A series of R 3 SnO 2 CR′ compounds, where R) Me (1), Et (2), n Bu (3), Ph (4), and cHex (5) and R′CO 2 is the carboxylate residue of 2-[(E)-2-(2-hydroxy-5-methylphenyl)-1-diazenyl]benzoic acid, has been shown by multinuclear magnetic resonance studies to be monomeric in solution. Crystallography shows that monomeric four-coordinate species are found in the solid state for 4 and 5 but polymeric structures with five-coordinate tin atoms are found for 1-3. The different behavior is ascribed to the steric demands of the tin-bound substituents. A fair correlation is found between the difference in 117 Sn chemical shift between the solution and solid states and the carbonyl oxygen-tin distance of the compounds 1-5, only when the data of 4, R) Ph, are omitted. This indicates that the mesomeric effect of the phenyl group does not express its influence to the same extent in the solid and solution states, unlike the inductive effects. By contrast, a good correlation including 4 is found between the Mössbauer quadrupole splitting and the difference in 117 Sn chemical shift between the solution and solid states. This shows that the nature of the organic group on the tin atom contributes to similar extents to the values of the 117 Sn chemical shifts in solution and solid state, independently of the existence or not of mesomeric effects, and that the parallel behavior of QS and 117 Sn chemical shifts is geometry independent.

Two S-(2-aminoethyl)L-cysteine (AEC) resistant lines were isolated by screening mutagenized protoplasts from diploid N. sylvestris plants. Both lines accumulated free lysine at levels 10 to 20-fold higher than in controls. Lysine overproduction and AEC-resistance were also expressed in plants regenerated from the variant cultures. A feedback insensitive form of dihydrodipicolinate synthase (DHPS), the pathway specific control enzyme for lysine synthesis, was detected in callus cultures and leaf extracts from the resistant lines. Aspartate kinase (AK), the other key enzyme in the regulation of lysine biosynthesis, was unaltered in the mutants. Crosses with wild type plants indicated that the mutation conferring insensitivity to feedback in DHPS, with as result overproduction of lysine and resistance to AEC, was inherited as a single dominant nuclear gene.

The self-aggregation and supramolecular micellar structure of two surfactants in aqueous solution, the anionic surfactant SDP2S (sodium dodecyl dioxyethylene-2 sulfate) and the nonionic surfactant Triton X-100 (octylphenol-polyoxyethylene ether with 9.5 ethoxy groups), were investigated by NMR spectroscopy. The critical micellar concentration (CMC), the size, and shape of the aggregates were determined by diffusion ordered NMR spectroscopy (DOSY), while 2D NOESY NMR spectra were used to study the mutual spatial arrangement of surfactant molecules in the aggregated state. A nonlinear increase of the micellar hydrodynamic radius, indicating possible sphere-to-rod shape transition, was found for SDP2S at higher surfactant concentrations. Triton X-100 micelles were found to be almost spherical at low surfactant concentrations, but formation of ellipsoid shaped particles and/or micellar aggregation was observed at higher concentrations. The NOESY data show that at low concentration Triton X-100 forms a two-layer spherical structure in the micelles, with partially overlapping internal and external layers of Triton X-100 molecules and no distinct hydrophilic-hydrophobic boundary.

Diffusion-ordered NMR spectroscopy (DOSY NMR) is presented as a tool for the determination of the diffusion coefficients of organic ligands in suspensions of titanium dioxide nanoparticles. The nanoparticles were prepared by a sol-gel process by hydrolysis and condensation reactions of titanium tetra-n-butoxide in the presence of pentane-2,4-dione (acacH: acetylacetone), as well as para-toluenesulfonic acid (pTsA) and n-butanol (nBuOH). NMR spectroscopic studies were performed in various deuterated solvents, on both dispersed xerosols and diluted sols. The bipolar-pulsed field gradient longitudinal eddy-current delay (LED) pulse sequence was used for data acquisition. The data were processed by inverse Laplace transformation (ILT), by using a maximum entropy algorithm, to afford 2D DOSY spectra. Different diffusion regimes for organic ligands in the bound and unbound states were successfully discriminated, more particularly in [D3]acetonitrile, thus allowing assessment of their interactions with the nanoparticles.

The cross-linked polystyrene grafted organotin [P-H](1−t)[P-(CH2)11-SnCl3] t , in which [P-H] represents the monomeric unit of the nonfunctionalized polymer and t is the functionalization degree, has been synthesized and characterized by 1D and 2D 1H, 13C, and 119Sn high-resolution magic angle spinning (HRMAS) NMR spectroscopy, elemental analysis, and IR spectrometry. Its catalytic activity was assessed in the transesterification model reaction between ethyl acetate and n-octanol. The catalyst displays an average conversion degree of 76% after 2 h and can be recycled at least nine times. The experimental concentration profiles were fitted to a mechanistic model, from which a turnover frequency in the range of 10−2 s−1 was calculated. Residual tin contents on the order of 5 ppm in the reaction products were assessed by inductively coupled plasma/atomic emission spectroscopy (ICP/AES). The combined use of 1H, 13C, and 119Sn HRMAS NMR and modulated DSC enables one to assess the chemical integrity of the catalyst upon recycling. Detailed analysis of 119Sn HRMAS NMR spectra under various chemical conditions mimicking the reaction mixtures allows gaining a better insight into the catalysis mechanism.

The X-ray diffraction analysis of crystals of {[Me2N(CH2)3]2SnF2·2H2O (3a) obtained by reaction of [Me2N(CH2)3]2SnR2 (R = Me, Ph) with Pr3SnF reveals a six-coordinate, distorted octahedral geometry at tin with the pairs of fluorine, nitrogen and carbon atoms bound to the metal atom being all in a mutual trans configuration. Room-temperature 119Sn, 19F, 1H, and 13C NMR spectra of 3a reveal exchange averaging with loss of the 1 J(119Sn−19F) coupling on the 119Sn and 19F NMR time scales. Below −50 °C, 119Sn and 19F NMR coupling data evidence the existence of only two isomers among the five a priori possible ones, a major (ca. 80%) and a minor species (ca. 20%). The methyl 13C resonance as well as the 1 J(119Sn−19F), 1 J(119Sn−13C), and 2 J(19F−13C) coupling patterns reveal the major species to have the same all-trans structure as in the crystal state, while the minor species has a cis arrangement for its fluorine and nitrogen atoms and the trans one for its carbon atoms. Gradient assisted 1H−119Sn HMQC spectroscopy establishes 3 J(119Sn−1H) correlations through the Me2N→Sn bond to exist in both slow- and fast-exchange ranges. Together with the loss of the 1 J(119Sn−19F) coupling at high temperature, this evidences the Me2N→Sn coordination to be maintained during the cis−trans isomerization and the latter to occur through a dissociative mechanism involving tin−fluorine bond rupture. Addition of Bu4N+F-·3H2O in CH2Cl2 yields under quaternization of one nitrogen zwitterionic {[Me2(ClCH2)N+(CH2)3][Me2N(CH2)3]SnF3 -}·H2O (3b).

Bio-inspired stabilization of aliphatic polycarbonate-based hydrogels has been carried out by the metal-free ring-opening co-polymerization (ROP) of 6-membered cyclic carbonates containing, respectively, protected guanidine and carboxylic acid functions. Polyethylene glycol (PEG) bound to methylcarboxy trimethylene carbonate at each extremity was used as the cross-linker, and the copolymerizations were performed in CH 2 Cl 2 for 24 h in the presence of 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) and N-(3,5-trifluoromethyl)phenyl-N 0 -cyclohexylthiourea (TU), the catalyst and co-catalyst, respectively. Well-defined hydrogels of various compositions and presenting a high gel fraction were obtained. HR-MAS NMR has been successfully employed to validate our purification technique as well as to assess the selective de-protection of the guanidine and carboxylic acid functions. Evidence of self-assembling properties has been attested by differential scanning calorimetry (DSC), HR-MAS NMR analysis and swelling test experiments in aqueous buffered solutions at pH 4 and 8.

Dialkyltin dichloride grafted to a cross-linked polystyrene, with the formula [P-H]((1-t))[P-(CH2)nSnBuCl2]t (P=[CH2CH(pC6H4)], t=the degree of functionalization, and n=6 or 11), is investigated as a recyclable catalyst in the ring-opening polymerization (ROP) of epsilon-caprolactone (CL). It is demonstrated that high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy is an invaluable tool to characterize completely the supported catalyst. The 2D 1H-13C HSQC HR-MAS spectrum, in particular, allowed extensive assignment of the 1H and 13C resonances, as well as accurate measurement of the (n)J((1)H-(117/119)Sn) and (n)J((13)C-(117/119)Sn) coupling constants. 1H and 119Sn HR-MAS NMR spectroscopy is presented as a monitoring tool for catalytic processes based on organotin compounds, particularly for the investigation of the extent to which polymerization residues are observable in situ in the material pores and for the assessment of the chemical integrity and recycling conditions of the grafted catalyst. From polymerization experiments with CL, initiated by n-propanol and with [P-H]((1-t))[P-(CH2)nSnBuCl2]t of various compositions as the supported catalyst, it appears that a partial 'burst' of the polystyrene support occurs when the length of the alkyl spacer is limited to n=6, as a result of polymer chains growing within the pores of the support. However, extension of the length of the aliphatic polymethylene spacer from 6 to 11 carbon atoms preserves the support integrity and allows the production of catalyst-deprived poly(epsilon-caprolactone) (PCL) oligomers. A preliminary attempt to recycle the heterogeneous catalyst has shown that very good reproducibility can be obtained, in terms of both catalyst activity and molecular-weight parameters of the as-recovered PCL polyester chains.