Structural Features of Highly Bioactive Citrus IntegroPectin Revealed by X-Ray Diffraction, Fourier Transform Infrared, and Nanoparticle Tracking Analysis Rosaria Ciriminna, Ana Rosa Garcia, Giuseppe Angellotti, Giovanna Li Petri, Chiara Valenza, et al. Chemistryopen, 2026 Citrus IntegroPectin denotes a family of flavonoid‐pectin bioconjugates with large therapeutic potential sourced via the green extraction CytroCav process consisting of cavitation of industrial citrus processing waste conducted in water only, followed by dialysis and lyophilization or spray‐drying. We investigate the structure of lemon, orange, and red (blood) orange IntegroPectin using X‐ray diffraction, infrared spectroscopy, and nanoparticle tracking analysis. The analysis unveils several structural nuances unique to this new class of bioconjugates of relevance to forthcoming studies on the use of citrus IntegroPectin for therapy and prevention of numerous diseases.
CytroCell: a computational study in aqueous solution and infrared spectroscopic structural characterization Anne-Sylvie Fabiano Tixier, Nicolas Michel, Rosaria Ciriminna, Giovanna Li Petri, Giuseppe Angellotti, et al. Materials Advances, 2026 Computational and infrared spectroscopy investigations of CytroCell in solution unveil important structural details of this family of nanocelluloses reproducibly sourced from citrus biowaste, soon employed in advanced industrial products and devices.
Long-Term Performance of Thermal Insulating Composite Systems Based on Water Resistance and Surface Multifunctionality Giovanni Borsoi, João L. Parracha, Jéssica D. Bersch, Ana R. Garcia, Amélia Dionísio, et al. Energies, 2025 External Thermal Insulation Composite Systems (ETICSs) are increasingly applied in both new construction and energy retrofitting, where long-term durability under environmental exposure is critical to preserving thermal efficiency. Moisture ingress represents a key degradation factor, reducing insulation performance and undermining energy savings promoted by the ETICS. The effectiveness of these systems is strongly influenced by surface protection, which also reflects aesthetic and biological resistance. This study investigates the influence of three commercial protective surface coatings, characterized by hydrophobicity, photocatalytic activity, and resistance to biological growth, on ETICS finishes based on acrylic, natural hydraulic lime (NHL), and silicate binders. An artificial aging protocol was employed to evaluate coating stability and compatibility with the finishing layers. Results show that acrylic-based finishes provided superior durability and protection, while coatings on NHL and silicate substrates exhibited lower performance. Notably, a TiO2 enriched photocatalytic coating, despite improved self-cleaning potential, demonstrated the least durability. The findings highlight that optimal ETICS protection requires coatings that combine low water absorption, effective drying, and biological resistance, thereby ensuring sustained thermal and energy performance over time.
Dynamic Behavior of the Glassy and Supercooled Liquid States of Aceclofenac Assessed by Dielectric and Calorimetric Techniques M. Teresa Viciosa, Joaquim J. Moura Ramos, Ana Rosa Garcia, Hermínio P. Diogo Molecules, 2025 Aceclofenac (ACF), a non-steroidal anti-inflammatory drug, was obtained in its amorphous state by cooling from melt. The glass transition was investigated using dielectric and calorimetric techniques, namely, dielectric relaxation spectroscopy (DRS), thermally stimulated depolarization currents (TSDC), and conventional and temperature-modulated differential scanning calorimetry (DSC and TM-DSC). The dynamic behavior in both the glassy and supercooled liquid states revealed multiple relaxation processes. Well below the glass transition, DRS was able to resolve two secondary relaxations, γ and β, the latter of which was also detectable by TSDC. The kinetic parameters indicated that both processes are associated with localized motions within the molecule. The main (α) relaxation was clearly observed by DRS and TSDC, and results from both techniques confirmed a non-Arrhenian temperature dependence of the relaxation times. However, the glass transition temperature (Tg) extrapolated from DRS data significantly differed from that obtained via TSDC, which in turn showed reasonable agreement with the calorimetric Tg (Tg-DSC = 9.2 °C). The values of the fragility index calculated by the three experimental techniques converged in attributing the character of a moderately fragile glass former to ACF. Above the α relaxation, TSDC showed a well-defined peak. In DRS, after “removing” the high-conductivity contribution using ε’ derivative analysis, a peak with shape parameters αHN = βHN = 1 was also detected. The origin of these peaks, found in the full supercooled liquid state, has been discussed in the context of structural and dynamic heterogeneity. This is supported by significant differences observed between the FTIR spectra of the amorphous and crystalline samples, which are likely related to aggregation differences resulting from variations in the hydrogen bonds between the two phases. Additionally, the pronounced decoupling between translational and relaxational motions, as deduced from the low value of the fractional exponent x = 0.72, derived from the fractional Debye–Stokes–Einstein (FDSE) relationship, further supports this interpretation.
Molecular Design of a Metal-Nitrosyl Ferroelectric with Reversible Photoisomerization Wei-Jian Xu, Mao-Fan Li, Ana R. Garcia, Konstantin Romanyuk, José M. G. Martinho, et al. Journal of the American Chemical Society, 2023 The development of photo-responsive ferroelectrics whose polarization may be remotely controlled by optical means is of fundamental importance for basic research and technological applications. Herein, we report the design and synthesis of a new metal-nitrosyl ferroelectric crystal (DMA)(PIP)[Fe(CN)5(NO)] (1) (DMA = dimethylammonium, PIP = piperidinium) with potential phototunable polarization via a dual-organic-cation molecular design strategy. Compared to the parent non-ferroelectric (MA)2[Fe(CN)5(NO)] (MA = methylammonium) material with a phase transition at 207 K, the introduction of larger dual organic cations both lowers the crystal symmetry affording robust ferroelectricity and increases the energy barrier of molecular motions, endowing 1 with a large polarization of up to 7.6 μC cm–2 and a high Curie temperature (Tc) of 316 K. Infrared spectroscopy shows that the reversible photoisomerization of the nitrosyl ligand is accomplished by light irradiation. Specifically, the ground state with the N-bound nitrosyl ligand conformation can be reversibly switched to both the metastable state I (MSI) with isonitrosyl conformation and the metastable state II (MSII) with side-on nitrosyl conformation. Quantum chemistry calculations suggest that the photoisomerization significantly changes the dipole moment of the [Fe(CN)5(NO)]2– anion, thus leading to three ferroelectric states with different values of macroscopic polarization. Such optical accessibility and controllability of different ferroelectric states via photoinduced nitrosyl linkage isomerization open up a new and attractive route to optically controllable macroscopic polarization.
Red Orange and Bitter Orange IntegroPectin: Structure and Main Functional Compounds Antonino Scurria, Marzia Sciortino, Ana Rosa Garcia, Mario Pagliaro, Giuseppe Avellone, et al. Molecules, 2022 DRIFT, HPLC-MS, and SPME-GC/MS analyses were used to unveil the structure and the main functional compounds of red (blood) orange (Citrus sinensis) and bitter orange (Citrus aurantium). The IntegroPectin samples show evidence that these new citrus pectins are comprised of pectin rich in RG-I hairy regions functionalized with citrus biophenols, chiefly flavonoids and volatile molecules, mostly terpenes. Remarkably, IntegroPectin from the peel of fresh bitter oranges is the first high methoxyl citrus pectin extracted via hydrodynamic cavitation, whereas the red orange IntegroPectin is a low methoxyl pectin. C. aurantium IntegroPectin has a uniquely high concentration of adsorbed flavonoids, especially the flavanone glycosides hesperidin, naringin, and eriocitrin.
The ultrafiltration performance of cellulose acetate asymmetric membranes: A new perspective on the correlation with the infrared spectra A. S. Figueiredo, A. R. García, M. Minhalma, L. Ilharco, M. D. Pinho Journal of Membrane Science and Research, 2020 Integral asymmetric cellulose acetate (CA) membranes were casted by phase-inversion with formamide varying content - 22, 30 and 34% - as pore promoter. These membranes, CA-22, CA-30 and CA-34, were analyzed by infrared spectroscopy in attenuated total reflection mode (ATR-FTIR) to investigate the porous membrane matrix influence on the polymer/water/solute interactions and the selective ultrafiltration of salts. The membranes covered a wide range of hydraulic permeabilities, from 3.5 to 81.0 kg.m-2.h-1.bar-1, and of molecular weight cut-offs, from 4.17 to 31.43 kDa. The experimental apparent rejection coefficients of neutral solutes of increasing molecular weight are related to their intrinsic rejection coefficients through the film model. The surface average pore radius, estimated by an iterative algorithm, ranges from 2.1 to 4.5 nm. The tighter membrane, CA-22, displays experimental apparent rejection coefficients to the Na2SO4, CaSO4, MgSO4 of 50% or higher values and this is in contrast with the lower values, between 14 and 18%, to the NaCl, CaCl2 and MgCl2 salts. The ATR-FTIR evidences that in the membranes with larger pores, CA-30 and CA-34, the water molecules are organized with a liquid-water-like structure, in which most molecules are hydrogen bonded to four or to two others; nevertheless, a fraction of water molecules is strongly bonded to the CA carbonyl groups. For the CA-22 membrane, there are more free carbonyl groups and a larger fraction of free water, both able to interact with solutes, such as the hydrated sulphate ions. Therefore, this ultrafiltration membrane has the capability of differentiating anionic species.
Structure and Properties of Cork-Silica Xerogel Nanocomposites: Influence of the Cork Content Ana R. Garcia, Maria de Fátima Júlio, Laura M. Ilharco Langmuir, 2019 Environmentally friendly nanocomposites were synthesized from a silica precursor and cork under mild conditions and dried at atmospheric pressure. Because of the covalent bonding between the components, these CorSil nanocomposites are homogeneous, light (apparent density in the range 360-750 kg m-3), machinable, with the Shore D hardness up to 67 and compressive strength up to 22.6 MPa. These properties place them as good replacements for wood, other natural products, and thermoplastic polymers, with the advantage of being flame-retardant. The influence of the cork content and grain size on the structure, porosity, and mechanical properties of the nanocomposites was studied using infrared spectroscopy, sorption isotherms, compressive strength, and Shore D hardness measurements.
