Local spin density in the Cr(7)Ni antiferromagnetic molecular ring and (53)Cr-NMR

We present (53)Cr-NMR spectra collected at low temperature in a single crystal of the heterometallic antiferromagnetic (AF) ring Cr(7)Ni in the S?=?1/2 ground state with the aim of establishing the distribution of the local electronic moment in the ring. Due to the poor S/N we observed only one signal which is ascribed to three almost equivalent (53)Cr nuclei in the ring. The calculated spin density in Cr(7)Ni in the ground state, with the applied magnetic field both parallel and perpendicular to the plane of the ring, turns out to be AF staggered with the greatest component of the local spin ?s? for the Cr(3+) ions next to the Ni(2+) ion. The (53)Cr-NMR frequency was found to be in good agreement with the local spin density calculated theoretically by assuming a core polarization field of H(cp)?=-?11?T/μ(B) for both orientations, close to the value found previously in Cr(7)Cd. The observed orientation dependence of the local spin moments is well reproduced by the theoretical calculation and evidences the importance of single-ion and dipolar anisotropies.     

On Codes Identifying Sets of Vertices in Hamming Spaces

A code is called (t, 2)-identifying if for all the words x, y(x y) and the sets (B _t (x) B _t (y)) C and are nonempty and different. Constructions of such codes and a lower bound on the cardinality of these codes are given. The lower bound is shown to be sharp in some cases. We also discuss a more general notion of -identifying codes and introduce weakly identifying codes.     

Spectral shaping of femtosecond pulses in aperiodic quasi-phase-matched gratings

We analyze the use of cascading second harmonic interactions in quadratic nonlinear crystals to mould the spectral characteristics of broadband near-infrared femtosecond pulses. Using a genetic algorithm, we optimize the design of the aperiodically poled ferroelectric crystal capable of generating the desired femtosecond infrared pulsed radiation.     

Dynamic MR imaging of brain tumors in low field using undersampled projection reconstruction

A new application of the projection reconstruction method was developed, enabling dynamic T(1)-weighted contrast-enhanced magnetic resonance image (MRI) of brain tumors in a low-field imager. Two undersampled projection reconstruction spin echo sequences were implemented in an open low-field (0.23-T) MR imager, one with 64 and another with 42 projections in [0,pi], repetition time 150 ms, echotime 15 ms, and six slices were used in both sequences. The possibility of using these sequences to image dynamic contrast enhancement of brain tumors was studied in laboratory experiments and in two patient cases, one with fibrotic and the other with meningothelial meningioma. The laboratory experiments showed a nearly linear response in signal intensity to the concentration of gadopentetate dimeglumine in purified water up to 1.25 mM. Increasing concentrations up to 5.0 mM did not significantly affect the signal intensity, though starting from 3.0 mM concentration T(2) shortening decreased intensities slightly. The patient cases showed results consistent with an earlier study performed in a high-field imager. The results show that the studied sequences can be used to follow dynamic contrast enhancement in a low-field imager.     

Bootstrap approximation for the exchange-correlation kernel of time-dependent density-functional theory

A new parameter-free approximation for the exchange-correlation kernel f(xc) of time-dependent density-functional theory is proposed. This kernel is expressed as an algorithm in which the exact Dyson equation for the response, as well as an approximate expression for f(xc) in terms of the dielectric function, are solved together self-consistently, leading to a simple parameter-free kernel. We apply this to the calculation of optical spectra for various small band gap (Ge, Si, GaAs, AlN, TiO(2), SiC), large band gap (C, LiF, Ar, Ne), and magnetic (NiO) insulators. The calculated spectra are in very good agreement with the experiment for this diverse set of materials, highlighting the universal applicability of the new kernel.     

Janus-like squaramide-based hosts: dual mode of binding and conformational transitions driven by ion-pair recognition

New tripodal squaramide-based hosts have been synthesised and structurally characterised by spectroscopic methods. In 2.5?% (v/v) [D(6)]DMSO in CDCl(3), compound 4 formed dimeric assemblies [log?K(dim)=3.68(8)] as demonstrated by (1)H?NMR spectroscopy and UV dilution experiments. AFM and SEM analyses revealed the formation of a network of bundled fibres, which indicates a preferential mechanism for aggregation. These C(3)-symmetric tripodal hosts exhibited two different and mutually exclusive modes of binding, each one easily accessible by simultaneous reorientation of the squaramide groups. In the first, a convergent disposition of the NH squaramide protons allowed the formation of an array of N-H???X(-) hydrogen bonds with anions. In the second mode, reorientation of carbonyl squaramide groups allowed multiple C=O???H interactions with ammonium cations. The titration of 4 with different tetraalkylammonium iodides persistently showed the formation of 1:1 complexes, as well as 1:2 and 1:3 complexes. The corresponding stoichiometries and binding affinities of the complexes were evaluated by multi-regression analysis. The formation of high-order complexes, supported by ROESY, NOESY and mass spectrometry experiments, has been attributed to the insertion of NR(4)I ion pairs between the carbonyl and NH protons of the squaramide groups located in adjacent arms of 4. The observed effects reflect the induction of significant conformational changes in the hosts, mainly in relation to the relative orientation of the squaramide groups adapting their geometries to incoming ion-pair complementary substrates. The results presented herein identify and fully describe two different modes of ion-pair recognition aimed at directing conformational transitions in the host, therefore establishing a base for controlling more elaborate movements of molecular devices through ion-pair recognition.     

N‐ and O‐linked glycosylation site profiling of the human basic salivary proline‐rich protein 3M

In the present study, we show that the heterogeneous mixture of glycoforms of the basic salivary proline‐rich protein 3M, encoded by PRB3‐M locus, is a major component of the acidic soluble fraction of human whole saliva in the first years of life. Reversed‐phase high‐performance liquid chromatography with high‐resolution electrospray ionization mass spectrometry analysis of the intact proteoforms before and after N‐deglycosylation with Peptide‐N‐Glycosidase F and tandem mass spectrometry sequencing of peptides obtained after Endoproteinase GluC digestion allowed the structural characterization of the peptide backbone and identification of N‐ and O‐glycosylation sites. The heterogeneous mixture of the proteoforms derives from the combination of 8 different neutral and sialylated glycans O‐linked to Threonine 50, and 33 different glycans N‐linked to Asparagine residues at positions 66, 87, 108, 129, 150, 171, 192, and 213.     

A new glucosidic phthalide from Helichrysum microphyllum subsp. tyrrhenicum from La Maddalena Island (Sardinia,Italy)

In this study, we reported the analysis of the medium polarity fraction obtained from an accession of Helichrysum microphyllum subsp. tyrrhenicum from La Maddalena Island. Besides several compounds already evidenced in this species and related genera, i.e. micropyrone (1), arzanol (2), helipyrone (3), acetyl-bitalin derivatives (4, 5), gnaphaliol (6), caffeic acid (7), ursolic acid (8), 7-O-β-(d-glucopyranosyl)-5-methoxy-1(3H)-isobenzofuranone (9), gnaphaliol-9-O-β-d-glucopyranoside (11) and gnaphaliol-3-O-β-d-glucopyranoside (12), the presence of a new glycosidic phthalide, 6-O-β-(d-glucopyranosyl)-4-methoxy-1(3H)-benzofuranone (10), was evidenced for the first time, which resulted in a structural isomer of compound (9). The occurrence of this new benzofuranone derivative is an additional evidence of the deep intraspecific variability expressed by this species, which was also stated for the non-volatile components, and may be a distinctive trait of the population growing on La Maddalena Island.     

Poly(N-vinylcaprolactam) nanocomposites containing nanocrystalline cellulose: a green approach to thermoresponsive hydrogels

In this work, we report on the synthesis and characterization of thermoresponsive poly(N-vinylcaprolactam), PNVCL, nanocomposite hydrogels containing nanocrystalline cellulose (CNC) by the use of frontal polymerization technique, which is a convenient, easy and low energy-consuming method of macromolecular synthesis. CNC was obtained by acid hydrolysis of commercial microcrystalline cellulose and dispersed in dimethylsulfoxide. The dispersion was characterized by TEM analysis and mixed with suitable amounts of N-vinylcaprolactam for the synthesis of PNVCL nanocomposite hydrogels having a CNC concentration ranging between 0.20 and 2.0 wt%. The nanocomposite hydrogels were analyzed by SEM and their swelling and rheological features were investigated. It was found that CNC decreases the swelling ratio even at small concentration. The rheological properties of the hydrogels indicated that CNC strongly influenced the viscoelastic modulus, even at concentrations as low as 0.1 wt%: both G′ and G″, and the viscosity increase with CNC content, indicating that the nanocellulose has a great potential to reinforce PNVCL polymer hydrogels.     

Development and validation of an integrated computational approach for the study of ionic species in solution by means of effective two-body potentials. The case of Zn2+, Ni2+, and Co2+ in aqueous solutions

In this paper we have developed an effective computational procedure for the structural and dynamical investigation of ions in aqueous solutions. Quantum mechanical potential energy surfaces for the interaction of a transition metal ion with a water molecule have been calculated taking into account the effect of bulk solvent by the polarizable continuum model (PCM). The effective ion-water interactions have been fitted by suitable analytical potentials, and have been utilized in molecular dynamics (MD) simulations to obtain structural and dynamical properties of the ionic aqueous solutions. This procedure has been successfully applied to the Co2+-H2O open-shell system and, for the first time, Co-oxygen and Co-hydrogen pair potential functions have been determined and employed in MD simulations. The reliability of the whole procedure has been assessed by applying it also to the Zn2+ and Ni2+ aqueous solutions, and the structural and dynamical properties of the three systems have been calculated by means of MD simulations and have been found to be in very good agreement with experimental results. The structural parameters of the first solvation shells issuing from the MD simulations provide an effective complement to extended X-ray absorption fine structure (EXAFS) experiments.