Water‐Soluble Polymeric Carbon Nitride Colloidal Nanoparticles for Highly Selective Quasi‐Homogeneous Photocatalysis

Heptazine‐based polymeric carbon nitrides (PCN) are promising photocatalysts for light‐driven redox transformations. However, their activity is hampered by low surface area resulting in low concentration of accessible active sites. Herein, we report a bottom‐up preparation of PCN nanoparticles with a narrow size distribution (ca. 10±3 nm), which are fully soluble in water showing no gelation or precipitation over several months. They allow photocatalysis to be carried out under quasi‐homogeneous conditions. The superior performance of water‐soluble PCN, compared to conventional solid PCN, is shown in photocatalytic H₂O₂ production via reduction of oxygen accompanied by highly selective photooxidation of 4‐methoxybenzyl alcohol and benzyl alcohol or lignocellulose‐derived feedstock (ethanol, glycerol, glucose). The dissolved photocatalyst can be easily recovered and re‐dissolved by simple modulation of the ionic strength of the medium, without any loss of activity and selectivity.     

Quartz crystal microbalance with dissipation monitoring of the enzymatic hydrolysis of steam-treated lignocellulosic nanofibrils

Quartz crystal microbalance with dissipation (QCM-D) monitoring was performed to investigate the impact of steam treatment (ST) on the enzymatic hydrolysis of lignocellulosic nanofibrils (LCNFs). ST at mild temperatures up to 140 °C mainly affected the hemicellulose content of LCNFs. The hemicellulose constituents in the water-soluble fraction and the residual LCNF were quantified. The impact of changes in hemicellulose by ST on enzymatic hydrolysis was monitored by QCM-D using Acremonium cellulase as a source of multicomponent enzymes including hemicellulases. LCNFs without ST showed distinctive initial changes in frequency and energy dissipation, which differed from those of pure cellulose film, whereas these changes shifted toward typical changes of enzymatic hydrolysis of pure cellulosic films with increasing ST temperature. The QCM-D results suggested that hemicellulose located around cellulose microfibrils is rapidly decomposed, thus exposing the cellulose surface shortly after initial enzymatic hydrolysis, and then the main enzymatic hydrolysis of cellulose occurs.     

Multi-analytical platform metabolomic approach to study miltefosine mechanism of action and resistance in Leishmania

Miltefosine (MT) (hexadecylphosphocholine) was implemented to cope with resistance against antimonials, the classical treatment in Leishmaniasis. Given the scarcity of anti- Leishmania (L) drugs and the increasing appearance of resistance, there is an obvious need for understanding the mechanism of action and development of such resistance. Metabolomics is an increasingly popular tool in the life sciences due to it being a relatively fast and accurate technique that can be applied either with a particular focus or in a global manner to reveal new knowledge about biological systems. Three analytical platforms, gas chromatography (GC), liquid chromatography (LC) and capillary electrophoresis (CE) have been coupled to mass spectrometry (MS) to obtain a broad picture of metabolic changes in the parasite. Impairment of the polyamine metabolism from arginine (Arg) to trypanothione in susceptible parasites treated with MT was in some way expected, considering the reactive oxygen species (ROS) production described for MT. Importantly, in resistant parasites an increase in the levels of amino acids was the most outstanding feature, probably related to the adaptation of the resistant strain for its survival inside the parasitophorous vacuole.

Separation of phthalates by cyclodextrin modified micellar electrokinetic chromatography: Quantitation in perfumes

A new CE method has been developed for the simultaneous separation of a group of parent phthalates. Due to the neutral character of these compounds, the addition of several bile salts as surfactants (sodium cholate (SC), sodium deoxycholate (SDC), sodium taurodeoxycholate (STDC), sodium taurocholate (STC)) to the separation buffer was explored showing the high potential of SDC as pseudostationary phase. However, the resolution of all the phthalates was not achieved when employing only this bile salt as additive, being necessary the addition of neutral cyclodextrins (CD) and organic modifiers to the separation media. The optimized cyclodextrin modified micellar electrokinetic chromatography (CD-MEKC) method consisted of the employ of a background electrolyte (BGE) containing 25 mM β-CD-100 mM SDC in a 100 mM borate buffer (pH 8.5) with a 10% (v/v) of acetonitrile, employing a voltage of 30 kV and a temperature of 25 °C. This separation medium enabled the total resolution of eight compounds and the partial resolution of two of the analytes, di-n-octyl phthalate (DNOP) and diethyl hexyl phthalate (DEHP) (Rs ~ 0.8), in only 12 min. The analytical characteristics of the developed method were studied showing their suitability for the determination of these compounds in commercial perfumes. In all the analyzed perfumes the most common phthalate was diethyl phthalate (DEP) that appeared in ten of the fifteen analyzed products. Also dimethyl phthalate (DMP), diallyl phthalate (DAP), dicyclohexyl phthalate (DCP), and di-n-pentyl phthalate (DNPP) were found in some of the analyzed samples.     

Fast Determination of Phenolic Compounds in Brazilian Wines from Vale do São Francisco Region by CE

Six phenolic compounds were separated and determined by capillary zone electrophoresis in red wine from Brazil’s region Vale do São Francisco with total analysis time of 12 min. The limit of detections varied from 1.59 to 2.24 mg L^?1. The relative standard deviations (for n = 6) varied from 0.28 to 3.50 %. The red wine samples analyzed were bought in the local market and the phenolic compound recoveries were in the range of 98–101 %. The concentrations of gallic acid in the samples of wines varied from 16.0 to 42.0 mg L^?1, caffeic acid (3.16–5.18 mg L^?1), syringic acid (5.73–13.0 mg L^?1), kaempferol (2.32–4.33 mg L^?1), quercetin (1.68–4.03 mg L^?1), myricetin (7.52–25.1 mg L^?1). The concentrations found agree with data reported in the literature.     

New Triterpenes from Gymnema sylvestre

Phytochemical investigation of the aerial parts of Gymnema sylvestre has led to the isolation of seven new triterpenes, six oleane types ( 5, 7 – 11 ) and a new lupane type ( 12 ), and of the six known analogues 1 – 4, 6 , and 13 . The structures and relative configurations of these compounds were elucidated by spectroscopic analyses, including 1D‐ and 2D‐NMR spectroscopy and mass spectrometry, and by the comparison of their NMR data with those of related compounds.     

A generalized truncated logarithm

Aequationes mathematicae - We introduce a generalization $$G^{(\alpha )}(X)$$ of the truncated logarithm $$\pounds _1(X)=\sum _{k=1}^{p-1}X^k/k$$ in prime characteristic p, which depends on a...     

Time-dependent propagation speed vs strong damping for degenerate linear hyperbolic equations

We consider a degenerate abstract wave equation with a time-dependent propagation speed. We investigate the influence of a strong dissipation, namely a friction term that depends on a power of the elastic operator.We discover a threshold effect. If the propagation speed is regular enough, then the damping prevails, and therefore the initial value problem is well-posed in Sobolev spaces. Solutions also exhibit a regularizing effect analogous to parabolic problems. As expected, the stronger is the damping, the lower is the required regularity.On the contrary, if the propagation speed is not regular enough, there are examples where the damping is ineffective, and the dissipative equation behaves as the non-dissipative one.     

Unusual Formation of 1,2,4-Oxadiazine Core in Reaction of Amidoximes with Maleic or Fumaric Esters

We have developed a simple and convenient method for the synthesis of 3-aryl- and 3-hetaryl-1,2,4-oxadiazin-5-ones bearing an easily functionalizable (methoxycarbonyl)methyl group at position 6 via the reaction of aryl or hetaryl amidoximes with maleates or fumarates. The conditions for this reaction were optimized. Different products can be synthesized selectively in good yields depending on the base used and the ratio of reactants: substituted (1,2,4-oxadiazin-6-yl)acetic acids, corresponding methyl esters, or hybrid 3-(aryl)-6-((3-(aryl)-1,2,4-oxadiazol-5-yl)methyl)-4H-1,2,4-oxadiazin-5(6H)-ones. The reaction is tolerant to substituents’ electronic and steric effects in amidoximes. As a result, a series of 2-(5-oxo-3-(p-tolyl)-5,6-dihydro-4H-1,2,4-oxadiazin-6-yl)acetic acids, their methyl esters, and 1,2,4-oxadiazoles based on them were prepared and characterized by HRMS, ¹H, and ¹³C NMR spectroscopy. The structures of three of them were elucidated with X-ray diffraction.     

Recent Advances in Copper-Based Organic Complexes and Nanoparticles for Tumor Theranostics

Treatment of drug-resistant forms of cancer requires consideration of their hallmark features, such as abnormal cell death mechanisms or mutations in drug-responding molecular pathways. Malignant cells differ from their normal counterparts in numerous aspects, including copper metabolism. Intracellular copper levels are elevated in various cancer types, and this phenomenon could be employed for the development of novel oncotherapeutic approaches. Copper maintains the cell oxidation levels, regulates the protein activity and metabolism, and is involved in inflammation. Various copper-based compounds, such as nanoparticles or metal-based organic complexes, show specific activity against cancer cells according to preclinical studies. Herein, we summarize the major principles of copper metabolism in cancer cells and its potential in cancer theranostics.