Synthesis,Photophysics and Nonlinear Optical Properties of Stilbenoid Pyrimidine‐Based Dyes Bearing Methylenepyran Donor Groups

The nonlinear properties and the photophysical behavior of two π‐conjugated chromophores that incorporate an electron‐deficient pyrimidine core (A) and γ‐methylenepyrans as terminal donor (D) groups have been thoroughly investigated. Both dipolar and quadrupolar branching strategies are explored and rationalized on the basis of the Frenkel exciton model. Even though a cooperative effect is clearly observed if the dimensionality is increased, the nonlinear optical (NLO) response of this series is moderate if one considers the nature of the D/A couple and the size of the chromophores (as measured by the number of π electrons). This effect was attributed to a disruption in the electronic conjugation within the dyes’ scaffold for which the geometry deviates from planarity owing to a noticeable twisting of the pyranylidene end‐groups. This latter structural parameter also has a strong influence on the excited‐state dynamics, which leads to a very efficient fluorescence quenching.     

Comparison of various silica‐based monoliths for the analysis of large biomolecules†

In the present study, three types of silica‐based monoliths, i.e. the first and second generations of commercial silica monolithic columns and a wide‐pore prototype monolith were compared for the analysis of large biomolecules. These molecules possess molecular weights between 1 and 66 kDa. The gradient kinetic performance of the first‐generation monolith was lower than that of the second generation, for large biomolecules (>14 kDa) but very close with smaller ones (1.3–5.8 kDa). In contrast, the wide‐pore prototype column was particularly attractive with proteins larger than 19 kDa (higher peak capacity). Among these three columns, the selectivity and retention remained quite similar but a possible larger number of accessible and charged residual silanols was noticed on the wide‐pore prototype material, which led to unpredicted small changes in selectivity and slightly broader peaks than expected. The peak shapes attained with the addition of 0.1% formic acid in the mobile phase remained acceptable for MS coupling, particularly for biomolecules of less than 6 kDa. It was found that one of the major issues with all of these silica‐based monoliths is the possible poor recovery of large biomolecules (principally with monoclonal antibody fragments of more than 25 kDa).     

CZE study on adsorption processes of aliphatic and aromatic amines on PMMA chip

Adsorption processes on a PMMA chip linked with CZE separations of a group of 13 aliphatic and aromatic mono‐ and di‐amines were studied. Due to the lack of chromophores within aliphatic amines, contact conductivity detection implemented directly onto the chip was used for monitoring of cationic CZE separations. To prevent an adsorption of studied amines to the chip channels, the surface of PMMA chip was modified by dynamic coating. Different surface modifiers, such as aliphatic oligoamines (diethylenetriamine and triethylenetetramine), were added to the BGE solutions filling the chip channels. The effect of various concentrations of surface modifiers on peak profiles and separation parameters of amines was monitored. Of these, mainly, aliphatic di‐amines and aromatic mono‐amines adversely affected the CZE resolution of a whole group of analytes by their strong adsorption to the chip channels. A propionate BGE with pH 3.2 containing 100 μM triethylenetetramine and 25 mM 18‐crown‐6‐ether was found suitable for CZE resolution of 12 from a total of 13 amines studied. Simple dynamic modification of the surface of PMMA chip enabled fast (analysis time lasted 9 min), sensitive (sub‐μM LODs reached) and reproducible (1–3% RSD of the peak areas) CZE analysis of the aliphatic and aromatic amines.     

Magnetic Hyperthermia Enhancement in Iron-based Materials Driven by Carbon Support Interactions

Magnetic hyperthermia (MH) shows great potential in clinical applications because of its very localized action and minimal side effects. Because of their high saturation magnetization values, reduced forms of iron are promising candidates for MH. However, they must be protected in order to overcome their toxicity and instability (i. e., oxidation) under biological conditions. In this work, a novel methodology for the protection of iron nanoparticles through confinement within graphitic carbon layers after thermal treatment of preformed nanoparticles supported on carbon is reported. We demonstrate that the size and composition of the nascent confined iron nanoparticles, as well as the thickness of their protective carbon layer can be controlled by selecting the nature of the carbon support. Our findings reveal that a higher nanoparticle–carbon interaction, mediated by the presence of oxygen-containing groups, induces the formation of small and well-protected α-Fe-based nanoparticles that exhibit promising results towards MH based on their enhanced specific absorption rate values.     

In Vitro Antiplasmodial and Cytotoxic Activities of Compounds from the Roots of Eriosema montanum Baker f. (Fabaceae)

Malaria remains one of the leading causes of death in sub-Saharan Africa, ranked in the top three infectious diseases in the world. Plants of the Eriosema genus have been reported to be used for the treatment of this disease, but scientific evidence is still missing for some of them. In the present study, the in vitro antiplasmodial activity of the crude extract and compounds from Eriosema montanum Baker f. roots were tested against the 3D7 strain of Plasmodium falciparum and revealed using the SYBR Green, a DNA intercalating compound. The cytotoxicity effect of the compounds on a human cancer cell line (THP-1) was assessed to determine their selectivity index. It was found that the crude extract of the plant displayed a significant antiplasmodial activity with an IC₅₀ (µg/mL) = 17.68 ± 4.030 and a cytotoxic activity with a CC₅₀ (µg/mL) = 101.5 ± 12.6, corresponding to a selective antiplasmodial activity of 5.7. Bioactivity-guided isolation of the major compounds of the roots’ crude extract afforded seven compounds, including genistein, genistin and eucomic acid. Under our experimental conditions, using Artemisinin as a positive control, eucomic acid showed the best inhibitory activity against the P. falciparum 3D7, a well-known chloroquine-sensitive strain. The present results provide a referential basis to support the traditional use of Eriosema species in the treatment of malaria.     

Titanium‐Catalyzed Hydroalumination of Conjugated Dienes: Access to Fulvene‐Derived Allylaluminium Reagents and Their Diastereoselective Reactions with Carbonyl Compounds

The described titanium‐catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminium reagents. The reaction is carried out by using diisobutylaluminium hydride (DIBAL‐H) and a catalytic amount of [Cp₂TiCl₂] (Cp=cyclopentadienyl). When applied to mono‐ and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner. The formed allylaluminium compounds react regio‐ and stereoselectively with both aldehydes and ketones to afford homoallylic alcohols that are suitable synthons for functionalized cyclopentanones. An extension of this methodology to simple dienes was also investigated. In the proposed mechanism, the initially formed bimetallic species (Ti/Al) are involved in the two possible catalytic cycles with a direct hydroalumination or/and a hydrotitanation followed by a titanium to aluminium transmetallation.     

Optimization of microfluidization for the homogeneous distribution of cellulose nanocrystals (CNCs) in biopolymeric matrix

Microfluidization, which is a high-pressure homogenization technique, was used to develop highly dispersed cellulose nanocrystal (CNC) reinforced chitosan based nanocomposite films. A three factor central composite design with five levels was designed to systematically optimize the microfluidization process. The three factors were the CNC content, the microfluidization pressure and the number of microfluidization cycles. Response surface methodology was used to obtain relationship between the mechanical properties of the nanocomposite films and the factors. Polynomial equations were generated based on the regression analysis of the factors and the predicted properties of the nanocomposite films were in good agreement with the experimental results. Microfluidization effectively reduced the CNC–chitosan aggregates and improved the mechanical properties of the nanocomposite films. Microscopic analysis of the microfluidized nanocomposite films revealed a 10–15 times reduction in the size of the aggregates compared to the non-microfluidized CNC/chitosan films and an increase in the root mean square surface roughness (Rq).     

Perfect state transfer on weighted graphs of the Johnson scheme

Letters in Mathematical Physics - We characterize quantum perfect state transfer on real-weighted graphs of the Johnson scheme $${\mathcal {J}}(n,k)$$ , which represent spin networks with...