Characterization of Pentaclethra macroloba oil

The Pracaxi oil—(Pentaclethra macroloba) contains high concentrations of fatty acids with emollient action that contribute to skin hydration. The use of this oil is supported by the utilization of natural resources thus enabling regional development and social contribution. The objective of this study was to characterize the P. macroloba oil by thermogravimetry (TG, DTG, and DTA), gas chromatography, Fourier transform infrared spectroscopy (FT-IR), and oxidation stability—Rancimat, aiming at the quality control of plant raw material. Three samples of crude oil sold by Amazon Oil Industry (Ananindeua, Pará, Brazil) were studied. The analysis of these oil samples showed different fatty acids, especially the behenic, oleic, linoleic, and lignoceric acids totalizing approximately 96 % of the grease composition and in smaller percentage arachidic, lauric, myristic, palmitic, and linolenic acids were found. The major acids have wide medicinal use. According to the TG/DTG curve, thermal stability was observed up to 220 °C, indicating a greater mass loss related to the dehydration and elimination of volatile substances. The thermal decomposition process occurred in the range of 430–450° C according to the DTG curve. The absorption spectrum in the infrared region (FT-IR) showed well-defined bands confirming the presence of functional groups present in the oil. Tests in a Rancimat have shown an induction period between 8 and 10 h demonstrating that the samples are in agreement with the standards required by ANP No. 14/2012 which requires at least 6 h of testing.     

3,3′‐Bi(1,2,4‐oxadiazoles) Featuring the Fluorodinitromethyl and Trinitromethyl Groups

Here we report on the preparation of two hydrogen atom free 3,3′‐bi(1,2,4‐oxadiazole) derivatives. 5,5′‐Bis(fluorodinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole) was synthesised by fluorination of diammonium 5,5′‐bis(dinitromethanide)‐3,3′‐bi(1,2,4‐oxadiazole). For our previously reported analogue 5,5′‐bis(trinitromethyl)‐3,3′‐bi(1,2,4‐oxadiazole), a new synthetic route starting from new 3,3′‐bi(1,2,4‐oxadiazolyl)‐5,5′‐diacetic acid was developed. In this course also hitherto unknown 5,5′‐dimethyl‐3,3′‐bi(1,2,4‐oxadiazole) was isolated. The compounds were characterised by multinuclear NMR spectroscopy, IR and Raman spectroscopy, elemental analysis as well as mass spectrometry. X‐ray diffraction studies were performed and the crystal structures for the 5,5'‐dimethyl and 5,5'‐(fluorodinitromethyl) derivatives are reported. The energetic 5,5'‐(fluorodinitromethyl) and 5,5'‐(trinitromethyl) compounds do not contain any hydrogen atoms and show remarkable high densities. Furthermore, the thermal stabilities and sensitivities were determined by differential scanning calorimetry (DSC) and standardised impact and friction tests. The heats of formation were calculated by the atomisation method based on CBS‐4M enthalpies. With these values and the room‐temperature X‐ray densities, several detonation and propulsion parameters, such as the detonation velocity and pressure as well as the specific impulse of mixtures with aluminium, were computed using the EXPLO5 code.     

Click approaches in sol–gel chemistry

The combination of the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction with sol–gel processing enables the versatile preparation of sol–gel materials under different shapes with targeted functionalities through a diversity-oriented approach. In this account, the development of the CuAAC reaction under anhydrous conditions for the synthesis of sol–gel precursors and for the assembling of magnetic nanoparticles on self-assembled monolayers is related, as well as the use of the classical CuAAC methodologies for the functionalization of mesoporous silica nanoparticles and microdots arrays. Coupling CuAAC and Sol–Gel will result in simplified preparations of multifunctional materials with controlled morphologies.     

Macrocybin,a Natural Mushroom Triglyceride,Reduces Tumor Growth In Vitro and In Vivo through Caveolin-Mediated Interference with the Actin Cytoskeleton

Mushrooms have been used for millennia as cancer remedies. Our goal was to screen several mushroom species from the rainforests of Costa Rica, looking for new antitumor molecules. Mushroom extracts were screened using two human cell lines: A549 (lung adenocarcinoma) and NL20 (immortalized normal lung epithelium). Extracts able to kill tumor cells while preserving non-tumor cells were considered “anticancer”. The mushroom with better properties was Macrocybe titans. Positive extracts were fractionated further and tested for biological activity on the cell lines. The chemical structure of the active compound was partially elucidated through nuclear magnetic resonance, mass spectrometry, and other ancillary techniques. Chemical analysis showed that the active molecule was a triglyceride containing oleic acid, palmitic acid, and a more complex fatty acid with two double bonds. The synthesis of all possible triglycerides and biological testing identified the natural compound, which was named Macrocybin. A xenograft study showed that Macrocybin significantly reduces A549 tumor growth. In addition, Macrocybin treatment resulted in the upregulation of Caveolin-1 expression and the disassembly of the actin cytoskeleton in tumor cells (but not in normal cells). In conclusion, we have shown that Macrocybin constitutes a new biologically active compound that may be taken into consideration for cancer treatment.     

MVF Sensor Enables Analysis of Nucleic Acids with Stable Secondary Structures

One major challenge in nucleic acids analysis by hybridization probes is a compromise between the probe's tight binding and sequence‐selective recognition of nucleic acid targets folded into stable secondary structures. We have been developing a four‐way junction (4WJ)‐based sensor that consists of a universal stem‐loop (USL) probe immobilized on an electrode surface and two adaptor strands (M and F). The sensor was shown to be highly selective towards single base mismatches at room temperature, able to detect multiple targets using the same USL probe, and have improved ability to detect folded nucleic acids. However, some nucleic acid targets, including natural RNA, are folded into very stable secondary and tertiary structures, which may represent a challenge even for the 4WJ sensors. This work describes a new sensor, named MVF since it uses three probe stands M, V and F, which further improves the performance of 4WJ sensors with folded targets. The MVF sensor interrogating a 16S rRNA NASBA amplicon with calculated folding energy of ?32.82 kcal/mol has demonstrated 2.5‐fold improvement in a signal‐to‐background ratio in comparison with a 4WJ sensor lacking strand V. The proposed design can be used as a general strategy in the analysis of folded nucleic acids including natural RNA.     

Real‐Time In Vivo Detection of Cellular Senescence through the Controlled Release of the NIR Fluorescent Dye Nile Blue

In vivo detection of cellular senescence is accomplished by using mesoporous silica nanoparticles loaded with the NIR‐FDA approved Nile blue (NB) dye and capped with a galactohexasaccharide ( S3 ). NB emission at 672 nm is highly quenched inside S3 , yet a remarkable emission enhancement is observed upon cap hydrolysis in the presence of β‐galactosidase and dye release. The efficacy of the probe to detect cellular senescence is tested in vitro in melanoma SK‐Mel‐103 and breast cancer 4T1 cells and in vivo in palbociclib‐treated BALB/cByJ mice bearing breast cancer tumor.     

Ring opening polymerization of cyclic organosilicon compounds: Recent progress

A novel initiator, i.e. trimethylsilylmethyllithium has been successfully used for the ring opening polymerization of cyclosiloxanes in toluene, in the presence of the cryptand [211]. Suitable conditions have been found in which monomodal distributions of molecular weights of polysiloxanes are observed by GPC, even in the case of D₄ and 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl cyclotetra siloxane (D₄Vi) polymerizations. Moreover, kinetics of propagation and of formation of cyclosiloxanes can be followed by ²⁹Si or ¹³C NMR spectroscopy on living polymer solutions. The rate of propagation of hexaethylcyclotrisiloxane is 120 times lower than that of the corresponding dimethylated analog D₃, under the same conditions.     

The Effects of Formulation on Imidacloprid Dissipation in Grapes and Vine Leaves and on Required Pre-Harvest Intervals under Lebanese Climatic Conditions

In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg⁻¹), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns.     

Chondroitin Sulfate Protects the Liver in an Experimental Model of Extra-Hepatic Cholestasis Induced by Common Bile Duct Ligation

During liver fibrogenesis, there is an imbalance between regeneration and wound healing. The current treatment is the withdrawal of the causing agent; thus, investigation of new and effective treatments is important. Studies have highlighted the action of chondroitin sulfate (CS) in different cells; thus, our aim was to analyze its effect on an experimental model of bile duct ligation (BDL). Adult Wistar rats were subjected to BDL and treated with CS for 7, 14, 21, or 28 days intraperitoneally. We performed histomorphometric analyses on Picrosirius-stained liver sections. Cell death was analyzed according to caspase-3 and cathepsin B activity and using a TUNEL assay. Regeneration was evaluated using PCNA immunohistochemistry. BDL led to increased collagen content with corresponding decreased liver parenchyma. CS treatment reduced total collagen and increased parenchyma content after 21 and 28 days. The treatment also promoted changes in the hepatic collagen type III/I ratio. Furthermore, it was observed that CS treatment reduced caspase-3 activity and the percentage of TUNEL-positive cells after 14 days and cathepsin B activity only after 28 days. The regeneration increased after 14, 21, and 28 days of CS treatment. In conclusion, our study showed a promising hepatoprotective action of CS in fibrogenesis induced by BDL.     

Hydrogen Bonding in the Dimer and Monohydrate of 2-Adamantanol: A Test Case for Dispersion-Corrected Density Functional Methods

Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterized using broadband chirped-pulse microwave spectroscopy in the 2–8 GHz frequency region. Two different gauche-gauche O-H···O hydrogen-bonded isomers were observed for the dimer of 2-adamantanol, while a single isomer was observed for the monomer and the monohydrate. The experimental rotational parameters were compared with molecular orbital calculations using density functional theory (B3LYP-D3(BJ), B2PLYP-D3(BJ), CAM-B3LYP-D3(BJ), ωB97XD), additionally providing energetic and electron density characterization. The shallow potential energy surface makes the dimer an interesting case study to benchmark dispersion-corrected computational methods and conformational search procedures.