Nanoporous magnets of chiral and racemic [{Mn(HL)}2Mn{Mo(CN)7}2] with switchable ordering temperatures (TC = 85 K <--> 106 K) driven by H2O sorption (L = N,N-dimethylalaninol)

Molecule-based solids represent a rare opportunity to combine, adjust, and interrelate structural and physical functionalities to develop multifunctional materials. Here we report on a series of porous supramolecular magnets whose magnetic properties are related to their sorption state. A family of magnets of the formula [{Mn(HL)(H2O)}2Mn{Mo(CN)7}2].2H2O have been obtained by assembling the heptacyano-metalate building unit {Mo(CN)7}4- with Mn(II) in the presence of protonated N,N-dimethylalaninol (L) as ligand, the latter being either as a racemic mixture or as a chiral R- or S-enantiomer. The resulting magnets possess an open framework structure and exhibit a TC with a switching behavior (TC = 85 K <--> 106 K) as a function of the hydration state. Moreover, chiral magnets are formed with the optically active ligands. The H2O and gas (N2, CO2, CO) sorption features, the magnetic behavior of both the hydrated and dehydrated magnets, and the crystal structures of the hydrated chiral (S) and racemic magnets are described.     

Structural basis of pyrazolopyrimidine derivatives as CAMKIIδ kinase inhibitors: insights from 3D QSAR,docking studies and in silico ADMET evaluation

Ca²⁺/calmodulin-dependent protein kinase II (CAMKIIδ) belongs to the serine/threonine kinase family, which is involved in a broad range of cellular events in cell survival and proliferation as well as a number of other signal transduction pathways. Thus, it is regarded a promising target for treatment of cancers. In the present paper, a three-dimensional quantitative structure–activity relationship and molecular docking were applied to investigate a series of new CAMKIIδ inhibitors of pyrazolopyrimidine derivatives. The determination coefficient (R²) and leave-one-out cross-validation coefficient (Q²) of CoMSIA model are 0.676 and 0.956, respectively. The predictive ability of this model was evaluated by the external validation using a test set of eight compounds with a predicted determination coefficient \(R^{ 2}_{\text{test}}\) of 0.80, besides the mean absolute error of the test set was 0.328 log units. Docking results are in concordance with CoMSIA contour maps, gave the information for interactive mode exploration. Based on those satisfactory results, newly designed molecules were predicted with highly potent CAMKIIδ inhibitory activity, additionally, they have showed promising results in the preliminary in silico ADMET evaluations. This study could expand our understanding of pyrazolopyrimidine derivatives as inhibitors of CAMKIIδ and would be of great help in lead optimization for early drug discovery of highly potent CAMKIIδ inhibitors.     

Optimization of a liquid chromatography ion mobility-mass spectrometry method for untargeted metabolomics using experimental design and multivariate data analysis

High-resolution mass spectrometry coupled with pattern recognition techniques is an established tool to perform comprehensive metabolite profiling of biological datasets. This paves the way for new, powerful and innovative diagnostic approaches in the post-genomic era and molecular medicine. However, interpreting untargeted metabolomic data requires robust, reproducible and reliable analytical methods to translate results into biologically relevant and actionable knowledge. The analyses of biological samples were developed based on ultra-high performance liquid chromatography (UHPLC) coupled to ion mobility - mass spectrometry (IM-MS). A strategy for optimizing the analytical conditions for untargeted UHPLC-IM-MS methods is proposed using an experimental design approach. Optimization experiments were conducted through a screening process designed to identify the factors that have significant effects on the selected responses (total number of peaks and number of reliable peaks). For this purpose, full and fractional factorial designs were used while partial least squares regression was used for experimental design modeling and optimization of parameter values. The total number of peaks yielded the best predictive model and is used for optimization of parameters setting.     

An LQP Method for Pseudomonotone Variational Inequalities

In this paper, we proposed a modified Logarithmic-Quadratic Proximal (LQP) method [Auslender et al.: Comput. Optim. Appl. 12, 31–40 (1999)] for solving variational inequalities problems. We solved the problem approximately, with constructive accuracy criterion. We show that the method is globally convergence under that the operator is pseudomonotone which is weaker than the monotonicity and the solution set is nonempty. Some preliminary computational results are given.The author was supported by the NSFC grants Nos: 70571033 and 10571083.     

Positive Elements and Automatic Continuity of Algebra Morphisms

We use positive elements of Hermitian algebras to give results on automatic continuity of algebra morphisms. Consequences and applications are also given.      

Continuite-Besov des operateurs definis par des integrales singulieres

Our purpose is to give necessary and sufficient conditions for continuity, on Besov spaces \(\dot B_p^{s,q} \) , of singular integral operators whose kernels satisfy: $$|\partial _x^\alpha K(x, y)| \leqslant C_\alpha |x - y|^{ - n - |\alpha |} for|\alpha | \leqslant m,$$ where m ∈ ? and 0 < s < m. The criterion is compared to the M.Meyer theorem [11] where 0 _p ^s,q spaces for s?1. For 0 _p ^s,p space is characterized by the localization and by Besov-capacity. In particular we show that the BMO ₁ ^s,1 space is characterized by generalized Carleson conditions.     

Effect of sterilization on non-woven polyethylene terephthalate fiber structures for vascular grafts

Non-woven polyethylene terephthalate (PET) fibers produced via melt blowing and compounded into a 6 mm diameter 3D tubular scaffold were developed with artery matching mechanical properties. This work compares the effects of ethylene oxide (EtO) and low temperature plasma (LTP) sterilization on PET surface chemistry and biocompatibility. As seen through X-ray photoelectron spectroscopy (XPS) analysis, LTP sterilization led to an increase in overall oxygen content and the creation of new hydroxyl groups. EtO sterilization induced alkylation of the PET polymer. The in vitro cytotoxicity showed similar fibroblastic viability on LTP- and EtO-treated PET fibers. However, TNF-α release levels, indicative of macrophage activation, were significantly higher when macrophages were incubated on EtO-treated PET fibers. Subcutaneous mice implantation revealed an inflammatory response with foreign body reaction to PET grafts independent of the sterilization procedure.     

Towards the limit of atropochiral stability: H-MIOP, an N-heterocyclic carbene precursor and cationic analogue of the H-MOP ligand

The configurational stability of biaryl motifs is addressed for the 1-naphthyl-N-benzimidazolyl motif substituted by a single diphenylphosphinyl group at the 2-position. The atropoenantiomers of the N-methylated cation H-MIOP, a less sterically locked analogue of the neutral H-MOP ligand, were resolved by enantiospecific cleavage of the N(2)C-P bond of the resolved enantiomers of BIMIONAP. The latter were obtained by enantiospecific N-methylation of the previously resolved enantiomers of neutral BIMINAP. PdCl(2) complexes of the P,C-chelating N-heterocyclic carbene (NHC)-phosphine ligands derived from (R)- and (S)-H-MIOP were prepared by two enantiospecific routes: by N(2)C-P bond cleavage from the (R)- and (S)-BIMIONAP-PdCl(2) complexes, or by simultaneous coordination of the P and C atoms of the in situ generated free NHC-phosphine. The enantiomerization pathways of H-MOP, H-MIOP, and corresponding NHC-phosphine have been investigated at the B3PW91/6-31G(d,p) level of theory. The calculated enantiomerization barriers of H-MOP and H-MIOP in acetonitrile are equal to 176.0 and 146.4 kJ mol(-1), respectively, and are mainly determined by the distortion of the naphthalene and/or benzimidazole motifs in the transition state. Beyond the stability of their optical rotation at room temperature, the respective calculated Oki's racemization temperatures of 334 and 225 °C allowed us to consider both ligands as configurationally stable.