” macrocycles: Synthesis,chirality and racemisation barriers

A new class of axially-chiral o,o′-bridged biphenyls containing etheroxime chains was obtained in good yields by the macrocyclisation reaction of o,o′-diformylbiphenyl dioxime with several ditosylated or dibrominated reagents. In all cases the enantiomers of the compounds were separated by HPLC using a chiral column (Chiralpack IC) and the stability of the enantiomers (barriers of racemisation) was investigated employing chiral HPLC or chiral Dynamic HPLC techniques. A slight influence on the barrier to rotation was noticed when the enantiomerisation was performed in the presence of suitable alkali cations.     

Monosodium glutamate in its anhydrous and monohydrate form: differentiation by Raman spectroscopies and density functional calculations

Monosodium glutamate (MSG), a common flavor enhancer, is detected in aqueous solutions by Raman and surface-enhanced Raman (SERS) spectroscopies at the micromolar level. The presence of different species, such as protonated and unprotonated MSG, is demonstrated by concentration and pH dependent Raman and SERS experiments. In particular, the symmetric bending modes of the amino group and the stretching modes of the carboxy moiety are employed as marker bands. The protonation of the NH(2) group at acidic pH values, for example, is detected in the Raman spectra. From the measured SERS spectra, a strong chemical interaction of MSG with the colloidal particles is deduced and a geometry of MSG adsorbed on the silver surface is proposed. In order to assign the observed Raman bands, calculations employing density functional theory (DFT) were performed. The calculated geometries, harmonic vibrational wavenumbers and Raman scattering activities for both MSG forms are in good agreement with experimental data. The set of theoretical data enables a complete vibrational assignment of the experimentally detected Raman spectra and the differentiation between the anhydrous and monohydrate forms of MSG.