Isocyanate-Free Synthesis and Characterization of Renewable Poly(hydroxy)urethanes from Syringaresinol

In the context of replacement of petro-sourced and toxic bisphenol A (<b>BPA</b>), syringaresinol, a naturally occurring bisphenol deriving from sinapic acid, has been proposed as a greener and safer alternative. This work focuses on its applications for nonisocyanate polyurethane (NIPU) synthesis. A five-membered cyclic carbonate <b>SYR-CC</b> has been prepared by carbon dioxide addition to bis-epoxy monomer <b>SYR-EPO</b> derived from syringaresinol. Upon polyaddition of <b>SYR-CC</b> with different biosourced and petrosourced diamines, the resulting polyhydroxyurethanes were fully characterized by structural (Fourier transform infrared, ¹H nuclear magnetic resonance, high performance liquid chromatography size exclusion chromatography) and thermal analyses (thermogravimetric analysis, differential scanning calorimetry). These thermoplastics displayed high molar mass (Mn̅ = 5.4 kg mol^–1), excellent thermal stabilities (<i>T</i>_d5% = 267–281 °C) and glass transition temperatures (<i>T</i>_g) ranging from 63 to 98 °C. The coupling of <b>SYR-CC</b> with a triamine gave a thermoset material with interesting <i>T</i>_g (62 °C) and high thermal stability (<i>T</i>_d5% = 225 °C)

Aliphatic-Aromatic Polyesters from Naturally Occurring Sinapic Acid through Acyclic-Diene Metathesis Polymerization in Bulk and Green Solvent Cyrene

Green synthesis of renewable alternatives to fossil fuel-based (macro)molecules/polymers is more than ever a necessity. We recently developed a sustainable pathway to produce 6-hydroxy-5,7-dimethoxy-2-naphthoic acid (DMNA), which resembles the fossil-derived 6-hydroxy-2-naphthoic acid, from sinapic acid. To investigate the potential of DMNA as a building block for polymer syntheses, three novel DMNA-derived α,ω-dienes (M1–M3) were synthesized and engaged in acyclic-diene metathesis (ADMET) polymerization in a three-step study to prepare renewable aliphatic-aromatic polyesters (P1–P3). The first step aimed to evaluate the activity of seven commercial metathesis catalysts for the solvent-free ADMET polymerization of M3. Although most of the studied catalysts exhibited good reactivity, the second-generation Hoveyda–Grubbs catalyst (C4) proved the best. The second step was then started by varying the catalyst loading and testing M1 and M2 toward ADMET polymerization. Aliphatic-aromatic polyesters with a number-average molecular weight (Mn) up to 19.4 kDa (Đ = 1.88) were obtained. Furthermore, the results showed that the properties can be finely tuned depending on the monomer and catalyst loading. Thermal analysis demonstrated that the glass transition temperature (Tg) and the temperature at which 5% of the mass is lost (Td5%) varied depending on the alkene chain length. A general thermal trend was established: Tg(P1) > Tg(P2) > Tg(P3) and Td5%(P1) Td5%(P2) Td5%(P3). The third step of the ADMET study was to evaluate the tolerance of M1–M3 and C4 toward Cyrene, a green and high boiling point solvent derived from cellulose. The results revealed that Cyrene merits further investigation as a “general” non-toxic solvent for ADMET polymerization of other monomers, particularly those with high melting points

Microstructural and Chemical Approach To Highlight How a Simple Methyl Group Affects the Mechanical Properties of a Natural Fibers Composite

Two ferulic acid derivatives (<b>BDF</b> and <b>BDF-Me</b>) were prepared using chemoenzymatic synthesis and used as additives for the pretreatment of hemp fibers. Incorporation of these fibers into a polycaprolactone matrix by hot-melt extrusion process aimed to improve the dispersion of the fibers and the mechanical properties of the resulting materials. Young’s modulus and tensile strength of the composites were investigated at the micrometer scale by chemical imaging. The very simple methylation of the phenolic functions led to significant mechanical properties differences due to the dispersion of the fibers caused by a plasticizing effect of the ferulic acid derivative. This significant plasticizing effect of <b>BDF-Me</b> is observed at a content as low as 0.8 w% and opens the way for synthesizing a new family of biobased plasticizers involving transition from crystal state to amorphous phase

Immobilization of Adenosine Derivatives onto Cellulose Nanocrystals via Click Chemistry for Biocatalysis Applications

Adenosine triphosphate (ATP) is a central molecule of organisms and is involved in many biological processes. It is also widely used in biocatalytic processes, especially as a substrate and precursor of many cofactorssuch as nicotinamide adenine dinucleotide phosphate (NADP(H)), coenzyme A (CoA), and S-adenosylmethionine (SAM). Despite its great scientific interest and pivotal role, its use in industrial processes is impeded by its prohibitory cost. To overcome this limitation, we developed a greener synthesis of adenosine derivatives and efficiently selectively grafted them onto organic nanoparticles. In this study, cellulose nanocrystals were used as a model combined with click chemistry via a copper-catalyzed azide/alkyne cycloaddition reaction (CuAAC). The grafted adenosine triphosphate derivative fully retains its biocatalytic capability, enabling heterobiocatalysis for modern biochemical processes

Ultrafast barrierless photoisomerization and strong ultraviolet absorption of photoproducts in plant sunscreens

Sunscreens are aimed at protecting skin from solar ultraviolet (UV) irradiation. By utilizing femtosecond transient absorption spectroscopy and time-dependent density functional theory, we explain nature's selection of sinapoyl malate rather than sinapic acid as the plant sunscreen molecule. In physiological pH conditions, the two molecules are deprotonated, and their excited pi pi* states are found to relax to the ground states in a few tens of picoseconds via a barrierless trans-cis photoisomerization. After the cis-photoproduct is formed, the efficacy of sinapic acid is greatly reduced. In contrast, the efficacy of sinapoyl malate is affected only slightly because the cis-product still absorbs UV light strongly. In addition, protonated sinapic acid is found to be a good potential sunscreen molecule

Plant Sunscreens in the UV-B: Ultraviolet Spectroscopy of Jet-Cooled Sinapoyl Malate, Sinapic Acid, and Sinapate Ester Derivatives

Ultraviolet spectroscopy of sinapoyl malate, an essential UV-B screening agent in plants, was carried out in the cold, isolated environment of a supersonic expansion to explore its intrinsic UV spectral properties in detail. Despite these conditions, sinapoyl malate displays anomalous spectral broadening extending well over 1000 cm^–1 in the UV-B region, presenting the tantalizing prospect that nature’s selection of UV-B sunscreen is based in part on the inherent quantum mechanical features of its excited states. Jet-cooling provides an ideal setting in which to explore this topic, where complications from intermolecular interactions are eliminated. In order to better understand the structural causes of this behavior, the UV spectroscopy of a series of sinapate esters was undertaken and compared with <i>ab initio</i> calculations, starting with the simplest sinapate chromophore sinapic acid, and building up the ester side chain to sinapoyl malate. This “deconstruction” approach provided insight into the active mechanism intrinsic to sinapoyl malate, which is tentatively attributed to mixing of the bright V (¹ππ*) state with an adiabatically lower ¹nπ* state which, according to calculations, shows unique charge-transfer characteristics brought on by the electron-rich malate side chain. All members of the series absorb strongly in the UV-B region, but significant differences emerge in the appearance of the spectrum among the series, with derivatives most closely associated with sinapoyl malate showing characteristic broadening even under jet-cooled conditions. The long vibronic progressions, conformational distribution, and large oscillator strength of the V (ππ*) transition in sinapates makes them ideal candidates for their role as UV-B screening agents in plants

Straightforward sustainable synthesis of novel non-endocrine disruptive bio-based organic UV-B filters with antimicrobial activity

With an increasing demand for safe and natural products from both industries and consumers, paired with the recent ban of decried molecules (i.e. octinoxate, avobenzone or octocrylene) due to their high negative impact on humans and the environment (i.e. endocrine disruption, coral bleaching), safe bio-based alternatives are a necessary and promising surrogate to substitute current commercialized petroleum-based UV filters. In this context, a class of bio-based molecules, displaying interesting UV-B filtering properties and great photostability were developed from furfural and 5-hydroxymethylfurfural (HMF), using the Knoevenagel condensation with a set of green conditions to minimize the impact on environment. Furthermore, those furfural- and HMF-based molecules demonstrated antimicrobial properties as secondary activity, highly sought by industries. Some furan derivatives being recognized to exhibit toxicological risks, in silico and in vitro assays were conducted and demonstrated the absence of endocrine disruption activity for these new molecules.</p

DataSheet1_Green synthesis of (R)-3-hydroxy-decanoic acid and analogs from levoglucosenone: a novel access to the fatty acid moiety of rhamnolipids.PDF

Rhamnolipids (RLs) are highly valuable molecules in the cosmetic, pharmaceutic, and agricultural sectors with outstanding biosurfactant properties. In agriculture, due to their potential to artificially stimulate the natural immune system of crops (also known as elicitation), they could represent a critical substitute to conventional pesticides. However, their current synthesis methods are complex and not aligned with green chemistry principles, posing a challenge for their industrial applications. In addition, their bioproduction is cumbersome with reproducibility issues and expensive downstream processing. This work offers a more straightforward and green access to RLs, crucial to decipher their mechanisms of action and design novel potent and eco-friendly elicitors. To achieve this, we propose an efficient seven-step synthetic pathway toward (R)-3-hydroxyfatty acid chains present in RLs, starting from cellulose-derived levoglucosenone, with Michael addition, Baeyer–Villiger oxidation, Bernet–Vasella reaction, and cross-metathesis homologation as key steps. This method allowed the production of (R)-3-hydroxyfatty acid chains and derivatives with an overall yield ranging from 24% to 36%.</p

Enzymatic Synthesis of Resveratrol α‑Glycosides from β‑Cyclodextrin-Resveratrol Complex in Water

Although resveratrol (3,5,4′-trihydroxy-stilbene) is one of the most studied natural product because of its biological properties such as antioxidant or anticancer, its low water solubility and stability (influenced by pH, light and increased temperature), as well as its propensity to oligomerize, limit its bioavailability and applications in nutraceutic, cosmetics or pharmaceutical industries. Besides, resveratrol production at the multigram scale through vine cell culture is limited by the tedious extraction of pure resveratrol from the bioconversion medium due to its complexation by cyclodextrins, the latter being used as elicitors in the bioproduction process. In this work, we have been able to overcome all these drawbacks by performing a single organic solvent-free enzymatic α-glycosylation directly from the β-cyclodextrin-resveratrol complex in water using β-cyclodextrin as glycoside-donor. The combined effects of five parameters (CGTase amount, cyclodextrin amount, cyclodextrin/resveratrol ratio, pH, and temperature) were studied by design of experiments (DoE) to maximize the glycosylation yield. The optimal setting point of parameters was obtained by response surface methodology (RSM). After optimization, an efficient α-glycosylation was performed being obtained 35% of molar yield. The major glycosidestwo monoglycosides: 3-<i>O</i>-α-d-glucosyl-resveratrol and 4′-<i>O</i>-α-d-glucosyl-resveratrol and two diglycosides: 3-<i>O</i>-α-d-maltosyl-resveratrol and 4′-<i>O</i>-α-d-maltosyl-resveratrolwere characterized using a hyphenated liquid chromatography-solid phase extraction-nuclear magnetic resonance system, then separated and purified using centrifugal partition chromatography (CPC). Their antiradical properties, as well as that of their crude mixture, were evaluated through DPPH analysis. Results confirmed that the position 4′–OH is the best position for the glycosylation to maintain the highest antiradical properties