FT-IR Determination of degree of esterification in polycarboxylic acid cross-link finishing of cotton

Cross-linking of cotton with polycarboxylic acids, applied with catalysts based on phosphorus-containing inorganic acids, produces fabrics with excellent smooth-drying properties and which release no formaldehyde at any stage of preparation or on storage. The reaction produces cellulose ester linkages and unreacted carboxylic acid groups. Fourier transform infrared spectroscopy was used to determine the degree of esterification of polycarboxylic acids that occurred on cross-linking of cotton. The height of the carbonyl peak at 1730 cm ^–1 was determined on the same treated fabrics after soaking in dilute acid to convert ionized groups to free acid and then in dilute base to convert free acid to carboxylate ion. The carbonyl peak for the base rinsed fabric (ester only) was ratioed against the same peak for the acid-rinsed fabric (total carbonyl, ester plus acid) to obtain a measure of the degree of esterification. This ratio minimizes the problems of different molar extinction coefficients that are encountered when peaks from different functional groups are used.     

Molecular Modeling and Experimental Evaluation of Non-Chiral Components of Bergamot Essential Oil with Inhibitory Activity against Human Monoamine Oxidases

Human monoamine oxidases (hMAOs) are well-established targets for the treatment of neurological disorders such as depression, Parkinson’s disease and Alzheimer’s disease. Despite the efforts carried out over the years, few selective and reversible MAO inhibitors are on the market. Thus, a continuous search for new compounds is needed. Herein, MAO inhibitors were searched among the non-chiral constituents of Bergamot Essential Oil (BEO) with the aid of computational tools. Accordingly, molecular modeling simulations were carried out on both hMAO-A and hMAO-B for the selected constituents. The theoretically predicted target recognition was then used to select the most promising compounds. Among the screened compounds, Bergamottin, a furocoumarin, showed selective hMAO-B inhibitory activity, fitting its active site well. Molecular dynamics simulations were used to deeply analyze the target recognition and to rationalize the selectivity preference. In agreement with the computational results, experimental studies confirmed both the hMAO inhibition properties of Bergamottin and its preference for the isoform B.     

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.     

Surface complexation studied via combined grazing-incidence EXAFS and surface diffraction: arsenate on hematite (0001) and (10-12)

X-ray diffraction [crystal-truncation-rod (CTR)] studies of the surface structure of moisture-equilibrated hematite reveal sites for complexation not present on the bulk oxygen-terminated surface, and impose constraints on the types of inner-sphere sorption topologies. We have used this improved model of the hematite surface to analyze grazing-incidence EXAFS results for arsenate sorption on the c (0001) and r (10–12) surfaces measured in two electric vector polarizations. This work shows that the reconfiguration of the surface under moist conditions is responsible for an increased adsorption density of arsenate complexes on the (0001) surface relative to predicted ideal termination, and an abundance of “edge-sharing” bidentate complexes on both studied surfaces. We consider possible limitations on combining the methods due to differing surface sensitivities, and discuss further analysis possibilities using both methods. An erratum to this article can be found at     

Three-photon luminescence in CdS

The non-linear luminescence in CdS has been studied using three-photon and two-photon excitation with a neo-dymium and a ruby laser, respectively. By comparing the intensities of the two spectra and using previous values of the two-photon non-linear cross section γ₂, a quantitative determination of γ₃ is obtained. The result is compared with theoretical calculations.     

Optical gain in GaSe due to exciton-exciton recombination

Measurements of the optical gain spectrum in high quality GaSe are reported. The mechanism for light amplification has been investigated, giving evidence that the exciton-exciton scattering process is responsible for stimulated emission.     

Three-photon non-linear cross-section of gallium phosphide

The luminescence of GaP which follows non-linear optical excitation has been studied by using three- and two-photon optical pumping by a neodymium and a ruby laser, respectively. By comparing the intensities of the excitonic A-line emission in the two spectra, the three-photon cross section is obtained. This result is compared with previous experimental and theoretical values.     

Natural Abundance 15N and 13C Solid‐State NMR Chemical Shifts: High Sensitivity Probes of the Halogen Bond Geometry

Solid‐state nuclear magnetic resonance (SSNMR) spectroscopy is a versatile characterization technique that can provide a plethora of information complementary to single crystal X‐ray diffraction (SCXRD) analysis. Herein, we present an experimental and computational investigation of the relationship between the geometry of a halogen bond (XB) and the SSNMR chemical shifts of the non‐quadrupolar nuclei either directly involved in the interaction (¹⁵N) or covalently bonded to the halogen atom (¹³C). We have prepared two series of X‐bonded co‐crystals based upon two different dipyridyl modules, and several halobenzenes and diiodoalkanes, as XB‐donors. SCXRD structures of three novel co‐crystals between 1,2‐bis(4‐pyridyl)ethane, and 1,4‐diiodobenzene, 1,6‐diiodododecafluorohexane, and 1,8‐diiodohexadecafluorooctane were obtained. For the first time, the change in the ¹⁵N SSNMR chemical shifts upon XB formation is shown to experimentally correlate with the normalized distance parameter of the XB. The same overall trend is confirmed by density functional theory (DFT) calculations of the chemical shifts. ¹³C NQS experiments show a positive, linear correlation between the chemical shifts and the C?I elongation, which is an indirect probe of the strength of the XB. These correlations can be of general utility to estimate the strength of the XB occurring in diverse adducts by using affordable SSNMR analysis.