Redox Properties and in Vivo Magnetic Resonance Imaging of Cyclodextrin-Polynitroxides Contrast Agents

This paper reports the synthesis, characterization and in vivo application of water-soluble supramolecular contrast agents (Mw: 5–5.6 kDa) for MRI obtained from β-cyclodextrin functionalized with different kinds of nitroxide radicals, both with piperidine structure ( CD2 and CD3 ) and with pyrrolidine structure ( CD4 and CD5 ). As to the stability of the radicals in presence of ascorbic acid, CD4 and CD5 have low second order kinetic constants (≤0.05 M⁻¹ s⁻¹) compared to CD2 (3.5 M⁻¹ s⁻¹) and CD3 (0.73 M⁻¹ s⁻¹). Relaxivity (r₁) measurements on compounds CD3 - CD5 were carried out at different magnetic field strength (0.7, 3, 7 and 9.4 T). At 0.7 T, r₁ values comprised between 1.5 mM⁻¹ s⁻¹ and 1.9 mM⁻¹ s⁻¹ were found while a significant reduction was observed at higher fields (r₁≈0.6-0.9 mM⁻¹ s⁻¹ at 9.4 T). Tests in vitro on HEK293 human embryonic kidney cells, L929 mouse fibroblasts and U87 glioblastoma cells indicated that all compounds were non-cytotoxic at concentrations below 1 μmol mL⁻¹. MRI in vivo was carried out at 9.4 T on glioma-bearing rats using the compounds CD3 - CD5 . The experiments showed a good lowering of T₁ relaxation in tumor with a retention of the contrast for at least 60 mins confirming improved stability also in vivo conditions.     

Complete 1H, 13C{1H}, and 31P NMR spectral parameters of some pyrophosphates

The ¹H, ¹³C{¹H}, and ³¹P NMR spectral parameters of some pyrophosphates were determined in CDCl₃. The most complicated ¹H spectrum can be solved fully only as (A₃MN)R₆XX′R₆′(MNA₃)′, where R₆ (= ―N(CH₃)₂) is coupled only to phosphorus (X). Second‐order coupling between phosphorus was found and solved with iterative analysis. A signal shape of one of the carbon resonance cannot be explained only with couplings. Explanation for exceptional shape was searched from molecular modeling results. Copyright © 2017 John Wiley & Sons, Ltd.     

Excitation energy transfer in isolated chlorosomes from Chlorobaculum tepidum and Prosthecochloris aestuarii

Excitation energy transfer in chlorosomes from photosynthetic green sulfur bacteria, Chlorobaculum (Cba.) tepidum and Prosthecochloris (Pst.) aestuarii, have been studied at room temperature by time-resolved femtosecond transient absorption spectroscopy. Bleach rise times from 117 to 270 fs resolved for both chlorosomes reflect extremely efficient intrachlorosomal energy transfer. Bleach relaxation times, from 1 to 3 ps and 25 to 35 ps, probed at 758 nm were tentatively assigned to intrachlorosomal energy transfer based on amplitude changes of the global fits and model calculations. The anisotropy decay constant of about 1 ps resolved at 807 nm probe wavelength for the chlorosomes from Chloroflexus aurantiacus, Pst. aestuarii and Cba. tepidum was related to energy transfer between bacteriochlorophyll a molecules of the baseplate and partly to intrachlorosomal energy transfer. The longer anisotropy components 6.6, 8.8 and 12.1 ps resolved for the three chlorosomes, respectively, were assigned to chlorosome to baseplate energy transfer. Global fits of magic-angle data also revealed longer chlorosome to baseplate energy transfer components from 95 to 135 ps, in accord with results from simulations.     

1H and 13C{1H} NMR spectral parameters of sulfur mustards,nitrogen mustards,and lewisites: Computing and Predicting of Reference Spectra for Chemical Identification

The ¹H and ¹³C{¹H} chemical shifts and ¹H spin–spin couplings of sulfur mustards, nitrogen mustards, and lewisites scheduled in the Chemical Weapons Convention, and those of bis(2‐chloromethyl)disulfide, were determined in CDCl₃, CD₂Cl₂, and (CD₃)₂CO. Accurate parameters of this kind of series can be used for evaluating the current molecular modeling programs and the chemical shift and coupling constant prediction possibilities of the programs. Several prediction tests were made with commercial programs, and the results are reported here. Copyright © 2012 John Wiley & Sons, Ltd.     

Study of mechanisms of light-induced dissociation of Ru(dcbpy)(CO)2I2 in solution down to 20 fs time resolution

Mechanisms of the light-induced ligand exchange reaction of (trans-I) Ru(dcbpy)(CO)2I2 (dcbpy = 4,4'-dicarboxylic acid-2,2'-bipyridine) in ethanol have been studied by transient absorption spectroscopy. Ultraviolet 20 fs excitation pulses centered at 325 nm were used to populate a vibrationally hot excited pi bipyridyl state of the reactant that quickly relaxes to a dissociative Ru-I state resulting in the release of one of the carbonyl groups. Quantum yield measurements have indicated that about 40% of the initially exited reactant molecules form the final photoproduct. A 62 fs rise component in the transient absorption (TA) signal was observed at all probe wavelengths in the visible region for the ongoing reaction, while the rise for the photoproduct was pulse limited (20 fs). We assign the observed 62 fs time component to the depopulation of the repulsive CO dissociative state. Vibrational coherences of the TA signals were observed at a wavenumber of 90 cm(-1). The resolved frequency, typical of I-Ru-I vibrational modes, is assigned to trans-cis isomerization of the iodines of the five-coordinated intermediate and damping of this oscillation in 500 fs to simultaneous solvent coordination. Cooling of the hot reactant and the product molecules occurs on a much slower time scale from 4 to 270 ps (Lehtovuori, V.; Aumanen, J.; Myllyperki?, P.; Rini, M.; Nibbering, E. T. J.; Korppi-Tommola, J. J. Phys. Chem. A 2004, 108, 1644).     

Variational Approximations for Generalized Linear Latent Variable Models

Generalized linear latent variable models (GLLVMs) are a powerful class of models for understanding the relationships among multiple, correlated responses. Estimation, however, presents a major challenge, as the marginal likelihood does not possess a closed form for nonnormal responses. We propose a variational approximation (VA) method for estimating GLLVMs. For the common cases of binary, ordinal, and overdispersed count data, we derive fully closed-form approximations to the marginal log-likelihood function in each case. Compared to other methods such as the expectation-maximization algorithm, estimation using VA is fast and straightforward to implement. Predictions of the latent variables and associated uncertainty estimates are also obtained as part of the estimation process. Simulations show that VA estimation performs similar to or better than some currently available methods, both at predicting the latent variables and estimating their corresponding coefficients. They also show that VA estimation offers dramatic reductions in computation time particularly if the number of correlated responses is large relative to the number of observational units. We apply the variational approach to two datasets, estimating GLLVMs to understanding the patterns of variation in youth gratitude and for constructing ordination plots in bird abundance data. R code for performing VA estimation of GLLVMs is available online. Supplementary materials for this article are available online.     

Transport properties of heterogeneous materials. Combining computerised X-ray micro-tomography and direct numerical simulations

Feasibility of a method for finding flow permeability of porous materials, based on combining computerised X-ray micro-tomography and numerical simulations, is assessed. The permeability is found by solving fluid flow through the complex 3D pore structures obtained by tomography for actual material samples. We estimate overall accuracy of the method and compare numerical and experimental results. Factors contributing to uncertainty of the method include numerical error arising from the finite resolution of tomographic images and the rather small sample size available with the present tomographic techniques. The total uncertainty of computed values of permeability is, however, not essentially larger than that of experimental results. We conclude that the method provides a feasible alternative for finding fluid flow properties of the kind of materials studied. It can be used to estimate all components of permeability tensor and is useful in cases where direct measurements are not achievable. Analogous methods can be applied to other modes of transport, such as diffusion and heat conduction.