Search Results (609)

Esterification is a key transformation in the production of lubricants, pharmaceuticals, and fine chemicals. Conventional processes employing homogeneous acid catalysts suffer from limitations such as corrosive byproducts, energy-intensive separation, and poor catalyst reusability. This review provides a comprehensive overview of heterogeneous catalytic systems, including ion exchange resins, zeolites, metal oxides, mesoporous materials, and others, for improved ester synthesis. Recent advances in membrane-integrated reactors, such as pervaporation and nanofiltration, which enable continuous water removal, shifting equilibrium and increasing conversion under milder conditions, are reviewed. Dual-functional membranes that combine catalytic activity with selective separation further enhance process efficiency and reduce energy consumption. Enzymatic systems using immobilized lipases present additional opportunities for mild and selective reactions. Future directions emphasize the integration of pervaporation membranes, hybrid catalyst systems combining biocatalysts and metals, and real-time optimization through artificial intelligence. Modular plug-and-play reactor designs are identified as a promising approach to flexible, scalable, and sustainable esterification. Overall, the interaction of catalyst development, membrane technology, and digital process control offers a transformative platform for next-generation ester synthesis aligned with green chemistry and industrial scalability. Full article

Developing and identifying the correct reactor model for a reaction system characterized by a high number of reaction pathways and flow regimes can be challenging. In this work, artificial neural networks (ANNs), used in deep learning, are used to develop a hybrid modelling framework for physics-based model discovery in reactions systems. The model discovery accuracy of the framework is investigated considering kinetic model parametric uncertainty, noise level, features in the data structure and experimental design optimization via a differential evolution algorithm (DEA). The hydrodynamic behaviours of both a continuously stirred tank reactor and a plug flow reactor and rival chemical kinetics models are combined to generate candidate physics-based models to describe a benzoic acid esterification synthesis in a rotating cylindrical reactor. ANNs are trained and validated from in silico data simulated by sampling the parameter space of the physics-based models. Results show that, when monitored using test data classification accuracy, ANN performance improved when the kinetic parameters uncertainty decreased. The performance improved further by increasing the number of features in the data set, optimizing the experimental design and decreasing the measurements error (low noise level). Full article

Novel lipophilic hydroxyalkyl esters were synthetized by Fischer esterification in good to excellent yields (60–96%) from a panel of hydroxyphenylacetic acids and increasing chain length (2 to 8 carbon atoms) α,ω-diols. The in vitro antioxidant activity of these compounds was evaluated by DPPH and ABTS assays. Hydroxybutyl esters and hydroxyphenylacetic acids were used as starting materials for the synthesis of novel lipophilic diesters (butyl diarylacetates) using Mitsunobu reaction. The final products were isolated in moderate to good yields (40–78%), and their structure–antioxidant activity relationships are discussed. Compounds bearing the catechol moiety on one of the two aromatic rings and high lipophilicity proved to be the strongest antioxidants and were selected for testing as antibacterials against Staphylococcus aureus and Escherichia coli, obtaining preliminary and promising results. Full article

Polylactic acid (PLA) is a renewable biopolymer that has attracted considerable interest due to its ability to replace petroleum-based synthetic polymers, thereby offering a more sustainable alternative to global environmental concerns. This study focused on evaluating the effect of catalyst concentration and reaction time on the efficiency of PLA synthesis via the Ring-Opening Polymerization (ROP) technique. The process involved a lactic acid esterification stage (using 88% lactic acid) to obtain lactide, employing 40% and 60% (v/v) sulfuric acid concentrations, followed by polymerization at various reaction times (10, 15, 20, and 30 min). Analysis of variance (ANOVA) results revealed that the 40% catalyst concentration had a statistically significant effect on polymer yield (p = 0.032), whereas reaction time showed no statistical significance (p = 0.196), although the highest yields were recorded at 10 and 15 min. Fourier Transform Infrared Spectroscopy (FTIR) confirmed the presence of the characteristic functional groups of PLA, and Differential Scanning Calorimetry (DSC) revealed a semi-crystalline structure with a high melting temperature, indicating good thermal stability. These results validate the viability of PLA as a functional and sustainable biopolymer. Full article

Polycarboxylate superplasticizer (PCE) is an important part of improving the overall performance of concrete. However, its synthetic raw materials are overly dependent on petrochemical products, and it also causes problems such as environmental pollution. With the development of the building material industry, the demand for petrochemical resources required for synthetic water-reducing agents will increase rapidly. Therefore, there is an urgent need to transition the synthetic raw materials of PCE from petrochemicals to biomass materials to reduce the consumption of nonrenewable resources as well as the burden on the environment. Biomass materials are inexpensive, readily available and renewable. Utilizing biomass resources to develop good-performing water-reducing agents can reduce the consumption of fossil resources. This is conducive to carbon emission reduction in the concrete material industry. In addition, it promotes the high-value utilization of biomass resources. Therefore, in this study, a biomass polyether monomer, acryloyl hydroxyethyl cellulose (AHEC), was synthesized from cellulose via the reaction route of ethylene oxide (EO) etherification and acrylic acid (AA) esterification. Biomass polycarboxylate superplasticizers (PCE-Cs) were synthesized through free radical polymerization by substituting AHEC for a portion of the frequently utilized polyether monomer isopentenyl polyoxyethylene ether (TPEG). This study primarily focused on the properties of PCE-Cs in relation to cement. The findings of this study indicated that the synthesized PCE-C5 at a dosing of 0.4% (expressed as mass fraction of cement) when the AHEC substitution ratio was 5% achieved good water reduction properties and significant delays. With the same fluidity, PCE-C5 could enhance the mechanical strength of cement mortar by 30% to 40%. This study utilized green and low-carbon biomass resources to develop synthetic raw materials for water-reducing agents, which exhibited effective water-reducing performance and enhanced the utilization rate of biomass resources, demonstrating significant application value. Full article

Biodiesel, a renewable and environmentally friendly alternative to fossil fuels, has attracted significant attention due to its potential to reduce greenhouse gas emissions. However, high production costs and complex processing remain challenges. Heterogeneous catalysts have shown promise in overcoming these barriers by offering benefits, such as easy separation, reusability, low-cost raw materials, and the ability to reduce reaction times and energy consumption. This review evaluates key classes of heterogeneous catalysts, such as metal oxides, ion exchange resins, and zeolites, and their performance in transesterification and esterification processes. It highlights the importance of catalyst preparation methods, textural properties, including surface area, pore volume, and pore size, activation techniques, and critical operational parameters, like the methanol-to-oil ratio, temperature, time, catalyst loading, and reusability. The analysis reveals that catalysts supported on high surface area materials often achieve higher biodiesel yields, while metal oxides derived from natural sources provide cost-effective and sustainable options. Challenges, such as catalyst deactivation, sensitivity to feedstock composition, and variability in performance, are discussed. Overall, the findings underscore the potential of heterogeneous catalysts to enhance biodiesel production efficiency, although further optimization and standardized evaluation protocols are necessary for their broader industrial application. Full article

The covalent conjugation of pharmaceutical compounds to polymeric carriers represents an effective strategy for enhancing drug properties, including improved bioavailability, targeted delivery, and sustained release, while reducing systemic toxicity and adverse effects. By exploiting the physicochemical characteristics of biopolymers—particularly molecular charge and weight—we engineered a polymeric platform for glucocorticoid delivery with precisely controlled parameters including particle size, surface charge, targeting capability, and release kinetics. This study reports a linker-free synthesis of hyaluronic acid-dexamethasone (HA-DEX) conjugates through Steglich esterification, catalyzed by 4-dimethylaminopyridine (DMAP), which facilitates the acylation of sterically hindered alcohols. The reaction specifically couples carboxyl groups of hyaluronic acid with the C21 hydroxyl group of dexamethasone. Incorporation of hydrophobic dexamethasone moieties induced self-assembly into nanoparticles featuring a hydrophobic core and negatively charged hydrophilic shell (−20 to −25 mV ζ-potential). In vitro characterization revealed pH-dependent release profiles, with 80–90% dexamethasone liberated in mildly acidic phosphate buffer (pH 5.2) versus 50–60% in phosphate-buffered saline (pH 7.4) over 35 days, demonstrating both sustained release and inflammation-responsive behavior. The conjugates exhibited potent anti-inflammatory activity in a human tumor necrosis factor-α (TNFα)-induced inflammation model. These findings position HA-DEX conjugates as promising candidates for targeted glucocorticoid delivery to specific anatomical sites including ocular, articular, and tympanic tissues, where their combination of CD44-targeting capability, enhanced permeability and retention effects, and stimulus-responsive release can optimize therapeutic outcomes while minimizing off-target effects. Full article

Oleochemicals, which are obtained from vegetable and animal fats and oils, have become indispensable in the food, cosmetics, pharmaceutical and biofuel industries. Traditionally, they are synthesized using chemical catalysts, a process that is often associated with high energy requirements and a considerable environmental impact. Biocatalysis, using enzymes such as lipases, has emerged as a transformative alternative that offers high specificity, environmental friendliness and cost-efficiency. This review comprehensively examines the current state of biocatalysis for oleochemical synthesis, highlighting key reactions such as esterification and transesterification and their integration into industrial processes. A bibliometric analysis uncovers global trends and collaborations, while case studies illustrate cost efficiency and scalability. The article outlines recommendations and future research directions to advance biocatalytic processes. This review is intended to be an important resource for researchers and industries transitioning to sustainable oleochemical production. Full article

Traditional designs often ignore the effect of catalyst particle shape, which suffers from capturing detailed local flow hydrodynamics, mass transport and reaction behaviors, and further significantly affects reactor phenomena. This study aims to perform particle-resolved computational fluid dynamics (CFD) simulations to investigate the influence of operating conditions and various catalyst particle shapes on fixed-bed reactor performance. Three important industrial reaction systems, including methanol to dimethyl ether, CO₂ hydrogenation to methanol, and levulinic acid esterification, are discussed in fixed-bed reactors. The numerical results demonstrate that reactor performance varies from the important interactive contributions of hydrodynamics characteristics and reaction behaviors. Specifically, exothermic reactions such as methanol to dimethyl ether and CO₂ hydrogenation to methanol are characterized by a gradual increase in temperature along the reactor height, while endothermic reactions such as valeric acid esterification exhibit a gradual decrease in temperature along the reactor height. For the methanol to dimethyl ether system, the increase in operating temperature leads to a decrease in axial methanol concentration, as well as an improvement in axial dimethyl ether concentration. However, the change in methanol molar concentration has little influence on its conversion. Furthermore, reactor phenomena strongly vary from the different catalyst shapes. The numerical results demonstrate that the fixed bed with hollow cylinders facilitates a more uniform flow distribution, whereas the fixed bed with solid cylinders achieves higher conversion rates within a specific temperature range (483.15 K to 523.15 K). This research provides valuable insights for fixed-bed reactor optimized design, emphasizing the need for precise control over temperature, feed rate, and catalyst configuration to improve reactant conversion in industrial applications. Full article

This study presents a multilayer magnetic Janus sub-micrometric particle (MMJSP) as a nanoreactor for lipase catalysis. The core of the nanoparticle is constructed from a core-shell Fe₃O₄@SiO₂ framework, which serves as a precursor for the sequential amino and aldehyde modifications using 3-aminopropyltriethoxysilane and benzaldehyde. Following localized etching and subsequent modification with N,N-dimethyldodecylamine, a Janus nanoparticle with distinct hydrophilic and hydrophobic domains is synthesized. The resulting MMJSP demonstrates a stable attachment to the reaction interface and significantly enhances lipase performance, exhibiting 1.4-fold and 1.6-fold enhancements in activity after immobilization during 1 h hydrolysis and 24 h esterification reactions, respectively. Additionally, the storage stability of the immobilized lipase is improved by 100% over a period of 30 days. Reusability assessments reveal that the immobilized enzyme retains 80.7% activity after 10 cycles of esterification and 80.6% after 50 cycles of hydrolysis, with the magnetic properties allowing for rapid separation and recovery of the immobilized enzyme. Full article

LDPE was crosslinked with novel dynamic or conventional crosslinking agents during melt processing. Both crosslinkers were synthesized by the esterification of Thiele’s acid or adipic acid with 4-hydroxy-TEMPO. ¹H-NMR showed that a temperature of 170 °C and a reaction time of 24 min are required for a successful crosslinking. The concentrations of crosslinking agents were 1.45, 2.9, and 5.8 mol%. Conventionally crosslinked LDPEs show a decrease in soluble content in hot xylene with increased crosslinker concentrations, while dynamically crosslinked LDPEs show no change after thermal treatment, indicating the scission of dynamic crosslinks. The rheology of both crosslinked LDPEs at 130 °C shows that the stress release is slower than that of neat LDPE, confirming crosslinking, while at 170 °C a shift in the stress release and also a shift in the flow properties of dynamically crosslinked LDPE towards those of neat LDPE are observed, both indicating the cleavage of dynamic crosslinks. Compared to neat LDPE, the mechanical properties of both crosslinked LDPEs show an increase in Young’s modulus and tensile strength and a decrease in elongation and creep when the concentration of both crosslinkers is increased. By increasing the processing temperature to 170 °C, the crystallinity index decreases, leading to a rather small improvement in the mechanical properties. Full article

Current hydrogels used for cartilage tissue engineering often lack the mechanical strength and structural integrity required to mimic native human cartilage. This study addresses this limitation by developing reinforced hydrogels based on a ternary polymer blend of poly(vinyl) alcohol (PVA), gelatin (GL), and chitosan (CH), with gentamicin sulfate (GS) as an antimicrobial agent and a crosslinker. The hydrogels were produced using two crosslinking methods, the freeze/thaw and heated cycles, and reinforced with forcespun polycaprolactone (PCL) nanofiber to improve mechanical performance. Chemical characterization revealed that GS forms weak hydrogen bonds with the ternary polymers, leading to esterification with PVA, and covalent bonds are formed as the result of the free amino group (-NH₂) of chitosan that reacts with the carboxylic acid group (-COOH) of gelatin. SEM images help us to see how the hydrogels are reinforced with polycaprolactone (PCL) fibers produced via force spinning technology, while mechanical properties were evaluated via uniaxial tensile and compressive tests. Water retention measurements were performed to examine the crosslinking process’s influence on the hydrogel’s water retention, while the hydrogel surface roughness was obtained via confocal microscopy images. A constitutive model based on non-Gaussian strain energy density was introduced to predict experimental mechanical behavior data of the hydrogel, considering a non-monotonous softening function. Loading and unloading tests demonstrated that GS enhanced crosslinking without compromising water retention or biocompatibility because of the reaction between the free amino group of CH and the carboxylic group of gelatin. The PCL-reinforced PVA/GL/CH hydrogel shows strong potential for cartilage repair and tissue engineering applications. Full article

In this study, novel biodegradable polycaprolactone (PCL)-based composites for sustainable packaging applications were developed by adding surface-treated wood fibers (WFs). Specifically, the WFs were treated with citric acid (CA) to improve the fiber/matrix adhesion and then melt compounded with a PCL matrix. The presence of an absorption peak at 1720 cm⁻¹ in the Fourier transform infrared (FTIR) spectra of CA-treated WFs, coupled with the increase in the storage modulus and complex viscosity in the rheological analysis, confirmed the occurrence of an esterification reaction between CA and WFs, with a consequent increase in interfacial interactions with the PCL matrix. Scanning electron microscopy (SEM) of the cryo-fractured surface of the composites highlighted that PCL was able to efficiently wet the fibers after the CA treatment, with limited fiber pull-out. Quasi-static tensile tests showed that the composites reinforced with CA-treated wood fibers exhibited a significant increase in yield strength (about 30% with a WF amount of 10% at 0 °C) and also a slight improvement in the VICAT softening temperature (about 6 °C with respect to neat PCL). Water absorption tests showed reduced water uptake in CA-treated composites, consistent with the reduced hydrophilicity confirmed by higher water contact angle values. Therefore, the results obtained in this work highlighted the potential of CA-treated WFs as reinforcement for PCL composites, contributing to the development of eco-sustainable and high-performance packaging materials. Full article

We developed a novel biodegradable poly(lactic-co-glycolic acid) (PLGA) polymer chemically modified with paclitaxel (PTX) to form a PLGA-PTX hybrid. Pre-modification of PTX enhanced its loading in PLGA-PTX nanoparticles (NPs). Background/Objectives: PTX is one of the most effective chemotherapy agents used in cancer therapy. The primary mode of PTX’s action is the hyperstabilization of microtubules leading to cell growth arrest. Although highly potent, the drug is water insoluble and requires the Cremophor EL excipient. The toxic effects of the free drug (e.g., neurotoxicity) as well as its solubilizing agent are well established. Thus, there is strong clinical rationale and need for exploring alternative PTX delivery approaches, retaining biological activity and minimizing systemic effects. Methods: The PTX modification method features reacting the C-2′ and C-7 residues with a linker (succinic anhydride) to produce easily accessible carboxyl groups on the PTX for enhanced coupling to the hydroxyl group of PLGA. The PLGA-PTX hybrid, formed via esterification reaction, was used to formulate lipid-coated PLGA-PTX NPs. As proof of concept, the PLGA-PTX NPs were tested in ovarian cancer (OvCA) models, including several patient-derived cell lines (PDCLs), one of which was generated from a platinum-resistant patient. Results: The PLGA-PTX NPs critically remained stable in water and serum while enabling slow drug release. Importantly, PLGA-PTX NPs demonstrated biological activity. Conclusions: We suggest that this approach offers both a new and effective PTX formulation and a possible path towards the development of a new generation of OvCA treatment. Full article

Background: A series of novel polysubstituted thiazole derivatives were synthesized, and their antiproliferative properties were evaluated using both 2D and 3D lung cancer models. Methods: The compounds were obtained via esterification, oximation, hydrazinolysis, and condensation reactions. Results: Structure–activity relationship analysis revealed that the antiproliferative activity was structure-dependent. Notably, oxime derivatives 21 and 22, along with carbohydrazides 25 and 26, exhibited low micromolar activity that was significantly greater than that of cisplatin (p < 0.005), a standard chemotherapeutic agent. These compounds demonstrated potent, antiproliferative activity against H69 small-cell lung carcinoma cells, as well as anthracycline-resistant H69AR cells. Moreover, compounds 21, 22, 25, and 26 effectively induced cell death in A549 agarose-based 3D spheroids, further supporting their potential therapeutic application. The in silico studies proposed that compound 22 is able to interact with human SIRT2 and EGFR via conserved amino acid residues. Conclusions: The ability of these thiazole derivatives to target both drug-sensitive and drug-resistant lung cancer models highlights their promise as scaffolds for further optimization and preclinical development. Future studies will focus on structural modifications to enhance potency, selectivity, and pharmacokinetic properties, paving the way for the development of novel thiazole-based antiproliferative agents. Full article