Preterm newborns are extremely vulnerable to morbidities, complications, and death. Preterm birth is a global public health problem due to its socioeconomic burden. Nurturing preterm newborns is a critical medical issue because they have limited nutrient stores and it is difficult to establish enteral feeding, which leads to inadequate growth frequently associated with poor neurodevelopmental outcomes. Parenteral nutrition (PN) provides nutrients to preterm newborns, but its biochemical effects are not completely known. To study the effect of PN treatment on preterm newborns, an untargeted metabolomic ¹H nuclear magnetic resonance (NMR) assay was performed on 107 urine samples from 34 hospitalized patients. Multivariate data (Principal Component Analysis, PCA, Orthogonal partial least squares discriminant analysis OPLS-DA, parallel factor analysis PARAFAC-2) and univariate analyses were used to identify the association of specific spectral data with different nutritional types (NTs) and gestational ages. Our results revealed changes in the metabolic profile related to the NT, with the tricarboxylic acid cycle and galactose metabolic pathways being the most impacted pathways. Low citrate and succinate levels, despite higher glucose relative urinary concentrations, seem to constitute the metabolic profile found in the studied critically ill preterm newborns who received PN, indicating an energetic dysfunction that must be taken into account for better nutritional management.

Harnessing mechanical motion in molecular crystals is a critical goal for developing novel energy conversion materials. Among known strategies, the ejection of guest molecules from the lattice via the jumping‐mate approach offers a direct means of propulsion. Here, we present isostructural cocrystals of indolo[3,2‐ a ]carbazole (ICZ) and ( E )‐1,2‐di(pyridin‐4‐yl)ethene (BPE) that incorporate solvents such as acetone, ethyl acetate, or tetrahydrofuran. X‐ray diffraction and solid‐state nuclear magnetic resonance (NMR) studies confirmed the presence of solvents or solvent mixtures. Upon heating, these channel‐type cocrystals exhibit a thermosalient effect, with temperature regulation achieved by releasing pure or solvent mixtures. Differential scanning calorimetry and thermogravimetry (DSC–TGA) analyses revealed that the transition temperatures changed progressively, demonstrating controllable thermal actuation through the release of occluded solvents. This work demonstrates a simple yet powerful way to regulate mechanical responses in molecular crystals, thereby advancing the design of responsive energy conversion materials.

We present a new design for multi-chromophoric molecules where the non-linear absorption properties of a central electron-donating core are used to confer indirect biphotonic absorption features to molecular actuators. This design allows for a general way to provide two-photon reactivity to molecular systems which, by themselves, could not be controlled by a non-linear optical input. The compounds are based on a two-photon-active N,N′-1,4-dihydropyrrolo[3,2-b]pyrrole central unit. This core is symmetrically substituted at the ends of its long axis by nitrophenyl groups defining a pseudo-centrosymmetric acceptor–donor–acceptor (A–D–A) antenna-unit. For this first proof-of-concept study, azo-isomerizable actuators were bonded to the central unit through the nitrogen atoms of the heterocyclic core. This design allows for the pyrrolo-pyrrole chromophore to act as a non-linear absorbing unit, so that E–Z isomerization of the actuators can be induced after excitation into higher states localized at the central unit, followed by energy transfer into acceptor-localized excited states. The non-linear isomerization of the actuators was observed using pulsed NIR light from a Ti:Sapphire laser in a setup that allows for significant accumulation of the actuator-isomerized product in macroscopic samples. We demonstrate that the two-photon photochemistry of the actuators is due to the coupling with the central core unit since models of the azo-actuator compounds alone do not undergo these transformations at the same irradiation levels. Time-resolved emission studies indicate that the population associated with higher core-centered ¹ππ* states evolve towards actuator-localized in a time-scale of picoseconds. These signals and the overall photochemistry are consistent with a mechanism where the formation of the actuator-localized ¹nπ* states is directly followed by the azo-isomerization reactions. Computational studies at the TD-DFT level of theory, together with the use of a quadratic response method were used to characterize the states responsible for the two-photon absorption properties. This kind of molecular assembly can be extended to induce non-linear photochemistry in other types of actuators, including dissociative systems or uncaging ligands, or to induce catalytic activity in highly localized environments.

Wine is a temperature, light, and oxygen-sensitive product, so its physicochemical characteristics can be modified by variations in temperature and time when samples are either sampled, transported, and/or analyzed. These changes can alter its metabolomic fingerprinting, impacting further classification tasks and quality/quantitative analyses. For these reasons, the aim of this work is to compare and analyze the information obtained by different chemometric methods used in a complementary form (PCA, ASCA, and PARAFAC) to study ¹H-NMR spectra variations of four red wine samples kept at different temperatures and time lapses. In conjunction, distinctive changes in the spectra are satisfactorily tracked with each chemometric method. The chemometric analyses reveal variations related to the wine sample, temperature, and time, as well as the interactions among these factors. Moreover, the magnitude and statistical significance of the effects are satisfactorily accounted for by ASCA, while the time-related effects variations are encountered by PARAFAC modeling. Acetaldehyde, formic acid, polyphenols, carbohydrates, lactic acid, ethyl lactate, methanol, choline, succinic acid, proline, acetoin, acetic acid, 1,3-propanediol, isopentanol, and some amino acids are identified as some of the metabolites which present the most important variations.

Metal-based compounds, known as metallodrugs, offer promising alternatives for cancers with limited treatment options, such as triple-negative breast cancer (TNBC). Casiopeinas^®, a family of copper-based compounds, have shown anticancer and antiproliferative effects both in vitro and in vivo. However, their long-term effects, particularly on metabolic pathways related to invasion and metastasis, remain unknown. This study addresses the sustained impact of Casiopeina IIIia (CasIIIia) and Casiopeina IIgly (CasIIgly) on TNBC cell metabolism, as well as their relationship with intra- and extracellular copper concentrations associated with these compounds. Our results revealed effects on several pathways, including those related to amino acid, lipid, and carbohydrate metabolism and energy production, all of which are involved in epithelial–mesenchymal transition (EMT), invasion, and metastasis. These metabolic changes were accompanied by progressive intracellular accumulation of Casiopeinas^®, suggesting a relationship between the concentration and their metabolic effects. These findings suggest that Casiopeinas^® could be a promising therapeutic option for TNBC treatment.

In this work, we report a detailed investigation on the factors affecting the in‐plane motion of tetrafluoro‐1,4‐benzoquinone (TFBQ) within a series of charge‐transfer (CT) cocrystals formed with various fused aromatic donors. Six crystalline materials were obtained, including four cocrystals, a polymorph, and a solid solution. These were characterized by single‐crystal X‐ray diffraction (SC XRD), solid‐state NMR, FTIR, UV‐Vis spectroscopy, and DFT calculations. All cocrystals exhibited short π‐stacking interactions and varied noncovalent interactions (NCI) modulating the in‐plane motion of TFBQ. ¹⁹ F T ₁ relaxation measurements allowed the quantification of the activation enthalpies ( ΔH ^‡ ) and entropies ( ΔS ^‡ ), with theoretical calculations backing these results. Cocrystal 4 is the solid with the most restricted motions due to the presence of strong hydrogen bonds. In contrast, cocrystal 3a depicts the highest in‐plane motional frequencies (up to 2.2 MHz at 300 K), owing to the weak contacts around TFBQ. Surprisingly, a solid solution ( 5 ), which resembled a mixture of cocrystals 2 and 3a , displayed no significant in‐plane motions, despite having similar packing and relaxation behavior to the binary cocrystals. This work illustrates how subtle variations in donor structure affect the in‐plane motions and photophysical properties of CT cocrystals, providing valuable insight into the rational design of functional materials.