A modified method for the synthesis of 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra(benzoyl)methoxycalix(4)arene (1) and 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra(acetoyl)methoxycalix(4)arene (2) using 18-crown-6 as phase transfer catalyst is reported. Ligand 1 was structurally (¹H NMR and X-ray crystallography) and thermodynamically characterised. An account of the steps required for the formulation of an equation representative of the complexation process involving metal cations and macrocycles is given using as an illustrative example the interaction of 1 with the Na(I) cation. Thus, detailed thermodynamics of this system are first reported taking into account the solution properties of the reactants and the product in various solvents with the aim of assessing quantitatively the medium effect on the complexation process. The sodium:monoacetonitrile:1 complex was isolated and its molecular structure was determinated from X-ray diffraction data. The calix now adopts a more symmetric cone conformation than the free ligand and its hydrophobic cavity is filled with an acetonitrile solvent molecule. The hydrophilic pocket hosts the sodium cation which is in an eight-fold coordination with the four ethereal oxygen atoms [average d(Na–O) = 2.45(4) Å] and the four carbonyl oxygen atoms [average d(Na–O) = 2.51(4) Å] forming the corners of a distorted Archimedean square antiprism. The key structural features relevant to the complexation process are discussed. ¹H NMR and conductance measurements have been used to assess the interaction of 1 and 2 with alkali metal cations. Final conclusions are given. Attention is drawn about the relevance of detailed thermodynamic studies on cation complexation processes involving calixarene derivatives. This is discussed within the context of selectivity and the factors controlling it in solution processes.

In Peru, rice grains, wheat, and their processed products are accessible due to their low cost; however, their sale does not have quality certification, so their safety is not guaranteed. This study quantified lead (Pb) and cadmium (Cd) by voltammetry in 16 samples of grains and processed products from four markets in Arequipa (Altiplano, Andrés Avelino Cáceres, Los Incas, and San Camilo) and evaluated their potential health risk. The maximum concentrations of Pb in rice, wheat, and their processed products were 4.821 mg/kg, 7.962 mg/kg, 4.717 mg/kg, and 6.440 mg/kg, respectively; only seven samples showed Cd. All samples exceeded the maximum level (ML) for Pb, and four samples exceeded the ML for Cd established by the Codex Alimentarius (0.200 mg/kg); the rice product had the highest concentration of Pb and Cd. In relation to the estimation of potential health risk, the estimated daily intake (EDI), target hazard quotient (THQ), and target cancer risk (TR), showed that the consumption of all processed rice and wheat products (except Andrés Avelino Cáceres rice and San Camilo wheat) represent a health threat associated with an increased probability of cancer development.

Knowledge of the sequencing of the 16S rRNA gene constitutes a true revolution in understanding the composition of the intestinal microbiota and its implication in health states. This study details microbial composition through next-generation sequencing (NGS) technology in children with anemia. Anemia is the most frequent hematological disorder that affects human beings. In Peru, it is one of the conditions that presents the most significant concern due to the adverse effects that cause it, such as delayed growth and psychomotor development, in addition to a deficiency in cognitive development.

The cytotoxic properties of two extracts from Chenopodium quinoa Willd. and three synthetic sapogenins were evaluated in different cancer cell lines (A549, SH-SY5Y, HepG2, and HeLa) to investigate their cytotoxic effects and determine if these cell lines activate the caspase pathway for apoptosis in response to saponin and sapogenin treatment. The saponin extracts were isolated from the agro-industrial waste of Chenopodium quinoa Willd., while the sapogenins were identified and quantitatively determined by High-Performance Liquid Chromatography (HPLC). Among these compounds, ursolic acid was the most active compound, with high IC₅₀ values measured in all cell lines. In addition, hederagenin demonstrated higher caspase-3 activity than staurosporine in HeLa cells, suggesting an anti-cytotoxic activity via a caspase-dependent apoptosis pathway. HPLC analysis showed that the concentration of hederagenin was higher than that of oleanolic acid in ethanolic extracts of white and red quinoa. The ethanolic extracts of white and red quinoa did not show cytotoxic activity. On the other hand, the synthetic sapogenins such as ursolic acid, oleanolic acid, and hederagenin significantly decreased the viability of the four cell lines studied. Finally, by Caspase-3 assay, it was found that HeLa undergoes apoptosis during cell death because hederagenin produces a significant increase in PARP-1 hydrolysis in HeLa cells.

Distribution experiments involving silver (I) perchlorate in the mutually saturated water–dichloromethane solvent system at 298.15 K were carried out. The data were used to calculate the partition, K_p and the distribution, K_d constants in this solvent system and the ion-pair formation constant, K_a in the water saturated organic phase. Comparison of K_d , K_p and K_a values with corresponding data in the water–nitrobenzene solvent system clearly reflect the medium effect on these parameters. Distribution data in the presence of various calix(4)arene amine derivatives were measured. These data show that in the water–dichloromethane solvent system the stoichiometry of the extraction process (1 : 2; ligand : metal-cation) has been altered relative to that in water–nitrobenzene (1 : 1). This is corroborated by conductometric titrations of silver (I) and these macrocycles in water saturated dichloromethane. An equation for the derivation of the extraction constant, K_ex and K_d from distribution data for a 1 : 2 (ligand : metal-cation) extraction process has been formulated and successfully applied. Good agreement is found between the K_d values derived from distribution data in the absence and in the presence of the macrocycle. The individual steps which contribute to the overall extraction of silver (I) from water to dichloromethane are discussed. Final conclusions are given.