Hydrogen-bond dynamics of water confined in cyclodextrin nanosponges hydrogel

Cyclodextrin nanosponges (CDNS) are a very promising class of cross-linked polymers, made up of cyclodextrins. CDNS swollen in aqueous solution give rise to cyclodextrin-based hydrogel in different states—gel or liquid suspension—depending on the hydration level of the system. Here we present a thorough inspection of the vibrational dynamics of these hydrogel by Raman scattering experiments, with the aim of clarifying the role played by the hydrogen-bond dynamics of water molecules confined into the nano-sized pores of nanosponges in determining the rigidity of the hydrogel network and their maximum water-holding capacity. Changes occurring in the spectral shape of the OH stretching band of water were interpreted by accounting the connectivity pattern of water molecules concurring to the gelation process. Spectral deconvolution analysis gives evidence of the existence of a characteristic cross-over hydration level associated to the rearrangement of water molecules in more cooperative, bulk-like networks as a consequence of saturation sites of water confinement of nanosponges. This interpretation is further confirmed by the inspection of the estimated collective intensities. These findings also support the existence of a specific phase diagram of the cyclodextrin nanosponges hydrogel, where the molecular structure of the cross-linking agent used during the synthesis of nanosponge plays a fundamental role in defining the nano- and microscopic properties of the system.     

Monolithic stationary phase coupled with coulometric detection: development of an ion-pair HPLC method for the analysis of quinone-bearing compounds

Memoquin, a recently discovered new drug candidate for the treatment of Alzheimer's disease (AD), is a compound able to interfere with different key targets of AD neurodegeneration. In the present work, the electroactivity of Memoquin, due to the presence of a quinone ring in the molecule, was exploited for the development of a sensitive and selective HPLC chromatographic method with coulometric detection system. For this purpose, a monolithic silica-based stationary phase (Chromolith C18) was coupled with ESA detector and under high flow rate condition (2 mL/min) gave an efficient coulometric detection without a significant backpressure. The monolithic stationary phase and the electrochemical detection were combined to obtain a very fast (less than 7 min) and sensitive analysis of the compound of interest. For this reason, the method was found suitable to determine Memoquin with very high sensitivity (LOD, 0.005 microg/mL; LOQ, 0.016 microg/mL), better than with UV and fluorescence detections, and selectivity resulting potentially suitable for its analysis in biological samples. Moreover, the HPLC method was employed for the separation of Memoquin from other quinone analogs (endowed with different substituent on the quinone ring and length of the lateral chain) and allowed the comparison of the electrochemical properties of the compounds of the series. In the optimized chromatographic conditions it was possible to separate each quinone and to evaluate the influence of the substituent of the quinone ring on the electrochemical properties of the molecule.     

Vibrational dynamics and hydrogen bond properties of β-CD nanosponges: an FTIR-ATR, Raman and solid-state NMR spectroscopic study

Cyclodextrin nanosponges (CDNS) are cross-linked polymers with remarkable inclusion/release properties. CDNS show swelling capability and a hydrophilicity/hydrophobicity balance that can be dramatically modified by the type and quantity of cross-linking agents. Here, we focus our attention on samples of β-cyclodextrin nanosponges (β-CDNS) obtained by reacting β-cyclodextrin (β-CD) with the cross-linking agent carbonyldiimidazole at different β-CD:cross-linking agent molar ratio. The vibrational properties of CDNS thus synthesized have been investigated by Fourier transform infrared spectroscopy in attenuated total reflectance geometry and Raman spectroscopy in the dry state at room temperature. The quantitative analysis of the O–H stretching region (3,000–3,800 cm^?1) allowed us to obtain structural information on the role played by primary and secondary OH groups in the hydrogen bond network of the polymer. Also, the contribution of interstitial and intracavity crystallization water molecules is reported. Solid-state NMR spectroscopy is used to study the molecular mobility of the polymer by measuring the ¹H spin–lattice relaxation time in the rotating frame (T_1ρ). The T_1ρ values obtained for the polymer β-CDNS are compared with free β-CD. The observed relaxation parameters point out that the ester formation occurs mainly at the primary OH groups of CDs, also supporting the interpretation of vibrational spectra.     

TCO/Ag/TCO transparent electrodes for solar cells application

Among transparent electrodes, transparent conductive oxides (TCO)/metal/TCO structures can achieve optical and electrical performances comparable to, or better than, single TCO layers and very thin metallic films. In this work, we report on thin multilayers based on aluminum zinc oxide (AZO), indium tin oxide (ITO) and Ag deposited by RF magnetron sputtering on soda lime glass at room temperature. The TCO/Ag/TCO structures with thicknesses of about 50/10/50 nm were deposited with all combinations of AZO and ITO as top and bottom layers. While the electrical conductivity is dominated by the Ag intralayer irrespective of the TCO nature, the optical transmissions show a dependence on the nature of the top and bottom TCOs, mainly due to the change in the reflectivity of the multilayers. Structural, electrical and optical properties are studied to optimize the structure for very thin transparent electrodes suitable for photovoltaic applications.     

Classes of Graded Ideals with Given Data in the Exterior Algebra

Let ? be the family of graded ideals J in the exterior algebra E of a n-dimensional vector space over a field K such that e(E/J) = dim _K (E/J) = e, indeg(E/J) = i and H _E/J (i) = dim _K (E/J) _i are fixed integers. It is shown that there exists a unique lexsegment graded ideal J(n, e, i) ? ? whose Betti numbers give an upper bound for the Betti numbers of the ideals of ?. The authors continue the computation of upper bounds for the Betti numbers of graded ideals with given data started in Crupi and Utano (1999 Crupi , M. , Utano , R. ( 1999 ). Upper bounds for the Betti numbers of graded ideals of a given length in the exterior algebra . Comm. Alg. 27 : 4607 – 4631 .[Taylor &; Francis Online], [Web of Science ®] , [Google Scholar]).     

Nature of depolarized quasi-elastic light scattering in associated and non-associated liquids

Summary An analysis of Rayleigh-wing spectra on two isomers of propanol (C₃H₇OH) and on two of their Br-based isomorphous systems (C₃H₇Br) is presented. The performed measurements, over a wide temperature range, allow us to identify two different processes characterizing the response of both the alcohols. A comparison between the rotational dynamics of the linear normal-propanol (1-propanol) and the more sterically hindered iso-propanol (2-propanol) is performed. At the same time, the role played by the H-bond in the associative properties of hydrogenous systems is investigated by comparing the dynamical response of the two alcohols with that of 1-bromopropane and 2-bromopropane, in which the O−H ?active? sites are replaced by ?inert? bromine atoms. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.