Microplastic label in microencapsulation field - Consequence of shell material selection.

Plastics make our lives easier in many ways; however, if they are not appropriately disposed of or recycled, they may end up in the environment where they stay for centuries and degrade into smaller and smaller pieces, called microplastics. Each year, approximately 42000 tonnes of microplastics end up in the environment when products containing them are used. According to the European Chemicals Agency (ECHA) one of the significant sources of microplastics are microcapsules formulated in home care and consumer care products. As part of the EU's plastics strategy, ECHA has proposed new regulations to ban intentionally added microplastics starting from 2022. It means that the current cross-linked microcapsules widely applied in consumer goods must be transformed into biodegradable shell capsules. The aim of this review is to provide the readers with a comprehensive and in-depth understanding of recent developments in the art of microencapsulation. Thus, considering the chemical structure of the capsule shell's materials, we discuss whether microcapsules should also be categorized as microplastic and therefore, feared and avoided or whether they should be used despite the persisting concern.

Dielectric Analysis of Blended Polysulfone/Polyethylenimine Membrane Contactors for CO2 Capture.

Polysulfone membranes, used as contactors for CO2 capture, are blended with two different hyperbranched polyethyleneimines modified with benzoyl chloride (Additive 1) and phenyl isocyanate (Additive 2) in different percentages. Fourier-transformed infrared spectra evidence the presence of urea and amide groups, whereas the field emission scanning electron microscopy images show differences in the microstructure of the blended membranes. Dielectric spectra determine the motions of the side and backbone chains, which can facilitate the diffusion of CO2 . The spectra consist of six dielectric processes; three of them are due to the polysulfone (γPSf , ßPSf , and αPSf ), whereas the rest are characteristic of the additive (γHPEI , ßHPEI , and αHPEI ). The benzoyl chloride and phenyl isocyanate functional groups introduce variations in molecular mobility and modify the relaxations associated with the hyperbranched polyethyleneimine (HPEI). The additives also increase the conductivity of the blended membranes, which can compromise the performance of the membranes, specifically in the case of Additive 1. Ion hopping is found to be the prevailing charge transport mechanism while both relaxations, αHPEI and αPSf , are actives. These results, together with the final morphology of the membranes, may explain the greater absorption capacity of the membranes prepared with the hyperbranched polyethyleneimine modified with Additive 2.

The Pragmatism of Polyphenols and Flavonoids Application as Drugs, from an Academic Lab to a Pharmacy Shelf.

Polyphenols and flavonoids, naturally occurring compounds found abundantly in plants, have gained considerable attention in recent years due to their potential health benefits. Research exploring their bioactive properties has revealed promising therapeutic applications in various diseases. This article aims to provide a comprehensive overview of the intricate journey from academic laboratory discoveries to the availability of polyphenols and flavonoids as drugs on pharmacy shelves. It was shown that the transformation of these natural compounds into effective therapies is a promising avenue for enhancing human health. Yet, fully realizing this potential necessitates sustained scientific exploration, cross-disciplinary collaboration, and continued investment in research and development. This article underscores the importance of sustained collaboration and investment as key pillars of progress towards innovative and effective therapies.

A Methodology for Multivariate Investigation on the Effect of Acrylate Molecular Structure on the Mechanical Properties and Delivery Efficiency of Microcapsules via In Situ Polymerization.

In the field of encapsulation, microcapsules containing perfume have emerged as effective vehicles for delivering active ingredients across various applications. The present study employed a multivariate analysis framework to examine polyacrylate microcapsules for household products synthesized using different acrylate monomers. The advanced multivariate approach allowed us to quantify critical properties such as the Molecular Weight between Cross-links (MWc), mechanical attributes, Encapsulation Efficiency (EE), and On-Fabric delivery. It is worth noting that the mechanical properties were gauged using a novel nanoindentation technique, which measures the Rupture Force per unit diameter (RFD). Both Encapsulation Efficiency and On-Fabric delivery were assessed using GC-MS. Our findings identified the optimal microcapsule system as one synthesized with 100% aromatic hexafunctional urethane acrylate, showcasing a 94.3% Encapsulation Efficiency and an optimal RFD of 85 N/mm. This system achieved an exemplary On-Fabric delivery rate of 307.5 nmol/L. In summary, this research provides crucial insights for customizing microcapsule design to achieve peak delivery efficiency. Furthermore, by designing acrylic monomers appropriately, there is potential to reduce the amount of active ingredients used, owing to enhanced delivery efficiency and the optimization of other microcapsule properties. Such advancements pave the way for more environmentally friendly and sustainable production processes in the fast-moving consumer goods industry.

Structural and mechanical analysis on mannuronate-rich alginate gels and xerogels beads based on Calcium, Copper and Zinc as crosslinkers.

Beads based on a mannuronate(M)-rich alginate (86 % M units) were prepared by adding the polysaccharide solution to a crosslinking bath containing different concentrations (0.5, 2 and 10 wt%) of XCl2 where X = Ca, Cu or Zn. Primarily focus was on Zn, due to its antioxidant, anti-inflammatory and anti-microbial capabilities. The beads were characterized by Field-Emission Scanning Electron Microscopy (FESEM), Fourier-Transform Infra-Red spectroscopy (FT-IR), Thermogravimetric Analysis (TGA), Small-Angle X-ray Scattering (SAXS) and compression tests. The crosslinking agent significantly influenced the properties of the resulting beads. Specifically, Ca-based beads exhibited a smoother surface, while Cu- and Zn-based beads appeared rougher. Interestingly, Zn-based beads displayed a core-shell structure. Young moduli ranged from 3500 and 7000 MPa, with the highest values observed for Zn-beads. SAXS investigation at 0.5 wt% XCl2 suggested increase in the densely packed domains amount in the order: Ca < Cu < Zn. Extended X-ray Absorption Fine Structure (EXAFS) showed that the coordination number was 4.3 ± 0.4 for Cu, and 4.0 ± 0.2 and 1.1 ± 0.1 for Zn in 0.5 wt% XCl2 alginate xerogels, in agreement with reported Density Functional Calculations on Cu2+- and Zn2+-MM complexes. The results from FT-IR, compositional analysis and EXAFS collectively suggested a bridging coordination for these systems.

Design and assembly of biodegradable capsules based on alginate hydrogel composite for the encapsulation of blue dye.

The encapsulation of bluing agents in biodegradable polymeric capsules is an emerging option in laundry detergents sector to substitute formaldehyde-based polymers, because they are non-biodegradable, carcinogenic and toxic. In this work, we present for the first time the successful encapsulation of a blue dye in biodegradable capsules which shell was formed by an alginate hydrogel and a polyethylene glycol network. Different types of capsules were synthesized (addition or not of the diacrylate monomer) and irradiation of the crosslinking solution at different times. Furthermore, a deep characterization of each type of capsules was performed (chemical and morphological characterization, assessment of their mechanical and thermal properties, evaluation of their biodegradability), noting that the incorporation of the diacrylate monomer (PEGDMA) and the two different irradiation times selected substantially affected the final properties of the capsules. The obtained results will serve to comprehend how the dye can be released from the capsules.

Christmas Tree Bio-Waste as a Power Source of Bioactive Materials with Anti-Proliferative Activities for Oral Care.

According to the American Cancer Society, roughly 54,000 new cases of oral cavity or oropharyngeal cancers have been detected in the United States of America in 2021, and they will cause about 10,850 deaths. The main therapies for cancer management, such as surgery and radio- and chemotherapy, have some own benefits, albeit they are often destructive for surrounding tissues; thus, deep investigations into non-surgical treatments for oral cavities are needed. Biologically active compounds (BACs) extracted from European Spruce needles were analyzed to determine the total phenolic and flavonoid content and were used as additional ingredients for oral hygiene products. An anti-proliferation investigation was carried out using extracts containing BACs with the use of several cell lines (cancer and a normal one). ESI-MS studies on BACs showed that luteolin, a natural flavonoid compound with anti-tumorigenic properties against various types of tumors, is the predominant component of the extracts. MTT, BrdU, and LIVE/DEAD studies demonstrated that BAC extracts obtained from Christmas tree needles possess anticancer properties against squamous cell carcinoma (with epithelial origins). We proved that BAC extracts contain high amounts of luteolin, which induces cytotoxicity toward cancer cells; along with their high selectivity, robustness, and nontoxicity, they are very promising materials in oral health applications.

Synthesis and characterization of dendritic compounds containing nitrogen: monomer precursors in the construction of biomimetic membranes.

In this article, we synthesized a novel dendritic 2-oxazoline, 2-(3,4,5-tris(4-dodecyloxybenzyloxy)phenyl)-4,5-dihydro-1,3-oxazole), and its amide precursor N-(2-hydroxyethyl)-3,4,5-tris(4-dodecyloxybenzyloxy)benzamide. Of the distinct synthetic routes explored, it was established that the direct amidation of esters with sodium methoxide followed by the dehydrative cyclisation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as oxidizing agent and triphenylphosphine was the most efficient route to synthesize the dendritic 2-oxazoline. Besides, N-(2-hydroxyethyl)-3,4,5-tris(4-dodecyloxybenzyloxy)benzamide exhibited a monotropic columnar mesophase, whilst the dendritic 2-oxazoline does not exhibited a liquid crystalline mesophase. At the end, the first attempts to polymerize the 2-oxazoline monomer via cationic ring opening polymerization showed promising results. Therefore, the dendritic 2-oxazoline could be used as a mesogenic monomer in the synthesis of side-chain liquid-crystalline polyoxazolines that might self-assembly into columnar structures.

Membranes for Cation Transport Based on Dendronized Poly(Epichlorohydrin-Co-Ethylene Oxide). Part 2: Membrane Characterization and Transport Properties.

In this paper, we report on the preparation and characterization of membranes out of two side-chain liquid crystalline copolymers, dendronized at two different extents (20 and 40%, CP20 and CP40, respectively). The membranes were characterized by atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM), contact angle (CA) analysis, and water uptake. Moreover, transport properties were studied by methanol and proton conductivity experiment and by linear sweep voltammetry (LSV). For the sake of comparison, the behavior of the grafted copolymers was compared with the unmodified copolyether CP0 and with Nafion 117. Results demonstrated that in CP20 and CP40, cation transport depends on the presence of defined cationic channels, not affected by water presence; the comparison between LSV experiments performed with different alkaline cations suggests that CP40 possesses channels with larger diameters and better-defined inner structures.

Membranes for Cation Transport Based on Dendronized Poly(epichlorohydrin-co-ethylene oxide). Part 1: The Effect of Dendron Amount and Column Orientation on Copolymer Mobility.

Dendronized polyethers give rise to columnar LC structures which can successfully act as cation transport materials. Therefore, we prepared two different materials, based on Poly(epichlorohydrin-co-ethylene oxide) (PECH-co-EO) grafted with methyl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, containing 20% or 40% modified units, respectively. The obtained polymers were characterized by differential scanning calorimetry (DSC), X-ray diffraction and optical microscopy between crossed polars (POM) and compared to the unmodified PECH-co-EO. In order to reach efficient transport properties, homeotropically oriented membranes were prepared by a fine-tuned thermal annealing treatment and were subsequently investigated by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA). We found that the presence of the dendrons induces a main chain partial crystallization of the polyether chain and coherently increases the polymer Tg. This effect is more evident in the oriented membranes. As for copolymer orientation upon annealing, the cooling rate and the annealing temperature were the most crucial factors. DMTA and DETA confirmed that grafting with the dendron strongly hinders copolymer motions, but did not show great differences between unoriented and oriented membranes, regardless of the amount of dendrons.

Molecular Mobility in Oriented and Unoriented Membranes Based on Poly[2-(Aziridin-1-yl)ethanol].

Unoriented and oriented membranes based on dendronized polymers and copolymers obtained by chemical modification of poly[2-(aziridin-1-yl) ethanol] (PAZE) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy]benzoate were considered. DSC, XRD, CP-MAS NMR and DETA, contribute to characterize the tendency to crystallize, the molecular mobility of the benzyloxy substituent, the dendritic liquid crystalline group and the clearing transition. The orientation of the mesogenic chain somewhat hindered this molecular motion, especially in the full substituted PAZE. The fragility, free volume and thermal expansion coefficients of these membranes near the glass transition are related to the orientation and the addition of the dendritic groups. PAZE-based membranes combine both order and mobility on a supramolecular and macroscopic level, controlled by the dendritic group and the thermal orientation, and open the possibility of preparing membranes with proper channel mobility that promotes selective ionic transport.

Medical Plaster Enhancement by Coating with Cistus L. Extracts within a Chitosan Matrix: From Natural Complexity to Health Care Simplicity.

Our investigation was focused on the preparation and characterization of novel plasters based on Carboxymethyl Chitosan derivative (CMC), to be used for the treatment of radiation dermatitis with Biologic Active Compounds (BACs) in a moist wound-healing environment. After performing the extraction and characterization of BACs from Cistus L., we optimized the BACs/CMC solution for subsequent plaster preparation. Then, plasters were prepared by dip-coating with a different number of layers, and we characterized them by Environmental Scanning Electron Microscopy (ESEM), Contact Angle (CA) and release tests in water for 24 h. Taking into account the flexibility of the plasters and the amount of released BACs after 24 h, the sample obtained after two dip-coating steps (2La) appeared promising in regard to comfortable mechanical properties and active principles administration. The 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test performed on keratinocytes cultured in standard medium shows that cells treated with released extract from 2La start to proliferate, extend cellular viability and form colonies typical for epidermal cells.

Alginate-based hydrogels for cancer therapy and research.

Cancer is a major health issue concerning to all of us. Current treatment options are still limited due to not-selective action. Encapsulation is contemplated as an innovative approach to address systemic toxicity and tumor resistance caused by traditional therapies, while increasing encapsulated compounds bioavailability. The coating material of capsules strongly determines the success of the system. Since alginate has been proved non-toxic, biocompatible and biodegradable, it is considered a potential vehicle for therapeutic factors encapsulation. Besides, it has the particular ability to form hydrogels, which hold a high-water content and greatly resemble to natural soft tissues. The present review exposes the state-of-the-art and the most sophisticated alginate-based systems for cancer therapy and research. It begins with an overview of alginate hydrogels and the qualities that make them especially suitable for biomedical applications. In the following section, the application of alginate hydrogels as pioneering strategies for cancer treatment is described. Several examples of alginate-based delivery systems of therapeutic drugs, proteins and nucleic acids are provided. Significant emphasis is placed in both oral delivery systems and colorectal cancer therapy. Moreover, the role of alginate 3-D scaffolds for both cell culture and delivery is explained. Lastly, other applications of alginate-based hydrogels such as tumor biomarkers immunosensing and fluorescent surgical marker are included.

Correction: Functionalized fluorescent terephthalate monomers and their attempted polyester formation.

Correction for 'Functionalized fluorescent terephthalate monomers and their attempted polyester formation' by Yvonne S. L. Choo et al., Org. Biomol. Chem., 2020, 18, 8735-8745, DOI: 10.1039/D0OB01533D.

Functionalized fluorescent terephthalate monomers and their attempted polyester formation.

The reaction of diethyl 2,5-bis(tert-butyl)phenoxy-3,6-dihydroxyterephthalate (1) with tetraethylene glycol di(p-toluenesulfonate) under high-dilution conditions afforded several isolated products. Two products were identified as macrocycles with one being the 1 + 1 crown ether derivative 3 (10% yield), and the second being the 2 + 2 crown ether compound D3 (19% yield). The X-ray structure for 3 was determined with the asymmetric unit observed to comprise half of the molecule. The small crown ether ring of 3 interacts with K+ or H+ ions in MeOH, but binding is weak and the macrocyclic cavity is too small to fully encapsulate the K+ ion. Transesterification of compounds 1, its methylated version 2 and 3 with diols such as ethylene glycol or 1,4-butandiol produced monomers (M1-M3) which were reacted with terephthaloyl chloride. Short oligomers were produced (PolyM1-PolyM3) rather than extensive polymeric materials and all displayed solid state fluorescence. The absorption and fluorescence properties of M1-M2 and their polymers can be related to subtle structural changes. The Stokes shift for M2 of 15 627 cm-1 in DCM is one of the largest observed for a simple organic chromophore in fluid solution.

Current Perspectives of the Applications of Polyphenols and Flavonoids in Cancer Therapy.

The development of anticancer therapies that involve natural drugs has undergone exponential growth in recent years. Among the natural compounds that produce beneficial effects on human health, polyphenols have shown potential therapeutic applications in cancer due to their protective functions in plants, their use as food additives, and their excellent antioxidant properties. The possibility of combining conventional drugs-which are usually more aggressive than natural compounds-with polyphenols offers very valuable advantages such as the building of more efficient anticancer therapies with less side effects on human health. This review shows a wide range of trials in which polyphenolic compounds play a crucial role as anticancer medicines alone or in combination with other drugs at different stages of cancer: cancer initiation, promotion, and growth or progression. Moreover, the future directions in applications of various polyphenols in cancer therapy are emphasized.

Contrasting Photo-Switching Rates in Azobenzene Derivatives: How the Nature of the Substituent Plays a Role.

A molecular design approach was used to create asymmetrical visible light-triggered azo-derivatives that can be good candidates for polymer functionalization. The specific electron-donor substituted molecules were characterized and studied by means of NMR analyses and UV-visible spectroscopy, comparing the results with Time Dependent Density Functional (TD-DFT) calculations. A slow rate of isomerization (ki = 1.5 × 10-4 s-1) was discovered for 4-((2-hydroxy-5methylphenyl) diazenyl)-3-methoxybenzoic acid (AZO1). By methylating this moiety, it was possible to unlock the isomerization mechanism for the second molecule, methyl 3-methoxy-4-((2-methoxy-5-methylphenyl) diazenyl)benzoate (AZO2), reaching promising isomerization rates with visible light irradiation in different solvents. It was discovered that this rate was heightened by one order of magnitude (ki = 3.1 × 10-3 s-1) for AZO2. A computational analysis using density functional (DFT/PBE0) and wavefunction (QD-NEVPT2) methodologies provided insight into the photodynamics of these systems. Both molecules require excitation to the second (S2) excited state situated in the visible region to initiate the isomerization. Two classic mechanisms were considered, namely rotation and inversion, with the former being energetically more favorable. These azo-derivatives show potential that paves the way for future applications as building blocks of functional polymers. Likewise, they could be really effective for the modification of existing commercial polymers, thus transferring their stimuli responsive properties to polymeric bulky structures, converting them into smart materials.

Stability and anti-proliferative properties of biologically active compounds extracted from Cistus L. after sterilization treatments.

The growing interest of oncologists in natural compounds such as polyphenols and flavonoids is encouraging the development of innovative and efficient carriers for the delivery of those drugs. This study examines carboxymethyl chitosan-based microcapsules created by spray drying as a method for delivering biologically active compounds isolated from the Cistus herb. Effects of sterilization and encapsulation on the polyphenol and flavonoid content of Cistus extract were investigated to optimize the production process. Furthermore, in vitro studies were carried out to examine the anticancer properties of sterilized polyphenols and flavonoids on glioblastoma cells isolated from oncological patients. Acquired results show high anticancer potential towards glioblastoma as well as low cytotoxicity towards non-cancer cell lines by the substances in question. Steam sterilization is shown to affect the content of biologically active compounds the least. We demonstrate that the investigated form of drug encapsulation is both efficient and potentially possible to scale up from the viewpoint of the pharmaceutical industry.

Encapsulation for Cancer Therapy.

The current rapid advancement of numerous nanotechnology tools is being employed in treatment of many terminal diseases such as cancer. Nanocapsules (NCs) containing an anti-cancer drug offer a very promising alternative to conventional treatments, mostly due to their targeted delivery and precise action, and thereby they can be used in distinct applications: as biosensors or in medical imaging, allowing for cancer detection as well as agents/carriers in targeted drug delivery. The possibility of using different systems-inorganic nanoparticles, dendrimers, proteins, polymeric micelles, liposomes, carbon nanotubes (CNTs), quantum dots (QDs), biopolymeric nanoparticles and their combinations-offers multiple benefits to early cancer detection as well as controlled drug delivery to specific locations. This review focused on the key and recent progress in the encapsulation of anticancer drugs that include methods of preparation, drug loading and drug release mechanism on the presented nanosystems. Furthermore, the future directions in applications of various nanoparticles are highlighted.