The Impact of Lignin Biopolymer Sources, Isolation, and Size Reduction from the Macro- to Nanoscale on the Performances of Next-Generation Sunscreen.

In recent years, concerns about the harmful effects of synthetic UV filters on the environment have highlighted the need for natural sun blockers. Lignin, the most abundant aromatic renewable biopolymer on Earth, is a promising candidate for next-generation sunscreen due to its inherent UV absorbance and its green, biodegradable, and biocompatible properties. Lignin's limitations, such as its dark color and poor dispersity, can be overcome by reducing particle size to the nanoscale, enhancing UV protection and formulation. In this study, 100-200 nm lignin nanoparticles (LNPs) were prepared from various biomass by-products (hardwood, softwood, and herbaceous material) using an eco-friendly anti-solvent precipitation method. Pure lignin macroparticles (LMPs) were extracted from beech, spruce, and wheat straw using an ethanol-organosolv treatment and compared with sulfur-rich kraft lignin (KL). Sunscreen lotions made from these LMPs and LNPs at various concentrations demonstrated novel UV-shielding properties based on biomass source and particle size. The results showed that transitioning from the macro- to nanoscale increased the sun protection factor (SPF) by at least 2.5 times, with the best results improving the SPF from 7.5 to 42 for wheat straw LMPs and LNPs at 5 wt%. This study underscores lignin's potential in developing high-quality green sunscreens, aligning with green chemistry principles.

Enhanced stability and photothermal efficiency of Indocyanine Green J-aggregates by nanoformulation with Calix[4]arene for photothermal therapy of cancers.

Photothermal therapy (PTT) is a method of growing attention, owing to its controllable process, high efficiency and minimal side effect. Indocyanine Green (ICG) is as Food and Drug Administration (FDA) approved agent that stands on the frontline of further developments of PTT toward clinics. However, the applicability of ICG-mediated PTT is limited by the rapid in vivo clearance and photo-degradation of ICG. To improve those parameters, nanosized ICG-loaded nanoparticles (ICG-J/CX) were fabricated in this study by co-assembly of anionic ICG J-aggregates (ICG-J) with cationic tetraguanidinium calix[4]arene (CX). This very simple approach produces ICG-J/CX with a well-defined nanometer range size and a close to neutral charge. The nanoparticles demonstrate high photothermal conversion efficiency (PCE) and dramatically improved photostability, as compared with ICG. The in vitro cellular uptake and cytotoxicity studies further demonstrated that the ICG-J/CX nanoparticles enhance uptake and photothermal efficiency in comparison with ICG or non-formulated ICG-J, overall demonstrating that ICG-J/CX mediated photothermal therapy have significant potential for attaining cancer treatment.

Biomimetic Photo-Switches Softening Model Lipid Membranes.

We report the synthesis and characterization of a novel photo-switch based on biomimetic cyclocurcumin analogous and interacting with the lipid bilayer, which can be used in the framework of oxygen-independent light-induced therapy. More specifically, by using molecular dynamics simulations and free energy techniques, we show that the inclusion of hydrophobic substituents is needed to allow insertion in the lipid membrane. After having confirmed experimentally that the substituents do not preclude the efficient photoisomerization, we show through UV-vis and dynamic light scattering measurements together with compression isotherms that the chromophore is internalized in both lipid vesicles and monomolecular film, respectively, inducing their fluidification. The irradiation of the chromophore-loaded lipid aggregates modifies their properties due to the different organization of the two diastereoisomers, E and Z. In particular, a competition between a fast structural reorganization and a slower expulsion of the chromophore after isomerization can be observed in the kinetic profiles recorded during E to Z photoisomerization. This report paves the way for future investigations in the optimization of biomimetic photoswitches potentially useful in modern light-induced therapeutic strategies.

Synthesis and Photoswitching Properties of Bioinspired Dissymmetric γ-Pyrone, an Analogue of Cyclocurcumin.

Cyclocurcumin (CC), a turmeric curcuminoid with potential therapeutic properties, is also a natural photoswitch that may undergo E/Z photoisomerization under UV light. To be further exploited in relevant biological applications, photoactivation under near-infrared (NIR) irradiation is required. Such requirement can be met through opportune chemical modifications, by favoring two-photon absorption (TPA) probability. Herein, a general and efficient synthesis of a biomimetic 2,6-disubstituted-γ-pyrone analogue of CC is described, motivated by the fact that molecular modeling previews an order of magnitude increase of its NIR TPA compared to CC. Three retrosynthetic pathways have been identified (i) via an aryl-oxazole intermediate or via aryl-diynone through (ii) a bottom-up or (iii) a top-down approach. While avoiding the passage through unstable synthons or low-yield intermediate reactions, only the latest approach could conveniently afford the 2,6-disubstituted-γ-pyrone analogue of CC, in ten steps and with an overall yield of 18%. The photophysical properties of our biomimetic analogue have also been characterized showing an improved photoisomerization yield over the parent natural compound. The potentially improved nonlinear optical properties, as well as enhanced stability, may be correlated to the enforcement of the planarity of the pyrone moiety leading to a quadrupolar D-π-A-π-D system.

trans-cis Photoisomerization of a biomimetic cyclocurcumin analogue rationalized by molecular modelling.

Cyclocurcumin is a natural compound extracted from turmeric and showing, in addition to antiinfective, antibacterial, and intinflammatory capabilities, solvent-dependent phtoswitching ability. The solvent-dependent photochemistry of cyclocurcumin has been rationalized on the basis of a competition between π-π* and n-π* states. Recently we have reported the synthesis of a biomimetic analogue showing enhanced photochemical properties and in particular presenting photoswitching capacity in various media. In the present contribution we rely on the use of molecular modeling and simulation, incuding density functional and wavefunction based methods to explore the excited states potential energy surface landscape. We see that the addition of a carbon-carbon double bond to the core of the natural compounds favors the population of the π-π* state, whatever the choice of the solvent, and hence leads to photoisomerisation, with fluorescence reduced to only a minor channel, rationalizing the experimental observations. In addition, the two photon absorption cross section is also strongly increased compared to the parent compound, paving the way to the use in biologically oriented applications.

Lipid-coated mesoporous silica microparticles for the controlled delivery of ß-galactosidase into intestines.

ß-Galactosidase has been drawing increasing attention for the treatment of lactose intolerance, but its delivery has been impeded by degradation under gastric conditions. We have demonstrated that the coating of mesoporous silica microparticles (diameter ≈ 9 µm, pore size ≈ 25 nm) with dioleoylphosphatidylcholine membranes significantly improved the loading capability and protected the enzymes from the loss of function under simulated gastric conditions. Once the particles are transferred to simulated intestinal conditions, the digestion of phosphatidylcholine with pancreatin led to the release of functional ß-galactosidase. The coating of mesoporous silica nanoparticles with a single phospholipid bilayer opens up a large potential towards the controlled release of orally administrated drugs or enzymes to the intestines.

Evolution of dissolved organic matter during abiotic oxidation of coal tar--comparison with contaminated soils under natural attenuation.

In former coal transformation plants (coking and gas ones), the major organic contamination of soils is coal tar, mainly composed of polycyclic aromatic compounds (PACs). Air oxidation of a fresh coal tar was chosen to simulate the abiotic natural attenuation impact on PAC-contaminated soils. Water-leaching experiments were subsequently performed on fresh and oxidized coal tars to study the influence of oxidation on dissolved organic matter (DOM) quality and quantity. The characterization of the DOM was performed using a combination of molecular and spectroscopic techniques (high-performance liquid chromatography-size-exclusion chromatography (HPLC-SEC), 3D fluorescence, and gas chromatography coupled with mass spectrometry (GC-MS)) and compared with the DOM from contaminated soils sampled on the field exposed to natural attenuation for several decades. An increase in the oxygenated polycyclic aromatic compound concentrations was observed with abiotic oxidation both in the coal tar and the associated DOM. Polycyclic aromatic hydrocarbon concentrations in the leachates exceeded pure water solubility limits, suggesting that co-solvation with other soluble organic compounds occurred. Furthermore, emission excitation matrix analysis combined with synchronous fluorescence spectra interpretation and size-exclusion chromatography suggests that oxidation induced condensation reactions which were responsible for the formation of higher-molecular weight compounds and potentially mobilized by water. Thus, the current composition of the DOM in aged soils may at least partly result from (1) a depletion in lower-molecular weight compounds of the initial contamination stock and (2) an oxidative condensation leading to the formation of a higher-molecular weight fraction. Abiotic oxidation and water leaching may therefore be a significant combination contributing to the evolution of coal tar-contaminated soils under natural attenuation.

Rationalization of the pKa values of alcohols and thiols using atomic charge descriptors and its application to the prediction of amino acid pKa's.

In a first step toward the development of an efficient and accurate protocol to estimate amino acids' pKa's in proteins, we present in this work how to reproduce the pKa's of alcohol and thiol based residues (namely tyrosine, serine, and cysteine) in aqueous solution from the knowledge of the experimental pKa's of phenols, alcohols, and thiols. Our protocol is based on the linear relationship between computed atomic charges of the anionic form of the molecules (being either phenolates, alkoxides, or thiolates) and their respective experimental pKa values. It is tested with different environment approaches (gas phase or continuum solvent-based approaches), with five distinct atomic charge models (Mulliken, Löwdin, NPA, Merz-Kollman, and CHelpG), and with nine different DFT functionals combined with 16 different basis sets. Moreover, the capability of semiempirical methods (AM1, RM1, PM3, and PM6) to also predict pKa's of thiols, phenols, and alcohols is analyzed. From our benchmarks, the best combination to reproduce experimental pKa's is to compute NPA atomic charge using the CPCM model at the B3LYP/3-21G and M062X/6-311G levels for alcohols (R(2) = 0.995) and thiols (R(2) = 0.986), respectively. The applicability of the suggested protocol is tested with tyrosine and cysteine amino acids, and precise pKa predictions are obtained. The stability of the amino acid pKa's with respect to geometrical changes is also tested by MM-MD and DFT-MD calculations. Considering its strong accuracy and its high computational efficiency, these pKa prediction calculations using atomic charges indicate a promising method for predicting amino acids' pKa in a protein environment.

Complexation of Cu(II) by original tartaric acid-based ligands in nonionic micellar media: thermodynamic study and applications.

The complexation of Cu(II) with original alkylamidotartaric acids (C(x)T) is investigated in homogeneous aqueous medium and in the presence of nonionic micelles of Brij 58 (C16EO20), thanks to various analytical techniques such as NMR self-diffusion experiments, CD and UV-vis spectroscopy, ESI mass spectrometry, pHmetry and micellar-enhanced ultrafiltration (MEUF). First, a complete speciation study proves the formation of dimeric complexes in water and provides their formation constants. Second, a similar study is led in the presence of nonionic micelles. It underlines a modification of the apparent equilibrium constants in micellar medium and demonstrates that the structure of the complexes is slightly modified in the presence of micelles. This thermodynamic and structural study is applied to modelize the evolution of the extraction yields of Cu(II) by the micelles as a function of pH and to identify the complexes extracted in the micelles. The effects of the chain length of the ligand (C3T vs C8T) on the solubilization properties are put into relief and discussed. Anionic species are proved to be more incorporated in the nonionic micelles than the cationic species. The extracting system constituted of octylamidotartaric acid (CsT) solubilized in nonionic micelles of Brij 58 is demonstrated to be very efficient for the extraction of Cu(II) by MEUF, this technique being an interesting green alternative to traditional solvent extraction.