The refocused INADEQUATE MAS NMR experiment in multiple spin-systems: interpreting observed correlation peaks and optimising lineshapes

The robustness of the refocused INADEQUATE MAS NMR pulse sequence for probing through-bond connectivities has been demonstrated in a large range of solid-state applications. This pulse sequence nevertheless suffers from artifacts when applied to multispin systems, e.g. uniformly labeled (13)C solids, which distort the lineshapes and can potentially result in misleading correlation peaks. In this paper, we present a detailed account that combines product-operator analysis, numerical simulations and experiments of the behavior of a three-spin system during the refocused INADEQUATE pulse sequence. The origin of undesired anti-phase contributions to the spectral lineshapes are described, and we show that they do not interfere with the observation of long-range correlations (e.g. two-bond (13)C-(13)C correlations). The suppression of undesired contributions to the refocused INADEQUATE spectra is shown to require the removal of zero-quantum coherences within a z-filter. A method is proposed to eliminate zero-quantum coherences through dephasing by heteronuclear dipolar couplings, which leads to pure in-phase spectra.     

Drug-loaded nano/microbubbles for combining ultrasonography and targeted chemotherapy

A new class of multifunctional nanoparticles that combine properties of polymeric drug carriers, ultrasound imaging contrast agents, and enhancers of ultrasound-mediated drug delivery has been developed. At room temperature, the developed systems comprise perfluorocarbon nanodroplets stabilized by the walls made of biodegradable block copolymers. Upon heating to physiological temperatures, the nanodroplets convert into nano/microbubbles. The phase state of the systems and bubble size may be controlled by the copolymer/perfluorocarbon volume ratio. Upon intravenous injections, a long-lasting, strong and selective ultrasound contrast is observed in the tumor volume indicating nanobubble extravasation through the defective tumor microvasculature, suggesting their coalescence into larger, highly echogenic microbubbles in the tumor tissue. Under the action of tumor-directed ultrasound, microbubbles cavitate and collapse resulting in a release of the encapsulated drug and dramatically enhanced intracellular drug uptake by the tumor cells. This effect is tumor-selective; no accumulation of echogenic microbubbles is observed in other organs. Effective chemotherapy of the MDA MB231 breast cancer tumors has been achieved using this technique.     

Anisotropic Analysis of Some Gaussian Models

Although the classical Fractional Brownian Motion is often used to describe porosity, it is not adapted to anisotropic situations. In the present work, we study a class of Gaussian fields with stationary increments and spectral density. They present asymptotic self-similarity properties and are good candidates to model a homogeneous anisotropic material, or its radiographic images. Unfortunately, the paths of all Gaussian fields with stationary increments have the same apparent regularity in all directions (except at most one). Hence we propose here a procedure to recover anisotropy from one realization: computing averages over all the hyperplanes which are orthogonal to a fixed direction, we get a process whose Hölder regularity depends explicitly on the asymptotic behavior of the spectral density in this direction.     

An anharmonic force field for carbonyl sulphide

A 16-parameter force field for OCS based on curvilinear coordinates is presented in table 2 and the agreement between observed and calculated transitions and rotational constants is indicated in tables 4, 5 and 6. The computational approach differs from that of Morino and Nakagawa [2] and similar work on other molecules by other authors, in that perturbation theory is eschewed and the calculated vibrational transitions and rotational constants are derived via the numerical solution of a large matrix. The usual parameters x_ij , y_ijk , α _i ^B and γ _ij ^B are thereby rendered inappropriate intermediates. The approach also leads to estimates of B _e - B ₀ for each isotopic species and thence suggests equilibrium distances r _CO = 1·155386(21) Å and r _CS = 1·562021(17) Å.     

Discovery of structurally diverse natural product antagonists of chemokine receptor CXCR3

The chemokines (CXCL9, CXCL10 and CXCL11) and associated CXCR3 receptor are expressed during the inflammatory process from multiple sclerosis, atherosclerosis or organ transplantation resulting in the recruitment of lymphocytes leading to tissue damage. It is hypothesized that blocking of the ligand/CXCR3 receptor interaction has potential to provide opportunity for development of agents that would block tissue rejection. In this paper, four classes of natural product inhibitors (IC₅₀ ranging 0.1–41 M) have been described that block the CXCR3 receptor interaction of IP-10 ligand. These include a cyclic thiopeptide (duramycin), polyketide glycosides (roselipins), steroidal glycosides (hypoglausin A and dioscin) and a novel alkyl pyridinium alkaloid that were isolated by bioassay-guided fractionation of the organic extracts derived from actinomycete, fungal, plant and marine sources and discovered using ¹²⁵ I IP-10/CXCR3 binding assay. Duramycin was the most potent with an IC₅₀ of 0.1 M. Roselipins 2A, 2B and 1A showed IC₅₀ values of 14.6, 23.5, and 41 M, respectively. Diosgenin glycosides dioscin, hypoglaucin A and kallstroemin D exhibited IC₅₀ values of 2.1, 0.47 and 3 M, respectively. A novel cyclic 3-alkyl pyridinium salt isolated from a sponge displayed a binding IC₅₀ of 0.67 M.     

Modelling of hundreds of wavelength long,highly resonant, 3D subwavelength patterned scattering structures

In this paper, we study the performances of the Dipole Discrete Approximation method for modelling the reflectivity of a highly resonant, 3D subwavelength patterned structure extending over tens of thousands wavelength square. The computation time of the whole reflectivity spectrum (80 wavelengths) was about 3 h on a computer and requires about 1.5 GB in memory. These performances make the DDA an unique numerical tool for modelling the scattering by large 3D structures supporting long-range interactions.     

Dynamics and non-equilibrium steady state in a system of coupled harmonic oscillators

A system of two coupled oscillators, each of them coupled to an independent reservoir, is analysed. The analytical solution of the non-rotating wave master equation is obtained in the high-temperature and weak coupling limits. No thermal entanglement is found in the high-temperature limit. In the weak coupling limit the system converges to an entangled non-equilibrium steady state. A critical temperature for the appearance of quantum correlations is found.     

Green ultrasound-assisted extraction of carotenoids based on the bio-refinery concept using sunflower oil as an alternative solvent

A green, inexpensive and easy-to-use method for carotenoids extraction from fresh carrots assisted by ultrasound was designed in this work. Sunflower oil was applied as a substitute to organic solvents in this green ultrasound-assisted extraction (UAE): a process which is in line with green extraction and bio-refinery concepts. The processing procedure of this original UAE was first compared with conventional solvent extraction (CSE) using hexane as solvent. Moreover, the UAE optimal conditions for the subsequent comparison were optimized using response surface methodology (RSM) and ultra performance liquid chromatography – diode array detector – mass spectroscopy (UPLC–DAD–MS). The results showed that the UAE using sunflower as solvent has obtained its highest β-carotene yield (334.75 mg/l) in 20 min only, while CSE using hexane as solvent obtained a similar yield (321.35 mg/l) in 60 min. The green UAE performed under optimal extraction conditions (carrot to oil ratio of 2:10, ultrasonic intensity of 22.5 W cm^?2, temperature of 40 °C and sonication time of 20 min) gave the best yield of β-carotene.     

Implementation of the Laser Diffraction Technique for Acoustic Cavitation Bubble Investigations

Knowledge of the acoustic cavitation cloud would be useful for improving ultrasound reactor design. Among the characterisation techniques, few are adapted to bubble investigations in an intense ultrasound field. Some problems raised by these measurements result from interactions between the acoustic pressure wave and the measuring light wave. This paper reports the implementation of the laser diffraction technique to determine the size and volume concentration of bubbles generated by a dipping horn operating at 20 kHz. Measurements were performed with a Malvern 2600 instrument. The size distribution, deduced from the diffraction pattern scattered by the bubble cloud crossed by a laser beam, is disturbed by the acoustic pressure wave involving deviation of a light beam at low diffusion angles (acousto‐optic effect). A bubble size correction procedure based on the subtraction of the light energy due to the ultrasound wave is described. The size measurements, and thus the correction procedure, were validated by a second laser technique based on a different measuring principle: phase Doppler interferometry. The measurement reliability was further confirmed by an original application of laser diffraction based on measurements performed just after sonication. These three methods lead to a mean bubble size (Sauter mean diameter) of about 10 μm at a high ultrasound power input. Concerning the void fraction, only measurements achieved after sonication and by laser diffraction predict a correct estimation of this parameter.