The investigation and optimization of the cinnamylated starch degree of substitution (DS) in basic media were carried out using a statistical approach based on the design of experiment (DoE) approach. An initial screening phase, conducted through a full factorial design, highlighted the following as the most critical parameters affecting the DS: (i) the base amount, (ii) the nature of the alkyl halide, (iii) the addition mode to the reaction mixture, and (iv) the equivalents used. The efficacy of different bases promoting the alkylation reaction was also studied, comparing sodium hydroxide, sodium alkoxides, and the dimsyl ion. Overall, the screening phase identified cinnamyl chloride and a sodium hydroxide DMSO dispersion as the optimal starting points for the optimization phase. The resulting model proved to be a robust tool for identifying optimal reaction conditions to achieve a high DS. The DoE statistical studies provided valuable insights into the mechanistic aspects and the complexity of the reaction system, extending beyond starch functionalization. These findings represent a significant advancement in the synthesis of starch-based materials, particularly for applications in the development of UV radiation-sensitive compounds, since they hold considerable potential across various industrial sectors.

This work details the synthesis of 2,4:3,5-di-O-methylene-d-glucitol (glux-diol), a bicyclic acetal derivative of d-glucose obtained from d-glucono-1,5-lactone, and also explores its subsequent polymerization to produce biobased polyesters. Key steps for the synthesis of glux-diol are (i) protection with paraformaldehyde, (ii) Fischer esterification, and (iii) reduction with lithium aluminum hydride (LiAlH₄). A new purification method was developed to effectively remove inorganic salt byproducts, which can hinder polymerization. The sugar-based monomer was then copolymerized with C4–C10 dimethyl esters using Candida antarctica lipase B as a biocatalyst in Cygnet 2.0, a green, high-boiling solvent. The biocatalytic polycondensation produced oligomers with number-average molecular weights (M _n) between 900 and 2200 g mol^–1. These materials exhibited thermal stabilities ranging from 391 to 419 °C, with the specific temperature depending on the molecular weight, degree of polymerization, and the carbon chain length of the chosen diester. Overall, this integrated approach, which combines efficient sugar functionalization with biocatalysis, offers a promising pathway for the synthesis of novel biobased polyesters.

Sericin, a silk-derived protein recovered as a by-product of the textile industry, is a re-newable biomacromolecule with considerable potential for sustainable material devel-opment. Chemical modification represents an effective strategy for its valorization. In this study, acetylation using acetyl chloride (AcCl) was selected as a model reaction to systematically investigate the reactivity of sericin in an N,N-dimethylacetamide/lithium chloride (DMA/LiCl) solvent system and to evaluate the in-fluence of reaction parameters on both the extent of functionalization and protein sec-ondary structure. A Design of Experiments (DoE) strategy, comprising an initial full factorial screening followed by Box–Behnken optimization, was employed to investi-gate the effects of AcCl equivalents, sericin concentration, and LiCl content. A quanti-tative FTIR workflow based on constrained Gaussian deconvolution was developed to derive functionalization (FI) and β-sheet (BI) indexes from both peak areas and peak in-tensities, enabling the simultaneous evaluation of chemical modification and structural organization. The exploratory screening identified AcCl as the dominant factor govern-ing sericin functionalization. During the optimization phase, the FI models described the general response trends, whereas the BI was successfully represented by robust quadratic models (R² = 0.977–0.978; adjusted R² = 0.936–0.938), revealing significant line-ar, interaction, and quadratic effects, with LiCl concentration and sericin concentration playing key roles in governing structural organization. The analytical workflow was verified by reproducibility assessment and independent validation experiments. Over-all, this study proposes a quantitative DoE–FTIR framework for systematically investi-gating sericin functionalization and its associated structural evolution, providing a support for future studies aimed at sericin industrial valorization.

Amides are fundamental and hugely widespread functional groups in key bioactive and industrially relevant molecules. However, conventional methods for amide bond formation, particularly in peptide synthesis, are challenging in terms of environmental impact, waste, and production costs. The most commonly used method for amide bond formation involves activating carboxylic acids with excess coupling agents, heavily affecting the atom economy of the process. Despite the need for more sustainable alternatives, research on catalytic methodologies to minimize such drawbacks remains limited. In this study, we explored the use of titanium alkoxides of general formula Ti(OAr) ₂ (OiPr) ₂ , as efficient and environmentally friendly catalysts for amide bond formation. Our results indicated that the replacement of isopropoxide ligands with the less basic phenolates 2,4‐dimethylphenolate and 2,6‐dimethylphenolate significantly improved the reactivity of the Ti‐center. Indeed, by using 5% mol of titanium bis(2,6‐dimethylphenoxy)diisopropoxy ( Ti2 ), or 10% mol of titanium bis(2,4‐dimethylphenoxy)diisopropoxy ( Ti1 ), we achieved efficient direct amidation between benzylamine and various carboxylic acids, including N ‐protected amino acids for which limited data are available in the literature. This work highlights the potential of titanium‐based catalysis as a sustainable and effective solution for amide bond formation, particularly in peptide synthesis.

The construction sector is under enormous pressure to reduce the overall environmental impact of its activities, which, for cement production alone, cause over 2 Gt/yr of CO₂ emissions (2022). Given the massive scale of concrete production, even minor components such as plasticizers, typically required in quantities of only a few percent of the dry cement mass, correspond to production volumes of many tens of Mt/yr, making their sustainability highly relevant. Lignin is the second most abundant renewable biopolymer on Earth and is currently used in concrete formulations mainly as a low-performance cement plasticizer. Despite this limited application, lignin represents an underexploited but highly attractive raw material for the development of environment-friendly concrete additives, owing to its abundance and availability from industrial biomass residues. The purpose of this review is to provide a specific and up-to-date overview of the various approaches for developing sustainable, high-performance concrete plasticizers based on lignins derived from industrial waste streams. The state of the art in the field is put into perspective by considering the various industrial sources of original technical lignins, the processes that led to their formation, and potential strategies for improving their characteristics. A quick overview of the patent history of the field complements the analysis of the scientific literature. An integral part of this work is a concise introduction to the fundamentals of cement chemistry and rheology, which are essential for understanding the technological requirements for effective concrete admixtures and for enabling cross-disciplinary research between the lignin and cement communities.