Dialysis membranes are not hemocompatible with human blood, as the patients are suffering from the blood-membrane interactions\' side effects. Zwitterionic structures have shown improved hemocompatibility; however, their complicated synthesis hinders their commercialization. The goal of the study is to achieve fast functionalization for carboxybetaine and sulfobetaine zwitterionic immobilization on PES membranes while comparing the stability and the targeted hemocompatibility. The chemical modification approach is based on an aminolysis reaction. Characterization, computational simulations, and clinical analysis were conducted to study the modified membranes. Atomic force microscopy (AFM) patterns showed a lower mean roughness for carboxybetaine-modified (6.3 nm) and sulfobetaine-modified (7.7 nm) membranes compared to the neat membrane (52.61 nm). The pore size of the membranes was reduced from values above 50 nm for the neat PES to values between 2 and 50 nm for zwitterionized membranes, using Brunauer-Emmett-Teller (BET) analysis. More hydrophilic surfaces led to a growth equilibrium water content (EWC) of nearly 6% for carboxybetaine and 10% for sulfobetaine-modified membranes. Differential scanning calorimetry (DSC) measurements were 12% and 16% stable water for carboxybetaine- and sulfobetaine-modified membranes, respectively. Sulfobetaine membranes showed better compatibility with blood with respect to C5a, IL-1a, and IL-6 biomarkers. Aminolysis-based zwitterionization was found to be suitable for the improvement of hemodialysis membranes. The approach introduced in this paper could be used to modify the current dialysis membranes with minimal change in the production facilities.

Biomaterial-based drug-carrying systems have scored enormous focus in the biomedical sector. Poly(lactic acid) (PLA) is a versatile material in this context. A porous and hydrophilic PLA surface can do this job better. We aimed to synthesize pH-responsive PLA-based porous films for uptaking and releasing amikacin sulfate in the aqueous media. The native PLA lacks functional/polar sites for the said purpose. So, we tended to aminolyze it for tailored physicochemical and surface properties. The amino (-NH2) group density on the treated films was examined using the ninhydrin assay. Electron microscopic analyses indicated the retention of porous morphology after aminolysis. Surface wettability and FTIR results expressed that the resultant films became hydrophilic after aminolysis. The thermal analysis expressed reasonable thermal stability of the aminolyzed films. The prepared films expressed pH-responsive behaviour for loading and releasing amikacin sulfate drug at pH 5.5 and 7.4, respectively. The drug release data best-fitted the first-order kinetic model based on Akaike information and model selection criteria. The prepared PLA-based aminolyzed films qualified as potential candidates for pH-responsive drug delivery applications. This study could be the first report on pH-responsive amikacin sulfate uptake and release on the swellable aminolyzed PLA-based porous films for effective drug delivery application.

A remarkable challenge in the anticancer drug delivery system is developing an implantable system that can improve the chemotherapeutic effect. Polyurethane is an excellent implantable substrate, with flaws in hydrophobicity. We modified polyurethane via the chemical aminolysis technique to enhance the wettability and protein interaction. The created pores can release the rutin complex incorporated in the polyurethane matrix. In this work, the hybrid polymer matrix consists of Mxene synthesized via a sustainable and simple method by introducing a toxic-free MAX phase and etchants. The incorporation of Mxene and PCL can enhance physicochemical and biological compatibility. Sustainable Mxene increases oxidative stress, cell death, and antibacterial activity, which also resulted in the Mxene@APU/PCL film. Meanwhile, the drug release with respect to pH sensitivity was demonstrated in which Mxene and Mxene@APU/PCL films showed the highest release at pH 5.2; this indicates that the prepared Mxene and aminolyzed polyurethane can function according to the biological system and release the drug from the polymer matrix on slow degradation and swellability. The Mxene and Mxene@APU/PCL films showed 93.2% drug release with oxidative stress on THP-1 cells, which causes rupturing and apoptosis of cancerous cells. The Mxene@APU/PCL film can show great potential in future implantable anticancer drug delivery systems.

Aminolysis is widely recognized as a valuable chemical route for depolymerizing polymeric materials containing ester, amide, or urethane functional groups, including polyurethane foams. Bio-based polyurethane foams, pristine and reinforced with 40 wt% of sustainable fillers, were depolymerized in the presence of bio-derived butane-1,4-diamine, BDA. A process comparison was made using fossil-derived ethane-1,2-diamine, EDA, by varying amine/polyurethane ratio (F/A, 1:1 and 1:0.6). The obtained depolymerized systems were analyzed by FTIR and NMR characterizations to understand the effect of both diamines on the degradation pathway. The use of bio-based BDA seemed to be more effective with respect to conventional EDA, owing to its stronger basicity (and thus higher nucleophilicity), corresponding to faster depolymerization rates. BDA-based depolymerized systems were then employed to prepare second-generation bio-based composite polyurethane foams by partial replacement of isocyanate components (20 wt%). The morphological, mechanical, and thermal conductivity properties of the second-generation polyurethane foams were evaluated. The best performances (σ10 %=71 ± 9 kPa, λ = 0.042 ± 0.015 W∙ m-1 ∙K-1) were attained by employing the lowest F/A ratio (1:0.6); this demonstrates their potential application in different sectors such as packaging or construction, fulfilling the paradigm of the circular economy.

Bio-based drug delivery devices have gained enormous interest in the biomedical field due to their biocompatible attributes. Extensive research is being conducted on chitosan-based devices for drug delivery applications. Chitosan being hydrophobic under neutral conditions makes it difficult to interact with a polar drug of curcumin. We tended to make it polar through sol-gel synthesis and modification via PEGylation, alkaline hydrolysis, and aminolysis. Such alterations could make the chitosan-based scaffolds porous, hydrophilic, amino-functionalized, and pH-responsive. The ninhydrin assay confirmed that a successful aminolysis occurred, and the chemical interaction among the precursors was explained under infrared spectroscopy. The scanning morphology of the optimum aminolyzed membrane appeared to be porous with an average pore size of 320 ± 20 nm. The aminolyzed chitosan membrane was found thermally stable up to 310 °C, hydrophilic with a water contact angle of 23.4°, moderate flowablity, and porous (97 ± 5 %, w/w) against ethanol. The curcumin-loaded chitosan membrane expressed the UV-protection behavior of 99 %. The curcumin-loading and release phenomena were found pH-responsive. The curcumin release results were evaluated through specific kinetic models. This study could be the first report on the amphiphilic, porous, and swellable drug-loaded gelatin/chitosan membrane with pH-responsive loading and release of curcumin for potential drug delivery applications.

Despite the tremendous progress in the development of functional materials from plastic waste to promote its recycling, only a few examples of hydrogel materials from plastic waste were reported. In this study, microwave-assisted depolymerization of waste PET plastic using polyamine was performed to prepare short aminophthalamide oligomers followed by chemically cross-linking into a hydrogel material. Catalyst-free microwave-assisted aminolysis of PET was completed within 30-40 s, demonstrating high efficiency of the depolymerization reaction. Subsequent epoxy cross-linking of the oligomers yielded a hydrogel with a swelling degree of ca. 92.1 times in pure water. The application of the obtained hydrogel for the removal of copper ions (Cu2+) from water was demonstrated. Efficient complexation of NH2 groups of the hydrogel with Cu2+ resulted in high adsorption capacities of the hydrogel material toward Cu2+ removal, which were the highest at neutral pHs and reached ca. 213 mg/g. The proposed type of environmental material is beneficial owing to its waste-derived nature and functionality that can be applied for the high-efficiency removal of a broad scope of known environmental pollutants.

Construction of artificial cells requires the development of straightforward methods for mimicking natural phospholipid membrane formation. Here we describe the use of direct aminolysis ligations to spontaneously generate biomimetic phospholipid membranes from water-soluble starting materials. Additionally, we explore the suitability of such biomimetic approaches for driving the in situ formation of native phospholipid membranes. Our studies suggest that non-enzymatic ligation reactions could have been important for the synthesis of phospholipid-like membranes during the origin of life, and might be harnessed as simplified methods to enable the generation of lipid compartments in artificial cells.

The waste management of polyethylene terephthalate (PET)-derived polyester (PES) textile is a global issue, and material recovery through chemical recycling can restore a circular economy. In our investigation, microwave-induced catalytic aminolysis and glycolysis of PES textile wastes using Ag-doped ZnO nanoparticles have been proposed. Ag-doped ZnO is prepared by the sol-gel method and characterised by XRD, FT-IR, UV-Vis, SEM-EDX and TEM. The reaction parameters such as PET-to-catalyst ratio, microwave power and irradiation time, temperature and catalyst recycling have been optimised. The catalyst was found to be more stable and could be recycled up to six times without losing its activity. Both the aminolysis and glycolysis of PES showed 100% conversion and afforded of bis (2-hydroxy ethylene) terephthalamide (BHETA) and bis (2-hydroxy ethylene) terephthalate (BHET), respectively. The depolymerisation of PES wastes using Ag-doped ZnO afforded BHETA and BHET for about 95 and 90%, respectively. The monomers BHET and BHETA confirmed by FT-IR, 1H NMR and mass spectroscopy. According to the findings, 2 mol% Ag-doped ZnO has higher catalytic activity.

Herein we present a nickel-catalyzed regio- and enantioselective ring opening reaction of 3,4-epoxy amides and esters with aromatic amines as nucleophiles. This method features high regiocontrol, diastereospecific SN 2 reaction pathway, broad substrate scope, and mild reaction conditions, furnishing a wide range of γ-amino acid derivatives in a highly enantioselective manner. Notably, the selective nucleophilic attack to the C-4 position of epoxides is controlled by the directing effect of the pendant carbonyl group.

New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2\',3\'-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine. Subsequently, fluorinated polymers bearing hydroxyurethane moieties (FPHUs) were prepared by reacting the bis-CC with different hexamethylenediamine amounts in bulk at 80 °C and the presence of a catalyst. The chemoselective polymerization reaction yielded three isomers bearing primary and secondary hydroxyl groups in 61-82% yield. The synthesized fluorinated CCs and the corresponding FPHUs were characterized by 1H, 19F, and 13C NMR spectroscopy. They were compared to their hydrogenated homologues synthesized in similar conditions. The gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) data of the FPHUs revealed a higher molar mass and a slight increase in glass transition and decomposition temperatures compared to those of the PHUs.