Integrated NMR and computational study of push-pull NLO probes: interplay of solvent and structural effects.

In this study we combined QM calculations and NMR measurements to understand at a detailed level the complex interplay of structural/electronic properties with the effects of the solvent in the NLO activity of push-pull systems, quantified in terms of variations of the static hyperpolarizability. Different parameters (bond lengths and bond length alternation, vibrational frequencies, electronic charge distribution) are introduced and tested to rationalize both the solvent sensitivity of three molecular systems (namely, p-nitroaniline, ethyl 4-ammino benzoate, and 5-nitro-1H-indole) and the differences among them. This analysis has finally allowed us to establish a clear correlation between the charge transfer behavior of the systems, their NLO properties, and NMR parameters also validating simplified but effective chemical analyses based on resonance limit forms.

Aggregation of perfluoroctanoate salts studied by 19F NMR and DFT calculations: counterion complexation, poly(ethylene glycol) addition, and conformational effects.

The aggregation of perfluoroctanoate salts in H(2)O is studied by (19)F NMR on solutions of LiPFO, NaPFO, and CsPFO, without and with the addition of two poly(ethylene glycol) (PEG) oligomers of molecular weight 1500 and 3400 Da, respectively, and with the addition of suitable crown ethers. The (19)F chemical shift (cs) trends are monitored, at 25 °C, in a concentration range including the critical micellar concentration (cmc) or, in the presence of PEG, the critical aggregation concentration (cac). The cac values in the samples with PEG are lower than the cmc values of the corresponding samples without PEG; moreover, the (19)F cs trends above the cac and above the polymer saturation concentration reveal and help to explain some peculiarities of the aggregation process of PEG on PFO micelles, which, in the first step, seems to occur while the surfactant concentration in water is still increasing. Also in LiPFO/H(2)O or NaPFO/H(2)O solutions containing 12-crown-4 or 15-crown-5 ethers, suitable to complex Li(+) or Na(+) ions, respectively, the cmc decreases. On the other hand, the micellization process in the presence of crown ethers does not show other peculiarities. The prevailing conformations of the PFO chain are discussed on the basis of quantum-mechanical calculations. The theoretical chemical shifts were computed at the DFT level of theory, taking into account the effects of the environment by means of the IEF-PCM method. The helical structure is the most stable one, but anti conformations are easily accessible, in both the aqueous and fluorinated environment. The comparison between computed and experimental chemical shifts indicates that anti conformations are more important in the micelles than in water and in CsPFO micelles than in LiPFO or NaPFO ones.

Structure and orientation of small molecules dissolved in the liquid crystalline phases of CsPFO/water system by multinuclear NMR.

Pyridine, L-alanine and L-phenylalanine dissolved in the liquid crystalline phases of the lyotropic system CsPFO/water are studied by means of (2)H, (13)C and (1)H NMR. The orientational order parameters of the solutes are determined in a wide temperature range, together with some relevant geometrical parameters. In particular, a prevailing conformation for L-phenylalanine interacting with the micelle is suggested and, for all solutes, convincing representations of their specific interactions with the micelle surface are inferred. From (19)F and (13)C NMR spectra in the nematic phase, the orientational order parameters for the perfluorooctanoate chain inside the micelles are estimated.

Structural and orientational properties of the ferro, antiferroelectric, and re-entrant smectic C phases of ZLL7/ by deuterium NMR and other experimental techniques.

In this work, two selectively deuterium-labeled isotopomers of the (S)-2-methylbutyl- [4'-(4' '-heptyloxyphenyl)-benzoyl-4-oxy-(S)-2-((S)-2')-benzoyl)-propionyl)]-propionate (ZLL 7/), one labeled on the phenyl ring (ZLL 7/-phe-D2) and the other one on the biphenyl fragment (ZLL 7/-biphe-D2), have been investigated by deuterium NMR (DNMR) spectroscopy and other experimental techniques. These compounds possess the paraelectric SmA, the ferroelectric SmC, the antiferroelectric SmC(A), the re-entrant ferroelectric SmC(re), and the ferroelectric hexatic phases down to room temperature. The orientational ordering properties of the two labeled fragments have been determined by means of DNMR, and the mesophase behavior at two magnetic fields is discussed. In particular, the effect of the magnetic field on the supramolecular structure of the SmC and SmC(re) phases is commented. This study revealed to be useful to understand the structural and conformational properties of the ferroelectric/antiferroelectric/re-entrant/hexatic smectic phases. Mesomorphic properties, spontaneous tilt angle, polarization, and layer spacing have been studied for the labeled materials and compared with those obtained for the nonlabeled compound. The two self-consistent set of data, from optical and DNMR measurements and X-ray results, allow us to associate at the transition from the SmC to the SmC(A) phase a change of the molecular conformation.

Solid state NMR investigation of the molecular dynamics of cocoon silks produced by different Bombyx mori (Lepidoptera) strains.

Cocoons produced by different strains of Bombyx mori larvae were investigated by a combination of several high- and low-resolution 1H and 13C solid-state NMR techniques in order to characterize and compare their dynamic behavior at a molecular level. A detailed interpretation in terms of molecular motions in these very complex systems was possible thanks to the integrated analysis of different relaxation measurements and high-resolution selective experiments. Untreated cocoons of all strains were found to be mainly constituted by two different types of rigid domains and by a third one, more mobile, due to physisorbed water molecules. Dynamic processes in the MHz and kHz ranges were characterized by means of different 1H and 13C relaxation times. Cocoons arising from different strains exhibit a different content of physisorbed water and also slightly different dynamic behavior, especially in the MHz regime.

Solid state (13)C NMR and FT-IR spectroscopy of the cocoon silk of two common spiders.

The structure of the silk from cocoons of two common spiders, Araneus diadematus (family Araneidae) and Achaearanea tepidariorum (family Theridiidae) was investigated by means of (13)C solid state NMR and FT-IR spectroscopies. The combined use of these two techniques allowed us to highlight differences in the two samples. The cocoon silk of Achaearanea tepidariorum is essentially constituted by helical and beta-sheet structures, whereas that of Araneus diadematus shows a more complex structure, containing also beta-strands and beta-turns. Moreover, the former silk is essentially crystalline while the latter contains more mobile domains. The structural differences of the two cocoon silks are ascribed to the different habitat of the two species.