Real-Time Functional Stratification of Tumor Cell Lines Using a Non-Cytotoxic Phospholipoproteomic Platform: A Label-Free Ex Vivo Model.

The development of scalable, non-invasive tools to assess tumor responsiveness to structurally active immunoformulations remains a critical unmet need in solid tumor immunotherapy. Here, we introduce a real-time, ex vivo functional system to classify tumor cell lines exposed to a phospholipoproteomic platform, without relying on cytotoxicity, co-culture systems, or molecular profiling. Tumor cells were monitored using IncuCyte S3 (Sartorius) real-time imaging under ex vivo neutral conditions.

Solvatochromism of π-Extended Pyridinium-Thienylene-Phenolates.

The synthesis and solvatochromic behavior of two series of pyridinium-thienylene-phenolates, which differ in the relative orientation and length of their donor/acceptor pairs, are reported. Increasing the donor/acceptor distance significantly influences the spectral behavior of the dyes, transforming the negative solvatochromism exhibited by the shorter analogs into a highly symmetrical inverted solvatochromic response when the π-system is increased. Through the application of multiparametric analysis, H NMR spectroscopy, and density functional theory (DFT) calculations, it was determined that the transition from negative to inverted solvatochromism is the result of an enhanced sensitivity of the π-extended dyes to solvent polarizability, with the 2,4-thienylene ring present in the bridge playing a crucial role.

The Simulation of Solvent Polarizabilities and Dipolarities with Polarizable Continuum Model.

The ability of polarizable continuum models (PCM) to simulate nonspecific solvent effects (dipolarity and polarizability) was evaluated by calculating the transition energies of 1,1,10,10-tetrabutyldecanonaene (ttbp9) and 2-,-dimethylamino-7-nitrofluorene (DMANF), basis of Catalán's polarizability () and dipolarity () solvent scales, respectively. Time-dependent density-functional theory (TD-DFT) calculations were performed at different levels of theory, employing four basis sets in 10 different solvents, covering the full range of the normalized and scales. Transition energies were calculated using linear response (LR) and corrected linear response (cLR) schemes.

Inverting the Solvatochromism of Pyridinium--phenolate Dyes by the Addition of a Second Pyridinium Unit.

Three bipyridinium phenolates were synthesized, and their spectral behavior was recorded at various solvent polarities and compared to a classic pyridinium phenolate dye possessing only one pyridinium acceptor ring in its structure. The addition of a second pyridinium unit to the classic solvatochromic core results in an unexpected change in the spectral behavior from negative solvatochromism (displacement of the absorption band to shorter wavelengths) to inverted solvatochromism, characterized by the transition from negative to positive solvatochromism (displacement of the absorption band to longer wavelengths) at moderate solvent polarities.

Governing the emissive properties of 4-aminobiphenyl-2-pyrimidine push-pull systems via the restricted torsion of N,N-disubstituted amino groups.

Donor-acceptor-substituted biphenyl derivatives are particularly interesting model compounds, which exhibit intramolecular charge transfer because of the extent of charge transfer between both substituents. The connection of a 4-[1,1'-biphenyl]-4-yl-2-pyrimidinyl) moiety to differently disubstituted amino groups at the biphenyl terminal can offer push-pull compounds with distinctive photophysical properties. Herein, we report a comprehensive study of the influence of the torsion angle of the disubstituted amino group on the emissive properties of two pull-push systems: 4-[4-(4-,-dimethylaminophenyl)phenyl]-2,6-diphenylpyrimidine () and 4-[4-(4-,-diphenylaminophenyl)phenyl]-2,6-diphenylpyrimidine ().

Use of Nonideality Parameters for the Analysis of the Thermodynamic Properties of Binary Mixtures.

Two parameters are introduced, a nonideality index (NII) and a nonideality area (NIA), for the analysis of the variations of thermodynamic properties of binary mixtures. Their calculation is based, for the NII, on experimental plots of the variation of a given property (density, refractive index, viscosity, etc.), and for the NIA, on experimental plots of its excess value (excess enthalpies, molar volumes, viscosities, refractive indices, isentropic compressibilities, etc.

The location of amphiphobic antioxidants in micellar systems: The diving-swan analogy.

A protocol for determining the location of antioxidants (AOs) in a micro-heterogeneous medium was applied to three series of AOs with increasing hydrophobicities: chromancarboxylic acid ("Trolox") esters, caffeic acid and its esters, and gallic acid and its esters. The observed paradoxical behaviour of these and other commonly encountered antioxidants was rationalized with the aid of a pictorial simile, the "diving-swan" analogy, that explains the orientation and location of an amphiphobic AO when it reacts with a radical probe in the micellar interface.

The Solvatofluorochromism of 2,4,6-Triarylpyrimidine Derivatives.

Seven new 2,4,6-triarylpyrimidines were synthesized and their solvatofluorochromism investigated in 12 solvents and in an aqueous micellar solution of reduced Triton X-100. A multiparametric analysis of their emission band showed that the solvent dipolarity and basicity were mainly responsible for their solvatofluorochromism, which arose from an internal charge-transfer from a donor fragment to the pyrimidine acceptor, confirmed by theoretical calculations. In the micellar system, quenching of their fluorescence by addition of derivatives of 2,2,6,6-tetramethylpiperidinoxyl (TEMPO) radical was investigated and the results were consistent with the spectral changes brought about by the micro-heterogeneous system.

New fluorescent bis-dithienylethene (DTE)-based bipyridines as reverse interrupters: single vs. double photochromism.

The synthesis and characterization of a series of fluorescent bis-dithienylethene (DTE)-based bipyridines, where the donor (D) and acceptor (A) groups are located on the same thiophene ring of the DTE unit, and their zinc(II) and rhenium(I) complexes are reported. Their photochromic properties have been investigated by UV-visible and (1)H NMR spectroscopy. These studies reveal that in non-polar solvents it is possible to modulate the photoreactivity, single vs.