The effect of the diffusion time and pulse gradient duration ratio on the diffraction pattern and the structural information estimated from q-space diffusion MR: experiments and simulations

q-Space diffusion MRI (QSI) provides a means of obtaining microstructural information about porous materials and neuronal tissues from diffusion data. However, the accuracy of this structural information depends on experimental parameters used to collect the MR data. q-Space diffusion MR performed on clinical scanners is generally collected with relatively long diffusion gradient pulses, in which the gradient pulse duration, δ, is comparable to the diffusion time, Δ. In this study, we used phantoms, consisting of ensembles of microtubes, and mathematical models to assess the effect of the ratio of the diffusion time and the duration of the diffusion pulse gradient, i.e., Δ/δ, on the MR signal attenuation vs. q, and on the measured structural information extracted therefrom. We found that for Δ/δ  1, the diffraction pattern obtained from q-space MR data are shallower than when the short gradient pulse (SGP) approximation is satisfied. For long δ the estimated compartment size is, as expected, smaller than the real size. Interestingly, for Δ/δ  1 the diffraction peaks are shifted to even higher q-values, even when δ is kept constant, giving the impression that the restricted compartments are even smaller than they are. When phantoms composed of microtubes of different diameters are used, it is more difficult to estimate the diameter distribution in this regime. Excellent agreement is found between the experimental results and simulations that explicitly account for the use of long duration gradient pulses. Using such experimental data and this mathematical framework, one can estimate the true compartment dimensions when long and finite gradient pulses are used even when Δ/δ  1.     

Interpolation of nonlinear positive or order preserving operators on Banach lattices

Positivity - We study the relationship between exact interpolation spaces for positive, linear operators, for order preserving, Lipschitz continuous operators, and for positive...     

Self-assembly of resorcin[4]arene in the presence of small alkylammonium guests in solution

We followed the self-assembly of C-alkyl-resorcin[4]arene (1a,1b) in the presence of tetraethylammonium salts (2). The X-ray structure of C-ethyl-resorcin[4]arene (1c) in the presence of TEABr (2b), showed a dimer encapsulating one guest. However, diffusion measurements reveal that two molecules of tetraethylammonium are encapsulated within the hexameric capsule of 1a,b in chloroform, regardless of the anion. Most importantly, the anion affects the role of water in the self-assembly and the nature of the formed capsules.     

On the number of significant mode-mode anharmonic couplings in vibrational calculations: Correlation-corrected vibrational self-consistent field treatment of di-, tri-, and tetrapeptides

A computational study is made of the number of important anharmonic mode-mode couplings in the context of vibrational calculations for di-, tri-, and tetrapeptides. The method employed is the correlation-corrected vibrational self-consistent field (CC-VSCF) algorithm, which includes correlation effects between different vibrational modes. It is found that results of good accuracy can be obtained in calculations that include only N log N mode-mode coupling terms, where N is the number of modes. This simplification significantly accelerates CC-VSCF calculations for large molecules. A criterion based on the characteristics of the normal-mode displacements is employed to predict a priori unimportant coupling terms. The criterion is tested statistically using Spearman's rank correlation coefficient. The results are illustrated by calculations for several di-, tri-, and tetrapeptides using semiempirical PM3 potential surfaces. These results are analyzed and a statistical model for error estimation is given. The decrease in the number of included coupling from N(2) to N log N opens possibilities of anharmonic vibrational calculations for large peptides.     

Calcium-Ligand Cooperation Promoted Activation of N2O,Amine, and H2 as well as Catalytic Hydrogenation of Imines,Quinoline, and Alkenes

Bond activation and catalysis using s-block metals are of great significance. Herein, a series of calcium pincer complexes with deprotonated side arms have been prepared using pyridine-based PNP and PNN ligands. The complexes were characterized by NMR and X-ray crystal diffraction. Utilizing the obtained calcium complexes, unprecedented N₂O activation by metal-ligand cooperation (MLC) involving dearomatization-aromatization of the pyridine ligand was achieved, generating aromatized calcium diazotate complexes as products. Additionally, the dearomatized calcium complexes were able to activate the N−H bond as well as reversibly activate H₂, offering an opportunity for the catalytic hydrogenation of various unsaturated molecules. DFT calculations were applied to analyze the electronic structures of the synthesized complexes and explore possible reaction mechanisms. This study is an important complement to the area of MLC and main-group metal chemistry.     

Relaxation dynamics of highly vibrationally excited picoline isomers (E(vib) = 38 300 cm(-1)) with CO2: the role of state density in impulsive collisions

Strong collisions of highly vibrationally excited picoline isomers and CO2 (00(0)0) were investigated using high resolution transient IR absorption probing to investigate the role of donor state density. Vibrationally excited 3-picoline and 4-picoline (3-methylpyridine and 4 methylpyridine) with E(vib) = 38300 cm(-1) were prepared by 266 nm excitation followed by rapid internal conversion. Transient IR probe measurements of the nascent rotational and translational energy gain in CO2 (00(0)0) show that large DeltaE collisions for 3- and 4-picoline are similar to those for excited 2-picoline. The probability distributions for the large DeltaE energy transfer of the three isomers have similar dependence on DeltaE. The results are compared with other earlier results demonstrating that the shape of the large DeltaE probability distribution correlates with the DeltaE dependence of the donor vibrational state density. The results are discussed in terms of the GRETCHEN model for collisional relaxation.     

Targeting deubiquitinases enabled by chemical synthesis of proteins

Ubiquitination/ubiquitylation is involved in a wide range of cellular processes in eukaryotes, such as protein degradation and DNA repair. Ubiquitination is a reversible post-translational modification, with the removal of the ubiquitin (Ub) protein being catalyzed by a family of enzymes known as deubiquitinases (DUBs). Approximately 100 DUBs are encoded in the human genome and are involved in a variety of regulatory processes, such as cell-cycle progression, tissue development, and differentiation. DUBs were, moreover, found to be associated with several diseases and as such are emerging as potential therapeutic targets. Several directions have been pursued in the search for lead anti-DUB compounds. However, none of these strategies have delivered inhibitors reaching advanced clinical stages due to several challenges in the discovery process, such as the absence of a highly sensitive and practically available high-throughput screening assay. In this study, we report on the design and preparation of a FRET-based assay for DUBs based on the application of our recent chemical method for the synthesis of Ub bioconjugates. In the assay, the ubiquitinated peptide was specifically labeled with a pair of FRET labels and used to screen a library comprising 1000 compounds against UCH-L3. Such analysis identified a novel and potent inhibitor able to inhibit this DUB in time-dependent manner with k(inact) = 0.065 min(-1) and K(i) = 0.8 μM. Our assay, which was also found suitable for the UCH-L1 enzyme, should assist in the ongoing efforts targeting the various components of the ubiquitin system and studying the role of DUBs in health and disease.     

New perspectives in turbulent Rayleigh-Bénard convection

Recent experimental, numerical and theoretical advances in turbulent Rayleigh-Bénard convection are presented. Particular emphasis is given to the physics and structure of the thermal and velocity boundary layers which play a key role for the better understanding of the turbulent transport of heat and momentum in convection at high and very high Rayleigh numbers. We also discuss important extensions of Rayleigh-Bénard convection such as non-Oberbeck-Boussinesq effects and convection with phase changes.     

Every ordinary differential equation with a strict Lyapunov function is a gradient system

We explain and prove the statement from the title. This allows us to formulate a new type of gradient inequality and to obtain a new stabilization result for gradient-like ordinary differential equations.     

Inhibition of Bacterial Adhesion and Biofilm Formation by Seed-Derived Ethanol Extracts from Persea americana Mill

The increase in antibiotic resistance demands innovative strategies to combat microorganisms. The current study evaluated the antibacterial and antivirulence effects of ethanol extracts from Persea americana seeds obtained by the Soxhlet (SE) and maceration (MaE) methods. The UHPLC-DAD-QTOF analysis showed mainly the presence of polyphenols and neolignan. Ethanol extracts were not cytotoxic to mammalian cells (CC₅₀ > 500 µg/mL) and displayed a moderate antibacterial activity against Pseudomonas aeruginosa (IC₅₀ = 87 and 187 µg/mL) and Staphylococcus aureus (IC₅₀ = 144 and 159 µg/mL). Interestingly, no antibacterial activity was found against Escherichia coli. SE and MaE extracts were also able to significantly reduce the bacterial adhesion to A549 lung epithelial cells. Additionally, both extracts inhibited the biofilm growth at 24 h and facilitated the release of internal cell components in P. aeruginosa, which might be associated with cell membrane destabilization. Real-time PCR and agarose electrophoresis gel analysis indicated that avocado seed ethanol extracts (64 µg/mL) downregulated virulence-related factors such as mexT and lasA genes. Our results support the potential of bioproducts from P. americana seeds as anti-adhesive and anti-biofilm agents.