Artificial intelligence-enhanced quantum chemical method with broad applicability

High-level quantum mechanical (QM) calculations are indispensable for accurate explanation of natural phenomena on the atomistic level. Their staggering computational cost, however, poses great limitations, which luckily can be lifted to a great extent by exploiting advances in artificial intelligence (AI). Here we introduce the general-purpose, highly transferable artificial intelligence–quantum mechanical method 1 (AIQM1). It approaches the accuracy of the gold-standard coupled cluster QM method with high computational speed of the approximate low-level semiempirical QM methods for the neutral, closed-shell species in the ground state. AIQM1 can provide accurate ground-state energies for diverse organic compounds as well as geometries for even challenging systems such as large conjugated compounds (fullerene C60) close to experiment. This opens an opportunity to investigate chemical compounds with previously unattainable speed and accuracy as we demonstrate by determining geometries of polyyne molecules—the task difficult for both experiment and theory. Noteworthy, our method’s accuracy is also good for ions and excited-state properties, although the neural network part of AIQM1 was never fitted to these properties.

Synthesis and photophysical properties of benzo[c]phenanthrene derivatives

Background: Three polycyclic aromatic hydrocarbons derived from benzo[c]phenanthrene have been synthesized through a one-step procedure involving palladium Suzuki coupling and are characterized by 1 H and 13C NMR, MS and HRMS spectroscopies. Methods: UV-vis absorption and fluorescence properties of these π-conjugated compounds have been evaluated in solutions and strong emission in the blue region of the visible spectrum was noted. Results: The optical spectra of these small polycyclic aromatic compounds are unusual because absorption is entirely in the UV region (λmax = 281-285 nm), yet fluorescence occurs at 410-422 nm. Conclusion: This equates to a Stokes shift of 1.32-1.39 eV (10756-11256 cm−1 ) and is among the large Stokes shifts that have been reported for small molecules, making them promising candidates for optoelectronic applications.

Intrinsic and Chemotherapeutic Stressors Modulate ABCC-Like Transport in Trypanosoma cruzi

Trypanosoma cruzi is the etiologic agent for Chagas disease, which affects 6–7 million people worldwide. The biological diversity of the parasite reflects on inefficiency of benznidazole, which is a first choice chemotherapy, on chronic patients. ABC transporters that extrude xenobiotics, metabolites, and mediators are overexpressed in resistant cells and contribute to chemotherapy failure. An ABCC-like transport was identified in the Y strain and extrudes thiol-conjugated compounds. As thiols represent a line of defense towards reactive species, we aimed to verify whether ABCC-like transport could participate in the regulation of responses to stressor stimuli. In order to achieve this, ABCC-like activity was measured by flow cytometry using fluorescent substrates. The present study reveals the participation of glutathione and ceramides on ABCC-like transport, which are both implicated in stress. Hemin modulated the ABCC-like efflux which suggests that this protein might be involved in cellular detoxification. Additionally, all strains evaluated exhibited ABCC-like activity, while no ABCB1-like activity was detected. Results suggest that ABCC-like efflux is not associated with natural resistance to benznidazole, since sensitive strains showed higher activity than the resistant ones. Although benznidazole is not a direct substrate, ABCC-like efflux increased after prolonged drug exposure and this indicates that the ABCC-like efflux mediated protection against cell stress depends on the glutathione biosynthesis pathway.

Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes

Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems.

Redox-active Tetraaryldibenzoquinodimethanes

Quinodimethanes (QDs) are a class of non-aromatic π-conjugated compounds that are well-known to be interconvertible scaffolds in many response systems. While parent ortho- and para-QDs (o-QD and p-QD) can be...

Design of Anion–π Interactions and Hydrogen Bonds to Recognition of the Chloride, Bromide and Nitrate Anions

The role of anions in several biochemical processes gives rise to an enormous interest in the identification/exploration of compounds with potential ability to recognize anions. Here, the anthracene–squaramide conjugated compounds,...

Siderophore Scaffold as Carrier for Antifungal Peptides in Therapy of Aspergillus fumigatus Infections

Antifungal resistance of human fungal pathogens represents an increasing challenge in modern medicine. Short antimicrobial peptides (AMP) display a promising class of antifungals with a different mode of action, but lack target specificity and metabolic stability. In this study the hexapeptide PAF26 (Ac-dArg-dLys-dLys-dTrp-dPhe-dTrp-NH2) and the three amino acid long peptide NLF (H2N-Asn-Leu-dPhe-COOH) were coupled to diacetylfusarinine C (DAFC), a derivative of the siderophore triacetylfusarinine C (TAFC) of Aspergillus fumigatus, to achieve targeted delivery for treatment of invasive aspergillosis. Conjugated compounds in various modifications were labelled with radioactive gallium-68 to perform in vitro and in vivo characterizations. LogD, serum stability, uptake- growth promotion- and minimal inhibitory concentration assays were performed, as well as in vivo stability tests and biodistribution in BALB/c mice. Uptake and growth assays revealed specific internalization of the siderophore conjugates by A. fumigatus. They showed a high stability in human serum and also in the blood of BALB/c mice but metabolites in urine, probably due to degradation in the kidneys. Only PAF26 showed growth inhibition at 8 µg/ml which was lost after conjugation to DAFC. Despite their lacking antifungal activity conjugates based on a siderophore scaffold have a potential to provide the basis for a new class of antifungals, which allow the combination of imaging by using PET/CT with targeted treatment, thereby opening a theranostic approach for personalized therapy.

Phenolic acid content and in vitro antioxidant capacity of einkorn water biscuits as affected by baking time

Aim of this research was to study the evolution of heat damage, phenolic acid content and in vitro antioxidant capacity of whole meal einkorn water biscuits baked at 205 °C for increasing times (10 min steps) from 25 to 75 min. The heat damage was gauged by determining furosine, hydroxymethylfurfural (HMF), furfural and glucosylisomaltol (GLI) contents. Furosine increased up to 50 min baking, when HMF started to form; furfural augmented only after 65 min treatment, whereas GLI did not change. An unknown compound, apparently related to the severity of the heat load, aroses through the aldolic condensation of HMF with the acetone used for the extraction of phenolic acids; hence the use of acetone-based solvents in thermally processed cereal products should be avoided. The conjugated phenolic acids ferulic, vanillic, syringic, p-coumaric, p-hydroxybenzoic and syringaldehyde and the bound phenolic acids ferulic, p-coumaric, syringic, and p-hydroxybenzoic were identified in water biscuits. The stronger heating treatments led to an increase of the soluble conjugated compounds, but did not influence the bound fraction. The in vitro antioxidant capacity of water biscuits augmented significantly as baking time increased, likely for the formation of antioxidant compounds as a consequence of heat damage.